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In the title complex, [Cu(C2H6N2S)4]I, the CuI atom lies on a {\bar 4} axis. Each CuI 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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680704024X/sj2330sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S160053680704024X/sj2330Isup2.hkl
Contains datablock I

CCDC reference: 660140

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

Comment top

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 CuI 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 top

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).

Experimental top

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.

Refinement top

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

Structure description top

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 CuI 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.

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).

Computing details top

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 top
[Figure 1] Fig. 1. The structure of the title compound, showing 50% probability displacement ellipsoids and the atomic numbering.
[Figure 2] 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 top
Crystal data top
[Cu(C2H6N2S)4]IDx = 1.739 Mg m3
Mr = 551.08Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I41/aCell parameters from 2767 reflections
Hall symbol: -I 4adθ = 2.2–37.5°
a = 12.5113 (6) ŵ = 2.91 mm1
c = 13.4435 (9) ÅT = 100 K
V = 2104.4 (2) Å3Plate, colourless
Z = 40.57 × 0.49 × 0.10 mm
F(000) = 1096
Data collection top
Bruker APEXII CCD area-detector
diffractometer
2767 independent reflections
Radiation source: fine-focus sealed tube2149 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.104
Detector resolution: 8.33 pixels mm-1θmax = 37.5°, θmin = 2.2°
ω scansh = 2121
Absorption correction: multi-scan
(SADABS; Bruker, 2005)
k = 1921
Tmin = 0.205, Tmax = 0.748l = 2223
19549 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.085All H-atom parameters refined
S = 1.02 w = 1/[σ2(Fo2) + (0.0359P)2 + 1.5035P]
where P = (Fo2 + 2Fc2)/3
2767 reflections(Δ/σ)max = 0.001
74 parametersΔρmax = 1.41 e Å3
0 restraintsΔρmin = 0.97 e Å3
Crystal data top
[Cu(C2H6N2S)4]IZ = 4
Mr = 551.08Mo Kα radiation
Tetragonal, I41/aµ = 2.91 mm1
a = 12.5113 (6) ÅT = 100 K
c = 13.4435 (9) Å0.57 × 0.49 × 0.10 mm
V = 2104.4 (2) Å3
Data collection top
Bruker APEXII CCD area-detector
diffractometer
2767 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2005)
2149 reflections with I > 2σ(I)
Tmin = 0.205, Tmax = 0.748Rint = 0.104
19549 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0340 restraints
wR(F2) = 0.085All H-atom parameters refined
S = 1.02Δρmax = 1.41 e Å3
2767 reflectionsΔρmin = 0.97 e Å3
74 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
I10.50000.25000.87500.02531 (7)
Cu10.50000.25000.37500.01643 (8)
S10.34596 (3)0.27148 (3)0.47100 (3)0.01687 (8)
N10.43604 (11)0.11480 (11)0.57710 (11)0.0221 (2)
N20.27169 (11)0.17292 (12)0.63020 (9)0.0191 (2)
C10.35269 (11)0.17989 (11)0.56670 (11)0.0166 (2)
C20.26350 (13)0.09411 (15)0.70884 (13)0.0244 (3)
H2A0.317 (2)0.104 (2)0.759 (2)0.038 (7)*
H2B0.274 (2)0.027 (2)0.688 (2)0.036 (7)*
H2C0.196 (2)0.0992 (19)0.7400 (18)0.029 (6)*
H1N10.487 (2)0.1281 (19)0.541 (2)0.030 (6)*
H2N10.441 (2)0.071 (2)0.6272 (16)0.020 (6)*
H1N20.216 (2)0.217 (2)0.6193 (17)0.032 (7)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I10.01276 (7)0.01276 (7)0.05041 (15)0.0000.0000.000
Cu10.01618 (10)0.01618 (10)0.01692 (15)0.0000.0000.000
S10.01308 (14)0.01761 (15)0.01992 (15)0.00135 (10)0.00048 (11)0.00227 (12)
N10.0165 (5)0.0232 (6)0.0267 (6)0.0041 (4)0.0037 (5)0.0083 (5)
N20.0127 (5)0.0240 (6)0.0205 (5)0.0013 (4)0.0004 (4)0.0030 (4)
C10.0133 (5)0.0169 (5)0.0195 (6)0.0002 (4)0.0020 (4)0.0002 (5)
C20.0187 (6)0.0317 (8)0.0229 (6)0.0009 (5)0.0012 (5)0.0080 (6)
Geometric parameters (Å, º) top
Cu1—S1i2.3349 (4)N1—H2N10.87 (2)
Cu1—S1ii2.3350 (4)N2—C11.3279 (19)
Cu1—S1iii2.3350 (4)N2—C21.449 (2)
Cu1—S12.3350 (4)N2—H1N20.90 (3)
S1—C11.7249 (15)C2—H2A0.96 (3)
N1—C11.3305 (19)C2—H2B0.90 (3)
N1—H1N10.82 (3)C2—H2C0.94 (2)
S1i—Cu1—S1ii107.789 (9)C1—N2—H1N2116.7 (16)
S1i—Cu1—S1iii107.789 (9)C2—N2—H1N2118.5 (17)
S1ii—Cu1—S1iii112.894 (18)N2—C1—N1119.36 (14)
S1i—Cu1—S1112.894 (18)N2—C1—S1119.07 (11)
S1ii—Cu1—S1107.786 (9)N1—C1—S1121.55 (12)
S1iii—Cu1—S1107.786 (9)N2—C2—H2A112.0 (16)
C1—S1—Cu1107.19 (5)N2—C2—H2B113.5 (18)
C1—N1—H1N1115.2 (17)H2A—C2—H2B104 (2)
C1—N1—H2N1121.5 (16)N2—C2—H2C110.0 (15)
H1N1—N1—H2N1122 (2)H2A—C2—H2C108 (2)
C1—N2—C2124.59 (14)H2B—C2—H2C109 (2)
S1i—Cu1—S1—C142.97 (5)C2—N2—C1—S1174.96 (12)
S1ii—Cu1—S1—C175.96 (5)Cu1—S1—C1—N2177.32 (10)
S1iii—Cu1—S1—C1161.90 (5)Cu1—S1—C1—N11.32 (14)
C2—N2—C1—N13.7 (2)
Symmetry codes: (i) x+1, y+1/2, z; (ii) y+3/4, x1/4, z+3/4; (iii) y+1/4, x+3/4, z+3/4.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N1···S1i0.82 (3)2.61 (2)3.3908 (15)159 (2)
N2—H1N2···I1iv0.90 (2)2.73 (3)3.5340 (14)148 (2)
N1—H2N1···S1v0.87 (2)2.64 (2)3.4407 (15)154 (2)
C2—H2A···N2v0.96 (3)2.62 (3)3.374 (2)135.4 (19)
Symmetry codes: (i) x+1, y+1/2, z; (iv) y1/4, x+3/4, z1/4; (v) y+1/4, x+1/4, z+1/4.

Experimental details

Crystal data
Chemical formula[Cu(C2H6N2S)4]I
Mr551.08
Crystal system, space groupTetragonal, I41/a
Temperature (K)100
a, c (Å)12.5113 (6), 13.4435 (9)
V3)2104.4 (2)
Z4
Radiation typeMo Kα
µ (mm1)2.91
Crystal size (mm)0.57 × 0.49 × 0.10
Data collection
DiffractometerBruker APEXII CCD area-detector
Absorption correctionMulti-scan
(SADABS; Bruker, 2005)
Tmin, Tmax0.205, 0.748
No. of measured, independent and
observed [I > 2σ(I)] reflections
19549, 2767, 2149
Rint0.104
(sin θ/λ)max1)0.856
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.034, 0.085, 1.02
No. of reflections2767
No. of parameters74
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)1.41, 0.97

Computer programs: APEX2 (Bruker, 2005), APEX2, SAINT (Bruker, 2005), SHELXTL (Sheldrick, 1998), SHELXTL and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N1···S1i0.82 (3)2.61 (2)3.3908 (15)159 (2)
N2—H1N2···I1ii0.90 (2)2.73 (3)3.5340 (14)148 (2)
N1—H2N1···S1iii0.87 (2)2.64 (2)3.4407 (15)154 (2)
C2—H2A···N2iii0.96 (3)2.62 (3)3.374 (2)135.4 (19)
Symmetry codes: (i) x+1, y+1/2, z; (ii) y1/4, x+3/4, z1/4; (iii) y+1/4, x+1/4, z+1/4.
 

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