Chloridobis[diphenyl­glyoximato(1–)-κ2N,N′](1H-imidazole-κN3)cobalt(III) hemihydrate

Meera, P.; Revathi, C.; Dayalan, A.

doi:10.1107/S160053680804347X

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 2| February 2009| Pages m140-m141

doi:10.1107/S160053680804347X

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Chloridobis[diphenylglyoximato(1–)-κ²N,N′](1H-imidazole-κN³)cobalt(III) hemihydrate

P. Meera,^a ^* C. Revathi ^a and A. Dayalan ^a

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

(Received 10 December 2008; accepted 20 December 2008; online 8 January 2009)

The Co centre in the title compound, [Co(C₁₄H₁₁N₂O₂)₂Cl(C₃H₄N₂)]·0.5H₂O, shows a slightly distorted octahedral coordination geometry. The glyoximate units of the molecule are linked by O—H⋯O hydrogen bonds with the H atom almost in the middle of the two O atoms. The crystal packing is stabilized through intermolecular N—H⋯O, N—H⋯N and O—H⋯Cl hydrogen bonds. The uncoordinated water molecule shows half-occupation.

Related literature

For related literature, see: Calleri et al. (1967 ); Gupta et al. (2001 , 2004 ); Lopez et al. (1991 ); Mandal & Gupta (2005 ); Silverstein & Bassler (1984 ); Toscano et al. (1983 ).

Experimental

Crystal data

[Co(C₁₄H₁₁N₂O₂)₂Cl(C₃H₄N₂)]·0.5H₂O
M_r = 649.97
Orthorhombic, P b c a
a = 19.1004 (11) Å
b = 12.0462 (7) Å
c = 26.9627 (18) Å
V = 6203.8 (7) Å³
Z = 8
Mo Kα radiation
μ = 0.69 mm⁻¹
T = 293 (2) K
0.30 × 0.20 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1999 ) T_min = 0.732, T_max = 0.850
28473 measured reflections
5282 independent reflections
3705 reflections with I > 2σ(I)
R_int = 0.051

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.104
S = 1.06
5282 reflections
415 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H2⋯O2	1.05 (4)	1.46 (4)	2.482 (3)	165 (3)
O3—H3⋯O1	1.07 (5)	1.39 (5)	2.456 (3)	174 (4)
N6—H6A⋯O2ⁱ	0.98 (4)	1.78 (4)	2.747 (4)	166 (3)
N6—H6A⋯N2ⁱ	0.98 (4)	2.50 (4)	3.326 (4)	141 (3)
O5—H5B⋯Cl1	0.946 (10)	2.69 (8)	3.331 (7)	126 (7)
Symmetry code: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, z]$ .

Data collection: APEX2 (Bruker, 2004 ); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); 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 global, I. DOI: 10.1107/S160053680804347X/bt2831sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680804347X/bt2831Isup2.hkl

checkCIF report

Comment top

The coordination geometry around cobalt is octahedral with the four nitrogen atoms of the diphenyl glyoximato ligand forming an approximate square plane. The bite angles N1—Co—N2 and N3—Co—N4 of the ligand are 81.40 (10)° and 80.32 (10)°, respectively. The coordinating chlorine and imidazole nitrogen [N5—Co1—Cl1 = 179.11 (7)°] are perpendicular to the equatorial plane composed by the four N atoms. The two glyoximate moieties are linked by strong O—H···O hydrogen bonds. Similar hydrogen bonds are found in nickel(II)glyoximate (Calleri, et al., 1967). The molecule is linked to its b-glide equivalent through a N—H···O hydrogen bond The water molecule forms a short O—H···Cl contact.

Related literature top

For related literature, see: Calleri et al. (1967); Gupta et al. (2001, 2004); Lopez et al. (1991); Mandal & Gupta (2005); Silverstein & Bassler (1984); Toscano et al. (1983). It would be much more useful to readers if the "Related literature" section had some kind of simple sub-division, so that, instead of just "For related literature, see···" it said, for example, "For general background, see···. For related structures, see···.? etc. Please revise this section as indicated.

Experimental top

Cobaltous chloride hexahydrate was thoroughly ground and exposed to microwave for 30 s. The dehydrated salt was mixed with diphenylglyoxime in 1:2 molar ratio in acetone medium and was stirred for an hour (Toscano, et al., 1983; Gupta, et al., 2001). Since the dichloro complex of diphenyl glyoxime was non-isolable, the complex solution was as such refluxed with equimolar ratio of imidazole for six hours to get the title compound. The resulting brown mass was filtered, washed with ether and dried in a vaccuum desiccator. The complex was dissolved in ethanol and kept in a dark room for crystallization. Brown crystals of the complex appeared in three days. The elemental analysis data, obtained by analytical methods agree well with the theoretical data expected for the formula of the complex proposed: Anal%, (cald%): C, 62.07(62.57); H, 4.82(4.71); N, 14.50(14.13). The C=N stretching vibration of oxime in the complex was observed at 1629 cm^-1 and the intra molecular hydrogen bonded OH around 3400 cm^-1. A moderate peak around 1252 cm^-1 may be assigned to the C=N—O stretching of the oxime. The peak around 537 cm^-1 could be attributed to cobalt(III)-nitrogen stretching. The ¹H NMR spectra of the complex in acetone-d₆ shows three different signals corresponding to diphenyl glyoximate ring protons (Gupta, et al., 2004; Lopez, et al., 1991). The ortho H atoms of the ring shows a doublet at d= 7.4 p.p.m., the meta protons and the para proton give triplets at d = 7.6 and 7.9 p.p.m. respectively. The oxime –OH resonates at d=8.3 p.p.m.. The axial protons also appeared as multiplets along with phenyl protons at 7.2 and 7.4 p.p.m. as three proton signal (Silverstein & Bassler, 1984; Mandal & Gupta, 2005).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SIR92 (Altornare 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
	Fig. 2. Packing of molecules in the unit cell. Hydrogen bonds are shown with dotted lines.

Chloridobis[diphenylglyoximato(1-)-κ²N,N'](1H- imidazole-κN³)cobalt(III) hemihydrate top

Crystal data top

[Co(C₁₄H₁₁N₂O₂)₂Cl(C₃H₄N₂)]·0.5H₂O	D_x = 1.392 Mg m⁻³
M_r = 649.97	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 5466 reflections
a = 19.1004 (11) Å	θ = 2.1–24.9°
b = 12.0462 (7) Å	µ = 0.69 mm⁻¹
c = 26.9627 (18) Å	T = 293 K
V = 6203.8 (7) Å³	Needle, brown
Z = 8	0.30 × 0.20 × 0.20 mm
F(000) = 2680

Data collection top

Bruker Kappa APEXII CCD diffractometer	5282 independent reflections
Radiation source: fine-focus sealed tube	3705 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.051
ω and ϕ scans	θ_max = 24.7°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −20→22
T_min = 0.732, T_max = 0.850	k = −14→13
28473 measured reflections	l = −31→18

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.104	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0434P)² + 2.9454P] where P = (F_o² + 2F_c²)/3
5282 reflections	(Δ/σ)_max = 0.001
415 parameters	Δρ_max = 0.35 e Å⁻³
3 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

[Co(C₁₄H₁₁N₂O₂)₂Cl(C₃H₄N₂)]·0.5H₂O	V = 6203.8 (7) Å³
M_r = 649.97	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 19.1004 (11) Å	µ = 0.69 mm⁻¹
b = 12.0462 (7) Å	T = 293 K
c = 26.9627 (18) Å	0.30 × 0.20 × 0.20 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	5282 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1999)	3705 reflections with I > 2σ(I)
T_min = 0.732, T_max = 0.850	R_int = 0.051
28473 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	3 restraints
wR(F²) = 0.104	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.35 e Å⁻³
5282 reflections	Δρ_min = −0.26 e Å⁻³
415 parameters

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	0.63561 (15)	0.1880 (3)	0.00280 (11)	0.0409 (7)
C2	0.70947 (14)	0.1624 (2)	0.01198 (11)	0.0381 (7)
C3	0.60509 (15)	0.2080 (3)	−0.04659 (11)	0.0464 (8)
C4	0.56950 (19)	0.3038 (3)	−0.05731 (13)	0.0639 (10)
H4	0.5658	0.3596	−0.0336	0.077*
C5	0.5390 (2)	0.3174 (4)	−0.10368 (17)	0.0861 (14)
H5	0.5154	0.3827	−0.1114	0.103*
C6	0.5438 (2)	0.2339 (5)	−0.13802 (16)	0.0882 (15)
H6	0.5224	0.2427	−0.1688	0.106*
C7	0.5790 (2)	0.1389 (5)	−0.12817 (15)	0.0837 (13)
H7	0.5823	0.0832	−0.1520	0.100*
C8	0.61007 (18)	0.1258 (3)	−0.08218 (13)	0.0624 (10)
H8	0.6346	0.0610	−0.0751	0.075*
C9	0.76536 (15)	0.1743 (3)	−0.02548 (10)	0.0406 (7)
C10	0.76866 (18)	0.2672 (3)	−0.05512 (12)	0.0575 (9)
H10	0.7342	0.3215	−0.0526	0.069*
C11	0.8230 (2)	0.2803 (4)	−0.08864 (14)	0.0707 (11)
H11	0.8251	0.3434	−0.1084	0.085*
C12	0.8733 (2)	0.2007 (4)	−0.09260 (14)	0.0701 (11)
H12	0.9094	0.2094	−0.1154	0.084*
C13	0.87115 (19)	0.1089 (4)	−0.06346 (14)	0.0664 (11)
H13	0.9060	0.0554	−0.0660	0.080*
C14	0.81727 (17)	0.0953 (3)	−0.03009 (12)	0.0529 (9)
H14	0.8158	0.0320	−0.0104	0.064*
C15	0.57331 (14)	0.0802 (2)	0.18684 (11)	0.0364 (7)
C16	0.64821 (14)	0.0580 (2)	0.19665 (10)	0.0365 (7)
C17	0.51700 (14)	0.0551 (3)	0.22257 (11)	0.0402 (7)
C18	0.46087 (16)	0.1271 (3)	0.22873 (13)	0.0550 (9)
H18	0.4589	0.1930	0.2108	0.066*
C19	0.40809 (19)	0.1009 (4)	0.26147 (15)	0.0737 (12)
H19	0.3707	0.1495	0.2657	0.088*
C20	0.41012 (19)	0.0049 (4)	0.28760 (15)	0.0781 (13)
H20	0.3743	−0.0119	0.3097	0.094*
C21	0.46428 (19)	−0.0669 (4)	0.28165 (15)	0.0758 (12)
H21	0.4651	−0.1331	0.2993	0.091*
C22	0.51801 (17)	−0.0419 (3)	0.24951 (12)	0.0554 (9)
H22	0.5553	−0.0909	0.2460	0.067*
C23	0.67758 (14)	0.0249 (3)	0.24497 (11)	0.0434 (8)
C24	0.66383 (18)	0.0875 (3)	0.28642 (13)	0.0623 (10)
H24	0.6353	0.1499	0.2840	0.075*
C25	0.6919 (2)	0.0584 (5)	0.33133 (14)	0.0855 (14)
H25	0.6824	0.1008	0.3594	0.103*
C26	0.7334 (2)	−0.0319 (5)	0.33480 (17)	0.0930 (16)
H26	0.7528	−0.0507	0.3653	0.112*
C27	0.7473 (2)	−0.0954 (4)	0.29465 (17)	0.0851 (14)
H27	0.7752	−0.1582	0.2978	0.102*
C28	0.71984 (18)	−0.0669 (3)	0.24888 (14)	0.0660 (10)
H28	0.7299	−0.1096	0.2210	0.079*
C29	0.57488 (16)	−0.0595 (3)	0.04757 (12)	0.0548 (9)
H29	0.5386	−0.0170	0.0346	0.066*
C30	0.58509 (18)	−0.1672 (3)	0.03882 (13)	0.0593 (9)
H30	0.5582	−0.2130	0.0187	0.071*
C31	0.66589 (16)	−0.1065 (3)	0.08821 (12)	0.0488 (8)
H31	0.7053	−0.1042	0.1084	0.059*
N1	0.59804 (12)	0.1815 (2)	0.04272 (9)	0.0426 (6)
N2	0.72105 (11)	0.13202 (19)	0.05738 (9)	0.0361 (6)
N3	0.56368 (11)	0.1196 (2)	0.14284 (9)	0.0383 (6)
N4	0.68677 (11)	0.0763 (2)	0.15816 (8)	0.0382 (6)
N5	0.62594 (11)	−0.0215 (2)	0.07856 (9)	0.0380 (6)
N6	0.64288 (15)	−0.1966 (3)	0.06536 (11)	0.0552 (7)
O1	0.52933 (10)	0.1998 (2)	0.04167 (8)	0.0542 (6)
O2	0.78462 (9)	0.10740 (17)	0.07404 (7)	0.0425 (5)
O3	0.49944 (10)	0.14234 (19)	0.12648 (8)	0.0520 (6)
O4	0.75702 (10)	0.0645 (2)	0.16194 (8)	0.0496 (6)
O5	0.5658 (4)	0.4699 (6)	0.0555 (3)	0.127 (2)	0.50
H5B	0.611 (2)	0.438 (7)	0.055 (4)	0.152*	0.50
H5A	0.535 (4)	0.425 (7)	0.074 (4)	0.152*	0.50
Co1	0.642761 (18)	0.12847 (3)	0.100084 (14)	0.03524 (13)
Cl1	0.66393 (4)	0.30158 (7)	0.12458 (3)	0.0560 (2)
H2	0.7759 (17)	0.087 (3)	0.1270 (14)	0.070 (11)*
H3	0.509 (2)	0.169 (4)	0.0893 (17)	0.106 (15)*
H6A	0.6632 (18)	−0.272 (3)	0.0650 (13)	0.075 (12)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0429 (17)	0.0496 (19)	0.0303 (18)	−0.0003 (14)	0.0007 (14)	0.0066 (14)
C2	0.0378 (16)	0.0466 (18)	0.0301 (18)	−0.0019 (13)	0.0026 (13)	0.0013 (13)
C3	0.0405 (17)	0.065 (2)	0.0334 (19)	−0.0075 (16)	0.0008 (14)	0.0093 (16)
C4	0.074 (2)	0.067 (3)	0.050 (2)	−0.002 (2)	−0.0123 (19)	0.0156 (19)
C5	0.082 (3)	0.102 (4)	0.075 (3)	−0.002 (3)	−0.020 (2)	0.043 (3)
C6	0.080 (3)	0.138 (5)	0.046 (3)	−0.030 (3)	−0.014 (2)	0.015 (3)
C7	0.075 (3)	0.131 (4)	0.045 (3)	−0.014 (3)	−0.003 (2)	−0.012 (3)
C8	0.055 (2)	0.089 (3)	0.043 (2)	0.0001 (19)	0.0009 (17)	−0.003 (2)
C9	0.0409 (16)	0.0508 (19)	0.0301 (17)	−0.0089 (15)	0.0017 (13)	−0.0025 (15)
C10	0.058 (2)	0.066 (2)	0.048 (2)	−0.0061 (18)	0.0019 (17)	0.0103 (18)
C11	0.080 (3)	0.080 (3)	0.052 (3)	−0.028 (2)	0.011 (2)	0.013 (2)
C12	0.059 (2)	0.100 (3)	0.052 (3)	−0.027 (2)	0.0202 (19)	−0.009 (2)
C13	0.058 (2)	0.084 (3)	0.057 (3)	−0.001 (2)	0.0203 (19)	−0.011 (2)
C14	0.059 (2)	0.058 (2)	0.042 (2)	−0.0033 (17)	0.0129 (16)	−0.0043 (16)
C15	0.0348 (15)	0.0451 (18)	0.0293 (17)	0.0025 (13)	0.0024 (12)	0.0010 (13)
C16	0.0341 (15)	0.0463 (18)	0.0293 (17)	0.0019 (13)	0.0021 (13)	−0.0015 (13)
C17	0.0342 (16)	0.054 (2)	0.0329 (17)	0.0007 (14)	0.0046 (13)	0.0020 (15)
C18	0.0485 (19)	0.060 (2)	0.057 (2)	0.0096 (17)	0.0165 (16)	0.0085 (17)
C19	0.054 (2)	0.090 (3)	0.078 (3)	0.019 (2)	0.031 (2)	0.012 (2)
C20	0.057 (2)	0.100 (3)	0.077 (3)	0.007 (2)	0.034 (2)	0.029 (3)
C21	0.061 (2)	0.085 (3)	0.082 (3)	0.006 (2)	0.028 (2)	0.033 (2)
C22	0.0460 (19)	0.063 (2)	0.057 (2)	0.0088 (16)	0.0122 (16)	0.0135 (19)
C23	0.0312 (15)	0.070 (2)	0.0294 (18)	0.0010 (15)	−0.0004 (13)	0.0039 (15)
C24	0.062 (2)	0.088 (3)	0.038 (2)	0.0011 (19)	−0.0025 (17)	−0.0001 (19)
C25	0.079 (3)	0.142 (4)	0.035 (2)	0.002 (3)	−0.011 (2)	−0.002 (2)
C26	0.069 (3)	0.161 (5)	0.049 (3)	−0.001 (3)	−0.014 (2)	0.037 (3)
C27	0.068 (3)	0.120 (4)	0.068 (3)	0.028 (2)	−0.005 (2)	0.036 (3)
C28	0.057 (2)	0.088 (3)	0.053 (2)	0.016 (2)	0.0057 (18)	0.015 (2)
C29	0.0425 (19)	0.067 (3)	0.054 (2)	−0.0026 (17)	−0.0135 (16)	0.0037 (18)
C30	0.057 (2)	0.063 (3)	0.057 (2)	−0.0122 (18)	−0.0107 (18)	−0.0093 (19)
C31	0.0416 (17)	0.058 (2)	0.047 (2)	0.0045 (16)	−0.0048 (15)	−0.0061 (16)
N1	0.0347 (13)	0.0580 (17)	0.0350 (15)	0.0065 (12)	−0.0001 (11)	0.0056 (12)
N2	0.0299 (12)	0.0463 (14)	0.0320 (14)	−0.0004 (11)	0.0003 (10)	−0.0002 (11)
N3	0.0294 (12)	0.0527 (15)	0.0330 (15)	0.0063 (11)	0.0025 (10)	0.0035 (12)
N4	0.0280 (12)	0.0570 (16)	0.0295 (14)	0.0033 (11)	−0.0008 (10)	−0.0025 (11)
N5	0.0324 (12)	0.0502 (15)	0.0316 (14)	0.0044 (11)	−0.0007 (11)	0.0012 (12)
N6	0.0563 (18)	0.0526 (19)	0.057 (2)	0.0056 (15)	0.0025 (14)	−0.0056 (15)
O1	0.0346 (11)	0.0849 (17)	0.0429 (14)	0.0141 (11)	−0.0007 (10)	0.0164 (12)
O2	0.0293 (10)	0.0635 (14)	0.0347 (12)	0.0020 (9)	0.0022 (9)	0.0051 (10)
O3	0.0279 (10)	0.0848 (17)	0.0432 (14)	0.0143 (10)	0.0013 (9)	0.0154 (12)
O4	0.0258 (10)	0.0886 (17)	0.0343 (13)	0.0043 (10)	0.0010 (9)	0.0078 (12)
O5	0.144 (7)	0.109 (6)	0.127 (7)	0.037 (5)	0.001 (5)	0.011 (4)
Co1	0.0288 (2)	0.0490 (2)	0.0280 (2)	0.00340 (18)	0.00147 (16)	0.00213 (18)
Cl1	0.0571 (5)	0.0530 (5)	0.0580 (6)	−0.0016 (4)	0.0119 (4)	−0.0087 (4)

Geometric parameters (Å, º) top

C1—N1	1.296 (4)	C21—C22	1.376 (4)
C1—C2	1.465 (4)	C21—H21	0.9300
C1—C3	1.473 (4)	C22—H22	0.9300
C2—N2	1.296 (3)	C23—C28	1.373 (5)
C2—C9	1.477 (4)	C23—C24	1.374 (5)
C3—C4	1.370 (5)	C24—C25	1.370 (5)
C3—C8	1.382 (5)	C24—H24	0.9300
C4—C5	1.389 (5)	C25—C26	1.348 (6)
C4—H4	0.9300	C25—H25	0.9300
C5—C6	1.370 (6)	C26—C27	1.352 (6)
C5—H5	0.9300	C26—H26	0.9300
C6—C7	1.354 (6)	C27—C28	1.384 (5)
C6—H6	0.9300	C27—H27	0.9300
C7—C8	1.384 (5)	C28—H28	0.9300
C7—H7	0.9300	C29—C30	1.333 (5)
C8—H8	0.9300	C29—N5	1.364 (4)
C9—C10	1.377 (4)	C29—H29	0.9300
C9—C14	1.380 (4)	C30—N6	1.362 (4)
C10—C11	1.385 (5)	C30—H30	0.9300
C10—H10	0.9300	C31—N5	1.304 (4)
C11—C12	1.362 (6)	C31—N6	1.324 (4)
C11—H11	0.9300	C31—H31	0.9300
C12—C13	1.357 (5)	N1—O1	1.331 (3)
C12—H12	0.9300	N1—Co1	1.879 (2)
C13—C14	1.377 (5)	N2—O2	1.328 (3)
C13—H13	0.9300	N2—Co1	1.888 (2)
C14—H14	0.9300	N3—O3	1.332 (3)
C15—N3	1.291 (3)	N3—Co1	1.903 (2)
C15—C17	1.475 (4)	N4—O4	1.353 (3)
C15—C16	1.479 (4)	N4—Co1	1.885 (2)
C16—N4	1.291 (3)	N5—Co1	1.924 (2)
C16—C23	1.474 (4)	N6—H6A	0.98 (4)
C17—C22	1.376 (4)	O1—H3	1.39 (5)
C17—C18	1.389 (4)	O2—H2	1.46 (4)
C18—C19	1.377 (4)	O3—H3	1.07 (5)
C18—H18	0.9300	O4—H2	1.05 (4)
C19—C20	1.355 (5)	O5—H5B	0.946 (10)
C19—H19	0.9300	O5—H5A	0.946 (10)
C20—C21	1.358 (5)	Co1—Cl1	2.2244 (9)
C20—H20	0.9300

N1—C1—C2	112.3 (3)	C28—C23—C24	119.5 (3)
N1—C1—C3	122.8 (3)	C28—C23—C16	120.7 (3)
C2—C1—C3	124.6 (3)	C24—C23—C16	119.8 (3)
N2—C2—C1	112.5 (2)	C25—C24—C23	120.2 (4)
N2—C2—C9	123.4 (3)	C25—C24—H24	119.9
C1—C2—C9	124.0 (3)	C23—C24—H24	119.9
C4—C3—C8	119.4 (3)	C26—C25—C24	119.9 (4)
C4—C3—C1	121.6 (3)	C26—C25—H25	120.1
C8—C3—C1	118.9 (3)	C24—C25—H25	120.1
C3—C4—C5	119.8 (4)	C25—C26—C27	121.0 (4)
C3—C4—H4	120.1	C25—C26—H26	119.5
C5—C4—H4	120.1	C27—C26—H26	119.5
C6—C5—C4	119.6 (4)	C26—C27—C28	120.0 (4)
C6—C5—H5	120.2	C26—C27—H27	120.0
C4—C5—H5	120.2	C28—C27—H27	120.0
C7—C6—C5	121.4 (4)	C23—C28—C27	119.4 (4)
C7—C6—H6	119.3	C23—C28—H28	120.3
C5—C6—H6	119.3	C27—C28—H28	120.3
C6—C7—C8	119.0 (4)	C30—C29—N5	109.3 (3)
C6—C7—H7	120.5	C30—C29—H29	125.3
C8—C7—H7	120.5	N5—C29—H29	125.3
C3—C8—C7	120.7 (4)	C29—C30—N6	106.2 (3)
C3—C8—H8	119.6	C29—C30—H30	126.9
C7—C8—H8	119.6	N6—C30—H30	126.9
C10—C9—C14	118.4 (3)	N5—C31—N6	110.9 (3)
C10—C9—C2	120.6 (3)	N5—C31—H31	124.5
C14—C9—C2	120.9 (3)	N6—C31—H31	124.5
C9—C10—C11	120.4 (4)	C1—N1—O1	121.2 (2)
C9—C10—H10	119.8	C1—N1—Co1	116.91 (19)
C11—C10—H10	119.8	O1—N1—Co1	121.47 (18)
C12—C11—C10	120.0 (4)	C2—N2—O2	122.6 (2)
C12—C11—H11	120.0	C2—N2—Co1	116.56 (19)
C10—C11—H11	120.0	O2—N2—Co1	120.84 (17)
C13—C12—C11	120.5 (3)	C15—N3—O3	120.7 (2)
C13—C12—H12	119.8	C15—N3—Co1	117.66 (18)
C11—C12—H12	119.8	O3—N3—Co1	121.26 (18)
C12—C13—C14	119.9 (4)	C16—N4—O4	119.1 (2)
C12—C13—H13	120.1	C16—N4—Co1	118.04 (19)
C14—C13—H13	120.1	O4—N4—Co1	122.67 (17)
C13—C14—C9	120.9 (3)	C31—N5—C29	106.1 (3)
C13—C14—H14	119.6	C31—N5—Co1	125.4 (2)
C9—C14—H14	119.6	C29—N5—Co1	128.3 (2)
N3—C15—C17	124.9 (2)	C31—N6—C30	107.5 (3)
N3—C15—C16	111.6 (2)	C31—N6—H6A	129 (2)
C17—C15—C16	123.5 (3)	C30—N6—H6A	124 (2)
N4—C16—C23	122.7 (2)	N1—O1—H3	101.9 (17)
N4—C16—C15	112.2 (2)	N2—O2—H2	105.3 (13)
C23—C16—C15	125.1 (2)	N3—O3—H3	102 (2)
C22—C17—C18	118.6 (3)	N4—O4—H2	104.2 (18)
C22—C17—C15	120.6 (3)	H5B—O5—H5A	110.0 (17)
C18—C17—C15	120.9 (3)	N1—Co1—N4	179.23 (11)
C19—C18—C17	119.9 (3)	N1—Co1—N2	81.39 (10)
C19—C18—H18	120.0	N4—Co1—N2	99.27 (10)
C17—C18—H18	120.0	N1—Co1—N3	99.02 (10)
C20—C19—C18	120.6 (3)	N4—Co1—N3	80.33 (10)
C20—C19—H19	119.7	N2—Co1—N3	178.07 (10)
C18—C19—H19	119.7	N1—Co1—N5	89.71 (11)
C19—C20—C21	120.3 (3)	N4—Co1—N5	90.69 (10)
C19—C20—H20	119.9	N2—Co1—N5	88.25 (10)
C21—C20—H20	119.9	N3—Co1—N5	89.86 (10)
C20—C21—C22	120.2 (4)	N1—Co1—Cl1	90.47 (8)
C20—C21—H21	119.9	N4—Co1—Cl1	89.13 (8)
C22—C21—H21	119.9	N2—Co1—Cl1	90.91 (7)
C17—C22—C21	120.5 (3)	N3—Co1—Cl1	90.97 (8)
C17—C22—H22	119.8	N5—Co1—Cl1	179.11 (7)
C21—C22—H22	119.8

N1—C1—C2—N2	4.0 (4)	C17—C15—N3—O3	0.9 (4)
C3—C1—C2—N2	−170.2 (3)	C16—C15—N3—O3	178.3 (2)
N1—C1—C2—C9	−173.5 (3)	C17—C15—N3—Co1	−172.4 (2)
C3—C1—C2—C9	12.3 (5)	C16—C15—N3—Co1	5.0 (3)
N1—C1—C3—C4	62.3 (4)	C23—C16—N4—O4	0.2 (4)
C2—C1—C3—C4	−124.1 (4)	C15—C16—N4—O4	177.1 (2)
N1—C1—C3—C8	−114.9 (4)	C23—C16—N4—Co1	−175.5 (2)
C2—C1—C3—C8	58.7 (4)	C15—C16—N4—Co1	1.4 (3)
C8—C3—C4—C5	−0.1 (5)	N6—C31—N5—C29	−0.4 (4)
C1—C3—C4—C5	−177.3 (3)	N6—C31—N5—Co1	−175.6 (2)
C3—C4—C5—C6	1.1 (6)	C30—C29—N5—C31	−0.3 (4)
C4—C5—C6—C7	−1.4 (7)	C30—C29—N5—Co1	174.7 (2)
C5—C6—C7—C8	0.7 (7)	N5—C31—N6—C30	0.9 (4)
C4—C3—C8—C7	−0.6 (5)	C29—C30—N6—C31	−1.0 (4)
C1—C3—C8—C7	176.6 (3)	C1—N1—Co1—N4	154 (9)
C6—C7—C8—C3	0.3 (6)	O1—N1—Co1—N4	−33 (9)
N2—C2—C9—C10	−132.9 (3)	C1—N1—Co1—N2	4.7 (2)
C1—C2—C9—C10	44.3 (4)	O1—N1—Co1—N2	177.4 (2)
N2—C2—C9—C14	44.1 (4)	C1—N1—Co1—N3	−173.4 (2)
C1—C2—C9—C14	−138.7 (3)	O1—N1—Co1—N3	−0.7 (2)
C14—C9—C10—C11	0.0 (5)	C1—N1—Co1—N5	−83.6 (2)
C2—C9—C10—C11	177.1 (3)	O1—N1—Co1—N5	89.1 (2)
C9—C10—C11—C12	0.3 (6)	C1—N1—Co1—Cl1	95.5 (2)
C10—C11—C12—C13	−0.8 (6)	O1—N1—Co1—Cl1	−91.7 (2)
C11—C12—C13—C14	0.9 (6)	C16—N4—Co1—N1	33 (9)
C12—C13—C14—C9	−0.5 (6)	O4—N4—Co1—N1	−142 (9)
C10—C9—C14—C13	0.1 (5)	C16—N4—Co1—N2	−177.2 (2)
C2—C9—C14—C13	−177.0 (3)	O4—N4—Co1—N2	7.3 (2)
N3—C15—C16—N4	−4.0 (4)	C16—N4—Co1—N3	0.9 (2)
C17—C15—C16—N4	173.4 (3)	O4—N4—Co1—N3	−174.6 (2)
N3—C15—C16—C23	172.8 (3)	C16—N4—Co1—N5	−88.8 (2)
C17—C15—C16—C23	−9.8 (5)	O4—N4—Co1—N5	95.6 (2)
N3—C15—C17—C22	136.0 (3)	C16—N4—Co1—Cl1	92.1 (2)
C16—C15—C17—C22	−41.1 (4)	O4—N4—Co1—Cl1	−83.5 (2)
N3—C15—C17—C18	−42.1 (5)	C2—N2—Co1—N1	−2.2 (2)
C16—C15—C17—C18	140.8 (3)	O2—N2—Co1—N1	176.0 (2)
C22—C17—C18—C19	0.4 (5)	C2—N2—Co1—N4	178.2 (2)
C15—C17—C18—C19	178.5 (3)	O2—N2—Co1—N4	−3.6 (2)
C17—C18—C19—C20	−0.4 (6)	C2—N2—Co1—N3	100 (3)
C18—C19—C20—C21	−0.2 (7)	O2—N2—Co1—N3	−82 (3)
C19—C20—C21—C22	0.9 (7)	C2—N2—Co1—N5	87.8 (2)
C18—C17—C22—C21	0.3 (5)	O2—N2—Co1—N5	−94.1 (2)
C15—C17—C22—C21	−177.9 (3)	C2—N2—Co1—Cl1	−92.5 (2)
C20—C21—C22—C17	−0.9 (6)	O2—N2—Co1—Cl1	85.63 (19)
N4—C16—C23—C28	−55.4 (4)	C15—N3—Co1—N1	176.9 (2)
C15—C16—C23—C28	128.1 (3)	O3—N3—Co1—N1	3.7 (2)
N4—C16—C23—C24	123.3 (3)	C15—N3—Co1—N4	−3.5 (2)
C15—C16—C23—C24	−53.2 (4)	O3—N3—Co1—N4	−176.7 (2)
C28—C23—C24—C25	−0.2 (5)	C15—N3—Co1—N2	75 (3)
C16—C23—C24—C25	−178.8 (3)	O3—N3—Co1—N2	−99 (3)
C23—C24—C25—C26	0.2 (6)	C15—N3—Co1—N5	87.2 (2)
C24—C25—C26—C27	−0.8 (7)	O3—N3—Co1—N5	−86.0 (2)
C25—C26—C27—C28	1.3 (7)	C15—N3—Co1—Cl1	−92.4 (2)
C24—C23—C28—C27	0.7 (5)	O3—N3—Co1—Cl1	94.3 (2)
C16—C23—C28—C27	179.3 (3)	C31—N5—Co1—N1	149.3 (3)
C26—C27—C28—C23	−1.2 (6)	C29—N5—Co1—N1	−24.8 (3)
N5—C29—C30—N6	0.8 (4)	C31—N5—Co1—N4	−31.4 (3)
C2—C1—N1—O1	−178.7 (3)	C29—N5—Co1—N4	154.5 (3)
C3—C1—N1—O1	−4.4 (5)	C31—N5—Co1—N2	67.9 (3)
C2—C1—N1—Co1	−5.9 (3)	C29—N5—Co1—N2	−106.2 (3)
C3—C1—N1—Co1	168.4 (2)	C31—N5—Co1—N3	−111.7 (3)
C1—C2—N2—O2	−178.4 (2)	C29—N5—Co1—N3	74.2 (3)
C9—C2—N2—O2	−0.9 (4)	C31—N5—Co1—Cl1	47 (5)
C1—C2—N2—Co1	−0.3 (3)	C29—N5—Co1—Cl1	−127 (5)
C9—C2—N2—Co1	177.2 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H2···O2	1.05 (4)	1.46 (4)	2.482 (3)	165 (3)
O3—H3···O1	1.07 (5)	1.39 (5)	2.456 (3)	174 (4)
N6—H6A···O2ⁱ	0.98 (4)	1.78 (4)	2.747 (4)	166 (3)
N6—H6A···N2ⁱ	0.98 (4)	2.50 (4)	3.326 (4)	141 (3)
O5—H5B···Cl1	0.95 (1)	2.69 (8)	3.331 (7)	126 (7)

Symmetry code: (i) −x+3/2, y−1/2, z.

Experimental details

Crystal data
Chemical formula	[Co(C₁₄H₁₁N₂O₂)₂Cl(C₃H₄N₂)]·0.5H₂O
M_r	649.97
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	293
a, b, c (Å)	19.1004 (11), 12.0462 (7), 26.9627 (18)
V (Å³)	6203.8 (7)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.69
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1999)
T_min, T_max	0.732, 0.850
No. of measured, independent and observed [I > 2σ(I)] reflections	28473, 5282, 3705
R_int	0.051
(sin θ/λ)_max (Å⁻¹)	0.589

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.104, 1.06
No. of reflections	5282
No. of parameters	415
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.26

Computer programs: APEX2 (Bruker, 2004), APEX2 and SAINT (Bruker, 2004), SAINT and XPREP (Bruker, 2004), SIR92 (Altornare et al., 1993), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H2···O2	1.05 (4)	1.46 (4)	2.482 (3)	165 (3)
O3—H3···O1	1.07 (5)	1.39 (5)	2.456 (3)	174 (4)
N6—H6A···O2ⁱ	0.98 (4)	1.78 (4)	2.747 (4)	166 (3)
N6—H6A···N2ⁱ	0.98 (4)	2.50 (4)	3.326 (4)	141 (3)
O5—H5B···Cl1	0.946 (10)	2.69 (8)	3.331 (7)	126 (7)

Symmetry code: (i) −x+3/2, y−1/2, z.

Acknowledgements

The authors are thankful to Rev. Fr A. Albert Muthumalai, S.J., Principal, Loyola College (Autonomous), Chennai, India, for providing the necessary facilities, the head, SAIF, CDRI, Lucknow, India, for supplying elemental data and the head, SAIF, IIT Madras, Chennai, India, for recording the NMR spectra and for the X-ray data collection.

References

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