catena-Poly[[trimeth­yl(4-sulfanylphen­yl)aza­nium] [(chloridocadmate)-di-μ-chlorido]]

Tang, X.-Y.; Lang, J.-P.

doi:10.1107/S1600536811050513

metal-organic compounds

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Volume 67| Part 12| December 2011| Page m1883

https://doi.org/10.1107/S1600536811050513

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catena-Poly[[trimethyl(4-sulfanylphenyl)azanium] [(chloridocadmate)-di-μ-chlorido]]

Xiao-Yan Tang ^a and Jian-Ping Lang ^b ^*

^aCollege of Chemistry & Materials Engineering, Jiangsu Laboratory of Advanced Functional Materials, Changshu Institute of Technology, Changshu, 215500, Jiangsu, People's Republic of China, and ^bKey Laboratory of Organic Synthesis of Jiangsu Province, School of Chemistry and Chemical Engineering, Suzhou Uinversity, Suzhou 215123, Jiangsu, People's Republic of China
^*Correspondence e-mail: chemxytang@hotmail.com

(Received 29 September 2011; accepted 24 November 2011; online 30 November 2011)

The title compound, {(C₉H₁₄NS)[CdCl₃]}_n, consists of a linear [CdCl₃]_nⁿ⁻ polyanion and a trimethyl(4-sulfanylphenyl)azanium cation. The Cd^II atom is pentacoordinated by four μ₂-Cl atoms and one terminal Cl atom in a trigonal–bipyramidal geometry. The trigonal–bipyramidal units are linked by two opposite shared faces, giving rise to infinite [CdCl₃]_n chains parallel to the a axis. The cations surround the chain and are linked to them by S—H⋯Cl and C—H⋯Cl hydrogen bonds, forming a three-dimensional network.

Related literature

For the synthesis of trimethylammoniumphenyl-4-thiol hexafluoridophosphate, see: DePamphilis et al. (1974 ).

Experimental

Crystal data

(C₉H₁₄NS)[CdCl₃]
M_r = 387.04
Monoclinic, P 2₁ /c
a = 7.3207 (15) Å
b = 20.971 (4) Å
c = 9.1613 (18) Å
β = 103.96 (3)°
V = 1364.9 (5) Å³
Z = 4
Mo Kα radiation
μ = 2.31 mm⁻¹
T = 223 K
0.50 × 0.30 × 0.20 mm

Data collection

Rigaku Mercury diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2001 ) T_min = 0.442, T_max = 0.635
12984 measured reflections
2491 independent reflections
2424 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.069
S = 1.11
2491 reflections
137 parameters
H-atom parameters constrained
Δρ_max = 0.56 e Å⁻³
Δρ_min = −0.79 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
S1—H1⋯Cl1ⁱ	1.20	2.55	3.746	180
C8—H8B⋯Cl2ⁱⁱ	0.97	2.72	3.640 (3)	158
Symmetry codes: (i) -x+2, -y+2, -z+2; (ii) $[x-1, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku/MSC, 2001); cell refinement: CrystalClear; data reduction: CrystalStructure (Rigaku/MSC, 2004 ); 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536811050513/ng5241sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811050513/ng5241Isup2.hkl

checkCIF report

Related literature top

For the synthesis of trimethylammoniumphenyl-4-thiol hexafluorophosphate, see: DePamphilis et al. (1974).

Experimental top

The synthesis of trimethylammoniumphenyl-4-thiol hexafluorophosphate was according to the literature procedure (DePamphilis et al., 1974). To a suspension containing TabHPF₆ (0.125 mg, 0.4 mmol) in MeOH (15 ml) was added Et₃N (0.5 ml). The resulting colorless solution was then treated with a solution of CdCl₂^.2.5H₂O (0.091 g, 0.4 mmol) in MeOH (10 ml). The mixture was stirred at room temperature for 1 h and treated with HCl to adjust the pH to 3, and then filtered. Diethyl ether (20 ml) was allowed to diffuse onto the filtrate. After standing it at ambient temperature for one week, colorless block crystals of (I) were formed. Yield: 0.100 g (65% based on Cd). The crystal used for the crystal structure determination was obtained directly from the above preparation. Analysis, found: C, 27.52; H, 3.31; N, 4.02%. calculated. for C₉H₁₄NSCdCl₃: C, 27.93; H, 3.65; N, 3.62%.

Structure description top

For the synthesis of trimethylammoniumphenyl-4-thiol hexafluorophosphate, see: DePamphilis et al. (1974).

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2001); cell refinement: CrystalClear (Rigaku/MSC, 2001); data reduction: CrystalStructure (Rigaku/MSC, 2004); 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: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. ORTEP plot of complex (I) at the 30% probability level. Hydrogen atoms are drawn as spheres of arbitrary radii.
	Fig. 2. One dimensional structure formed by S—H···Cl interactions.
	Fig. 3. Three dimensional networks formed by S—H···Cl and C—H···Cl interactions.

catena-Poly[[trimethyl(4-sulfanylphenyl)azanium] [(chloridocadmate)-di-µ-chlorido]] top

Crystal data top

(C₉H₁₄NS)[CdCl₃]	F(000) = 760
M_r = 387.04	D_x = 1.883 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3007 reflections
a = 7.3207 (15) Å	θ = 3.0–25.4°
b = 20.971 (4) Å	µ = 2.31 mm⁻¹
c = 9.1613 (18) Å	T = 223 K
β = 103.96 (3)°	Block, colorless
V = 1364.9 (5) Å³	0.50 × 0.30 × 0.20 mm
Z = 4

Data collection top

Rigaku Mercury diffractometer	2491 independent reflections
Radiation source: fine-focus sealed tube	2424 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ω scans	θ_max = 25.4°, θ_min = 3.0°
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC2001)	h = −8→7
T_min = 0.442, T_max = 0.635	k = −22→25
12984 measured reflections	l = −11→11

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)] = 0.026	H-atom parameters constrained
wR(F²) = 0.069	w = 1/[σ²(F_o²) + (0.038P)² + 0.9902P] where P = (F_o² + 2F_c²)/3
S = 1.11	(Δ/σ)_max < 0.001
2491 reflections	Δρ_max = 0.56 e Å⁻³
137 parameters	Δρ_min = −0.79 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: 0.0059 (5)

Crystal data top

(C₉H₁₄NS)[CdCl₃]	V = 1364.9 (5) Å³
M_r = 387.04	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.3207 (15) Å	µ = 2.31 mm⁻¹
b = 20.971 (4) Å	T = 223 K
c = 9.1613 (18) Å	0.50 × 0.30 × 0.20 mm
β = 103.96 (3)°

Data collection top

Rigaku Mercury diffractometer	2491 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC2001)	2424 reflections with I > 2σ(I)
T_min = 0.442, T_max = 0.635	R_int = 0.027
12984 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	0 restraints
wR(F²) = 0.069	H-atom parameters constrained
S = 1.11	Δρ_max = 0.56 e Å⁻³
2491 reflections	Δρ_min = −0.79 e Å⁻³
137 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
Cd1	0.73386 (3)	0.993777 (10)	0.92593 (2)	0.02485 (11)
Cl1	0.95247 (10)	1.08537 (3)	0.99446 (8)	0.02873 (17)
Cl2	0.68785 (10)	0.96938 (3)	0.66114 (7)	0.03076 (18)
Cl3	0.59419 (8)	0.93630 (3)	1.11069 (7)	0.03094 (18)
S1	0.67638 (8)	0.79389 (3)	0.84461 (7)	0.0484 (2)
H1	0.7952	0.8326	0.8962	0.058*
C1	0.5039 (4)	0.74912 (14)	0.9045 (3)	0.0285 (6)
C2	0.3807 (4)	0.77654 (14)	0.9805 (3)	0.0319 (6)
H2	0.3876	0.8205	1.0016	0.038*
C3	0.2478 (4)	0.73917 (14)	1.0253 (3)	0.0303 (6)
H3	0.1638	0.7577	1.0760	0.036*
C4	0.2392 (4)	0.67468 (13)	0.9952 (3)	0.0238 (6)
C5	0.3603 (4)	0.64695 (14)	0.9182 (3)	0.0278 (6)
H5	0.3540	0.6030	0.8977	0.033*
C6	0.4898 (4)	0.68458 (14)	0.8721 (3)	0.0301 (6)
H6	0.5700	0.6662	0.8177	0.036*
C7	0.2022 (4)	0.58027 (15)	1.1450 (4)	0.0350 (7)
H7A	0.2689	0.5534	1.0889	0.053*
H7B	0.1119	0.5548	1.1813	0.053*
H7C	0.2914	0.5991	1.2297	0.053*
C8	−0.0195 (4)	0.66781 (15)	1.1295 (3)	0.0342 (7)
H8A	0.0607	0.6878	1.2174	0.051*
H8B	−0.1042	0.6381	1.1610	0.051*
H8C	−0.0922	0.7003	1.0654	0.051*
C9	−0.0285 (4)	0.60310 (16)	0.9076 (3)	0.0357 (7)
H9A	−0.0869	0.6365	0.8389	0.054*
H9B	−0.1251	0.5785	0.9381	0.054*
H9C	0.0436	0.5754	0.8578	0.054*
N1	0.1003 (3)	0.63245 (11)	1.0439 (2)	0.0250 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.02433 (16)	0.02926 (16)	0.02258 (16)	−0.00438 (7)	0.00880 (10)	−0.00082 (7)
Cl1	0.0240 (3)	0.0261 (4)	0.0358 (4)	−0.0021 (3)	0.0065 (3)	−0.0020 (3)
Cl2	0.0328 (4)	0.0364 (4)	0.0230 (3)	0.0030 (3)	0.0066 (3)	−0.0025 (3)
Cl3	0.0280 (4)	0.0330 (4)	0.0359 (4)	0.0061 (3)	0.0157 (3)	0.0131 (3)
S1	0.0499 (5)	0.0405 (5)	0.0632 (6)	−0.0145 (4)	0.0301 (4)	0.0025 (4)
C1	0.0287 (15)	0.0301 (15)	0.0267 (14)	−0.0036 (11)	0.0066 (11)	0.0032 (11)
C2	0.0352 (16)	0.0247 (15)	0.0366 (16)	−0.0010 (12)	0.0105 (12)	−0.0012 (12)
C3	0.0336 (16)	0.0282 (16)	0.0322 (15)	0.0008 (12)	0.0141 (12)	−0.0046 (12)
C4	0.0220 (13)	0.0257 (14)	0.0240 (14)	−0.0025 (11)	0.0065 (10)	0.0012 (11)
C5	0.0310 (15)	0.0246 (15)	0.0297 (15)	−0.0001 (11)	0.0112 (12)	−0.0034 (11)
C6	0.0296 (15)	0.0310 (16)	0.0337 (16)	0.0005 (12)	0.0152 (12)	−0.0025 (12)
C7	0.0374 (17)	0.0319 (17)	0.0379 (17)	0.0022 (13)	0.0133 (13)	0.0094 (13)
C8	0.0333 (16)	0.0372 (17)	0.0377 (17)	−0.0009 (13)	0.0197 (13)	−0.0029 (13)
C9	0.0304 (16)	0.0440 (18)	0.0339 (16)	−0.0111 (13)	0.0101 (12)	−0.0082 (13)
N1	0.0265 (12)	0.0262 (12)	0.0245 (11)	−0.0007 (9)	0.0102 (9)	0.0000 (9)

Geometric parameters (Å, º) top

Cd1—Cl2	2.4219 (8)	C4—N1	1.496 (3)
Cd1—Cl1	2.4819 (8)	C5—C6	1.375 (4)
Cd1—Cl3	2.4896 (7)	C5—H5	0.9400
Cd1—Cl3ⁱ	2.7643 (7)	C6—H6	0.9400
Cd1—Cl1ⁱⁱ	2.7842 (9)	C7—N1	1.509 (4)
Cl1—Cd1ⁱⁱ	2.7842 (9)	C7—H7A	0.9700
Cl3—Cd1ⁱ	2.7643 (7)	C7—H7B	0.9700
S1—C1	1.764 (3)	C7—H7C	0.9700
S1—H1	1.1999	C8—N1	1.505 (4)
C1—C6	1.384 (4)	C8—H8A	0.9700
C1—C2	1.390 (4)	C8—H8B	0.9700
C2—C3	1.386 (4)	C8—H8C	0.9700
C2—H2	0.9400	C9—N1	1.503 (4)
C3—C4	1.379 (4)	C9—H9A	0.9700
C3—H3	0.9400	C9—H9B	0.9700
C4—C5	1.387 (4)	C9—H9C	0.9700

Cl2—Cd1—Cl1	110.02 (3)	C5—C6—C1	121.1 (3)
Cl2—Cd1—Cl3	126.73 (3)	C5—C6—H6	119.4
Cl1—Cd1—Cl3	123.24 (3)	C1—C6—H6	119.4
Cl2—Cd1—Cl3ⁱ	94.80 (3)	N1—C7—H7A	109.5
Cl1—Cd1—Cl3ⁱ	96.23 (3)	N1—C7—H7B	109.5
Cl3—Cd1—Cl3ⁱ	81.49 (3)	H7A—C7—H7B	109.5
Cl2—Cd1—Cl1ⁱⁱ	92.47 (3)	N1—C7—H7C	109.5
Cl1—Cd1—Cl1ⁱⁱ	87.38 (3)	H7A—C7—H7C	109.5
Cl3—Cd1—Cl1ⁱⁱ	88.93 (3)	H7B—C7—H7C	109.5
Cl3ⁱ—Cd1—Cl1ⁱⁱ	170.23 (2)	N1—C8—H8A	109.5
Cd1—Cl1—Cd1ⁱⁱ	92.62 (3)	N1—C8—H8B	109.5
Cd1—Cl3—Cd1ⁱ	98.51 (3)	H8A—C8—H8B	109.5
C1—S1—H1	138.0	N1—C8—H8C	109.5
C6—C1—C2	119.2 (3)	H8A—C8—H8C	109.5
C6—C1—S1	118.4 (2)	H8B—C8—H8C	109.5
C2—C1—S1	122.4 (2)	N1—C9—H9A	109.5
C3—C2—C1	120.1 (3)	N1—C9—H9B	109.5
C3—C2—H2	120.0	H9A—C9—H9B	109.5
C1—C2—H2	120.0	N1—C9—H9C	109.5
C4—C3—C2	119.8 (3)	H9A—C9—H9C	109.5
C4—C3—H3	120.1	H9B—C9—H9C	109.5
C2—C3—H3	120.1	C4—N1—C9	109.2 (2)
C3—C4—C5	120.6 (3)	C4—N1—C8	112.8 (2)
C3—C4—N1	121.5 (2)	C9—N1—C8	107.9 (2)
C5—C4—N1	117.9 (2)	C4—N1—C7	109.9 (2)
C6—C5—C4	119.2 (3)	C9—N1—C7	109.3 (2)
C6—C5—H5	120.4	C8—N1—C7	107.6 (2)
C4—C5—H5	120.4

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
S1—H1···Cl1ⁱⁱ	1.20	2.55	3.746	180
C8—H8B···Cl2ⁱⁱⁱ	0.97	2.72	3.640 (3)	158

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

Experimental details

Crystal data
Chemical formula	(C₉H₁₄NS)[CdCl₃]
M_r	387.04
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	223
a, b, c (Å)	7.3207 (15), 20.971 (4), 9.1613 (18)
β (°)	103.96 (3)
V (Å³)	1364.9 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.31
Crystal size (mm)	0.50 × 0.30 × 0.20

Data collection
Diffractometer	Rigaku Mercury
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC2001)
T_min, T_max	0.442, 0.635
No. of measured, independent and observed [I > 2σ(I)] reflections	12984, 2491, 2424
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.069, 1.11
No. of reflections	2491
No. of parameters	137
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.56, −0.79

Computer programs: CrystalClear (Rigaku/MSC, 2001), CrystalStructure (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
S1—H1···Cl1ⁱ	1.20	2.55	3.746	180.0
C8—H8B···Cl2ⁱⁱ	0.97	2.72	3.640 (3)	158.4

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

Acknowledgements

This work was supported by the Natural Science Foundation of the Education Commission of Jiangsu Province of China (No.11KJB150001) and a start-up grant from Changshu Institute of Technology (No. ky2009069).

References

DePamphilis, B. V., Averill, B. A., Herskovitz, T., Que, L. & Holm, R. H. (1974). J. Am. Chem. Soc. 96, 4159–4167. CrossRef CAS PubMed Web of Science Google Scholar
Rigaku/MSC (2001). CrystalClear. Rigaku and Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar
Rigaku/MSC (2004). CrystalStructure. Rigaku and Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 12| December 2011| Page m1883

https://doi.org/10.1107/S1600536811050513

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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

catena-Poly[[trimeth­yl(4-sulfanylphen­yl)aza­nium] [(chloridocadmate)-di-μ-chlorido]]

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

catena-Poly[[trimethyl(4-sulfanylphenyl)azanium] [(chloridocadmate)-di-μ-chlorido]]