catena-Poly[[[bis-(thio-urea-κS)copper(I)]-μ-thio-urea-κS:S] iodide acetonitrile hemisolvate].

The title complex, {[Cu(CH(4)N(2)S)(3)]I·0.5CH(3)CN}(n), was formed by the reaction of CuI and thio-urea in acetonitrile. There are two independent Cu(I) ions in the asymmetric unit which are coordinated by two terminal and two bridging thio-urea ligands to form a one-dimensional helical chain structure progagating in the a-axis direction. Each Cu(I) ion is in a distorted tetra-hedral 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 = 439.33

Orthorhombic,

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[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.077

S = 1.00

4963 reflections

280 parameters

H-atom parameters constrained

Δρmax = 0.75 e Å−3

Δρmin = −0.56 e Å−3

Absolute structure: Flack (1983 ▶), 2149 Friedel pairs

Flack parameter: −0.01 (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.

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Cu(CH4N2S)3]I·0.5C2H3N	F000 = 1704
Mr = 439.33	Dx = 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 = 2.4–24.6º
b = 13.874 (9) Å	µ = 4.14 mm−1
c = 15.289 (9) Å	T = 298 (2) K
V = 2841 (3) Å3	Block, colorless
Z = 8	0.43 × 0.39 × 0.31 mm

Bruker SMART CCD diffractometer	4963 independent reflections
Radiation source: fine-focus sealed tube	4175 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.058
T = 298(2) K	θmax = 25.0º
φ and ω scans	θmin = 2.0º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)	h = −15→15
Tmin = 0.269, Tmax = 0.360	k = −14→16
14883 measured reflections	l = −18→18

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.034	w = 1/[σ2(Fo2) + (0.0355P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.077	(Δ/σ)max = 0.001
S = 1.00	Δρmax = 0.75 e Å−3
4963 reflections	Δρmin = −0.56 e Å−3
280 parameters	Extinction correction: none
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 2149 Friedel pairs
Secondary atom site location: difference Fourier map	Flack parameter: −0.01 (2)

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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

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···I1iv	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···N13v	0.86	2.41	3.192 (10)	152
N5—H5A···I2iv	0.86	3.32	3.796 (8)	118
N7—H7A···I1vi	0.86	3.04	3.839 (7)	156
N7—H7B···I2iv	0.86	3.02	3.837 (7)	159
N8—H8A···I1vi	0.86	2.93	3.759 (6)	161
N8—H8B···S5	0.86	2.69	3.526 (6)	166
N9—H9A···I2vii	0.86	3.12	3.922 (6)	155
N9—H9B···S4	0.86	2.61	3.429 (7)	161
N10—H10A···I1vii	0.86	3.01	3.716 (7)	141
N11—H11A···I1viii	0.86	2.99	3.791 (6)	155
N11—H11B···S2ii	0.86	2.63	3.466 (6)	163
N12—H12A···I1viii	0.86	2.92	3.732 (6)	158
N12—H12B···S1	0.86	2.54	3.338 (6)	155
N6—H6A···S2v	0.86	2.89	3.397 (6)	119
N6—H6A···N13v	0.86	2.51	3.266 (11)	147

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) .

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⋯I1iv	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⋯N13v	0.86	2.41	3.192 (10)	152
N5—H5A⋯I2iv	0.86	3.32	3.796 (8)	118
N7—H7A⋯I1vi	0.86	3.04	3.839 (7)	156
N7—H7B⋯I2iv	0.86	3.02	3.837 (7)	159
N8—H8A⋯I1vi	0.86	2.93	3.759 (6)	161
N8—H8B⋯S5	0.86	2.69	3.526 (6)	166
N9—H9A⋯I2vii	0.86	3.12	3.922 (6)	155
N9—H9B⋯S4	0.86	2.61	3.429 (7)	161
N10—H10A⋯I1vii	0.86	3.01	3.716 (7)	141
N11—H11A⋯I1viii	0.86	2.99	3.791 (6)	155
N11—H11B⋯S2iii	0.86	2.63	3.466 (6)	163
N12—H12A⋯I1viii	0.86	2.92	3.732 (6)	158
N12—H12B⋯S1	0.86	2.54	3.338 (6)	155
N6—H6A⋯S2v	0.86	2.89	3.397 (6)	119
N6—H6A⋯N13v	0.86	2.51	3.266 (11)	147

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) .