catena-Poly[[[bis­(thio­urea-κS)copper(I)]-μ-thio­urea-κ2S:S] iodide acetonitrile hemisolvate]

Jia, L.; Kong, L.-Q.; Li, D.-C.

doi:10.1107/S1600536808007265

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 4| April 2008| Pages m568-m569

doi:10.1107/S1600536808007265

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catena-Poly[[[bis(thiourea-κS)copper(I)]-μ-thiourea-κ²S:S] iodide acetonitrile hemisolvate]

Li Jia,^a,^b Ling-Qian Kong ^c and Da-Cheng Li ^a ^*

^aSchool of Chemistry and Chemical Engineering, Liaocheng University, Shandong 252059, People's Republic of China, ^bLiaocheng Vocational and Technical College, Liaocheng, Shandong 252000, People's Republic of China, and ^cDongchang College of Liaocheng University, Liaocheng, Shandong 252000, People's Republic of China
^*Correspondence e-mail: lidacheng62@lcu.edu.cn

(Received 30 January 2008; accepted 17 March 2008; online 20 March 2008)

The title complex, {[Cu(CH₄N₂S)₃]I·0.5CH₃CN}_n, was formed by the reaction of CuI and thiourea in acetonitrile. There are two independent Cu^I ions in the asymmetric unit which are coordinated by two terminal and two bridging thiourea ligands to form a one-dimensional helical chain structure progagating in the a-axis direction. Each Cu^I ion is in a distorted tetrahedral coordination environment. The crystal structure is stabilized by weak N—H⋯S and N—H⋯I hydrogen bonds.

Related literature

For related literature, see: Bombicz et al. (2004 ); Bott et al. (1998 ); Stocker et al. (1996 ).

Experimental

Crystal data

[Cu(CH₄N₂S)₃]I·0.5C₂H₃N
M_r = 439.33
Orthorhombic, P 2₁ 2₁ 2₁
a = 13.392 (8) Å
b = 13.874 (9) Å
c = 15.289 (9) Å
V = 2841 (3) Å³
Z = 8
Mo Kα radiation
μ = 4.14 mm⁻¹
T = 298 (2) K
0.43 × 0.39 × 0.31 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.269, T_max = 0.360 (expected range = 0.207–0.277)
14883 measured reflections
4963 independent reflections
4175 reflections with I > 2σ(I)
R_int = 0.058

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.077
S = 1.00
4963 reflections
280 parameters
H-atom parameters constrained
Δρ_max = 0.75 e Å⁻³
Δρ_min = −0.56 e Å⁻³
Absolute structure: Flack (1983 ), 2149 Friedel pairs
Flack parameter: −0.01 (2)

Table 1
Selected bond lengths (Å)

Cu1—S3	2.275 (2)
Cu1—S2	2.309 (2)
Cu1—S1	2.382 (2)
Cu1—S6ⁱ	2.411 (2)
Cu2—S4	2.299 (2)
Cu2—S5	2.335 (2)
Cu2—S1	2.341 (2)
Cu2—S6	2.435 (2)
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯I2ⁱⁱ	0.86	2.97	3.799 (7)	161
N1—H1B⋯S6ⁱ	0.86	2.68	3.524 (7)	167
N2—H2A⋯I2ⁱⁱ	0.86	3.14	3.929 (6)	154
N2—H2B⋯S5	0.86	2.96	3.752 (7)	154
N2—H2B⋯I1ⁱⁱⁱ	0.86	3.17	3.667 (7)	119
N3—H3A⋯I2	0.86	2.87	3.645 (6)	150
N3—H3B⋯I1^iv	0.86	3.06	3.720 (6)	135
N4—H4A⋯I2	0.86	3.11	3.837 (7)	144
N4—H4A⋯I1	0.86	3.22	3.706 (6)	119
N4—H4B⋯S6ⁱ	0.86	2.73	3.563 (7)	165
N5—H5A⋯N13^v	0.86	2.41	3.192 (10)	152
N5—H5A⋯I2^iv	0.86	3.32	3.796 (8)	118
N7—H7A⋯I1^vi	0.86	3.04	3.839 (7)	156
N7—H7B⋯I2^iv	0.86	3.02	3.837 (7)	159
N8—H8A⋯I1^vi	0.86	2.93	3.759 (6)	161
N8—H8B⋯S5	0.86	2.69	3.526 (6)	166
N9—H9A⋯I2^vii	0.86	3.12	3.922 (6)	155
N9—H9B⋯S4	0.86	2.61	3.429 (7)	161
N10—H10A⋯I1^vii	0.86	3.01	3.716 (7)	141
N11—H11A⋯I1^viii	0.86	2.99	3.791 (6)	155
N11—H11B⋯S2ⁱⁱⁱ	0.86	2.63	3.466 (6)	163
N12—H12A⋯I1^viii	0.86	2.92	3.732 (6)	158
N12—H12B⋯S1	0.86	2.54	3.338 (6)	155
N6—H6A⋯S2^v	0.86	2.89	3.397 (6)	119
N6—H6A⋯N13^v	0.86	2.51	3.266 (11)	147
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (ii) x, y+1, z; (iii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (iv) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (v) $[-x+{\script{1\over 2}}, -y+1, z+{\script{1\over 2}}]$ ; (vi) $[-x+{\script{1\over 2}}, -y+1, z-{\script{1\over 2}}]$ ; (vii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (viii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Siemens, 1996 ); 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) and DIAMOND (Brandenburg & Berndt, 2006 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808007265/lh2596sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808007265/lh2596Isup2.hkl

checkCIF report

Comment top

Some copper(I) compounds containing thiourea ligands have been described previously (Bombicz et al., 2004; Bott et al., 1998; Stocker et al., 1996). In this paper, we report the synthesis and the structure of a complex formed by the reaction of thiourea with cuprous iodide. The asymmetric unit of the title compound is shown in Fig. 1. The Cu^I ions have distorted tetrahedral coordination geometries formed by two bridging thiourea ligands and two terminal thiourea ligands. A one-dimensional helical chain structure parallel to the a axis direction is formed (Fig. 2). An iodide counter ion and half an acetonitrile solvent molecule complete the formula unit although there are two formula units in the asymmetric unit of the crystal structure. The Cu—S distances are in the range of 2.275 (2)–2.435 (2) Å, and agree with those in related structures (Bombicz et al., 2004). In the title compound, the S=C distances are the same within experimental error.

In the crystal structure, there are two different types of hydrogen bonds. Intramolecular N—H···S interactions appear to influence the conformation of the helical chains while intermolecular N—H···S and N—H···I interactions stabilize the crystal structure.

Related literature top

For related literature, see: Bombicz et al. (2004); Bott et al. (1998); Stocker et al. (1996).

Experimental top

CuI (0.19 g 1 mmol) and thiourea (0.16 g 2 mmol) in 10 ml acetonitrile were refluxed for 24 h, forming a colorless solution. After filtration, the solution was allowed to evaporate slowly and crystals suitable for X-ray diffraction were obtained after several days.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXS97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenberg & Berndt, 2006); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit with atom labels and 30% probability displacement ellipsoids. H atoms are not shown.
	Fig. 2. Part of the one-dimensional helical chain structure of the title complex.

catena-Poly[[[bis(thiourea-κS)copper(I)]-µ-thiourea-κ²S:S] iodide acetonitrile hemisolvate] top

Crystal data top

[Cu(CH₄N₂S)₃]I·0.5C₂H₃N	F(000) = 1704
M_r = 439.33	D_x = 2.055 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 6067 reflections
a = 13.392 (8) Å	θ = 2.4–24.6°
b = 13.874 (9) Å	µ = 4.14 mm⁻¹
c = 15.289 (9) Å	T = 298 K
V = 2841 (3) Å³	Block, colorless
Z = 8	0.43 × 0.39 × 0.31 mm

Data collection top

Bruker SMART CCD diffractometer	4963 independent reflections
Radiation source: fine-focus sealed tube	4175 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.058
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −15→15
T_min = 0.269, T_max = 0.360	k = −14→16
14883 measured reflections	l = −18→18

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.034	H-atom parameters constrained
wR(F²) = 0.077	w = 1/[σ²(F_o²) + (0.0355P)²] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max = 0.001
4963 reflections	Δρ_max = 0.75 e Å⁻³
280 parameters	Δρ_min = −0.56 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 2149 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.01 (2)

Crystal data top

[Cu(CH₄N₂S)₃]I·0.5C₂H₃N	V = 2841 (3) Å³
M_r = 439.33	Z = 8
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 13.392 (8) Å	µ = 4.14 mm⁻¹
b = 13.874 (9) Å	T = 298 K
c = 15.289 (9) Å	0.43 × 0.39 × 0.31 mm

Data collection top

Bruker SMART CCD diffractometer	4963 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	4175 reflections with I > 2σ(I)
T_min = 0.269, T_max = 0.360	R_int = 0.058
14883 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	H-atom parameters constrained
wR(F²) = 0.077	Δρ_max = 0.75 e Å⁻³
S = 1.00	Δρ_min = −0.56 e Å⁻³
4963 reflections	Absolute structure: Flack (1983), 2149 Friedel pairs
280 parameters	Absolute structure parameter: −0.01 (2)
0 restraints

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	0.43289 (6)	0.62730 (6)	0.51306 (5)	0.0352 (2)
Cu2	0.21551 (6)	0.78050 (6)	0.36342 (6)	0.0378 (2)
I1	0.73774 (3)	0.35628 (3)	0.66369 (3)	0.03691 (12)
I2	0.56899 (4)	0.12983 (4)	0.53537 (3)	0.04740 (14)
N1	0.5123 (4)	0.8657 (5)	0.4926 (4)	0.0528 (18)
H1A	0.5402	0.9200	0.5043	0.063*
H1B	0.5389	0.8129	0.5106	0.063*
N2	0.3902 (5)	0.9446 (5)	0.4202 (5)	0.064 (2)
H2A	0.4189	0.9984	0.4325	0.077*
H2B	0.3358	0.9442	0.3903	0.077*
N3	0.3841 (5)	0.3114 (4)	0.4764 (4)	0.0459 (16)
H3A	0.4073	0.2612	0.5024	0.055*
H3B	0.3327	0.3064	0.4430	0.055*
N4	0.5048 (5)	0.3993 (5)	0.5388 (4)	0.0566 (19)
H4A	0.5263	0.3479	0.5640	0.068*
H4B	0.5345	0.4534	0.5474	0.068*
N5	0.2276 (5)	0.5314 (6)	0.6094 (5)	0.067 (2)
H5A	0.1708	0.5049	0.6202	0.081*
H5B	0.2535	0.5267	0.5581	0.081*
N6	0.2313 (5)	0.5839 (5)	0.7483 (4)	0.0615 (19)
H6A	0.1745	0.5566	0.7571	0.074*
H6B	0.2602	0.6146	0.7901	0.074*
N7	−0.0075 (5)	0.5530 (5)	0.2887 (5)	0.057 (2)
H7A	−0.0649	0.5543	0.2634	0.068*
H7B	0.0118	0.5018	0.3154	0.068*
N8	0.0191 (4)	0.7058 (4)	0.2453 (4)	0.0462 (17)
H8A	−0.0385	0.7056	0.2204	0.055*
H8B	0.0561	0.7564	0.2431	0.055*
N9	0.2578 (5)	0.7295 (5)	0.1506 (4)	0.0568 (18)
H9A	0.2765	0.7019	0.1030	0.068*
H9B	0.2487	0.6959	0.1972	0.068*
N10	0.2579 (7)	0.8700 (6)	0.0790 (4)	0.089 (3)
H10A	0.2767	0.8410	0.0321	0.107*
H10B	0.2486	0.9314	0.0786	0.107*
N11	0.1163 (4)	0.9243 (5)	0.6331 (4)	0.0478 (16)
H11A	0.1405	0.9268	0.6851	0.057*
H11B	0.0637	0.9570	0.6201	0.057*
N12	0.2399 (5)	0.8212 (5)	0.5951 (4)	0.065 (2)
H12A	0.2631	0.8245	0.6474	0.078*
H12B	0.2691	0.7856	0.5568	0.078*
N13	0.4435 (6)	0.5766 (7)	0.2168 (5)	0.080 (3)
S1	0.37489 (12)	0.75471 (12)	0.42179 (11)	0.0289 (4)
S2	0.38359 (13)	0.49427 (13)	0.43325 (11)	0.0347 (4)
S3	0.38436 (12)	0.63528 (15)	0.65547 (11)	0.0409 (4)
S4	0.16498 (11)	0.62484 (13)	0.33684 (12)	0.0377 (4)
S5	0.20735 (14)	0.88344 (13)	0.24281 (11)	0.0407 (4)
S6	0.11161 (11)	0.86565 (13)	0.46883 (10)	0.0300 (3)
C1	0.4293 (5)	0.8635 (5)	0.4470 (4)	0.0371 (16)
C2	0.4269 (5)	0.3951 (5)	0.4876 (4)	0.0351 (16)
C3	0.2741 (5)	0.5786 (5)	0.6706 (5)	0.0375 (16)
C4	0.0505 (4)	0.6292 (5)	0.2864 (4)	0.0339 (15)
C5	0.2434 (5)	0.8202 (6)	0.1521 (4)	0.0462 (19)
C6	0.1593 (4)	0.8707 (5)	0.5735 (4)	0.0306 (14)
C7	0.4660 (6)	0.6535 (9)	0.2169 (5)	0.060 (3)
C8	0.4976 (7)	0.7529 (7)	0.2179 (7)	0.075 (3)
H8C	0.4444	0.7925	0.2398	0.112*
H8D	0.5143	0.7728	0.1595	0.112*
H8E	0.5551	0.7595	0.2549	0.112*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0331 (4)	0.0335 (5)	0.0391 (5)	−0.0031 (4)	0.0053 (4)	−0.0024 (4)
Cu2	0.0300 (4)	0.0451 (5)	0.0383 (5)	−0.0036 (4)	−0.0070 (4)	−0.0002 (4)
I1	0.0318 (2)	0.0460 (3)	0.0330 (2)	−0.0026 (2)	0.00101 (19)	−0.0021 (2)
I2	0.0590 (3)	0.0338 (3)	0.0494 (3)	0.0017 (3)	0.0004 (2)	0.0003 (3)
N1	0.041 (3)	0.030 (3)	0.087 (5)	−0.005 (3)	−0.032 (3)	−0.001 (4)
N2	0.049 (4)	0.033 (4)	0.110 (6)	−0.015 (3)	−0.035 (4)	0.013 (4)
N3	0.052 (4)	0.039 (4)	0.047 (4)	−0.001 (3)	−0.006 (3)	0.003 (3)
N4	0.060 (5)	0.043 (4)	0.067 (5)	−0.004 (3)	−0.033 (4)	0.013 (4)
N5	0.042 (4)	0.082 (5)	0.078 (5)	−0.022 (4)	0.012 (4)	−0.004 (4)
N6	0.067 (5)	0.062 (4)	0.055 (4)	−0.004 (4)	0.032 (4)	0.006 (3)
N7	0.047 (4)	0.037 (4)	0.087 (5)	−0.008 (3)	−0.012 (4)	0.008 (4)
N8	0.024 (3)	0.042 (4)	0.072 (5)	0.000 (3)	−0.012 (3)	0.004 (4)
N9	0.058 (4)	0.072 (5)	0.041 (4)	0.015 (4)	0.011 (3)	−0.018 (3)
N10	0.146 (8)	0.089 (6)	0.032 (4)	−0.057 (7)	0.019 (5)	−0.008 (4)
N11	0.042 (3)	0.069 (5)	0.032 (3)	0.018 (3)	−0.006 (3)	−0.016 (3)
N12	0.049 (4)	0.117 (6)	0.028 (3)	0.039 (4)	−0.005 (3)	−0.004 (3)
N13	0.066 (5)	0.106 (7)	0.066 (5)	−0.018 (5)	−0.025 (4)	0.011 (5)
S1	0.0239 (8)	0.0303 (9)	0.0326 (9)	0.0005 (7)	−0.0038 (7)	0.0001 (7)
S2	0.0379 (9)	0.0327 (10)	0.0336 (10)	−0.0020 (8)	−0.0104 (8)	0.0010 (8)
S3	0.0372 (8)	0.0529 (11)	0.0327 (9)	−0.0054 (9)	0.0030 (8)	−0.0016 (9)
S4	0.0291 (8)	0.0365 (10)	0.0474 (10)	0.0026 (7)	−0.0061 (8)	0.0006 (9)
S5	0.0527 (11)	0.0376 (10)	0.0319 (9)	0.0019 (8)	−0.0045 (8)	0.0017 (8)
S6	0.0214 (7)	0.0422 (10)	0.0265 (8)	0.0012 (8)	0.0006 (6)	−0.0039 (9)
C1	0.035 (3)	0.035 (4)	0.042 (4)	0.003 (4)	−0.004 (3)	0.001 (3)
C2	0.032 (4)	0.042 (4)	0.031 (4)	−0.009 (3)	−0.003 (3)	−0.004 (3)
C3	0.038 (4)	0.032 (4)	0.042 (4)	0.007 (3)	0.010 (4)	0.008 (3)
C4	0.030 (3)	0.034 (4)	0.038 (4)	0.001 (3)	0.003 (3)	−0.004 (3)
C5	0.037 (4)	0.068 (6)	0.034 (4)	−0.011 (4)	−0.003 (4)	−0.003 (4)
C6	0.025 (3)	0.042 (4)	0.025 (3)	−0.003 (3)	−0.001 (3)	0.003 (3)
C7	0.040 (5)	0.100 (9)	0.041 (5)	−0.003 (5)	0.000 (4)	0.012 (5)
C8	0.059 (6)	0.096 (8)	0.069 (7)	−0.013 (5)	0.028 (5)	0.000 (6)

Geometric parameters (Å, º) top

Cu1—S3	2.275 (2)	N7—H7B	0.8600
Cu1—S2	2.309 (2)	N8—C4	1.303 (9)
Cu1—S1	2.382 (2)	N8—H8A	0.8600
Cu1—S6ⁱ	2.411 (2)	N8—H8B	0.8600
Cu2—S4	2.299 (2)	N9—C5	1.273 (10)
Cu2—S5	2.335 (2)	N9—H9A	0.8600
Cu2—S1	2.341 (2)	N9—H9B	0.8600
Cu2—S6	2.435 (2)	N10—C5	1.328 (10)
N1—C1	1.313 (8)	N10—H10A	0.8600
N1—H1A	0.8600	N10—H10B	0.8600
N1—H1B	0.8600	N11—C6	1.309 (8)
N2—C1	1.307 (9)	N11—H11A	0.8600
N2—H2A	0.8600	N11—H11B	0.8600
N2—H2B	0.8600	N12—C6	1.321 (9)
N3—C2	1.307 (8)	N12—H12A	0.8600
N3—H3A	0.8600	N12—H12B	0.8600
N3—H3B	0.8600	N13—C7	1.109 (12)
N4—C2	1.306 (8)	S1—C1	1.719 (7)
N4—H4A	0.8600	S2—C2	1.708 (7)
N4—H4B	0.8600	S3—C3	1.689 (7)
N5—C3	1.301 (10)	S4—C4	1.718 (6)
N5—H5A	0.8600	S5—C5	1.711 (8)
N5—H5B	0.8600	S6—C6	1.725 (6)
N6—C3	1.321 (9)	S6—Cu1ⁱⁱ	2.411 (2)
N6—H6A	0.8600	C7—C8	1.442 (14)
N6—H6B	0.8600	C8—H8C	0.9600
N7—C4	1.313 (8)	C8—H8D	0.9600
N7—H7A	0.8600	C8—H8E	0.9600

S3—Cu1—S2	117.58 (8)	C6—N11—H11A	120.0
S3—Cu1—S1	115.55 (8)	C6—N11—H11B	120.0
S2—Cu1—S1	100.97 (8)	H11A—N11—H11B	120.0
S3—Cu1—S6ⁱ	99.89 (6)	C6—N12—H12A	120.0
S2—Cu1—S6ⁱ	112.14 (7)	C6—N12—H12B	120.0
S1—Cu1—S6ⁱ	111.15 (7)	H12A—N12—H12B	120.0
S4—Cu2—S5	114.90 (8)	C1—S1—Cu2	109.7 (2)
S4—Cu2—S1	101.08 (7)	C1—S1—Cu1	112.4 (2)
S5—Cu2—S1	115.93 (7)	Cu2—S1—Cu1	129.34 (8)
S4—Cu2—S6	113.86 (7)	C2—S2—Cu1	106.8 (2)
S5—Cu2—S6	101.49 (8)	C3—S3—Cu1	111.0 (3)
S1—Cu2—S6	110.05 (7)	C4—S4—Cu2	108.0 (3)
C1—N1—H1A	120.0	C5—S5—Cu2	108.3 (3)
C1—N1—H1B	120.0	C6—S6—Cu1ⁱⁱ	105.0 (2)
H1A—N1—H1B	120.0	C6—S6—Cu2	115.0 (2)
C1—N2—H2A	120.0	Cu1ⁱⁱ—S6—Cu2	131.52 (7)
C1—N2—H2B	120.0	N2—C1—N1	119.0 (7)
H2A—N2—H2B	120.0	N2—C1—S1	121.1 (5)
C2—N3—H3A	120.0	N1—C1—S1	119.9 (6)
C2—N3—H3B	120.0	N4—C2—N3	117.9 (6)
H3A—N3—H3B	120.0	N4—C2—S2	121.8 (5)
C2—N4—H4A	120.0	N3—C2—S2	120.2 (5)
C2—N4—H4B	120.0	N5—C3—N6	117.9 (7)
H4A—N4—H4B	120.0	N5—C3—S3	123.7 (6)
C3—N5—H5A	120.0	N6—C3—S3	118.5 (6)
C3—N5—H5B	120.0	N8—C4—N7	118.6 (6)
H5A—N5—H5B	120.0	N8—C4—S4	122.2 (5)
C3—N6—H6A	120.0	N7—C4—S4	119.2 (6)
C3—N6—H6B	120.0	N9—C5—N10	118.6 (8)
H6A—N6—H6B	120.0	N9—C5—S5	124.3 (6)
C4—N7—H7A	120.0	N10—C5—S5	117.1 (7)
C4—N7—H7B	120.0	N11—C6—N12	118.8 (6)
H7A—N7—H7B	120.0	N11—C6—S6	120.3 (5)
C4—N8—H8A	120.0	N12—C6—S6	120.8 (5)
C4—N8—H8B	120.0	N13—C7—C8	178.6 (11)
H8A—N8—H8B	120.0	C7—C8—H8C	109.5
C5—N9—H9A	120.0	C7—C8—H8D	109.5
C5—N9—H9B	120.0	H8C—C8—H8D	109.5
H9A—N9—H9B	120.0	C7—C8—H8E	109.5
C5—N10—H10A	120.0	H8C—C8—H8E	109.5
C5—N10—H10B	120.0	H8D—C8—H8E	109.5
H10A—N10—H10B	120.0

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···I2ⁱⁱⁱ	0.86	2.97	3.799 (7)	161
N1—H1B···S6ⁱ	0.86	2.68	3.524 (7)	167
N2—H2A···I2ⁱⁱⁱ	0.86	3.14	3.929 (6)	154
N2—H2B···S5	0.86	2.96	3.752 (7)	154
N2—H2B···I1ⁱⁱ	0.86	3.17	3.667 (7)	119
N3—H3A···I2	0.86	2.87	3.645 (6)	150
N3—H3B···I1^iv	0.86	3.06	3.720 (6)	135
N4—H4A···I2	0.86	3.11	3.837 (7)	144
N4—H4A···I1	0.86	3.22	3.706 (6)	119
N4—H4B···S6ⁱ	0.86	2.73	3.563 (7)	165
N5—H5A···N13^v	0.86	2.41	3.192 (10)	152
N5—H5A···I2^iv	0.86	3.32	3.796 (8)	118
N7—H7A···I1^vi	0.86	3.04	3.839 (7)	156
N7—H7B···I2^iv	0.86	3.02	3.837 (7)	159
N8—H8A···I1^vi	0.86	2.93	3.759 (6)	161
N8—H8B···S5	0.86	2.69	3.526 (6)	166
N9—H9A···I2^vii	0.86	3.12	3.922 (6)	155
N9—H9B···S4	0.86	2.61	3.429 (7)	161
N10—H10A···I1^vii	0.86	3.01	3.716 (7)	141
N11—H11A···I1^viii	0.86	2.99	3.791 (6)	155
N11—H11B···S2ⁱⁱ	0.86	2.63	3.466 (6)	163
N12—H12A···I1^viii	0.86	2.92	3.732 (6)	158
N12—H12B···S1	0.86	2.54	3.338 (6)	155
N6—H6A···S2^v	0.86	2.89	3.397 (6)	119
N6—H6A···N13^v	0.86	2.51	3.266 (11)	147

Symmetry codes: (i) x+1/2, −y+3/2, −z+1; (ii) x−1/2, −y+3/2, −z+1; (iii) x, y+1, z; (iv) x−1/2, −y+1/2, −z+1; (v) −x+1/2, −y+1, z+1/2; (vi) −x+1/2, −y+1, z−1/2; (vii) −x+1, y+1/2, −z+1/2; (viii) −x+1, y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	[Cu(CH₄N₂S)₃]I·0.5C₂H₃N
M_r	439.33
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	298
a, b, c (Å)	13.392 (8), 13.874 (9), 15.289 (9)
V (Å³)	2841 (3)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	4.14
Crystal size (mm)	0.43 × 0.39 × 0.31

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.269, 0.360
No. of measured, independent and observed [I > 2σ(I)] reflections	14883, 4963, 4175
R_int	0.058
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.077, 1.00
No. of reflections	4963
No. of parameters	280
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.75, −0.56
Absolute structure	Flack (1983), 2149 Friedel pairs
Absolute structure parameter	−0.01 (2)

Computer programs: SMART (Bruker, 1997), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenberg & Berndt, 2006), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Cu1—S3	2.275 (2)	Cu2—S4	2.299 (2)
Cu1—S2	2.309 (2)	Cu2—S5	2.335 (2)
Cu1—S1	2.382 (2)	Cu2—S1	2.341 (2)
Cu1—S6ⁱ	2.411 (2)	Cu2—S6	2.435 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···I2ⁱⁱ	0.86	2.97	3.799 (7)	161.3
N1—H1B···S6ⁱ	0.86	2.68	3.524 (7)	167.3
N2—H2A···I2ⁱⁱ	0.86	3.14	3.929 (6)	154.2
N2—H2B···S5	0.86	2.96	3.752 (7)	154.0
N2—H2B···I1ⁱⁱⁱ	0.86	3.17	3.667 (7)	118.9
N3—H3A···I2	0.86	2.87	3.645 (6)	150.1
N3—H3B···I1^iv	0.86	3.06	3.720 (6)	135.1
N4—H4A···I2	0.86	3.11	3.837 (7)	143.6
N4—H4A···I1	0.86	3.22	3.706 (6)	118.5
N4—H4B···S6ⁱ	0.86	2.73	3.563 (7)	164.9
N5—H5A···N13^v	0.86	2.41	3.192 (10)	151.6
N5—H5A···I2^iv	0.86	3.32	3.796 (8)	117.8
N7—H7A···I1^vi	0.86	3.04	3.839 (7)	156.2
N7—H7B···I2^iv	0.86	3.02	3.837 (7)	159.3
N8—H8A···I1^vi	0.86	2.93	3.759 (6)	161.3
N8—H8B···S5	0.86	2.69	3.526 (6)	166.0
N9—H9A···I2^vii	0.86	3.12	3.922 (6)	155.4
N9—H9B···S4	0.86	2.61	3.429 (7)	160.8
N10—H10A···I1^vii	0.86	3.01	3.716 (7)	141.1
N11—H11A···I1^viii	0.86	2.99	3.791 (6)	155.0
N11—H11B···S2ⁱⁱⁱ	0.86	2.63	3.466 (6)	162.8
N12—H12A···I1^viii	0.86	2.92	3.732 (6)	157.9
N12—H12B···S1	0.86	2.54	3.338 (6)	154.7
N6—H6A···S2^v	0.86	2.89	3.397 (6)	119.4
N6—H6A···N13^v	0.86	2.51	3.266 (11)	147.4

Symmetry codes: (i) x+1/2, −y+3/2, −z+1; (ii) x, y+1, z; (iii) x−1/2, −y+3/2, −z+1; (iv) x−1/2, −y+1/2, −z+1; (v) −x+1/2, −y+1, z+1/2; (vi) −x+1/2, −y+1, z−1/2; (vii) −x+1, y+1/2, −z+1/2; (viii) −x+1, y+1/2, −z+3/2.

Acknowledgements

We acknowledge the Natural Science Foundation of Liaocheng University (X051002) forsupport.

References

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