metal-organic compounds
cis-Bromido(n-butylamine-κN)bis(ethene-1,2-diamine-κ2N,N′)cobalt(III) dibromide
aDepartment of Chemistry, BWDA Arts and Science College, Tindivanam 604 304, India, bDepartment of Physics, Thanthai Hans Rover College, Perambalur 621 220, India, cDepartment of Chemistry, Pondicherry University, Pondicherry 605 014, India, dP.G. & Research Department of Physics, A. A. Govt. Arts College, Villupuram, India, and eDepartment of Physics, Thiruvalluvar University, College of Arts and Science, Thiruvennainallur 607 203, India
*Correspondence e-mail: e.govindan84@gmail.com
In the title compound, [CoBr(C2H8N2)2(C4H11N)]Br2, the cobalt(III) ion has a distorted octahedral coordination environment and is surrounded by four N atoms in the equatorial plane made up of three N atoms from the two ethylenediamine ligands and the remaining N from the n-butyl substituent, with the other N atom from the ethylenediamine ligand 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. The crystal studied was refined as a two-component inversion twin.
Keywords: crystal structure; cobalt(III)dibromide; hydrogen bonding.
CCDC reference: 894716
Structure description
Mixed-ligand cobalt(III) complexes exhibit antitumor, antibacterial, antimicrobial, radiosenzitation and cytotoxicity activities (Sayed et al., 1992; Teicher et al., 1990; Arslan et al., 2009; 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 its bioavailability, for instance, vitamin B12 by microorganisms present in the gut. In addition, cobalt(III) complexes are known for electron-transfer and ligand-substitution reactions, which find applications in chemical and biological systems. Our present research concerns the design and synthesis of cobalt(III) complexes with the objective of understanding the structure–reactivity correlation. Substituting a different amino ligand for the MeNH2 moiety can yield complexes of similar structure, but with differing electron-transfer rates (Anbalagan, 2011; Anbalagan et al., 2011). Against this background and to ascertain the molecular conformation, the of the title compound has been carried out.
X-ray analysis confirms the molecular structure and atom connectivity as illustrated in Fig. 1. The Co—N bond lengths are comparable with literature values [1.9722 (2)–1.988 (2) Å: Manimaran et al., 2018; 1.948 (7)–1.963 (7) Å: Lee et al., 2007; Ramesh et al., 2008; Anbalagan et al., 2009; Ravichandran et al., 2009]. The whole molecule is not planar, the dihedral angle between the two chelate rings being 79.4 (4)°. One of the five-membered rings in the molecule adopts a half-chair conformation.
In the crystal, C—H⋯Br and N—H⋯Br hydrogen bonds (Table 1) link the molecules into a three-dimensional framework, as shown in Figs 2 and 3.
Synthesis and crystallization
trans-[Co(en)2Br2]Br solid (2 g) was made into a paste using 3–4 drops of water. To the solid mass, about 2 ml of N-butylamine was dropped for 20 min and mixed well. The mixing was continued until the colour changed from dull green to red. The reaction mixture was set aside until no further change was observed and the mixture was allowed to stand overnight. Finally, the obtained solid was washed with ethanol and dissolved in 5–10 ml of water pre-heated to 70°C and allowed to crystallize using hot acidified water (yield 0.85 g). The crystals were filtered, washed with ethanol and dried under vacuum. X-ray quality crystals were obtained by repeated recrystallization from hot acidified distilled water. Microcrystalline pink crystals were obtained for analysis.
Refinement
Crystal data, data collection and structure . The crystal studied was refined as a two-component inversion twin.
details are summarized in Table 2
|
Structural data
CCDC reference: 894716
https://doi.org/10.1107/S2414314618010222/bv4019sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618010222/bv4019Isup2.hkl
Data collection: APEX2 (Bruker, 2008); cell
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).[CoBr(C2H8N2)2(C4H11N)]Br2 | F(000) = 484 |
Mr = 492.00 | Dx = 1.837 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.6336 (7) Å | Cell parameters from 2458 reflections |
b = 7.5810 (3) Å | θ = 2.9–25.0° |
c = 12.0809 (7) Å | µ = 7.69 mm−1 |
β = 114.028 (7)° | T = 123 K |
V = 889.49 (10) Å3 | Block, pink |
Z = 2 | 0.23 × 0.17 × 0.11 mm |
Bruker SMART APEXII area-detector diffractometer | 1769 reflections with I > 2σ(I) |
ω and φ scans | Rint = 0.037 |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | θmax = 25.0°, θmin = 3.3° |
Tmin = 0.165, Tmax = 0.361 | h = −7→12 |
2398 measured reflections | k = −8→8 |
2398 independent reflections | l = −14→12 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.042 | H-atom parameters constrained |
wR(F2) = 0.085 | w = 1/[σ2(Fo2) + (0.0424P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.92 | (Δ/σ)max < 0.001 |
2398 reflections | Δρmax = 0.78 e Å−3 |
156 parameters | Δρmin = −0.72 e Å−3 |
1 restraint | Absolute structure: Refined as an inversion twin |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.08 (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. Refined as a 2-component inversion twin. The H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = ranging from 0.95 to 0.99 Å and N—H 0.90 Å. Uiso(H) = xUeq(C), where x = 1.5 for methyl H atoms and 1.2 for all other C and N bound H atoms. |
x | y | z | Uiso*/Ueq | ||
Br1 | 1.03734 (13) | 0.48014 (17) | 0.62170 (11) | 0.0420 (4) | |
Co1 | 0.86142 (14) | 0.3543 (2) | 0.67319 (11) | 0.0192 (3) | |
N1 | 0.8910 (9) | 0.1217 (11) | 0.6194 (7) | 0.026 (2) | |
H1A | 0.808973 | 0.070057 | 0.577554 | 0.032* | |
H1B | 0.934073 | 0.133357 | 0.569254 | 0.032* | |
N2 | 1.0045 (8) | 0.2816 (11) | 0.8297 (7) | 0.024 (2) | |
H2A | 1.063969 | 0.370871 | 0.862055 | 0.029* | |
H2B | 0.965869 | 0.253471 | 0.881155 | 0.029* | |
N3 | 0.7102 (9) | 0.2722 (11) | 0.7171 (8) | 0.026 (2) | |
H3A | 0.645306 | 0.217550 | 0.653245 | 0.031* | |
H3B | 0.743506 | 0.194250 | 0.778545 | 0.031* | |
N4 | 0.8408 (10) | 0.5759 (11) | 0.7439 (8) | 0.028 (2) | |
H4C | 0.924563 | 0.621362 | 0.788221 | 0.034* | |
H4D | 0.794962 | 0.652962 | 0.684421 | 0.034* | |
N5 | 0.7236 (9) | 0.4307 (12) | 0.5110 (7) | 0.029 (2) | |
H5A | 0.640727 | 0.432547 | 0.514638 | 0.035* | |
H5B | 0.743627 | 0.542937 | 0.499738 | 0.035* | |
C1 | 0.9733 (13) | 0.0091 (15) | 0.7212 (10) | 0.040 (3) | |
H1C | 1.019060 | −0.085105 | 0.694447 | 0.048* | |
H1D | 0.914632 | −0.046286 | 0.757530 | 0.048* | |
C2 | 1.0779 (12) | 0.1281 (16) | 0.8109 (9) | 0.034 (3) | |
H2C | 1.127138 | 0.065188 | 0.888472 | 0.041* | |
H2D | 1.146204 | 0.166546 | 0.779520 | 0.041* | |
C3 | 0.6490 (11) | 0.4226 (15) | 0.7535 (10) | 0.035 (3) | |
H3C | 0.603590 | 0.382502 | 0.806183 | 0.042* | |
H3D | 0.579195 | 0.480660 | 0.681181 | 0.042* | |
C4 | 0.7650 (12) | 0.5509 (14) | 0.8220 (10) | 0.032 (3) | |
H4A | 0.727491 | 0.664551 | 0.835414 | 0.039* | |
H4B | 0.826389 | 0.501359 | 0.901613 | 0.039* | |
C5 | 0.7084 (12) | 0.3309 (18) | 0.4017 (8) | 0.036 (3) | |
H5C | 0.663946 | 0.216313 | 0.402205 | 0.044* | |
H5D | 0.800965 | 0.306121 | 0.404319 | 0.044* | |
C6 | 0.6245 (12) | 0.4262 (16) | 0.2852 (9) | 0.041 (3) | |
H6A | 0.532247 | 0.451988 | 0.283059 | 0.049* | |
H6B | 0.669402 | 0.540265 | 0.284472 | 0.049* | |
C7 | 0.6072 (14) | 0.325 (2) | 0.1734 (9) | 0.059 (4) | |
H7A | 0.699580 | 0.290312 | 0.179469 | 0.071* | |
H7B | 0.555810 | 0.215341 | 0.171365 | 0.071* | |
C8 | 0.5347 (16) | 0.420 (2) | 0.0568 (11) | 0.086 (7) | |
H8A | 0.519280 | 0.339169 | −0.010801 | 0.129* | |
H8B | 0.591162 | 0.519581 | 0.052262 | 0.129* | |
H8C | 0.446030 | 0.463682 | 0.052249 | 0.129* | |
Br2 | 0.84875 (14) | 0.1393 (2) | 1.00875 (12) | 0.0503 (4) | |
Br3 | 0.38253 (12) | 0.35525 (18) | 0.45593 (11) | 0.0385 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0407 (9) | 0.0524 (8) | 0.0383 (7) | −0.0145 (7) | 0.0215 (7) | 0.0064 (7) |
Co1 | 0.0198 (8) | 0.0217 (7) | 0.0150 (7) | −0.0008 (8) | 0.0060 (6) | −0.0012 (8) |
N1 | 0.034 (6) | 0.027 (5) | 0.019 (5) | −0.006 (5) | 0.011 (4) | 0.006 (5) |
N2 | 0.017 (6) | 0.030 (5) | 0.023 (5) | −0.004 (4) | 0.007 (4) | −0.002 (4) |
N3 | 0.022 (6) | 0.027 (5) | 0.026 (6) | −0.007 (4) | 0.007 (5) | 0.001 (5) |
N4 | 0.028 (6) | 0.028 (6) | 0.023 (5) | 0.006 (4) | 0.004 (5) | −0.003 (5) |
N5 | 0.023 (6) | 0.039 (5) | 0.019 (5) | 0.001 (4) | 0.003 (4) | 0.003 (5) |
C1 | 0.060 (10) | 0.024 (7) | 0.034 (7) | 0.017 (6) | 0.018 (7) | 0.007 (6) |
C2 | 0.033 (8) | 0.040 (7) | 0.028 (6) | 0.025 (7) | 0.010 (6) | 0.011 (7) |
C3 | 0.024 (7) | 0.061 (9) | 0.022 (6) | 0.015 (6) | 0.011 (5) | −0.002 (6) |
C4 | 0.042 (8) | 0.028 (6) | 0.019 (6) | 0.021 (6) | 0.006 (6) | −0.009 (5) |
C5 | 0.049 (8) | 0.042 (8) | 0.015 (5) | 0.004 (7) | 0.011 (6) | −0.001 (6) |
C6 | 0.041 (9) | 0.049 (8) | 0.032 (7) | 0.005 (6) | 0.015 (6) | 0.007 (6) |
C7 | 0.065 (11) | 0.090 (12) | 0.015 (6) | 0.014 (10) | 0.010 (6) | −0.002 (8) |
C8 | 0.077 (13) | 0.14 (2) | 0.033 (8) | 0.017 (12) | 0.020 (8) | 0.015 (10) |
Br2 | 0.0412 (9) | 0.0702 (9) | 0.0393 (8) | 0.0142 (8) | 0.0161 (7) | 0.0307 (8) |
Br3 | 0.0263 (7) | 0.0326 (6) | 0.0448 (7) | −0.0020 (7) | 0.0023 (6) | −0.0047 (7) |
Br1—Co1 | 2.3967 (18) | C1—H1C | 0.9900 |
Co1—N4 | 1.937 (8) | C1—H1D | 0.9900 |
Co1—N1 | 1.949 (9) | C2—H2C | 0.9900 |
Co1—N2 | 1.962 (8) | C2—H2D | 0.9900 |
Co1—N3 | 1.988 (9) | C3—C4 | 1.524 (15) |
Co1—N5 | 1.996 (8) | C3—H3C | 0.9900 |
N1—C1 | 1.460 (13) | C3—H3D | 0.9900 |
N1—H1A | 0.8999 | C4—H4A | 0.9900 |
N1—H1B | 0.9001 | C4—H4B | 0.9900 |
N2—C2 | 1.469 (13) | C5—C6 | 1.509 (14) |
N2—H2A | 0.9001 | C5—H5C | 0.9900 |
N2—H2B | 0.8993 | C5—H5D | 0.9900 |
N3—C3 | 1.467 (13) | C6—C7 | 1.498 (15) |
N3—H3A | 0.8998 | C6—H6A | 0.9900 |
N3—H3B | 0.9003 | C6—H6B | 0.9900 |
N4—C4 | 1.481 (13) | C7—C8 | 1.487 (16) |
N4—H4C | 0.9006 | C7—H7A | 0.9900 |
N4—H4D | 0.9002 | C7—H7B | 0.9900 |
N5—C5 | 1.473 (13) | C8—H8A | 0.9800 |
N5—H5A | 0.9002 | C8—H8B | 0.9800 |
N5—H5B | 0.9005 | C8—H8C | 0.9800 |
C1—C2 | 1.498 (16) | ||
N4—Co1—N1 | 174.0 (4) | C2—C1—H1C | 110.6 |
N4—Co1—N2 | 90.1 (4) | N1—C1—H1D | 110.6 |
N1—Co1—N2 | 84.3 (3) | C2—C1—H1D | 110.6 |
N4—Co1—N3 | 84.5 (4) | H1C—C1—H1D | 108.7 |
N1—Co1—N3 | 93.6 (4) | N2—C2—C1 | 107.7 (9) |
N2—Co1—N3 | 92.8 (4) | N2—C2—H2C | 110.2 |
N4—Co1—N5 | 90.6 (4) | C1—C2—H2C | 110.2 |
N1—Co1—N5 | 95.1 (4) | N2—C2—H2D | 110.2 |
N2—Co1—N5 | 177.0 (4) | C1—C2—H2D | 110.2 |
N3—Co1—N5 | 90.2 (4) | H2C—C2—H2D | 108.5 |
N4—Co1—Br1 | 90.6 (3) | N3—C3—C4 | 107.4 (9) |
N1—Co1—Br1 | 91.4 (3) | N3—C3—H3C | 110.2 |
N2—Co1—Br1 | 88.9 (2) | C4—C3—H3C | 110.2 |
N3—Co1—Br1 | 174.8 (3) | N3—C3—H3D | 110.2 |
N5—Co1—Br1 | 88.2 (3) | C4—C3—H3D | 110.2 |
C1—N1—Co1 | 111.7 (7) | H3C—C3—H3D | 108.5 |
C1—N1—H1A | 109.3 | N4—C4—C3 | 105.4 (9) |
Co1—N1—H1A | 109.2 | N4—C4—H4A | 110.7 |
C1—N1—H1B | 109.3 | C3—C4—H4A | 110.7 |
Co1—N1—H1B | 109.3 | N4—C4—H4B | 110.7 |
H1A—N1—H1B | 107.9 | C3—C4—H4B | 110.7 |
C2—N2—Co1 | 109.0 (6) | H4A—C4—H4B | 108.8 |
C2—N2—H2A | 109.8 | N5—C5—C6 | 113.5 (10) |
Co1—N2—H2A | 109.8 | N5—C5—H5C | 108.9 |
C2—N2—H2B | 109.9 | C6—C5—H5C | 108.9 |
Co1—N2—H2B | 109.9 | N5—C5—H5D | 108.9 |
H2A—N2—H2B | 108.4 | C6—C5—H5D | 108.9 |
C3—N3—Co1 | 110.0 (6) | H5C—C5—H5D | 107.7 |
C3—N3—H3A | 109.6 | C7—C6—C5 | 113.9 (10) |
Co1—N3—H3A | 109.6 | C7—C6—H6A | 108.8 |
C3—N3—H3B | 109.7 | C5—C6—H6A | 108.8 |
Co1—N3—H3B | 109.6 | C7—C6—H6B | 108.8 |
H3A—N3—H3B | 108.2 | C5—C6—H6B | 108.8 |
C4—N4—Co1 | 111.0 (7) | H6A—C6—H6B | 107.7 |
C4—N4—H4C | 109.5 | C8—C7—C6 | 115.6 (13) |
Co1—N4—H4C | 109.4 | C8—C7—H7A | 108.4 |
C4—N4—H4D | 109.5 | C6—C7—H7A | 108.4 |
Co1—N4—H4D | 109.4 | C8—C7—H7B | 108.4 |
H4C—N4—H4D | 108.0 | C6—C7—H7B | 108.4 |
C5—N5—Co1 | 120.0 (7) | H7A—C7—H7B | 107.4 |
C5—N5—H5A | 107.4 | C7—C8—H8A | 109.5 |
Co1—N5—H5A | 107.4 | C7—C8—H8B | 109.5 |
C5—N5—H5B | 107.2 | H8A—C8—H8B | 109.5 |
Co1—N5—H5B | 107.4 | C7—C8—H8C | 109.5 |
H5A—N5—H5B | 106.8 | H8A—C8—H8C | 109.5 |
N1—C1—C2 | 105.7 (9) | H8B—C8—H8C | 109.5 |
N1—C1—H1C | 110.6 | ||
Co1—N1—C1—C2 | −37.0 (11) | N3—C3—C4—N4 | 49.8 (11) |
Co1—N2—C2—C1 | −40.7 (10) | Co1—N5—C5—C6 | −167.2 (8) |
N1—C1—C2—N2 | 50.1 (12) | N5—C5—C6—C7 | −179.5 (11) |
Co1—N3—C3—C4 | −36.4 (10) | C5—C6—C7—C8 | −175.3 (12) |
Co1—N4—C4—C3 | −41.3 (10) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···Br3i | 0.90 | 2.51 | 3.348 (9) | 156 |
N1—H1B···Br1ii | 0.90 | 2.71 | 3.467 (8) | 143 |
N2—H2A···Br2iii | 0.90 | 2.50 | 3.335 (8) | 154 |
N2—H2B···Br2 | 0.90 | 2.50 | 3.392 (8) | 173 |
N3—H3A···Br3 | 0.90 | 3.03 | 3.680 (9) | 131 |
N3—H3A···Br3i | 0.90 | 3.01 | 3.695 (9) | 134 |
N3—H3B···Br2 | 0.90 | 2.57 | 3.372 (9) | 148 |
N4—H4C···Br2iii | 0.90 | 2.65 | 3.468 (9) | 151 |
N4—H4D···Br3iv | 0.90 | 2.49 | 3.359 (9) | 163 |
N5—H5A···Br3 | 0.90 | 2.61 | 3.458 (9) | 158 |
N5—H5B···Br3iv | 0.90 | 2.88 | 3.487 (9) | 126 |
C3—H3D···Br3 | 0.99 | 2.84 | 3.594 (11) | 134 |
C4—H4B···Br2 | 0.99 | 3.00 | 3.739 (11) | 132 |
C5—H5D···Br1 | 0.99 | 3.10 | 3.607 (12) | 114 |
C5—H5D···Br1ii | 0.99 | 3.10 | 3.884 (13) | 137 |
Symmetry codes: (i) −x+1, y−1/2, −z+1; (ii) −x+2, y−1/2, −z+1; (iii) −x+2, y+1/2, −z+2; (iv) −x+1, y+1/2, −z+1. |
Acknowledgements
The authors thank the Department of Chemistry, Pondicherry University, Pondicherry, for the data collection.
Funding information
MM and EG gratefully acknowledge the DST–SERB for a young scientist start-up research grant (YSS/2014/000561) and the DST–FIST for providing NMR facilities to the department.
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