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

Bing, Y.; Li, X.; Zha, M.; Lu, Y.

doi:10.1107/S1600536810043977

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 11| November 2010| Page m1500

https://doi.org/10.1107/S1600536810043977

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

Yue Bing,^a Xing Li,^a ^* Meiqin Zha ^a and Yue Lu ^a

^aFaculty of Materials Science and Chemical Engineering, Ningbo University, Ningbo, Zhejiang 315211, People's Republic of China
^*Correspondence e-mail: lix905@126.com

(Received 19 October 2010; accepted 27 October 2010; online 31 October 2010)

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].

Related literature

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

Experimental

Crystal data

[Cd(C₃H₆NS₂)₂]
M_r = 352.82
Orthorhombic, P c c n
a = 10.055 (2) Å
b = 14.744 (3) Å
c = 7.9518 (17) Å
V = 1178.9 (4) Å³
Z = 4
Mo Kα radiation
μ = 2.52 mm⁻¹
T = 296 K
0.54 × 0.22 × 0.17 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.519, T_max = 0.652
9543 measured reflections
1370 independent reflections
1221 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.017
wR(F²) = 0.044
S = 1.07
1370 reflections
63 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Selected bond lengths (Å)

Cd1—S1	2.6255 (7)
Cd1—S2	2.7909 (6)
Cd1—S2ⁱ	2.7194 (6)
Symmetry code: (i) $[-x+{\script{3\over 2}}, y, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; 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).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810043977/hy2367sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810043977/hy2367Isup2.hkl

checkCIF report

Comment top

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 top

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).

Experimental top

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%).

Structure description top

Computing details top

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 top

	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)] top

Crystal data top

[Cd(C₃H₆NS₂)₂]	F(000) = 696
M_r = 352.82	D_x = 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) Å³	Block, colorless
Z = 4	0.54 × 0.22 × 0.17 mm

Data collection top

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

Refinement top

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)] = 0.017	H-atom parameters constrained
wR(F²) = 0.044	w = 1/[σ²(F_o²) + (0.0174P)² + 0.6307P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
1370 reflections	Δρ_max = 0.29 e Å⁻³
63 parameters	Δρ_min = −0.34 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0036 (3)

Crystal data top

[Cd(C₃H₆NS₂)₂]	V = 1178.9 (4) Å³
M_r = 352.82	Z = 4
Orthorhombic, Pccn	Mo Kα radiation
a = 10.055 (2) Å	µ = 2.52 mm⁻¹
b = 14.744 (3) Å	T = 296 K
c = 7.9518 (17) Å	0.54 × 0.22 × 0.17 mm

Data collection top

Bruker APEXII CCD diffractometer	1370 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1221 reflections with I > 2σ(I)
T_min = 0.519, T_max = 0.652	R_int = 0.030
9543 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.017	0 restraints
wR(F²) = 0.044	H-atom parameters constrained
S = 1.07	Δρ_max = 0.29 e Å⁻³
1370 reflections	Δρ_min = −0.34 e Å⁻³
63 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
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) top

Cd1—S1	2.6255 (7)	N1—C3	1.469 (3)
Cd1—S2	2.7909 (6)	C2—H2A	0.9800
Cd1—S2ⁱ	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—Cd1ⁱⁱ	2.7194 (6)	C3—H3B	0.9800
N1—C1	1.331 (2)	C3—H3C	0.9800
N1—C2	1.464 (3)

S1—Cd1—S1ⁱⁱⁱ	160.37 (3)	C1—N1—C2	121.94 (18)
S1—Cd1—S2ⁱ	96.922 (18)	C1—N1—C3	122.66 (17)
S1ⁱⁱⁱ—Cd1—S2ⁱ	97.039 (16)	C2—N1—C3	115.34 (17)
S1—Cd1—S2^iv	97.039 (16)	N1—C1—S1	121.09 (14)
S1ⁱⁱⁱ—Cd1—S2^iv	96.922 (18)	N1—C1—S2	119.88 (14)
S2ⁱ—Cd1—S2^iv	89.07 (3)	S1—C1—S2	119.03 (10)
S1—Cd1—S2ⁱⁱⁱ	98.326 (18)	N1—C2—H2A	109.5
S1ⁱⁱⁱ—Cd1—S2ⁱⁱⁱ	66.812 (15)	N1—C2—H2B	109.5
S2ⁱ—Cd1—S2ⁱⁱⁱ	163.74 (2)	H2A—C2—H2B	109.5
S2^iv—Cd1—S2ⁱⁱⁱ	94.63 (2)	N1—C2—H2C	109.5
S1—Cd1—S2	66.812 (15)	H2A—C2—H2C	109.5
S1ⁱⁱⁱ—Cd1—S2	98.326 (18)	H2B—C2—H2C	109.5
S2ⁱ—Cd1—S2	94.63 (2)	N1—C3—H3A	109.5
S2^iv—Cd1—S2	163.74 (2)	N1—C3—H3B	109.5
S2ⁱⁱⁱ—Cd1—S2	86.22 (3)	H3A—C3—H3B	109.5
C1—S1—Cd1	89.95 (6)	N1—C3—H3C	109.5
C1—S2—Cd1ⁱⁱ	98.61 (6)	H3A—C3—H3C	109.5
C1—S2—Cd1	84.06 (6)	H3B—C3—H3C	109.5
Cd1ⁱⁱ—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.

Experimental details

Crystal data
Chemical formula	[Cd(C₃H₆NS₂)₂]
M_r	352.82
Crystal system, space group	Orthorhombic, Pccn
Temperature (K)	296
a, b, c (Å)	10.055 (2), 14.744 (3), 7.9518 (17)
V (Å³)	1178.9 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.52
Crystal size (mm)	0.54 × 0.22 × 0.17

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.519, 0.652
No. of measured, independent and observed [I > 2σ(I)] reflections	9543, 1370, 1221
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.017, 0.044, 1.07
No. of reflections	1370
No. of parameters	63
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.34

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Cd1—S1	2.6255 (7)	Cd1—S2ⁱ	2.7194 (6)
Cd1—S2	2.7909 (6)

Symmetry code: (i) −x+3/2, y, z+1/2.

Acknowledgements

This work was supported by the Ningbo Natural Science Foundation (grant No. 2010 A610060), the `Qianjiang Talent' Projects of Zhejiang Province (grant No. 2009R10032), the Program for Innovative Research Team of Ningbo Novel Photoelectric Materials and Devices (grant No. 2009B21007), and the K. C. Wong Magna Fund of Ningbo University.

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