Chloridobis(dimethyl­glyoximato-κ2N,N′)(4-methyl­pyridine-κN)cobalt(III) hemihydrate

Amutha Selvi, M.; Arun Kumar, K.; Dayalan, A.

doi:10.1107/S1600536811020162

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 7| July 2011| Pages m851-m852

doi:10.1107/S1600536811020162

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Chloridobis(dimethylglyoximato-κ²N,N′)(4-methylpyridine-κN)cobalt(III) hemihydrate

Madhavan Amutha Selvi,^a Kannan Arun Kumar ^a and Arunachalam Dayalan ^a ^*

^aDepartment of Chemistry, Loyola College (Autonomous), Chennai 600 034, India
^*Correspondence e-mail: dayalan77@gmail.com

(Received 21 May 2011; accepted 26 May 2011; online 4 June 2011)

In the title complex, [Co(C₄H₇N₂O₂)₂Cl(C₆H₇N)]·0.5H₂O, the central Co^III ion, chelated by four N atoms of the two bidenate glyoximate ligands, exhibits a slightly distorted octahedral geometry. The axial positions are occupied by a chloride ion and the 4-methylpyridine N atom. Intermolecular O—H⋯O hydrogen bonds link the molecules in the crystal via the water molecules, while the glyoximate ligands exhibit intramolecular O—H⋯O hydrogen bonds.

Related literature

For similar structures, see: Revathi et al. (2009 ); Kavitha et al. (2008 ). For vitamin-B₁₂ models, see: Brown et al. (2005 ); Randaccio et al. (1989 ). For structure–property relationships, see: Gupta et al. (2004 ); Dutta et al. (2009 ). For intramolecular hydrogen bonding, see: Reemers & Englert (2002 ); Dolphin (1982 ); For details of the synthesis, see: Ramesh et al. (2008 ); Toscano et al. (1983 ). For spectroscopic details, see: Dayalan & Vijayaraghavan (2001 ); Silverstein & Bassler (1984 ); Bline & Hadzi (1958 ). For chemical properties of cobaloximes, see: Schrauzer & Windgassen (1966 ).

Experimental

Crystal data

[Co(C₄H₇N₂O₂)₂Cl(C₆H₇N)]·0.5H₂O
M_r = 425.74
Orthorhombic, P 2₁ 2₁ 2₁
a = 8.330 (5) Å
b = 14.365 (5) Å
c = 15.634 (5) Å
V = 1870.8 (14) Å³
Z = 4
Mo Kα radiation
μ = 1.09 mm⁻¹
T = 293 K
0.25 × 0.20 × 0.20 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker 2008 ) T_min = 0.772, T_max = 0.811
10519 measured reflections
4642 independent reflections
4143 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.077
S = 1.02
4642 reflections
248 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.38 e Å⁻³
Absolute structure: Flack (1983 ), 1983 Friedel pairs
Flack parameter: 0.014 (13)

Table 1
Selected interatomic distances (Å)

O1⋯O5	2.911 (8)
O5⋯O3ⁱ	3.013 (7)
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O1	0.90 (1)	1.61 (1)	2.499 (3)	168 (3)
O2—H2⋯O4	0.91 (1)	1.60 (2)	2.483 (3)	162 (4)

Data collection: APEX2 (Bruker, 2008); cell refinement: APEX2 and SAINT-Plus (Bruker, 2008); data reduction: SAINT-Plus and XPREP (Bruker, 2008); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811020162/jh2292sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811020162/jh2292Isup2.hkl

checkCIF report

Comment top

Cobaloximes have been used extensively as structural and functional mimics for vitamin-B₁₂ (Brown, 2005 and Randaccio et al., 1989).Their chemical properties have been widely studied (Schrauzer et al.,1966).The two aspects of cobaloxime chemistry are their (a) inertness with respect to ligand exchange making them to serve as ideal system for studies relating to electron transfer reactions and (b)crystal parameters.The distance between glyoximato oxygen atoms in these complexes amount to 2.4–2.6 Å, a distance range of considerable interest for strong intra molecular hydrogen bonding (Reemers et al., 2002).Compared to cobalamins, cobaloximes have shorter Co—N axial bond distance. It is known that coenzymes are related to number of 1,2-intra molecular rearrangement reactions (Dolphin et al.,1982).Most of the recent studies on cobaloximes have been focused on their structure–property relationships (Gupta et al., 2004 and Dutta et al., 2009).

In this title complex, the coordination about the Co^III ion is slightly distorted octahedral (Revathi et al., 2009 and Kavitha et al., 2008) with the 4-methylpyridine and chloride ligands occupying the axial positions and the two dimethylglyoximato ligands occupying the equatorial sites. The bite angles N1—Co—N2 and N3—Co—N4 of the ligand are 81.45 (8)⁰ and 81.17 (8)°, respectively.The coordinated chloride and the pyridine ring nitrogen are collinear with cobalt(III) froming an axial bond angle [N5—Co—Cl] = 178.89 (5)° and are perpendicular to the equatorial plane.The two glyoximate moiteies are linked together by strong inter molecular hydrogen bonding.

Related literature top

For similar structures, see: Revathi et al. (2009); Kavitha et al. (2008). For vitamin-B₁₂ models, see: Brown et al. (2005); Randaccio et al. (1989). For structure–property relationships, see: Gupta et al. (2004); Dutta et al. (2009). For intramolecular hydrogen bonding, see: Reemers & Englert (2002); Dolphin (1982); For details of the synthesis, see: Ramesh et al. (2008); Toscano et al. (1983). For spectroscopic details, see: Dayalan & Vijayaraghavan (2001); Silverstein & Bassler (1984); Bline & Hadzi (1958). For chemical properties of cobaloximes, see: Schrauzer & Windgassen(1966).

Experimental top

The complex was prepared by the literature method (Schrauzer et al.,1966) using H[Co(dmgH)₂ Cl₂] as the starting material (Ramesh et al.,2008). The dichloro cobaloxime was mixed with 4-methylpyridine in 1:1 molar ratio in about 60 ml of ethanol and allowed to stir for 3 hrs. The resulting brown coloured complex was filtered,washed with absolute ethanol followed by ether and dried over vacuum desicator. Crystals of the complex were grown in ethanol by slow evaporation method. The complex was characterized by UV, IR and H¹NMR spectra. A moderately intense band around 250 nm may be ascribed to π- π* transition of the dmgH ^- group. A shoulder around 330 nm may be due to the ligand to metal charge transfer transition, LMCT (Dayalan et al., 2001). The C=N stretching vibration of the oxime in its complex was observed at 1580 cm^-1 and the intra molecular hydrogen bonded –OH around 3450 cm^-1. A moderate peak at 1094 cm^-1 may be assigned to the C=N—O stretching of the oxime. The peak at 513 cm^-1 could be attributed to cobalt(III)-nitrogen stretching (Bline et al.,1958). The ¹H NMR spectrum of the complex in DMSO-d₆ shows a sharp intense singlet at 2.4 p.p.m. corresponding to methyl protons of the dimethylglyoximate. A singlet at 3.2 p.p.m. may be due to methyl protons of axial 4-methylpyridine ligand. The oxime –OH proton resonates at 8.28 p.p.m.. The two doublets at 8.07 and 7.4 p.p.m. correspond to pyridine ring protons at 2 & 6 and 3 & 5 positions, respectively of 4-methylpyridine at the axial position of the complex (Silverstein et al.,1984).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: APEX2 and SAINT-Plus (Bruker, 2008); data reduction: SAINT-Plus and XPREP (Bruker, 2008); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The ORTEP representation of the complex drawn at 30% probability level with the atom labelling scheme.
	Fig. 2. Packing of complex in the unit cell.

Chloridobis(dimethylglyoximato-κ²N,N')(4-methylpyridine- κN)cobalt(III) hemihydrate top

Crystal data top

[Co(C₄H₇N₂O₂)₂Cl(C₆H₇N)]·0.5H₂O	D_x = 1.512 Mg m⁻³
M_r = 425.74	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 5528 reflections
a = 8.330 (5) Å	θ = 2.6–28.2°
b = 14.365 (5) Å	µ = 1.09 mm⁻¹
c = 15.634 (5) Å	T = 293 K
V = 1870.8 (14) Å³	Block, brown
Z = 4	0.25 × 0.20 × 0.20 mm
F(000) = 880

Data collection top

Bruker SMART APEXII CCD diffractometer	4642 independent reflections
Radiation source: fine-focus sealed tube	4143 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ω and ϕ scans	θ_max = 28.4°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker 2008)	h = −10→10
T_min = 0.772, T_max = 0.811	k = −19→18
10519 measured reflections	l = −20→20

Refinement top

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)] = 0.029	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.077	w = 1/[σ²(F_o²) + (0.0405P)²] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.001
4642 reflections	Δρ_max = 0.40 e Å⁻³
248 parameters	Δρ_min = −0.38 e Å⁻³
2 restraints	Absolute structure: Flack (1983), 1983 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.014 (13)

Crystal data top

[Co(C₄H₇N₂O₂)₂Cl(C₆H₇N)]·0.5H₂O	V = 1870.8 (14) Å³
M_r = 425.74	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 8.330 (5) Å	µ = 1.09 mm⁻¹
b = 14.365 (5) Å	T = 293 K
c = 15.634 (5) Å	0.25 × 0.20 × 0.20 mm

Data collection top

Bruker SMART APEXII CCD diffractometer	4642 independent reflections
Absorption correction: multi-scan (SADABS; Bruker 2008)	4143 reflections with I > 2σ(I)
T_min = 0.772, T_max = 0.811	R_int = 0.028
10519 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.077	Δρ_max = 0.40 e Å⁻³
S = 1.02	Δρ_min = −0.38 e Å⁻³
4642 reflections	Absolute structure: Flack (1983), 1983 Friedel pairs
248 parameters	Absolute structure parameter: 0.014 (13)
2 restraints

Special details top

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.

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.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.7398 (3)	0.39874 (18)	0.25266 (16)	0.0398 (5)
C2	0.7058 (3)	0.49050 (18)	0.28872 (15)	0.0408 (6)
C3	0.8891 (3)	0.3435 (2)	0.2701 (2)	0.0643 (9)
H3A	0.8637	0.2783	0.2702	0.097*
H3B	0.9319	0.3608	0.3249	0.097*
H3C	0.9672	0.3560	0.2265	0.097*
C4	0.8147 (4)	0.5421 (3)	0.3478 (2)	0.0741 (10)
H4A	0.7709	0.6026	0.3591	0.111*
H4B	0.9185	0.5485	0.3218	0.111*
H4C	0.8248	0.5083	0.4005	0.111*
C5	0.1881 (3)	0.40417 (17)	0.08949 (15)	0.0406 (6)
C6	0.1538 (3)	0.49521 (17)	0.12558 (16)	0.0392 (5)
C7	0.0753 (4)	0.3542 (3)	0.0314 (2)	0.0759 (10)
H7A	0.0627	0.3891	−0.0206	0.114*
H7B	−0.0270	0.3477	0.0589	0.114*
H7C	0.1177	0.2937	0.0183	0.114*
C8	0.0047 (3)	0.5485 (3)	0.1072 (2)	0.0644 (9)
H8A	0.0054	0.6055	0.1393	0.097*
H8B	−0.0870	0.5121	0.1232	0.097*
H8C	−0.0004	0.5625	0.0472	0.097*
C9	0.2872 (3)	0.43850 (15)	0.35158 (13)	0.0331 (4)
H9	0.2853	0.5030	0.3467	0.040*
C10	0.2280 (3)	0.39842 (16)	0.42473 (15)	0.0387 (5)
H10	0.1854	0.4358	0.4677	0.046*
C11	0.2313 (3)	0.30297 (17)	0.43490 (15)	0.0376 (5)
C12	0.2910 (3)	0.25176 (16)	0.36721 (16)	0.0376 (5)
H12	0.2935	0.1871	0.3707	0.045*
C13	0.3464 (3)	0.29497 (15)	0.29503 (15)	0.0351 (5)
H13	0.3846	0.2588	0.2501	0.042*
C14	0.1738 (4)	0.2569 (2)	0.51559 (18)	0.0596 (8)
H14A	0.0587	0.2530	0.5148	0.089*
H14B	0.2075	0.2928	0.5641	0.089*
H14C	0.2184	0.1954	0.5193	0.089*
N1	0.6300 (2)	0.36941 (12)	0.20091 (12)	0.0341 (4)
N2	0.5693 (3)	0.52355 (12)	0.26275 (11)	0.0349 (4)
N3	0.3268 (3)	0.37229 (13)	0.11255 (12)	0.0346 (4)
N4	0.2679 (2)	0.52672 (12)	0.17406 (12)	0.0334 (4)
N5	0.3474 (2)	0.38848 (11)	0.28726 (11)	0.0269 (4)
O1	0.6426 (2)	0.28837 (12)	0.15990 (12)	0.0484 (4)
O2	0.5187 (3)	0.60675 (11)	0.28888 (12)	0.0476 (5)
O3	0.3788 (3)	0.29032 (14)	0.08378 (12)	0.0524 (5)
O4	0.2592 (2)	0.61073 (11)	0.21081 (12)	0.0483 (5)
Cl1	0.56856 (8)	0.51419 (4)	0.07531 (4)	0.04044 (14)
Co1	0.44843 (3)	0.447668 (17)	0.188051 (17)	0.02570 (8)
O5	0.8676 (9)	0.1476 (5)	0.1002 (5)	0.117 (2)	0.50
H3	0.4797 (19)	0.288 (2)	0.104 (2)	0.066 (11)*
H2	0.426 (3)	0.621 (3)	0.261 (2)	0.087 (13)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0293 (12)	0.0521 (14)	0.0381 (12)	−0.0008 (10)	−0.0037 (10)	0.0140 (11)
C2	0.0345 (12)	0.0535 (14)	0.0345 (12)	−0.0124 (11)	−0.0104 (10)	0.0099 (10)
C3	0.0362 (14)	0.080 (2)	0.076 (2)	0.0095 (14)	−0.0095 (14)	0.0267 (18)
C4	0.069 (2)	0.090 (2)	0.0638 (19)	−0.023 (2)	−0.0352 (17)	0.0010 (18)
C5	0.0370 (13)	0.0506 (13)	0.0341 (12)	−0.0111 (11)	−0.0101 (10)	0.0045 (10)
C6	0.0277 (12)	0.0510 (13)	0.0388 (12)	0.0003 (11)	−0.0027 (10)	0.0144 (10)
C7	0.071 (2)	0.089 (2)	0.068 (2)	−0.024 (2)	−0.0365 (18)	−0.0029 (18)
C8	0.0343 (14)	0.087 (2)	0.0724 (19)	0.0160 (14)	−0.0032 (13)	0.0242 (18)
C9	0.0363 (11)	0.0300 (10)	0.0331 (10)	−0.0003 (9)	0.0018 (9)	−0.0065 (9)
C10	0.0412 (13)	0.0441 (12)	0.0309 (10)	−0.0013 (10)	0.0052 (11)	−0.0101 (10)
C11	0.0328 (12)	0.0482 (13)	0.0317 (11)	−0.0059 (10)	−0.0030 (10)	0.0040 (10)
C12	0.0405 (13)	0.0306 (10)	0.0415 (12)	0.0002 (10)	0.0020 (11)	0.0042 (9)
C13	0.0402 (12)	0.0278 (9)	0.0372 (12)	0.0029 (9)	0.0023 (10)	−0.0032 (8)
C14	0.067 (2)	0.0712 (18)	0.0405 (16)	−0.0139 (16)	0.0089 (15)	0.0088 (14)
N1	0.0303 (9)	0.0373 (9)	0.0348 (10)	0.0051 (7)	0.0020 (8)	0.0029 (8)
N2	0.0413 (11)	0.0320 (8)	0.0312 (9)	−0.0089 (9)	−0.0018 (9)	−0.0001 (7)
N3	0.0401 (12)	0.0355 (9)	0.0283 (9)	−0.0036 (8)	−0.0025 (8)	−0.0054 (7)
N4	0.0344 (10)	0.0315 (8)	0.0343 (10)	0.0049 (7)	0.0001 (8)	0.0037 (7)
N5	0.0273 (9)	0.0251 (7)	0.0282 (8)	0.0018 (7)	−0.0005 (7)	−0.0013 (6)
O1	0.0480 (10)	0.0418 (8)	0.0553 (11)	0.0150 (8)	0.0079 (9)	−0.0052 (8)
O2	0.0639 (13)	0.0307 (7)	0.0482 (10)	−0.0095 (8)	−0.0048 (9)	−0.0084 (7)
O3	0.0678 (13)	0.0433 (9)	0.0463 (11)	0.0021 (9)	−0.0060 (10)	−0.0203 (8)
O4	0.0586 (12)	0.0314 (8)	0.0549 (11)	0.0134 (8)	0.0025 (9)	−0.0017 (8)
Cl1	0.0367 (3)	0.0529 (3)	0.0317 (2)	−0.0044 (3)	−0.0007 (3)	0.0089 (2)
Co1	0.02577 (13)	0.02728 (12)	0.02404 (12)	0.00065 (11)	−0.00294 (11)	−0.00153 (10)
O5	0.119 (5)	0.121 (4)	0.111 (5)	0.036 (5)	0.008 (4)	0.015 (4)

Geometric parameters (Å, º) top

C1—N1	1.292 (3)	C9—H9	0.9300
C1—C2	1.461 (4)	C10—C11	1.381 (3)
C1—C3	1.500 (3)	C10—H10	0.9300
C2—N2	1.297 (3)	C11—C12	1.382 (3)
C2—C4	1.491 (4)	C11—C14	1.503 (3)
C3—H3A	0.9600	C12—C13	1.368 (3)
C3—H3B	0.9600	C12—H12	0.9300
C3—H3C	0.9600	C13—N5	1.349 (3)
C4—H4A	0.9600	C13—H13	0.9300
C4—H4B	0.9600	C14—H14A	0.9600
C4—H4C	0.9600	C14—H14B	0.9600
C5—N3	1.294 (3)	C14—H14C	0.9600
C5—C6	1.453 (4)	N1—O1	1.333 (3)
C5—C7	1.491 (4)	N1—Co1	1.8951 (19)
C6—N4	1.297 (3)	N2—O2	1.332 (3)
C6—C8	1.487 (4)	N2—Co1	1.8885 (19)
C7—H7A	0.9600	N3—O3	1.333 (3)
C7—H7B	0.9600	N3—Co1	1.8953 (19)
C7—H7C	0.9600	N4—O4	1.339 (2)
C8—H8A	0.9600	N4—Co1	1.897 (2)
C8—H8B	0.9600	N5—Co1	1.9589 (18)
C8—H8C	0.9600	O2—H2	0.907 (10)
C9—N5	1.334 (3)	O3—H3	0.900 (10)
C9—C10	1.372 (3)	Cl1—Co1	2.2408 (8)

O1···O5	2.911 (8)	O5···O3ⁱ	3.013 (7)

N1—C1—C2	113.5 (2)	C13—C12—C11	120.8 (2)
N1—C1—C3	121.9 (3)	C13—C12—H12	119.6
C2—C1—C3	124.6 (2)	C11—C12—H12	119.6
N2—C2—C1	112.3 (2)	N5—C13—C12	121.9 (2)
N2—C2—C4	123.0 (3)	N5—C13—H13	119.1
C1—C2—C4	124.7 (3)	C12—C13—H13	119.1
C1—C3—H3A	109.5	C11—C14—H14A	109.5
C1—C3—H3B	109.5	C11—C14—H14B	109.5
H3A—C3—H3B	109.5	H14A—C14—H14B	109.5
C1—C3—H3C	109.5	C11—C14—H14C	109.5
H3A—C3—H3C	109.5	H14A—C14—H14C	109.5
H3B—C3—H3C	109.5	H14B—C14—H14C	109.5
C2—C4—H4A	109.5	C1—N1—O1	122.0 (2)
C2—C4—H4B	109.5	C1—N1—Co1	115.98 (16)
H4A—C4—H4B	109.5	O1—N1—Co1	122.00 (15)
C2—C4—H4C	109.5	C2—N2—O2	120.7 (2)
H4A—C4—H4C	109.5	C2—N2—Co1	116.73 (17)
H4B—C4—H4C	109.5	O2—N2—Co1	122.61 (17)
N3—C5—C6	112.7 (2)	C5—N3—O3	120.6 (2)
N3—C5—C7	124.2 (3)	C5—N3—Co1	116.65 (17)
C6—C5—C7	123.1 (3)	O3—N3—Co1	122.76 (18)
N4—C6—C5	113.4 (2)	C6—N4—O4	121.7 (2)
N4—C6—C8	123.0 (3)	C6—N4—Co1	116.06 (16)
C5—C6—C8	123.6 (2)	O4—N4—Co1	122.21 (15)
C5—C7—H7A	109.5	C9—N5—C13	117.81 (19)
C5—C7—H7B	109.5	C9—N5—Co1	121.65 (14)
H7A—C7—H7B	109.5	C13—N5—Co1	120.40 (15)
C5—C7—H7C	109.5	N2—O2—H2	109 (2)
H7A—C7—H7C	109.5	N3—O3—H3	103 (2)
H7B—C7—H7C	109.5	N2—Co1—N1	81.44 (9)
C6—C8—H8A	109.5	N2—Co1—N3	179.57 (9)
C6—C8—H8B	109.5	N1—Co1—N3	98.84 (9)
H8A—C8—H8B	109.5	N2—Co1—N4	98.54 (9)
C6—C8—H8C	109.5	N1—Co1—N4	179.31 (9)
H8A—C8—H8C	109.5	N3—Co1—N4	81.17 (9)
H8B—C8—H8C	109.5	N2—Co1—N5	89.43 (8)
N5—C9—C10	122.5 (2)	N1—Co1—N5	90.09 (8)
N5—C9—H9	118.7	N3—Co1—N5	90.89 (8)
C10—C9—H9	118.7	N4—Co1—N5	90.60 (8)
C9—C10—C11	120.4 (2)	N2—Co1—Cl1	90.12 (6)
C9—C10—H10	119.8	N1—Co1—Cl1	88.85 (7)
C11—C10—H10	119.8	N3—Co1—Cl1	89.57 (7)
C10—C11—C12	116.6 (2)	N4—Co1—Cl1	90.46 (6)
C10—C11—C14	121.9 (2)	N5—Co1—Cl1	178.90 (6)
C12—C11—C14	121.5 (2)

N1—C1—C2—N2	1.4 (3)	C2—N2—Co1—Cl1	−90.64 (17)
C3—C1—C2—N2	179.3 (2)	O2—N2—Co1—Cl1	89.93 (16)
N1—C1—C2—C4	−177.8 (3)	C1—N1—Co1—N2	2.65 (17)
C3—C1—C2—C4	0.1 (4)	O1—N1—Co1—N2	−178.23 (18)
N3—C5—C6—N4	−0.3 (3)	C1—N1—Co1—N3	−177.67 (17)
C7—C5—C6—N4	−179.6 (2)	O1—N1—Co1—N3	1.44 (18)
N3—C5—C6—C8	178.2 (2)	C1—N1—Co1—N4	91 (8)
C7—C5—C6—C8	−1.1 (4)	O1—N1—Co1—N4	−89 (8)
N5—C9—C10—C11	1.1 (4)	C1—N1—Co1—N5	−86.76 (17)
C9—C10—C11—C12	−2.2 (4)	O1—N1—Co1—N5	92.35 (17)
C9—C10—C11—C14	177.4 (2)	C1—N1—Co1—Cl1	92.94 (17)
C10—C11—C12—C13	1.3 (4)	O1—N1—Co1—Cl1	−87.94 (17)
C14—C11—C12—C13	−178.4 (2)	C5—N3—Co1—N2	−50 (13)
C11—C12—C13—N5	0.9 (4)	O3—N3—Co1—N2	130 (13)
C2—C1—N1—O1	177.96 (19)	C5—N3—Co1—N1	179.18 (17)
C3—C1—N1—O1	0.0 (3)	O3—N3—Co1—N1	−0.80 (19)
C2—C1—N1—Co1	−2.9 (3)	C5—N3—Co1—N4	−1.52 (17)
C3—C1—N1—Co1	179.11 (19)	O3—N3—Co1—N4	178.50 (19)
C1—C2—N2—O2	−179.79 (19)	C5—N3—Co1—N5	88.95 (18)
C4—C2—N2—O2	−0.5 (4)	O3—N3—Co1—N5	−91.03 (18)
C1—C2—N2—Co1	0.8 (3)	C5—N3—Co1—Cl1	−92.05 (17)
C4—C2—N2—Co1	−180.0 (2)	O3—N3—Co1—Cl1	87.97 (18)
C6—C5—N3—O3	−178.62 (19)	C6—N4—Co1—N2	−178.99 (16)
C7—C5—N3—O3	0.7 (4)	O4—N4—Co1—N2	2.02 (18)
C6—C5—N3—Co1	1.4 (3)	C6—N4—Co1—N1	92 (8)
C7—C5—N3—Co1	−179.3 (2)	O4—N4—Co1—N1	−87 (8)
C5—C6—N4—O4	178.05 (19)	C6—N4—Co1—N3	1.33 (16)
C8—C6—N4—O4	−0.4 (3)	O4—N4—Co1—N3	−177.66 (18)
C5—C6—N4—Co1	−0.9 (3)	C6—N4—Co1—N5	−89.47 (17)
C8—C6—N4—Co1	−179.41 (19)	O4—N4—Co1—N5	91.53 (17)
C10—C9—N5—C13	1.1 (3)	C6—N4—Co1—Cl1	90.82 (16)
C10—C9—N5—Co1	−174.48 (18)	O4—N4—Co1—Cl1	−88.17 (16)
C12—C13—N5—C9	−2.1 (4)	C9—N5—Co1—N2	47.81 (18)
C12—C13—N5—Co1	173.54 (18)	C13—N5—Co1—N2	−127.67 (19)
C2—N2—Co1—N1	−1.82 (17)	C9—N5—Co1—N1	129.25 (18)
O2—N2—Co1—N1	178.75 (18)	C13—N5—Co1—N1	−46.23 (18)
C2—N2—Co1—N3	−133 (13)	C9—N5—Co1—N3	−131.90 (18)
O2—N2—Co1—N3	47 (13)	C13—N5—Co1—N3	52.61 (18)
C2—N2—Co1—N4	178.87 (17)	C9—N5—Co1—N4	−50.73 (18)
O2—N2—Co1—N4	−0.56 (18)	C13—N5—Co1—N4	133.79 (18)
C2—N2—Co1—N5	88.36 (17)	C9—N5—Co1—Cl1	114 (3)
O2—N2—Co1—N5	−91.07 (17)	C13—N5—Co1—Cl1	−62 (3)

Symmetry code: (i) x+1/2, −y+1/2, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O1	0.90 (1)	1.61 (1)	2.499 (3)	168 (3)
O2—H2···O4	0.91 (1)	1.60 (2)	2.483 (3)	162 (4)

Experimental details

Crystal data
Chemical formula	[Co(C₄H₇N₂O₂)₂Cl(C₆H₇N)]·0.5H₂O
M_r	425.74
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	293
a, b, c (Å)	8.330 (5), 14.365 (5), 15.634 (5)
V (Å³)	1870.8 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.09
Crystal size (mm)	0.25 × 0.20 × 0.20

Data collection
Diffractometer	Bruker SMART APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker 2008)
T_min, T_max	0.772, 0.811
No. of measured, independent and observed [I > 2σ(I)] reflections	10519, 4642, 4143
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.077, 1.02
No. of reflections	4642
No. of parameters	248
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.38
Absolute structure	Flack (1983), 1983 Friedel pairs
Absolute structure parameter	0.014 (13)

Computer programs: APEX2 (Bruker, 2008), APEX2 and SAINT-Plus (Bruker, 2008), SAINT-Plus and XPREP (Bruker, 2008), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006).

Selected interatomic distances (Å) top

O1···O5

2.911 (8)

O5···O3ⁱ

3.013 (7)

Symmetry code: (i) x+1/2, −y+1/2, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O1	0.900 (10)	1.611 (13)	2.499 (3)	168 (3)
O2—H2···O4	0.907 (10)	1.604 (15)	2.483 (3)	162 (4)

Acknowledgements

The authors are thankful to Rev. Fr B. Jeyaraj, SJ, Principal, Loyola College, for providing the necessary facilities and the head, SAIF, IIT Madras, Chennai, India, for recording the ¹H NMR spectra and for the X-ray data collection

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