catena-Poly[trimethyl­phenyl­ammonium [[bromidocad­mate(II)]-μ-bromido-μ-chlorido]]

Lo, K.M.; Ng, S.W.

doi:10.1107/S1600536810005817

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 3| March 2010| Page m308

doi:10.1107/S1600536810005817

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catena-Poly[trimethylphenylammonium [[bromidocadmate(II)]-μ-bromido-μ-chlorido]]

Kong Mun Lo ^a and Seik Weng Ng ^a ^*

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 10 February 2010; accepted 12 February 2010; online 17 February 2010)

In the title salt, (C₉H₁₄N)[CdBr₂Cl], the Cd^II atom is five-coordinated in a trigonal-bipyramidal coordination environment. All three of the halogen sites show disorder as a result of substitution of Cl for Br or Br for Cl. Two of the three halogen atoms are involved in bridging a pair of Cd^II atoms, generating a linear polyanionic chain motif.

Related literature

For the crystal structure of bis[4-(dimethylamino)pyridinium]tetrabromidocadmate monohydrate, see: Lo & Ng (2009 ).

Experimental

Crystal data

(C₉H₁₄N)[CdBr₂Cl]
M_r = 443.88
Monoclinic, C c
a = 12.9403 (2) Å
b = 14.7059 (2) Å
c = 7.3866 (1) Å
β = 95.1590 (8)°
V = 1399.97 (3) Å³
Z = 4
Mo Kα radiation
μ = 7.43 mm⁻¹
T = 293 K
0.30 × 0.25 × 0.20 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.378, T_max = 0.746
6431 measured reflections
3068 independent reflections
2966 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.070
S = 1.06
3068 reflections
124 parameters
10 restraints
H-atom parameters constrained
Δρ_max = 0.67 e Å⁻³
Δρ_min = −0.68 e Å⁻³
Absolute structure: Flack (1983 ), 1451 Friedel pairs
Flack parameter: 0.021 (9)

Data collection: APEX2 (Bruker, 2009 ); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810005817/ci5034sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810005817/ci5034Isup2.hkl

checkCIF report

Related literature top

For the crystal structure of bis[4-(dimethylamino)pyridinium]tetrabromidocadmate monohydrate, see: Lo & Ng (2009).

Experimental top

Cadmium chloride hemipentahydrate (0.45 g , 2 mmol) and trimethylphenylammonium tribromide (0.76 g, 2mmol) were heated in ethanol for 1 h. After filtering of the reaction mixture, colourless crystals were obtained upon slow evaporation of the yellow filtrate.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. Displacement ellipsoid plot (Barbour, 2001) of a portion of polymeric C₉H₁₄N⁺ [CdBr₂Cl]^- at the 50% probability level. H are drawn as spheres of arbitrary radius. The disorder in the halogen sites not shown.

catena-Poly[trimethylphenylammonium [[bromidocadmate(II)]µ-bromido-µ-chlorido]] top

Crystal data top

(C₉H₁₄N)[CdBr₂Cl]	F(000) = 840
M_r = 443.88	D_x = 2.106 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 5267 reflections
a = 12.9403 (2) Å	θ = 2.7–28.3°
b = 14.7059 (2) Å	µ = 7.43 mm⁻¹
c = 7.3866 (1) Å	T = 293 K
β = 95.1590 (8)°	Block, colourless
V = 1399.97 (3) Å³	0.30 × 0.25 × 0.20 mm
Z = 4

Data collection top

Bruker SMART APEX diffractometer	3068 independent reflections
Radiation source: fine-focus sealed tube	2966 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
ω scans	θ_max = 27.5°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −16→16
T_min = 0.378, T_max = 0.746	k = −19→19
6431 measured reflections	l = −9→9

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)] = 0.027	H-atom parameters constrained
wR(F²) = 0.070	w = 1/[σ²(F_o²) + (0.0296P)² + 0.0436P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
3068 reflections	Δρ_max = 0.67 e Å⁻³
124 parameters	Δρ_min = −0.68 e Å⁻³
10 restraints	Absolute structure: Flack (1983), 1451 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.021 (9)

Crystal data top

(C₉H₁₄N)[CdBr₂Cl]	V = 1399.97 (3) Å³
M_r = 443.88	Z = 4
Monoclinic, Cc	Mo Kα radiation
a = 12.9403 (2) Å	µ = 7.43 mm⁻¹
b = 14.7059 (2) Å	T = 293 K
c = 7.3866 (1) Å	0.30 × 0.25 × 0.20 mm
β = 95.1590 (8)°

Data collection top

Bruker SMART APEX diffractometer	3068 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2966 reflections with I > 2σ(I)
T_min = 0.378, T_max = 0.746	R_int = 0.026
6431 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	H-atom parameters constrained
wR(F²) = 0.070	Δρ_max = 0.67 e Å⁻³
S = 1.06	Δρ_min = −0.68 e Å⁻³
3068 reflections	Absolute structure: Flack (1983), 1451 Friedel pairs
124 parameters	Absolute structure parameter: 0.021 (9)
10 restraints

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cd1	0.50000 (2)	0.451513 (19)	0.50000 (3)	0.04131 (10)
Br1	0.63269 (6)	0.51023 (6)	0.29653 (9)	0.04153 (19)	0.302 (2)
Br2	0.36460 (4)	0.55946 (3)	0.61951 (6)	0.04104 (14)	0.861 (2)
Br3	0.48809 (5)	0.28104 (3)	0.54560 (8)	0.05001 (16)	0.837 (2)
Cl1	0.63269 (6)	0.51023 (6)	0.29653 (9)	0.04153 (19)	0.698 (2)
Cl2	0.36460 (4)	0.55946 (3)	0.61951 (6)	0.04104 (14)	0.139 (2)
Cl3	0.48809 (5)	0.28104 (3)	0.54560 (8)	0.05001 (16)	0.163 (2)
N1	0.6446 (3)	0.8091 (3)	0.5732 (4)	0.0399 (8)
C1	0.5525 (2)	0.8692 (2)	0.5708 (5)	0.0405 (9)
C2	0.4530 (3)	0.8337 (2)	0.5711 (6)	0.0623 (14)
H2	0.4432	0.7710	0.5716	0.075*
C3	0.3682 (2)	0.8917 (3)	0.5705 (8)	0.089 (2)
H3	0.3017	0.8679	0.5706	0.106*
C4	0.3830 (3)	0.9854 (3)	0.5696 (8)	0.091 (3)
H4	0.3262	1.0242	0.5692	0.109*
C5	0.4825 (4)	1.02091 (19)	0.5694 (7)	0.082 (2)
H5	0.4923	1.0835	0.5688	0.098*
C6	0.5673 (3)	0.9628 (2)	0.5700 (6)	0.0594 (14)
H6	0.6339	0.9866	0.5698	0.071*
C7	0.6156 (6)	0.7104 (3)	0.5704 (10)	0.0697 (16)
H7A	0.5714	0.6975	0.4620	0.104*
H7B	0.5796	0.6966	0.6751	0.104*
H7C	0.6773	0.6740	0.5722	0.104*
C8	0.7023 (4)	0.8299 (5)	0.4097 (7)	0.0624 (14)
H8A	0.6595	0.8148	0.3009	0.094*
H8B	0.7650	0.7946	0.4153	0.094*
H8C	0.7193	0.8934	0.4086	0.094*
C9	0.7151 (4)	0.8261 (5)	0.7446 (7)	0.0623 (15)
H9A	0.7481	0.8843	0.7365	0.093*
H9B	0.7670	0.7794	0.7583	0.093*
H9C	0.6749	0.8255	0.8476	0.093*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.04678 (18)	0.03161 (15)	0.04784 (18)	0.00106 (13)	0.01690 (13)	−0.00100 (13)
Br1	0.0383 (4)	0.0526 (5)	0.0341 (3)	−0.0033 (3)	0.0054 (3)	0.0011 (3)
Br2	0.0381 (3)	0.0426 (3)	0.0431 (3)	0.00585 (18)	0.00755 (18)	−0.00786 (17)
Br3	0.0605 (3)	0.0296 (2)	0.0590 (3)	0.0028 (2)	0.0003 (2)	0.00449 (19)
Cl1	0.0383 (4)	0.0526 (5)	0.0341 (3)	−0.0033 (3)	0.0054 (3)	0.0011 (3)
Cl2	0.0381 (3)	0.0426 (3)	0.0431 (3)	0.00585 (18)	0.00755 (18)	−0.00786 (17)
Cl3	0.0605 (3)	0.0296 (2)	0.0590 (3)	0.0028 (2)	0.0003 (2)	0.00449 (19)
N1	0.0381 (19)	0.042 (2)	0.0400 (18)	−0.0041 (15)	0.0046 (14)	0.0012 (14)
C1	0.040 (2)	0.040 (2)	0.041 (2)	−0.0041 (17)	0.0006 (17)	−0.0010 (16)
C2	0.047 (3)	0.068 (4)	0.072 (4)	−0.014 (3)	0.005 (2)	0.005 (3)
C3	0.046 (3)	0.120 (7)	0.098 (5)	0.005 (4)	0.001 (3)	−0.006 (5)
C4	0.084 (5)	0.103 (6)	0.082 (5)	0.047 (5)	−0.013 (4)	−0.011 (4)
C5	0.091 (5)	0.064 (4)	0.089 (5)	0.025 (4)	−0.003 (4)	−0.008 (4)
C6	0.065 (4)	0.040 (3)	0.071 (3)	−0.004 (2)	−0.004 (3)	0.005 (2)
C7	0.082 (4)	0.038 (3)	0.090 (5)	−0.001 (3)	0.007 (3)	−0.002 (3)
C8	0.046 (3)	0.093 (5)	0.050 (3)	0.001 (3)	0.017 (2)	−0.001 (3)
C9	0.051 (3)	0.085 (4)	0.048 (3)	0.002 (3)	−0.008 (2)	0.001 (3)

Geometric parameters (Å, º) top

Cd1—Br1	2.5332 (8)	C3—H3	0.93
Cd1—Br3	2.5361 (6)	C4—C5	1.39
Cd1—Br2	2.5782 (5)	C4—H4	0.93
Cd1—Cl1ⁱ	2.7178 (8)	C5—C6	1.39
Cd1—Br1ⁱ	2.7178 (8)	C5—H5	0.93
Cd1—Br2ⁱⁱ	3.1795 (5)	C6—H6	0.93
Br1—Cd1ⁱⁱ	2.7178 (8)	C7—H7A	0.96
N1—C1	1.483 (4)	C7—H7B	0.96
N1—C7	1.499 (6)	C7—H7C	0.96
N1—C8	1.507 (5)	C8—H8A	0.96
N1—C9	1.513 (5)	C8—H8B	0.96
C1—C2	1.39	C8—H8C	0.96
C1—C6	1.39	C9—H9A	0.96
C2—C3	1.39	C9—H9B	0.96
C2—H2	0.93	C9—H9C	0.96
C3—C4	1.39

Br1—Cd1—Br3	117.92 (3)	C4—C3—H3	120.0
Br1—Cd1—Br2	120.74 (3)	C2—C3—H3	120.0
Br3—Cd1—Br2	120.79 (2)	C3—C4—C5	120.0
Br1—Cd1—Cl1ⁱ	89.70 (2)	C3—C4—H4	120.0
Br3—Cd1—Cl1ⁱ	98.00 (2)	C5—C4—H4	120.0
Br2—Cd1—Cl1ⁱ	89.78 (2)	C6—C5—C4	120.0
Br1—Cd1—Br1ⁱ	89.70 (2)	C6—C5—H5	120.0
Br3—Cd1—Br1ⁱ	98.00 (2)	C4—C5—H5	120.0
Br2—Cd1—Br1ⁱ	89.78 (2)	C5—C6—C1	120.0
Cl1ⁱ—Cd1—Br1ⁱ	0.00 (4)	C5—C6—H6	120.0
Br1—Cd1—Br2ⁱⁱ	80.904 (19)	C1—C6—H6	120.0
Br3—Cd1—Br2ⁱⁱ	91.835 (17)	N1—C7—H7A	109.5
Br2—Cd1—Br2ⁱⁱ	89.796 (16)	N1—C7—H7B	109.5
Cl1ⁱ—Cd1—Br2ⁱⁱ	168.79 (2)	H7A—C7—H7B	109.5
Br1ⁱ—Cd1—Br2ⁱⁱ	168.79 (2)	N1—C7—H7C	109.5
Cd1—Br1—Cd1ⁱⁱ	97.81 (3)	H7A—C7—H7C	109.5
C1—N1—C7	112.1 (4)	H7B—C7—H7C	109.5
C1—N1—C8	109.0 (4)	N1—C8—H8A	109.5
C7—N1—C8	109.1 (5)	N1—C8—H8B	109.5
C1—N1—C9	109.5 (4)	H8A—C8—H8B	109.5
C7—N1—C9	107.6 (4)	N1—C8—H8C	109.5
C8—N1—C9	109.4 (4)	H8A—C8—H8C	109.5
C2—C1—C6	120.0	H8B—C8—H8C	109.5
C2—C1—N1	121.3 (3)	N1—C9—H9A	109.5
C6—C1—N1	118.7 (3)	N1—C9—H9B	109.5
C3—C2—C1	120.0	H9A—C9—H9B	109.5
C3—C2—H2	120.0	N1—C9—H9C	109.5
C1—C2—H2	120.0	H9A—C9—H9C	109.5
C4—C3—C2	120.0	H9B—C9—H9C	109.5

Br3—Cd1—Br1—Cd1ⁱⁱ	103.65 (3)	C9—N1—C1—C2	−117.8 (4)
Br2—Cd1—Br1—Cd1ⁱⁱ	−67.89 (3)	C7—N1—C1—C6	−179.0 (4)
Cl1ⁱ—Cd1—Br1—Cd1ⁱⁱ	−157.45 (4)	C8—N1—C1—C6	−58.1 (4)
Br1ⁱ—Cd1—Br1—Cd1ⁱⁱ	−157.45 (4)	C9—N1—C1—C6	61.6 (4)
Br2ⁱⁱ—Cd1—Br1—Cd1ⁱⁱ	16.407 (19)	N1—C1—C2—C3	179.4 (4)
C7—N1—C1—C2	1.6 (5)	N1—C1—C6—C5	−179.5 (3)
C8—N1—C1—C2	122.5 (4)

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

Experimental details

Crystal data
Chemical formula	(C₉H₁₄N)[CdBr₂Cl]
M_r	443.88
Crystal system, space group	Monoclinic, Cc
Temperature (K)	293
a, b, c (Å)	12.9403 (2), 14.7059 (2), 7.3866 (1)
β (°)	95.1590 (8)
V (Å³)	1399.97 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	7.43
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.378, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	6431, 3068, 2966
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.070, 1.06
No. of reflections	3068
No. of parameters	124
No. of restraints	10
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.67, −0.68
Absolute structure	Flack (1983), 1451 Friedel pairs
Absolute structure parameter	0.021 (9)

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Acknowledgements

The authors thank the University of Malaya (RG020/09AFR) for supporting this study.

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Lo, K. M. & Ng, S. W. (2009). Acta Cryst. E65, m560. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). publCIF. In preparation. Google Scholar

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