Di-aqua-bis-(3-chloro-benzoato-κO)bis-(nicotinamide-κN (1))cobalt(II).

In the title complex, [Co(C7H4ClO2)2(C6H6N2O)2(H2O)2], the Co(II) atom is located on an inversion center and is coordinated by two 3-chloro-benzoate (CB) anions, two nicotinamide (NA) ligands and two water mol-ecules. The four O atoms in the equatorial plane form a slightly distorted square-planar arrangement, while the slightly distorted octa-hedral coordination is completed by the two N atoms of the NA ligands in the axial positions. The dihedral angle between the carboxyl-ate group and the adjacent benzene ring is 9.14 (9)°, while the pyridine and benzene rings are oriented at a dihedral angle of 82.18 (8)°. In the crystal, N-H⋯O and O-H⋯O hydrogen bonds link the mol-ecules into a two-dimensional network lying parallel to (101). π-π stacking between parallel pyridine rings of adjacent mol-ecules [centroid-centroid distance = 3.7765 (8) Å] further stabilizes the crystal structure.

Related literature

For literature on niacin, see: Krishnamachari (1974 ▶). For information on the nicotinic acid derivative N,N-di­ethyl­nicotinamide, see: Bigoli et al. (1972 ▶). For related structures, see: Aydın et al. (2012 ▶); Hökelek et al. (1996 ▶, 2009a ▶,b ▶); Hökelek & Necefoğlu (1998 ▶, 2007 ▶); Necefoğlu et al. (2011a ▶,b ▶); Sertçelik et al. (2012a ▶,b ▶,c ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

[Co(C7H4ClO2)2(C6H6N2O)2(H2O)2]

M = 650.32

Monoclinic,

a = 11.5181 (3) Å

b = 8.8191 (2) Å

c = 13.5089 (3) Å

β = 90.546 (2)°

V = 1372.16 (6) Å3

Z = 2

Mo Kα radiation

μ = 0.88 mm−1

T = 294 K

0.35 × 0.22 × 0.18 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2012 ▶) T min = 0.793, T max = 0.854

18960 measured reflections

2797 independent reflections

2667 reflections with I > 2σ(I)

R int = 0.027

Refinement

R[F 2 > 2σ(F 2)] = 0.027

wR(F 2) = 0.074

S = 1.11

2797 reflections

204 parameters

52 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.32 e Å−3

Δρmin = −0.33 e Å−3

Data collection: APEX2 (Bruker, 2012 ▶); cell refinement: SAINT (Bruker, 2012 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶) and PLATON (Spek, 2009 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681301458X/su2606sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681301458X/su2606Isup2.hkl

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

[Co(C7H4ClO2)2(C6H6N2O)2(H2O)2]	F(000) = 666
Mr = 650.32	Dx = 1.574 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4857 reflections
a = 11.5181 (3) Å	θ = 2.3–24.4°
b = 8.8191 (2) Å	µ = 0.88 mm−1
c = 13.5089 (3) Å	T = 294 K
β = 90.546 (2)°	Block, pink
V = 1372.16 (6) Å3	0.35 × 0.22 × 0.18 mm
Z = 2

Bruker APEXII CCD area-detector diffractometer	2797 independent reflections
Radiation source: fine-focus sealed tube	2667 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
φ and ω scans	θmax = 26.4°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −14→14
Tmin = 0.793, Tmax = 0.854	k = −11→10
18960 measured reflections	l = −16→16

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)] = 0.027	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.074	w = 1/[σ2(Fo2) + (0.0393P)2 + 0.5258P] where P = (Fo2 + 2Fc2)/3
S = 1.11	(Δ/σ)max = 0.001
2797 reflections	Δρmax = 0.32 e Å−3
204 parameters	Δρmin = −0.33 e Å−3
52 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: 0.0334 (17)

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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 > 2sigma(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.

	x	y	z	Uiso*/Ueq
Co1	0.00000	1.00000	1.00000	0.0221 (1)
Cl1	0.57400 (4)	0.77742 (8)	0.87425 (3)	0.0604 (2)
O1	0.17264 (10)	0.87980 (18)	1.18080 (9)	0.0518 (4)
O2	0.17291 (8)	0.94984 (12)	1.02212 (8)	0.0299 (3)
O3	0.16810 (10)	0.34420 (12)	0.81282 (10)	0.0415 (4)
O4	0.04558 (10)	1.07995 (12)	0.85606 (8)	0.0298 (3)
N1	−0.02319 (10)	0.77771 (13)	0.93492 (9)	0.0258 (3)
N2	0.23334 (16)	0.56716 (18)	0.76095 (16)	0.0592 (6)
C1	0.21833 (12)	0.88839 (17)	1.09796 (11)	0.0293 (4)
C2	0.33518 (12)	0.81535 (17)	1.08465 (11)	0.0286 (4)
C3	0.39495 (13)	0.83285 (18)	0.99657 (11)	0.0316 (4)
C4	0.49988 (13)	0.7599 (2)	0.98487 (12)	0.0368 (5)
C5	0.54679 (15)	0.6700 (2)	1.05879 (14)	0.0464 (6)
C6	0.48691 (17)	0.6533 (2)	1.14586 (14)	0.0496 (6)
C7	0.38168 (15)	0.7255 (2)	1.15907 (12)	0.0388 (5)
C8	0.06524 (12)	0.70512 (15)	0.89207 (11)	0.0268 (4)
C9	0.05526 (12)	0.56102 (15)	0.85229 (10)	0.0258 (4)
C10	−0.05151 (14)	0.48869 (16)	0.85705 (12)	0.0314 (4)
C11	−0.14353 (13)	0.56408 (18)	0.89921 (13)	0.0356 (5)
C12	−0.12591 (12)	0.70790 (16)	0.93721 (11)	0.0303 (4)
C13	0.15664 (14)	0.48213 (16)	0.80673 (12)	0.0304 (4)
H3	0.36460	0.89300	0.94610	0.0380*
H5	0.61770	0.62160	1.04990	0.0560*
H6	0.51750	0.59290	1.19620	0.0590*
H7	0.34200	0.71360	1.21820	0.0470*
H8	0.13670	0.75380	0.88890	0.0320*
H10	−0.06090	0.39100	0.83220	0.0380*
H11	−0.21640	0.51890	0.90200	0.0430*
H12	−0.18830	0.75810	0.96560	0.0360*
H21	0.221 (2)	0.659 (3)	0.7492 (19)	0.066 (7)*
H22	0.293 (2)	0.526 (3)	0.7323 (19)	0.063 (7)*
H41	−0.028 (2)	1.098 (3)	0.8311 (18)	0.069 (7)*
H42	0.079 (2)	1.163 (3)	0.8530 (17)	0.055 (6)*

	U11	U22	U33	U12	U13	U23
Co1	0.0201 (2)	0.0183 (2)	0.0280 (2)	0.0011 (1)	0.0066 (1)	−0.0026 (1)
Cl1	0.0389 (2)	0.1013 (4)	0.0412 (3)	0.0171 (2)	0.0140 (2)	0.0029 (2)
O1	0.0339 (6)	0.0875 (10)	0.0342 (6)	0.0108 (6)	0.0090 (5)	0.0038 (6)
O2	0.0230 (5)	0.0306 (5)	0.0362 (5)	0.0039 (4)	0.0044 (4)	0.0007 (4)
O3	0.0403 (6)	0.0194 (5)	0.0651 (8)	0.0024 (4)	0.0211 (5)	−0.0007 (5)
O4	0.0297 (5)	0.0267 (6)	0.0332 (5)	−0.0023 (4)	0.0098 (4)	−0.0001 (4)
N1	0.0256 (6)	0.0205 (5)	0.0313 (6)	0.0005 (4)	0.0049 (5)	−0.0027 (4)
N2	0.0569 (10)	0.0231 (7)	0.0985 (14)	0.0036 (7)	0.0507 (10)	0.0049 (8)
C1	0.0247 (7)	0.0308 (7)	0.0324 (7)	−0.0020 (5)	0.0034 (5)	−0.0042 (6)
C2	0.0261 (7)	0.0297 (7)	0.0301 (7)	0.0001 (6)	−0.0001 (5)	−0.0025 (6)
C3	0.0273 (7)	0.0369 (8)	0.0307 (7)	0.0051 (6)	0.0000 (6)	0.0031 (6)
C4	0.0286 (7)	0.0489 (10)	0.0331 (8)	0.0054 (6)	0.0038 (6)	−0.0028 (7)
C5	0.0344 (8)	0.0564 (11)	0.0482 (10)	0.0200 (8)	−0.0027 (7)	0.0004 (8)
C6	0.0479 (10)	0.0572 (11)	0.0435 (10)	0.0165 (9)	−0.0075 (8)	0.0127 (8)
C7	0.0401 (9)	0.0459 (9)	0.0303 (8)	0.0038 (7)	0.0005 (6)	0.0045 (7)
C8	0.0251 (6)	0.0214 (6)	0.0339 (7)	−0.0006 (5)	0.0068 (5)	−0.0010 (5)
C9	0.0292 (7)	0.0197 (6)	0.0287 (7)	0.0017 (5)	0.0063 (5)	0.0004 (5)
C10	0.0336 (8)	0.0220 (7)	0.0388 (8)	−0.0030 (5)	0.0051 (6)	−0.0062 (5)
C11	0.0270 (7)	0.0312 (8)	0.0486 (9)	−0.0058 (6)	0.0062 (6)	−0.0072 (7)
C12	0.0249 (7)	0.0276 (7)	0.0384 (8)	0.0010 (5)	0.0073 (6)	−0.0032 (6)
C13	0.0320 (8)	0.0211 (7)	0.0382 (8)	0.0000 (5)	0.0112 (6)	−0.0025 (6)

Co1—O2	2.0592 (9)	C2—C3	1.389 (2)
Co1—O4	2.1385 (11)	C3—C4	1.380 (2)
Co1—N1	2.1640 (12)	C4—C5	1.381 (2)
Co1—O2i	2.0592 (9)	C5—C6	1.377 (3)
Co1—O4i	2.1385 (11)	C6—C7	1.382 (3)
Co1—N1i	2.1640 (12)	C8—C9	1.3841 (19)
Cl1—C4	1.7350 (16)	C9—C13	1.497 (2)
O1—C1	1.2435 (19)	C9—C10	1.387 (2)
O2—C1	1.2676 (18)	C10—C11	1.379 (2)
O3—C13	1.2262 (18)	C11—C12	1.383 (2)
O4—H41	0.92 (2)	C3—H3	0.9300
O4—H42	0.83 (3)	C5—H5	0.9300
N1—C12	1.3344 (18)	C6—H6	0.9300
N1—C8	1.3392 (18)	C7—H7	0.9300
N2—C13	1.317 (2)	C8—H8	0.9300
N2—H21	0.84 (3)	C10—H10	0.9300
N2—H22	0.87 (2)	C11—H11	0.9300
C1—C2	1.504 (2)	C12—H12	0.9300
C2—C7	1.384 (2)
O2—Co1—O4	87.55 (4)	Cl1—C4—C3	119.73 (12)
O2—Co1—N1	88.84 (4)	C3—C4—C5	121.47 (15)
O2—Co1—O2i	180.00	Cl1—C4—C5	118.79 (13)
O2—Co1—O4i	92.45 (4)	C4—C5—C6	118.90 (16)
O2—Co1—N1i	91.16 (4)	C5—C6—C7	120.53 (17)
O4—Co1—N1	87.69 (4)	C2—C7—C6	120.25 (15)
O2i—Co1—O4	92.45 (4)	N1—C8—C9	123.09 (13)
O4—Co1—O4i	180.00	C8—C9—C13	121.62 (13)
O4—Co1—N1i	92.31 (4)	C8—C9—C10	118.33 (13)
O2i—Co1—N1	91.16 (4)	C10—C9—C13	120.05 (12)
O4i—Co1—N1	92.31 (4)	C9—C10—C11	118.86 (13)
N1—Co1—N1i	180.00	C10—C11—C12	119.01 (14)
O2i—Co1—O4i	87.55 (4)	N1—C12—C11	122.80 (13)
O2i—Co1—N1i	88.84 (4)	N2—C13—C9	117.24 (13)
O4i—Co1—N1i	87.69 (4)	O3—C13—N2	121.59 (16)
Co1—O2—C1	126.89 (9)	O3—C13—C9	121.16 (14)
H41—O4—H42	105 (2)	C2—C3—H3	120.00
Co1—O4—H41	99.0 (15)	C4—C3—H3	120.00
Co1—O4—H42	117.1 (16)	C4—C5—H5	121.00
Co1—N1—C8	121.14 (9)	C6—C5—H5	121.00
Co1—N1—C12	120.97 (9)	C5—C6—H6	120.00
C8—N1—C12	117.88 (12)	C7—C6—H6	120.00
H21—N2—H22	117 (2)	C2—C7—H7	120.00
C13—N2—H21	121.8 (16)	C6—C7—H7	120.00
C13—N2—H22	120.5 (17)	N1—C8—H8	118.00
O1—C1—O2	125.34 (14)	C9—C8—H8	118.00
O1—C1—C2	117.92 (13)	C9—C10—H10	121.00
O2—C1—C2	116.70 (13)	C11—C10—H10	121.00
C1—C2—C3	120.41 (13)	C10—C11—H11	121.00
C1—C2—C7	119.92 (13)	C12—C11—H11	120.00
C3—C2—C7	119.63 (14)	N1—C12—H12	119.00
C2—C3—C4	119.23 (14)	C11—C12—H12	119.00
O4—Co1—O2—C1	−177.85 (12)	O2—C1—C2—C7	−169.65 (14)
N1—Co1—O2—C1	−90.11 (12)	C1—C2—C3—C4	−177.53 (14)
O4i—Co1—O2—C1	2.15 (12)	C7—C2—C3—C4	0.1 (2)
N1i—Co1—O2—C1	89.89 (12)	C1—C2—C7—C6	177.50 (15)
O2—Co1—N1—C8	−26.16 (11)	C3—C2—C7—C6	−0.1 (2)
O2—Co1—N1—C12	153.10 (11)	C2—C3—C4—Cl1	178.62 (12)
O4—Co1—N1—C8	61.44 (11)	C2—C3—C4—C5	0.0 (2)
O4—Co1—N1—C12	−119.31 (11)	Cl1—C4—C5—C6	−178.62 (14)
O2i—Co1—N1—C8	153.84 (11)	C3—C4—C5—C6	0.1 (3)
O2i—Co1—N1—C12	−26.90 (11)	C4—C5—C6—C7	−0.1 (3)
O4i—Co1—N1—C8	−118.56 (11)	C5—C6—C7—C2	0.1 (3)
O4i—Co1—N1—C12	60.69 (11)	N1—C8—C9—C10	0.1 (2)
Co1—O2—C1—O1	−18.0 (2)	N1—C8—C9—C13	−178.77 (13)
Co1—O2—C1—C2	159.69 (10)	C8—C9—C10—C11	1.3 (2)
Co1—N1—C8—C9	177.93 (11)	C13—C9—C10—C11	−179.86 (14)
C12—N1—C8—C9	−1.4 (2)	C8—C9—C13—O3	146.12 (16)
Co1—N1—C12—C11	−177.98 (12)	C8—C9—C13—N2	−33.2 (2)
C8—N1—C12—C11	1.3 (2)	C10—C9—C13—O3	−32.7 (2)
O1—C1—C2—C3	−174.24 (15)	C10—C9—C13—N2	148.03 (17)
O1—C1—C2—C7	8.2 (2)	C9—C10—C11—C12	−1.3 (2)
O2—C1—C2—C3	7.9 (2)	C10—C11—C12—N1	0.0 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···O3ii	0.84 (3)	2.24 (3)	2.876 (2)	133 (2)
N2—H22···O4iii	0.87 (2)	2.27 (2)	3.012 (2)	143 (2)
O4—H41···O1i	0.92 (2)	1.68 (2)	2.5822 (16)	164 (2)
O4—H42···O3iv	0.83 (3)	1.98 (3)	2.7892 (15)	166 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H21⋯O3i	0.84 (3)	2.24 (3)	2.876 (2)	133 (2)
N2—H22⋯O4ii	0.87 (2)	2.27 (2)	3.012 (2)	143 (2)
O4—H41⋯O1iii	0.92 (2)	1.68 (2)	2.5822 (16)	164 (2)
O4—H42⋯O3iv	0.83 (3)	1.98 (3)	2.7892 (15)	166 (2)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .