Diiodidobis(thio­acetamide-κS)cadmium(II)

Thio­acetamide complexes are used for the synthesis of metal sulfide powders. In the title mol­ecular complex, [CdI₂(C₂H₅NS)₂], the Cd^II atom is located on a twofold rotation axis and is tetra­hedrally coordinated by two iodine atoms and two thio­acetamide mol­ecules. The Cd—I distance is 2.7615 (17) Å and the Cd—S distance is 2.5586 (17) Å.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](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

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S1. Comment

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.

Related literature

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).

S2. Experimental

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%.

S3. Refinement

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, U_iso(H) = 1.2 (for NH₂ and 1.5 (for CH₃) times U_eq of the parent atom.

Computing details

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).

Figures

Fig. 1. ORTEP-3 (Farrugia, 1997) view of the title complex, with the atom numbering scheme. Displacement ellipsoids are presented with 50% probability level. H atoms are drawn as spheres of arbitrary radius. Symmetry code: (i) -x + 1, y, -z + 3/2.

Diiodidobis(thioacetamide-κS)cadmium(II)

Crystal data

[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) Å^3	Prism, colourless
Z = 4	0.4 × 0.4 × 0.4 mm

Data collection

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

Refinement on F^2	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.029	w = 1/[σ^2(Fo^2) + (0.0215P)^2 + 0.5736P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 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

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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—S1^i	103.61 (9)	C1—N1—H1B	120.0
S1—Cd1—I1	112.11 (4)	H1A—N1—H1B	119.9
S1—Cd1—I1^i	107.77 (5)	C1—C2—H2A	109.5
I1—Cd1—I1^i	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.