cis-Bromido(methyl-amine)-bis-(propane-1,3-di-amine)-cobalt(III) dibromide.

In the title compound, [CoBr(CH5N)(C3H10N2)2]Br2, the cobalt(III) ion has a distorted octa-hedral coordination environment and is surrounded by four N atoms in the equatorial plane, with an additional N atom and the Br atom occupying the axial positions. In the crystal, the complex cation and the two counter anions are linked via N-H⋯Br and C-H⋯Br hydrogen bonds, forming a three-dimensional network.

Related literature

In the synthesis of cobalt(III) complexes, substituting an amino ligand for the MeNH2 moiety can yield complexes of similar structure, but with differing electron-transfer rates, see: Anbalagan (2011 ▶); Anbalagan et al. (2011 ▶). For the biological activity and potential applications of mixed-ligand cobalt(III) complexes, see: Arslan et al. (2009 ▶); Delehanty et al. (2008 ▶); Sayed et al. (1992 ▶); Teicher et al. (1990 ▶); Chang et al. (2010 ▶). For related structures, see: Anbalagan et al. (2009 ▶); Lee et al. (2007 ▶); Ramesh et al. (2008 ▶); Ravichandran et al. (2009 ▶). For Co—N bond lengths, see: Maheshwaran et al. (2013 ▶).

Experimental

Crystal data

[CoBr(CH5N)(C3H10N2)2]Br2

M = 477.95

Monoclinic,

a = 13.4418 (2) Å

b = 8.3088 (1) Å

c = 15.1538 (2) Å

β = 110.61 (2)°

V = 1584.16 (4) Å3

Z = 4

Mo Kα radiation

μ = 8.64 mm−1

T = 293 K

0.25 × 0.22 × 0.19 mm

Data collection

Oxford Diffraction Xcalibur Eos diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T min = 0.133, T max = 0.194

6000 measured reflections

2784 independent reflections

1701 reflections with I > 2σ(I)

R int = 0.042

Refinement

R[F 2 > 2σ(F 2)] = 0.073

wR(F 2) = 0.238

S = 1.07

2784 reflections

146 parameters

H-atom parameters constrained

Δρmax = 1.50 e Å−3

Δρmin = −2.69 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2009 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681301516X/rn2115sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681301516X/rn2115Isup2.hkl

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

[CoBr(CH5N)(C3H10N2)2]Br2	F(000) = 936
Mr = 477.95	Dx = 2.004 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybc	Cell parameters from 2784 reflections
a = 13.4418 (2) Å	θ = 2.8–25.0°
b = 8.3088 (1) Å	µ = 8.64 mm−1
c = 15.1538 (2) Å	T = 293 K
β = 110.61 (2)°	Block, pink
V = 1584.16 (4) Å3	0.25 × 0.22 × 0.19 mm
Z = 4

Oxford Diffraction Xcalibur Eos diffractometer	2784 independent reflections
Radiation source: fine-focus sealed tube	1701 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.042
ω and φ scans	θmax = 25.0°, θmin = 2.8°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	h = −15→15
Tmin = 0.133, Tmax = 0.194	k = −9→9
6000 measured reflections	l = −18→18

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)] = 0.073	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.238	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.1435P)2] where P = (Fo2 + 2Fc2)/3
2784 reflections	(Δ/σ)max < 0.001
146 parameters	Δρmax = 1.50 e Å−3
0 restraints	Δρmin = −2.69 e Å−3

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.

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 > 2sigma(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.

	x	y	z	Uiso*/Ueq
C1	0.7910 (12)	−0.1257 (17)	0.3267 (9)	0.045 (4)
H1A	0.7559	−0.2250	0.3325	0.054*
H1B	0.8575	−0.1541	0.3190	0.054*
C2	0.7216 (13)	−0.038 (2)	0.2389 (10)	0.056 (4)
H2A	0.7566	0.0620	0.2334	0.067*
H2B	0.7157	−0.1030	0.1842	0.067*
C3	0.6107 (12)	0.0016 (18)	0.2366 (10)	0.050 (4)
H3A	0.5682	0.0407	0.1744	0.060*
H3B	0.5774	−0.0953	0.2488	0.060*
C4	0.8425 (12)	0.4274 (18)	0.4830 (12)	0.057 (4)
H4A	0.7892	0.4891	0.4979	0.068*
H4B	0.8831	0.5004	0.4588	0.068*
C5	0.9195 (13)	0.336 (2)	0.5754 (11)	0.058 (5)
H5A	0.9642	0.2605	0.5579	0.070*
H5B	0.9651	0.4139	0.6189	0.070*
C6	0.8508 (14)	0.245 (2)	0.6238 (11)	0.066 (5)
H6A	0.8962	0.2131	0.6866	0.079*
H6B	0.7977	0.3187	0.6305	0.079*
C7	0.6526 (9)	−0.2195 (12)	0.4742 (10)	0.032 (3)
H7A	0.6497	−0.2628	0.4146	0.047*
H7B	0.6053	−0.2787	0.4970	0.047*
H7C	0.7238	−0.2280	0.5186	0.047*
N1	0.6135 (8)	0.1214 (12)	0.3058 (7)	0.030 (2)
H1C	0.5473	0.1264	0.3074	0.036*
H1D	0.6251	0.2161	0.2822	0.036*
N2	0.8141 (7)	−0.0346 (11)	0.4126 (7)	0.027 (2)
H2C	0.8726	0.0238	0.4188	0.033*
H2D	0.8332	−0.1067	0.4599	0.033*
N3	0.7916 (8)	0.3030 (13)	0.4129 (8)	0.036 (3)
H3C	0.8430	0.2608	0.3947	0.043*
H3D	0.7466	0.3545	0.3623	0.043*
N4	0.7983 (7)	0.1060 (13)	0.5734 (7)	0.032 (3)
H4C	0.7564	0.0679	0.6037	0.038*
H4D	0.8488	0.0312	0.5795	0.038*
N5	0.6215 (8)	−0.0543 (14)	0.4628 (8)	0.040 (3)
H5C	0.6091	−0.0255	0.5152	0.047*
H5D	0.5584	−0.0503	0.4151	0.047*
Co1	0.71072 (12)	0.11628 (19)	0.43861 (10)	0.0226 (5)
Br1	0.59629 (16)	0.3048 (2)	0.47361 (15)	0.0770 (7)
Br2	0.63730 (10)	0.49197 (15)	0.20461 (9)	0.0347 (4)
Br3	1.01970 (11)	0.19252 (18)	0.37939 (10)	0.0427 (5)

	U11	U22	U33	U12	U13	U23
C1	0.066 (10)	0.044 (9)	0.038 (8)	−0.001 (8)	0.033 (8)	−0.007 (7)
C2	0.068 (11)	0.070 (11)	0.026 (8)	−0.016 (9)	0.014 (8)	−0.020 (8)
C3	0.047 (9)	0.066 (11)	0.023 (7)	−0.011 (8)	−0.003 (7)	0.002 (8)
C4	0.054 (10)	0.040 (9)	0.068 (12)	−0.025 (8)	0.012 (9)	−0.021 (9)
C5	0.045 (9)	0.076 (12)	0.035 (9)	−0.002 (9)	−0.009 (8)	−0.009 (9)
C6	0.076 (12)	0.074 (11)	0.024 (8)	0.019 (10)	−0.012 (8)	−0.017 (8)
C7	0.021 (6)	0.008 (6)	0.074 (10)	−0.004 (5)	0.028 (7)	0.001 (6)
N1	0.026 (6)	0.036 (6)	0.025 (6)	0.004 (5)	0.004 (5)	0.012 (5)
N2	0.027 (6)	0.026 (5)	0.022 (6)	−0.008 (5)	0.001 (5)	−0.011 (5)
N3	0.023 (5)	0.043 (6)	0.030 (6)	0.006 (5)	−0.006 (5)	0.003 (6)
N4	0.023 (5)	0.050 (7)	0.020 (5)	0.003 (5)	0.006 (4)	−0.004 (5)
N5	0.025 (6)	0.062 (8)	0.030 (6)	−0.009 (6)	0.008 (5)	0.005 (6)
Co1	0.0207 (9)	0.0284 (9)	0.0152 (8)	0.0014 (7)	0.0021 (7)	0.0000 (7)
Br1	0.0685 (13)	0.0820 (14)	0.0784 (15)	0.0148 (10)	0.0233 (11)	0.0000 (11)
Br2	0.0320 (8)	0.0419 (8)	0.0268 (7)	0.0045 (6)	0.0061 (6)	0.0049 (6)
Br3	0.0342 (8)	0.0514 (10)	0.0363 (9)	0.0058 (7)	0.0046 (6)	0.0074 (7)

C1—N2	1.442 (15)	C7—N5	1.427 (15)
C1—C2	1.52 (2)	C7—H7A	0.9600
C1—H1A	0.9700	C7—H7B	0.9600
C1—H1B	0.9700	C7—H7C	0.9600
C2—C3	1.51 (2)	N1—Co1	1.977 (9)
C2—H2A	0.9700	N1—H1C	0.9000
C2—H2B	0.9700	N1—H1D	0.9000
C3—N1	1.436 (17)	N2—Co1	2.012 (9)
C3—H3A	0.9700	N2—H2C	0.9000
C3—H3B	0.9700	N2—H2D	0.9000
C4—N3	1.467 (16)	N3—Co1	2.010 (11)
C4—C5	1.61 (2)	N3—H3C	0.9000
C4—H4A	0.9700	N3—H3D	0.9000
C4—H4B	0.9700	N4—Co1	1.967 (9)
C5—C6	1.56 (2)	N4—H4C	0.9000
C5—H5A	0.9700	N4—H4D	0.9000
C5—H5B	0.9700	N5—Co1	1.973 (10)
C6—N4	1.429 (18)	N5—H5C	0.9000
C6—H6A	0.9700	N5—H5D	0.9000
C6—H6B	0.9700	Co1—Br1	2.383 (2)
N2—C1—C2	114.2 (12)	Co1—N1—H1C	106.2
N2—C1—H1A	108.7	C3—N1—H1D	106.2
C2—C1—H1A	108.7	Co1—N1—H1D	106.2
N2—C1—H1B	108.7	H1C—N1—H1D	106.4
C2—C1—H1B	108.7	C1—N2—Co1	124.1 (8)
H1A—C1—H1B	107.6	C1—N2—H2C	106.3
C3—C2—C1	114.9 (12)	Co1—N2—H2C	106.3
C3—C2—H2A	108.6	C1—N2—H2D	106.3
C1—C2—H2A	108.6	Co1—N2—H2D	106.3
C3—C2—H2B	108.6	H2C—N2—H2D	106.4
C1—C2—H2B	108.6	C4—N3—Co1	123.3 (9)
H2A—C2—H2B	107.5	C4—N3—H3C	106.5
N1—C3—C2	111.1 (11)	Co1—N3—H3C	106.5
N1—C3—H3A	109.4	C4—N3—H3D	106.5
C2—C3—H3A	109.4	Co1—N3—H3D	106.5
N1—C3—H3B	109.4	H3C—N3—H3D	106.5
C2—C3—H3B	109.4	C6—N4—Co1	121.5 (9)
H3A—C3—H3B	108.0	C6—N4—H4C	107.0
N3—C4—C5	107.0 (12)	Co1—N4—H4C	107.0
N3—C4—H4A	110.3	C6—N4—H4D	107.0
C5—C4—H4A	110.3	Co1—N4—H4D	107.0
N3—C4—H4B	110.3	H4C—N4—H4D	106.7
C5—C4—H4B	110.3	C7—N5—Co1	122.8 (8)
H4A—C4—H4B	108.6	C7—N5—H5C	106.6
C6—C5—C4	109.3 (13)	Co1—N5—H5C	106.6
C6—C5—H5A	109.8	C7—N5—H5D	106.6
C4—C5—H5A	109.8	Co1—N5—H5D	106.6
C6—C5—H5B	109.8	H5C—N5—H5D	106.6
C4—C5—H5B	109.8	N4—Co1—N5	87.5 (4)
H5A—C5—H5B	108.3	N4—Co1—N1	175.7 (4)
N4—C6—C5	113.8 (12)	N5—Co1—N1	88.7 (4)
N4—C6—H6A	108.8	N4—Co1—N3	93.9 (4)
C5—C6—H6A	108.8	N5—Co1—N3	175.2 (4)
N4—C6—H6B	108.8	N1—Co1—N3	89.7 (4)
C5—C6—H6B	108.8	N4—Co1—N2	88.5 (4)
H6A—C6—H6B	107.7	N5—Co1—N2	95.5 (4)
N5—C7—H7A	109.5	N1—Co1—N2	93.9 (4)
N5—C7—H7B	109.5	N3—Co1—N2	89.1 (4)
H7A—C7—H7B	109.5	N4—Co1—Br1	89.7 (3)
N5—C7—H7C	109.5	N5—Co1—Br1	87.1 (3)
H7A—C7—H7C	109.5	N1—Co1—Br1	88.0 (3)
H7B—C7—H7C	109.5	N3—Co1—Br1	88.4 (3)
C3—N1—Co1	124.5 (8)	N2—Co1—Br1	176.8 (3)
C3—N1—H1C	106.2
N2—C1—C2—C3	−63.7 (17)	C7—N5—Co1—Br1	−167.0 (11)
C1—C2—C3—N1	68.7 (16)	C3—N1—Co1—N4	−104 (6)
N3—C4—C5—C6	−70.6 (16)	C3—N1—Co1—N5	−75.2 (11)
C4—C5—C6—N4	72.2 (17)	C3—N1—Co1—N3	109.4 (11)
C2—C3—N1—Co1	−47.0 (15)	C3—N1—Co1—N2	20.3 (11)
C2—C1—N2—Co1	35.9 (16)	C3—N1—Co1—Br1	−162.3 (10)
C5—C4—N3—Co1	54.3 (15)	C4—N3—Co1—N4	−31.1 (11)
C5—C6—N4—Co1	−51.8 (16)	C4—N3—Co1—N5	76 (6)
C6—N4—Co1—N5	−148.1 (11)	C4—N3—Co1—N1	146.5 (11)
C6—N4—Co1—N1	−119 (5)	C4—N3—Co1—N2	−119.5 (11)
C6—N4—Co1—N3	27.3 (11)	C4—N3—Co1—Br1	58.5 (10)
C6—N4—Co1—N2	116.4 (11)	C1—N2—Co1—N4	162.3 (10)
C6—N4—Co1—Br1	−61.0 (11)	C1—N2—Co1—N5	74.9 (10)
C7—N5—Co1—N4	−77.1 (11)	C1—N2—Co1—N1	−14.2 (10)
C7—N5—Co1—N1	105.0 (11)	C1—N2—Co1—N3	−103.8 (10)
C7—N5—Co1—N3	175 (5)	C1—N2—Co1—Br1	−142 (5)
C7—N5—Co1—N2	11.1 (11)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···Br2i	0.90	2.67	3.489 (11)	152
N1—H1D···Br2	0.90	2.61	3.504 (10)	174
N2—H2C···Br3	0.90	2.66	3.526 (10)	162
N2—H2D···Br3ii	0.90	2.64	3.419 (10)	146
N3—H3C···Br3	0.90	2.53	3.406 (12)	164
N3—H3D···Br2	0.90	2.59	3.482 (11)	171
N4—H4C···Br2iii	0.90	2.62	3.511 (10)	170
N4—H4D···Br3ii	0.90	2.49	3.379 (11)	170
N5—H5C···Br2iii	0.90	2.77	3.632 (11)	160
N5—H5D···Br2i	0.90	2.64	3.532 (12)	170
C6—H6A···Br3iii	0.97	2.91	3.773 (16)	148
C7—H7B···Br1iv	0.96	2.90	3.766 (13)	150

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1C⋯Br2i	0.90	2.67	3.489 (11)	152
N1—H1D⋯Br2	0.90	2.61	3.504 (10)	174
N2—H2C⋯Br3	0.90	2.66	3.526 (10)	162
N2—H2D⋯Br3ii	0.90	2.64	3.419 (10)	146
N3—H3C⋯Br3	0.90	2.53	3.406 (12)	164
N3—H3D⋯Br2	0.90	2.59	3.482 (11)	171
N4—H4C⋯Br2iii	0.90	2.62	3.511 (10)	170
N4—H4D⋯Br3ii	0.90	2.49	3.379 (11)	170
N5—H5C⋯Br2iii	0.90	2.77	3.632 (11)	160
N5—H5D⋯Br2i	0.90	2.64	3.532 (12)	170
C6—H6A⋯Br3iii	0.97	2.91	3.773 (16)	148
C7—H7B⋯Br1iv	0.96	2.90	3.766 (13)	150

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .