English

• Cuprous halide complexes have been of great interest for their various structure, unique topologies^[1-3], as well as attractive properties such as luminescence^[4-5], pores^[6] and high reactivity in numerous organic and biochemical reactions^[7-8]. (Cu_xX_y)^x-y (X=halide)^[9] have richer aggregates of different geometries: Cu₂X₂, Cu₃X₃, Cu₃X₇, Cu₃X₈, Cu₄X₄, Cu₄X₁₁, Cu₄X₉, Cu₆X₆^[10-14], and so on. Neutral cuprous halide clusters show Cu₂X₂, Cu₄X₄, and Cu₆X₆. These aggregates can be linked by organic ligands to form cuprous halide coordination polymers. It has been reported N-donor ligands such as pyrazine, bipyridyl^[11], imidazole, triazole^{[13, 15]}, tetrazole^[9], benzotriazole^[16]. To date, a large number of cuprous halide complexes containing triazole ligands have been reported^[17-19]. What we are interested in is that cuprous iodide with 4-aminotriazole shows diversities of Cu(Ⅰ) coordination geometry and new 4-aminotriazole ligands are self-assembled by the condensation reaction or the reductive deaminization^[20]. Herein, we report the syntheses and crystal structures of two Cu₄I₄ aggregates complexes {[Cu₂(aadmtrz)I₂]·CH₃CN}_n (1) and [Cu₂(dptrz)I]_n (2), and illustrate that the length of alkyl side chains of 4-aminotriazole has a certain extent influence on the product formations, structures and topologies. The complexes were characterized by X-ray single crystal analysis and studied by various spectroscopic techniques.

  1   Experimental

  1.1   Materials and methods

  All reagents were purchased commercially and used without further purification. Ligands dmatrz and dpatrz were synthesized according to the literature^[21]. Elemental analyses (C, H, and N) were performed on an Elementar Vario EL Ⅲ analyzer. FTIR spectra were recorded from KBr pellets in the range of 4 000 ~400 cm^-1 on a Bruker Tensor 27 spectrometer. PXRD data were collected in a Bruker D8 Advance X-ray diffractometer using Cu Kα radiation (λ=0.154 059 8 nm) at 30 kV and 15 mA over the 2θ range of 5°~50°. The simulated patterns of 1 and 2 were derived from free Mercury Version 2.2 software. Luminescence spectra were recorded on a CARY Eclipse (Varian, USA) fluorescence spectrophotometer at room temperature.

  1.2   Synthesis of complex {[Cu₂(aadmtrz)I₂]·CH₃CN}_n (1)

  A mixture containing CuI (0.10 g, 0.53 mmol), dmatrz (0.056 g, 0.50 mmol), CH₃CN (1 mL) and H₂O (5 mL) was sealed in a 23 mL of Teflon-lined stainless steel vessel, which was heated at 150 ℃ for 4 days, and cooled to room temperature. Light-green block crystals of 1 were obtained, and picked out, washed with CH₃CN/H₂O (1:5, V/V) and dried in air. Yield: 47.5%. Anal. Calcd. for C₈H₁₄Cu₂I₂N₆(%): C, 16.71; H, 2.45; N, 14.61. Found(%): C, 16.68; H, 2.51; N, 14.62. IR (cm^-1): 3 315 (s), 3 216 (m), 3 004 (w), 2 968 (w), 2 914 (w), 1 622 (s), 1 543 (s), 1 427 (s), 1 373 (m), 1 266 (m), 1 043 (m), 990(m), 891(s), 758(s), 742(m).

  1.3   Synthesis of complex [Cu₂(dptrz)I]_n (2)

  The same synthetic procedure as that for 1 was used except that dmatrz was replaced with dpatrz (0.084 g, 0.50 mmol), giving pale-green octahedral crystals 2 in 25.8% yield. Anal. Calcd. for C₈H₁₄Cu₂ N₃I(%): C, 23.65; H, 3.47; N, 10.34, Found(%): C, 23.58; H, 3.44; N, 10.32%. IR (cm^-1): 3 318 (s), 3 255(m), 3 198 (s), 2 970 (s), 2 927 (m), 2 880 (m), 2 052 (s), 1 621 (s), 1 544 (s), 1 460 (m), 1 390 (m), 1 343 (w), 1 293 (w), 1 210 (w), 1 072 (w), 946 (m), 889 (w), 715 (m).

  1.4   X-ray crystallography

  Single-crystal X-ray diffraction data for comp-lexes 1 and 2 were collected in Beijing Synchrotron Radiation Facility (BSRF) beamline 3W1A which mounted with a MARCCD-165 detector (λ=0.072 00 nm) with storage ring working at 2.5 GeV. In the process, the crystals were protected by liquid nitrogen at 100(2) K. Data were collected by the MARCCD and processed using HKL 2000^[22]. Absorption correc-tions were applied by using the multi-scan program SCALEPACK^[22]. All the structures were solved by the direct methods and refined by the full-matrix least-squares technique using the SHELXL-2014^[23] with all non-hydrogen atoms refined anisotropically. Hydrogen atoms attached to C and N atoms were added theoretically and treated as riding on the concerned atoms. The final cycle of full-matrix least-squares refinement was based on observed reflections and variable parameters. Further crystallographic data and structural refinement details are summarized in Table 1. Selected bond lengths and bond angles are given in Table 2.

  Table 1.  Crystallographic data and structure refinement for 1 and 2

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  	1	2
  Formula	C8H14Cu2I2N6	C8H14Cu2N3I
  Formula weight	575.13	406.20
  Crystal system	Monoclinic	Tetragonal
  Space group	P21/c	I41/a
  a / nm	0.954 7(1)	1.625 3(2)
  b/ nm	1.187 3(2)	1.625 3(2)
  c / nm	1.494 9(5)	1.907 8(4)
  β/(°)	111.23(3)
  V / nm3	1.579 5(7)	5.039 5(1)
  Crystal size / mm	0.45×0.40×0.40	0.05×0.04×0.03
  Z	4	16
  Dc / (g·cm-3)	2.419	2.142
  μ/ mm-1	6.59	5.794
  F(000)	1 072	3 104
  θ range / (°)	2.9~26.0	2.51~25.05
  Gocxlness-of-fit on F2	1.41	1.046
  Reflection collected, unique	3 075, 3 067	2 234, 1 940
  Rint	0.017	0.028 7
  R1, wR2[I>2σ(I)]	0.019 1, 0.058 6	0.032 9, 0.089 2
  R1, wR2(all data)	0.020 9, 0.072 5	0.038 6, 0.092 8
  (Δ/σ)max	0.002	0.004
  Largest diff peak and hole / (e • nm-3)	1 180, -1 580	697, -1 880

  Table 2.  Selected bond lengths (nm) and bond angles (°) of complexes 1 and 2

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  1
  Сu(1)-N(1)	0.201 2(3)	Cu(1)-N(4)	0.206 3(3)	Cu(1)-I(1)	0.268 9(0)
  Сu(1)-I(2)	0.267 1(1)	Cu(2)-N(2)	0.200 1(3)	Cu(2)-I(1)	0.258 0(1)
  Сu(2)-I(2)ⅰ	0.252 3(1)	Сu(1)...Сu(2)ⅰ	0.288 4(1)	Сu(2)-Сu(1)ⅰ	0.288 4(1)
  Cu(2)-I(1)-Cu(1)	81.61(2)	Сu(2)ⅰ-1(2)-Сu(1)	67.41(3)	N(1)-Cu(1)-N(4)	120.04(1)
  N(1)-Cu(1)-I(2)	110.45(9)	N(4)-Cu(1)-I(2)	103.08(8)	N(1)-Cu(1)-I(1)	102.81(9)
  N(4)-Cu(1)-I(1)	104.16(9)	I(2)-Cu(1)-I(1)	116.90(3)	N(1)-Cu(1)-Cu(2)ⅰ	88.55(9)
  N(4)-Cu(1)-Cu(2)ⅰ	149.84(8)	I(2)-Сu(1)-Сu(2)ⅰ	53.84(2)	I(1)-Сu(1)-Сu(2)ⅰ	75.91(3)
  N(2)-Cu(2)-I(2)ⅰ	128.18(9)	N(2)-Cu(2)-I(1)	105.90(8)	I(2) i-Cu(2)-I(1)	122.09(3)
  N(2)-Cu(2)-Cu(1)ⅰ	121.26(9)	I(2)ⅰ-Сu(2)-Сu(1)ⅰ	58.75(2)	I(1)-Сu(2)-Сu(1)ⅰ	112.17(2)
  2
  Сu(1)-N(1)	0.191 5(4)	Cu(1)-I(1)	0.249 1(1)	Cu(1)…Сu(1)ⅰ	0.254 4(1)
  Сu(1)-І(1)ⅱ	0.259 9(1)	Cu(1)…Cu(1)ⅲ	0.261 1(1)	Cu(1)…Сu(1)ⅱ	0.261 1(1)
  Сu(1)-I(1)ⅰ	0.273 4(1)	Cu(2)-N(2)ⅲ	0.180 5(4)	Cu(2)-N(3)ⅳ	0.180 8(4)
  Cu(2)-I(1)	0.298 8(1)	I(1)-Cu(1)ⅲ	0.259 9(1)	І(1)-Cu(1)ⅰ	0.273 4(1)
  N(1)-Cu(1)-I(1)	119.6(1)	N(1)-Сu(1)-Сu(1)ⅰ	137.22(11)	I(1)-Сu(1)-Сu(1)ⅰ	65.76(3)
  N(1)-Сu(1)-I(1)	103.8(1)	I(1)-Сu(1)-I(1)ⅱ	115.26(3)	Сu(1)і-Сu1-I(1)ⅱ	111.2(1)
  N(1)-Cu(1)-Cu(1)ⅲ	161.81(1)	I(1)-Сu(1)-Сu(1)ⅲ	61.19(2)	Сu(1) i-Сu1-Сu(1)ⅲ	60.83(1)
  I(1)ⅱ-Сu(1)-Сu(1)ⅲ	63.32(3)	N(1)-Cu(1)-Cu(1)ⅱ	127.33(14)	І(1)-Сu(1)-Сu(1)ⅱ	112.55(3)
  N(1)-Сu(1)-I(1)ⅰ	90.8(1)	I(1)-Сu(1)-I(1)ⅰ	116.74(3)	Сu(1)ⅰ-Сu(1)-I(1)ⅰ	56.18(3)
  I(1)ⅱ-Сu(1)-I(1)ⅰ	107.43(2)	Сu(1)ⅲ-Сu(1)-І(1)ⅰ	105.09(2)	Сu(1)ⅱ-Сu(1)-I(1)ⅰ	58.13(2)
  N(2)ⅲ-Cu(2)-N(3)ⅳ	163.8(2)	N(2)ⅲ-Cu(2)-I(1)	96.10(15)	N(3)ⅳ-Cu(2)-I(1)	95.79(15)
  Cu(1)-I(1)-Cu(1)ⅲ	61.67(3)	Сu(1)-I(1)-Сu(1)ⅰ	58.06(3)	Сu(1)ⅲ-I(1)-Сu(1)ⅰ	58.55(3)
  Cu(1)-I(1)-Cu(2)	75.49(2)	Сu(1)ⅲ-I(1)-Сu(2)	69.93(2)	Сu(1)ⅰ-I(1)-Сu(2)	121.86(2)
  Symmetry codes: ⅰ -x+1, -y, -z+1; ⅱ -x+1, y+1/2, -z+1/2; ⅲ -x+1, y-1/2, -z+1/2 for 1; ⅰ -x+2, -y+1/2, z; ⅱ -y+5/4, x-3/4, -z+9/4; ⅲ y+3/4, -x+5/4, -z+9/4; ⅳ -x+2, -y+1, -z+2 for 2.

  CCDC: 1437794, 1; 1437795, 2.

  2   Results and discussion

  2.1   Syntheses of the complexes

  The aadmtrz ligand in complex 1 is in situ prepared from the condensation reaction of acetonitrile and 3, 5-dimethyl-4-amino-1, 2, 4-triazole. This conden-sation reaction is observed between amino compounds and nitrile compounds under solvothermal conditions. The formation mechanism of in situ alkylation is suggested as follows: under high temperature and autogenous pressure, the hydrolysis breaks CH₃CN molecules into CH₃CONH₂; the nucleophilic substitu-tion reaction of dmatrz and CH₃CONH₂ can generate aadmtrz, which attacks the nitrogen atom of dmatrz to form the 1-aminoethylidene group. The ligand in complex 2, dptrz, is from the reductive deaminization of the 3, 5-propyl-4-amino-1, 2, 4-triazole ligand. The cuprous iodide in both reactions serves not only as the metal catalyst for the other triazole ligands, but also as the source of the cuprous-iodide aggregates.

  2.2   Structure description

  2.2.1   Structure of {[Cu₂(aadmtrz)I₂]·CH₃CN}_n (1)

  Complex 1 is a 2D coordination polymer with the monoclinic space group P2₁/c, and the asymmetric unit consists of two crystallographically independent cuprous ions, one aadmtrz group, two iodides, one CH₃CN solvent molecule. As shown in Fig. 1a, its monomer is composed of a Cu₄I₄ cluster and two tridentate aadmtrz molecules. The Cu(Ⅰ) atoms are precisely coplanar, thus forming a parallelogram. Cu(1) shows tetrahedral coordination geometries [CuN₂I₂] by two I ions (I(1), I(2)) and two nitrogen atoms (N(1), N(4)) from the different addmtrz ligands. The distance of Cu(1)-N(1) (0.201 2(3) nm) is longer than that of Cu(1)-N(4) (0.206 3(3) nm), meanwhile the distance of Cu(1)-I(1) (0.268 9(1) nm) is also longer than that of Cu(1)-I(2) (0.267 1(1) nm). Cu(2) is in a slightly distorted [CuNI₂] triangular planar site with one μ₂-I(1) and two nitrogen atoms from different aadmtrz groups (N(2)^ⅲ, N(3)^ⅳ, Symmetry codes: ^ⅲ y+1/4, -x+7/4, -z+3/4; ^ⅳ -x+3/2, -y+3/2, -z+1/2). The dista-nces of Cu(2)-N (0.180 5(4) and 0.180 8(4) nm) are shorter than those of Cu(1)-N, and the distances of Cu(2)-I (0.257 8(1) and 0.252 2(1) nm) are shorter than that of Cu(1)-I (0.268 9(1) nm). The Cu(1)…Cu(2) interactions (0.288 4(1) nm) are crucial to build the Cu₄I₄ aggregates. The parallelogram Cu₄I₄ unit (Fig. 1b) has an inversion center and is formed by four iodine atoms bridges four copper atoms in the μ₂-bridging modes, generating an 8-membered ring that has the chair-chair conformation of cyclooctane. This chair-chair conformation is similar to those similar complexes such as [Cu₂I₂(aadtz)]_n^[20].

  图Scheme1 Syntheses of ligands of 1 and 2 Scheme1. Syntheses of ligands of 1 and 2

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  图1 (a) ORTEP drawing of 1 with 30% thermal ellipsoids; (b) Basic building block of Cu₄I₄ cluster Figure1. (a) ORTEP drawing of 1 with 30% thermal ellipsoids; (b) Basic building block of Cu₄I₄ cluster

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  In this complex, each aadmtrz ligand bridges two Cu(Ⅰ) atoms on the longer side of the Cu parallelo-gram through N(1) and N(2) nitrogen donors, while 4-substituent N(4) and N(5) atoms link an adjacent Cu₄I₄ unit to form a 2D network (Fig. 2a). The overall structure of 1 can thus be simplified as a 2D (4, 4) rhombic-grid network with 4-connecting node of the Cu₄I₄ aggregates (Fig. 2b). The coplanar sheets of 1 are further built into a 3D supramolecular architecture through the hydrogen bonding interactions (Table 3).

  图2 (a) View of the 2D network in 1; (b) Topological representation of the 4-connected network in 1 Figure2. (a) View of the 2D network in 1; (b) Topological representation of the 4-connected network in 1

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  Table 3.  Hydrogen bonds geometry for 1 and 2

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  D-H…A	d(D-H) / nm	d(Н…A)/nm	d(D …A) / nm	∠D-H …A/(°)
  1
  N(5) -H(5) A...N(6)	0.091	0.252	0.326 4(7)	139
  N(5)-H(5) B...I(1)ⅳ	0.091	0.293	0.373 7(4)	149
  С(2)-Н(2)В...I(1)ⅱ	0.098	0.321	0.417 7(4)	169
  C(4)-H(4)А...I(2)ⅰ	0.098	0.326	0.417 2(4)	155
  C(6)-H(6) C...I(1)ⅴ	0.098	0.314	0.390 0(4)	135
  С(8)-Н(8)А...І(1)ⅵ	0.098	0.326	0.399 7(5)	134
  2
  C(2)-H(2) A …I(1)	0.097	0.296	0.385 5(5)	153
  С(2)-Н(2)В...І(1)ⅴ	0.097	0.298	0.392 5(5)	164
  С(6) -Н(6)В…І(1)ⅳ	0.097	0.312	0.393 8(6)	143
  С(2)-Н(2)А...І(1)	0.097	0.296	0.385 5(5)	153
  С(2) -Н(2)В...І(1)ⅴ	0.097	0.298	0.392 5(5)	164
  С(6)-Н(6)В...І(1)ⅳ	0.097	0.312	0.393 8(6)	143
  Symmetry codes: ⅰ -x+1, -y, -z+1; ⅱ -x+1, y+1/2, -z+1/2; ⅳ x, -y-1/2, z-1/2; ⅴ -x+2, -y, -z+1; vi -x+2, y+1/2, -z+1/2; vii -x+1, -y, -z for 1; ⅳ -x+3/2, -y+3/2, -z+1/2; ⅴ y-1/4, -x+7/4, z-1/4 for 2.

  Furthermore, complex 1 is different from previously reported [Cu₄I₄(C₄H₈N₄)₄]^[15] with the similar reaction, where the ligand 3, 5-dimethyl-4-amino-1, 2, 4-triazole took part in the compound directly. This case is different from 3, 5-diethyl-4-amino-1, 2, 4-triazole compounds^[20], where may attribute to the shorter -CH2 in the 3, 5-position of 1, 2, 4-triazole.

  2.2.2   Structure of [Cu₂(dptrz)I]_n (2)

  Complex 2 shows an interesting 3D porous structure with the tetragonal space group I4₁/a. As shown in Fig. 3a, the asymmetric unit of complex 2 contains two crystallographically independent Cu(Ⅰ) ions, one dptrz ligand, one iodide anions. Each Cu(1) or I(1) links three neighboring I(1) or Cu(1) to form a distorted Cu₄I₄ cubane unit (Fig. 3b), which is similar to those reported Cu₄I₄ tetramer units^[24-25]. Each Cu(1) is tetrahedrally coordinated [CuNI₃] by three I ions and a nitrogen from the bridging dptrz ligand. The distances of Cu(1)-I, Cu(1)-N and Cu…Cu are 0.249 1(1)~0.273 4(1), 0.191 4(4) and 0.254 4(1)~0.261 1(1) nm, respectively, which are shorter than those of isostruc-tural complex [Cu₂(dtz)I]^[20], due to the longer -CH₂ group in the ligand of 2. Furthermore, these values are comparable to those found in other cubane-like Cu₄I₄L₄ complexes (L=nitrogen-containing ligand)^[26]. Cu(2) is in a slightly distorted [CuN₂I] triangular planar site with one μ₃-I(1) and two nitrogen atoms from different dptrz groups (N(2)ⅲ, N(3)^ⅳ, Symmetry codes: ^ⅲ y+1/4, -x+7/4, -z+3/4; ^ⅳ -x+3/2, -y+3/2, -z +1/2). The distances of Cu(2)-N (0.180 5(4), 0.180 8(4) nm) are shorter than those of Cu(1)-N, and the distance of Cu(2)-I is 0.298 7(7) nm, which is longer than that of Cu(1)-I. The angle of N(2)^ⅲ-Cu(2)-N(3)^ⅳ is 163.7(1)°.

  图3 (a) ORTEP drawing of 2 with 30% thermal ellipsoids; (b) Basic building block of Cu₄I₄ cluster Figure3. (a) ORTEP drawing of 2 with 30% thermal ellipsoids; (b) Basic building block of Cu₄I₄ cluster

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  Cu(2) atoms are bridged by μ_{1, 2}-dptrz ligands forming single-stranded helices, with the helices being left-and right-handed along the fourfold axis (Cu₄I₄ unit locates on the fourfold inversion axes), respectively (Fig. 4a). Each helical chain along the c axis is further linked through Cu(1) of the Cu₄I₄ unit, forming a non-interpenetrating 3D framework (Fig. 4b). Topologically, when the Cu₄I₄ SBU are depicted as four-connecting nodes, and dptrz ligands are regarded as three-connecting nodes, complex 2 can be defined as a (3, 4)-connected framework, which is similar to the isostructural [Cu₂I(dtz)]_n^[20]. Interesting, PLATON calculations^[27] show that the potential solvent area volume of 2 is estimated to be 0.982 3 nm³, 19.5% of the unit cell volume (5.039 6 nm³), which may hold 10 H₂O molecules. This may indicate that the construction of the cage-like motifs is accomplished by the -(CH₂)_n spacers of 3, 5-dialkyl-1, 2, 4-triazole.

  图4 (a) Local coordination environment around the Cu₄I₄ cluster in 2; (b)View of a 3D framework in 2 Figure4. (a) Local coordination environment around the Cu₄I₄ cluster in 2; (b)View of a 3D framework in 2

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  2.3   PXRD analysis

  As shown in Fig. 5, the experiment PXRD patterns for 1 and 2 are in agreement with the simulated ones from the single-crystal X-ray data. The result indicates that the growth of crystals of both complexes is well-proportioned and consistent. The structures are representative of the bulk materials.

  图5 PXRD patterns of complexes 1 and 2 Figure5. PXRD patterns of complexes 1 and 2

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  2.4   Luminescence properties

  The emission spectra for 1 and 2 and the ligands dmatrz, dpatrz in the solid state at room temperature are shown in Fig. 6. The emission peaks of luminescence of ligands dmatrz, dpatrz are the same at 419 nm. It can be observed that complex 1 and 2 exhibit green emission bands at 498, 493 nm upon excitation at 266, 254 nm, respectively. The emission spectra for both complexes may be assigned, in chara-cter, to iodide(X)-to-ligand charge transfer (XLCT).

  图6 Emission spectra of the ligands dmatrz, dpatrz, and complexes 1~2 Figure6. Emission spectra of the ligands dmatrz, dpatrz, and complexes 1~2

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  3   Conclusions

  In summary, two cuprous halide coordination polymers containing Cu₄I₄ clusters layers as structural motifs have been successfully synthesized, which are further linked by 1, 2, 4-triazole to form extended 2D 4-connected grid frameworks (1) and 3D (3, 4)-connected (2) frameworks with 19.5% porosity. The Cu₄I₄ cluster in complex 1 is an inorganic 8-membered ring with a chair-chair conformation, while the one in complex 2 is a distorted cubane. The large spacers of alkyl side chains of 4-aminotriazole may accomplished the construction of the cage-like motifs. This provides a method to design the porous metal-organic frameworks (PMOFs). Both complexes exhibit similar green photo-luminescence at room temperature in the solid state.

  Acknowledgements: The authors thank Dr. GAO Zeng-Qiang at line 3W1A of BSRF for his help in the single-crystal X-ray diffraction data collection and reduction.

  Supporting information is available at http://www.wjhxxb.cn

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• 

  Scheme1  Syntheses of ligands of 1 and 2

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  Figure 1  (a) ORTEP drawing of 1 with 30% thermal ellipsoids; (b) Basic building block of Cu₄I₄ cluster

  Symmetry codes: ⅰ-x+1, -y, -z+1; ⅱ -x+1, y+1/2, -z+1/2

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  Figure 2  (a) View of the 2D network in 1; (b) Topological representation of the 4-connected network in 1

  Hydrogen atoms are omitted for clarity

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  Figure 3  (a) ORTEP drawing of 2 with 30% thermal ellipsoids; (b) Basic building block of Cu₄I₄ cluster

  Symmetry codes: ⅰ-x+2, -y+1/2, z; ⅱ-y+5/4, x-3/4, -z+9/4; ⅲ y+3/4, -x+5/4, -z+9/Ⅳ

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  Figure 4  (a) Local coordination environment around the Cu₄I₄ cluster in 2; (b)View of a 3D framework in 2

  Hydrogen atoms are omitted for clarity

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  Figure 5  PXRD patterns of complexes 1 and 2

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  Figure 6  Emission spectra of the ligands dmatrz, dpatrz, and complexes 1~2

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  Table 1.  Crystallographic data and structure refinement for 1 and 2

  	1	2
  Formula	C8H14Cu2I2N6	C8H14Cu2N3I
  Formula weight	575.13	406.20
  Crystal system	Monoclinic	Tetragonal
  Space group	P21/c	I41/a
  a / nm	0.954 7(1)	1.625 3(2)
  b/ nm	1.187 3(2)	1.625 3(2)
  c / nm	1.494 9(5)	1.907 8(4)
  β/(°)	111.23(3)
  V / nm3	1.579 5(7)	5.039 5(1)
  Crystal size / mm	0.45×0.40×0.40	0.05×0.04×0.03
  Z	4	16
  Dc / (g·cm-3)	2.419	2.142
  μ/ mm-1	6.59	5.794
  F(000)	1 072	3 104
  θ range / (°)	2.9~26.0	2.51~25.05
  Gocxlness-of-fit on F2	1.41	1.046
  Reflection collected, unique	3 075, 3 067	2 234, 1 940
  Rint	0.017	0.028 7
  R1, wR2[I>2σ(I)]	0.019 1, 0.058 6	0.032 9, 0.089 2
  R1, wR2(all data)	0.020 9, 0.072 5	0.038 6, 0.092 8
  (Δ/σ)max	0.002	0.004
  Largest diff peak and hole / (e • nm-3)	1 180, -1 580	697, -1 880

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  Table 2.  Selected bond lengths (nm) and bond angles (°) of complexes 1 and 2

  1
  Сu(1)-N(1)	0.201 2(3)	Cu(1)-N(4)	0.206 3(3)	Cu(1)-I(1)	0.268 9(0)
  Сu(1)-I(2)	0.267 1(1)	Cu(2)-N(2)	0.200 1(3)	Cu(2)-I(1)	0.258 0(1)
  Сu(2)-I(2)ⅰ	0.252 3(1)	Сu(1)...Сu(2)ⅰ	0.288 4(1)	Сu(2)-Сu(1)ⅰ	0.288 4(1)
  Cu(2)-I(1)-Cu(1)	81.61(2)	Сu(2)ⅰ-1(2)-Сu(1)	67.41(3)	N(1)-Cu(1)-N(4)	120.04(1)
  N(1)-Cu(1)-I(2)	110.45(9)	N(4)-Cu(1)-I(2)	103.08(8)	N(1)-Cu(1)-I(1)	102.81(9)
  N(4)-Cu(1)-I(1)	104.16(9)	I(2)-Cu(1)-I(1)	116.90(3)	N(1)-Cu(1)-Cu(2)ⅰ	88.55(9)
  N(4)-Cu(1)-Cu(2)ⅰ	149.84(8)	I(2)-Сu(1)-Сu(2)ⅰ	53.84(2)	I(1)-Сu(1)-Сu(2)ⅰ	75.91(3)
  N(2)-Cu(2)-I(2)ⅰ	128.18(9)	N(2)-Cu(2)-I(1)	105.90(8)	I(2) i-Cu(2)-I(1)	122.09(3)
  N(2)-Cu(2)-Cu(1)ⅰ	121.26(9)	I(2)ⅰ-Сu(2)-Сu(1)ⅰ	58.75(2)	I(1)-Сu(2)-Сu(1)ⅰ	112.17(2)
  2
  Сu(1)-N(1)	0.191 5(4)	Cu(1)-I(1)	0.249 1(1)	Cu(1)…Сu(1)ⅰ	0.254 4(1)
  Сu(1)-І(1)ⅱ	0.259 9(1)	Cu(1)…Cu(1)ⅲ	0.261 1(1)	Cu(1)…Сu(1)ⅱ	0.261 1(1)
  Сu(1)-I(1)ⅰ	0.273 4(1)	Cu(2)-N(2)ⅲ	0.180 5(4)	Cu(2)-N(3)ⅳ	0.180 8(4)
  Cu(2)-I(1)	0.298 8(1)	I(1)-Cu(1)ⅲ	0.259 9(1)	І(1)-Cu(1)ⅰ	0.273 4(1)
  N(1)-Cu(1)-I(1)	119.6(1)	N(1)-Сu(1)-Сu(1)ⅰ	137.22(11)	I(1)-Сu(1)-Сu(1)ⅰ	65.76(3)
  N(1)-Сu(1)-I(1)	103.8(1)	I(1)-Сu(1)-I(1)ⅱ	115.26(3)	Сu(1)і-Сu1-I(1)ⅱ	111.2(1)
  N(1)-Cu(1)-Cu(1)ⅲ	161.81(1)	I(1)-Сu(1)-Сu(1)ⅲ	61.19(2)	Сu(1) i-Сu1-Сu(1)ⅲ	60.83(1)
  I(1)ⅱ-Сu(1)-Сu(1)ⅲ	63.32(3)	N(1)-Cu(1)-Cu(1)ⅱ	127.33(14)	І(1)-Сu(1)-Сu(1)ⅱ	112.55(3)
  N(1)-Сu(1)-I(1)ⅰ	90.8(1)	I(1)-Сu(1)-I(1)ⅰ	116.74(3)	Сu(1)ⅰ-Сu(1)-I(1)ⅰ	56.18(3)
  I(1)ⅱ-Сu(1)-I(1)ⅰ	107.43(2)	Сu(1)ⅲ-Сu(1)-І(1)ⅰ	105.09(2)	Сu(1)ⅱ-Сu(1)-I(1)ⅰ	58.13(2)
  N(2)ⅲ-Cu(2)-N(3)ⅳ	163.8(2)	N(2)ⅲ-Cu(2)-I(1)	96.10(15)	N(3)ⅳ-Cu(2)-I(1)	95.79(15)
  Cu(1)-I(1)-Cu(1)ⅲ	61.67(3)	Сu(1)-I(1)-Сu(1)ⅰ	58.06(3)	Сu(1)ⅲ-I(1)-Сu(1)ⅰ	58.55(3)
  Cu(1)-I(1)-Cu(2)	75.49(2)	Сu(1)ⅲ-I(1)-Сu(2)	69.93(2)	Сu(1)ⅰ-I(1)-Сu(2)	121.86(2)
  Symmetry codes: ⅰ -x+1, -y, -z+1; ⅱ -x+1, y+1/2, -z+1/2; ⅲ -x+1, y-1/2, -z+1/2 for 1; ⅰ -x+2, -y+1/2, z; ⅱ -y+5/4, x-3/4, -z+9/4; ⅲ y+3/4, -x+5/4, -z+9/4; ⅳ -x+2, -y+1, -z+2 for 2.

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  Table 3.  Hydrogen bonds geometry for 1 and 2

  D-H…A	d(D-H) / nm	d(Н…A)/nm	d(D …A) / nm	∠D-H …A/(°)
  1
  N(5) -H(5) A...N(6)	0.091	0.252	0.326 4(7)	139
  N(5)-H(5) B...I(1)ⅳ	0.091	0.293	0.373 7(4)	149
  С(2)-Н(2)В...I(1)ⅱ	0.098	0.321	0.417 7(4)	169
  C(4)-H(4)А...I(2)ⅰ	0.098	0.326	0.417 2(4)	155
  C(6)-H(6) C...I(1)ⅴ	0.098	0.314	0.390 0(4)	135
  С(8)-Н(8)А...І(1)ⅵ	0.098	0.326	0.399 7(5)	134
  2
  C(2)-H(2) A …I(1)	0.097	0.296	0.385 5(5)	153
  С(2)-Н(2)В...І(1)ⅴ	0.097	0.298	0.392 5(5)	164
  С(6) -Н(6)В…І(1)ⅳ	0.097	0.312	0.393 8(6)	143
  С(2)-Н(2)А...І(1)	0.097	0.296	0.385 5(5)	153
  С(2) -Н(2)В...І(1)ⅴ	0.097	0.298	0.392 5(5)	164
  С(6)-Н(6)В...І(1)ⅳ	0.097	0.312	0.393 8(6)	143
  Symmetry codes: ⅰ -x+1, -y, -z+1; ⅱ -x+1, y+1/2, -z+1/2; ⅳ x, -y-1/2, z-1/2; ⅴ -x+2, -y, -z+1; vi -x+2, y+1/2, -z+1/2; vii -x+1, -y, -z for 1; ⅳ -x+3/2, -y+3/2, -z+1/2; ⅴ y-1/4, -x+7/4, z-1/4 for 2.

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