



Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536810028102/wm2371sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536810028102/wm2371Isup2.hkl |
CCDC reference: 772365
Key indicators
- Single-crystal X-ray study
- T = 292 K
- Mean
(N-C) = 0.005 Å
- R factor = 0.021
- wR factor = 0.052
- Data-to-parameter ratio = 25.9
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Cd1 -- Br1 .. 9.63 su PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L= 0.600 5
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
0.35 g (1.0 mmol) cadmium(II) bromide tetrahydrate dissolved in 10 ml water were added to two equivalents of tetramethylthiourea in methanol. A white precipitate formed and was filtered off. The filtrate was kept for crystallization. As a result, an off-white crystalline product suitable for single crystal X-ray diffraction was obtained.
H atoms were placed in calculated positions with a C—H distance of 0.96 Å and Uiso(H) = 1.5 Ueq(C).
The coordination chemistry of thioureas with metal ions has been the subject of several recent investigations because of their variable binding modes and because of the relevance of their binding sites to those in living systems. Crystallographic reports about d10 metal complexes of thioureas established that these ligands are coordinated via the sulfur atom (Al-Arfaj et al., 1998; Moloto et al., 2003). Spectroscopic data is also consistent with this finding (Isab et al., 2009; Ali et al., 2009). Herein, we report the crystal structure of a cadmium bromide complex with tetramethylthiourea (tmtu), [Cd(C5H12N2S2)2Br2], (I).
The crystal structure of (I) consists of discrete molecular species in which the cadmium atom is located on a twofold rotation axis (Fig. 1). It exhibits a distorted tetrahedral coordination environment defined by two tetramethylthiourea (tmtu) ligands and two bromide ions. The tmtu ligand is terminally bound to the CdII atom via coordination of the S1 atom. The Cd—S and Cd—Br bond lengths are 2.5580 (6) and 2.5735 (3) Å, respectively. These values are in agreement with those reported for related compounds, e.g. (Al-Arfaj et al., 1998; Lobana et al. 2008; Marcos et al., 1998; Moloto et al., 2003). The bond angles around Cd are indicative of a slight tetrahedral distortion, with the S—Cd—S angle showing the largest deviation (117.70 (3)°) from the ideal value. The SCN2— moiety of the tmtu ligand is essentially planar, the maximum deviation from the mean plane being 0.007 (2) Å for the carbon atom. The fragments N1—C1—C2—C3 and N2—C1—C4—C5 are also close to planarity. The maximum deviations from the mean planes are 0.072 (2) Å and 0.065 (2) Å for N1 and N2, respectively. These values are consistent with a significant C—N double bond character and electron delocalization in the SCN2— moiety. The steric effect of the two adjacent 1,3-methyl groups imposes a dihedral angle of 47.4 (2) ° for the two mean planes and therefore a tilted conformation. The latter is likely stabilized by non-classical intramolecular hydrogen bonding interactions involving methyl H atoms with sulfur and nitrogen atoms (C2—H2A ···N2 and C5—H5A···S1). The molecules pack to form columns approximately parallel to [110] direction (Fig. 2).
The structure of (I) is isotypic with [Cd(tmtu)2I2] (Nawaz et al., 2010a), with an equivalent degree of distortion from the ideal tetrahedral configuration and similar Cd—S and C—N bond lengths. The tmtu bond lengths are also consistent with those found for the likewise isotypic compound [Hg(tmtu)2Cl2] (Nawaz et al., 2010b), in which a significantly higher distortion of the metal ion coordination sphere is observed.
For crystallographic and spectroscopic studies of thiourea complexes, see: Al-Arfaj et al. (1998); Ali et al. (2009); Isab et al. (2009); Lobana et al. (2008); Marcos et al. (1998); Moloto et al. (2003). The structure of the title compound is isotypic with [Cd(tmtu)2I2] (Nawaz et al., 2010a) and [Hg(tmtu)2Cl2] (Nawaz et al., 2010b).
Data collection: SMART (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
[CdBr2(C5H12N2S)2] | F(000) = 1048 |
Mr = 536.67 | Dx = 1.868 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 12678 reflections |
a = 18.6133 (17) Å | θ = 2.5–28.3° |
b = 10.0690 (9) Å | µ = 5.54 mm−1 |
c = 13.4600 (12) Å | T = 292 K |
β = 130.834 (1)° | Block, colorless |
V = 1908.6 (3) Å3 | 0.24 × 0.23 × 0.20 mm |
Z = 4 |
Bruker SMART APEX area-detector diffractometer | 2379 independent reflections |
Radiation source: normal-focus sealed tube | 2114 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
ω scans | θmax = 28.3°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −24→24 |
Tmin = 0.350, Tmax = 0.404 | k = −13→13 |
12678 measured reflections | l = −17→17 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.021 | H-atom parameters constrained |
wR(F2) = 0.052 | w = 1/[σ2(Fo2) + (0.025P)2 + 1.3001P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
2379 reflections | Δρmax = 0.44 e Å−3 |
92 parameters | Δρmin = −0.45 e Å−3 |
0 restraints | Extinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0068 (2) |
[CdBr2(C5H12N2S)2] | V = 1908.6 (3) Å3 |
Mr = 536.67 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 18.6133 (17) Å | µ = 5.54 mm−1 |
b = 10.0690 (9) Å | T = 292 K |
c = 13.4600 (12) Å | 0.24 × 0.23 × 0.20 mm |
β = 130.834 (1)° |
Bruker SMART APEX area-detector diffractometer | 2379 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2114 reflections with I > 2σ(I) |
Tmin = 0.350, Tmax = 0.404 | Rint = 0.028 |
12678 measured reflections |
R[F2 > 2σ(F2)] = 0.021 | 0 restraints |
wR(F2) = 0.052 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.44 e Å−3 |
2379 reflections | Δρmin = −0.45 e Å−3 |
92 parameters |
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 | ||
Cd1 | 1.0000 | 0.70441 (2) | 0.2500 | 0.03969 (8) | |
Br1 | 1.149352 (17) | 0.56647 (3) | 0.34643 (3) | 0.05549 (9) | |
S1 | 1.03619 (4) | 0.83583 (7) | 0.44089 (5) | 0.04794 (14) | |
N1 | 0.91758 (14) | 0.76405 (19) | 0.4771 (2) | 0.0474 (4) | |
N2 | 0.85096 (13) | 0.8900 (2) | 0.29223 (18) | 0.0471 (4) | |
C1 | 0.92634 (14) | 0.82923 (19) | 0.39910 (19) | 0.0366 (4) | |
C2 | 0.8527 (2) | 0.8077 (3) | 0.4968 (3) | 0.0672 (7) | |
H2A | 0.8267 | 0.8928 | 0.4562 | 0.101* | |
H2B | 0.8867 | 0.8145 | 0.5891 | 0.101* | |
H2C | 0.8022 | 0.7444 | 0.4580 | 0.101* | |
C3 | 0.9861 (2) | 0.6637 (3) | 0.5706 (3) | 0.0724 (8) | |
H3A | 1.0111 | 0.6189 | 0.5359 | 0.109* | |
H3B | 0.9552 | 0.6004 | 0.5851 | 0.109* | |
H3C | 1.0369 | 0.7056 | 0.6522 | 0.109* | |
C4 | 0.75337 (18) | 0.8418 (3) | 0.2186 (3) | 0.0694 (8) | |
H4A | 0.7550 | 0.7542 | 0.2480 | 0.104* | |
H4B | 0.7211 | 0.8394 | 0.1266 | 0.104* | |
H4C | 0.7203 | 0.9005 | 0.2330 | 0.104* | |
C5 | 0.8609 (2) | 0.9921 (3) | 0.2254 (3) | 0.0697 (8) | |
H5A | 0.9218 | 1.0340 | 0.2870 | 0.105* | |
H5B | 0.8118 | 1.0573 | 0.1892 | 0.105* | |
H5C | 0.8557 | 0.9524 | 0.1561 | 0.105* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd1 | 0.04286 (13) | 0.04283 (13) | 0.04311 (13) | 0.000 | 0.03237 (11) | 0.000 |
Br1 | 0.05068 (15) | 0.05784 (16) | 0.05843 (16) | 0.01407 (10) | 0.03588 (13) | 0.00638 (11) |
S1 | 0.0391 (3) | 0.0665 (4) | 0.0425 (3) | −0.0082 (2) | 0.0286 (2) | −0.0132 (2) |
N1 | 0.0572 (11) | 0.0471 (10) | 0.0559 (11) | 0.0041 (9) | 0.0448 (10) | 0.0036 (8) |
N2 | 0.0448 (10) | 0.0540 (11) | 0.0427 (10) | 0.0038 (8) | 0.0287 (9) | −0.0020 (8) |
C1 | 0.0406 (10) | 0.0363 (10) | 0.0371 (10) | −0.0014 (8) | 0.0272 (9) | −0.0061 (8) |
C2 | 0.0799 (19) | 0.0800 (19) | 0.0815 (19) | −0.0012 (15) | 0.0702 (18) | −0.0047 (15) |
C3 | 0.090 (2) | 0.0600 (16) | 0.082 (2) | 0.0174 (15) | 0.0627 (19) | 0.0238 (15) |
C4 | 0.0393 (13) | 0.101 (2) | 0.0573 (16) | 0.0026 (14) | 0.0268 (12) | −0.0123 (15) |
C5 | 0.0804 (19) | 0.0721 (18) | 0.0571 (15) | 0.0165 (15) | 0.0451 (15) | 0.0201 (14) |
Cd1—S1 | 2.5580 (6) | C2—H2B | 0.9600 |
Cd1—S1i | 2.5580 (6) | C2—H2C | 0.9600 |
Cd1—Br1i | 2.5735 (3) | C3—H3A | 0.9600 |
Cd1—Br1 | 2.5735 (3) | C3—H3B | 0.9600 |
S1—C1 | 1.731 (2) | C3—H3C | 0.9600 |
N1—C1 | 1.335 (3) | C4—H4A | 0.9600 |
N1—C3 | 1.460 (3) | C4—H4B | 0.9600 |
N1—C2 | 1.463 (3) | C4—H4C | 0.9600 |
N2—C1 | 1.331 (3) | C5—H5A | 0.9600 |
N2—C5 | 1.455 (3) | C5—H5B | 0.9600 |
N2—C4 | 1.471 (3) | C5—H5C | 0.9600 |
C2—H2A | 0.9600 | ||
S1—Cd1—S1i | 117.70 (3) | H2A—C2—H2C | 109.5 |
S1—Cd1—Br1i | 105.899 (14) | H2B—C2—H2C | 109.5 |
S1i—Cd1—Br1i | 106.524 (15) | N1—C3—H3A | 109.5 |
S1—Cd1—Br1 | 106.524 (15) | N1—C3—H3B | 109.5 |
S1i—Cd1—Br1 | 105.899 (14) | H3A—C3—H3B | 109.5 |
Br1i—Cd1—Br1 | 114.676 (17) | N1—C3—H3C | 109.5 |
C1—S1—Cd1 | 100.04 (7) | H3A—C3—H3C | 109.5 |
C1—N1—C3 | 122.1 (2) | H3B—C3—H3C | 109.5 |
C1—N1—C2 | 122.3 (2) | N2—C4—H4A | 109.5 |
C3—N1—C2 | 114.2 (2) | N2—C4—H4B | 109.5 |
C1—N2—C5 | 121.5 (2) | H4A—C4—H4B | 109.5 |
C1—N2—C4 | 122.8 (2) | N2—C4—H4C | 109.5 |
C5—N2—C4 | 114.6 (2) | H4A—C4—H4C | 109.5 |
N2—C1—N1 | 119.41 (19) | H4B—C4—H4C | 109.5 |
N2—C1—S1 | 121.32 (16) | N2—C5—H5A | 109.5 |
N1—C1—S1 | 119.26 (16) | N2—C5—H5B | 109.5 |
N1—C2—H2A | 109.5 | H5A—C5—H5B | 109.5 |
N1—C2—H2B | 109.5 | N2—C5—H5C | 109.5 |
H2A—C2—H2B | 109.5 | H5A—C5—H5C | 109.5 |
N1—C2—H2C | 109.5 | H5B—C5—H5C | 109.5 |
Symmetry code: (i) −x+2, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2A···N2 | 0.96 | 2.53 | 2.855 (4) | 100 |
C5—H5A···S1 | 0.96 | 2.65 | 3.026 (3) | 104 |
Experimental details
Crystal data | |
Chemical formula | [CdBr2(C5H12N2S)2] |
Mr | 536.67 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 292 |
a, b, c (Å) | 18.6133 (17), 10.0690 (9), 13.4600 (12) |
β (°) | 130.834 (1) |
V (Å3) | 1908.6 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 5.54 |
Crystal size (mm) | 0.24 × 0.23 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART APEX area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.350, 0.404 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12678, 2379, 2114 |
Rint | 0.028 |
(sin θ/λ)max (Å−1) | 0.668 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.021, 0.052, 1.05 |
No. of reflections | 2379 |
No. of parameters | 92 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.44, −0.45 |
Computer programs: SMART (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2A···N2 | 0.9600 | 2.5300 | 2.855 (4) | 100.00 |
C5—H5A···S1 | 0.9600 | 2.6500 | 3.026 (3) | 104.00 |
The coordination chemistry of thioureas with metal ions has been the subject of several recent investigations because of their variable binding modes and because of the relevance of their binding sites to those in living systems. Crystallographic reports about d10 metal complexes of thioureas established that these ligands are coordinated via the sulfur atom (Al-Arfaj et al., 1998; Moloto et al., 2003). Spectroscopic data is also consistent with this finding (Isab et al., 2009; Ali et al., 2009). Herein, we report the crystal structure of a cadmium bromide complex with tetramethylthiourea (tmtu), [Cd(C5H12N2S2)2Br2], (I).
The crystal structure of (I) consists of discrete molecular species in which the cadmium atom is located on a twofold rotation axis (Fig. 1). It exhibits a distorted tetrahedral coordination environment defined by two tetramethylthiourea (tmtu) ligands and two bromide ions. The tmtu ligand is terminally bound to the CdII atom via coordination of the S1 atom. The Cd—S and Cd—Br bond lengths are 2.5580 (6) and 2.5735 (3) Å, respectively. These values are in agreement with those reported for related compounds, e.g. (Al-Arfaj et al., 1998; Lobana et al. 2008; Marcos et al., 1998; Moloto et al., 2003). The bond angles around Cd are indicative of a slight tetrahedral distortion, with the S—Cd—S angle showing the largest deviation (117.70 (3)°) from the ideal value. The SCN2— moiety of the tmtu ligand is essentially planar, the maximum deviation from the mean plane being 0.007 (2) Å for the carbon atom. The fragments N1—C1—C2—C3 and N2—C1—C4—C5 are also close to planarity. The maximum deviations from the mean planes are 0.072 (2) Å and 0.065 (2) Å for N1 and N2, respectively. These values are consistent with a significant C—N double bond character and electron delocalization in the SCN2— moiety. The steric effect of the two adjacent 1,3-methyl groups imposes a dihedral angle of 47.4 (2) ° for the two mean planes and therefore a tilted conformation. The latter is likely stabilized by non-classical intramolecular hydrogen bonding interactions involving methyl H atoms with sulfur and nitrogen atoms (C2—H2A ···N2 and C5—H5A···S1). The molecules pack to form columns approximately parallel to [110] direction (Fig. 2).
The structure of (I) is isotypic with [Cd(tmtu)2I2] (Nawaz et al., 2010a), with an equivalent degree of distortion from the ideal tetrahedral configuration and similar Cd—S and C—N bond lengths. The tmtu bond lengths are also consistent with those found for the likewise isotypic compound [Hg(tmtu)2Cl2] (Nawaz et al., 2010b), in which a significantly higher distortion of the metal ion coordination sphere is observed.