Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807044649/ci2443sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807044649/ci2443Isup2.hkl |
CCDC reference: 663610
To a solution of copper(I) iodide (0.19 g, 1.0 mmol) in acetonitrile (15 ml) was added 2 molar equivalents of N,N'-dibutylthiourea in acetonitrile (10 ml). The mixture was stirred for half an hour. A clear solution was obtained. The solution was concentrated by slow evaporation at room temperature to yield colourless single crystals of the title compound suitable for x-ray stucture determination after several days.
All H atoms were positioned geometrically and allowed to ride on their parent atoms, with N—H = 0.86 Å and C—H = 0.96 or 0.97 Å. 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. A rotating group model was used for the methyl groups. The H atoms of the partially occupied disordered water molecule could not be located. The highest residual peak is located 1.03 Å from I1 and the deepest hole is located 0.80 Å from I1.
Crystal structures of several copper(I) complexes of thiourea and its derivatives have been reported (Eller et al., 1977; Stocker et al., 1996; Girling & Amma, 1971; Atkinson et al., 1985; Dubler & Bensch, 1986). They show that a wide variety of stoichiometries and structural diversity exist for these complexes, with the copper to sulfur ratio ranging from 1:4 as in monomeric [Cu(tu)4(SiF6)0.5] (Hunt et al., 1979) to 1:1.5 as in tetrameric [Cu4(tu)6(NO3)4].4H2O (Griffith et al., 1976). We are interested in understanding the correlation of the geometries of such complexes with the nature of substituents on thiourea and the strength and size of the other coordinating ligands. Previously, we have reported the crystal structure of tetrakis(N-methylthiourea-κS)copper(I) iodide (Mufakkar et al., 2007). Now we report here the crystal structure of the title complex.
In the molecule of the title complex, atoms Cu1 and I1 lie on a threefold rotation axis and the asymmetric unit therefore contains one third of the complex molecule (Fig. 1). The asymmetric unit also contains a partially occupied water molecule, disordered across a inversion center. The coordination of Cu1 is a distorted tetrahedron, being coordinated by the S atoms of the three N,N'-dibutylthiourea ligands, with S—Cu—S angles of 99.32 (4)° (Table 1). These angles are smaller than those observed in related structures (Bombicz et al., 2004; Lobana et al., 2006; Mufakkar et al., 2007). However, the Cu—S bond distances [2.3543 (12) 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; Mufakkar et al., 2007). The fourth coordination of CuI is occupied by the I1 atom with a Cu1—I1 distance of 2.6251 (10) Å and S—Cu—I angle of 118.34 (3)°. The dihedral angle between the mean planes of S1/N1/N2/C1/C2/C6/C7 and C2/C3/C4/C5 is 80.2 (6)°. All other bond lengths and angles are in normal ranges (Allen et al., 1987).
The I atom is involved in an intramolecular N—H···I hydrogen bond and the S atoms form weak C—H···S intramolecular interactions (Fig. 1). Intermolecular N—H···S hydrogen bonds stabilize the crystal structure (Table 2). In the crystal packing (Fig. 2), the molecules are arranged into a two-dimensional network parallel to the ab plane.
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); Mufakkar et al. (2007). For related literature on the coordination chemistry of copper, see: Atkinson et al. (1985); Bombicz et al. (2004); Dubler & Bensch (1986); Eller et al. (1977); Girling & Amma (1971); Griffith et al. (1976); Hunt et al. (1979); Kaim & Schwederski (1994); Lobana et al. (2006); Stocker et al. (1996).
Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 1998); program(s) used to refine structure: SHELXTL (Sheldrick, 1998); molecular graphics: SHELXTL (Sheldrick, 1998); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003).
[Cu(C9H20N2S)3I]·0.6(H2O) | Dx = 1.396 Mg m−3 |
Mr = 766.24 | Mo Kα radiation, λ = 0.71073 Å |
Trigonal, P3 | Cell parameters from 3632 reflections |
Hall symbol: -P 3 | θ = 1.7–30.4° |
a = 13.5514 (3) Å | µ = 1.65 mm−1 |
c = 11.4588 (6) Å | T = 100 K |
V = 1822.38 (11) Å3 | Plate, colourless |
Z = 2 | 0.48 × 0.27 × 0.10 mm |
F(000) = 800 |
Bruker SMART APEXII CCD area-detector diffractometer | 3632 independent reflections |
Radiation source: fine-focus sealed tube | 2454 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.090 |
Detector resolution: 8.33 pixels mm-1 | θmax = 30.4°, θmin = 1.7° |
ω scans | h = −19→18 |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | k = −18→18 |
Tmin = 0.508, Tmax = 0.851 | l = −15→15 |
21130 measured reflections |
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)] = 0.062 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.173 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0894P)2 + 1.4942P] where P = (Fo2 + 2Fc2)/3 |
3632 reflections | (Δ/σ)max = 0.001 |
120 parameters | Δρmax = 2.54 e Å−3 |
0 restraints | Δρmin = −1.13 e Å−3 |
[Cu(C9H20N2S)3I]·0.6(H2O) | Z = 2 |
Mr = 766.24 | Mo Kα radiation |
Trigonal, P3 | µ = 1.65 mm−1 |
a = 13.5514 (3) Å | T = 100 K |
c = 11.4588 (6) Å | 0.48 × 0.27 × 0.10 mm |
V = 1822.38 (11) Å3 |
Bruker SMART APEXII CCD area-detector diffractometer | 3632 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | 2454 reflections with I > 2σ(I) |
Tmin = 0.508, Tmax = 0.851 | Rint = 0.090 |
21130 measured reflections |
R[F2 > 2σ(F2)] = 0.062 | 0 restraints |
wR(F2) = 0.173 | H-atom parameters constrained |
S = 1.05 | Δρmax = 2.54 e Å−3 |
3632 reflections | Δρmin = −1.13 e Å−3 |
120 parameters |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
I1 | 0.6667 | 0.3333 | 0.71844 (4) | 0.02975 (18) | |
Cu1 | 0.6667 | 0.3333 | 0.94753 (8) | 0.0274 (2) | |
S1 | 0.70138 (9) | 0.50061 (9) | 1.04506 (9) | 0.0267 (3) | |
N1 | 0.6251 (4) | 0.6474 (3) | 1.0253 (3) | 0.0312 (9) | |
H1 | 0.6035 | 0.6851 | 0.9824 | 0.037* | |
N2 | 0.6362 (4) | 0.5666 (3) | 0.8559 (3) | 0.0317 (9) | |
H2 | 0.6547 | 0.5227 | 0.8197 | 0.038* | |
C1 | 0.6508 (4) | 0.5764 (4) | 0.9706 (4) | 0.0247 (9) | |
C2 | 0.6302 (5) | 0.6675 (5) | 1.1508 (4) | 0.0433 (13) | |
H2A | 0.6334 | 0.6061 | 1.1909 | 0.052* | |
H2B | 0.5608 | 0.6659 | 1.1751 | 0.052* | |
C3 | 0.7295 (5) | 0.7776 (5) | 1.1870 (5) | 0.0484 (14) | |
H3A | 0.7337 | 0.8383 | 1.1386 | 0.058* | |
H3B | 0.7990 | 0.7748 | 1.1755 | 0.058* | |
C4 | 0.7200 (6) | 0.8035 (6) | 1.3162 (5) | 0.0582 (17) | |
H4A | 0.6477 | 0.8005 | 1.3286 | 0.070* | |
H4B | 0.7211 | 0.7454 | 1.3647 | 0.070* | |
C5 | 0.8158 (7) | 0.9192 (7) | 1.3530 (6) | 0.077 (2) | |
H5A | 0.8021 | 0.9356 | 1.4309 | 0.115* | |
H5B | 0.8196 | 0.9763 | 1.3006 | 0.115* | |
H5C | 0.8866 | 0.9192 | 1.3509 | 0.115* | |
C6 | 0.5907 (5) | 0.6256 (4) | 0.7868 (4) | 0.0337 (11) | |
H6A | 0.6413 | 0.7072 | 0.7937 | 0.040* | |
H6B | 0.5170 | 0.6078 | 0.8179 | 0.040* | |
C7 | 0.5777 (6) | 0.5925 (5) | 0.6594 (5) | 0.0478 (14) | |
H7A | 0.5342 | 0.5101 | 0.6527 | 0.057* | |
H7B | 0.6524 | 0.6182 | 0.6258 | 0.057* | |
C8 | 0.5178 (7) | 0.6442 (5) | 0.5911 (5) | 0.0553 (16) | |
H8A | 0.5101 | 0.6196 | 0.5105 | 0.066* | |
H8B | 0.4417 | 0.6148 | 0.6226 | 0.066* | |
C9 | 0.5787 (7) | 0.7727 (6) | 0.5941 (6) | 0.071 (2) | |
H9A | 0.5432 | 0.7995 | 0.5401 | 0.106* | |
H9B | 0.6571 | 0.8026 | 0.5728 | 0.106* | |
H9C | 0.5746 | 0.7977 | 0.6714 | 0.106* | |
O1W | 0.0000 | 0.0000 | 0.042 (7) | 0.31 (4) | 0.60 |
U11 | U22 | U33 | U12 | U13 | U23 | |
I1 | 0.0312 (2) | 0.0312 (2) | 0.0267 (3) | 0.01562 (11) | 0.000 | 0.000 |
Cu1 | 0.0270 (3) | 0.0270 (3) | 0.0283 (5) | 0.01350 (17) | 0.000 | 0.000 |
S1 | 0.0267 (6) | 0.0264 (6) | 0.0275 (5) | 0.0137 (5) | −0.0003 (4) | −0.0003 (4) |
N1 | 0.041 (2) | 0.033 (2) | 0.0266 (19) | 0.0237 (19) | −0.0042 (16) | −0.0031 (16) |
N2 | 0.044 (2) | 0.034 (2) | 0.0259 (19) | 0.026 (2) | 0.0012 (17) | −0.0026 (16) |
C1 | 0.020 (2) | 0.024 (2) | 0.028 (2) | 0.0097 (17) | 0.0004 (16) | 0.0002 (17) |
C2 | 0.060 (4) | 0.044 (3) | 0.035 (3) | 0.032 (3) | −0.011 (2) | −0.010 (2) |
C3 | 0.053 (4) | 0.043 (3) | 0.050 (3) | 0.025 (3) | −0.004 (3) | 0.003 (3) |
C4 | 0.066 (4) | 0.057 (4) | 0.042 (3) | 0.024 (3) | −0.006 (3) | −0.009 (3) |
C5 | 0.085 (6) | 0.075 (5) | 0.049 (4) | 0.024 (4) | −0.020 (4) | −0.022 (4) |
C6 | 0.047 (3) | 0.034 (3) | 0.027 (2) | 0.026 (2) | −0.001 (2) | 0.0024 (19) |
C7 | 0.073 (4) | 0.051 (3) | 0.035 (3) | 0.042 (3) | −0.004 (3) | −0.004 (2) |
C8 | 0.084 (5) | 0.057 (4) | 0.034 (3) | 0.042 (4) | −0.016 (3) | −0.005 (3) |
C9 | 0.095 (6) | 0.067 (5) | 0.058 (4) | 0.047 (5) | −0.003 (4) | 0.006 (3) |
O1W | 0.30 (3) | 0.30 (3) | 0.32 (13) | 0.149 (15) | 0.000 | 0.000 |
I1—Cu1 | 2.6251 (10) | C4—H4A | 0.97 |
Cu1—S1 | 2.3543 (12) | C4—H4B | 0.97 |
Cu1—S1i | 2.3543 (12) | C5—H5A | 0.96 |
Cu1—S1ii | 2.3543 (12) | C5—H5B | 0.96 |
S1—C1 | 1.720 (4) | C5—H5C | 0.96 |
N1—C1 | 1.331 (5) | C6—C7 | 1.513 (7) |
N1—C2 | 1.460 (6) | C6—H6A | 0.97 |
N1—H1 | 0.86 | C6—H6B | 0.97 |
N2—C1 | 1.326 (6) | C7—C8 | 1.527 (8) |
N2—C6 | 1.462 (6) | C7—H7A | 0.97 |
N2—H2 | 0.86 | C7—H7B | 0.97 |
C2—C3 | 1.484 (8) | C8—C9 | 1.509 (9) |
C2—H2A | 0.97 | C8—H8A | 0.97 |
C2—H2B | 0.97 | C8—H8B | 0.97 |
C3—C4 | 1.543 (8) | C9—H9A | 0.96 |
C3—H3A | 0.97 | C9—H9B | 0.96 |
C3—H3B | 0.97 | C9—H9C | 0.96 |
C4—C5 | 1.512 (9) | ||
S1—Cu1—S1i | 99.32 (4) | C3—C4—H4B | 109.2 |
S1—Cu1—S1ii | 99.32 (4) | H4A—C4—H4B | 107.9 |
S1i—Cu1—S1ii | 99.32 (4) | C4—C5—H5A | 109.5 |
S1—Cu1—I1 | 118.34 (3) | C4—C5—H5B | 109.5 |
S1i—Cu1—I1 | 118.34 (3) | H5A—C5—H5B | 109.5 |
S1ii—Cu1—I1 | 118.34 (3) | C4—C5—H5C | 109.5 |
C1—S1—Cu1 | 113.09 (15) | H5A—C5—H5C | 109.5 |
C1—N1—C2 | 126.5 (4) | H5B—C5—H5C | 109.5 |
C1—N1—H1 | 116.8 | N2—C6—C7 | 112.2 (4) |
C2—N1—H1 | 116.8 | N2—C6—H6A | 109.2 |
C1—N2—C6 | 124.4 (4) | C7—C6—H6A | 109.2 |
C1—N2—H2 | 117.8 | N2—C6—H6B | 109.2 |
C6—N2—H2 | 117.8 | C7—C6—H6B | 109.2 |
N2—C1—N1 | 117.3 (4) | H6A—C6—H6B | 107.9 |
N2—C1—S1 | 121.1 (3) | C6—C7—C8 | 111.6 (5) |
N1—C1—S1 | 121.6 (3) | C6—C7—H7A | 109.3 |
N1—C2—C3 | 113.4 (5) | C8—C7—H7A | 109.3 |
N1—C2—H2A | 108.9 | C6—C7—H7B | 109.3 |
C3—C2—H2A | 108.9 | C8—C7—H7B | 109.3 |
N1—C2—H2B | 108.9 | H7A—C7—H7B | 108.0 |
C3—C2—H2B | 108.9 | C9—C8—C7 | 114.1 (6) |
H2A—C2—H2B | 107.7 | C9—C8—H8A | 108.7 |
C2—C3—C4 | 111.1 (5) | C7—C8—H8A | 108.7 |
C2—C3—H3A | 109.4 | C9—C8—H8B | 108.7 |
C4—C3—H3A | 109.4 | C7—C8—H8B | 108.7 |
C2—C3—H3B | 109.4 | H8A—C8—H8B | 107.6 |
C4—C3—H3B | 109.4 | C8—C9—H9A | 109.5 |
H3A—C3—H3B | 108.0 | C8—C9—H9B | 109.5 |
C5—C4—C3 | 112.2 (6) | H9A—C9—H9B | 109.5 |
C5—C4—H4A | 109.2 | C8—C9—H9C | 109.5 |
C3—C4—H4A | 109.2 | H9A—C9—H9C | 109.5 |
C5—C4—H4B | 109.2 | H9B—C9—H9C | 109.5 |
S1i—Cu1—S1—C1 | 162.01 (17) | Cu1—S1—C1—N1 | 155.8 (3) |
S1ii—Cu1—S1—C1 | −96.85 (17) | C1—N1—C2—C3 | 104.8 (6) |
I1—Cu1—S1—C1 | 32.58 (17) | N1—C2—C3—C4 | 170.6 (5) |
C6—N2—C1—N1 | −2.0 (7) | C2—C3—C4—C5 | −175.9 (6) |
C6—N2—C1—S1 | 178.3 (4) | C1—N2—C6—C7 | −176.8 (5) |
C2—N1—C1—N2 | 177.3 (5) | N2—C6—C7—C8 | 173.5 (5) |
C2—N1—C1—S1 | −3.0 (7) | C6—C7—C8—C9 | 59.6 (8) |
Cu1—S1—C1—N2 | −24.4 (4) |
Symmetry codes: (i) −x+y+1, −x+1, z; (ii) −y+1, x−y, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···S1iii | 0.86 | 2.57 | 3.347 (5) | 151 |
N2—H2···I1 | 0.86 | 2.89 | 3.735 (4) | 167 |
C2—H2A···S1 | 0.97 | 2.65 | 3.114 (7) | 110 |
Symmetry code: (iii) y, −x+y+1, −z+2. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C9H20N2S)3I]·0.6(H2O) |
Mr | 766.24 |
Crystal system, space group | Trigonal, P3 |
Temperature (K) | 100 |
a, c (Å) | 13.5514 (3), 11.4588 (6) |
V (Å3) | 1822.38 (11) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.65 |
Crystal size (mm) | 0.48 × 0.27 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2005) |
Tmin, Tmax | 0.508, 0.851 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 21130, 3632, 2454 |
Rint | 0.090 |
(sin θ/λ)max (Å−1) | 0.712 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.062, 0.173, 1.05 |
No. of reflections | 3632 |
No. of parameters | 120 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 2.54, −1.13 |
Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 1998), SHELXTL and PLATON (Spek, 2003).
I1—Cu1 | 2.6251 (10) | Cu1—S1 | 2.3543 (12) |
S1—Cu1—S1i | 99.32 (4) | S1—Cu1—I1 | 118.34 (3) |
Symmetry code: (i) −x+y+1, −x+1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···S1ii | 0.86 | 2.57 | 3.347 (5) | 151 |
N2—H2···I1 | 0.86 | 2.89 | 3.735 (4) | 167 |
C2—H2A···S1 | 0.97 | 2.65 | 3.114 (7) | 110 |
Symmetry code: (ii) y, −x+y+1, −z+2. |
Crystal structures of several copper(I) complexes of thiourea and its derivatives have been reported (Eller et al., 1977; Stocker et al., 1996; Girling & Amma, 1971; Atkinson et al., 1985; Dubler & Bensch, 1986). They show that a wide variety of stoichiometries and structural diversity exist for these complexes, with the copper to sulfur ratio ranging from 1:4 as in monomeric [Cu(tu)4(SiF6)0.5] (Hunt et al., 1979) to 1:1.5 as in tetrameric [Cu4(tu)6(NO3)4].4H2O (Griffith et al., 1976). We are interested in understanding the correlation of the geometries of such complexes with the nature of substituents on thiourea and the strength and size of the other coordinating ligands. Previously, we have reported the crystal structure of tetrakis(N-methylthiourea-κS)copper(I) iodide (Mufakkar et al., 2007). Now we report here the crystal structure of the title complex.
In the molecule of the title complex, atoms Cu1 and I1 lie on a threefold rotation axis and the asymmetric unit therefore contains one third of the complex molecule (Fig. 1). The asymmetric unit also contains a partially occupied water molecule, disordered across a inversion center. The coordination of Cu1 is a distorted tetrahedron, being coordinated by the S atoms of the three N,N'-dibutylthiourea ligands, with S—Cu—S angles of 99.32 (4)° (Table 1). These angles are smaller than those observed in related structures (Bombicz et al., 2004; Lobana et al., 2006; Mufakkar et al., 2007). However, the Cu—S bond distances [2.3543 (12) 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; Mufakkar et al., 2007). The fourth coordination of CuI is occupied by the I1 atom with a Cu1—I1 distance of 2.6251 (10) Å and S—Cu—I angle of 118.34 (3)°. The dihedral angle between the mean planes of S1/N1/N2/C1/C2/C6/C7 and C2/C3/C4/C5 is 80.2 (6)°. All other bond lengths and angles are in normal ranges (Allen et al., 1987).
The I atom is involved in an intramolecular N—H···I hydrogen bond and the S atoms form weak C—H···S intramolecular interactions (Fig. 1). Intermolecular N—H···S hydrogen bonds stabilize the crystal structure (Table 2). In the crystal packing (Fig. 2), the molecules are arranged into a two-dimensional network parallel to the ab plane.