Dibromido(2,3,9,10-tetra-methyl-1,4,8,11-tetra-azacyclo-tetra-deca-1,3,8,10-tetra-ene)cobalt(III) bromide.

In the title compound, [CoBr(2)(C(14)H(24)N(4))]·Br, the Co(III) ion is located on an inversion centre and possesses a distorted octa-hedral coordination geometry in which four nitro-gen donors of the ligand mol-ecule are in the equatorial plane and two Br(-) ions occupy both the axial sites to give a trans isomer. The Br(- )counter- anion is also located on an inversion centre.

Related literature

For background to macrocyclic ligands and their metal complexes, see: Baird et al. (1993 ▶); Chandra & Verma (2008 ▶) and references therein; Chaudhary et al. (2002 ▶); Comba et al. (1986 ▶); Douglas (1978 ▶); Jones et al. (1979 ▶). For background to H2 evolution catalysis of macrocyclic metal complexes, see: Du et al. (2008 ▶); Fihri, Artero, Pereira & Fontecave (2008 ▶); Fihri, Artero, Raza­vet et al. (2008 ▶); Hu et al. (2007 ▶); Yamauchi et al. (2009 ▶). For the synthesis, see: Jackels et al. (1972 ▶).

Experimental

Crystal data

[CoBr2(C14H24N4)]·Br

M = 547.03

Triclinic,

a = 7.3888 (10) Å

b = 7.5157 (10) Å

c = 8.1929 (11) Å

α = 84.647 (10)°

β = 84.760 (10)°

γ = 84.094 (10)°

V = 449.04 (10) Å3

Z = 1

Mo Kα radiation

μ = 7.63 mm−1

T = 100 K

0.60 × 0.40 × 0.30 mm

Data collection

Bruker SMART APEXII CCD-detector diffractometer

Absorption correction: multi-scan (; Sheldrick, 1996 ▶) T min = 0.045, T max = 0.101

4629 measured reflections

1758 independent reflections

1739 reflections with I > 2σ(I)

R int = 0.015

Refinement

R[F 2 > 2σ(F 2)] = 0.016

wR(F 2) = 0.040

S = 1.15

1758 reflections

105 parameters

H-atom parameters constrained

Δρmax = 0.39 e Å−3

Δρmin = −0.72 e Å−3

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: KENX (Sakai, 2004 ▶); software used to prepare material for publication: SHELXL97, TEXSAN (Molecular Structure Corporation, 2001 ▶), KENX and ORTEPII (Johnson, 1976 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680904166X/is2468sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680904166X/is2468Isup2.hkl

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

[CoBr2(C14H24N4)]·Br	Z = 1
Mr = 547.03	F(000) = 268
Triclinic, P1	? # Insert any comments here.
Hall symbol: -P 1	Dx = 2.023 Mg m−3
a = 7.3888 (10) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.5157 (10) Å	Cell parameters from 4684 reflections
c = 8.1929 (11) Å	θ = 2.5–28.3°
α = 84.647 (10)°	µ = 7.63 mm−1
β = 84.76 (1)°	T = 100 K
γ = 84.094 (10)°	Brocks, dark green
V = 449.04 (10) Å3	0.60 × 0.40 × 0.30 mm

Bruker SMART APEX CCD-detector diffractometer	1758 independent reflections
Radiation source: sealed tube	1739 reflections with I > 2σ(I)
graphite	Rint = 0.015
φ and ω scans	θmax = 26.0°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.045, Tmax = 0.101	k = −9→9
4629 measured reflections	l = −10→10

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)] = 0.016	H-atom parameters constrained
wR(F2) = 0.040	w = 1/[σ2(Fo2) + (0.0205P)2 + 0.2736P] where P = (Fo2 + 2Fc2)/3
S = 1.15	(Δ/σ)max = 0.001
1758 reflections	Δρmax = 0.39 e Å−3
105 parameters	Δρmin = −0.72 e Å−3
0 restraints	Extinction correction: SHELXL
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.036 (4)

Experimental. The first 50 frames were rescanned at the end of data collection to evaluate any possible decay phenomenon. Since it was judged to be negligible, no decay correction was applied to the data.

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.Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)4.5770 (0.0058) x + 4.5950 (0.0059) y - 3.7053 (0.0042) z = 0.8322 (0.0063)* 0.0209 (0.0009) C4 * -0.0208 (0.0009) C6_$1 * -0.0182 (0.0008) N2 * 0.0181 (0.0008) N1_$1Rms deviation of fitted atoms = 0.0195- 2.0878 (0.0161) x + 6.6317 (0.0050) y - 1.8850 (0.0100) z = 2.7313 (0.0098)Angle to previous plane (with approximate e.s.d.) = 60.77 (0.11)* 0.0000 (0.0000) C4 * 0.0000 (0.0000) C5_$1 * 0.0000 (0.0000) C6_$1Rms deviation of fitted atoms = 0.0000

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.

	x	y	z	Uiso*/Ueq
Br1	0.32441 (2)	0.29517 (2)	1.169271 (18)	0.01131 (7)
Br2	0.0000	0.0000	0.5000	0.01880 (8)
Co1	0.5000	0.5000	1.0000	0.00682 (8)
N1	0.57154 (18)	0.31635 (18)	0.85246 (16)	0.0103 (3)
N2	0.30942 (18)	0.55749 (18)	0.85385 (16)	0.0097 (3)
C1	0.4642 (2)	0.3094 (2)	0.7383 (2)	0.0117 (3)
C2	0.3142 (2)	0.4563 (2)	0.7350 (2)	0.0109 (3)
C3	0.1898 (2)	0.4778 (3)	0.5990 (2)	0.0169 (4)
H3A	0.1135	0.3808	0.6109	0.025*
H3B	0.2612	0.4768	0.4951	0.025*
H3C	0.1150	0.5898	0.6038	0.025*
C4	0.1733 (2)	0.7132 (2)	0.8684 (2)	0.0143 (3)
H4A	0.0653	0.6924	0.8167	0.017*
H4B	0.2226	0.8187	0.8109	0.017*
C5	0.8791 (2)	0.2526 (2)	0.9535 (2)	0.0145 (3)
H5A	0.9114	0.3638	0.8933	0.017*
H5B	0.9864	0.1668	0.9480	0.017*
C6	0.7296 (2)	0.1820 (2)	0.8706 (2)	0.0148 (3)
H6A	0.7777	0.1473	0.7628	0.018*
H6B	0.6902	0.0758	0.9349	0.018*
C7	0.4802 (3)	0.1698 (2)	0.6181 (2)	0.0174 (4)
H7A	0.5370	0.2163	0.5150	0.026*
H7B	0.3608	0.1382	0.6021	0.026*
H7C	0.5531	0.0652	0.6598	0.026*

	U11	U22	U33	U12	U13	U23
Br1	0.01353 (10)	0.01049 (10)	0.01015 (10)	−0.00325 (6)	−0.00175 (6)	0.00102 (6)
Br2	0.01990 (13)	0.01933 (14)	0.01523 (13)	0.00443 (10)	0.00017 (9)	0.00027 (10)
Co1	0.00848 (15)	0.00660 (14)	0.00573 (15)	−0.00006 (11)	−0.00254 (11)	−0.00114 (11)
N1	0.0123 (7)	0.0092 (6)	0.0097 (6)	−0.0010 (5)	−0.0021 (5)	−0.0005 (5)
N2	0.0107 (6)	0.0098 (6)	0.0085 (6)	−0.0012 (5)	−0.0019 (5)	0.0003 (5)
C1	0.0148 (8)	0.0110 (7)	0.0096 (7)	−0.0023 (6)	−0.0010 (6)	−0.0010 (6)
C2	0.0122 (8)	0.0120 (7)	0.0091 (7)	−0.0035 (6)	−0.0022 (6)	0.0002 (6)
C3	0.0185 (9)	0.0210 (9)	0.0125 (8)	0.0014 (7)	−0.0081 (7)	−0.0044 (7)
C4	0.0145 (8)	0.0140 (8)	0.0143 (8)	0.0047 (6)	−0.0057 (6)	−0.0020 (6)
C5	0.0133 (8)	0.0136 (8)	0.0162 (8)	0.0036 (6)	−0.0031 (6)	−0.0020 (7)
C6	0.0168 (8)	0.0120 (8)	0.0162 (8)	0.0038 (6)	−0.0046 (7)	−0.0063 (6)
C7	0.0232 (9)	0.0159 (8)	0.0147 (8)	0.0005 (7)	−0.0058 (7)	−0.0077 (7)

Br1—Co1	2.3792 (2)	C3—H3C	0.9600
Co1—N2	1.9208 (13)	C4—H4A	0.9700
Co1—N1	1.9210 (13)	C4—H4B	0.9700
N1—C1	1.288 (2)	C5—C6	1.513 (2)
N1—C6	1.472 (2)	C5—H5A	0.9700
N2—C2	1.286 (2)	C5—H5B	0.9700
N2—C4	1.469 (2)	C6—H6A	0.9700
C1—C2	1.482 (2)	C6—H6B	0.9700
C1—C7	1.494 (2)	C7—H7A	0.9600
C2—C3	1.495 (2)	C7—H7B	0.9600
C3—H3A	0.9600	C7—H7C	0.9600
C3—H3B	0.9600
N2i—Co1—N2	180.000 (1)	C2—C3—H3C	109.5
N2—Co1—N1i	98.31 (6)	H3A—C3—H3C	109.5
N2i—Co1—N1	98.31 (6)	H3B—C3—H3C	109.5
N2—Co1—N1	81.69 (6)	N2—C4—H4A	109.3
N1i—Co1—N1	180.0	C5i—C4—H4A	109.3
N2—Co1—Br1i	88.22 (4)	N2—C4—H4B	109.3
N1—Co1—Br1i	90.86 (4)	C5i—C4—H4B	109.3
N2i—Co1—Br1	88.22 (4)	H4A—C4—H4B	108.0
N2—Co1—Br1	91.78 (4)	C6—C5—H5A	108.8
N1i—Co1—Br1	90.86 (4)	C4i—C5—H5A	108.8
N1—Co1—Br1	89.14 (4)	C6—C5—H5B	108.8
C1—N1—C6	120.39 (14)	C4i—C5—H5B	108.8
C1—N1—Co1	115.40 (11)	H5A—C5—H5B	107.7
C6—N1—Co1	124.08 (10)	N1—C6—C5	112.00 (13)
C2—N2—C4	121.39 (14)	N1—C6—H6A	109.2
C2—N2—Co1	115.56 (11)	C5—C6—H6A	109.2
C4—N2—Co1	122.93 (11)	N1—C6—H6B	109.2
N1—C1—C2	113.55 (14)	C5—C6—H6B	109.2
N1—C1—C7	125.76 (15)	H6A—C6—H6B	107.9
C2—C1—C7	120.68 (14)	C1—C7—H7A	109.5
N2—C2—C1	113.57 (14)	C1—C7—H7B	109.5
N2—C2—C3	126.51 (15)	H7A—C7—H7B	109.5
C1—C2—C3	119.89 (14)	C1—C7—H7C	109.5
C2—C3—H3A	109.5	H7A—C7—H7C	109.5
C2—C3—H3B	109.5	H7B—C7—H7C	109.5
H3A—C3—H3B	109.5
C6—N1—C1—C2	−178.89 (14)	C7—C1—C2—N2	174.67 (15)
Co1—N1—C1—C2	5.11 (18)	N1—C1—C2—C3	173.64 (15)
C6—N1—C1—C7	1.7 (3)	C7—C1—C2—C3	−6.9 (2)
Co1—N1—C1—C7	−174.28 (13)	C2—N2—C4—C5i	148.20 (15)
C4—N2—C2—C1	178.26 (14)	Co1—N2—C4—C5i	−35.93 (19)
Co1—N2—C2—C1	2.11 (18)	C1—N1—C6—C5	154.97 (15)
C4—N2—C2—C3	0.0 (3)	Co1—N1—C6—C5	−29.39 (19)
Co1—N2—C2—C3	−176.16 (14)	C4i—C5—C6—N1	66.89 (18)
N1—C1—C2—N2	−4.8 (2)