cis-Bis(2,2′-bipyridine-κ² N,N′)dichloridocobalt(II) trihydrate

Abstract

In the title complex, [CoCl₂(C₁₀H₈N₂)₂]·3H₂O, the Co(II) ion is situated on a twofold rotation axis and exhibits a slightly distorted octa­hedral geometry and is chelated by four N atoms of the two bidentate 2,2′-bipyridine ligands and two Cl⁻ ions. The crystal packing is stabilized by hydrogen bonding formed between chloride ions and adjacent water mol­ecules. One of the two independent water molecules in the asymmetric unit is disordered over two sets of sites, each on a twofold rotation axis, in a 0.734 (17):0.269 (17) ratio.

Related literature

For the anti­bacterial activity of similar complexes, see: Senthilkumar & Arunachalam (2008 ▶). For similar complexes applied in the immunoassay of carcinoma anti­gen-125, see: Shihong et al. (2009 ▶). For the application of similar complexes as biosensors, see: Ying et al. (2006 ▶).

Experimental

Crystal data

• [CoCl₂(C₁₀H₈N₂)₂]·3H₂O

• M _r = 496.25

• Monoclinic,

• a = 18.3644 (8) Å

• b = 13.1902 (8) Å

• c = 10.8854 (6) Å

• β = 120.030 (4)°

• V = 2282.8 (2) ų

• Z = 4

• Mo Kα radiation

• μ = 1.01 mm⁻¹

• T = 293 K

• 0.30 × 0.20 × 0.20 mm

Data collection

• Bruker Kappa APEXII CCD diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T _min = 0.721, T _max = 0.823

• 18022 measured reflections

• 2123 independent reflections

• 1731 reflections with I > 2σ(I)

• R _int = 0.051

Refinement

• R[F ² > 2σ(F ²)] = 0.045

• wR(F ²) = 0.143

• S = 1.19

• 2123 reflections

• 152 parameters

• 4 restraints

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.67 e Å⁻³

• Δρ_min = −0.65 e Å⁻³

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 (Bruno et al., 2002 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶).

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯Cl1	0.86 (6)	2.43 (5)	3.250 (4)	160 (5)
O1—H1B⋯Cl1i	0.85 (3)	2.37 (4)	3.218 (4)	172 (4)

Symmetry code: (i) .

supplementary crystallographic information

Comment

2,2-Bipyridine and 1,10-phenanthroline have been extensively used to form different complexes with transition metal ions in their various oxidation states. Tris(2,2'-bipyridine)cobalt(III) complexed with bovine serum albumin has been reported as biosensors (Ying et al., 2006). Bipyridine cobalt complexes were found to have considerable antibacterial activities (Senthilkumar & Arunachalam, 2008). The use of tris(bipyridine)cobalt(II) for immunoassay of carcinoma antigen-125 has been reported recently (Shihong et al., 2009).

The cobalt(II) ion has site symmetry 2 and assumes octahedral geometry with two symmetry related 2,2'- bipyridine ligands and two chloride ions. Cobalt(II) is linked to two 2,2'- bipyridine bidentate ligands via four nitrogen atoms and two chloride ions. The two 2,2'- bipyridine ligands are in cis position with mutually perpendicular to each other. The hydrated water molecules in the crystal packing helps the stabilization of crystal packing by forming hydrogen bonding between adjacent chloride ions.

Experimental

The complex was prepared by adding a solution of 2,2'- bipyridine (0.01 mole) in 60 ml of acetone, to a solution of cobalt(II) chloride (0.005 mole) in 60 ml of acetone. The resulting solution was stirred for two hours, filtered and dried over vacuum desiccator to get red colour complex (yield 90%). The dark red colored crystals, suitable for x-ray analysis, were obtained by slow evaporation from alcoholic solution.

Refinement

There is 1.5 water molecules per asymmetric unit. The H atoms of water oxygen O1 could be located in difference Fourier map. These H atoms were restrained to be at a distance of 0.85 Å from O1. The inter hydrogen distance was restrained to be 1.388 Å so as to retain the tetrahedral H—O—H angle. The other half molecule was disordered in two positions (O2 and O3). Their occupancies were refined initially as free variables and later the sum of the occupancies restrained as 0.5. The H atoms of disordered water molecules could not be located. The aromatic H atoms were constrained as riding atoms with d(C—H) = 0.93 Å and U_iso(H) = 1.2U_equ(C).

Figures

Fig. 1.

ORTEP of [Co(bpy)2(Cl)2].3H2O drawn with 50% displacement ellipsoid level. Water molecules have been omitted for clarity.

Fig. 2.

The crystal packing of [Co(bpy)2(Cl)2].3H2O viewed along the c axis.

Crystal data

[CoCl2(C10H8N2)2]·3H2O	F(000) = 1020
Mr = 496.25	Dx = 1.444 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C2yc	Cell parameters from 6958 reflections
a = 18.3644 (8) Å	θ = 2.4–25.4°
b = 13.1902 (8) Å	µ = 1.01 mm−1
c = 10.8854 (6) Å	T = 293 K
β = 120.030 (4)°	Block, red
V = 2282.8 (2) Å3	0.30 × 0.20 × 0.20 mm
Z = 4

Data collection

Bruker Kappa APEXII CCD diffractometer	2123 independent reflections
Radiation source: fine-focus sealed tube	1731 reflections with I > 2σ(I)
graphite	Rint = 0.051
ω and φ scans	θmax = 25.6°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −22→19
Tmin = 0.721, Tmax = 0.823	k = −15→15
18022 measured reflections	l = −13→13

Refinement

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)] = 0.045	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.143	w = 1/[σ2(Fo2) + (0.0754P)2 + 3.251P] where P = (Fo2 + 2Fc2)/3
S = 1.19	(Δ/σ)max < 0.001
2123 reflections	Δρmax = 0.67 e Å−3
152 parameters	Δρmin = −0.64 e Å−3
4 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0015 (5)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.9376 (3)	0.3673 (3)	0.5122 (5)	0.0632 (11)
H1	0.9858	0.3506	0.5089	0.076*
C2	0.8848 (3)	0.4410 (4)	0.4210 (6)	0.0774 (14)
H2	0.8973	0.4740	0.3583	0.093*
C3	0.8134 (3)	0.4643 (4)	0.4254 (6)	0.0772 (14)
H3	0.7768	0.5140	0.3658	0.093*
C4	0.7964 (3)	0.4142 (3)	0.5176 (5)	0.0610 (11)
H4	0.7476	0.4288	0.5202	0.073*
C5	0.8517 (2)	0.3418 (2)	0.6070 (4)	0.0428 (8)
C6	0.8377 (2)	0.2843 (2)	0.7097 (3)	0.0394 (8)
C7	0.7668 (2)	0.2959 (3)	0.7214 (4)	0.0518 (9)
H7	0.7247	0.3408	0.6623	0.062*
C8	0.7588 (2)	0.2405 (4)	0.8212 (5)	0.0599 (10)
H8	0.7120	0.2486	0.8319	0.072*
C9	0.8211 (2)	0.1730 (3)	0.9046 (4)	0.0576 (10)
H9	0.8171	0.1344	0.9725	0.069*
C10	0.8893 (2)	0.1635 (3)	0.8859 (4)	0.0472 (8)
H10	0.9310	0.1172	0.9419	0.057*
N1	0.92249 (18)	0.3194 (2)	0.6043 (3)	0.0449 (7)
N2	0.89867 (17)	0.2174 (2)	0.7915 (3)	0.0392 (6)
O1	0.8926 (3)	−0.0960 (3)	0.7511 (4)	0.0902 (12)
Cl1	0.92474 (5)	0.07552 (7)	0.56901 (9)	0.0448 (3)
Co1	1.0000	0.20323 (5)	0.7500	0.0367 (3)
O2	1.0000	−0.2593 (12)	0.7500	0.169 (6)	0.734 (17)
O3	1.0000	−0.4227	0.7500	0.174 (19)	0.269 (17)
H1A	0.911 (4)	−0.046 (3)	0.724 (5)	0.11 (2)*
H1B	0.904 (4)	−0.085 (4)	0.836 (3)	0.11 (2)*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.043 (2)	0.068 (3)	0.071 (3)	−0.0005 (18)	0.023 (2)	0.021 (2)
C2	0.061 (3)	0.076 (3)	0.083 (3)	0.003 (2)	0.027 (2)	0.042 (3)
C3	0.057 (3)	0.062 (3)	0.088 (3)	0.011 (2)	0.018 (2)	0.036 (2)
C4	0.046 (2)	0.050 (2)	0.070 (3)	0.0110 (17)	0.016 (2)	0.0131 (19)
C5	0.0330 (17)	0.0354 (17)	0.0441 (18)	−0.0011 (13)	0.0074 (14)	−0.0034 (14)
C6	0.0301 (17)	0.0368 (17)	0.0399 (17)	0.0027 (12)	0.0089 (14)	−0.0068 (14)
C7	0.0332 (19)	0.059 (2)	0.051 (2)	0.0130 (15)	0.0122 (16)	−0.0016 (17)
C8	0.045 (2)	0.077 (3)	0.064 (2)	0.014 (2)	0.032 (2)	0.001 (2)
C9	0.049 (2)	0.074 (3)	0.053 (2)	0.0112 (19)	0.0282 (19)	0.007 (2)
C10	0.0359 (18)	0.055 (2)	0.0461 (19)	0.0082 (16)	0.0174 (15)	0.0074 (17)
N1	0.0331 (15)	0.0416 (16)	0.0487 (16)	−0.0004 (12)	0.0120 (13)	0.0027 (13)
N2	0.0265 (14)	0.0427 (16)	0.0394 (14)	0.0044 (11)	0.0098 (11)	0.0005 (12)
O1	0.101 (3)	0.110 (3)	0.064 (2)	−0.057 (2)	0.044 (2)	−0.018 (2)
Cl1	0.0335 (5)	0.0513 (6)	0.0415 (5)	−0.0071 (3)	0.0128 (4)	−0.0062 (3)
Co1	0.0238 (4)	0.0402 (4)	0.0382 (4)	0.000	0.0097 (3)	0.000
O2	0.133 (10)	0.217 (14)	0.117 (8)	0.000	0.032 (7)	0.000
O3	0.20 (3)	0.28 (5)	0.11 (2)	0.000	0.12 (2)	0.000

Geometric parameters (Å, °)

C1—N1	1.327 (5)	C8—C9	1.373 (6)
C1—C2	1.381 (6)	C8—H8	0.9300
C1—H1	0.9300	C9—C10	1.373 (5)
C2—C3	1.370 (7)	C9—H9	0.9300
C2—H2	0.9300	C10—N2	1.329 (5)
C3—C4	1.362 (6)	C10—H10	0.9300
C3—H3	0.9300	N1—Co1	2.151 (3)
C4—C5	1.379 (5)	N2—Co1	2.132 (3)
C4—H4	0.9300	O1—H1A	0.86 (6)
C5—N1	1.348 (4)	O1—H1B	0.85 (3)
C5—C6	1.476 (5)	Cl1—Co1	2.4298 (9)
C6—N2	1.351 (4)	Co1—N2i	2.132 (3)
C6—C7	1.378 (5)	Co1—N1i	2.151 (3)
C7—C8	1.377 (6)	Co1—Cl1i	2.4298 (9)
C7—H7	0.9300
N1—C1—C2	122.8 (4)	C8—C9—H9	120.6
N1—C1—H1	118.6	N2—C10—C9	123.1 (3)
C2—C1—H1	118.6	N2—C10—H10	118.4
C3—C2—C1	118.2 (4)	C9—C10—H10	118.4
C3—C2—H2	120.9	C1—N1—C5	118.7 (3)
C1—C2—H2	120.9	C1—N1—Co1	125.8 (3)
C4—C3—C2	119.5 (4)	C5—N1—Co1	115.4 (2)
C4—C3—H3	120.2	C10—N2—C6	118.2 (3)
C2—C3—H3	120.2	C10—N2—Co1	125.5 (2)
C3—C4—C5	119.8 (4)	C6—N2—Co1	116.2 (2)
C3—C4—H4	120.1	H1A—O1—H1B	109 (5)
C5—C4—H4	120.1	N2—Co1—N2i	169.92 (15)
N1—C5—C4	120.9 (4)	N2—Co1—N1i	96.14 (11)
N1—C5—C6	116.1 (3)	N2i—Co1—N1i	76.58 (11)
C4—C5—C6	123.0 (3)	N2—Co1—N1	76.58 (11)
N2—C6—C7	121.4 (3)	N2i—Co1—N1	96.14 (11)
N2—C6—C5	115.7 (3)	N1i—Co1—N1	89.19 (16)
C7—C6—C5	122.9 (3)	N2—Co1—Cl1	91.72 (8)
C8—C7—C6	119.5 (3)	N2i—Co1—Cl1	95.26 (8)
C8—C7—H7	120.2	N1i—Co1—Cl1	171.64 (8)
C6—C7—H7	120.2	N1—Co1—Cl1	89.88 (8)
C9—C8—C7	118.9 (3)	N2—Co1—Cl1i	95.26 (8)
C9—C8—H8	120.6	N2i—Co1—Cl1i	91.72 (8)
C7—C8—H8	120.6	N1i—Co1—Cl1i	89.88 (8)
C10—C9—C8	118.8 (4)	N1—Co1—Cl1i	171.64 (8)
C10—C9—H9	120.6	Cl1—Co1—Cl1i	92.22 (5)
N1—C1—C2—C3	−0.8 (8)	C7—C6—N2—C10	−0.9 (5)
C1—C2—C3—C4	−0.5 (8)	C5—C6—N2—C10	180.0 (3)
C2—C3—C4—C5	1.0 (8)	C7—C6—N2—Co1	176.4 (3)
C3—C4—C5—N1	−0.3 (6)	C5—C6—N2—Co1	−2.7 (4)
C3—C4—C5—C6	−180.0 (4)	C10—N2—Co1—N2i	−136.3 (3)
N1—C5—C6—N2	1.5 (4)	C6—N2—Co1—N2i	46.6 (2)
C4—C5—C6—N2	−178.8 (3)	C10—N2—Co1—N1i	−93.0 (3)
N1—C5—C6—C7	−177.5 (3)	C6—N2—Co1—N1i	89.9 (2)
C4—C5—C6—C7	2.2 (5)	C10—N2—Co1—N1	179.3 (3)
N2—C6—C7—C8	1.9 (5)	C6—N2—Co1—N1	2.2 (2)
C5—C6—C7—C8	−179.1 (3)	C10—N2—Co1—Cl1	89.8 (3)
C6—C7—C8—C9	−1.5 (6)	C6—N2—Co1—Cl1	−87.3 (2)
C7—C8—C9—C10	0.3 (7)	C10—N2—Co1—Cl1i	−2.6 (3)
C8—C9—C10—N2	0.7 (6)	C6—N2—Co1—Cl1i	−179.7 (2)
C2—C1—N1—C5	1.5 (6)	C1—N1—Co1—N2	−179.5 (3)
C2—C1—N1—Co1	179.7 (4)	C5—N1—Co1—N2	−1.3 (2)
C4—C5—N1—C1	−1.0 (5)	C1—N1—Co1—N2i	7.5 (3)
C6—C5—N1—C1	178.7 (3)	C5—N1—Co1—N2i	−174.3 (2)
C4—C5—N1—Co1	−179.3 (3)	C1—N1—Co1—N1i	83.9 (3)
C6—C5—N1—Co1	0.4 (4)	C5—N1—Co1—N1i	−97.9 (3)
C9—C10—N2—C6	−0.4 (5)	C1—N1—Co1—Cl1	−87.7 (3)
C9—C10—N2—Co1	−177.4 (3)	C5—N1—Co1—Cl1	90.5 (2)

Symmetry codes: (i) −x+2, y, −z+3/2.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···Cl1	0.86 (6)	2.43 (5)	3.250 (4)	160 (5)
O1—H1B···Cl1ii	0.85 (3)	2.37 (4)	3.218 (4)	172 (4)

Symmetry codes: (ii) x, −y, z+1/2.