Redetermination of catena-poly[[chlorido-(thio-urea-κS)copper(I)]-μ-thio-urea-κS:S] at 100 K.

The structure of the polymeric title compound, [CuCl(CH(4)N(2)S)(2)](n), has been redetermined to modern standards of precision with anisotropic refinement and location of the H atoms. The previous structure report [Spofford & Amma (1970 ▶). Acta Cryst. B26, 1474-1483] is generally confirmed to higher precision [typical Cu-S bond length s.u. values = 0.005 (old) and 0.001 Å (new)]. The asymmetric unit contains two formula units, with both Cu(I) atoms coordinated by one terminal S atom and two bridging S atoms of thio-urea ligands. This connectivity leads to polymeric [100] chains in the crystal. If very long contacts to nearby chloride ions [2.8687 (9) and 3.1394 (12) Å] are considered to be bonding, then very distorted CuS(3)Cl tetra-hedral coordination polyhedra arise. The crystal structure is consolidated by weak intra- and inter-chain N-H⋯S and N-H⋯Cl hydrogen bonds.

Related literature

For the structure of a related thio­urea salt, see: Zouihri (2012 ▶). For the previous structure determination of the title compound, see: Spofford & Amma (1970 ▶).

Experimental

Crystal data

[CuCl(CH4N2S)2]

M = 251.24

Monoclinic,

a = 5.8043 (2) Å

b = 8.1292 (3) Å

c = 35.9657 (12) Å

β = 92.326 (2)°

V = 1695.62 (10) Å3

Z = 8

Mo Kα radiation

μ = 3.32 mm−1

T = 100 K

0.45 × 0.18 × 0.07 mm

Data collection

Bruker APEXII CCD detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.493, T max = 0.793

18106 measured reflections

4089 independent reflections

3372 reflections with I > 2σ(I)

R int = 0.040

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.081

S = 1.15

4089 reflections

245 parameters

16 restraints

All H-atom parameters refined

Δρmax = 0.58 e Å−3

Δρmin = −0.85 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812004448/hb6598sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812004448/hb6598Isup2.hkl

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

[CuCl(CH4N2S)2]	F(000) = 1008
Mr = 251.24	Dx = 1.968 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 368 reflections
a = 5.8043 (2) Å	θ = 1.7–27.2°
b = 8.1292 (3) Å	µ = 3.32 mm−1
c = 35.9657 (12) Å	T = 100 K
β = 92.326 (2)°	Prism, colourless
V = 1695.62 (10) Å3	0.45 × 0.18 × 0.07 mm
Z = 8

Bruker APEXII CCD detector diffractometer	4089 independent reflections
Radiation source: fine-focus sealed tube	3372 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
ω and φ scans	θmax = 28.0°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→7
Tmin = 0.493, Tmax = 0.793	k = −10→10
18106 measured reflections	l = −47→33

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.081	All H-atom parameters refined
S = 1.15	w = 1/[σ2(Fo2) + (0.0226P)2 + 3.6977P] where P = (Fo2 + 2Fc2)/3
4089 reflections	(Δ/σ)max = 0.001
245 parameters	Δρmax = 0.58 e Å−3
16 restraints	Δρmin = −0.85 e Å−3

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	0.20578 (8)	0.31958 (6)	0.100266 (15)	0.02808 (13)
Cu2	−0.13231 (8)	0.24956 (6)	0.157138 (12)	0.02293 (12)
Cl1	−0.45164 (14)	0.01524 (10)	0.18514 (2)	0.01749 (17)
Cl2	0.35733 (14)	0.18063 (12)	0.02357 (3)	0.0253 (2)
S3	0.05347 (13)	0.07669 (10)	0.11866 (2)	0.01369 (17)
S4	0.06418 (14)	0.35188 (12)	0.20688 (3)	0.0207 (2)
S2	0.02223 (14)	0.52774 (12)	0.06966 (3)	0.01974 (19)
S1	0.55003 (14)	0.38438 (11)	0.13126 (3)	0.01895 (19)
C4	−0.1303 (6)	0.3857 (4)	0.24079 (10)	0.0203 (8)
C3	−0.1615 (5)	0.0262 (4)	0.08459 (9)	0.0148 (7)
C1	0.5411 (6)	0.5852 (4)	0.14784 (10)	0.0183 (7)
C2	0.2234 (6)	0.6102 (4)	0.04098 (10)	0.0179 (7)
N3	0.4489 (5)	0.5983 (5)	0.04812 (10)	0.0268 (8)
N1	0.7193 (6)	0.6469 (4)	0.16698 (10)	0.0277 (8)
N7	−0.3535 (5)	0.3549 (5)	0.23575 (10)	0.0298 (8)
N2	0.3566 (5)	0.6769 (4)	0.14099 (9)	0.0224 (7)
N4	0.1543 (5)	0.6897 (5)	0.01073 (9)	0.0259 (7)
N6	−0.3721 (5)	−0.0059 (4)	0.09504 (9)	0.0227 (7)
N5	−0.1090 (5)	0.0156 (4)	0.04974 (8)	0.0218 (7)
N8	−0.0560 (6)	0.4419 (5)	0.27368 (10)	0.0295 (8)
H5A	0.026 (4)	0.043 (5)	0.0426 (12)	0.037 (13)*
H6A	−0.482 (6)	−0.015 (6)	0.0781 (11)	0.049 (15)*
H7A	−0.398 (7)	0.304 (5)	0.2160 (8)	0.034 (13)*
H8A	−0.148 (6)	0.478 (6)	0.2898 (10)	0.040 (14)*
H3A	0.500 (7)	0.538 (4)	0.0666 (8)	0.023 (11)*
H4A	0.258 (5)	0.731 (5)	−0.0024 (10)	0.024 (11)*
H5B	−0.207 (6)	−0.017 (5)	0.0328 (9)	0.028 (11)*
H6B	−0.401 (7)	0.005 (5)	0.1181 (6)	0.027 (12)*
H7B	−0.443 (7)	0.391 (6)	0.2526 (10)	0.043 (14)*
H8B	0.082 (4)	0.477 (6)	0.2753 (14)	0.048 (15)*
H2B	0.358 (7)	0.775 (3)	0.1496 (11)	0.025 (12)*
H1B	0.817 (6)	0.573 (4)	0.1748 (11)	0.025 (11)*
H4B	0.016 (4)	0.692 (5)	0.0030 (12)	0.030 (12)*
H3B	0.537 (7)	0.639 (6)	0.0320 (10)	0.041 (14)*
H2A	0.249 (5)	0.639 (5)	0.1260 (9)	0.026 (11)*
H1A	0.715 (8)	0.743 (3)	0.1764 (13)	0.044 (14)*

	U11	U22	U33	U12	U13	U23
Cu1	0.0184 (2)	0.0208 (2)	0.0442 (3)	−0.00450 (19)	−0.0103 (2)	0.0088 (2)
Cu2	0.0198 (2)	0.0286 (3)	0.0199 (2)	0.00834 (19)	−0.00549 (18)	−0.0093 (2)
Cl1	0.0177 (4)	0.0183 (4)	0.0164 (4)	0.0011 (3)	0.0005 (3)	−0.0003 (3)
Cl2	0.0123 (4)	0.0327 (5)	0.0309 (5)	−0.0007 (4)	0.0013 (3)	0.0069 (4)
S3	0.0108 (3)	0.0163 (4)	0.0139 (4)	0.0007 (3)	−0.0005 (3)	−0.0006 (3)
S4	0.0119 (4)	0.0297 (5)	0.0202 (4)	0.0024 (3)	−0.0022 (3)	−0.0077 (4)
S2	0.0102 (4)	0.0267 (5)	0.0223 (5)	0.0015 (3)	0.0006 (3)	0.0057 (4)
S1	0.0160 (4)	0.0135 (4)	0.0266 (5)	0.0012 (3)	−0.0077 (4)	−0.0010 (3)
C4	0.0162 (16)	0.0191 (18)	0.0251 (19)	0.0030 (14)	−0.0043 (14)	−0.0062 (15)
C3	0.0121 (15)	0.0167 (17)	0.0156 (17)	−0.0031 (13)	−0.0002 (13)	−0.0031 (13)
C1	0.0169 (16)	0.0179 (18)	0.0200 (18)	−0.0008 (14)	0.0007 (14)	0.0027 (14)
C2	0.0138 (15)	0.0233 (19)	0.0166 (17)	0.0016 (14)	−0.0019 (13)	−0.0019 (14)
N3	0.0121 (14)	0.042 (2)	0.0262 (19)	−0.0001 (14)	0.0008 (13)	0.0125 (16)
N1	0.0277 (17)	0.0149 (17)	0.039 (2)	0.0035 (14)	−0.0143 (15)	−0.0072 (15)
N7	0.0121 (14)	0.051 (2)	0.0263 (19)	−0.0026 (15)	0.0018 (14)	−0.0180 (17)
N2	0.0181 (15)	0.0173 (16)	0.0314 (18)	0.0034 (13)	−0.0036 (13)	−0.0054 (15)
N4	0.0114 (14)	0.041 (2)	0.0249 (18)	−0.0017 (14)	−0.0019 (13)	0.0098 (15)
N6	0.0153 (14)	0.0362 (19)	0.0166 (16)	−0.0091 (14)	0.0006 (13)	−0.0030 (15)
N5	0.0152 (15)	0.0377 (19)	0.0123 (15)	−0.0063 (14)	−0.0001 (12)	−0.0044 (13)
N8	0.0185 (16)	0.046 (2)	0.0237 (18)	−0.0033 (16)	−0.0016 (14)	−0.0193 (16)

Cu1—S1	2.3091 (9)	C1—N2	1.320 (4)
Cu1—S2	2.2617 (10)	C2—N4	1.314 (5)
Cu1—S3	2.2728 (10)	C2—N3	1.327 (4)
Cu1—Cl2	3.1394 (12)	N3—H3A	0.867 (19)
Cu2—S1i	2.3081 (9)	N3—H3B	0.853 (19)
Cu2—S3	2.2747 (9)	N1—H1B	0.862 (19)
Cu2—S4	2.2421 (9)	N1—H1A	0.855 (19)
Cu2—Cl1	2.8687 (9)	N7—H7A	0.854 (19)
Cu1—Cu2	2.9470 (7)	N7—H7B	0.867 (19)
S3—C3	1.761 (3)	N2—H2B	0.852 (19)
S4—C4	1.717 (4)	N2—H2A	0.867 (19)
S2—C2	1.725 (4)	N4—H4A	0.852 (19)
S1—C1	1.739 (4)	N4—H4B	0.837 (19)
S1—Cu2ii	2.3081 (9)	N6—H6A	0.866 (19)
C4—N8	1.324 (5)	N6—H6B	0.857 (19)
C4—N7	1.325 (4)	N5—H5A	0.862 (19)
C3—N5	1.305 (4)	N5—H5B	0.856 (19)
C3—N6	1.320 (4)	N8—H8A	0.856 (19)
C1—N1	1.319 (5)	N8—H8B	0.852 (19)
Cl2—Cu1—S1	103.79 (3)	N5—C3—S3	119.8 (2)
Cl2—Cu1—S2	89.13 (4)	N6—C3—S3	119.1 (3)
Cl2—Cu1—S3	93.98 (3)	N1—C1—N2	119.7 (3)
S1—Cu1—S2	116.46 (4)	N1—C1—S1	120.1 (3)
S1—Cu1—S3	113.38 (4)	N2—C1—S1	120.1 (3)
S2—Cu1—S3	127.63 (4)	N4—C2—N3	117.5 (3)
Cl1—Cu2—S3	97.61 (3)	N4—C2—S2	119.7 (3)
Cl1—Cu2—S4	106.33 (3)	N3—C2—S2	122.8 (3)
Cl1—Cu2—S1i	86.56 (3)	C2—N3—H3A	120 (3)
S2—Cu1—S3	127.63 (4)	C2—N3—H3B	117 (3)
S2—Cu1—S1	116.46 (4)	H3A—N3—H3B	123 (4)
S3—Cu1—S1	113.38 (4)	C1—N1—H1B	113 (3)
S2—Cu1—Cu2	99.70 (3)	C1—N1—H1A	122 (3)
S3—Cu1—Cu2	49.63 (2)	H1B—N1—H1A	122 (4)
S1—Cu1—Cu2	107.25 (3)	C4—N7—H7A	118 (3)
S4—Cu2—S3	118.44 (3)	C4—N7—H7B	117 (3)
S4—Cu2—S1i	121.18 (4)	H7A—N7—H7B	125 (4)
S3—Cu2—S1i	116.02 (4)	C1—N2—H2B	118 (3)
S4—Cu2—Cu1	98.66 (3)	C1—N2—H2A	118 (3)
S3—Cu2—Cu1	49.58 (3)	H2B—N2—H2A	124 (4)
S1i—Cu2—Cu1	99.90 (3)	C2—N4—H4A	117 (3)
C3—S3—Cu1	105.83 (12)	C2—N4—H4B	123 (3)
C3—S3—Cu2	103.14 (11)	H4A—N4—H4B	120 (4)
Cu1—S3—Cu2	80.79 (3)	C3—N6—H6A	119 (3)
C4—S4—Cu2	107.36 (12)	C3—N6—H6B	118 (3)
C2—S2—Cu1	105.36 (12)	H6A—N6—H6B	122 (4)
C1—S1—Cu2ii	110.00 (12)	C3—N5—H5A	121 (3)
C1—S1—Cu1	110.01 (12)	C3—N5—H5B	122 (3)
Cu2ii—S1—Cu1	138.40 (4)	H5A—N5—H5B	117 (4)
N8—C4—N7	117.9 (4)	C4—N8—H8A	122 (3)
N8—C4—S4	119.4 (3)	C4—N8—H8B	117 (3)
N7—C4—S4	122.7 (3)	H8A—N8—H8B	117 (5)
N5—C3—N6	121.0 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1iii	0.85 (3)	2.44 (3)	3.230 (3)	154 (4)
N1—H1B···S4ii	0.87 (3)	2.55 (3)	3.404 (4)	171 (3)
N2—H2A···S2	0.87 (3)	2.54 (3)	3.379 (3)	164 (3)
N2—H2B···Cl1iii	0.86 (3)	2.56 (3)	3.344 (3)	153 (3)
N3—H3A···S1	0.87 (3)	2.65 (3)	3.488 (4)	164 (3)
N3—H3B···Cl2iv	0.86 (4)	2.57 (4)	3.373 (4)	156 (4)
N4—H4A···Cl2iv	0.85 (3)	2.49 (3)	3.309 (3)	161 (3)
N4—H4B···Cl2v	0.84 (3)	2.55 (3)	3.340 (3)	157 (4)
N5—H5A···Cl2	0.86 (3)	2.35 (3)	3.197 (3)	167 (4)
N5—H5B···Cl2vi	0.86 (3)	2.55 (4)	3.356 (3)	157 (3)
N6—H6A···Cl2i	0.87 (4)	2.66 (4)	3.323 (3)	134 (4)
N6—H6B···Cl1	0.86 (2)	2.44 (2)	3.296 (3)	174 (3)
N7—H7A···Cl1	0.85 (3)	2.61 (4)	3.343 (4)	145 (3)
N7—H7B···Cl1vii	0.87 (4)	2.55 (4)	3.367 (4)	157 (3)
N8—H8A···Cl1vii	0.86 (4)	2.54 (4)	3.326 (4)	152 (3)
N8—H8B···Cl1viii	0.85 (3)	2.55 (3)	3.298 (4)	148 (4)

Table 1

Selected bond lengths (Å)

Cu1—S1	2.3091 (9)
Cu1—S2	2.2617 (10)
Cu1—S3	2.2728 (10)
Cu1—Cl2	3.1394 (12)
Cu2—S1i	2.3081 (9)
Cu2—S3	2.2747 (9)
Cu2—S4	2.2421 (9)
Cu2—Cl1	2.8687 (9)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl1ii	0.85 (3)	2.44 (3)	3.230 (3)	154 (4)
N1—H1B⋯S4iii	0.87 (3)	2.55 (3)	3.404 (4)	171 (3)
N2—H2A⋯S2	0.87 (3)	2.54 (3)	3.379 (3)	164 (3)
N2—H2B⋯Cl1ii	0.86 (3)	2.56 (3)	3.344 (3)	153 (3)
N3—H3A⋯S1	0.87 (3)	2.65 (3)	3.488 (4)	164 (3)
N3—H3B⋯Cl2iv	0.86 (4)	2.57 (4)	3.373 (4)	156 (4)
N4—H4A⋯Cl2iv	0.85 (3)	2.49 (3)	3.309 (3)	161 (3)
N4—H4B⋯Cl2v	0.84 (3)	2.55 (3)	3.340 (3)	157 (4)
N5—H5A⋯Cl2	0.86 (3)	2.35 (3)	3.197 (3)	167 (4)
N5—H5B⋯Cl2vi	0.86 (3)	2.55 (4)	3.356 (3)	157 (3)
N6—H6A⋯Cl2i	0.87 (4)	2.66 (4)	3.323 (3)	134 (4)
N6—H6B⋯Cl1	0.86 (2)	2.44 (2)	3.296 (3)	174 (3)
N7—H7A⋯Cl1	0.85 (3)	2.61 (4)	3.343 (4)	145 (3)
N7—H7B⋯Cl1vii	0.87 (4)	2.55 (4)	3.367 (4)	157 (3)
N8—H8A⋯Cl1vii	0.86 (4)	2.54 (4)	3.326 (4)	152 (3)
N8—H8B⋯Cl1viii	0.85 (3)	2.55 (3)	3.298 (4)	148 (4)

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