Bis[4-(dimethyl­amino)pyridinium] tetra­bromidocobaltate(II)

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

doi:10.1107/S1600536809024398

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page m859

doi:10.1107/S1600536809024398

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Bis[4-(dimethylamino)pyridinium] tetrabromidocobaltate(II)

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 24 June 2009; accepted 24 June 2009; online 1 July 2009)

The metal atom in the title salt, (C₇H₁₁N₂)₂[CoBr₄], shows a slightly distorted tetrahedral coordination. The cation forms an N—H⋯Br hydrogen bond to one of the two Br atoms. The Co^II atom lies on a special position of 2 site symmetry.

Related literature

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

Experimental

Crystal data

(C₇H₁₁N₂)₂[CoBr₄]
M_r = 624.93
Monoclinic, C 2/c
a = 10.4020 (2) Å
b = 12.1601 (2) Å
c = 16.9167 (2) Å
β = 104.270 (1)°
V = 2073.76 (6) Å³
Z = 4
Mo Kα radiation
μ = 8.54 mm⁻¹
T = 140 K
0.40 × 0.35 × 0.30 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.131, T_max = 0.184 (expected range = 0.055–0.077)
8405 measured reflections
2386 independent reflections
2228 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.021
wR(F²) = 0.054
S = 1.06
2386 reflections
111 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.75 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯Br1	0.87 (1)	2.71 (2)	3.454 (2)	144 (3)

Data collection: APEX2 (Bruker, 2008 ); cell refinement: SAINT (Bruker, 2008); 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, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809024398/bt2980sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809024398/bt2980Isup2.hkl

checkCIF report

Related literature top

For bis(4-dimethylaminopyridinium) tetrabromidocadmate, see: Lo & Ng (2009).

Experimental top

Cobalt nitrate hexahydrate (0.89 g, 3 mmol) dissolved in a minimum volume of water was mixed with 4-dimethylaminopyridinium hydrobromide perbromide (1.1 g, 3 mmol) dissolved in 50 ml ethanol. The mixture was heated for 1 hour. The red solution slowly turned to blue solution. This was set aside for the growth of crystals.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); 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, 2009).

Figures top

Fig. 1. Anisotropic displacement ellipsoid plot (Barbour, 2001) of the title compound at the 70% probability level. H atoms are drawn as spheres of arbitrary radius.

Bis[4-(dimethylamino)pyridinium] tetrabromidocobaltate(II) top

Crystal data top

(C₇H₁₁N₂)₂[CoBr₄]	F(000) = 1204
M_r = 624.93	D_x = 2.002 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 6526 reflections
a = 10.4020 (2) Å	θ = 2.5–28.4°
b = 12.1601 (2) Å	µ = 8.54 mm⁻¹
c = 16.9167 (2) Å	T = 140 K
β = 104.270 (1)°	Block, blue
V = 2073.76 (6) Å³	0.40 × 0.35 × 0.30 mm
Z = 4

Data collection top

Bruker SMART APEX diffractometer	2386 independent reflections
Radiation source: fine-focus sealed tube	2228 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ω scans	θ_max = 27.5°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→13
T_min = 0.131, T_max = 0.184	k = −15→15
8405 measured reflections	l = −21→21

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.021	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.054	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0282P)² + 3.2278P] where P = (F_o² + 2F_c²)/3
2386 reflections	(Δ/σ)_max = 0.001
111 parameters	Δρ_max = 0.49 e Å⁻³
1 restraint	Δρ_min = −0.75 e Å⁻³

Crystal data top

(C₇H₁₁N₂)₂[CoBr₄]	V = 2073.76 (6) Å³
M_r = 624.93	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 10.4020 (2) Å	µ = 8.54 mm⁻¹
b = 12.1601 (2) Å	T = 140 K
c = 16.9167 (2) Å	0.40 × 0.35 × 0.30 mm
β = 104.270 (1)°

Data collection top

Bruker SMART APEX diffractometer	2386 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2228 reflections with I > 2σ(I)
T_min = 0.131, T_max = 0.184	R_int = 0.024
8405 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.021	1 restraint
wR(F²) = 0.054	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.49 e Å⁻³
2386 reflections	Δρ_min = −0.75 e Å⁻³
111 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	U_iso*/U_eq
Br1	0.66045 (2)	0.777934 (17)	0.345907 (13)	0.02380 (7)
Br2	0.36829 (2)	0.555780 (17)	0.314578 (12)	0.02431 (7)
Co1	0.5000	0.67093 (3)	0.2500	0.01636 (9)
N1	0.7776 (2)	0.51482 (16)	0.39578 (13)	0.0268 (4)
H1	0.746 (3)	0.5670 (19)	0.3610 (16)	0.044 (9)*
N2	0.94584 (19)	0.27718 (16)	0.56095 (11)	0.0238 (4)
C1	0.8017 (2)	0.53686 (18)	0.47578 (15)	0.0267 (5)
H1A	0.7809	0.6076	0.4929	0.032*
C2	0.8555 (2)	0.46012 (18)	0.53283 (14)	0.0235 (4)
H2	0.8709	0.4770	0.5892	0.028*
C3	0.88849 (19)	0.35447 (17)	0.50763 (12)	0.0183 (4)
C4	0.8593 (2)	0.33468 (17)	0.42225 (12)	0.0194 (4)
H4	0.8782	0.2650	0.4024	0.023*
C5	0.8047 (2)	0.41504 (19)	0.36914 (13)	0.0243 (4)
H5	0.7851	0.4009	0.3122	0.029*
C6	0.9690 (3)	0.2937 (3)	0.64888 (14)	0.0364 (6)
H6A	0.8871	0.3194	0.6616	0.055*
H6B	1.0390	0.3488	0.6668	0.055*
H6C	0.9966	0.2241	0.6772	0.055*
C7	0.9865 (2)	0.17184 (19)	0.53287 (15)	0.0289 (5)
H7A	1.0364	0.1850	0.4916	0.043*
H7B	0.9076	0.1277	0.5090	0.043*
H7C	1.0426	0.1323	0.5792	0.043*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.01960 (12)	0.02113 (11)	0.02904 (12)	−0.00386 (8)	0.00292 (9)	−0.00728 (8)
Br2	0.03047 (13)	0.02293 (12)	0.02059 (11)	−0.00884 (8)	0.00829 (9)	0.00109 (7)
Co1	0.01504 (19)	0.01626 (17)	0.01751 (18)	0.000	0.00345 (14)	0.000
N1	0.0223 (10)	0.0229 (9)	0.0346 (10)	0.0040 (7)	0.0060 (8)	0.0059 (8)
N2	0.0206 (9)	0.0335 (10)	0.0166 (8)	0.0013 (7)	0.0029 (7)	0.0029 (7)
C1	0.0198 (11)	0.0233 (10)	0.0391 (13)	−0.0010 (8)	0.0110 (9)	−0.0074 (9)
C2	0.0178 (10)	0.0300 (11)	0.0245 (10)	−0.0046 (8)	0.0085 (8)	−0.0094 (8)
C3	0.0112 (9)	0.0249 (10)	0.0190 (9)	−0.0028 (7)	0.0042 (7)	−0.0007 (8)
C4	0.0170 (10)	0.0218 (9)	0.0191 (9)	0.0013 (8)	0.0040 (7)	−0.0012 (7)
C5	0.0214 (10)	0.0290 (11)	0.0212 (10)	0.0004 (9)	0.0030 (8)	0.0005 (8)
C6	0.0301 (13)	0.0608 (17)	0.0166 (10)	−0.0005 (12)	0.0027 (9)	0.0048 (10)
C7	0.0251 (12)	0.0268 (11)	0.0320 (12)	0.0034 (9)	0.0019 (9)	0.0071 (9)

Geometric parameters (Å, º) top

Br1—Co1	2.4033 (3)	C2—C3	1.422 (3)
Br2—Co1	2.4019 (3)	C2—H2	0.9500
Co1—Br2ⁱ	2.4019 (3)	C3—C4	1.421 (3)
Co1—Br1ⁱ	2.4033 (3)	C4—C5	1.354 (3)
N1—C1	1.341 (3)	C4—H4	0.9500
N1—C5	1.348 (3)	C5—H5	0.9500
N1—H1	0.872 (10)	C6—H6A	0.9800
N2—C3	1.337 (3)	C6—H6B	0.9800
N2—C6	1.461 (3)	C6—H6C	0.9800
N2—C7	1.464 (3)	C7—H7A	0.9800
C1—C2	1.360 (3)	C7—H7B	0.9800
C1—H1A	0.9500	C7—H7C	0.9800

Br2—Co1—Br2ⁱ	108.678 (18)	C4—C3—C2	116.79 (19)
Br2—Co1—Br1	112.808 (7)	C5—C4—C3	120.1 (2)
Br2ⁱ—Co1—Br1	104.098 (8)	C5—C4—H4	119.9
Br2—Co1—Br1ⁱ	104.099 (8)	C3—C4—H4	119.9
Br2ⁱ—Co1—Br1ⁱ	112.808 (7)	N1—C5—C4	121.0 (2)
Br1—Co1—Br1ⁱ	114.444 (18)	N1—C5—H5	119.5
C1—N1—C5	121.0 (2)	C4—C5—H5	119.5
C1—N1—H1	119 (2)	N2—C6—H6A	109.5
C5—N1—H1	120 (2)	N2—C6—H6B	109.5
C3—N2—C6	121.6 (2)	H6A—C6—H6B	109.5
C3—N2—C7	120.84 (18)	N2—C6—H6C	109.5
C6—N2—C7	117.52 (19)	H6A—C6—H6C	109.5
N1—C1—C2	121.4 (2)	H6B—C6—H6C	109.5
N1—C1—H1A	119.3	N2—C7—H7A	109.5
C2—C1—H1A	119.3	N2—C7—H7B	109.5
C1—C2—C3	119.6 (2)	H7A—C7—H7B	109.5
C1—C2—H2	120.2	N2—C7—H7C	109.5
C3—C2—H2	120.2	H7A—C7—H7C	109.5
N2—C3—C4	120.97 (19)	H7B—C7—H7C	109.5
N2—C3—C2	122.24 (19)

C5—N1—C1—C2	0.7 (3)	C1—C2—C3—N2	177.6 (2)
N1—C1—C2—C3	0.7 (3)	C1—C2—C3—C4	−1.6 (3)
C6—N2—C3—C4	−176.2 (2)	N2—C3—C4—C5	−178.1 (2)
C7—N2—C3—C4	3.1 (3)	C2—C3—C4—C5	1.0 (3)
C6—N2—C3—C2	4.7 (3)	C1—N1—C5—C4	−1.2 (3)
C7—N2—C3—C2	−176.0 (2)	C3—C4—C5—N1	0.3 (3)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Br1	0.87 (1)	2.71 (2)	3.454 (2)	144 (3)

Experimental details

Crystal data
Chemical formula	(C₇H₁₁N₂)₂[CoBr₄]
M_r	624.93
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	140
a, b, c (Å)	10.4020 (2), 12.1601 (2), 16.9167 (2)
β (°)	104.270 (1)
V (Å³)	2073.76 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	8.54
Crystal size (mm)	0.40 × 0.35 × 0.30

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.131, 0.184
No. of measured, independent and observed [I > 2σ(I)] reflections	8405, 2386, 2228
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.021, 0.054, 1.06
No. of reflections	2386
No. of parameters	111
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.75

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Br1	0.87 (1)	2.71 (2)	3.454 (2)	144 (3)

Acknowledgements

We 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 (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. 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. (2009). publCIF. In preparation. Google Scholar