(3,5-Dichloro­salicylaldehyde thio­semi­carbazonato-κ3S,N1,O)(N,N′-dimethyl­formamide-κO)copper(II) dimethyl­formamide solvate

Wang, Y.; Liu, Z.; Gao, J.-Y.

doi:10.1107/S1600536808008982

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 5| May 2008| Pages m633-m634

doi:10.1107/S1600536808008982

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(3,5-Dichlorosalicylaldehyde thiosemicarbazonato-κ³S,N¹,O)(N,N′-dimethylformamide-κO)copper(II) dimethylformamide solvate

Yuan Wang,^a Zheng Liu ^a and Jiong-Yang Gao ^a ^*

^aKey Laboratory of Non-ferrous Metal Materials and New Processing Technology, Department of Materials and Chemical Engineering, Guilin University of Technology, Ministry of Education, Guilin 541004, People's Republic of China
^*Correspondence e-mail: lisa4.6@163.com

(Received 14 March 2008; accepted 3 April 2008; online 10 April 2008)

In the title compound, [Cu(C₈H₅Cl₂N₃OS)(C₃H₇NO)]·C₃H₇NO, the Cu^II atom is coordinated in a slightly distorted square-planar geometry by an O, an S and an N atom from the tridentate ligand 3,5-dichlorosalicylaldehyde thiosemicarbazonate ligand and one O atom from dimethylformamide. At the same time, the Cu atom is in contact with S and Cl atoms from another two complexes [Cu⋯S and Cu⋯Cl = 2.9791 (2) and 3.3800 (3) Å, respectively], thereby forming a [4 + 2] coordination geometry. The crystal structure exhibits N—H⋯O and N—H⋯N hydrogen bonds.

Related literature

For studies of thiosemicarbazone complexes containing amino acids, see: Garcia-Orozco et al. (2002 ); Seena et al. (2007 ); Valdes-Martinez et al. (1995 ); Singh et al. (1997 ); Shen et al. (1997 ); Zimmer et al. (1991 ).

Experimental

Crystal data

[Cu(C₈H₅Cl₂N₃OS)(C₃H₇NO)]·C₃H₇NO
M_r = 471.84
Monoclinic, P 2₁ /n
a = 9.4979 (10) Å
b = 9.8057 (12) Å
c = 21.744 (2) Å
β = 94.263 (2)°
V = 2019.5 (4) Å³
Z = 4
Mo Kα radiation
μ = 1.47 mm⁻¹
T = 298 (2) K
0.49 × 0.47 × 0.24 mm

Data collection

Bruker SMART 1000 diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.532, T_max = 0.719
9869 measured reflections
3558 independent reflections
2587 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.098
S = 1.06
3558 reflections
235 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.50 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Cu1—O1	1.909 (2)
Cu1—N1	1.954 (3)
Cu1—O2	1.985 (2)
Cu1—S1	2.2567 (10)

O1—Cu1—N1	93.55 (11)
O1—Cu1—O2	90.55 (11)
N1—Cu1—O2	172.04 (11)
O1—Cu1—S1	176.26 (8)
N1—Cu1—S1	86.04 (8)
O2—Cu1—S1	89.43 (8)
C4—O1—Cu1	127.5 (2)
C9—O2—Cu1	123.8 (3)
C1—S1—Cu1	94.29 (11)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯N2ⁱ	0.86	2.14	2.992 (4)	170
N3—H3B⋯O3ⁱⁱ	0.86	2.08	2.886 (4)	157
Symmetry codes: (i) -x+2, -y+1, -z+1; (ii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808008982/om2219sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808008982/om2219Isup2.hkl

checkCIF report

Comment top

As a special kind of Schiff base, thiosemicarbazones and their metal complexes have become the subjects of intensive study because of their wide ranging biological activities, analytical applications and interesting chemical and structural properties (Zimmer, et al., 1991). In addition, salicylaldehyde thiosemicarbazone and its substituent analogs as well as their copper complexes has been synthesized. The N—S donor also have theoretical interest, as they are capable of furnishing an environment of controlled geometry and ligand field strength.

In the title compound there is a DMF molecule coordinated through O, in addition to one N, one O and one S atom from the tridentate ligand 3,5-dichlorosalicylaldehyde thiosemicarbazone forming a slightly distorted planar square geometry (Fig. 1). In the unit cell, above and below the distorted square plane are Cl and S atoms at a long distance forming a "4 + 2" geometry. The weak interaction length of S–Cu is 2.9791 (2) Å. This bond distance are in the range of upper values for a long coordination distance (2.5–3.0 Å) in Cu(II) compounds. The length of Cl–Cu is 3.3800 (3) Å (Fig. 2). All of these facts can be seen as the result of the Jahn-Teller effect (Garcia-Orozco et al., 2002). A three-dimensional network is formed through these Cl–Cu, S–Cu contacts, N–H···N and N–H···O hydrogen bonds (Fig.3).

Related literature top

For studies of thiosemicarbazone complexes containing amino acids, see: Garcia-Orozco et al. (2002); Seena et al. (2007); Valdes-Martinez et al. (1995); Singh et al. (1997); Shen et al. (1997); Zimmer et al. (1991).

Experimental top

An EtOH solution (15 ml) of 3,5-dichlorosalicylaldehyde (5 mmol) was added dropwise to the solution (15 ml) of thiosemicarbazide (5 mmol) and 0.75 ml acetic anhydride with stirring at ca 70°C for 4.5 h. The light brown precipitate was removed by filtration and recrystallized from 1:1 (v/v) MeOH/EtOH solution. Then a mixture of the ligand (0.5 mmol) and copper nitrate (0.5 mmol) in EtOH (35 ml) was stirred at ca 65° C for 2 h to give the desired complex. The Cu complex was dissolved in DMF, and ether slowly diffused into the DMF solution to afford almost quantitatively green crystals of the mononuclear complex at ambient temperature after several days.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SMART (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit showing 30% probability displacement ellipsoids. Carbon-bound H atoms have been omitted for clarity.
	Fig. 2. The interactions of Cl···Cu and S···Cu in the asymmetric unit one-dimensional chains.
	Fig. 3. A view down the b axis, broken line showing short Cl–Cu and S···Cu contacts and hydrogen bonds.

(3,5-Dichlorosalicylaldehyde thiosemicarbazonato-κ³S,N¹,O)(N,N'- dimethylformamide-κO)copper(II) dimethylformamide solvate top

Crystal data top

[Cu(C₈H₅Cl₂N₃OS)(C₃H₇NO)]·C₃H₇NO	F(000) = 964
M_r = 471.84	D_x = 1.552 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.4979 (10) Å	Cell parameters from 3442 reflections
b = 9.8057 (12) Å	θ = 2.3–26.8°
c = 21.744 (2) Å	µ = 1.47 mm⁻¹
β = 94.263 (2)°	T = 298 K
V = 2019.5 (4) Å³	Block, green
Z = 4	0.49 × 0.47 × 0.24 mm

Data collection top

Bruker SMART 1000 diffractometer	3558 independent reflections
Radiation source: fine-focus sealed tube	2587 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→10
T_min = 0.532, T_max = 0.719	k = −9→11
9869 measured reflections	l = −23→25

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.098	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0377P)² + 1.6178P] where P = (F_o² + 2F_c²)/3
3558 reflections	(Δ/σ)_max = 0.001
235 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.50 e Å⁻³

Crystal data top

[Cu(C₈H₅Cl₂N₃OS)(C₃H₇NO)]·C₃H₇NO	V = 2019.5 (4) Å³
M_r = 471.84	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.4979 (10) Å	µ = 1.47 mm⁻¹
b = 9.8057 (12) Å	T = 298 K
c = 21.744 (2) Å	0.49 × 0.47 × 0.24 mm
β = 94.263 (2)°

Data collection top

Bruker SMART 1000 diffractometer	3558 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2587 reflections with I > 2σ(I)
T_min = 0.532, T_max = 0.719	R_int = 0.034
9869 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.098	H-atom parameters constrained
S = 1.06	Δρ_max = 0.31 e Å⁻³
3558 reflections	Δρ_min = −0.50 e Å⁻³
235 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cu1	0.54152 (4)	0.31930 (4)	0.51062 (2)	0.04237 (15)
Cl1	0.29920 (11)	−0.05605 (11)	0.41172 (6)	0.0706 (3)
Cl2	0.69572 (16)	−0.09500 (13)	0.24825 (6)	0.0928 (4)
N1	0.7172 (3)	0.3290 (3)	0.46944 (12)	0.0353 (6)
N2	0.8232 (3)	0.4197 (3)	0.48940 (14)	0.0433 (7)
N3	0.8875 (3)	0.5886 (3)	0.55631 (15)	0.0592 (9)
H3A	0.9666	0.5938	0.5396	0.071*
H3B	0.8710	0.6418	0.5864	0.071*
N4	0.1645 (3)	0.2314 (4)	0.58339 (19)	0.0736 (11)
N5	0.3114 (4)	0.6470 (4)	0.24057 (17)	0.0673 (10)
O1	0.4724 (2)	0.1664 (2)	0.46316 (13)	0.0515 (6)
O2	0.3799 (2)	0.3059 (3)	0.56320 (12)	0.0536 (7)
O3	0.4168 (4)	0.7162 (4)	0.15577 (16)	0.0890 (10)
S1	0.63125 (9)	0.49051 (9)	0.57083 (4)	0.0431 (2)
C1	0.7899 (3)	0.4974 (3)	0.53551 (15)	0.0386 (8)
C2	0.7456 (3)	0.2575 (3)	0.42245 (17)	0.0427 (8)
H2	0.8309	0.2751	0.4055	0.051*
C3	0.6572 (3)	0.1521 (3)	0.39345 (17)	0.0430 (8)
C4	0.5275 (4)	0.1113 (3)	0.41651 (18)	0.0440 (9)
C5	0.4564 (4)	0.0012 (3)	0.38446 (19)	0.0496 (10)
C6	0.5066 (5)	−0.0603 (4)	0.3345 (2)	0.0604 (11)
H6	0.4566	−0.1317	0.3150	0.072*
C7	0.6330 (5)	−0.0162 (4)	0.31267 (18)	0.0579 (10)
C8	0.7069 (4)	0.0878 (4)	0.34189 (18)	0.0517 (10)
H8	0.7916	0.1163	0.3272	0.062*
C9	0.2784 (4)	0.2276 (4)	0.55256 (19)	0.0568 (10)
H9	0.2831	0.1632	0.5214	0.068*
C10	0.1465 (5)	0.3332 (6)	0.6303 (3)	0.1007 (19)
H10A	0.2270	0.3927	0.6334	0.151*
H10B	0.1377	0.2890	0.6692	0.151*
H10C	0.0629	0.3854	0.6195	0.151*
C11	0.0480 (5)	0.1379 (6)	0.5678 (3)	0.118 (2)
H11A	−0.0330	0.1885	0.5517	0.178*
H11B	0.0252	0.0896	0.6042	0.178*
H11C	0.0750	0.0740	0.5374	0.178*
C12	0.3156 (6)	0.7130 (5)	0.1874 (2)	0.0765 (14)
H12	0.2351	0.7607	0.1731	0.092*
C13	0.4330 (6)	0.5683 (5)	0.2633 (3)	0.1003 (18)
H13A	0.4152	0.4732	0.2556	0.151*
H13B	0.4508	0.5831	0.3068	0.151*
H13C	0.5139	0.5963	0.2425	0.151*
C14	0.1882 (5)	0.6465 (6)	0.2757 (2)	0.0926 (16)
H14A	0.1149	0.7001	0.2547	0.139*
H14B	0.2121	0.6847	0.3158	0.139*
H14C	0.1557	0.5546	0.2800	0.139*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0313 (2)	0.0425 (3)	0.0537 (3)	−0.00725 (18)	0.00661 (18)	0.0006 (2)
Cl1	0.0498 (6)	0.0584 (6)	0.1019 (9)	−0.0229 (5)	−0.0066 (6)	0.0054 (6)
Cl2	0.1295 (12)	0.0781 (8)	0.0717 (8)	−0.0265 (8)	0.0131 (8)	−0.0339 (7)
N1	0.0274 (14)	0.0357 (15)	0.0427 (16)	−0.0085 (11)	0.0012 (12)	−0.0040 (13)
N2	0.0286 (14)	0.0462 (17)	0.0556 (19)	−0.0114 (12)	0.0064 (13)	−0.0158 (15)
N3	0.0365 (17)	0.072 (2)	0.071 (2)	−0.0200 (16)	0.0127 (15)	−0.0359 (18)
N4	0.039 (2)	0.089 (3)	0.094 (3)	−0.0100 (18)	0.0143 (19)	0.029 (2)
N5	0.077 (3)	0.068 (2)	0.057 (2)	−0.009 (2)	0.0072 (19)	0.0059 (19)
O1	0.0362 (13)	0.0408 (14)	0.0782 (19)	−0.0120 (11)	0.0087 (12)	−0.0043 (13)
O2	0.0386 (14)	0.0559 (16)	0.0681 (18)	−0.0111 (12)	0.0152 (12)	0.0063 (13)
O3	0.098 (3)	0.101 (3)	0.067 (2)	−0.024 (2)	−0.0003 (19)	0.0309 (19)
S1	0.0349 (5)	0.0519 (5)	0.0431 (5)	−0.0045 (4)	0.0068 (4)	−0.0034 (4)
C1	0.0312 (17)	0.044 (2)	0.0401 (19)	−0.0040 (15)	−0.0008 (15)	−0.0022 (16)
C2	0.0309 (18)	0.044 (2)	0.054 (2)	−0.0099 (15)	0.0033 (16)	−0.0054 (18)
C3	0.0384 (19)	0.0362 (19)	0.054 (2)	−0.0046 (15)	−0.0019 (16)	−0.0013 (17)
C4	0.0380 (19)	0.0337 (19)	0.059 (2)	−0.0007 (15)	−0.0046 (17)	0.0041 (17)
C5	0.044 (2)	0.037 (2)	0.066 (3)	−0.0097 (16)	−0.0119 (19)	0.0091 (19)
C6	0.070 (3)	0.039 (2)	0.068 (3)	−0.011 (2)	−0.021 (2)	−0.004 (2)
C7	0.074 (3)	0.047 (2)	0.051 (2)	−0.008 (2)	−0.007 (2)	−0.0089 (19)
C8	0.053 (2)	0.047 (2)	0.055 (2)	−0.0087 (18)	0.0024 (19)	−0.0049 (19)
C9	0.045 (2)	0.063 (3)	0.063 (3)	−0.004 (2)	0.008 (2)	0.013 (2)
C10	0.072 (3)	0.134 (5)	0.102 (4)	0.014 (3)	0.045 (3)	0.024 (4)
C11	0.048 (3)	0.141 (5)	0.167 (6)	−0.033 (3)	0.011 (3)	0.042 (5)
C12	0.089 (4)	0.066 (3)	0.072 (3)	−0.015 (3)	−0.010 (3)	0.013 (3)
C13	0.118 (5)	0.099 (4)	0.087 (4)	0.023 (3)	0.029 (3)	0.041 (3)
C14	0.083 (4)	0.119 (4)	0.077 (3)	−0.017 (3)	0.012 (3)	−0.007 (3)

Geometric parameters (Å, º) top

Cu1—O1	1.909 (2)	C2—H2	0.9300
Cu1—N1	1.954 (3)	C3—C8	1.398 (5)
Cu1—O2	1.985 (2)	C3—C4	1.421 (5)
Cu1—S1	2.2567 (10)	C4—C5	1.427 (5)
Cl1—C5	1.740 (4)	C5—C6	1.359 (6)
Cl2—C7	1.743 (4)	C6—C7	1.393 (6)
N1—C2	1.284 (4)	C6—H6	0.9300
N1—N2	1.388 (3)	C7—C8	1.367 (5)
N2—C1	1.316 (4)	C8—H8	0.9300
N3—C1	1.342 (4)	C9—H9	0.9300
N3—H3A	0.8600	C10—H10A	0.9600
N3—H3B	0.8600	C10—H10B	0.9600
N4—C9	1.315 (5)	C10—H10C	0.9600
N4—C10	1.446 (6)	C11—H11A	0.9600
N4—C11	1.458 (6)	C11—H11B	0.9600
N5—C12	1.328 (6)	C11—H11C	0.9600
N5—C14	1.444 (6)	C12—H12	0.9300
N5—C13	1.446 (6)	C13—H13A	0.9600
O1—C4	1.294 (4)	C13—H13B	0.9600
O2—C9	1.241 (4)	C13—H13C	0.9600
O3—C12	1.223 (6)	C14—H14A	0.9600
S1—C1	1.743 (3)	C14—H14B	0.9600
C2—C3	1.447 (4)	C14—H14C	0.9600

O1—Cu1—N1	93.55 (11)	C5—C6—H6	120.1
O1—Cu1—O2	90.55 (11)	C7—C6—H6	120.1
N1—Cu1—O2	172.04 (11)	C8—C7—C6	119.9 (4)
O1—Cu1—S1	176.26 (8)	C8—C7—Cl2	120.7 (3)
N1—Cu1—S1	86.04 (8)	C6—C7—Cl2	119.4 (3)
O2—Cu1—S1	89.43 (8)	C7—C8—C3	121.1 (4)
C2—N1—N2	114.1 (3)	C7—C8—H8	119.4
C2—N1—Cu1	125.1 (2)	C3—C8—H8	119.4
N2—N1—Cu1	120.8 (2)	O2—C9—N4	123.0 (4)
C1—N2—N1	113.5 (3)	O2—C9—H9	118.5
C1—N3—H3A	120.0	N4—C9—H9	118.5
C1—N3—H3B	120.0	N4—C10—H10A	109.5
H3A—N3—H3B	120.0	N4—C10—H10B	109.5
C9—N4—C10	121.6 (4)	H10A—C10—H10B	109.5
C9—N4—C11	120.2 (5)	N4—C10—H10C	109.5
C10—N4—C11	118.0 (4)	H10A—C10—H10C	109.5
C12—N5—C14	122.7 (4)	H10B—C10—H10C	109.5
C12—N5—C13	118.8 (4)	N4—C11—H11A	109.5
C14—N5—C13	118.4 (4)	N4—C11—H11B	109.5
C4—O1—Cu1	127.5 (2)	H11A—C11—H11B	109.5
C9—O2—Cu1	123.8 (3)	N4—C11—H11C	109.5
C1—S1—Cu1	94.29 (11)	H11A—C11—H11C	109.5
N2—C1—N3	116.3 (3)	H11B—C11—H11C	109.5
N2—C1—S1	125.3 (2)	O3—C12—N5	125.3 (5)
N3—C1—S1	118.4 (3)	O3—C12—H12	117.3
N1—C2—C3	126.0 (3)	N5—C12—H12	117.3
N1—C2—H2	117.0	N5—C13—H13A	109.5
C3—C2—H2	117.0	N5—C13—H13B	109.5
C8—C3—C4	120.6 (3)	H13A—C13—H13B	109.5
C8—C3—C2	116.9 (3)	N5—C13—H13C	109.5
C4—C3—C2	122.5 (3)	H13A—C13—H13C	109.5
O1—C4—C3	124.8 (3)	H13B—C13—H13C	109.5
O1—C4—C5	119.6 (3)	N5—C14—H14A	109.5
C3—C4—C5	115.6 (3)	N5—C14—H14B	109.5
C6—C5—C4	123.0 (4)	H14A—C14—H14B	109.5
C6—C5—Cl1	119.3 (3)	N5—C14—H14C	109.5
C4—C5—Cl1	117.7 (3)	H14A—C14—H14C	109.5
C5—C6—C7	119.8 (3)	H14B—C14—H14C	109.5

O1—Cu1—N1—C2	7.1 (3)	N1—C2—C3—C4	−2.9 (6)
O2—Cu1—N1—C2	127.9 (7)	Cu1—O1—C4—C3	3.3 (5)
S1—Cu1—N1—C2	−176.6 (3)	Cu1—O1—C4—C5	−176.6 (2)
O1—Cu1—N1—N2	−174.1 (2)	C8—C3—C4—O1	−178.8 (3)
O2—Cu1—N1—N2	−53.3 (9)	C2—C3—C4—O1	3.1 (5)
S1—Cu1—N1—N2	2.2 (2)	C8—C3—C4—C5	1.2 (5)
C2—N1—N2—C1	176.6 (3)	C2—C3—C4—C5	−176.9 (3)
Cu1—N1—N2—C1	−2.3 (4)	O1—C4—C5—C6	179.0 (3)
N1—Cu1—O1—C4	−7.1 (3)	C3—C4—C5—C6	−1.0 (5)
O2—Cu1—O1—C4	179.7 (3)	O1—C4—C5—Cl1	−1.6 (4)
S1—Cu1—O1—C4	−90.6 (13)	C3—C4—C5—Cl1	178.5 (3)
O1—Cu1—O2—C9	−7.4 (3)	C4—C5—C6—C7	0.1 (6)
N1—Cu1—O2—C9	−128.4 (7)	Cl1—C5—C6—C7	−179.4 (3)
S1—Cu1—O2—C9	176.3 (3)	C5—C6—C7—C8	0.7 (6)
O1—Cu1—S1—C1	82.5 (12)	C5—C6—C7—Cl2	−179.5 (3)
N1—Cu1—S1—C1	−1.24 (14)	C6—C7—C8—C3	−0.5 (6)
O2—Cu1—S1—C1	172.22 (14)	Cl2—C7—C8—C3	179.7 (3)
N1—N2—C1—N3	−179.1 (3)	C4—C3—C8—C7	−0.5 (6)
N1—N2—C1—S1	0.9 (4)	C2—C3—C8—C7	177.7 (3)
Cu1—S1—C1—N2	0.6 (3)	Cu1—O2—C9—N4	−171.5 (3)
Cu1—S1—C1—N3	−179.4 (3)	C10—N4—C9—O2	3.2 (7)
N2—N1—C2—C3	177.6 (3)	C11—N4—C9—O2	179.0 (4)
Cu1—N1—C2—C3	−3.5 (5)	C14—N5—C12—O3	−179.7 (5)
N1—C2—C3—C8	178.9 (3)	C13—N5—C12—O3	−1.9 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N2ⁱ	0.86	2.14	2.992 (4)	170
N3—H3B···O3ⁱⁱ	0.86	2.08	2.886 (4)	157

Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x+1/2, −y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula	[Cu(C₈H₅Cl₂N₃OS)(C₃H₇NO)]·C₃H₇NO
M_r	471.84
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	9.4979 (10), 9.8057 (12), 21.744 (2)
β (°)	94.263 (2)
V (Å³)	2019.5 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.47
Crystal size (mm)	0.49 × 0.47 × 0.24

Data collection
Diffractometer	Bruker SMART 1000 diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.532, 0.719
No. of measured, independent and observed [I > 2σ(I)] reflections	9869, 3558, 2587
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.098, 1.06
No. of reflections	3558
No. of parameters	235
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.50

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Cu1—O1	1.909 (2)	Cu1—O2	1.985 (2)
Cu1—N1	1.954 (3)	Cu1—S1	2.2567 (10)

O1—Cu1—N1	93.55 (11)	O2—Cu1—S1	89.43 (8)
O1—Cu1—O2	90.55 (11)	C4—O1—Cu1	127.5 (2)
N1—Cu1—O2	172.04 (11)	C9—O2—Cu1	123.8 (3)
O1—Cu1—S1	176.26 (8)	C1—S1—Cu1	94.29 (11)
N1—Cu1—S1	86.04 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N2ⁱ	0.86	2.14	2.992 (4)	170
N3—H3B···O3ⁱⁱ	0.86	2.08	2.886 (4)	157

Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x+1/2, −y+3/2, z+1/2.

Acknowledgements

We acknowledge financial support by the Key Laboratory of Non-ferrous Metal Materials and New Processing Technology, Ministry of Education, China.

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