Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807044820/rk2044sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807044820/rk2044Isup2.hkl |
CCDC reference: 667121
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.008 Å
- R factor = 0.029
- wR factor = 0.055
- Data-to-parameter ratio = 26.8
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT061_ALERT_3_B Tmax/Tmin Range Test RR' too Large ............. 0.64
Alert level C PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.80 PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) I1 - Cd1 .. 9.87 su PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C1 PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.46
Alert level G ABSTM02_ALERT_3_G When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.797 Tmax scaled 0.069 Tmin scaled 0.055 PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT794_ALERT_5_G Check Predicted Bond Valency for Cd1 (2) 2.19
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 4 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 3 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 1 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
Cadmium iodide (1.0 g) and thioacetamide (0.4 g) were dissolved in water (6 ml) at room temperature. The solution was layered on a liquid perfluorinated hydrocarbon (1-methyldecahydronaphthalene). In 0.5 h colorless crystals formed and felt in 1-methyldecahydronaphthalene which served as protective environment. Yield 20%.
H atoms were positioned geometrically and refined using a riding model (including free rotation about C—C bond), with C—H = 0.96 Å, N—H = 0.86 Å, Uiso(H) = 1.2 (for NH2 and 1.5 (for CH3) times Ueq of the parent atom.
Thioacetamide complexes are used for synthesis of metal sulfide powders (Trindade et al., 1994; Grau & Akinc, 1997). Several structures of metal complexes with thioacetamide are reported. Cadmium chloride complex with thioacetamide CdCl2.CH3CSNH2 contains double chains of cadmium atoms with bridging chlorine atoms (Rolies & De Ranter, 1978). Two chains are shared through tridentate bridging chlorine atoms. Every cadmium atom is coordinated by five chlorine atoms and one sulfur atom of terminal thioacetamide molecule. In the zinc chloride complex with thioacetamide ZnCl2.2CH3CSNH2, zinc is tetrahedrally coordinated by two chlorine atoms and two thioacetamide molecules (Rolies & De Ranter, 1977a). The mercury chloride complex with thioacetamide HgCl2.2CH3CSNH2 is polymeric; adjacent mercury atoms linked through two bridging chlorine atoms (Rolies & De Ranter, 1977b). In this work, we report the crystal structure of diiodobis(thioacetamide)cadmium [Cd(CH3CSNH2)2I2]. The complex is molecular, cadmium is located on a twofold axis and tetrahedrally coordinated by two chlorine atoms and two thioacetamide molecules. Cd1—I1 distance is 2.7615 (17) Å and Cd1—S1 is 2.5586 (17) Å.
For the synthesis of metal sulfide powders, see: Trindade et al. (1994); Grau & Akinc (1997). For the structures of Zn, Cd and Hg halide complexes with thioacetamide, see: Rolies & De Ranter (1977a,b, 1978).
Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
[Cd(I)2(C2H5NS)2] | F(000) = 936 |
Mr = 516.49 | Dx = 2.637 Mg m−3 |
Orthorhombic, Pbcn | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2n 2ab | Cell parameters from 25 reflections |
a = 10.369 (9) Å | θ = 13–14° |
b = 9.809 (6) Å | µ = 6.70 mm−1 |
c = 12.792 (8) Å | T = 293 K |
V = 1301.1 (16) Å3 | Prism, colourless |
Z = 4 | 0.4 × 0.4 × 0.4 mm |
Enraf–Nonius CAD4 diffractometer | Rint = 0 |
ω scans | θmax = 27.0°, θmin = 2.9° |
Absorption correction: ψ scan (North et al., 1968) | h = −13→0 |
Tmin = 0.069, Tmax = 0.086 | k = 0→12 |
1418 measured reflections | l = 0→16 |
1418 independent reflections | 1 standard reflections every 120 min |
1115 reflections with I > 2σ(I) | intensity decay: 1% |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.029 | w = 1/[σ2(Fo2) + (0.0215P)2 + 0.5736P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.055 | (Δ/σ)max = 0.001 |
S = 1.03 | Δρmax = 0.49 e Å−3 |
1418 reflections | Δρmin = −0.58 e Å−3 |
53 parameters |
[Cd(I)2(C2H5NS)2] | V = 1301.1 (16) Å3 |
Mr = 516.49 | Z = 4 |
Orthorhombic, Pbcn | Mo Kα radiation |
a = 10.369 (9) Å | µ = 6.70 mm−1 |
b = 9.809 (6) Å | T = 293 K |
c = 12.792 (8) Å | 0.4 × 0.4 × 0.4 mm |
Enraf–Nonius CAD4 diffractometer | 1115 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0 |
Tmin = 0.069, Tmax = 0.086 | 1 standard reflections every 120 min |
1418 measured reflections | intensity decay: 1% |
1418 independent reflections |
R[F2 > 2σ(F2)] = 0.029 | 0 restraints |
wR(F2) = 0.055 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.49 e Å−3 |
1418 reflections | Δρmin = −0.58 e Å−3 |
53 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 > 2σ(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 | ||
I1 | 0.71665 (3) | 1.06035 (4) | 0.70992 (3) | 0.04723 (12) | |
Cd1 | 0.5000 | 0.90519 (6) | 0.7500 | 0.03851 (14) | |
S1 | 0.44664 (13) | 0.74390 (15) | 0.59888 (10) | 0.0504 (4) | |
C1 | 0.5480 (4) | 0.7604 (5) | 0.4977 (4) | 0.0379 (11) | |
N1 | 0.6340 (4) | 0.8524 (5) | 0.4899 (3) | 0.0656 (15) | |
H1A | 0.6821 | 0.8560 | 0.4352 | 0.079* | |
H1B | 0.6439 | 0.9110 | 0.5392 | 0.079* | |
C2 | 0.5367 (6) | 0.6619 (6) | 0.4086 (4) | 0.0641 (17) | |
H2A | 0.5244 | 0.7114 | 0.3446 | 0.096* | |
H2B | 0.4643 | 0.6028 | 0.4201 | 0.096* | |
H2C | 0.6140 | 0.6085 | 0.4039 | 0.096* |
U11 | U22 | U33 | U12 | U13 | U23 | |
I1 | 0.03944 (19) | 0.0613 (2) | 0.04098 (19) | −0.01312 (17) | 0.00435 (14) | −0.00932 (16) |
Cd1 | 0.0327 (2) | 0.0548 (3) | 0.0280 (2) | 0.000 | 0.0044 (2) | 0.000 |
S1 | 0.0453 (7) | 0.0710 (10) | 0.0348 (7) | −0.0217 (7) | 0.0110 (6) | −0.0112 (7) |
C1 | 0.035 (2) | 0.051 (3) | 0.028 (2) | 0.001 (2) | 0.001 (2) | 0.001 (2) |
N1 | 0.066 (3) | 0.091 (4) | 0.040 (3) | −0.035 (3) | 0.028 (2) | −0.020 (3) |
C2 | 0.093 (5) | 0.051 (3) | 0.048 (3) | −0.007 (3) | 0.016 (3) | −0.012 (3) |
I1—Cd1 | 2.7615 (17) | N1—H1A | 0.8607 |
Cd1—S1 | 2.5586 (17) | N1—H1B | 0.8607 |
S1—C1 | 1.675 (5) | C2—H2A | 0.9600 |
C1—N1 | 1.272 (6) | C2—H2B | 0.9600 |
C1—C2 | 1.499 (7) | C2—H2C | 0.9600 |
S1—Cd1—S1i | 103.61 (9) | C1—N1—H1B | 120.0 |
S1—Cd1—I1 | 112.11 (4) | H1A—N1—H1B | 119.9 |
S1—Cd1—I1i | 107.77 (5) | C1—C2—H2A | 109.5 |
I1—Cd1—I1i | 113.11 (6) | C1—C2—H2B | 109.5 |
C1—S1—Cd1 | 112.85 (19) | H2A—C2—H2B | 109.5 |
N1—C1—C2 | 116.9 (4) | C1—C2—H2C | 109.5 |
N1—C1—S1 | 124.7 (4) | H2A—C2—H2C | 109.5 |
C2—C1—S1 | 118.4 (4) | H2B—C2—H2C | 109.5 |
C1—N1—H1A | 120.0 |
Symmetry code: (i) −x+1, y, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | [Cd(I)2(C2H5NS)2] |
Mr | 516.49 |
Crystal system, space group | Orthorhombic, Pbcn |
Temperature (K) | 293 |
a, b, c (Å) | 10.369 (9), 9.809 (6), 12.792 (8) |
V (Å3) | 1301.1 (16) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 6.70 |
Crystal size (mm) | 0.4 × 0.4 × 0.4 |
Data collection | |
Diffractometer | Enraf–Nonius CAD4 |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.069, 0.086 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1418, 1418, 1115 |
Rint | 0 |
(sin θ/λ)max (Å−1) | 0.638 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.055, 1.03 |
No. of reflections | 1418 |
No. of parameters | 53 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.49, −0.58 |
Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
Thioacetamide complexes are used for synthesis of metal sulfide powders (Trindade et al., 1994; Grau & Akinc, 1997). Several structures of metal complexes with thioacetamide are reported. Cadmium chloride complex with thioacetamide CdCl2.CH3CSNH2 contains double chains of cadmium atoms with bridging chlorine atoms (Rolies & De Ranter, 1978). Two chains are shared through tridentate bridging chlorine atoms. Every cadmium atom is coordinated by five chlorine atoms and one sulfur atom of terminal thioacetamide molecule. In the zinc chloride complex with thioacetamide ZnCl2.2CH3CSNH2, zinc is tetrahedrally coordinated by two chlorine atoms and two thioacetamide molecules (Rolies & De Ranter, 1977a). The mercury chloride complex with thioacetamide HgCl2.2CH3CSNH2 is polymeric; adjacent mercury atoms linked through two bridging chlorine atoms (Rolies & De Ranter, 1977b). In this work, we report the crystal structure of diiodobis(thioacetamide)cadmium [Cd(CH3CSNH2)2I2]. The complex is molecular, cadmium is located on a twofold axis and tetrahedrally coordinated by two chlorine atoms and two thioacetamide molecules. Cd1—I1 distance is 2.7615 (17) Å and Cd1—S1 is 2.5586 (17) Å.