catena-Poly[cadmium-bis­(μ-N,N-dimethyl­dithio­carbamato-κ³S,S′:S)]

In the title compound, [Cd(C₃H₆NS₂)₂]_n, the Cd^II atom, lying on a twofold rotation axis, is coordinated by six S atoms from four different N,N-dimethyl­dithio­carbamate ligands in a distorted octa­hedral geometry. The bridging of S atoms of the ligands leads to the formation of a one-dimensional structure along [001].

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](N-C) = 0.003 Å
• R factor = 0.017
• wR factor = 0.044
• Data-to-parameter ratio = 21.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Cd1    --  S1      ..       9.97 su

Alert level G
PLAT794_ALERT_5_G Note: Tentative Bond Valency for Cd1     .......       2.03

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   1 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
   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
   0 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

Rapid development of metal–organic frameworks has been made in recent years not only for their potential applications in materials science but also for fascinating architectures and topologies (Kitagawa et al., 2006; Papaefstathiou & MacGillivray, 2003; Yaghi et al., 1998). Dimethyldithiocarbamic acid is widely used in latex industry. Its natrium, zinc and copper salts are applied widely in antimicrobial, antisepsis and accelerant (Einstein & Field, 1974; Oskarsson & Ymén, 1983). Meanwhile, dimethyldithiocarbamic acid, possessing two S atoms, is a good candidate to coordinate metal atoms and generates rich hydrogen bonding modes. Herein we report the preparation and characterization of the first cadmium complex of dimethyldithiocarbamic acid.

In the title complex, the Cd^II ion is coordinated in an octahedral geometry by six S atoms from four different dimethyldithiocarbamate ligands (Fig. 1), with the Cd—S distances ranging from 2.6255 (7) to 2.7909 (6) Å (Table 1). Through the bridging of S2 atoms, the title complex forms a one-dimensional structure (Fig. 2).

Related literature

For general background to metal–organic frameworks, see: Kitagawa et al. (2006); Papaefstathiou & MacGillivray (2003); Yaghi et al. (1998). For the natrium, zinc and copper salts of dimethyldithiocarbamate, see: Einstein & Field (1974); Oskarsson & Ymén (1983).

S2. Experimental

A mixture containing 0.005 mmol of Cd(NO₃)₂.4H₂O and 0.010 mmol of dimethyldithiocarbamic acid was placed in a small vial containing MeOH (3.0 ml), DMF (1.0 ml) and H₂O (0.5 ml). The vial was sealed, heated at 373 K for 2 d and allowed to cool to room temperature. Colorless crystals suitable for X-ray diffraction were collected and dried in air (yield: 50%).

S3. Refinement

H atoms were placed in calculated positions and treated using a riding model, with C—H = 0.98 Å and with U_iso(H) = 1.5U_eq(C).

Computing details

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The asymmetric unit of the title compound, showing the Cd coordination. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (i) 3/2-x, y, 1/2+z; (ii) 3/2-x, 1/2-y, z; (iii) x, 1/2-y, 1/2+z.]
	Fig. 2. One-dimensional chain in the title complex. H atoms have been omitted for clarity.

catena-Poly[cadmium-bis(µ-N,N- dimethyldithiocarbamato-κ³S,S':S)]

Crystal data

[Cd(C3H6NS2)2]	F(000) = 696
Mr = 352.82	Dx = 1.988 Mg m^−3
Orthorhombic, Pccn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ab 2ac	Cell parameters from 4468 reflections
a = 10.055 (2) Å	θ = 2.5–27.6°
b = 14.744 (3) Å	µ = 2.52 mm^−1
c = 7.9518 (17) Å	T = 296 K
V = 1178.9 (4) Å^3	Block, colorless
Z = 4	0.54 × 0.22 × 0.17 mm

Data collection

Bruker APEXII CCD diffractometer	1370 independent reflections
Radiation source: fine-focus sealed tube	1221 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
φ and ω scans	θmax = 27.6°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→13
Tmin = 0.519, Tmax = 0.652	k = −16→19
9543 measured reflections	l = −10→10

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.017	H-atom parameters constrained
wR(F^2) = 0.044	w = 1/[σ^2(Fo^2) + (0.0174P)^2 + 0.6307P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.001
1370 reflections	Δρmax = 0.29 e Å^−3
63 parameters	Δρmin = −0.34 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0036 (3)

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

	x	y	z	Uiso*/Ueq
Cd1	0.7500	0.2500	0.17288 (2)	0.03178 (9)
S1	0.49818 (5)	0.28596 (4)	0.11658 (7)	0.04016 (14)
S2	0.71139 (5)	0.37665 (3)	−0.08336 (6)	0.03093 (12)
N1	0.45119 (16)	0.39753 (11)	−0.1396 (2)	0.0335 (4)
C1	0.54274 (18)	0.35704 (12)	−0.0449 (2)	0.0279 (4)
C2	0.3088 (2)	0.38157 (18)	−0.1150 (3)	0.0473 (5)
H2A	0.2952	0.3465	−0.0118	0.071*
H2B	0.2734	0.3477	−0.2112	0.071*
H2C	0.2626	0.4399	−0.1057	0.071*
C3	0.4855 (2)	0.45777 (16)	−0.2802 (3)	0.0481 (5)
H3A	0.5549	0.5003	−0.2446	0.072*
H3B	0.4063	0.4917	−0.3151	0.072*
H3C	0.5181	0.4215	−0.3749	0.072*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.02789 (12)	0.04207 (14)	0.02537 (12)	0.00462 (8)	0.000	0.000
S1	0.0295 (2)	0.0507 (3)	0.0403 (3)	0.0030 (2)	0.0035 (2)	0.0156 (2)
S2	0.0294 (2)	0.0340 (2)	0.0294 (2)	−0.00350 (18)	−0.00062 (18)	−0.00097 (18)
N1	0.0323 (8)	0.0348 (9)	0.0333 (8)	0.0051 (7)	−0.0036 (7)	0.0015 (7)
C1	0.0298 (9)	0.0284 (9)	0.0256 (9)	0.0017 (7)	−0.0001 (7)	−0.0039 (7)
C2	0.0331 (11)	0.0580 (14)	0.0509 (13)	0.0091 (10)	−0.0074 (10)	0.0033 (11)
C3	0.0544 (13)	0.0434 (12)	0.0466 (12)	0.0058 (10)	−0.0070 (11)	0.0154 (10)

Geometric parameters (Å, º)

Cd1—S1	2.6255 (7)	N1—C3	1.469 (3)
Cd1—S2	2.7909 (6)	C2—H2A	0.9800
Cd1—S2^i	2.7194 (6)	C2—H2B	0.9800
S1—C1	1.7169 (19)	C2—H2C	0.9800
S2—C1	1.7473 (19)	C3—H3A	0.9800
S2—Cd1^ii	2.7194 (6)	C3—H3B	0.9800
N1—C1	1.331 (2)	C3—H3C	0.9800
N1—C2	1.464 (3)
S1—Cd1—S1^iii	160.37 (3)	C1—N1—C2	121.94 (18)
S1—Cd1—S2^i	96.922 (18)	C1—N1—C3	122.66 (17)
S1^iii—Cd1—S2^i	97.039 (16)	C2—N1—C3	115.34 (17)
S1—Cd1—S2^iv	97.039 (16)	N1—C1—S1	121.09 (14)
S1^iii—Cd1—S2^iv	96.922 (18)	N1—C1—S2	119.88 (14)
S2^i—Cd1—S2^iv	89.07 (3)	S1—C1—S2	119.03 (10)
S1—Cd1—S2^iii	98.326 (18)	N1—C2—H2A	109.5
S1^iii—Cd1—S2^iii	66.812 (15)	N1—C2—H2B	109.5
S2^i—Cd1—S2^iii	163.74 (2)	H2A—C2—H2B	109.5
S2^iv—Cd1—S2^iii	94.63 (2)	N1—C2—H2C	109.5
S1—Cd1—S2	66.812 (15)	H2A—C2—H2C	109.5
S1^iii—Cd1—S2	98.326 (18)	H2B—C2—H2C	109.5
S2^i—Cd1—S2	94.63 (2)	N1—C3—H3A	109.5
S2^iv—Cd1—S2	163.74 (2)	N1—C3—H3B	109.5
S2^iii—Cd1—S2	86.22 (3)	H3A—C3—H3B	109.5
C1—S1—Cd1	89.95 (6)	N1—C3—H3C	109.5
C1—S2—Cd1^ii	98.61 (6)	H3A—C3—H3C	109.5
C1—S2—Cd1	84.06 (6)	H3B—C3—H3C	109.5
Cd1^ii—S2—Cd1	92.35 (2)

Symmetry codes: (i) −x+3/2, y, z+1/2; (ii) −x+3/2, y, z−1/2; (iii) −x+3/2, −y+1/2, z; (iv) x, −y+1/2, z+1/2.