4-(Dimethyl-amino)pyridinium tri-bromido-{3-[bromo/hydro-(0.9/0.1)]-4-(dimethyl-amino)pyridine-κN}cobaltate(II).

The reaction of a cobalt(II) salt with 4-(dimethyl-amino)pyridinium hydro-bromide perbromide yielded the title compound, (C(7)H(11)N(2))[CoBr(3)(C(7)H(9.1)Br(0.9)N(2))]. In the anion, the Co(II) atom is coordinated in a distorted tetra-hedral geometry by three Br atoms and the pyridine N atom of a bromine-substituted 4-(dimethyl-amino)pyridine mol-ecule, whose formation probably results from an incomplete substitution (90%) catalysed by the Co(II) ion. One of the three bromine atoms bonded to the metal is disordered over two sites in a 0.9:0.1 ratio. An N-H⋯Br hydrogen bond connects the cation and anion.

Related literature

For bis­(4-(dimethyl­amino)pyridinium) tetra­bromidocobaltate, see: Lo & Ng (2009 ▶). For other trihalocobaltate(II) anions having a pyridine-type donor ligand, see: Bogdanović et al. (2001 ▶); Crane et al. (2004 ▶); Divjaković et al. (1982 ▶); Hahn et al. (1997 ▶); Mueller-Westerhoff et al. (1996 ▶); Sumner & Steinmetz (1985 ▶).

Experimental

Crystal data

(C7H11N2)[CoBr3(C7H9.1Br0.9N2)]

M = 615.02

Triclinic,

a = 8.3768 (2) Å

b = 10.2622 (2) Å

c = 12.4691 (3) Å

α = 99.028 (2)°

β = 98.927 (1)°

γ = 106.933 (2)°

V = 989.57 (4) Å3

Z = 2

Mo Kα radiation

μ = 8.74 mm−1

T = 150 K

0.40 × 0.20 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.128, T max = 0.475 (expected range = 0.112–0.417)

7974 measured reflections

4451 independent reflections

3019 reflections with I > 2σ(I)

R int = 0.053

Refinement

R[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 0.130

S = 0.97

4451 reflections

221 parameters

7 restraints

H-atom parameters constrained

Δρmax = 1.29 e Å−3

Δρmin = −1.04 e Å−3

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: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809027913/hy2210sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809027913/hy2210Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

(C7H11N2)[CoBr3(C7H9.1Br0.9N2)]	Z = 2
Mr = 615.02	F(000) = 591.2
Triclinic, P1	Dx = 2.064 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.3768 (2) Å	Cell parameters from 6987 reflections
b = 10.2622 (2) Å	θ = 2.4–28.3°
c = 12.4691 (3) Å	µ = 8.74 mm−1
α = 99.028 (2)°	T = 150 K
β = 98.927 (1)°	Block, brown
γ = 106.933 (2)°	0.40 × 0.20 × 0.10 mm
V = 989.57 (4) Å3

Bruker APEXII CCD diffractometer	4451 independent reflections
Radiation source: fine-focus sealed tube	3019 reflections with I > 2σ(I)
graphite	Rint = 0.053
φ and ω scans	θmax = 27.5°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
Tmin = 0.128, Tmax = 0.475	k = −12→13
7974 measured reflections	l = −16→16

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.130	H-atom parameters constrained
S = 0.97	w = 1/[σ2(Fo2) + (0.0634P)2] where P = (Fo2 + 2Fc2)/3
4451 reflections	(Δ/σ)max = 0.001
221 parameters	Δρmax = 1.29 e Å−3
7 restraints	Δρmin = −1.04 e Å−3

	x	y	z	Uiso*/Ueq	Occ. (<1)
Br1	0.26488 (9)	0.68358 (8)	0.54136 (5)	0.0375 (2)
Br2	0.64945 (8)	0.59464 (7)	0.69989 (5)	0.03080 (18)
Br3	0.49021 (18)	0.89737 (12)	0.84679 (11)	0.0315 (3)	0.90
Br3'	0.531 (2)	0.8775 (13)	0.8695 (11)	0.068 (5)	0.10
Br4	0.30233 (9)	0.25573 (8)	0.96716 (6)	0.0350 (2)	0.90
Co1	0.41492 (10)	0.67837 (9)	0.72097 (7)	0.0271 (2)
N1	0.2478 (6)	0.5344 (5)	0.7796 (4)	0.0280 (12)
N2	−0.0965 (6)	0.2792 (5)	0.9321 (4)	0.0276 (12)
N3	0.6361 (7)	0.7246 (6)	0.4462 (5)	0.0414 (15)
H3	0.5580	0.6723	0.4751	0.050*
N4	1.0006 (7)	0.9742 (6)	0.3157 (4)	0.0318 (12)
C1	0.2977 (8)	0.4510 (6)	0.8403 (5)	0.0267 (13)
H1	0.4135	0.4540	0.8492	0.032*
C2	0.1936 (7)	0.3618 (6)	0.8904 (5)	0.0226 (12)
H2'	0.2368	0.3026	0.9293	0.027*	0.10
C3	0.0191 (7)	0.3572 (6)	0.8846 (5)	0.0248 (13)
C4	−0.0282 (8)	0.4425 (7)	0.8152 (5)	0.0320 (15)
H4	−0.1438	0.4404	0.8015	0.038*
C5	0.0825 (8)	0.5267 (7)	0.7677 (6)	0.0338 (15)
H5	0.0420	0.5830	0.7239	0.041*
C6	−0.0620 (10)	0.1971 (10)	1.0125 (8)	0.063 (3)
H6A	0.0449	0.2503	1.0660	0.094*
H6B	−0.0516	0.1101	0.9737	0.094*
H6C	−0.1559	0.1756	1.0518	0.094*
C7	−0.2699 (8)	0.2868 (7)	0.9146 (6)	0.0377 (16)
H7A	−0.3213	0.2596	0.8349	0.057*
H7B	−0.2661	0.3824	0.9433	0.057*
H7C	−0.3385	0.2234	0.9537	0.057*
C8	0.7904 (10)	0.7112 (7)	0.4577 (5)	0.0362 (16)
H8	0.8148	0.6441	0.4962	0.043*
C9	0.9138 (9)	0.7919 (7)	0.4155 (5)	0.0320 (15)
H9	1.0236	0.7811	0.4254	0.038*
C10	0.8813 (7)	0.8921 (6)	0.3568 (4)	0.0240 (13)
C11	0.7136 (9)	0.9012 (7)	0.3454 (5)	0.0360 (16)
H11	0.6826	0.9655	0.3062	0.043*
C12	0.5987 (9)	0.8172 (8)	0.3908 (6)	0.0405 (17)
H12	0.4871	0.8243	0.3831	0.049*
C13	0.9613 (11)	1.0765 (8)	0.2567 (6)	0.051 (2)
H13A	0.9162	1.1366	0.3038	0.076*
H13B	0.8758	1.0282	0.1881	0.076*
H13C	1.0654	1.1334	0.2384	0.076*
C14	1.1733 (9)	0.9648 (8)	0.3293 (6)	0.048 (2)
H14A	1.2214	0.9768	0.4084	0.073*
H14B	1.2452	1.0380	0.2994	0.073*
H14C	1.1689	0.8733	0.2893	0.073*

	U11	U22	U33	U12	U13	U23
Br1	0.0327 (4)	0.0541 (5)	0.0345 (4)	0.0205 (3)	0.0109 (3)	0.0188 (3)
Br2	0.0220 (3)	0.0369 (4)	0.0365 (4)	0.0102 (3)	0.0092 (3)	0.0119 (3)
Br3	0.0321 (5)	0.0292 (5)	0.0328 (5)	0.0089 (4)	0.0070 (3)	0.0071 (4)
Br3'	0.076 (9)	0.060 (7)	0.057 (7)	0.001 (5)	0.034 (6)	0.001 (5)
Br4	0.0253 (4)	0.0469 (5)	0.0403 (4)	0.0144 (3)	0.0087 (3)	0.0237 (4)
Co1	0.0236 (5)	0.0288 (5)	0.0310 (5)	0.0068 (4)	0.0110 (3)	0.0108 (4)
N1	0.025 (3)	0.030 (3)	0.031 (3)	0.008 (2)	0.009 (2)	0.011 (2)
N2	0.022 (3)	0.031 (3)	0.029 (3)	0.003 (2)	0.010 (2)	0.013 (2)
N3	0.033 (3)	0.047 (4)	0.034 (3)	−0.005 (3)	0.011 (3)	0.007 (3)
N4	0.026 (3)	0.038 (3)	0.026 (3)	0.002 (2)	0.003 (2)	0.010 (2)
C1	0.017 (3)	0.033 (4)	0.028 (3)	0.007 (3)	0.007 (2)	0.002 (3)
C2	0.023 (3)	0.023 (3)	0.025 (3)	0.009 (2)	0.008 (2)	0.010 (2)
C3	0.020 (3)	0.025 (3)	0.024 (3)	0.000 (2)	0.006 (2)	0.000 (2)
C4	0.023 (3)	0.035 (4)	0.039 (4)	0.007 (3)	0.004 (3)	0.015 (3)
C5	0.024 (3)	0.039 (4)	0.046 (4)	0.014 (3)	0.011 (3)	0.020 (3)
C6	0.036 (5)	0.085 (7)	0.083 (6)	0.017 (5)	0.021 (4)	0.058 (5)
C7	0.024 (4)	0.042 (4)	0.049 (4)	0.008 (3)	0.017 (3)	0.010 (3)
C8	0.055 (5)	0.029 (4)	0.023 (3)	0.011 (3)	0.007 (3)	0.007 (3)
C9	0.036 (4)	0.031 (4)	0.027 (3)	0.012 (3)	0.001 (3)	0.002 (3)
C10	0.027 (3)	0.025 (3)	0.015 (3)	0.003 (3)	0.002 (2)	0.003 (2)
C11	0.033 (4)	0.045 (4)	0.030 (4)	0.014 (3)	0.002 (3)	0.013 (3)
C12	0.023 (4)	0.059 (5)	0.033 (4)	0.007 (3)	0.002 (3)	0.008 (3)
C13	0.060 (5)	0.035 (4)	0.050 (5)	−0.001 (4)	0.008 (4)	0.022 (4)
C14	0.031 (4)	0.056 (5)	0.045 (5)	−0.003 (4)	0.013 (3)	−0.002 (4)

Co1—Br1	2.4086 (11)	C4—H4	0.9500
Co1—Br2	2.3958 (10)	C5—H5	0.9500
Co1—Br3	2.3814 (13)	C6—H6A	0.9800
Co1—Br3'	2.376 (9)	C6—H6B	0.9800
Br4—C2	1.888 (6)	C6—H6C	0.9800
Co1—N1	2.032 (5)	C7—H7A	0.9800
N1—C1	1.340 (8)	C7—H7B	0.9800
N1—C5	1.347 (8)	C7—H7C	0.9800
N2—C3	1.343 (7)	C8—C9	1.356 (9)
N2—C6	1.454 (9)	C8—H8	0.9500
N2—C7	1.461 (8)	C9—C10	1.416 (8)
N3—C8	1.328 (9)	C9—H9	0.9500
N3—C12	1.338 (9)	C10—C11	1.421 (9)
N3—H3	0.8800	C11—C12	1.353 (9)
N4—C10	1.333 (7)	C11—H11	0.9500
N4—C13	1.456 (9)	C12—H12	0.9500
N4—C14	1.463 (9)	C13—H13A	0.9800
C1—C2	1.368 (8)	C13—H13B	0.9800
C1—H1	0.9500	C13—H13C	0.9800
C2—C3	1.439 (8)	C14—H14A	0.9800
C2—H2'	0.9500	C14—H14B	0.9800
C3—C4	1.415 (9)	C14—H14C	0.9800
C4—C5	1.350 (9)
N1—Co1—Br3'	105.5 (5)	N2—C6—H6A	109.5
N1—Co1—Br3	107.98 (15)	N2—C6—H6B	109.5
Br3'—Co1—Br3	12.5 (4)	H6A—C6—H6B	109.5
N1—Co1—Br2	106.97 (14)	N2—C6—H6C	109.5
Br3'—Co1—Br2	104.7 (4)	H6A—C6—H6C	109.5
Br3—Co1—Br2	114.67 (5)	H6B—C6—H6C	109.5
N1—Co1—Br1	105.94 (15)	N2—C7—H7A	109.5
Br3'—Co1—Br1	123.1 (4)	N2—C7—H7B	109.5
Br3—Co1—Br1	111.17 (5)	H7A—C7—H7B	109.5
Br2—Co1—Br1	109.64 (4)	N2—C7—H7C	109.5
C1—N1—C5	116.2 (5)	H7A—C7—H7C	109.5
C1—N1—Co1	122.3 (4)	H7B—C7—H7C	109.5
C5—N1—Co1	121.2 (4)	N3—C8—C9	121.1 (6)
C3—N2—C6	125.9 (5)	N3—C8—H8	119.5
C3—N2—C7	119.4 (5)	C9—C8—H8	119.5
C6—N2—C7	114.3 (5)	C8—C9—C10	120.9 (6)
C8—N3—C12	120.3 (6)	C8—C9—H9	119.5
C8—N3—H3	119.9	C10—C9—H9	119.5
C12—N3—H3	119.9	N4—C10—C9	122.3 (6)
C10—N4—C13	120.2 (6)	N4—C10—C11	121.8 (6)
C10—N4—C14	121.2 (6)	C9—C10—C11	115.9 (6)
C13—N4—C14	118.6 (6)	C12—C11—C10	119.2 (6)
N1—C1—C2	124.6 (5)	C12—C11—H11	120.4
N1—C1—H1	117.7	C10—C11—H11	120.4
C2—C1—H1	117.7	N3—C12—C11	122.6 (6)
C1—C2—C3	120.5 (5)	N3—C12—H12	118.7
C1—C2—Br4	114.0 (4)	C11—C12—H12	118.7
C3—C2—Br4	125.5 (4)	N4—C13—H13A	109.5
C1—C2—H2'	119.8	N4—C13—H13B	109.5
C3—C2—H2'	119.8	H13A—C13—H13B	109.5
N2—C3—C4	120.3 (5)	N4—C13—H13C	109.5
N2—C3—C2	127.4 (6)	H13A—C13—H13C	109.5
C4—C3—C2	112.2 (5)	H13B—C13—H13C	109.5
C5—C4—C3	123.4 (6)	N4—C14—H14A	109.5
C5—C4—H4	118.3	N4—C14—H14B	109.5
C3—C4—H4	118.3	H14A—C14—H14B	109.5
N1—C5—C4	122.9 (6)	N4—C14—H14C	109.5
N1—C5—H5	118.6	H14A—C14—H14C	109.5
C4—C5—H5	118.6	H14B—C14—H14C	109.5
Br3'—Co1—N1—C1	−83.8 (6)	Br4—C2—C3—C4	−176.4 (5)
Br3—Co1—N1—C1	−96.6 (5)	N2—C3—C4—C5	177.9 (6)
Br2—Co1—N1—C1	27.3 (5)	C2—C3—C4—C5	−5.0 (9)
Br1—Co1—N1—C1	144.2 (4)	C1—N1—C5—C4	1.3 (9)
Br3'—Co1—N1—C5	90.1 (7)	Co1—N1—C5—C4	−173.0 (5)
Br3—Co1—N1—C5	77.3 (5)	C3—C4—C5—N1	1.8 (11)
Br2—Co1—N1—C5	−158.8 (5)	C12—N3—C8—C9	1.0 (10)
Br1—Co1—N1—C5	−41.9 (5)	N3—C8—C9—C10	−0.6 (10)
C5—N1—C1—C2	−0.6 (9)	C13—N4—C10—C9	−179.5 (6)
Co1—N1—C1—C2	173.6 (5)	C14—N4—C10—C9	0.0 (9)
N1—C1—C2—C3	−3.0 (9)	C13—N4—C10—C11	−0.2 (9)
N1—C1—C2—Br4	178.6 (5)	C14—N4—C10—C11	179.3 (6)
C6—N2—C3—C4	−174.2 (7)	C8—C9—C10—N4	179.1 (6)
C7—N2—C3—C4	−2.0 (9)	C8—C9—C10—C11	−0.3 (9)
C6—N2—C3—C2	9.1 (10)	N4—C10—C11—C12	−178.6 (6)
C7—N2—C3—C2	−178.7 (6)	C9—C10—C11—C12	0.7 (9)
C1—C2—C3—N2	−177.7 (6)	C8—N3—C12—C11	−0.5 (10)
Br4—C2—C3—N2	0.5 (9)	C10—C11—C12—N3	−0.3 (11)
C1—C2—C3—C4	5.4 (8)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···Br1	0.88	2.74	3.434 (6)	137

Table 1

Selected bond lengths (Å)

Co1—Br1	2.4086 (11)
Co1—Br2	2.3958 (10)
Co1—Br3	2.3814 (13)
Co1—Br3′	2.376 (9)
Co1—N1	2.032 (5)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯Br1	0.88	2.74	3.434 (6)	137