注册 English

Ni2MⅡTe2ⅣO2(PO4)2(OH)4 (MⅡ = Ni, Zn): Synthesis, Crystal Structure, and Magnetic Properties

Jia-Ze CHEN ,  Rong-Chuan ZHUANG ,  Jin-Xiao MI ,  Ya-Xi HUANG

downloadPDF
Citation:  Jia-Ze CHEN, Rong-Chuan ZHUANG, Jin-Xiao MI, Ya-Xi HUANG. Ni2MⅡTe2ⅣO2(PO4)2(OH)4 (MⅡ = Ni, Zn): Synthesis, Crystal Structure, and Magnetic Properties[J]. Chinese Journal of Structural Chemistry, 2021, 40(11): 1439-1448. doi: 10.14102/j.cnki.0254–5861.2011–3194 shu

Ni2MⅡTe2ⅣO2(PO4)2(OH)4 (MⅡ = Ni, Zn): Synthesis, Crystal Structure, and Magnetic Properties

English

  • 1. INTRODUCTION

    The non-centrosymmetric (NCS) crystal structure compounds have attracted much attention due to their special physical properties, such as piezoelectricity, ferroelectricity, and second-order nonlinear optical (NLO) behavior[1-4]. Great efforts have been made to design and explore NCS crystal structures. One effective strategy is to introduce asymmetric structural units intentionally into the crystal structure, such as the use of cations (Pb2+, Bi3+, Te4+) with stereo-chemically active lone pair (SCALP), the d0 transition metal cations (Ti4+, Mo6+, W6+) and d10 transition metal cations (Zn2+, Cd2+) with strong polar displacements[4-8]. As a result, various NCS crystal structure compounds have been designed and synthesized with wide applications[9-12].

    Te4+ ion contains stereo-chemically active lone pair (SCALP). It can not only form asymmetric units with second-order Jahn-Teller (SOJT) distortion[4, 13, 14], but can also form various structural building units TeOx (x = 3, 4 or 5) polyhedra[4, 15-17]. The combination of these TeOx polyhedra with perfect binding group PO4 can effectively give compounds with abundant structure types, which could be a very promising direction to search for non-centrosymmetric crystal structure. Up to date, dozens of tellurite phosphates or telluro-phosphates with rich structure chemistry[2, 5, 7, 18-27] have been reported, for example, such as the 1D chain compound Ba2TeO(PO4)2[19], the 2D layer compounds Te2O3HPO4[25], NaTePO5[27], K2TeP2O8[12], Ba2Cu2Te2P2O13[26] and SrTeP2O8[27], and the 3D framework compounds Na3Ca4(TeO3)(PO4)3[24], Ba2Zn2TeP2O11[22], Te2O(PO4)2[7] and Co3Te2O2(PO4)2(OH)4[21]. Recently, our group have also reported a tellurite phosphate β-Te3O3(PO4)2[16], which is polymorphic with α-Te3O3(PO4)2[18]. In our processive study on tellurite phosphate, we attempt to add d10 transition metal Zn with polar displacements into TeO2-P2O5 system to deepen the understanding on the essential factors controlling the formation of non-centrosymmetric crystal structure. As a result, a new nickel zinc tellurite phosphate Ni2ZnTe2ⅣO2(PO4)2(OH)4 (designated as NiZnTePO) and an unitary nickel tellurite phosphate Ni3Te2ⅣO2(PO4)2(OH)4 (designated as NiTePO) have been observed, while the zinc tellurite phosphate has not been obtained successfully. Here we report the synthesis, crystal structure, and characterizations of two tellurite phosphates, and the discussion of the origin of centrosymmetric crystal structure.

    2. EXPERIMENTAL

    2.1 Synthesis

    The single crystals of Ni2ZnTe2ⅣO2(PO4)2(OH)4 were synthesized via a modified hydrothermal method. A mixture of NiCl2·6H2O (0.238 g, 1.0 mmol), ZnCl2 (0.136 g, 1.0 mmol), TeO2 (0.160 g, 1.0 mmol) and (NH4)H2PO4 (0.445 g, 3.0 mmol) were loaded into a Teflon-lined stainless-steel autoclave containing 3 mL of deionized water without stirring, followed by heating at 190 ℃ for 7 days, and then cooled down to room temperature naturally.

    The resulting solid products were washed with deionized water in the ultrasonic machine for several times and then dried in air. Light green prism crystals of Ni2ZnTe2ⅣO2(PO4)2(OH)4 (Fig. 1) were obtained in 90% yields based on Te mass. The presence of Ni, Zn, Te and P has been confirmed by EDX results with a molar ratio of Ni: Zn: Te: P ≈ 2:1:2:2. The experimental PXRD pattern shown in Fig. 2 agrees well with the calculated one based on single crystal data.

    Figure 1

    Figure 1.  SEM images and EDX results of (a) Ni2ZnTe2ⅣO2(PO4)2(OH)4 single crystal and (b) Ni3Te2ⅣO2(PO4)2(OH)4
    DownLoad: Full-Size Img PowerPoint

    Figure 2

    Figure 2.  Observed and calculated PXRD patterns of Ni2ZnTe2ⅣO2(PO4)2(OH)4 together with the observed PXRD pattern of Ni3Te2ⅣO2(PO4)2(OH)4
    DownLoad: Full-Size Img PowerPoint

    From the perspective of nonlinear optical crystals, we hope to get zinc tellurite phosphate in which the Zn2+ ions have large band gaps for optical transmission. The attempt to get unitary zinc tellurite phosphate was failed. However, by only adding a mixture of NiCl2·6H2O (0.238 g, 1.0 mmol), TeO2 (0.160 g, 1.0 mmol) and (NH4)H2PO4 (0.445 g, 3.0 mmol) but removing ZnCl2 from reactants, we can get a new unitary nickel tellurite phosphate Ni3Te2ⅣO2(PO4)2(OH)4 isostructural to Ni2ZnTe2ⅣO2(PO4)2(OH)4 confirmed by PXRD (Figs. 2 and 3) and EDX (Fig. 1b) results. However, it is difficult to get single crystals to determine the single-crystal structure of this nickel tellurite phosphate, since only bundles of crystals were obtained due to its uncontrollable crystallization behavior under current reaction conditions. Therefore, herein we only report the single crystal structure of Ni2ZnTe2ⅣO2(PO4)2(OH)4.

    Figure 3

    Figure 3.  Experimental (black dot) and calculated (red line) X-ray diffraction patterns of Ni3Te2ⅣO2(PO4)2(OH)4. The difference profile (blue) and background (black) from Rietveld refinement (a = 19.2500(15) Å, b = 5.9352(6) Å, c = 4.7625(4) Å, β = 103.853(8)°, V = 528.31(2) Å3, Z = 2, Rp = 4.121, Rwp = 6.177). The Bragg positions are indicated by the vertical bars below the patterns
    DownLoad: Full-Size Img PowerPoint

    2.2 Characterization methods

    Powder X-ray diffraction (PXRD) Powder X-ray diffraction data were collected on a Bruker D8 Advance powder X-ray diffractometer with CuKα radiation (λ = 1.5418 Å, Ni filter, 40 kV and 40 mA).

    Scanning electron microscopy/energy-dispersive analysis by X-ray (SEM/EDX) The crystal morphologies and element contents were investigated by utilizing a field-emission scanning electron microscopy (FE-SEM) system (Hitachi SU70) that was equipped with an energy-dispersive X-ray spectrometry device.

    Infrared spectroscopy The infrared spectrum in the range of 400~4000 cm−1 was recorded on a Nicolet iS10 FT-IR spectrometer at room temperature.

    Thermal analysis Thermal analyses were performed on a SDT Q600 thermogravimetric/differential scanning calorimetry (TG/DSC) instrument under conditions ranging from room temperature to 800 ℃ at a heating rate of 10 ℃·min−1 in a N2 gas flow of 100 mL·min−1.

    UV-vis-NIR diffuse reflectance spectroscopy The diffuse reflectance spectra were performed on a Varian Cary 5000 UV-Vis-NIR scan spectrometer, using BaSO4 as the standard in the spectral range of 200~800 nm at room temperature.

    Magnetic properties The magnetic susceptibilities were measured in gelatin capsules at a magnetic field of 1000 Oe using a Quantum Design MPMS XL-7 SQUID magnetometer in the temperature range of 2~300 K.

    2.3 Structure determination

    A suitable single crystal (0.12mm × 0.03mm × 0.03mm) of Ni2ZnTe2ⅣO2(PO4)2(OH)4 for single-crystal X-ray diffraction analysis has been selected under a binocular optical microscope, and further checked via its transparency and extinction under a polarized microscope. The data were collected on an Oxford Gemini S Ultra diffractometer with MoKα radiation (λ = 0.71073 Å, 50 kV and 40 mA) at 193(2) K. In the range of 3.58≤θ≤28.26º, a total number of 1730 reflections were collected and 664 were independent with Rint = 0.0355, of which 639 were observed with I > 2σ(I). Multi-scan absorption correction has been performed. The crystal structure was solved by direct methods and refined by full-matrix least-squares technique using the SHELX programs[28] included in the WinGX package[29], and further checked for missing symmetry elements by using PLATON[30]. The atomic positions of Te, Ni, Zn, P and some coordinated O atoms were determined by direct methods. The rest O atom sites were located from difference Fourier maps. The bond valence sum calculations showing a low value of 1.63 for O(1) and 1.26 for O(2) indicate that the O(2) is a donor while the O(1) is an acceptor of hydroxyl group. However, no suitable position in difference Fourier maps could be located as H site. Hence, the H atoms were determined from theoretical calculation according to the empirical O−H distances 0.82(2) Å and the hydrogen bond requirement between O(1) and O(2) atoms. Meanwhile, the displacement parameters of H2 were constrained to be 0.05 e·Å–3. The final full-matrix least-squares refinement converged to R = 0.0369 and wR = 0.1086 for 639 observed reflections with I > 2σ(I), S = 1.103, Dc = 4.517 g·cm−3, μ(MoKα) = 11.434 mm–1 and F(000) = 672. The largest diffraction peak and hole are 1.49 and −1.91 e·Å–3, respectively. The chemical formula was defined to be Ni2ZnTe2ⅣO2(PO4)2(OH)4. The selected bond lengths and bond angles and the hydrogen bond lengths and bond angles of Ni2ZnTe2ⅣO2(PO4)2(OH)4 are given in Tables 1 and 2, respectively.

    Table 1

    Table 1.  Selected Bond Lengths (Å) and Bond Angles (°) of Ni2ZnTe2ⅣO2(PO4)2(OH)4
    DownLoad: CSV
    Bond Dist. Bond Dist. Bond Dist.
    Te(1)–O(5) 1.864(7) Ni(1)–O(4) 2.074(5) Zn(1)–O(2)vii 2.104(5)
    Te(1)–O(2)i 2.003(5) Ni(1)–O(5)ii 2.114(5) P(1)–O(3) 1.523(7)
    Te(1)–O(2) 2.003(5) Ni(1)–O(5) 2.114(5) P(1)–O(1) 1.532(7)
    Te(1)–O(4) 2.314(5) Zn(1)–O(1) 2.060(6) P(1)–O(4)viii 1.544(5)
    Te(1)–O(4)i 2.314(5) Zn(1)–O(1)iii 2.060(6) P(1)–O(4)ix 1.544(5)
    Ni(1)–O(3)ii 2.045(5) Zn(1)–O(2)iv 2.104(5) O(2)–H(2) 0.821(5)
    Ni(1)–O(3) 2.045(5) Zn(1)–O(2)v 2.104(5)
    Ni(1)–O(4)ii 2.074(5) Zn(1)–O(2)vi 2.104(5)
    Angle (°) Angle (°) Angle (°)
    O(5)–Te(1)–O(2)i 92.7(2) O(4)ii–Ni(1)–O(5)ii 78.3(2) O(2)v–Zn(1)–O(2)vii 84.5(3)
    O(5)–Te(1)–O(2) 92.7(2) O(3)–Ni(1)–O(5) 95.8(2) O(2)vi–Zn(1)–O(2)vii 180.0(3)
    O(2)i–Te(1)–O(2) 90.9(3) O(3)ii–Ni(1)–O(5) 84.2(2) O(3)–P(1)–O(1) 108.7(4)
    O(5)–Te(1)–O(4) 77.71(18) O(4)–Ni(1)–O(5) 78.3(2) O(3)–P(1)–O(4)viii 110.0(2)
    O(2)i–Te(1)–O(4) 85.30(19) O(4)ii–Ni(1)–O(5) 101.7(2) O(1)–P(1)–O(4)viii 109.6(2)
    O(2)–Te(1)–O(4) 169.51(19) O(5)ii–Ni(1)–O(5) 180.0 O(3)–P(1)–O(4)ix 110.0(2)
    O(5)–Te(1)–O(4)i 77.71(18) O(1)iii–Zn(1)–O(1) 180.0 O(1)–P(1)–O(4)ix 109.6(2)
    O(2)i–Te(1)–O(4)i 169.51(19) O(1)iii–Zn(1)–O(2)iv 92.65(19) O(4)viii–P(1)–O(4)ix 108.8(4)
    O(2)–Te(1)–O(4)i 85.30(19) O(1)–Zn(1)–O(2)iv 87.35(19) P(1)–O(1)–Zn(1) 128.1(4)
    O(4)–Te(1)–O(4)i 96.7(2) O(1)iii–Zn(1)–O(2)v 87.35(19) Te(1)–O(2)–Zn(1)x 122.6(2)
    O(3)–Ni(1)–O(3)ii 180.0 O(1)–Zn(1)–O(2)v 92.65(19) P(1)–O(3)–Ni(1)xi 130.89(18)
    O(3)–Ni(1)–O(4) 90.3(2) O(2)iv–Zn(1)–O(2)v 180.0(4) P(1)–O(3)–Ni(1) 130.89(18)
    O(3)ii–Ni(1)–O(4) 89.7(2) O(1)iii–Zn(1)–O(2)vi 87.35(19) Ni(1)xi–O(3)–Ni(1) 93.8(3)
    O(3)–Ni(1)–O(4)ii 89.7(2) O(1)–Zn(1)–O(2)vi 92.65(19) P(1)xii–O(4)–Ni(1) 131.2(3)
    O(3)ii–Ni(1)–O(4)ii 90.3(2) O(2)iv–Zn(1)–O(2)vi 84.5(3) P(1)xii–O(4)–Te(1) 125.8(3)
    O(4)–Ni(1)–O(4)ii 180.0 O(2)v–Zn(1)–O(2)vi 95.5(3) Ni(1)–O(4)–Te(1) 95.04(18)
    O(3)–Ni(1)–O(5)ii 84.2(2) O(1)iii–Zn(1)–O(2)vii 92.65(19) Te(1)–O(5)–Ni(1) 108.9(2)
    O(3)ii–Ni(1)–O(5)ii 95.8(2) O(1)–Zn(1)–O(2)vii 87.35(19) Te(1)–O(5)–Ni(1)xiii 108.9(2)
    O(4)–Ni(1)–O(5)ii 101.7(2) O(2)iv–Zn(1)–O(2)vii 95.5(3) Ni(1)–O(5)–Ni(1)xiii 89.8(3)
    Symmetry codes: (i) x, −y+1, z; (ii) −x+1/2, −y+1/2, −z+1; (iii) −x+1, −y, −z; (iv) −x+1, −y+1, −z+1; (v) x, y−1, z−1; (vi) x, −y+1, z−1; (vii) −x+1, y−1, −z+1; (viii) x, −y, z−1; (ix) x, y, z−1; (x) x, y+1, z+1; (xi) −x+1/2, y−1/2, −z+1; (xii) x, y, z+1; (xiii) −x+1/2, y+1/2, −z+1

    Table 2

    Table 2.  Hydrogen Bond Lengths (Å) and Bond Angles (°) of Ni2ZnTe2ⅣO2(PO4)2(OH)4
    DownLoad: CSV
    D–H···A d(D–H) d(H···A) d(D···A) ∠DHA
    O(2)–H(2)···O(1)xiv 0.82 2.00 2.819(8) 180
    Symmetry code: (xiv) x, y+1, z

    3. RESULTS AND DISCUSSION

    3.1 Crystal structure description

    Both Ni3Te2ⅣO2(PO4)2(OH)4 and Ni2ZnTe2ⅣO2(PO4)2(OH)4 are new tellurite phosphates crystallizing in the monoclinic space group C2/m (No. 12) and isostructural to Co3Te2O2(PO4)2(OH)4[21]. Therefore, in the crystal structure of Ni3Te2ⅣO2(PO4)2(OH)4, Ni atoms have two positions Ni(1) and Ni(2) according to the structure of Co3Te2O2(PO4)2(OH)4[21], while in Ni2ZnTe2ⅣO2(PO4)2(OH)4, the original position of Ni(2) is completely replaced by Zn(1), which is confirmed by the results of single-crystal structure refinement and magnetic properties.

    For Ni2ZnTe2ⅣO2(PO4)2(OH)4, there is one unique site each for Te, Ni, Zn and P atoms, and five for O atoms in the asymmetric unit. The Te(1) atom, sited at the special position 4i (m), is five-coordinated to three O atoms and two OH groups to form a tetragonal pyramidal TeO3(OH)2. The Ni(1) atom (at an inversion center 4f (-1)) is in an octahedral coordination environment coordinated to six O atoms, resulting in a distorted NiO6 octahedron. The Zn(1) atom occupied the special position of 2b (2/m) is six-coordinated to four OH groups at the equatorial plane and two O atoms at the apexes to form a compressed octahedral ZnO2(OH)4. The P(1) atom also sites at a special position 4i (m) which is four-coordinated to O atoms to form a regular PO4 tetrahedron. The bond lengths of Te−O, Ni−O, Zn−O and P−O fall in the ranges of 1.864(7)~2.314(5), 2.045(5)~2.114(5), 2.060(6)~2.104(5) and 1.523(7)~1.544(5) Å, respectively. Meanwhile, the bond angles of O–Te–O, O–Ni–O, O–Zn–O and O–P–O vary from 77.71(18) to 169.51(19)º, 78.3(2) to 180.0º, 84.5(3) to 180.0º, and 108.7(4) to 110.0(2)º, respectively. These values are consistent with those related compounds reported previously[8, 16, 31]. The bond valence sum calculations[32] results on Ni2ZnTe2ⅣO2(PO4)2(OH)4 are given in Table 3, revealing 1.92 Å for Ni(1), 2.12 Å for Zn(1), 4.00 Å for Te(1) and 4.98 Å for P(1) respectively, which are in their expected values[8, 16, 31].

    Table 3

    Table 3.  Bond Valence Sum Calculations of the Atoms in Ni2ZnTe2ⅣO2(PO4)2(OH)4
    DownLoad: CSV
    Atom Ni(1) Zn(1) Te(1) P(1) BVS
    O(1) - +0.38
    (+0.38×2)    		 - +1.25
    (+1.25)    		 1.63
    O(2) - +0.34
    (+0.34×4)    		 +0.92
    (+0.92×2)    		 - 1.26
    O(3) +0.35×2
    (+0.35×2)*    		 - +1.29
    (+1.29)    		 1.99
    O(4) +0.32
    (+0.32×2)    		 - +0.40
    (+0.40×2)    		 +1.22
    (+1.22×2)    		 1.94
    O(5) +0.29×2
    (+0.29×2)    		 - +1.36
    (+1.36)    		 - 1.94
    BVS 1.92 2.12 4.00 4.98 -
    *(+n) is for the BVS of line atoms and +n for the BVS of column atoms.

    As is shown in Fig. 4, each NiO6 octahedron connects the neighboring counterparts via trans-edge-sharing to form an infinite linear chain along the b-axis (Fig. 4a). Neighboring linear chains are intra- and inter-connected by PO4 tetrahedra via vertex-sharing, forming 4-membered rings (4-MR) and 3-membered rings (3-MR) (Fig. 4b) which result in the [Ni2O2(PO4)2]6− layers parallel to the bc-plane (Fig. 4b, 4c, 4e). Each ZnO2(OH)4 octahedron shares four equatorial OH groups each with a TeO3(OH)2 tetragonal pyramid forming a four-member ring (4-MR) single chain [ZnTe2O2(OH)4]2+ running along the b-axis (Fig. 4d). Finally, the [Ni2O2(PO4)2]6− layers are interconnected by [ZnTe2O2(OH)4]2+ single chains via vertex-sharing to form a three-dimensional framework structure (Fig. 4e & 4f). In a unit cell, the neighboring [Ni2O2(PO4)2]6− layers are antiparallelly arranged, leading to the extra-large a-axis (a = 19.3247(10) Å). Alternately, the crystal structure can also be looked as isolated ZnO2(OH)4 octahedra at the middle points of [100] and [010] edges linked to the trans-edge sharing [NiO6] linear chains at (1/4, y, 1/2) and (3/4, y, 1/2) via isolated [PO4] tetrahedra and TeO3(OH)2 tetragonal pyramids to form a three-dimensional crystal structure (Fig. 4e & 4f).

    Figure 4

    Figure 4.  Crystal structure of Ni2ZnTe2ⅣO2(PO4)2(OH)4. (a) 1D linear NiO6 octahedral chain running along the b-axis; (b) [Ni2O2(PO4)2]6− layer paralleling to the bc-plane built from linear NiO6 octahedral chains intra- and inter-connected by PO4 tetrahedra via vertex sharing; (c) [Ni2O2(PO4)2]6− layer viewed along the c-axis; (d) [ZnTe2O2(OH)4]2+ single chain running along the b-axis built from ZnO2(OH)4 octahedra and TeO3(OH)2 tetragonal pyramids; (e) Crystal structure viewed along the b-axis; (f) Crystal structure viewed along the c-axis. NiO6 octahedra, dark-gray; ZnO2(OH)4 octahedra, light-gray; PO4 tetrahedra, black; Te atoms, dark-gray balls; Ni atoms, medium-gray balls; O atoms, light-gray balls; H atoms, small black balls
    DownLoad: Full-Size Img PowerPoint

    It is needed to note that, due to the existence of SCALP, the Te4+ located at mirror plane (y = 0 or 1/2) forms an acentric tetragonal pyramid TeO3(OH)2, which has inherent dipole moment. The calculated value of TeO3(OH)2 dipole moment is 8.39 Debyes according to the method described by Maggard et al.[33]. However, as shown in Fig. 5, TeO3(OH)2 tetragonal pyramids do not connect to each other, and arrange in a centrosymmetric (2/m) correlation in the unit cell, i.e. the dipole moment directions are arranged in an antiparallel manner. As a result, the adjacent dipole moments offset each other, which leads to the formation of a centrosymmetric crystal structure. The isolated acentric TeO3(OH)2 units are easily affected by other structural units and aligned in a centrosymmetric arrangement. We suppose that the polymerization of acentric units TeOx may reserve their non-centrosymmetric characteristics and that could be an efficient route to design non-centrosymmetric crystal structure.

    Figure 5

    Figure 5.  Site arrangement of TeO3(OH)2 in the unit cell with symmetry graphical symbol, where black arrows represent the dipole moments. Other atoms are omitted for clarity
    DownLoad: Full-Size Img PowerPoint

    3.2 Infrared spectroscopy

    The infrared spectra (Fig. 6) of Ni2ZnTe2ⅣO2(PO4)2(OH)4 and Ni3Te2ⅣO2(PO4)2(OH)4 reveals that both compounds show similar absorption bands and consist of P−O, Te−O, Te−O−P and O−H vibrations. In the following assignments, two absorption band values (value 1/value 2) belong to Ni2ZnTe2ⅣO2(PO4)2(OH)4/Ni3Te2ⅣO2(PO4)2(OH)4, respectively. The broad bands at around 3209/3205 cm−1 are assigned to the O−H stretching vibrations. The absorption bands at 1047~975/1047~976 cm−1 can be assigned to the P−O stretching vibrations whereas the bands at 725/719 cm−1 can be attributed to the Te−O stretching vibrations. The bands at 608/610 cm−1 can be assigned to the Te−O−P vibrations, whereas the bands at 538/540 and 447/449 cm−1 can be attributed to the P−O bending vibrations. The above band absorptions are similar with those in related compounds[16, 34], confirming the existence of OH, TeO3(OH)2 and PO4 groups.

    Figure 6

    Figure 6.  Infrared spectra of Ni2ZnTe2ⅣO2(PO4)2(OH)4 and Ni3Te2ⅣO2(PO4)2(OH)4.
    DownLoad: Full-Size Img PowerPoint

    3.3 Thermal analysis

    The thermal analysis results of Ni2ZnTe2ⅣO2(PO4)2(OH)4 and Ni3Te2ⅣO2(PO4)2(OH)4 are shown in Fig. 7. TG curves of two compounds show significant weight loss in the temperature range of 300~600 ℃. For Ni2ZnTe2ⅣO2(PO4)2(OH)4, the observed weight loss is 5.68 wt%, which agrees with the calculated value of 4.94 wt% for removing OH groups (2×H2O per formula unit). For Ni3Te2ⅣO2(PO4)2(OH)4, the observed weight loss is 6.32 wt%, also consistent with the calculated value of 4.99 wt% for removing OH groups. The relatively large observed weight loss of both compounds could be attributed to the condensation of OH groups accompanied with the evaporation of TeO2. The results further confirm the existence of OH groups.

    Figure 7

    Figure 7.  TG-DTG curves of Ni2ZnTe2ⅣO2(PO4)2(OH)4 (a) and Ni3Te2ⅣO2(PO4)2(OH)4 (b).
    DownLoad: Full-Size Img PowerPoint

    3.4 UV-Vis-NIR diffuse reflectance spectroscopy

    The UV-Vis-NIR diffuse reflectance spectra of Ni2ZnTe2ⅣO2(PO4)2(OH)4 and Ni3Te2ⅣO2(PO4)2(OH)4 (Fig. 8) show that the transmission ranges are limited by nickel element. They have wide absorption ranges in the UV and near infrared range together with a valley at around 400 nm. The highest reflectance peaks at 533 nm are consistent with the green color of the observed crystals for the title two compounds.

    Figure 8

    Figure 8.  UV-Vis-NIR diffuse reflectance spectra of Ni2ZnTe2ⅣO2(PO4)2(OH)4 (black curve) and Ni3Te2ⅣO2(PO4)2(OH)4 (gray curve)
    DownLoad: Full-Size Img PowerPoint

    3.5 Magnetic properties

    Fig. 9 shows the magnetic susceptibility (χ) and reciprocal susceptibility (1/χ) curves of Ni3Te2ⅣO2(PO4)2(OH)4 and Ni2ZnTe2ⅣO2(PO4)2(OH)4 in the temperature range of 2~300 K.

    Figure 9

    Figure 9.  Temperature dependence of magnetic susceptibility (χ) and the corresponding reciprocal susceptibility (1/χ) for (a) Ni3Te2ⅣO2(PO4)2(OH)4 and (b) Ni2ZnTe2ⅣO2(PO4)2(OH)4. Hollow circle, magnetic susceptibility; solid gray circle, the reciprocal of susceptibility; black line, the fitting line
    DownLoad: Full-Size Img PowerPoint

    For Ni3Te2ⅣO2(PO4)2(OH)4, the Curie-Weiss law is observed between 30 and 250 K and gives the Weiss temperature θ = −22.6 K which indicates predominant antiferromagnetic spin-exchange interaction. The effective magnetic moment μeff(Ni-atom) = 3.31 μB indicates the existence of orbital coupling effect besides the interaction between electron spins only (μspin-only = 2.83 μB). Its magnetic characteristics are similar to those of Co3Te2O2(PO4)2(OH)4[21]. Two maxima are observed at low temperature. The maximum at 20 K is most likely due to a two-dimensional antiferromagnetic ordering of linear [Ni(1)O6] chains coupled by interchain interaction via [PO4] groups in the [Ni2O2(PO4)2]6− layer (Fig. 4b). The second maximum at around 5 K is probably due to the Ni(2) entities via super-super exchange involving [PO4] and [TeO3(OH)2] groups.

    For Ni2ZnTe2ⅣO2(PO4)2(OH)4, from 30 to 250 K its magnetic susceptibility follows the Curie-Weiss law, with a Weiss temperature θ = −10.9 K and effective magnetic moment of μeff(Ni-atom) = 3.11 μB. Only one maximum is observed at low temperature. Obviously, the magnetic properties of two compounds are quite different, indicating magnetic structure difference between them.

    The magnetic species in both compounds are Ni atoms. Generally, from the perspective of crystallography, Ni and Zn may co-occupy in one site due to their similar radius and coordination environments. If this is the case for Ni2ZnTe2ⅣO2(PO4)2(OH)4, the magnetic ordering at low temperature of Ni2ZnTe2ⅣO2(PO4)2(OH)4 should be similar to that of Ni3Te2ⅣO2(PO4)2(OH)4. However, Ni2ZnTe2ⅣO2(PO4)2(OH)4 takes another magnetic susceptibility compared to Ni3Te2ⅣO2(PO4)2(OH)4. Furthermore, counting on the molar ratio of Ni: Zn = 2:1 according to EDX results, Zn sitting at the special position 2b of Ni(2) while Ni locating at the special position 4f of Ni(1) just fits the molar ratio requirement that could lead to different magnetic structures compared with Ni3Te2ⅣO2(PO4)2(OH)4. Therefore, Zn(1) does not partially replace both Ni(1) and Ni(2) positions but completely substitute the Ni(2) position. The results further confirm the single crystal refinement results.

    4. CONCLUSION

    In summary, we have successfully synthesized two isostructural tellurite phosphates Ni2MⅡTe2ⅣO2(PO4)2(OH)4 (MⅡ = Ni, Zn) via hydrothermal method. The crystal structure of Ni2MⅡTe2ⅣO2(PO4)2(OH)4 (MⅡ = Ni, Zn) features a 3D framework composed of [Ni2O2(PO4)2]6− layers interconnected by [MTe2O2(OH)4]2+ single chains. Different magnetic susceptibility results at low temperature of the two title compounds confirm that Zn(1) completely occupies the Ni(2) position but not partially substitutes both Ni(1) and Ni(2) position atoms. The acentric TeO3(OH)2 tetragonal pyramids are aligned in an antiparallel manner, resulting in the crystallization of centrosymmetric (C2/m) crystal structure for the title compound. The investigation of the origin of centrosymmetric crystal structure with strong dipole moment units provides deeper understanding for future rational design of non-centrosymmetric crystal structure. To the best of our knowledge, Ni2ZnTe2ⅣO2(PO4)2(OH)4 is the first mix transition metal tellurite phosphate up to now.


    1. [1]

      Halasyamani, P. S.; Poeppelmeier, K. R. Noncentrosymmetric oxides. Chem. Mater. 1998, 10, 2753–2769. doi: 10.1021/cm980140w

    2. [2]

      Guesdon, A.; Raveau, B. A series of Mo(VI) monophosphates involving the lone pair cation Te(Ⅳ): A2TeMo2O6(PO4)2 (A = K, Rb, Tl, Cs). Chem. Mater. 2000, 12, 2239–2243. doi: 10.1021/cm000035y

    3. [3]

      Halasyamani, P. S. Asymmetric cation coordination in oxide materials: influence of lone-pair cations on the intra-octahedral distortion in d0 transition metals. Chem. Mater. 2004, 16, 3586–3592. doi: 10.1021/cm049297g

    4. [4]

      Mao, J. G.; Jiang, H. L.; Kong, F. Structures and properties of functional metal selenites and tellurites. Inorg. Chem. 2008, 47, 8498–8510. doi: 10.1021/ic8005629

    5. [5]

      Ok, K. M.; Orzechowski, J.; Halasyamani, P. S. Synthesis, structure, and characterization of two new layered mixed-metal phosphates, BaTeMO4(PO4) (M = Nb5+ or Ta5+). Inorg. Chem. 2004, 43, 964–968. doi: 10.1021/ic0350335

    6. [6]

      Ok, K. M.; Halasyamani, P. S. Asymmetric cationic coordination environments in new oxide materials:  synthesis and characterization of Pb4Te6M10O41 (M = Nb5+ or Ta5+). Inorg. Chem. 2004, 43, 4248–4253. doi: 10.1021/ic049534h

    7. [7]

      Kim, M. K.; Kim, S. H.; Chang, H. Y.; Halasyamani, P. S.; Ok, K. M. New noncentrosymmetric tellurite phosphate material: synthesis, characterization, and calculations of Te2O(PO4)2. Inorg. Chem. 2010, 49, 7028–7034. doi: 10.1021/ic100706n

    8. [8]

      Tang, X. Y.; Mi, J. X.; Zhuang, R. C.; Wang, S. H.; Wu, S. F.; Pan, Y. M.; Huang, Y. X. Rational design and synthesis of a deep-ultraviolet nonlinear optical fluorinated orthophosphate: BaZn(PO4)F. Inorg. Chem. 2019, 58, 4508–4514. doi: 10.1021/acs.inorgchem.9b00073

    9. [9]

      Tang, R. L.; Hu, C. L.; Wu, B. L.; Fang, Z.; Chen, Y.; Mao, J. G. Cs2Bi2O(Ge2O7) (CBGO): a larger SHG effect induced by synergistic polarizations of BiO5 polyhedra and GeO4 tetrahedra. Angew. Chem. Int. Ed. 2019, 58, 15358–15361. doi: 10.1002/anie.201909735

    10. [10]

      Wen, M.; Hu, C.; Wu, H. P.; Yang, Z. H.; Yu, H. H.; Pan, S. L. Three non-centrosymmetric bismuth phosphates, Li2ABi(PO4)2 (A = K, Rb, and Cs): effects of cations on the crystal structure and SHG response. Inorg. Chem. Front. 2020, 7, 3364–3370. doi: 10.1039/D0QI00778A

    11. [11]

      Ma, Y. X.; Gong, Y. P.; Hu, C. L.; Kong, F.; Mao, J. G. BiGa(SeO3)3: a phase matchable SHG material achieved by cation substitution. Inorg. Chem. 2020, 59, 7852–7859. doi: 10.1021/acs.inorgchem.0c00984

    12. [12]

      Wen, M.; Hu, C.; Yang, Z. H.; Wu, X. H.; Pan, S. L. K2TeP2O8: a new telluro-phosphate with a pentagonal Te-P-O layer structure. Dalton Trans. 2018, 47, 9453–9458. doi: 10.1039/C8DT01576G

    13. [13]

      Pearson, R. G. The second-order Jahn-Teller effect. J. Mol. Struct. Theochem. 1983, 12, 25–34.

    14. [14]

      Ok, K. M.; Halasyamani, P. S. Mixed-metal tellurites: synthesis, structure, and characterization of Na1.4Nb3Te4.9O18 and NaNb3Te4O16. Inorg. Chem. 2005, 44, 3919–3925. doi: 10.1021/ic050256b

    15. [15]

      Christy, A. G.; Mills, S. J.; Kampf, A. R. A review of the structural architecture of tellurium oxycompounds. Mineral. Mag. 2016, 80, 415–545. doi: 10.1180/minmag.2016.080.093

    16. [16]

      Li, L.; Zhuang, R. C.; Mi, J. X.; Huang, Y. X. A new modification of tellurite phosphate β-Te3O3(PO4)2. Chin. J. Struct. Chem. 2018, 37, 1417–1425.

    17. [17]

      Kim, J. H.; Halasyamani, P. S. A rare multi-coordinate tellurite, NH4ATe4O9·2H2O (A = Rb or Cs): the occurrence of TeO3, TeO4, and TeO5 polyhedra in the same material. J. Solid State Chem. 2008, 181, 2108–2112. doi: 10.1016/j.jssc.2008.04.032

    18. [18]

      Mayer, H.; Weil, M. Synthesis and crystal structure of Te3O3(PO4)2, a compound with 5-fold coordinate tellurium (Ⅳ). Z. Anorg. Allg. Chem. 2003, 629, 1068–1072. doi: 10.1002/zaac.200300036

    19. [19]

      Ok, K. M.; Halasyamani, P. S. Synthesis, structure, and characterization of a new one-dimensional tellurite phosphate, Ba2TeO(PO4)2. J. Solid State Chem. 2006, 179, 1345–1350. doi: 10.1016/j.jssc.2006.01.045

    20. [20]

      Schmidt, P.; Dallmann, H.; Kadner, G.; Krug, J.; Philipp, F.; Teske, K. The thermochemical behaviour of Te8O10(PO4)4 and its use for phosphide telluride synthesis. Z. Anorg. Allg. Chem. 2009, 635, 2153–2161. doi: 10.1002/zaac.200900350

    21. [21]

      Zimmermann, I.; Kremer, R. K.; Johnsson, M. Synthesis, crystal structure and magnetic properties of the open framework compound Co3Te2O2(PO4)2(OH)4. J. Solid State Chem. 2011, 184, 3080–3084. doi: 10.1016/j.jssc.2011.09.023

    22. [22]

      Xia, M. J.; Li, R. K. Structural variety in zinc telluro-phosphates: syntheses, crystal structures and characterizations of Sr2Zn3Te2P2O14, Pb2Zn3Te2P2O14 and Ba2Zn2TeP2O11. Dalton Trans. 2016, 45, 7492–7499. doi: 10.1039/C6DT00058D

    23. [23]

      Shen, Y. G.; Zhao, S. G.; Luo, J. H. Study on nonlinear optical properties of Te2HPO7 crystal. J. Synth. Cryst. 2016, 45, 1487–1491.

    24. [24]

      Li, Z.; Zhang, S. Z.; Yin, W. L.; Lin, Z. S.; Yao, J. Y.; Wu, Y. C. Na3Ca4(TeO3)(PO4)3: a new noncentrosymmetric tellurite phosphate with fascinating multimember-ring architectures and intriguing nonlinear optical performance. Dalton Trans. 2018, 47, 17198–17201. doi: 10.1039/C8DT04354J

    25. [25]

      Alcock, N. W.; Harrision, W. D. Refinement of the structure of tellurium phosphate Te2O3HPO4. Acta Crystallogr. Sect. B: Struct. Sci. 1982, 38, 1809–1811. doi: 10.1107/S0567740882007274

    26. [26]

      Xia, M. J.; Shen, S. P.; Lu, J.; Sun, Y.; Li, R. K. Ba2Cu2Te2P2O13: a new telluro-phosphate with S = 1/2 heisenberg chain. J. Solid State Chem. 2015, 230, 75–79. doi: 10.1016/j.jssc.2015.06.023

    27. [27]

      Zhao, M.; Sun, Y. J.; Wu, Y. D.; Mei, D. J.; Wen, S. G.; Doert, T. NaTePO5, SrTeP2O8 and Ba2TeP2O9: three tellurite-phosphates with large birefringence. J. Alloys Compd. 2021, 854, 157243–11. doi: 10.1016/j.jallcom.2020.157243

    28. [28]

      Sheldrick, G. Crystal structure refinement with SHELXL. Acta Crystallogr. Sect. C: Cryst. Struct. Commun. 2015, 71, 3–8. doi: 10.1107/S2053229614024218

    29. [29]

      Farrugia, L. J. Wingx: suite for small-molecule single-crystal crystallography. J. Appl. Crystallogr. 1999, 32, 837–838. doi: 10.1107/S0021889899006020

    30. [30]

      Spek, A. Single-crystal structure validation with the program PLATON. J. Appl. Crystallogr. 2003, 36, 7–13. doi: 10.1107/S0021889802022112

    31. [31]

      Liu, L. C.; Ren, W. J.; Huang, Y. X.; Pan, Y. M.; Mi, J. X. Canted antiferromagnetism in KNi3[PO3(F, OH)]2[PO2(OH)2]F2 with a stair-case kagome lattice. J. Solid State Chem. 2017, 254, 160–165. doi: 10.1016/j.jssc.2017.07.011

    32. [32]

      Brese, N. E.; Okeeffe, M. Bond-valence parameters for solids. Acta Crystallogr. Sect. B: Struct. Sci. 1991, 47, 192–197. doi: 10.1107/S0108768190011041

    33. [33]

      Maggard, P. A.; Nault, T. S.; Stern, C. L.; Poeppelmeier, K. R. Alignment of acentric MoO3F33- anions in a polar material: (Ag3MoO3F3)(Ag3MoO4)Cl. J. Solid State Chem. 2003, 175, 27–33. doi: 10.1016/S0022-4596(03)00090-2

    34. [34]

      Yang, D.; Zhuang, R. C.; Mi, J. X.; Huang, Y. X. Two alkali metal germanophosphates Na3[Ge(OH)(PO4)2]·2H2O and Li2Na[GeO(HPO4)(PO4)]: crystal structures and thermal stability. Chin. J. Struct. Chem. 2021, 40, 114–124.

  • Figure 1  SEM images and EDX results of (a) Ni2ZnTe2ⅣO2(PO4)2(OH)4 single crystal and (b) Ni3Te2ⅣO2(PO4)2(OH)4

    下载: 全尺寸图片 幻灯片

    Figure 2  Observed and calculated PXRD patterns of Ni2ZnTe2ⅣO2(PO4)2(OH)4 together with the observed PXRD pattern of Ni3Te2ⅣO2(PO4)2(OH)4

    下载: 全尺寸图片 幻灯片

    Figure 3  Experimental (black dot) and calculated (red line) X-ray diffraction patterns of Ni3Te2ⅣO2(PO4)2(OH)4. The difference profile (blue) and background (black) from Rietveld refinement (a = 19.2500(15) Å, b = 5.9352(6) Å, c = 4.7625(4) Å, β = 103.853(8)°, V = 528.31(2) Å3, Z = 2, Rp = 4.121, Rwp = 6.177). The Bragg positions are indicated by the vertical bars below the patterns

    下载: 全尺寸图片 幻灯片

    Figure 4  Crystal structure of Ni2ZnTe2ⅣO2(PO4)2(OH)4. (a) 1D linear NiO6 octahedral chain running along the b-axis; (b) [Ni2O2(PO4)2]6− layer paralleling to the bc-plane built from linear NiO6 octahedral chains intra- and inter-connected by PO4 tetrahedra via vertex sharing; (c) [Ni2O2(PO4)2]6− layer viewed along the c-axis; (d) [ZnTe2O2(OH)4]2+ single chain running along the b-axis built from ZnO2(OH)4 octahedra and TeO3(OH)2 tetragonal pyramids; (e) Crystal structure viewed along the b-axis; (f) Crystal structure viewed along the c-axis. NiO6 octahedra, dark-gray; ZnO2(OH)4 octahedra, light-gray; PO4 tetrahedra, black; Te atoms, dark-gray balls; Ni atoms, medium-gray balls; O atoms, light-gray balls; H atoms, small black balls

    下载: 全尺寸图片 幻灯片

    Figure 5  Site arrangement of TeO3(OH)2 in the unit cell with symmetry graphical symbol, where black arrows represent the dipole moments. Other atoms are omitted for clarity

    下载: 全尺寸图片 幻灯片

    Figure 6  Infrared spectra of Ni2ZnTe2ⅣO2(PO4)2(OH)4 and Ni3Te2ⅣO2(PO4)2(OH)4.

    下载: 全尺寸图片 幻灯片

    Figure 7  TG-DTG curves of Ni2ZnTe2ⅣO2(PO4)2(OH)4 (a) and Ni3Te2ⅣO2(PO4)2(OH)4 (b).

    下载: 全尺寸图片 幻灯片

    Figure 8  UV-Vis-NIR diffuse reflectance spectra of Ni2ZnTe2ⅣO2(PO4)2(OH)4 (black curve) and Ni3Te2ⅣO2(PO4)2(OH)4 (gray curve)

    下载: 全尺寸图片 幻灯片

    Figure 9  Temperature dependence of magnetic susceptibility (χ) and the corresponding reciprocal susceptibility (1/χ) for (a) Ni3Te2ⅣO2(PO4)2(OH)4 and (b) Ni2ZnTe2ⅣO2(PO4)2(OH)4. Hollow circle, magnetic susceptibility; solid gray circle, the reciprocal of susceptibility; black line, the fitting line

    下载: 全尺寸图片 幻灯片

    Table 1.  Selected Bond Lengths (Å) and Bond Angles (°) of Ni2ZnTe2ⅣO2(PO4)2(OH)4

    Bond Dist. Bond Dist. Bond Dist.
    Te(1)–O(5) 1.864(7) Ni(1)–O(4) 2.074(5) Zn(1)–O(2)vii 2.104(5)
    Te(1)–O(2)i 2.003(5) Ni(1)–O(5)ii 2.114(5) P(1)–O(3) 1.523(7)
    Te(1)–O(2) 2.003(5) Ni(1)–O(5) 2.114(5) P(1)–O(1) 1.532(7)
    Te(1)–O(4) 2.314(5) Zn(1)–O(1) 2.060(6) P(1)–O(4)viii 1.544(5)
    Te(1)–O(4)i 2.314(5) Zn(1)–O(1)iii 2.060(6) P(1)–O(4)ix 1.544(5)
    Ni(1)–O(3)ii 2.045(5) Zn(1)–O(2)iv 2.104(5) O(2)–H(2) 0.821(5)
    Ni(1)–O(3) 2.045(5) Zn(1)–O(2)v 2.104(5)
    Ni(1)–O(4)ii 2.074(5) Zn(1)–O(2)vi 2.104(5)
    Angle (°) Angle (°) Angle (°)
    O(5)–Te(1)–O(2)i 92.7(2) O(4)ii–Ni(1)–O(5)ii 78.3(2) O(2)v–Zn(1)–O(2)vii 84.5(3)
    O(5)–Te(1)–O(2) 92.7(2) O(3)–Ni(1)–O(5) 95.8(2) O(2)vi–Zn(1)–O(2)vii 180.0(3)
    O(2)i–Te(1)–O(2) 90.9(3) O(3)ii–Ni(1)–O(5) 84.2(2) O(3)–P(1)–O(1) 108.7(4)
    O(5)–Te(1)–O(4) 77.71(18) O(4)–Ni(1)–O(5) 78.3(2) O(3)–P(1)–O(4)viii 110.0(2)
    O(2)i–Te(1)–O(4) 85.30(19) O(4)ii–Ni(1)–O(5) 101.7(2) O(1)–P(1)–O(4)viii 109.6(2)
    O(2)–Te(1)–O(4) 169.51(19) O(5)ii–Ni(1)–O(5) 180.0 O(3)–P(1)–O(4)ix 110.0(2)
    O(5)–Te(1)–O(4)i 77.71(18) O(1)iii–Zn(1)–O(1) 180.0 O(1)–P(1)–O(4)ix 109.6(2)
    O(2)i–Te(1)–O(4)i 169.51(19) O(1)iii–Zn(1)–O(2)iv 92.65(19) O(4)viii–P(1)–O(4)ix 108.8(4)
    O(2)–Te(1)–O(4)i 85.30(19) O(1)–Zn(1)–O(2)iv 87.35(19) P(1)–O(1)–Zn(1) 128.1(4)
    O(4)–Te(1)–O(4)i 96.7(2) O(1)iii–Zn(1)–O(2)v 87.35(19) Te(1)–O(2)–Zn(1)x 122.6(2)
    O(3)–Ni(1)–O(3)ii 180.0 O(1)–Zn(1)–O(2)v 92.65(19) P(1)–O(3)–Ni(1)xi 130.89(18)
    O(3)–Ni(1)–O(4) 90.3(2) O(2)iv–Zn(1)–O(2)v 180.0(4) P(1)–O(3)–Ni(1) 130.89(18)
    O(3)ii–Ni(1)–O(4) 89.7(2) O(1)iii–Zn(1)–O(2)vi 87.35(19) Ni(1)xi–O(3)–Ni(1) 93.8(3)
    O(3)–Ni(1)–O(4)ii 89.7(2) O(1)–Zn(1)–O(2)vi 92.65(19) P(1)xii–O(4)–Ni(1) 131.2(3)
    O(3)ii–Ni(1)–O(4)ii 90.3(2) O(2)iv–Zn(1)–O(2)vi 84.5(3) P(1)xii–O(4)–Te(1) 125.8(3)
    O(4)–Ni(1)–O(4)ii 180.0 O(2)v–Zn(1)–O(2)vi 95.5(3) Ni(1)–O(4)–Te(1) 95.04(18)
    O(3)–Ni(1)–O(5)ii 84.2(2) O(1)iii–Zn(1)–O(2)vii 92.65(19) Te(1)–O(5)–Ni(1) 108.9(2)
    O(3)ii–Ni(1)–O(5)ii 95.8(2) O(1)–Zn(1)–O(2)vii 87.35(19) Te(1)–O(5)–Ni(1)xiii 108.9(2)
    O(4)–Ni(1)–O(5)ii 101.7(2) O(2)iv–Zn(1)–O(2)vii 95.5(3) Ni(1)–O(5)–Ni(1)xiii 89.8(3)
    Symmetry codes: (i) x, −y+1, z; (ii) −x+1/2, −y+1/2, −z+1; (iii) −x+1, −y, −z; (iv) −x+1, −y+1, −z+1; (v) x, y−1, z−1; (vi) x, −y+1, z−1; (vii) −x+1, y−1, −z+1; (viii) x, −y, z−1; (ix) x, y, z−1; (x) x, y+1, z+1; (xi) −x+1/2, y−1/2, −z+1; (xii) x, y, z+1; (xiii) −x+1/2, y+1/2, −z+1
    下载: 导出CSV

    Table 2.  Hydrogen Bond Lengths (Å) and Bond Angles (°) of Ni2ZnTe2ⅣO2(PO4)2(OH)4

    D–H···A d(D–H) d(H···A) d(D···A) ∠DHA
    O(2)–H(2)···O(1)xiv 0.82 2.00 2.819(8) 180
    Symmetry code: (xiv) x, y+1, z
    下载: 导出CSV

    Table 3.  Bond Valence Sum Calculations of the Atoms in Ni2ZnTe2ⅣO2(PO4)2(OH)4

    Atom Ni(1) Zn(1) Te(1) P(1) BVS
    O(1) - +0.38
    (+0.38×2)    		 - +1.25
    (+1.25)    		 1.63
    O(2) - +0.34
    (+0.34×4)    		 +0.92
    (+0.92×2)    		 - 1.26
    O(3) +0.35×2
    (+0.35×2)*    		 - +1.29
    (+1.29)    		 1.99
    O(4) +0.32
    (+0.32×2)    		 - +0.40
    (+0.40×2)    		 +1.22
    (+1.22×2)    		 1.94
    O(5) +0.29×2
    (+0.29×2)    		 - +1.36
    (+1.36)    		 - 1.94
    BVS 1.92 2.12 4.00 4.98 -
    *(+n) is for the BVS of line atoms and +n for the BVS of column atoms.
    下载: 导出CSV
  • 加载中
WeChat 扫一扫看文章
计量
  • PDF下载量:  1
  • 文章访问数:  663
  • HTML全文浏览量:  2
文章相关
  • 发布日期:  2021-11-01
  • 收稿日期:  2021-03-26
  • 接受日期:  2021-06-07
通讯作者: 陈斌, bchen63@163.com
  • 1. 

    沈阳化工大学材料科学与工程学院 沈阳 110142

  1. 本站搜索
  2. 百度学术搜索
  3. 万方数据库搜索
  4. CNKI搜索

/

返回文章

All Rights Reserved by the Chinese Chemical Society   中国化学会 版权所有 京ICP备05002797号

本系统由北京仁和汇智信息技术有限公司开发    技术支持: info@rhhz.net