English

• 0.   Introduction

  Over the past few decades, 3, 4, 5-triarylsubstituted 1, 2, 4-triazoles have attracted considerable attention in coordination chemistry^[1] because these triazole derivatives can be used as flexible bridging ligands and linkers between transition metal ions^[2-5]. In particular, some Fe (Ⅱ) complexes with substituted triazoles can show fascinating spin crossover properties and may find potential applications in molecular switches, display devices, sensors and data storages^[6-9]. In our previous work, a series of 3, 4, 5-triarylsubstituted 1, 2, 4-triazoles with the pyridyl, phenyl, pyrrolyl, imidazolyl, benzimidazolyl and quinolyl groups and their metal complexes have been reported^[10-24]. However, only a Co(Ⅱ) complex with thienyl substituted triaryltriazoles has been reported until now^[25-26]. As a continuation of our exploration of asymmetrically substituted 1, 2, 4-triazoles, we prepared two new triaryltriazoles with a thienyl group: 3-(2-pyridyl)-4-phenyl-5-(2-thienyl)-1, 2, 4-triazole (L¹) and 3-(2-pyridyl)-4-(p-chlorophenyl)-5-(2-thienyl)-1, 2, 4-triazole (L²) (Scheme 1). Herein we report the syntheses, crystal structures and spectral characterization of two mononuclear copper(Ⅱ) complexes based on the designed ligands: trans-[Cu(L¹)₂(MeOH)₂] (ClO₄)₂ (1) and trans-[Cu(L²)₂(ClO₄)₂]·2MeCN (2).

  Scheme 1

  

  Scheme 1.  Structures of ligands L¹ and L²

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  1.   Experimental

  1.1   Materials and measurements

  All chemicals and solvents purchased were of analytical grade. Solvents were purified by conventional methods. Melting points were determined with an X - 4 digital microscope melting - point apparatus (Beijing) and are uncorrected. Elemental analyses (C, H, N, S) were carried out with a Thermo Finnigan Flash 1112A elemental analyzer. FT - IR spectra were recorded on a Nicolet Avatar 380 FT -IR instrument using KBr disks from 4 000 to 400 cm^-1. ¹H NMR spectra were measured on a Bruker AM 400 MHz spectrometer in DMSO-d₆ solution. Electrospray ionization mass spectra (ESI- MS) were recorded with a LCQ ADVANTAGE MAX mass spectrometer. Powder X - ray diffraction (PXRD) data were collected on a Bruker D8 ADVANCE diffrac- tometer using Cu Kα radiation (λ =0.154 06 nm) at 40 kV and 40 mA in a range of 5°~50°.

  1.2   Characterization of ligands L¹ and L²

  Ligands L¹ and L² were synthesized based on our reported method^[21].

  3-(2-pyridyl)-4-phenyl-5-(2-thienyl)-1, 2, 4-triazole (L¹): m.p. 201~203 ℃. Anal. Calcd. for C₁₇H₁₂N₄S (%): C, 67.08; H, 3.97; N, 18.41; S, 10.53. Found (%): C, 67.34; H, 4.24; N, 18.65; S, 10.81. IR (KBr, cm^-1): 3 072(w), 1 585(m), 1 489(s), 1 438(m), 1 002(m), 798 (m), 722(m). ¹H NMR (400 MHz): δ 8.31(d, 1H, Py-H), 8.03(d, 1H, Py-H), 7.91(t, 1H, Py-H), 7.66(d, 1H, thie- nyl-H), 7.54(t, 1H, Ph-H), 7.51(d, 2H, Ph-H), 7.47(d, 2H, Ph-H), 7.35(t, 1H, Py-H), 7.01(d, 1H, thienyl-H), 6.71(d, 1H, thienyl-H). ESI-MS: m/z=305.08, [L¹+H]⁺.

  3-(2-pyridyl)-4-(p-chlorophenyl)-5-(2-thienyl)-1, 2, 4- triazole (L²): m. p. 192~194 ℃. Anal. Calcd. for C₁₇H₁₁N₄SCl(%): C, 60.26; H, 3.27; N, 16.54; S, 9.46. Found(%): C, 60.42; H, 3.42; N, 16.39; S, 9.72. IR (KBr, cm^-1): 3 054(w), 1 590(m), 1 498(s), 1 443(s), 1 089(m), 997(m), 841(m), 721(m). ¹H NMR (400 MHz): δ 8.33(d, 1H, Py-H), 8.08(d, 1H, Py-H), 7.93(t, 1H, Py-H), 7.69(d, 1H, thienyl-H), 7.59(d, 2H, Ph-H), 7.57(d, 2H, Ph-H), 7.36(t, 1H, Py-H), 7.06(t, 1H, thienyl- H), 6.83(d, 1H, thienyl-H). ESI-MS: m/z=339.05, [L²+H]⁺.

  1.3   Syntheses of complexes 1 and 2

  trans-[Cu(L¹)₂(MeOH)₂] (ClO₄)₂ (1): A solution of Cu(NO₃)₂·3H₂O (0.05 mmol) and NaClO₄ (0.1 mmol) in anhydrous MeOH (4 mL) was added to a solution of L¹ (0.1 mmol) in MeOH (4 mL). The mixture was stirred for 4 h at room temperature. The green precipitate was separated by filtration, and washed with water, then dried under vacuum to obtain complex 1 in a yield of 82%. The green block-shaped single crystals of 1 suitable for X-ray diffraction were obtained by slow evaporation from MeOH solution. Anal. Calcd. for C₃₆H₃₂Cl₂CuN₈O₁₀S₂(%): C, 46.23; H, 3.45; N, 11.98; S, 6.86. Found(%): C, 46.52; H, 3.51; N, 11.77; S, 6.54. IR (KBr, cm^-1): 3 449(m, b), 3 082(w), 2 917(w), 1 617 (w), 1 562(m), 1 493(s), 1 388(m), 1 112(vs), 929(w), 859(w), 731(m), 626(s).

  trans-[Cu(L²)₂(ClO₄)₂] ·2MeCN (2): The prepared procedure for 2 was the same as that for 1 except using L² (0.1 mmol) to replace L¹. The well-shaped single crystals of 2 suitable for X -ray diffraction were obtained by slow evaporation from MeCN solution. Yield: 87%. Anal. Calcd. for C₃₈H₂₈Cl₄CuN₁₀O₈S₂(%): C, 44.65; H, 2.76; N, 13.70; S, 6.27. Found(%): C, 44.27; H, 2.93; N, 13.82; S, 6.41. IR (KBr, cm^-1): 3 077 (w), 2 921(w), 2 347(w), 1 613(m), 1 566(m), 1 493(s), 1 114(vs), 1 098(s), 930(w), 859(m), 726(m), 621(s).

  1.4   Crystal structure determination

  Suitable single crystals of 1 and 2 were selected for lattice parameter determination and collection of intensity data on a Bruker SMART APEX Ⅱ CCD diffractometer with a graphite - monochromated Mo Kα(λ=0.071 073 nm) radiation using a φ-ω scan mode at 296(2) K. Multi-scan absorption corrections were applied to all intensity data using SADABS. The structures were solved by direct methods and refined on F² by full-matrix least squares procedures using SHELXTL software^[27]. All non-hydrogen atoms were anisotropically refined. All hydrogen atoms were fixed in calculated positions and refined isotropically. The ClO₄^- ions in 1 were disordered over two positions with an occupancy of 0.677(14) for O2, O3, O4 and O5 and 0.323(14) for O2A, O3A, O4A and O5A. The two O atoms of coordinated ClO₄^- in 2 were also disordered over two positions with an occupancy of 0.548(7) for O2 and O3 and 0.452(7) for O2A and O3A. The crystallographic data of 1 and 2 are summarized in Table 1 and the selected bond lengths and angles are given in Table 2.

  Table 1

  

  Table 1.  Crystal data and structure refinements for 1 and 2

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  Complex	1	2
  Empirical formula	C36H32Cl2CuN8O10S2	C38H28Cl4CuN10O8S2
  Formula weight	935.25	1 022.16
  Crystal system	Monoclinic	Monoclinic
  Space group	P21/c	P21/c
  a/nm	0.846 57(19)	0.830 66(11)
  b/nm	1.547 9(4)	1.541 0(2)
  c /nm	1.566 7(4)	3.404 6(5)
  β/(°)	98.002(3)	93.925(2)
  V /nm3	2.033 0(8)	4.347 8(10)
  Z	2	4
  Dc/(g·cm-3)	1.528	1.562
  μ/mm-1	0.838	0.908
  F(000)	958	2 076
  Crystal size/mm	0.17×0.13×0.09	0.15×0.12×0.09
  θrange/ (°)	1.86~25.00	1.20~25.00
  Reflection collected	14 399	30 959
  Independent reflection	3 569 (Rint=0.033 3)	7 645 (Rint=0.033 9)
  Reflection observed [I > 2σ(I)]	2 877	6 127
  Data, restraint, parameter	3 569, 67, 306	7 645, 30, 589
  Goodness-of-fit on F2	1.066	1.071
  R1, wR2[I > 2σ(I)]	0.039 3, 0.102 5	0.050 7, 0.135 8
  R1, wR2(all data)	0.053 0, 0.108 8	0.064 9, 0.143 6
  (Δρ)max, (Δρ)min/(e·nm-3)	409, -332	654, -471

  Table 2

  

  Table 2.  Selected bond distances (nm) and bond angles (°) for 1 and 2

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  1
  Cu1-N1	0.205 6(2)	Cu1-N2	0.198 4(2)	Cu1-O1	0.240 6(2)
  N2-N3	0.138 2(3)	S1-C8	0.171 7(3)	S1-C11	0.170 0(4)
  N1-Cu1-N2	79.42(9)	N1-Cu1-O1	84.20(9)	N2-Cu1-O1	92.75(9)
  C1-N1-Cu1	126.4(18)	C5-N1-Cu1	115.5(17)	C6-N2-Cu1	115.3(3)
  2
  Cu1-N1	0.205 3(3)	Cu1-N2	0.197 4(3)	Cu1-O1	0.252 9(3)
  Cu1-N5	0.205 3(3)	Cu1-N6	0.196 7(5)	Cu1-O5	0.242 8(3)
  N2-N3	0.137 2(4)	S1-C8	0.170 6(4)	C15-Cl1	0.173 4(4)
  N6-N7	0.137 3(2)	S2-C25	0.171 2(4)	C32-Cl2	0.174 0(4)
  N1-Cu1-N2	80.46(11)	N1-Cu1-O1	86.45(13)	N2-Cu1-O1	89.08(12)
  N5-Cu1-N6	80.09(8)	N5-Cu1-O5	91.69(7)	N6-Cu1-O5	90.74(11)
  C1-N1-Cu1	127.4(2)	C5-N1-Cu1	114.0(2)	C6-N2-Cu1	113.8(2)
  C18-N5-Cu1	127.12(5)	C22-N5-Cu1	114.49(8)	C23-N6-Cu1	115.0(5)

  CCDC: 2423470, 1; 2423471, 2.

  2.   Results and discussion

  2.1   Synthesis

  Asymmetrically thienyl substituted 3, 4, 5-triaryl-1, 2, 4-triazoles (L¹ and L²) reacted with Cu(NO₃)₂ ·3H₂O and NaClO₄ in molar ratio of 2: 1: 2 to lead the formation of two mononuclear complexes, trans-[Cu(L¹)₂ (MeOH)₂](ClO₄)₂ (1) and trans-[Cu(L²)₂ (ClO₄)₂]·2MeCN (2), which are stable in air. The yields for 1 and 2 were 82% and 87%, respectively. The elemental analyses were satisfactory and indicate that 1 contains one Cu(Ⅱ), two L¹ ligands, two MeOH molecules and two ClO₄^- ions, and 2 has one Cu(Ⅱ), two L² ligands, two MeCN molecules and two ClO₄^- anions.

  2.2   Crystal structures of 1 and 2

  Although both 1 and 2 crystallize in the monoclinic space group P2₁/c (Fig. 1), Z=2 and c=1.566 7(4) nm in 1 while Z=4 and c=3.404 6(5) nm in 2. Thus, there is an inversion center at the Cu(Ⅱ) ion in 1 but none occurs in 2. The asymmetric unit of 1 is composed of half Cu(Ⅱ) cation, one L¹ ligand, one coordinated MeOH molecule and one ClO₄^- anion, which is consistent with the elemental analysis result. The Cu1 ion of 1 is coordinated by four nitrogen atoms from two L¹ ligands in the equatorial plane and two oxygen atoms from two MeOH molecules in the axial positions to form a distorted octahedral [CuN₄O₂] geometry. Each L¹ ligand coordinates to Cu1 ion via N1 atom of the pyridyl and N2 atom of the triazole, similar to the coordinated modes in some related Cu(Ⅱ) complexes^{[14, 16, 24]}. The thienyl group of L¹ ligand does not take part in coordination, which is similar to the Co (Ⅱ) complex with a thienyl substituted triaryltriazole: trans-[CoL₂(NCS)₂] (L=3-(2-pyridyl)-4-(p-methoxyphenyl)-5-(2-thienyl)-1, 2, 4-triazole)^[25]. However, the S1 atom of thienyl group in 1 does not orient to the phenyl ring, which is quite distinct from that observed in the trans-[CoL₂(NCS)₂] complex^[25]. The distance of Cu1—O1 is 0.240 6(4) nm. The Cu—N bond lengths are within the normal ranges found for the octahedral Cu(Ⅱ) complexes^[28-31]. Nevertheless, the Cu—N bond to the triazole nitrogen is 0.007 3 nm shorter than that to the pyridyl one. The analogous feature has been observed in the similar Cu(Ⅱ) complexes^[24]. The ligand L¹ in 1 is non - planar. The triazole makes dihedral angles of 6.2(4)°, 29.7(6)° and 64.6(3)° with the pyridyl ring, the thienyl ring and phenyl ring, respectively.

  Figure 1

  

  Figure 1.  Projection of structures of 1 and 2 with 30% thermal ellipsoids probability

  All H atoms, MeCN solvent and disordered O atoms are omitted for clarity; Symmetry code: ⁱ 1-x, 1-y, 1-z for 1

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  Different from 1, the asymmetric unit of 2 consists of a Cu(Ⅱ) cation, two L² ligands, two ClO₄^- ions and two MeCN molecules. The Cu(Ⅱ) ion of 2 is coordinated by four nitrogen atoms from two L² ligands in the equatorial plane and two oxygen atoms from two ClO₄^- in the axial positions to build a distorted octahedral [CuN ₄O₂] geometry. Each L² ligand coordinates to Cu1 atom via N1 (or N5) atom of the pyridyl and N2 (or N6) atom of the triazole whereas the thienyl group of L² ligand is also uncoordinated, which is very similar to the coordination mode of L¹ in 1. The distance of Cu1—O1 (0.253 nm) is longer than that of the Cu1— O5 (0.242 8 nm). The Cu—N bond lengths are within the normal ranges observed for some octahedral Cu(Ⅱ) complexes, whereas Cu—N bond to the triazole nitrogen is 0.008 6 nm shorter than that to the pyridyl one. The triazole ring containing N2 atom forms dihedral angles of 2.4(2)°, 6.9(9)° and 89.2(8)° with the pyridyl ring with N1 atom, the thienyl ring with S1 atom and phenyl ring with Cl1 atom, respectively. And the triazole ring having N6 atom makes dihedral angles of 4.1(7)°, 9.6(4)° and 87.6(3)° with the pyridyl ring with N5 atom, the thienyl ring with S2 atom and phenyl ring with Cl2 atom, respectively. Therefore, the pyridyl, triazole and thienyl ring of L² in 2 is almost coplanar. Notably, the S atoms (S1 and S2) of thienyl groups in 2 orient to the p-chlorophenyl ring, which is similar to that found in the trans-[CoL₂(NCS)₂] complex^[25].

  There are abundant intermolecular hydrogen bonds interactions in 1: (1) between MeOH and ClO₄^-anion (O1—H1A…O4); (2) between pyridyl and triazole ring (C1—H1…N3ⁱ); (3) between phenyl and ClO₄^-anion (C13—H13…O2ⁱⁱⁱ and C17—H17…O2ⁱ); (4) between pyridyl and ClO₄^- anion (C3—H3…O5ⁱⁱ). In addition, there are an intramolecular edge - to - face C—H… π interaction involving C4—H4 and phenyl ring (H4…π 0.308 nm and ∠C4—H4…π =148°) and an intermolecular edge - to - face C—H… π interaction involving MeOH and pyridyl ring (H18C…π 0.326 nm and ∠C18—H18C… π=139°) (Fig. 2, Table 3). These interactions further connect the mononuclear 1 to form a 3D framework (Fig. 3).

  Figure 2

  

  Figure 2.  Hydrogen-bonding, C—H…π and π…π interactions in 1 and 2

  Symmetry codes: ⁱ 1-x, 1-y, 1-z; ⁱⁱ 2-x, 1-y, 1-z; ⁱⁱⁱ x, 1/2-y, 1/2+z for 1; ⁱ x-1, y, z; ⁱⁱ 1+x, y, z; ⁱⁱⁱ 2-x, 1-y, 1-z; ^iv 1-x, y-1/2, 1.5-z; ^v 1-x, 1-y, 1-z; ^vi-x, 1-y, 1-z for 2

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  Table 3

  

  Table 3.  Hydrogen-bond geometry and C—H…π interactions in 1 and 2

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  D-H…A	d(D-H)/nm	d(H…A)/nm	d(D…A)/nm	∠D-H…A/(°)
  1
  O1-H1A…O4	0.086	0.203	0.279 6(6)	148
  C1-H1…N3i	0.093	0.236	0.316 1(4)	144
  C3-H3…O5ii	0.093	0.261	0.335 9(3)	138
  C4-H4…π(Ph)	0.093	0.308	0.389 7(2)	148
  C13-H13…O2iii	0.093	0.257	0.342 8(7)	154
  C17-H17…O2i	0.093	0.260	0.349 2(8)	162
  C18-H18C…π(Py)	0.096	0.326	0.402 9(8)	139
  2
  C1-H1…N7	0.093	0.233	0.310 2(5)	140
  C2-H2…O2i	0.093	0.237	0.307 0(7)	131
  C4-H4…π(Ph)	0.093	0.284	0.368 6(7)	152
  C9-H9…O7ii	0.093	0.246	0.337 6(6)	168
  C10-H10…N9iii	0.093	0.268	0.354 0(7)	154
  C16-H16…O4iv	0.093	0.256	0.334 7(5)	142
  C17-H17…O3iv	0.093	0.251	0.310 0(9)	122
  C18-H18…N3	0.093	0.239	0.318 6(5)	143
  C19-H19…O7ii	0.093	0.263	0.331 4(5)	130
  C20-H20…O6v	0.093	0.258	0.350 8(7)	173
  C21-H21…π(Ph)	0.093	0.302	0.384 6(6)	150
  C26-H26…O1i	0.093	0.270	0.331 4(8)	123
  C27-H27…N10vi	0.093	0.259	0.350 5(6)	168
  Symmetry codes: i 1-x, 1-y, 1-z; ii 2-x, 1-y, 1-z; iii x, 1/2-y, 1/2+z for 1; i x-1, y, z; ii 1+x, y, z; iii 2-x, 1-y, 1-z; iv 1-x, y-1/2, 1.5-z; v 1-x, 1-y, 1-z; vi -x, 1-y, 1-z for 2.

  Figure 3

  

  Figure 3.  Three dimensional frameworks of 1 and 2

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  Complex 2 has richer C—H…O interactions including: (1) between pyridyl and ClO₄^- (C2—H2… O2ⁱ, C19—H19…O7ⁱⁱ and C20—H20…O6^v); (2) between thienyl and ClO₄^- (C9—H9…O7ⁱⁱ and C26—H26…O1ⁱ); (3) between phenyl and ClO₄^- (C16—H16… O4^iv and C17—H17…O3^iv). There are two kinds of C—H…N interactions in 2 including: (1) between pyridyl and triazole (C1—H1…N7 and C18—H18…N3); (2) between thienyl and MeCN (C10— H10…N9ⁱⁱⁱ and C27—H27…N10^vi). In addition, there are two kinds of π - π stacking interactions between triazole rings and the MeCN molecules (π…π (C≡N9)^v 0.331 6 nm, π…π (C≡N10)^v 0.330 4 nm) (Table 3, Fig. 2). All the interactions assemble the mononuclear 2 into a 3D network (Fig. 3).

  2.3   IR spectra

  In the IR spectra of 1 and 2, a broad band at 3 447 cm^-1 in 1 is due to the O—H stretching vibrations of MeOH, while a weak band at 2 347 cm^-1 in 2 is assigned to characteristic C≡N stretching vibrations of MeCN^[32]. A medium band at 1 562 cm^-1 in 1 or 1 566 cm^-1 in 2 can be assigned to the coordinated pyridyl ring vibrations. In 1 (or 2), the bands around 1 112 (or 1 114), 929 (or 930), 626 (or 621) cm^-1 can be assigned to the IR-allowed ν mode, IR-forbidden ν mode and the non - degenerate ClO₃ symmetrical bending frequency of the ClO₄^- anions, respectively^[33]. Additionally, the stretching vibration of Cl - C(Ph) in 2 is found at 1 098 cm^-1[34]. These features are in consistent with the X-ray analysis results.

  2.4   PXRD

  The PXRD patterns and simulated ones of 1 and 2 are shown in Fig. 4. The experimental patterns are in well agreement with the simulated ones from the single X -ray crystal data, revealing that the high phase purity of the bulk products of 1 and 2.

  Figure 4

  

  Figure 4.  PXRD patterns of 1 and 2

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  3.   Conclusions

  Two new Cu(Ⅱ) complexes based on the thienyl and pyridyl substituted triarytriazole, trans-[Cu(L¹)₂ (MeOH)₂](ClO₄) ₂ (1) and trans-[Cu(L²)₂(ClO₄)₂]·2MeCN (2), have been synthesized and characterized by IR, PXRD and X-ray crystallography. The structural analyses reveal that two complexes have a similar pseudooctahedral [CuN₄O₂] core with two MeOH molecules in the trans -positions in 1 but two ClO₄^- ions in the trans- positions in 2.

  
  
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  Scheme 1  Structures of ligands L¹ and L²

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  Figure 1  Projection of structures of 1 and 2 with 30% thermal ellipsoids probability

  All H atoms, MeCN solvent and disordered O atoms are omitted for clarity; Symmetry code: ⁱ 1-x, 1-y, 1-z for 1

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  Figure 2  Hydrogen-bonding, C—H…π and π…π interactions in 1 and 2

  Symmetry codes: ⁱ 1-x, 1-y, 1-z; ⁱⁱ 2-x, 1-y, 1-z; ⁱⁱⁱ x, 1/2-y, 1/2+z for 1; ⁱ x-1, y, z; ⁱⁱ 1+x, y, z; ⁱⁱⁱ 2-x, 1-y, 1-z; ^iv 1-x, y-1/2, 1.5-z; ^v 1-x, 1-y, 1-z; ^vi-x, 1-y, 1-z for 2

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  Figure 3  Three dimensional frameworks of 1 and 2

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  Figure 4  PXRD patterns of 1 and 2

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  Table 1.  Crystal data and structure refinements for 1 and 2

  Complex	1	2
  Empirical formula	C36H32Cl2CuN8O10S2	C38H28Cl4CuN10O8S2
  Formula weight	935.25	1 022.16
  Crystal system	Monoclinic	Monoclinic
  Space group	P21/c	P21/c
  a/nm	0.846 57(19)	0.830 66(11)
  b/nm	1.547 9(4)	1.541 0(2)
  c /nm	1.566 7(4)	3.404 6(5)
  β/(°)	98.002(3)	93.925(2)
  V /nm3	2.033 0(8)	4.347 8(10)
  Z	2	4
  Dc/(g·cm-3)	1.528	1.562
  μ/mm-1	0.838	0.908
  F(000)	958	2 076
  Crystal size/mm	0.17×0.13×0.09	0.15×0.12×0.09
  θrange/ (°)	1.86~25.00	1.20~25.00
  Reflection collected	14 399	30 959
  Independent reflection	3 569 (Rint=0.033 3)	7 645 (Rint=0.033 9)
  Reflection observed [I > 2σ(I)]	2 877	6 127
  Data, restraint, parameter	3 569, 67, 306	7 645, 30, 589
  Goodness-of-fit on F2	1.066	1.071
  R1, wR2[I > 2σ(I)]	0.039 3, 0.102 5	0.050 7, 0.135 8
  R1, wR2(all data)	0.053 0, 0.108 8	0.064 9, 0.143 6
  (Δρ)max, (Δρ)min/(e·nm-3)	409, -332	654, -471

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  Table 2.  Selected bond distances (nm) and bond angles (°) for 1 and 2

  1
  Cu1-N1	0.205 6(2)	Cu1-N2	0.198 4(2)	Cu1-O1	0.240 6(2)
  N2-N3	0.138 2(3)	S1-C8	0.171 7(3)	S1-C11	0.170 0(4)
  N1-Cu1-N2	79.42(9)	N1-Cu1-O1	84.20(9)	N2-Cu1-O1	92.75(9)
  C1-N1-Cu1	126.4(18)	C5-N1-Cu1	115.5(17)	C6-N2-Cu1	115.3(3)
  2
  Cu1-N1	0.205 3(3)	Cu1-N2	0.197 4(3)	Cu1-O1	0.252 9(3)
  Cu1-N5	0.205 3(3)	Cu1-N6	0.196 7(5)	Cu1-O5	0.242 8(3)
  N2-N3	0.137 2(4)	S1-C8	0.170 6(4)	C15-Cl1	0.173 4(4)
  N6-N7	0.137 3(2)	S2-C25	0.171 2(4)	C32-Cl2	0.174 0(4)
  N1-Cu1-N2	80.46(11)	N1-Cu1-O1	86.45(13)	N2-Cu1-O1	89.08(12)
  N5-Cu1-N6	80.09(8)	N5-Cu1-O5	91.69(7)	N6-Cu1-O5	90.74(11)
  C1-N1-Cu1	127.4(2)	C5-N1-Cu1	114.0(2)	C6-N2-Cu1	113.8(2)
  C18-N5-Cu1	127.12(5)	C22-N5-Cu1	114.49(8)	C23-N6-Cu1	115.0(5)

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  Table 3.  Hydrogen-bond geometry and C—H…π interactions in 1 and 2

  D-H…A	d(D-H)/nm	d(H…A)/nm	d(D…A)/nm	∠D-H…A/(°)
  1
  O1-H1A…O4	0.086	0.203	0.279 6(6)	148
  C1-H1…N3i	0.093	0.236	0.316 1(4)	144
  C3-H3…O5ii	0.093	0.261	0.335 9(3)	138
  C4-H4…π(Ph)	0.093	0.308	0.389 7(2)	148
  C13-H13…O2iii	0.093	0.257	0.342 8(7)	154
  C17-H17…O2i	0.093	0.260	0.349 2(8)	162
  C18-H18C…π(Py)	0.096	0.326	0.402 9(8)	139
  2
  C1-H1…N7	0.093	0.233	0.310 2(5)	140
  C2-H2…O2i	0.093	0.237	0.307 0(7)	131
  C4-H4…π(Ph)	0.093	0.284	0.368 6(7)	152
  C9-H9…O7ii	0.093	0.246	0.337 6(6)	168
  C10-H10…N9iii	0.093	0.268	0.354 0(7)	154
  C16-H16…O4iv	0.093	0.256	0.334 7(5)	142
  C17-H17…O3iv	0.093	0.251	0.310 0(9)	122
  C18-H18…N3	0.093	0.239	0.318 6(5)	143
  C19-H19…O7ii	0.093	0.263	0.331 4(5)	130
  C20-H20…O6v	0.093	0.258	0.350 8(7)	173
  C21-H21…π(Ph)	0.093	0.302	0.384 6(6)	150
  C26-H26…O1i	0.093	0.270	0.331 4(8)	123
  C27-H27…N10vi	0.093	0.259	0.350 5(6)	168
  Symmetry codes: i 1-x, 1-y, 1-z; ii 2-x, 1-y, 1-z; iii x, 1/2-y, 1/2+z for 1; i x-1, y, z; ii 1+x, y, z; iii 2-x, 1-y, 1-z; iv 1-x, y-1/2, 1.5-z; v 1-x, 1-y, 1-z; vi -x, 1-y, 1-z for 2.

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