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• 

  In the past few decades, thiosemicarbazones (TSCs) and their metal complexes have been a focus of chemists and biologists because of their wide range of pharmacological effects, such as antibacterial, antiviral, antifungal, and, most intriguingly, antitumor activity^[1]. It is noted that the presence of a heterocyclic ring in the synthesized TSCs plays a major role in extending their pharmacological properties^[1]. As a result, the transition metal complexes of TSCs derived from 2-acylpyridine/2-acylpyrazine have been exten-sively investigated as potential anticancer agents^[1-11]. However, the studies on the complexes with TSCs bearing condensed heterocycles are relatively few ^[12-14].

  On the other hand, the biological activities of TSCs metals depend on not only the structures of the ligands but also the metal centers^[6-8]. In most case of TSCs, metal-ligand synergism could occur^[1]. Recently, it has been demonstrated that several transition metal complexes with (quinolin-8-yl) methylene)-thiosemicarbazide have been reported to be potential antitumor agents^[12-14]. As the continuation of our work on metal-TSCs^[14], four transition metal complexes with 4-methyl-1-((quinolin-8-yl) methylene)-thiosemicarbazide (HL, Scheme 1) have been synthesized and structural determined by single-crystal X-ray diffraction. In addition, the interactions between the compounds and ct-DNA have been studied by ethidium bromide (EB) fluorescence probe.

  Figure Scheme 1.  Synthetic route for the synthesis of HL

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  1   Experimental

  1.1   Materials and measurements

  Solvents and starting materials for syntheses were purchased commercially and used as received. Elemental analyses were carried out on an Elemental Vario EL analyzer. ¹H NMR spectra of HL was acquired with Bruker AV400 NMR instrument in DMSO-d₆ solution with TMS as internal standard. The IR spectra (ν=4 000~400 cm^-1) were determined by the KBr pressed disc method on a Bruker V70 FTIR spectrophotometer. The interactions between the compounds and ct-DNA are measured using literature method^[14] via emission spectra on a Varian CARY Eclipse spectrophotometer.

  1.2   Preparations of the ligand and complexes 1~4

  The TSC ligand HL was produced according to the literature method, while using 4-methylthiosemicabazide instead of thiosemicabazide^[13-14]. Anal. Calcd. For C₁₂H₁₂N₄S (%): C: 58.99; H: 4.95; N: 22.93. Found (%): C: 59.12; H: 5.14; N: 22.86. FTIR (cm^-1): ν(C=N)1 598, ν(C=N)_quinoline1 545, ν(C=S) 822. ¹H NMR (400 MHz) : δ 11.80 (s, 1H, NH), 9.75~9.77 (q, 1H, NH), 8.95~8.97(1H)/8.47~8.88(2H)/8.09~8.17(1H)/7.68~7.75(2H) for quinoline-H, 8.22 (s, 1H, CH =N), 3.00~3.04 (d, 3H, CH₃).

  The complexes 1, 2 and 4 were generated by reaction of HL (5 mmol) with equimolar of Ni (NO₃)₂, Zn (NO₃)₂ and CuCl₂ in methanol (10 mL) solution, respectively, while using Cd (NO₃)₂ in ethanol (10 mL) solution for the synthesis of complex 3. Crystals of 1~4 suitable for X-ray diffraction analysis were obtained by evaporating the corresponding reaction solutions at room temperature.

  1: brown rods. Anal. Calcd. For C₂₆H₃₀N₈O₂S₂Ni (%): C: 51.24; H: 4.96; N: 18.39. Found (%): C: 51.32; H: 5.14; N: 18.26. FTIR (cm^-1): ν(C=N)1 570, ν(N=C)_quinoline1 482, ν(C-S)758.

  2: yellow blocks. Anal. Calcd. for C₂₅H₂₆N₈OS₂Zn (%): C: 51.41; H: 4.49; N: 19.19. Found (%): C: 51.33; H: 4.29; N: 19.28. FTIR (cm^-1): ν(C=N)1 571, ν(N=C)_quinoline1 487, ν(C-S)755.

  3: yellow blocks. Anal. Calcd. for C₂₆H₂₈N₈OS₂Cd (%): C: 48.41; H: 4.37; N: 17.37. Found (%): C: 48.44; H: 4.29; N: 17.45. FTIR (cm^-1): ν(C=N)1 568, ν(N=C)_quinoline1 495, ν(C-S)759.

  4: green blocks. Anal. Calcd. for C₂₄H₂₄N₈Cl₄S₂Cu₂ (%): C: 38.05; H: 3.19; N: 14.79. Found (%): C: 38.18; H: 3.29; N: 14.68. FTIR (cm^-1): ν(C=N)1 575, ν(N=C)_quinoline1 502, ν(C=S)780.

  1.3.1   X-ray crystallography

  The X-ray diffraction measurement for complexes 1~4 was performed on a Bruker SMART APEX Ⅱ CCD diffractometer equipped with a graphite monochromatized Mo Kα radiation (λ=0.071 073 nm) by using φ-ω scan mode. Semi-empirical absorption correction was applied to the intensity data using the SADABS program^[15]. The structures were solved by direct methods and refined by full matrix least-square on F² using the SHELXTL-97 program^[16]. All non-hydrogen atoms were refined anisotropically. All H atoms were positioned geometrically and refined using a riding model. SQUEEZE procedure was applied to deal with the existence of the voids of complex 3. Details of the crystal parameters, data collection and refinements for complexes 1~4 are summarized in Table 1.

  Table 1.  Selected crystallographic data for complexes 1~4

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  Table 1.  Selected crystallographic data for complexes 1~4

  CCDC: 1518183, 1; 1518184, 2; 1518185, 4; 1518186, 4.

  2   Results and discussion

  2.1   Crystal structures description

  The diamond drawings of the asymmetric unit of 1~4 are shown in Fig. 1. Selected bond distances and angles are listed in Table 2. Hydrogen bonds information is in Table 3. The lengths of C-S bond are in the range of 0.169 0(5) and 0.173 3(5) nm in complexes 1~3, while that in complex 4 being 0.167 5(3) nm. This fact indicates that the ligand HL has thiolated and deprotonated in complexes 1~3^[14], whilst acts as neutral ligand in complex 4.

  Figure 1.  Diamond drawing of the asymmetric unit of 1~4 (a~d) with 30% thermal ellipsoids

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  Table 2.  Selected bond lengths (nm) and angles (°) in complexes 1~4

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  1
  Nil-Nl	0.2l4 5(3)	Nil-N2	0.205 6(3)	Nil-N5	0.2l5 2(3)
  Nil-N6	0.205 0(3)	Nil-Sl	0.238 34(l0)	Nil-S2	0.239 0l (ll)
  N6-Nil-N2	l70.53(l0)	Nl-Nil-N5	84.05(l0)	N6-Nil-S2	8l.74(8)
  N6-Nil-Nl	98.85(l0)	N6-Nil-Sl	9l.97(8)	N2-Nil-S2	9l.70(8)
  N2-Nil-Nl	87.90(l0)	N2-Nil-Sl	82.0l (8)	Nl-Nil-S2	89.8l (8)
  N6-Nil-N5	88.79(l0)	Nl-Nil-Sl	l67.95(8)	N5-Nil-S2	l67.8l (8)
  N2-Nil-N5	98.56(ll)	N5-Nil-Sl	90.93(8)	Sl-Nil-S2	97.0l (4)
  2
  Znl-Nl	0.224 0(4)	Znl-N2	0.2l6 0(4)	Znl-N5	0.225 5(4)
  Znl-N6	0.2l4 3(3)	Znl-Sl	0.238 88(l3)	Znl-S2	0.240 92(l5)
  N6-Znl-N2	l7l.74(l4)	Nl-Znl-N5	80.42(l4)	N6-Znl-S2	79.78(l0)
  N6-Znl-Nl	l04.83(l4)	N6-Znl-Sl	93.39(l0)	N2-Znl-S2	96.98(l0)
  N2-Znl-Nl	82.53(l4)	N2-Znl-Sl	80.04(l0)	Nl-Znl-S2	87.9l (l2)
  N6-Znl-N5	84.56(l3)	Nl-Znl-Sl	l59.4l (ll)	N5-Znl-S2	l57.39(l0)
  N2-Znl-N5	l00.58(l3)	N5-Znl-Sl	92.07(l0)	Sl-Znl-S2	l04.97(6)
  3
  Cdl-Nl	0.240 7(7)	Cdl-N2	0.237 l (6)	Cdl-N5	0.243 7(6)
  Cdl-N6	0.235 6(6)	Cdl-Sl	0.252 6(2)	Cdl-S2	0.254 3(3)
  N6-Cdl-N2	l7l.2(2)	Nl-Cdl-N5	80.3(2)	N6-Cdl-S2	75.63(l7)
  N6-Cdl-Nl	ll0.7(2)	N6-Cdl-Sl	95.43(l7)	N2-Cdl-S2	l04.77(l7)
  N2-Cdl-Nl	78.l (2)	N2-Cdl-Sl	76.l6(l6)	Nl-Cdl-S2	89.4(2)
  N6-Cdl-N5	78.5(2)	Nl-Cdl-Sl	l50.00(l8)	N5-Cdl-S2	l46.60(l7)
  N2-Cdl-N5	l04.0(2)	N5-Cdl-Sl	9l.24(l7)	Sl-Cdl-S2	lll.80(ll)
  4
  Cul-Nl	0.202 2(3)	Cul-N2	0.l94 4(3)	Cul-Sl	0.227 32(l9)
  Cul-Cll	0.223 7(2)	Cul-Cl2	0.284 9(2)	Cul-Cllⅰ	0.298 9(2)
  N2-Cul-Nl	90.22(l2)	Cll-Cul-Sl	87.9l (6)	N2-Cul-Cllⅰ	87.l4(9)
  N2-Cul-Cll	l7l.67(7)	N2-Cul-Cl2	86.8l (9)	Nl-Cul-Cllⅰ	84.98(l0)
  Nl-Cul-Cll	97.7l (9)	Nl-Cul-Cl2	92.33(l0)	Cll-Cul-Cllⅰ	90.99(7)
  N2-Cul-Sl	83.96(9)	Cll-Cul-Cl2	95.38(7)	Sl-Cul-Cllⅰ	89.48(8)
  Nl-Cul-Sl	l72.l6(7)	Sl-Cul-Cl2	92.58(9)	Cl2-Cul-Cllⅰ	l73.37(3)
  Symmetry codes: ⅰ-x+2, -y, -z+2

  Table 2.  Selected bond lengths (nm) and angles (°) in complexes 1~4
  Table 3.  Hydrogen bonds information in complexes 1~4

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  D-H…A	d(D-H)/nm	d(H…A)/nm	d(D…A) nm	∠D-H…A/(°)
  1
  N (4)-H (4)…N (7)ⅱ	0.086	0.2l7	0.296 0(4)	l53.4
  0(l)-H (lA)…N (3)	0.082	0.206	0.287 9(4)	l72.6
  0(2)-H (2A)…0(l)	0.082	0.2l6	0.288 3(8)	l47.6
  2
  N (4)-H (4)…N (7)ⅵ	0.086	0.219	0.301 9(6)	160.7
  N (8)-H (8)…0(1)ⅴ	0.086	0.223	0.303 3(6)	156.1
  0(1)-H (1A)…N (3)	0.082	0.221	0.294 4(7)	149.4
  3
  N (4)-H (4)…N (7)ⅱ	0.086	0.228	0.312 5(4)	169.2
  4
  N (3)-H (3A)…Cl (2)ⅶ	0.086	0.216	0.297 9(3)	160.0
  N (4)-H (4)…Cl (1)ⅶ	0.086	0.258	0.325 7(4)	135.9
  Symmetry codes: ⅱ-x+1, y+1/2, -z+1/2; ⅳ-x, y+1/2, -z+1/2; ⅴ x, -y+1/2, z+1/2; ⅶ-x+1, y-1/2, -z+3/2

  Table 3.  Hydrogen bonds information in complexes 1~4

  As shown in Fig. 1a~1c, the structures of complexes 1~3 are quite similar, while with different crystal solvent molecules. The metal ion in each complex with a distorted octahedron geometry is surrounded by two anionic TSC ligands with N₄S₂ donor set. The distances of metal-N/S bonds (Table 2) were comparable with those found in the reported complexes with similar donor set^[14]. In the crystals of complexes 1 and 3, intermolecular N-H…N hydrogen bonds link the complex molecules into one-dimentional chains along b axis (Fig. 2a and 2c). Furthermore, the intermolecular O-H···N and OH…O hydrogen bonds between the lattice methanol molecules and complex molecules are also present in 1 (Table 3). By contrast, in the crystal of 2, the intermolecular N-H…N, N-H…O and O-H…N hydrogen bonds link the complexes and lattice methanol molecules into extended 2D supramolecular network (Fig. 2b).

  Figure 2.  Chain-like structures along b axis formed via hydrogen bonds in complex 1(a) and 3(c); Extended 2D supramolecular structure in complex 2(b) and 4(d)

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  However, complex 4 is binuclear, and the asymmetric unit contains a half of the molecule (Fig. 1d). Each central Cu(Ⅱ) ion of the dimer is surrounded by one independent neutral ligand and three coordinated chloride anions, two of which act as μ²-bridges, thus giving a distorted octahedron geometry. It should be noted that the bond lengths of Cu1-Cl2 and Cu1-Cl1^ⅰ (Symmetry codes: ^ⅰ-x+2, -y, -z+2) are 0.284 9(2) and 0.298 9(2) nm, respectively, which are much longer than that of the normal Cu-Cl bond (Cu1-Cl1 0.223 7(2) nm). In the solid state, the intermolecular N-H…Cl hydrogen bonds are helpful to construct an extended 2D supramolecular network (Fig. 2d).

  2.2   IR spectra

  The most useful for determining the mode of coordination of the TSC ligand in infrared spectral bands are the ν(N=C), ν(N=C, quinoline) and ν(S=C) vibrations. Such three bonds of the free TSC is found at 1 598, 1 545 and 822 cm^-1, while they shifts to lower frequency in complexes 1~4, clearly indicating the coordination of imine nitrogen, quinoline nitrogen and sulfur atoms ^[13-14], which is in accordance with the X-ray diffraction analysis result.

  2.3   EB-DNA binding study by fluorescence spectrum

  It is well known that EB can intercalate nonspecifically into DNA, which causes it to fluoresce strongly. Competitive binding of other drugs to DNA and EB will result in displacement of bound EB and thus decreasing the fluorescence intensity^[17]. The effects of the ligand and complexes on the fluorescence spectra of EB-DNA system are presented in Fig. 3. The fluorescence intensities of EB bound to ct-DNA at about 600 nm show remarkable decreasing trends with the increasing concentration of the tested compounds, indicating that some EB molecules are released into solution after the exchange with the compounds. The quenching of EB bound to DNA by the compounds is in agreement with the linear Stern-Volmer equation: I₀/I=1+K_sq r^[18], where I₀ and I represent the fluorescence intensities in the absence and presence of quencher, respectively, K_sq is the linear Stern-Volmer quenching constant, r is the ratio of the concentration of quencher and DNA. In the quenching plots of I₀/I versus r, K_sq values are given by the slopes. The K_sq values are 0.808, 0.552, 0.487 and 2.315 for complexes 1~4, respectively, while that of the ligand HL is tested to be 0.387. The results indicate that interactions of the complexes with DNA are stronger than that of the ligand HL, probably due to the higher rigidity of the complexes, which is in accordance with the literature ^[14]. In addition, complex 4 has the highest quenching ability among the tested complexes, this could be explained from two aspects: (1) Cu(Ⅱ) plays a significant role in biological systems, and Cu(Ⅱ) complexes usually have higher biological activities than the other transition metal ones^[19]; (2) the ligand HL in complex 4 is neutral, and thus the N-H bond at N2 position could act as an additional hydrogen bond donor, making it insert base pairs of DNA more easily than complexes 1~3.

  Figure 3.  Emission spectra of EB-DNA system in the presence of HL (a) and complexes 1~4 (b~e), respectively

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• 1. [1]

     Majid R, Hassan K. Coord. Chem. Rev., 2014, 280:203-253 doi: 10.1016/j.ccr.2014.06.007

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      毛盼东, 闫玲玲, 王文静, 等.无机化学学报, 2016, 32:555-561 https://www.researchgate.net/publication/301584710_Syntheses_Crystal_Structures_and_DNA-Binding_Properties_of_CoIICdII_Complexes_with_Quinoline_Thiosemicarbazone_LigandMAO Pan-Dong, YAN Ling-Ling, WANG Wen-Jing, et al. Chinese J. Inorg. Chem., 2016, 32:555-561 https://www.researchgate.net/publication/301584710_Syntheses_Crystal_Structures_and_DNA-Binding_Properties_of_CoIICdII_Complexes_with_Quinoline_Thiosemicarbazone_Ligand

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• 

  Scheme 1  Synthetic route for the synthesis of HL

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  Figure 1  Diamond drawing of the asymmetric unit of 1~4 (a~d) with 30% thermal ellipsoids

  Symmetry codes: ^ⅰ-x+2, -y, -z+2

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  Figure 2  Chain-like structures along b axis formed via hydrogen bonds in complex 1(a) and 3(c); Extended 2D supramolecular structure in complex 2(b) and 4(d)

  Hydrogen bonds shown in dashed line; H atoms for C-H bonds are omitted for clarity; Symmetry codes: ^ⅰ-x+2, -y, -z+2; ^ⅱ-x+1, y+1/2, -z+1/2; ^ⅲ-x+1, y-1/2, -z+1/2; ^ⅳ-x, y+1/2, -z+1/2; ^ⅴ x, -y+1/2, z+1/2; ^ⅵ x, -y+5/2, z-1/2; ^ⅶ-x+1, y-1/2, -z+3/2

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  Figure 3  Emission spectra of EB-DNA system in the presence of HL (a) and complexes 1~4 (b~e), respectively

  Arrow shows the fluorescence intensities change of EB-DNA system upon increasing tested compound concentration; Inset: plot of I₀/I versus r

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  Table 1.  Selected crystallographic data for complexes 1~4

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  Table 2.  Selected bond lengths (nm) and angles (°) in complexes 1~4

  1
  Nil-Nl	0.2l4 5(3)	Nil-N2	0.205 6(3)	Nil-N5	0.2l5 2(3)
  Nil-N6	0.205 0(3)	Nil-Sl	0.238 34(l0)	Nil-S2	0.239 0l (ll)
  N6-Nil-N2	l70.53(l0)	Nl-Nil-N5	84.05(l0)	N6-Nil-S2	8l.74(8)
  N6-Nil-Nl	98.85(l0)	N6-Nil-Sl	9l.97(8)	N2-Nil-S2	9l.70(8)
  N2-Nil-Nl	87.90(l0)	N2-Nil-Sl	82.0l (8)	Nl-Nil-S2	89.8l (8)
  N6-Nil-N5	88.79(l0)	Nl-Nil-Sl	l67.95(8)	N5-Nil-S2	l67.8l (8)
  N2-Nil-N5	98.56(ll)	N5-Nil-Sl	90.93(8)	Sl-Nil-S2	97.0l (4)
  2
  Znl-Nl	0.224 0(4)	Znl-N2	0.2l6 0(4)	Znl-N5	0.225 5(4)
  Znl-N6	0.2l4 3(3)	Znl-Sl	0.238 88(l3)	Znl-S2	0.240 92(l5)
  N6-Znl-N2	l7l.74(l4)	Nl-Znl-N5	80.42(l4)	N6-Znl-S2	79.78(l0)
  N6-Znl-Nl	l04.83(l4)	N6-Znl-Sl	93.39(l0)	N2-Znl-S2	96.98(l0)
  N2-Znl-Nl	82.53(l4)	N2-Znl-Sl	80.04(l0)	Nl-Znl-S2	87.9l (l2)
  N6-Znl-N5	84.56(l3)	Nl-Znl-Sl	l59.4l (ll)	N5-Znl-S2	l57.39(l0)
  N2-Znl-N5	l00.58(l3)	N5-Znl-Sl	92.07(l0)	Sl-Znl-S2	l04.97(6)
  3
  Cdl-Nl	0.240 7(7)	Cdl-N2	0.237 l (6)	Cdl-N5	0.243 7(6)
  Cdl-N6	0.235 6(6)	Cdl-Sl	0.252 6(2)	Cdl-S2	0.254 3(3)
  N6-Cdl-N2	l7l.2(2)	Nl-Cdl-N5	80.3(2)	N6-Cdl-S2	75.63(l7)
  N6-Cdl-Nl	ll0.7(2)	N6-Cdl-Sl	95.43(l7)	N2-Cdl-S2	l04.77(l7)
  N2-Cdl-Nl	78.l (2)	N2-Cdl-Sl	76.l6(l6)	Nl-Cdl-S2	89.4(2)
  N6-Cdl-N5	78.5(2)	Nl-Cdl-Sl	l50.00(l8)	N5-Cdl-S2	l46.60(l7)
  N2-Cdl-N5	l04.0(2)	N5-Cdl-Sl	9l.24(l7)	Sl-Cdl-S2	lll.80(ll)
  4
  Cul-Nl	0.202 2(3)	Cul-N2	0.l94 4(3)	Cul-Sl	0.227 32(l9)
  Cul-Cll	0.223 7(2)	Cul-Cl2	0.284 9(2)	Cul-Cllⅰ	0.298 9(2)
  N2-Cul-Nl	90.22(l2)	Cll-Cul-Sl	87.9l (6)	N2-Cul-Cllⅰ	87.l4(9)
  N2-Cul-Cll	l7l.67(7)	N2-Cul-Cl2	86.8l (9)	Nl-Cul-Cllⅰ	84.98(l0)
  Nl-Cul-Cll	97.7l (9)	Nl-Cul-Cl2	92.33(l0)	Cll-Cul-Cllⅰ	90.99(7)
  N2-Cul-Sl	83.96(9)	Cll-Cul-Cl2	95.38(7)	Sl-Cul-Cllⅰ	89.48(8)
  Nl-Cul-Sl	l72.l6(7)	Sl-Cul-Cl2	92.58(9)	Cl2-Cul-Cllⅰ	l73.37(3)
  Symmetry codes: ⅰ-x+2, -y, -z+2

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  Table 3.  Hydrogen bonds information in complexes 1~4

  D-H…A	d(D-H)/nm	d(H…A)/nm	d(D…A) nm	∠D-H…A/(°)
  1
  N (4)-H (4)…N (7)ⅱ	0.086	0.2l7	0.296 0(4)	l53.4
  0(l)-H (lA)…N (3)	0.082	0.206	0.287 9(4)	l72.6
  0(2)-H (2A)…0(l)	0.082	0.2l6	0.288 3(8)	l47.6
  2
  N (4)-H (4)…N (7)ⅵ	0.086	0.219	0.301 9(6)	160.7
  N (8)-H (8)…0(1)ⅴ	0.086	0.223	0.303 3(6)	156.1
  0(1)-H (1A)…N (3)	0.082	0.221	0.294 4(7)	149.4
  3
  N (4)-H (4)…N (7)ⅱ	0.086	0.228	0.312 5(4)	169.2
  4
  N (3)-H (3A)…Cl (2)ⅶ	0.086	0.216	0.297 9(3)	160.0
  N (4)-H (4)…Cl (1)ⅶ	0.086	0.258	0.325 7(4)	135.9
  Symmetry codes: ⅱ-x+1, y+1/2, -z+1/2; ⅳ-x, y+1/2, -z+1/2; ⅴ x, -y+1/2, z+1/2; ⅶ-x+1, y-1/2, -z+3/2

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