cis-Aqua­chloridobis(1,10-phenanthroline-κ2N,N′)cobalt(II) chloride 2.5-hydrate

Arun Kumar, K.; Dayalan, A.; SethuSankar, K.

doi:10.1107/S1600536809038422

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Pages m1300-m1301

https://doi.org/10.1107/S1600536809038422

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cis-Aquachloridobis(1,10-phenanthroline-κ²N,N′)cobalt(II) chloride 2.5-hydrate

K. Arun Kumar,^a ^* A. Dayalan ^a and K. SethuSankar ^b

^aDepartment of Chemistry, Loyola College (Autonomous), Chennai-34, India, and ^bDepartment of Physics, RKM Vivekananda College, Chennai-4, India
^*Correspondence e-mail: dayalan77@gmail.com

(Received 27 August 2009; accepted 22 September 2009; online 3 October 2009)

In the title complex, [CoCl(C₁₂H₈N₂)₂(H₂O)]Cl·2.5H₂O, the Co^II ion is coordinated by four N atoms of two bis-chelating 1,10-phenanthroline (phen) ligands, one water molecule and a chloride ligand in a distorted octahedral environment. The dihedral angle between the two phen ligands is 84.21 (3)°. In the crystal structure, complex molecules and chloride ions are linked into centrosymmetric four-component clusters by intermolecular O—H⋯Cl hydrogen bonds. Of the 2.5 solvent water molecules in the asymmetric unit, two were refined as disordered over two sites with fixed occupancies of ratios 0.50:0.50 and 0.60:0.40, while another was refined with half occupancy.

Related literature

1,10-Phenanthroline is a versatile ligand capable of forming highly stable complexes with transition metal ions, see: Nobufumi (1969 ). Metal complexes functionalized with 1,10-phenanthrolines have been used as catalyst for the enantio selective hydrolysis of N-protected amino acid esters and in enantio selective reduction of acetophenone, see: Weijnen et al. (1992 ). For some examples of the applications of substituted phenanthroline compounds, see Garuti et al. (1989 ). For the crystal structures of related cobalt complexes of 1,10-phenanthroline, see: Sun & Feng (2006 ); Zhong et al. (2006 ). For the crystal structure of the title complex with thioacetamide solvent rather than water, see: Zhong et al. (2007 ). For the use of metal complexes of 1,10-phenanthroline in developing new diagnostic and therapeutic agents that can recognize and cleave DNA, see: Arai et al. (2005 ); Müller et al. (1987 ). Oxovanadium complexes of dimethyl-substituted phenanthroline will induce apoptosis in human cancer cells, and may be useful for the treatment of cancer, see: Rama Krishna et al. (2000 ). Weijnen et al. (1992); Nobufumi (1969).

Experimental

Crystal data

[CoCl(C₁₂H₈N₂)₂(H₂O)]Cl·2.5H₂O
M_r = 553.29
Triclinic, $[P \overline 1]$
a = 9.6597 (3) Å
b = 11.4386 (3) Å
c = 12.9886 (4) Å
α = 64.224 (1)°
β = 86.377 (2)°
γ = 78.303 (1)°
V = 1265.01 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.93 mm⁻¹
T = 293 K
0.30 × 0.30 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.722, T_max = 0.812
34458 measured reflections
9683 independent reflections
7380 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.138
S = 1.10
9683 reflections
343 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.72 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯Cl2ⁱ	0.90 (2)	2.290 (19)	3.1530 (18)	162 (2)
O1—H1B⋯Cl2ⁱⁱ	0.90 (2)	2.190 (16)	3.0836 (15)	173 (3)
Symmetry codes: (i) -x+2, -y+1, -z+1; (ii) x, y+1, z-1.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536809038422/lh2895sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809038422/lh2895Isup2.hkl

checkCIF report

Comment top

1,10-phenanthroline is a versatile ligand capable of forming highly stable complexes with transition metal ions (Nobufumi, 1969). Complexes of 1,10-phenanthroline are frequently employed for catalytic reactions. For example metal complexes functionalized with 1,10-phenanthrolines have been used as catalyst for the enantio selective hydrolysis of N-protected amino acid esters and in enantio selective reduction of acetophenone (Weijnen, et al. 1992). The synthesis of some phenanthroline -2,9-disubstituted compounds along with their in vitro antimicrobial properties against gram-positive and gram – negative bacteria and fungi have been reported (Garuti et al.,1989). Metal complexes of 1,10-phenanthroline have been found to be attractive species for developing new diagnostic and therapeutic agents that can recognize and cleave DNA (Müller et al., 1987, Arai et al., 2005). Experimental evidence has been provided to prove oxovanadium complexes of dimethyl substituted phenanthroline will induce apoptosis in human cancer cells, and may be useful for the treatment of cancer (Rama Krishna, et al. 2000).

The molecular structure of the cation is shown in Fig. 1. The asymmetric unit contains one complex cation a chloride anion and 2.5 molecules of solvent water. The Co^II ion is coordinated in a distorted octahedral environment by four nitrogen atoms of two 1,10-phenanthroline ligands, a chloride ion, and a water molecule. The dihedral angle between the two phen ligands is 84.21 (3) °. In the crystal structure, complex molecules and chloride ions are linked into centrosymmetric four component clusters by intermolecular O—H···Cl hydrogen bonds. .

Related literature top

1,10-Phenanthroline is a versatile ligand capable of forming highly stable complexes with transition metal ions, see: Nobufumi (1969). Metal complexes functionalized with 1,10-phenanthrolines have been used as catalyst for the enantio selective hydrolysis of N-protected amino acid esters and in enantio selective reduction of acetophenone, see: Weijnen et al. (1992). For some examples of the applications of substituted phenanthroline compounds, see Garuti et al. (1989). For the crystal structures of related cobalt complexes of 1,10-phenanthroline, see: Sun & Feng (2006); Zhong et al. (2006). For the crystal structure of the title complex with thioacetamide solvent rather than water, see: Zhong et al. (2007). For the use of metal complexes of 1,10-phenanthroline in developing new diagnostic and therapeutic agents that can recognize and cleave DNA, see: Arai et al. (2005); Müller et al. (1987). Oxovanadium complexes of dimethyl-substituted phenanthroline will induce apoptosis in human cancer cells, and may be useful for the treatment of cancer, see: Rama Krishna et al. (2000). Weijnen et al. (1992); Nobufumi (1969).

Experimental top

Cobalt(II) chloride hexahydrate was thoroughly grinded and exposed to microwave radiation for 30s. The dehydrated cobalt(II) chloride (0.05 mol) was dissolved in 100 ml of acetone. 1,10-phenanathroline monohydrate (0.1 mol) was dissolved in 100 ml of acetone. The solution of 1,10-phenanathroline was slowly added with constant stirring to the solution of cobalt(II) chloride and allowed to react for two hours. After completion of the reaction, a reddish orange coloured solution was formed. The stirring was stopped and the reaction mixture was allowed to settle for one hour. The reddish orange coloured product was filtered and washed with acetone and dried over a desicator. Single crystals were obtained by slow evaporation of a methanolic solution of the title complex.

Structure description top

1,10-Phenanthroline is a versatile ligand capable of forming highly stable complexes with transition metal ions, see: Nobufumi (1969). Metal complexes functionalized with 1,10-phenanthrolines have been used as catalyst for the enantio selective hydrolysis of N-protected amino acid esters and in enantio selective reduction of acetophenone, see: Weijnen et al. (1992). For some examples of the applications of substituted phenanthroline compounds, see Garuti et al. (1989). For the crystal structures of related cobalt complexes of 1,10-phenanthroline, see: Sun & Feng (2006); Zhong et al. (2006). For the crystal structure of the title complex with thioacetamide solvent rather than water, see: Zhong et al. (2007). For the use of metal complexes of 1,10-phenanthroline in developing new diagnostic and therapeutic agents that can recognize and cleave DNA, see: Arai et al. (2005); Müller et al. (1987). Oxovanadium complexes of dimethyl-substituted phenanthroline will induce apoptosis in human cancer cells, and may be useful for the treatment of cancer, see: Rama Krishna et al. (2000). Weijnen et al. (1992); Nobufumi (1969).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. FMolecular structure of the cation of the title compound. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Part of the crystal structure showing O—H···Cl hydrogen bonds as dashed lines. The H atoms not involved in hydrogen bonds have been ommited. The solvent water molecules are not shown.

cis-Aquachloridobis(1,10-phenanthroline- κ²N,N')cobalt(II) chloride 2.5-hydrate top

Crystal data top

[CoCl(C₁₂H₈N₂)₂(H₂O)]Cl·2.5H₂O	Z = 2
M_r = 553.29	F(000) = 576
Triclinic, P1	D_x = 1.463 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.6597 (3) Å	Cell parameters from 7839 reflections
b = 11.4386 (3) Å	θ = 2.7–32.5°
c = 12.9886 (4) Å	µ = 0.93 mm⁻¹
α = 64.224 (1)°	T = 293 K
β = 86.377 (2)°	Plate, red
γ = 78.303 (1)°	0.30 × 0.30 × 0.20 mm
V = 1265.01 (6) Å³

Data collection top

Bruker Kappa APEXII CCD diffractometer	9683 independent reflections
Radiation source: fine-focus sealed tube	7380 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ω and φ scans	θ_max = 33.4°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→14
T_min = 0.722, T_max = 0.812	k = −17→17
34458 measured reflections	l = −19→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)] = 0.042	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.138	w = 1/[σ²(F_o²) + (0.0685P)² + 0.4443P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max = 0.001
9683 reflections	Δρ_max = 0.72 e Å⁻³
343 parameters	Δρ_min = −0.42 e Å⁻³
2 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0038 (12)

Crystal data top

[CoCl(C₁₂H₈N₂)₂(H₂O)]Cl·2.5H₂O	γ = 78.303 (1)°
M_r = 553.29	V = 1265.01 (6) Å³
Triclinic, P1	Z = 2
a = 9.6597 (3) Å	Mo Kα radiation
b = 11.4386 (3) Å	µ = 0.93 mm⁻¹
c = 12.9886 (4) Å	T = 293 K
α = 64.224 (1)°	0.30 × 0.30 × 0.20 mm
β = 86.377 (2)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	9683 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	7380 reflections with I > 2σ(I)
T_min = 0.722, T_max = 0.812	R_int = 0.028
34458 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	2 restraints
wR(F²) = 0.138	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	Δρ_max = 0.72 e Å⁻³
9683 reflections	Δρ_min = −0.42 e Å⁻³
343 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	0.6979 (2)	0.9429 (3)	0.1406 (2)	0.0498 (5)
H1	0.7847	0.9396	0.1056	0.060*
C2	0.6035 (3)	0.8711 (3)	0.1298 (3)	0.0634 (7)
H2	0.6280	0.8205	0.0891	0.076*
C3	0.4749 (3)	0.8757 (3)	0.1794 (3)	0.0593 (6)
H3	0.4102	0.8295	0.1718	0.071*
C4	0.4415 (2)	0.9510 (2)	0.24212 (18)	0.0413 (4)
C5	0.3106 (2)	0.9586 (2)	0.3001 (2)	0.0485 (5)
H5	0.2420	0.9155	0.2936	0.058*
C6	0.2858 (2)	1.0266 (2)	0.36317 (19)	0.0444 (5)
H6	0.2015	1.0276	0.4019	0.053*
C7	0.38682 (18)	1.09809 (18)	0.37217 (15)	0.0355 (4)
C8	0.3665 (2)	1.1707 (2)	0.43717 (17)	0.0426 (4)
H8	0.2844	1.1737	0.4782	0.051*
C9	0.4674 (2)	1.2367 (2)	0.44004 (18)	0.0436 (4)
H9	0.4545	1.2861	0.4822	0.052*
C10	0.5913 (2)	1.22959 (19)	0.37879 (17)	0.0377 (4)
H10	0.6594	1.2755	0.3810	0.045*
C11	0.51474 (17)	1.09520 (16)	0.31430 (14)	0.0300 (3)
C12	0.54289 (17)	1.01907 (18)	0.24953 (15)	0.0319 (3)
C13	0.9632 (2)	1.2764 (2)	0.31592 (19)	0.0430 (4)
H13	0.9838	1.1955	0.3800	0.052*
C14	1.0192 (3)	1.3822 (3)	0.3113 (3)	0.0567 (6)
H14	1.0759	1.3711	0.3713	0.068*
C15	0.9900 (3)	1.5015 (2)	0.2182 (3)	0.0565 (6)
H15	1.0279	1.5720	0.2137	0.068*
C16	0.9028 (2)	1.5171 (2)	0.1295 (2)	0.0449 (5)
C17	0.8652 (3)	1.6387 (2)	0.0285 (3)	0.0590 (7)
H17	0.9002	1.7123	0.0201	0.071*
C18	0.7806 (3)	1.6483 (2)	−0.0541 (2)	0.0606 (7)
H18	0.7584	1.7283	−0.1188	0.073*
C19	0.7241 (2)	1.5380 (2)	−0.04446 (18)	0.0460 (5)
C20	0.6344 (3)	1.5425 (3)	−0.1270 (2)	0.0594 (7)
H20	0.6094	1.6204	−0.1933	0.071*
C21	0.5838 (3)	1.4333 (3)	−0.1105 (2)	0.0579 (6)
H21	0.5228	1.4362	−0.1644	0.069*
C22	0.6249 (2)	1.3163 (2)	−0.01098 (18)	0.0444 (4)
H22	0.5913	1.2415	−0.0009	0.053*
C23	0.75899 (18)	1.41697 (17)	0.05320 (15)	0.0334 (3)
C24	0.85017 (18)	1.40623 (17)	0.14098 (16)	0.0334 (3)
O2'	0.6535 (14)	0.3986 (11)	0.6280 (11)	0.195 (6)	0.40
O2	0.3871 (11)	0.4705 (7)	0.6502 (7)	0.190 (4)	0.60
O3	0.9469 (11)	0.3167 (6)	0.6132 (6)	0.125 (3)	0.50
O3'	1.0826 (15)	0.2976 (8)	0.6422 (8)	0.180 (5)	0.50
O4	1.1914 (12)	0.4501 (10)	0.5278 (7)	0.171 (4)	0.50
N1	0.66940 (16)	1.01569 (16)	0.19855 (14)	0.0350 (3)
N2	0.61525 (15)	1.16040 (14)	0.31806 (12)	0.0299 (3)
N3	0.88180 (15)	1.28706 (15)	0.23231 (13)	0.0319 (3)
N4	0.70912 (16)	1.30782 (15)	0.06895 (13)	0.0329 (3)
O1	0.95884 (15)	1.10031 (14)	0.11464 (12)	0.0382 (3)
Cl1	0.92546 (5)	0.95686 (5)	0.38472 (4)	0.03919 (11)
Cl2	0.88362 (6)	0.18004 (6)	0.86264 (5)	0.04968 (13)
Co1	0.79827 (2)	1.13428 (2)	0.222016 (18)	0.02766 (7)
H1A	1.006 (3)	1.0167 (13)	0.138 (2)	0.062 (8)*
H1B	0.930 (3)	1.129 (3)	0.0417 (11)	0.058 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0438 (11)	0.0636 (14)	0.0639 (14)	−0.0216 (10)	0.0158 (10)	−0.0447 (12)
C2	0.0605 (14)	0.0834 (18)	0.0834 (19)	−0.0336 (13)	0.0197 (13)	−0.0640 (17)
C3	0.0521 (13)	0.0754 (17)	0.0757 (17)	−0.0336 (12)	0.0103 (12)	−0.0476 (15)
C4	0.0346 (9)	0.0504 (11)	0.0434 (10)	−0.0180 (8)	0.0024 (7)	−0.0203 (9)
C5	0.0328 (9)	0.0598 (13)	0.0524 (12)	−0.0216 (9)	0.0032 (8)	−0.0187 (10)
C6	0.0258 (8)	0.0540 (11)	0.0452 (11)	−0.0110 (7)	0.0057 (7)	−0.0134 (9)
C7	0.0270 (7)	0.0379 (8)	0.0308 (8)	−0.0038 (6)	0.0030 (6)	−0.0062 (7)
C8	0.0337 (9)	0.0462 (10)	0.0366 (9)	−0.0005 (7)	0.0083 (7)	−0.0114 (8)
C9	0.0455 (10)	0.0461 (10)	0.0385 (10)	−0.0022 (8)	0.0072 (8)	−0.0212 (8)
C10	0.0383 (9)	0.0393 (9)	0.0371 (9)	−0.0065 (7)	0.0037 (7)	−0.0188 (7)
C11	0.0253 (7)	0.0319 (7)	0.0263 (7)	−0.0047 (5)	0.0001 (5)	−0.0069 (6)
C12	0.0270 (7)	0.0362 (8)	0.0313 (8)	−0.0094 (6)	0.0004 (6)	−0.0119 (6)
C13	0.0411 (10)	0.0462 (10)	0.0478 (11)	−0.0080 (8)	−0.0065 (8)	−0.0251 (9)
C14	0.0518 (12)	0.0613 (14)	0.0757 (17)	−0.0144 (11)	−0.0087 (11)	−0.0440 (13)
C15	0.0506 (12)	0.0496 (12)	0.0876 (18)	−0.0215 (10)	0.0092 (12)	−0.0424 (13)
C16	0.0410 (10)	0.0345 (9)	0.0619 (13)	−0.0133 (7)	0.0157 (9)	−0.0226 (9)
C17	0.0592 (14)	0.0306 (9)	0.0793 (18)	−0.0159 (9)	0.0251 (13)	−0.0165 (10)
C18	0.0700 (16)	0.0306 (9)	0.0575 (14)	−0.0056 (9)	0.0199 (12)	−0.0016 (9)
C19	0.0458 (10)	0.0358 (9)	0.0371 (10)	0.0030 (8)	0.0101 (8)	−0.0040 (7)
C20	0.0609 (14)	0.0527 (13)	0.0353 (10)	0.0138 (11)	−0.0021 (10)	−0.0023 (9)
C21	0.0543 (13)	0.0698 (16)	0.0361 (10)	0.0118 (12)	−0.0160 (9)	−0.0184 (11)
C22	0.0410 (10)	0.0521 (11)	0.0378 (10)	0.0014 (8)	−0.0075 (8)	−0.0206 (9)
C23	0.0313 (8)	0.0306 (7)	0.0312 (8)	−0.0017 (6)	0.0070 (6)	−0.0094 (6)
C24	0.0306 (7)	0.0305 (7)	0.0386 (9)	−0.0075 (6)	0.0086 (6)	−0.0149 (7)
O2'	0.207 (12)	0.110 (7)	0.169 (10)	−0.002 (7)	0.033 (9)	0.015 (7)
O2	0.282 (10)	0.100 (5)	0.180 (7)	−0.020 (5)	−0.061 (7)	−0.051 (5)
O3	0.238 (9)	0.059 (3)	0.062 (3)	−0.024 (5)	0.029 (5)	−0.017 (2)
O3'	0.349 (16)	0.074 (5)	0.123 (7)	−0.049 (8)	0.064 (9)	−0.053 (5)
O4	0.242 (10)	0.192 (9)	0.128 (6)	−0.078 (8)	0.062 (7)	−0.107 (7)
N1	0.0306 (7)	0.0418 (8)	0.0396 (8)	−0.0130 (6)	0.0071 (6)	−0.0221 (7)
N2	0.0283 (6)	0.0313 (6)	0.0281 (6)	−0.0055 (5)	0.0021 (5)	−0.0114 (5)
N3	0.0306 (7)	0.0323 (7)	0.0332 (7)	−0.0076 (5)	0.0009 (5)	−0.0138 (6)
N4	0.0329 (7)	0.0350 (7)	0.0289 (7)	−0.0032 (5)	0.0017 (5)	−0.0137 (6)
O1	0.0384 (7)	0.0389 (7)	0.0338 (7)	−0.0044 (5)	0.0073 (5)	−0.0147 (5)
Cl1	0.0372 (2)	0.0397 (2)	0.0311 (2)	−0.00573 (16)	−0.00006 (16)	−0.00724 (16)
Cl2	0.0557 (3)	0.0504 (3)	0.0480 (3)	−0.0067 (2)	0.0007 (2)	−0.0273 (2)
Co1	0.02642 (11)	0.02914 (11)	0.02756 (12)	−0.00822 (8)	0.00243 (8)	−0.01140 (8)

Geometric parameters (Å, º) top

C1—N1	1.328 (3)	C14—H14	0.9300
C1—C2	1.394 (3)	C15—C16	1.397 (4)
C1—H1	0.9300	C15—H15	0.9300
C2—C3	1.365 (4)	C16—C24	1.406 (3)
C2—H2	0.9300	C16—C17	1.433 (3)
C3—C4	1.405 (3)	C17—C18	1.343 (4)
C3—H3	0.9300	C17—H17	0.9300
C4—C12	1.401 (2)	C18—C19	1.428 (4)
C4—C5	1.437 (3)	C18—H18	0.9300
C5—C6	1.338 (3)	C19—C20	1.397 (4)
C5—H5	0.9300	C19—C23	1.406 (3)
C6—C7	1.434 (3)	C20—C21	1.359 (4)
C6—H6	0.9300	C20—H20	0.9300
C7—C8	1.401 (3)	C21—C22	1.401 (3)
C7—C11	1.407 (2)	C21—H21	0.9300
C8—C9	1.360 (3)	C22—N4	1.318 (3)
C8—H8	0.9300	C22—H22	0.9300
C9—C10	1.403 (3)	C23—N4	1.357 (2)
C9—H9	0.9300	C23—C24	1.432 (3)
C10—N2	1.322 (2)	C24—N3	1.353 (2)
C10—H10	0.9300	N1—Co1	2.1389 (15)
C11—N2	1.354 (2)	N2—Co1	2.1453 (14)
C11—C12	1.432 (3)	N3—Co1	2.1241 (15)
C12—N1	1.354 (2)	N4—Co1	2.1738 (15)
C13—N3	1.329 (2)	O1—Co1	2.1108 (13)
C13—C14	1.398 (3)	O1—H1A	0.896 (10)
C13—H13	0.9300	O1—H1B	0.898 (10)
C14—C15	1.363 (4)	Cl1—Co1	2.3835 (5)

N1—C1—C2	122.9 (2)	C17—C18—C19	121.3 (2)
N1—C1—H1	118.5	C17—C18—H18	119.4
C2—C1—H1	118.5	C19—C18—H18	119.4
C3—C2—C1	119.5 (2)	C20—C19—C23	117.1 (2)
C3—C2—H2	120.2	C20—C19—C18	123.8 (2)
C1—C2—H2	120.2	C23—C19—C18	119.1 (2)
C2—C3—C4	119.1 (2)	C21—C20—C19	120.1 (2)
C2—C3—H3	120.5	C21—C20—H20	120.0
C4—C3—H3	120.5	C19—C20—H20	120.0
C12—C4—C3	117.69 (18)	C20—C21—C22	119.1 (2)
C12—C4—C5	119.22 (19)	C20—C21—H21	120.4
C3—C4—C5	123.07 (19)	C22—C21—H21	120.4
C6—C5—C4	121.13 (18)	N4—C22—C21	122.7 (2)
C6—C5—H5	119.4	N4—C22—H22	118.6
C4—C5—H5	119.4	C21—C22—H22	118.6
C5—C6—C7	121.14 (18)	N4—C23—C19	122.64 (19)
C5—C6—H6	119.4	N4—C23—C24	117.64 (15)
C7—C6—H6	119.4	C19—C23—C24	119.72 (18)
C8—C7—C11	117.27 (17)	N3—C24—C16	122.97 (19)
C8—C7—C6	123.58 (17)	N3—C24—C23	117.24 (15)
C11—C7—C6	119.15 (18)	C16—C24—C23	119.78 (18)
C9—C8—C7	119.68 (17)	C1—N1—C12	117.90 (16)
C9—C8—H8	120.2	C1—N1—Co1	128.30 (13)
C7—C8—H8	120.2	C12—N1—Co1	113.80 (12)
C8—C9—C10	119.29 (19)	C10—N2—C11	118.18 (15)
C8—C9—H9	120.4	C10—N2—Co1	128.29 (13)
C10—C9—H9	120.4	C11—N2—Co1	113.53 (11)
N2—C10—C9	122.77 (19)	C13—N3—C24	117.96 (16)
N2—C10—H10	118.6	C13—N3—Co1	127.18 (13)
C9—C10—H10	118.6	C24—N3—Co1	114.83 (12)
N2—C11—C7	122.79 (17)	C22—N4—C23	118.33 (17)
N2—C11—C12	117.62 (14)	C22—N4—Co1	128.70 (14)
C7—C11—C12	119.59 (16)	C23—N4—Co1	112.74 (12)
N1—C12—C4	122.85 (17)	Co1—O1—H1A	116.3 (19)
N1—C12—C11	117.43 (15)	Co1—O1—H1B	114.6 (18)
C4—C12—C11	119.72 (16)	H1A—O1—H1B	107 (3)
N3—C13—C14	122.6 (2)	O1—Co1—N3	93.44 (6)
N3—C13—H13	118.7	O1—Co1—N1	94.48 (6)
C14—C13—H13	118.7	N3—Co1—N1	166.38 (6)
C15—C14—C13	119.6 (2)	O1—Co1—N2	171.52 (6)
C15—C14—H14	120.2	N3—Co1—N2	93.79 (6)
C13—C14—H14	120.2	N1—Co1—N2	77.58 (6)
C14—C15—C16	119.52 (19)	O1—Co1—N4	85.36 (5)
C14—C15—H15	120.2	N3—Co1—N4	77.19 (6)
C16—C15—H15	120.2	N1—Co1—N4	92.42 (6)
C15—C16—C24	117.4 (2)	N2—Co1—N4	91.91 (5)
C15—C16—C17	123.7 (2)	O1—Co1—Cl1	90.18 (4)
C24—C16—C17	118.9 (2)	N3—Co1—Cl1	96.39 (4)
C18—C17—C16	121.3 (2)	N1—Co1—Cl1	94.66 (5)
C18—C17—H17	119.4	N2—Co1—Cl1	93.43 (4)
C16—C17—H17	119.4	N4—Co1—Cl1	171.92 (4)

N1—C1—C2—C3	0.7 (5)	C9—C10—N2—Co1	−178.68 (14)
C1—C2—C3—C4	−1.1 (5)	C7—C11—N2—C10	−0.1 (2)
C2—C3—C4—C12	0.6 (4)	C12—C11—N2—C10	−179.13 (16)
C2—C3—C4—C5	−178.1 (3)	C7—C11—N2—Co1	179.45 (13)
C12—C4—C5—C6	−1.8 (3)	C12—C11—N2—Co1	0.39 (18)
C3—C4—C5—C6	176.9 (2)	C14—C13—N3—C24	−1.5 (3)
C4—C5—C6—C7	2.1 (3)	C14—C13—N3—Co1	176.37 (17)
C5—C6—C7—C8	−179.9 (2)	C16—C24—N3—C13	1.9 (3)
C5—C6—C7—C11	−0.6 (3)	C23—C24—N3—C13	−178.24 (17)
C11—C7—C8—C9	1.4 (3)	C16—C24—N3—Co1	−176.25 (14)
C6—C7—C8—C9	−179.36 (19)	C23—C24—N3—Co1	3.6 (2)
C7—C8—C9—C10	−0.8 (3)	C21—C22—N4—C23	−0.7 (3)
C8—C9—C10—N2	−0.3 (3)	C21—C22—N4—Co1	−174.82 (17)
C8—C7—C11—N2	−1.0 (3)	C19—C23—N4—C22	0.1 (3)
C6—C7—C11—N2	179.73 (16)	C24—C23—N4—C22	179.86 (17)
C8—C7—C11—C12	178.05 (16)	C19—C23—N4—Co1	175.15 (14)
C6—C7—C11—C12	−1.2 (3)	C24—C23—N4—Co1	−5.10 (19)
C3—C4—C12—N1	0.5 (3)	C13—N3—Co1—O1	−98.21 (17)
C5—C4—C12—N1	179.22 (19)	C24—N3—Co1—O1	79.76 (12)
C3—C4—C12—C11	−178.9 (2)	C13—N3—Co1—N1	136.3 (2)
C5—C4—C12—C11	−0.1 (3)	C24—N3—Co1—N1	−45.7 (3)
N2—C11—C12—N1	1.3 (2)	C13—N3—Co1—N2	86.24 (17)
C7—C11—C12—N1	−177.80 (16)	C24—N3—Co1—N2	−95.79 (12)
N2—C11—C12—C4	−179.35 (17)	C13—N3—Co1—N4	177.34 (17)
C7—C11—C12—C4	1.6 (3)	C24—N3—Co1—N4	−4.69 (12)
N3—C13—C14—C15	0.1 (4)	C13—N3—Co1—Cl1	−7.64 (17)
C13—C14—C15—C16	1.0 (4)	C24—N3—Co1—Cl1	170.32 (12)
C14—C15—C16—C24	−0.7 (3)	C1—N1—Co1—O1	4.1 (2)
C14—C15—C16—C17	179.6 (2)	C12—N1—Co1—O1	−175.11 (13)
C15—C16—C17—C18	−179.8 (2)	C1—N1—Co1—N3	129.5 (3)
C24—C16—C17—C18	0.4 (3)	C12—N1—Co1—N3	−49.7 (3)
C16—C17—C18—C19	0.3 (4)	C1—N1—Co1—N2	−179.0 (2)
C17—C18—C19—C20	179.3 (2)	C12—N1—Co1—N2	1.85 (13)
C17—C18—C19—C23	−0.5 (3)	C1—N1—Co1—N4	89.6 (2)
C23—C19—C20—C21	0.6 (3)	C12—N1—Co1—N4	−89.58 (13)
C18—C19—C20—C21	−179.1 (2)	C1—N1—Co1—Cl1	−86.5 (2)
C19—C20—C21—C22	−1.1 (4)	C12—N1—Co1—Cl1	94.34 (13)
C20—C21—C22—N4	1.2 (4)	C10—N2—Co1—O1	−160.7 (3)
C20—C19—C23—N4	−0.1 (3)	C11—N2—Co1—O1	19.8 (4)
C18—C19—C23—N4	179.69 (18)	C10—N2—Co1—N3	−12.39 (16)
C20—C19—C23—C24	−179.81 (18)	C11—N2—Co1—N3	168.16 (12)
C18—C19—C23—C24	−0.1 (3)	C10—N2—Co1—N1	178.27 (17)
C15—C16—C24—N3	−0.8 (3)	C11—N2—Co1—N1	−1.18 (11)
C17—C16—C24—N3	178.91 (19)	C10—N2—Co1—N4	−89.67 (16)
C15—C16—C24—C23	179.33 (18)	C11—N2—Co1—N4	90.87 (12)
C17—C16—C24—C23	−0.9 (3)	C10—N2—Co1—Cl1	84.26 (15)
N4—C23—C24—N3	1.1 (2)	C11—N2—Co1—Cl1	−95.20 (11)
C19—C23—C24—N3	−179.10 (16)	C22—N4—Co1—O1	85.00 (17)
N4—C23—C24—C16	−179.01 (16)	C23—N4—Co1—O1	−89.41 (12)
C19—C23—C24—C16	0.7 (3)	C22—N4—Co1—N3	179.59 (18)
C2—C1—N1—C12	0.3 (4)	C23—N4—Co1—N3	5.19 (11)
C2—C1—N1—Co1	−178.9 (2)	C22—N4—Co1—N1	−9.31 (17)
C4—C12—N1—C1	−0.9 (3)	C23—N4—Co1—N1	176.29 (12)
C11—C12—N1—C1	178.44 (19)	C22—N4—Co1—N2	−86.96 (17)
C4—C12—N1—Co1	178.38 (15)	C23—N4—Co1—N2	98.64 (12)
C11—C12—N1—Co1	−2.3 (2)	C22—N4—Co1—Cl1	141.7 (3)
C9—C10—N2—C11	0.7 (3)	C23—N4—Co1—Cl1	−32.7 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···Cl2ⁱ	0.90 (2)	2.29 (2)	3.1530 (18)	162 (2)
O1—H1B···Cl2ⁱⁱ	0.90 (2)	2.19 (2)	3.0836 (15)	173 (3)

Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x, y+1, z−1.

Experimental details

Crystal data
Chemical formula	[CoCl(C₁₂H₈N₂)₂(H₂O)]Cl·2.5H₂O
M_r	553.29
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	9.6597 (3), 11.4386 (3), 12.9886 (4)
α, β, γ (°)	64.224 (1), 86.377 (2), 78.303 (1)
V (Å³)	1265.01 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.93
Crystal size (mm)	0.30 × 0.30 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.722, 0.812
No. of measured, independent and observed [I > 2σ(I)] reflections	34458, 9683, 7380
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.775

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.138, 1.10
No. of reflections	9683
No. of parameters	343
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)	0.72, −0.42

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···Cl2ⁱ	0.90 (2)	2.290 (19)	3.1530 (18)	162 (2)
O1—H1B···Cl2ⁱⁱ	0.90 (2)	2.190 (16)	3.0836 (15)	173 (3)

Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x, y+1, z−1.

Acknowledgements

The authors are thankful to Rev. Fr Dr A. Albert Muthumali, S.J., Principal, Loyola College (Autonomous), Chennai-34, India, for providing the necessary facilities and the Head, SAIF, IIT Madras, Chennai-36, India, for recording the X-ray data.

References

Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343–350. CrossRef Web of Science IUCr Journals Google Scholar
Arai, T., Hayashi, K., Ozaki, H. & Sawai, H. (2005). Nippon Kagakkai Koen Yokoshu Jpn, 85, 1336–1337. Google Scholar
Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Garuti, L., Ferranti, A., Burnelli, S., Varoli, L., Giovanninetti, G., Brigidi, P. & Casolari, A. (1989). Boll. Chim. Farm. 128, 136–140. CAS PubMed Google Scholar
Müller, B. C., Raphael, A. L. & Barton, J. K. (1987). Proc. Natl Acad. Sci. USA, 84, 1764–1768. PubMed Web of Science Google Scholar
Nobufumi, M. (1969). Bull. Chem. Soc. Jpn, 42, 2275–2281. Google Scholar
Rama Krishna, N., Yanhong, D., Osmond, J., D′Cruz, C. N. & Fatih, M. U. (2000). Clin. Cancer Res. 6, 1546–1556. Web of Science PubMed Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sun, J.-H. & Feng, X. (2006). Acta Cryst. E62, m3370–m3372. Web of Science CSD CrossRef IUCr Journals Google Scholar
Weijnen, J. G. J., Koudijs, A. & Engbersen, J. F. J. (1992). J. Org. Chem. 57, 7258–7265. CrossRef CAS Web of Science Google Scholar
Zhong, H., Zeng, X.-R. & Luo, Q.-Y. (2006). Acta Cryst. E62, m3330–m3332. Web of Science CrossRef IUCr Journals Google Scholar
Zhong, H., Zeng, X.-R. & Luo, Q.-Y. (2007). Acta Cryst. E63, m221–m223. Web of Science Google Scholar