Tetra­kis(N-methyl­thio­urea-κS)copper(I) iodide

In the title complex, [Cu(C₂H₆N₂S)₄]I, the Cu^I atom lies on a axis. Each Cu^I centre binds to the S atoms of four N-methyl­thio­urea ligands in a distorted tetra­hedral environment. In the crystal structure, inter­molecular N—H...S and N—H...I hydrogen bonds, together with weak C—H...N inter­actions, link the cations and anions into a three-dimensional network.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](N-C) = 0.002 Å
• R factor = 0.034
• wR factor = 0.085
• Data-to-parameter ratio = 37.4

checkCIF/PLATON results

No syntax errors found



Alert level C
RINTA01_ALERT_3_C  The value of Rint is greater than 0.10
            Rint given   0.104
PLAT020_ALERT_3_C The value of Rint is greater than 0.10 .........       0.10
PLAT164_ALERT_4_C Nr. of Refined C-H H-Atoms in Heavy-At Struct...          3
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          3

Alert level G
PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1         (2)       1.87

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

The study of coordination and structural chemistry of copper(I) complexes with sulfur containing ligands has been a matter of interest over the last decades due to their promising biological applications as well as due to their ability to adopt different geometries with variable nuclearities and structural diversity (Eller et al., 1977; Kaim & Schwederski, 1994; Lobana et al., 2006). Consequently, a number of attempts have been made to explore the structures of several copper(I) complexes with thiourea and its derivatives, and these structures have been reported (Bombicz et al., 2004); Dubler & Bensch, 1986; Lobana et al., 2006). Such studies provide models for naturally occurring copper–sulfur containing metalloproteins. As part of our continuing interest in the structural chemistry of metal–sulfur interactions, we report here the crystal structure of the title complex.

In the molecule of the title complex, Cu1 lies on a fourfold roto-inversion axis and the asymmetric unit therefore contain a quarter of the molecule (Fig. 1). The coordination of Cu1 is a distorted tetrahedron, being coordinated by the S atoms of the four N-methylthiourea ligands, with S—Cu—S angles of 107.19 (5) and 112.894 (18)° (Table 1). The Cu—S bond distances [2.3349 (4) and 2.3350 (4) Å] of the title complex lie within the range of those found in the Cu^I complexes with tetrahedral geometry (Bombicz et al., 2004; Lobana et al., 2006). The orientation of the ligand around Cu1 is indicated by the dihedral angle between the mean planes of Cu1/S1/C1/N1/N2 and C1/C2/N1/N2 [3.86 (9)°]. All other bond lengths and angles are in normal ranges (Allen et al., 1987).

In the crystal packing (Fig. 2), the cations are linked by N1—H1N1···S1(1 - x, 1/2 - y, z) and N1—H2N1···S1(1/4 + y, 1/4 - x, 1/4 + z) hydrogen bonds, and these cations are linked to iodide anions by an N2—H1N2···I1(-1/4 + y, 3/4 - x, -1/4 + z) hydrogen bond to form molecular sheets parallel to the ac plane and these sheets are further connected by weak C2—H2A···N2(1/4 + y, 1/4 - x, 1/4 + z) interactions to form a three-dimensional network.

Related literature

For related literature on values of bond lengths, see: Allen et al. (1987). For related structures, see: Bombicz et al. (2004); Lobana et al. (2006). For related literature on the coordination chemistry of copper, see, for example: Dubler & Bensch (1986); Eller et al. (1977); Kaim & Schwederski (1994); Lobana et al. (2006).

S2. Experimental

To a solution of copper(I) iodide (0.19 g, 1.0 mmol) in acetonitrile (15 ml) was added 2 molar equivalents of N-methylthiourea in acetonitrile (10 ml). The mixture was stirred for half an hour. Then a clear solution was obtained. The solution was concentrated by slow evaporation at room temperature to yield colorless single crystals of the title compound suitable for X-ray stucture determination after a few days.

S3. Refinement

All H atoms were located from the difference map and refined isotropically The U_iso values were constrained to be 1.5U_eq of the carrier atom for methyl H atoms and 1.2U_eq for the remaining H atoms.

Computing details

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 1998); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003).

Figures

	Fig. 1. The structure of the title compound, showing 50% probability displacement ellipsoids and the atomic numbering.
	Fig. 2. The crystal packing of the title compound, viewed along the b axis. Hydrogen bonds are shown as dashed lines.

Tetrakis(N-methylthiourea-κS)copper(I) iodide

Crystal data

[Cu(C2H6N2S)4]I	Dx = 1.739 Mg m^−3
Mr = 551.08	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I41/a	Cell parameters from 2767 reflections
Hall symbol: -I 4ad	θ = 2.2–37.5°
a = 12.5113 (6) Å	µ = 2.91 mm^−1
c = 13.4435 (9) Å	T = 100 K
V = 2104.4 (2) Å^3	Plate, colourless
Z = 4	0.57 × 0.49 × 0.10 mm
F(000) = 1096

Data collection

Bruker APEXII CCD area-detector diffractometer	2767 independent reflections
Radiation source: fine-focus sealed tube	2149 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.104
Detector resolution: 8.33 pixels mm^-1	θmax = 37.5°, θmin = 2.2°
ω scans	h = −21→21
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −19→21
Tmin = 0.205, Tmax = 0.748	l = −22→23
19549 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.085	All H-atom parameters refined
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0359P)^2 + 1.5035P] where P = (Fo^2 + 2Fc^2)/3
2767 reflections	(Δ/σ)max = 0.001
74 parameters	Δρmax = 1.41 e Å^−3
0 restraints	Δρmin = −0.97 e Å^−3

Special details

Experimental. The low-temparture data was collected with the Oxford Cyrosystem Cobra low-temperature attachment.

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 (Ų)

	x	y	z	Uiso*/Ueq
I1	0.5000	0.2500	0.8750	0.02531 (7)
Cu1	0.5000	0.2500	0.3750	0.01643 (8)
S1	0.34596 (3)	0.27148 (3)	0.47100 (3)	0.01687 (8)
N1	0.43604 (11)	0.11480 (11)	0.57710 (11)	0.0221 (2)
N2	0.27169 (11)	0.17292 (12)	0.63020 (9)	0.0191 (2)
C1	0.35269 (11)	0.17989 (11)	0.56670 (11)	0.0166 (2)
C2	0.26350 (13)	0.09411 (15)	0.70884 (13)	0.0244 (3)
H2A	0.317 (2)	0.104 (2)	0.759 (2)	0.038 (7)*
H2B	0.274 (2)	0.027 (2)	0.688 (2)	0.036 (7)*
H2C	0.196 (2)	0.0992 (19)	0.7400 (18)	0.029 (6)*
H1N1	0.487 (2)	0.1281 (19)	0.541 (2)	0.030 (6)*
H2N1	0.441 (2)	0.071 (2)	0.6272 (16)	0.020 (6)*
H1N2	0.216 (2)	0.217 (2)	0.6193 (17)	0.032 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.01276 (7)	0.01276 (7)	0.05041 (15)	0.000	0.000	0.000
Cu1	0.01618 (10)	0.01618 (10)	0.01692 (15)	0.000	0.000	0.000
S1	0.01308 (14)	0.01761 (15)	0.01992 (15)	0.00135 (10)	−0.00048 (11)	0.00227 (12)
N1	0.0165 (5)	0.0232 (6)	0.0267 (6)	0.0041 (4)	0.0037 (5)	0.0083 (5)
N2	0.0127 (5)	0.0240 (6)	0.0205 (5)	0.0013 (4)	0.0004 (4)	0.0030 (4)
C1	0.0133 (5)	0.0169 (5)	0.0195 (6)	−0.0002 (4)	−0.0020 (4)	−0.0002 (5)
C2	0.0187 (6)	0.0317 (8)	0.0229 (6)	−0.0009 (5)	0.0012 (5)	0.0080 (6)

Geometric parameters (Å, º)

Cu1—S1^i	2.3349 (4)	N1—H2N1	0.87 (2)
Cu1—S1^ii	2.3350 (4)	N2—C1	1.3279 (19)
Cu1—S1^iii	2.3350 (4)	N2—C2	1.449 (2)
Cu1—S1	2.3350 (4)	N2—H1N2	0.90 (3)
S1—C1	1.7249 (15)	C2—H2A	0.96 (3)
N1—C1	1.3305 (19)	C2—H2B	0.90 (3)
N1—H1N1	0.82 (3)	C2—H2C	0.94 (2)
S1^i—Cu1—S1^ii	107.789 (9)	C1—N2—H1N2	116.7 (16)
S1^i—Cu1—S1^iii	107.789 (9)	C2—N2—H1N2	118.5 (17)
S1^ii—Cu1—S1^iii	112.894 (18)	N2—C1—N1	119.36 (14)
S1^i—Cu1—S1	112.894 (18)	N2—C1—S1	119.07 (11)
S1^ii—Cu1—S1	107.786 (9)	N1—C1—S1	121.55 (12)
S1^iii—Cu1—S1	107.786 (9)	N2—C2—H2A	112.0 (16)
C1—S1—Cu1	107.19 (5)	N2—C2—H2B	113.5 (18)
C1—N1—H1N1	115.2 (17)	H2A—C2—H2B	104 (2)
C1—N1—H2N1	121.5 (16)	N2—C2—H2C	110.0 (15)
H1N1—N1—H2N1	122 (2)	H2A—C2—H2C	108 (2)
C1—N2—C2	124.59 (14)	H2B—C2—H2C	109 (2)
S1^i—Cu1—S1—C1	−42.97 (5)	C2—N2—C1—S1	174.96 (12)
S1^ii—Cu1—S1—C1	75.96 (5)	Cu1—S1—C1—N2	−177.32 (10)
S1^iii—Cu1—S1—C1	−161.90 (5)	Cu1—S1—C1—N1	1.32 (14)
C2—N2—C1—N1	−3.7 (2)

Symmetry codes: (i) −x+1, −y+1/2, z; (ii) −y+3/4, x−1/4, −z+3/4; (iii) y+1/4, −x+3/4, −z+3/4.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···S1^i	0.82 (3)	2.61 (2)	3.3908 (15)	159 (2)
N2—H1N2···I1^iv	0.90 (2)	2.73 (3)	3.5340 (14)	148 (2)
N1—H2N1···S1^v	0.87 (2)	2.64 (2)	3.4407 (15)	154 (2)
C2—H2A···N2^v	0.96 (3)	2.62 (3)	3.374 (2)	135.4 (19)

Symmetry codes: (i) −x+1, −y+1/2, z; (iv) y−1/4, −x+3/4, z−1/4; (v) y+1/4, −x+1/4, z+1/4.