cis-Bromido­bis­(1,2-di­amino­ethane-κ2N,N′)(ethylamine-κN)cobalt(III) dibromide

Manimaran, S.; Manjunathan, M.; Govindan, E.; Sambathkumar, K.; Anbalagan, K.

doi:10.1107/S2414314618008556

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 3| Part 6| June 2018| x180855

https://doi.org/10.1107/S2414314618008556

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cis-Bromidobis(1,2-diaminoethane-κ²N,N′)(ethylamine-κN)cobalt(III) dibromide

S. Manimaran,^a ^* M. Manjunathan,^b E. Govindan,^c K. Sambathkumar ^d and K. Anbalagan ^e

^aDepartment of Physics, Thanthai Hans Rover College, Perambalur 621 220, India, ^bDepartment of Chemistry, BWDA Arts and Science College, Tindivanam 604 304, India, ^cDepartment of Physics, Thiruvalluvar University College of Arts and Science, Thiruvennainallur 607 203, India, ^dP.G. Research Department of Physics, A.A. Govt. Arts College, Villupuram, India, and ^eDepartment of Chemistry, Pondicherry University, Pondicherry 605 014, India
^*Correspondence e-mail: drmanirec@gmail.com

Edited by S. Bernès, Benemérita Universidad Autónoma de Puebla, México (Received 5 March 2018; accepted 10 June 2018; online 15 June 2018)

In the title complex, [CoBr(C₂H₇N)(C₂H₈N₂)₂]Br₂, the Co^III centre has a distorted octahedral 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. The complex is isostructural with the Cl compound for which the X-ray structure has also been reported [Anbalagan, Mahalakshmi & Ganeshraja (2011 ). J. Mol. Struct. 1005, 45–52]. In the crystal, the complex cation and the two counter-anions are linked via N—H⋯Br hydrogen bonds, forming a three-dimensional network.

Keywords: crystal structure; cobalt(III); diaminoethane; hydrogen bonding.

CCDC reference: 785726

Structure description

Mixed-ligand cobalt(III) complexes have potential applications in the fields of antitumor, antibacterial, antimicrobial, radiosensitization and cytotoxicity activities (Sayed et al., 1992 ; Teicher et al., 1990 ; Delehanty et al., 2008 ). Cobalt is an essential and integral component of vitamin B₁₂ and is therefore found physiologically in most tissues. Complexes of cobalt are useful for nutritional supplementation to provide cobalt in a form which effectively increases the bioavailability, for instance, through the production of vitamin B₁₂ by microorganisms present in the gut. In addition, cobalt(III) complexes are known for electron-transfer and ligand-substitution reactions, which are of interest in some chemical and biological systems.

Our current research deals with the design and synthesis of cobalt(III) complexes with the aim of understanding the correlation between their structure and reactivity. Substituting an amino ligand such as MeNH₂ by a different amine can afford structurally related complexes with different electron-transfer rates (Anbalagan, 2011 ; Anbalagan et al., 2009 ). Against this background and to ascertain the molecular conformation, the structure determination of the title compound has been carried out.

The X-ray analysis confirms the molecular structure and atom connectivity as illustrated in Fig. 1. The Co—N coordination bond lengths are in agreement with those reported in the literature for Co^III complexes (e.g. Kannan et al., 2013 ; Lee et al., 2007 ; Ramesh et al., 2008 ; Anbalagan et al., 2009, 2011; Ravichandran et al., 2009 ). Both ethylenediamine (en) units behave as chelating ligands, forming five-membered matallacycles with a half-chair conformation. The packing features N—H⋯Br interactions, forming a three-dimensional network in the crystal (Table 1 and Fig. 2). Additionally, weak C—H⋯Br contacts are observed (Fig. 3).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1C⋯Br3ⁱ	0.89	2.77	3.574 (5)	151
N1—H1D⋯Br3ⁱⁱ	0.89	2.48	3.310 (5)	155
N2—H2C⋯Br3	0.89	2.59	3.451 (5)	162
N2—H2D⋯Br2ⁱⁱⁱ	0.89	3.07	3.838 (5)	145
N3—H3C⋯Br3	0.89	2.60	3.427 (5)	155
N3—H3D⋯Br2	0.89	2.93	3.617 (5)	135
N4—H4C⋯Br2^iv	0.89	2.52	3.395 (6)	168
N4—H4D⋯Br2ⁱⁱⁱ	0.89	2.58	3.418 (5)	156
N5—H5C⋯Br2^iv	0.89	2.89	3.631 (5)	142
N5—H5D⋯Br2	0.89	2.78	3.651 (5)	166
C4—H4A⋯Br1^v	0.97	2.95	3.897 (7)	166
C4—H4B⋯Br2	0.97	2.91	3.566 (7)	126
C5—H5A⋯Br1	0.97	3.04	3.582 (8)	117
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) x, y+1, z; (iv) -x+2, -y+1, -z; (v) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Figure 1
Molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level. All H atoms omitted

Figure 2
A packing view of the title compound approximately down the b axis. Intermolecular N—H⋯Br contacts are depicted with dashed bonds.

Figure 3
A packing view of the title compound down the a axis. Intermolecular contacts involving the Br ions are represented with dashed bonds.

Synthesis and crystallization

A suspension of trans-[Co(en)₂Br₂]Br was prepared by adding drops of water to the solid (2 g). To the solid mass, about 2 ml of ethylamine was dropped for 20 min and mixed well. The grinding was continued until the colour turned from dull green to red. The reaction mixture was set aside until no further change was observed and the product was allowed to stand overnight. Finally, the solid was washed with ethanol. The resulting solid was dissolved in 5–10 ml of water pre-heated at 343 K and allowed to crystallize using hot acidified water, yielding 0.85 g of the complex. The pink crystals were filtered, washed with ethanol and dried under vacuum. X-ray quality crystals were obtained by repeated recrystallizations from hot acidified distilled water.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	[CoBr(C₂H₇N)(C₂H₈N₂)₂]Br₂
M_r	463.95
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	300
a, b, c (Å)	12.2323 (4), 8.4841 (2), 14.8964 (4)
β (°)	107.266 (3)
V (Å³)	1476.28 (8)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	9.26
Crystal size (mm)	0.23 × 0.17 × 0.11

Data collection
Diffractometer	Bruker SMART APEXII
Absorption correction	Multi-scan (SADABS; Bruker, 2008 )
T_min, T_max	0.165, 0.361
No. of measured, independent and observed [I > 2σ(I)] reflections	6551, 3425, 2273
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.689

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.148, 1.07
No. of reflections	3425
No. of parameters	137
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.20, −2.10
Computer programs: APEX2 and SAINT (Bruker, 2008), SHELXS97 and SHELXTL (Sheldrick, 2008 ) and SHELXL2018 (Sheldrick, 2015 ).

Structural data

CCDC reference: 785726

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314618008556/bh4035sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618008556/bh4035Isup3.hkl

checkCIF report

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: SHELXL2018 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

cis-Bromidobis(1,2-diaminoethane-κ²N,N')(ethylamine-κN)cobalt(III) dibromide top

Crystal data top

[CoBr(C₂H₇N)(C₂H₈N₂)₂]Br₂	F(000) = 904
M_r = 463.95	D_x = 2.087 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 12.2323 (4) Å	Cell parameters from 1908 reflections
b = 8.4841 (2) Å	θ = 25.0–2.9°
c = 14.8964 (4) Å	µ = 9.26 mm⁻¹
β = 107.266 (3)°	T = 300 K
V = 1476.28 (8) Å³	Block, pink
Z = 4	0.23 × 0.17 × 0.11 mm

Data collection top

Bruker SMART APEXII diffractometer	3425 independent reflections
Radiation source: fine-focus sealed tube	2273 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ω and φ scans	θ_max = 29.3°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −16→12
T_min = 0.165, T_max = 0.361	k = −10→11
6551 measured reflections	l = −18→16

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.148	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0841P)²] where P = (F_o² + 2F_c²)/3
3425 reflections	(Δ/σ)_max < 0.001
137 parameters	Δρ_max = 1.20 e Å⁻³
0 restraints	Δρ_min = −2.10 e Å⁻³
0 constraints

Special details top

Refinement. All H atoms were placed in calculated positions, and refined as riding to their carrier C/N atom, with isotropic displacement parameters.

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

	x	y	z	U_iso*/U_eq
Co1	0.76749 (7)	0.78619 (9)	0.04025 (6)	0.0137 (2)
Br1	0.68504 (7)	0.94805 (10)	−0.09241 (6)	0.0444 (3)
Br2	0.94231 (7)	0.27863 (8)	0.09070 (7)	0.0378 (2)
Br3	0.86031 (6)	0.85295 (8)	0.35349 (5)	0.0289 (2)
C1	0.5816 (6)	0.7765 (8)	0.1167 (6)	0.0302 (17)
H1A	0.618177	0.726722	0.176719	0.036*
H1B	0.499275	0.767240	0.103596	0.036*
C2	0.6156 (6)	0.9471 (8)	0.1194 (6)	0.0323 (18)
H2A	0.567841	1.001747	0.064538	0.039*
H2B	0.606217	0.997424	0.175153	0.039*
C3	0.9958 (6)	0.8476 (8)	0.1437 (5)	0.0278 (16)
H3A	0.981692	0.916951	0.190802	0.033*
H3B	1.074018	0.862937	0.142641	0.033*
C4	0.9771 (6)	0.6795 (8)	0.1657 (5)	0.0278 (17)
H4A	1.018388	0.655680	0.230595	0.033*
H4B	1.003559	0.609172	0.125234	0.033*
C5	0.6932 (6)	0.5267 (10)	−0.1040 (6)	0.039 (2)
H5A	0.635993	0.601290	−0.138414	0.047*
H5B	0.659449	0.464764	−0.064303	0.047*
C6	0.7241 (7)	0.4183 (10)	−0.1731 (6)	0.046 (2)
H6A	0.755801	0.479010	−0.213785	0.069*
H6B	0.656666	0.364526	−0.210005	0.069*
H6C	0.779496	0.342498	−0.139563	0.069*
N1	0.6189 (5)	0.6999 (6)	0.0412 (4)	0.0203 (12)
H1C	0.567171	0.716897	−0.014243	0.024*
H1D	0.624865	0.596314	0.050886	0.024*
N2	0.7377 (4)	0.9537 (6)	0.1208 (4)	0.0179 (11)
H2C	0.782957	0.941210	0.179387	0.021*
H2D	0.752782	1.047235	0.100142	0.021*
N3	0.8510 (4)	0.6605 (6)	0.1491 (4)	0.0186 (12)
H3C	0.832419	0.691869	0.199691	0.022*
H3D	0.831895	0.559464	0.138880	0.022*
N4	0.9159 (4)	0.8816 (6)	0.0516 (4)	0.0218 (12)
H4C	0.943442	0.843791	0.006895	0.026*
H4D	0.907846	0.985398	0.043793	0.026*
N5	0.7925 (4)	0.6151 (6)	−0.0435 (4)	0.0205 (12)
H5C	0.829306	0.657399	−0.080921	0.025*
H5D	0.839717	0.545146	−0.007231	0.025*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0142 (4)	0.0110 (4)	0.0138 (4)	−0.0004 (3)	0.0007 (3)	0.0001 (4)
Br1	0.0470 (5)	0.0451 (5)	0.0356 (5)	0.0050 (4)	0.0039 (4)	0.0083 (4)
Br2	0.0446 (5)	0.0205 (4)	0.0558 (6)	0.0005 (3)	0.0264 (4)	−0.0051 (4)
Br3	0.0349 (4)	0.0243 (4)	0.0244 (4)	0.0043 (3)	0.0040 (3)	−0.0060 (3)
C1	0.029 (4)	0.033 (4)	0.036 (4)	−0.004 (3)	0.021 (3)	−0.006 (4)
C2	0.027 (4)	0.031 (4)	0.036 (4)	0.006 (3)	0.005 (3)	−0.012 (4)
C3	0.018 (3)	0.024 (3)	0.038 (4)	−0.001 (3)	0.003 (3)	−0.006 (4)
C4	0.017 (3)	0.028 (4)	0.031 (4)	0.003 (3)	−0.004 (3)	−0.003 (3)
C5	0.025 (4)	0.040 (4)	0.046 (5)	−0.002 (3)	0.002 (4)	−0.024 (4)
C6	0.041 (5)	0.044 (5)	0.047 (5)	0.000 (4)	0.004 (4)	−0.031 (4)
N1	0.020 (3)	0.017 (3)	0.022 (3)	0.004 (2)	0.003 (2)	−0.002 (2)
N2	0.022 (3)	0.014 (2)	0.016 (3)	0.003 (2)	0.003 (2)	−0.001 (2)
N3	0.023 (3)	0.012 (2)	0.019 (3)	0.000 (2)	0.004 (2)	0.000 (2)
N4	0.018 (3)	0.019 (3)	0.027 (3)	−0.004 (2)	0.004 (2)	−0.001 (3)
N5	0.023 (3)	0.018 (3)	0.022 (3)	0.004 (2)	0.009 (2)	−0.004 (2)

Geometric parameters (Å, º) top

Co1—N4	1.949 (5)	C4—H4B	0.9700
Co1—N3	1.956 (5)	C5—N5	1.483 (8)
Co1—N2	1.963 (5)	C5—C6	1.510 (11)
Co1—N1	1.963 (5)	C5—H5A	0.9700
Co1—N5	1.996 (5)	C5—H5B	0.9700
Co1—Br1	2.3717 (11)	C6—H6A	0.9600
C1—N1	1.484 (9)	C6—H6B	0.9600
C1—C2	1.503 (10)	C6—H6C	0.9600
C1—H1A	0.9700	N1—H1C	0.8900
C1—H1B	0.9700	N1—H1D	0.8900
C2—N2	1.489 (8)	N2—H2C	0.8900
C2—H2A	0.9700	N2—H2D	0.8900
C2—H2B	0.9700	N3—H3C	0.8900
C3—N4	1.458 (9)	N3—H3D	0.8900
C3—C4	1.496 (10)	N4—H4C	0.8900
C3—H3A	0.9700	N4—H4D	0.8900
C3—H3B	0.9700	N5—H5C	0.8900
C4—N3	1.496 (8)	N5—H5D	0.8900
C4—H4A	0.9700

N4—Co1—N3	84.9 (2)	C6—C5—H5A	108.9
N4—Co1—N2	89.1 (2)	N5—C5—H5B	108.9
N3—Co1—N2	91.9 (2)	C6—C5—H5B	108.9
N4—Co1—N1	174.2 (2)	H5A—C5—H5B	107.7
N3—Co1—N1	92.7 (2)	C5—C6—H6A	109.5
N2—Co1—N1	85.7 (2)	C5—C6—H6B	109.5
N4—Co1—N5	92.5 (2)	H6A—C6—H6B	109.5
N3—Co1—N5	89.0 (2)	C5—C6—H6C	109.5
N2—Co1—N5	178.2 (2)	H6A—C6—H6C	109.5
N1—Co1—N5	92.7 (2)	H6B—C6—H6C	109.5
N4—Co1—Br1	89.22 (16)	C1—N1—Co1	109.6 (4)
N3—Co1—Br1	174.03 (16)	C1—N1—H1C	109.8
N2—Co1—Br1	88.86 (15)	Co1—N1—H1C	109.8
N1—Co1—Br1	93.21 (17)	C1—N1—H1D	109.8
N5—Co1—Br1	90.38 (17)	Co1—N1—H1D	109.8
N1—C1—C2	107.3 (6)	H1C—N1—H1D	108.2
N1—C1—H1A	110.3	C2—N2—Co1	109.4 (4)
C2—C1—H1A	110.3	C2—N2—H2C	109.8
N1—C1—H1B	110.3	Co1—N2—H2C	109.8
C2—C1—H1B	110.3	C2—N2—H2D	109.8
H1A—C1—H1B	108.5	Co1—N2—H2D	109.8
N2—C2—C1	107.8 (6)	H2C—N2—H2D	108.2
N2—C2—H2A	110.2	C4—N3—Co1	109.7 (4)
C1—C2—H2A	110.2	C4—N3—H3C	109.7
N2—C2—H2B	110.2	Co1—N3—H3C	109.7
C1—C2—H2B	110.2	C4—N3—H3D	109.7
H2A—C2—H2B	108.5	Co1—N3—H3D	109.7
N4—C3—C4	106.9 (5)	H3C—N3—H3D	108.2
N4—C3—H3A	110.3	C3—N4—Co1	110.3 (4)
C4—C3—H3A	110.3	C3—N4—H4C	109.6
N4—C3—H3B	110.3	Co1—N4—H4C	109.6
C4—C3—H3B	110.3	C3—N4—H4D	109.6
H3A—C3—H3B	108.6	Co1—N4—H4D	109.6
C3—C4—N3	106.5 (5)	H4C—N4—H4D	108.1
C3—C4—H4A	110.4	C5—N5—Co1	119.9 (4)
N3—C4—H4A	110.4	C5—N5—H5C	107.4
C3—C4—H4B	110.4	Co1—N5—H5C	107.4
N3—C4—H4B	110.4	C5—N5—H5D	107.4
H4A—C4—H4B	108.6	Co1—N5—H5D	107.4
N5—C5—C6	113.4 (6)	H5C—N5—H5D	106.9
N5—C5—H5A	108.9

N1—C1—C2—N2	−49.0 (8)	C3—C4—N3—Co1	37.0 (6)
N4—C3—C4—N3	−50.2 (7)	C4—C3—N4—Co1	41.0 (6)
C2—C1—N1—Co1	38.1 (7)	C6—C5—N5—Co1	171.6 (6)
C1—C2—N2—Co1	37.3 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···Br3ⁱ	0.89	2.77	3.574 (5)	151
N1—H1D···Br3ⁱⁱ	0.89	2.48	3.310 (5)	155
N2—H2C···Br3	0.89	2.59	3.451 (5)	162
N2—H2D···Br2ⁱⁱⁱ	0.89	3.07	3.838 (5)	145
N2—H2D···Br3^iv	0.89	3.11	3.651 (5)	121
N3—H3C···Br3	0.89	2.60	3.427 (5)	155
N3—H3D···Br2	0.89	2.93	3.617 (5)	135
N3—H3D···Br3ⁱⁱ	0.89	2.96	3.665 (5)	137
N4—H4C···Br2^v	0.89	2.52	3.395 (6)	168
N4—H4D···Br2ⁱⁱⁱ	0.89	2.58	3.418 (5)	156
N5—H5C···Br2^v	0.89	2.89	3.631 (5)	142
N5—H5D···Br2	0.89	2.78	3.651 (5)	166
C4—H4A···Br1^vi	0.97	2.95	3.897 (7)	166
C4—H4B···Br2	0.97	2.91	3.566 (7)	126
C5—H5A···Br1	0.97	3.04	3.582 (8)	117

Symmetry codes: (i) x−1/2, −y+3/2, z−1/2; (ii) −x+3/2, y−1/2, −z+1/2; (iii) x, y+1, z; (iv) −x+3/2, y+1/2, −z+1/2; (v) −x+2, −y+1, −z; (vi) x+1/2, −y+3/2, z+1/2.

Acknowledgements

The authors thank the Department of Chemistry, Pondicherry University, for the data collection.

Funding information

S. Manimaran gratefully acknowledges the DST–SERB for young scientist start-up research grant (YSS/2014/000561) and DST–FIST for providing NMR facilities to the department.

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