Diaqua-bis-(4-formyl-benzoato-κO(1))bis-(nicotinamide-κN(1))cobalt(II).

In the title complex, [Co(C(8)H(5)O(3))(2)(C(6)H(6)N(2)O)(2)(H(2)O)(2)], the Co(II) cation is located on an inversion center and is coordinated by two 4-formyl-benzoate (FB) anions, two nicotinamide (NA) ligands and two water mol-ecules. The four O atoms in the equatorial plane around the Co(II) cation 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 23.91 (9)°, while the pyridine and benzene rings are oriented at a dihedral angle of 88.84 (4)°. The coordinating water mol-ecule links with the carboxyl-ate group via an intra-molecular O-H⋯O hydrogen bond. In the crystal, N-H⋯O, O-H⋯O and weak C-H⋯O hydrogen bonds link the mol-ecules into a three-dimensional supra-molecular network. π-π stacking between the parallel benzene rings of adjacent mol-ecules [centroid-centroid distance = 3.8505 (8) Å] may further stabilize the structure. A weak C-H⋯π inter-action also occurs in the crystal.

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 ▶, 2009 ▶); Hökelek & Necefoğlu (1998 ▶, 2007 ▶); Necefoğlu et al. (2011 ▶); Sertçelik et al. (2012 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

[Co(C8H5O3)2(C6H6N2O)2(H2O)2]

M = 637.46

Triclinic,

a = 7.7784 (2) Å

b = 9.7988 (3) Å

c = 9.8970 (3) Å

α = 78.080 (3)°

β = 71.395 (2)°

γ = 86.638 (4)°

V = 699.48 (4) Å3

Z = 1

Mo Kα radiation

μ = 0.68 mm−1

T = 100 K

0.33 × 0.17 × 0.10 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.808, T max = 0.937

12735 measured reflections

3527 independent reflections

3301 reflections with I > 2σ(I)

R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.026

wR(F 2) = 0.069

S = 1.05

3527 reflections

216 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.42 e Å−3

Δρmin = −0.36 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); 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, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812032205/xu5597sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812032205/xu5597Isup2.hkl

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

[Co(C8H5O3)2(C6H6N2O)2(H2O)2]	Z = 1
Mr = 637.46	F(000) = 329
Triclinic, P1	Dx = 1.513 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.7784 (2) Å	Cell parameters from 7533 reflections
b = 9.7988 (3) Å	θ = 2.8–28.5°
c = 9.8970 (3) Å	µ = 0.68 mm−1
α = 78.080 (3)°	T = 100 K
β = 71.395 (2)°	Block, orange
γ = 86.638 (4)°	0.33 × 0.17 × 0.10 mm
V = 699.48 (4) Å3

Bruker Kappa APEXII CCD area-detector diffractometer	3527 independent reflections
Radiation source: fine-focus sealed tube	3301 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
φ and ω scans	θmax = 28.5°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −10→9
Tmin = 0.808, Tmax = 0.937	k = −13→13
12735 measured reflections	l = −13→13

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.069	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0309P)2 + 0.3387P] where P = (Fo2 + 2Fc2)/3
3527 reflections	(Δ/σ)max < 0.001
216 parameters	Δρmax = 0.42 e Å−3
0 restraints	Δρmin = −0.36 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 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	0.0000	0.0000	0.0000	0.01057 (7)
O1	0.12202 (11)	0.18006 (9)	0.01007 (10)	0.01452 (18)
O2	−0.11185 (12)	0.27803 (9)	0.15705 (10)	0.01572 (18)
O3	0.49561 (15)	0.66922 (13)	0.31971 (16)	0.0403 (3)
O4	−0.43334 (12)	0.00199 (10)	−0.33497 (10)	0.01763 (19)
O5	0.26433 (12)	−0.08141 (10)	−0.07947 (10)	0.01505 (18)
H51	0.345 (3)	−0.041 (2)	−0.147 (2)	0.029 (5)*
H52	0.236 (3)	−0.151 (2)	−0.110 (2)	0.040 (5)*
N1	−0.00257 (14)	0.09276 (10)	−0.21360 (11)	0.0129 (2)
N2	−0.32789 (16)	0.13287 (12)	−0.56018 (12)	0.0176 (2)
H21	−0.244 (3)	0.1859 (19)	−0.628 (2)	0.028 (5)*
H22	−0.413 (3)	0.1007 (19)	−0.584 (2)	0.029 (5)*
C1	0.05487 (16)	0.26423 (12)	0.09348 (13)	0.0123 (2)
C2	0.18468 (16)	0.35171 (12)	0.12577 (13)	0.0126 (2)
C3	0.12393 (17)	0.47283 (13)	0.18014 (14)	0.0168 (2)
H3	0.0067	0.5042	0.1877	0.020*
C4	0.23769 (17)	0.54602 (13)	0.22256 (15)	0.0192 (3)
H4	0.1976	0.6270	0.2579	0.023*
C5	0.41275 (17)	0.49803 (13)	0.21208 (14)	0.0170 (2)
C6	0.47496 (17)	0.37952 (13)	0.15538 (14)	0.0166 (2)
H6	0.5927	0.3489	0.1469	0.020*
C7	0.36129 (16)	0.30652 (12)	0.11124 (14)	0.0150 (2)
H7	0.4033	0.2278	0.0721	0.018*
C8	0.53655 (19)	0.57111 (16)	0.26075 (18)	0.0256 (3)
H8	0.658 (2)	0.5327 (18)	0.2431 (19)	0.026 (4)*
C9	−0.14389 (16)	0.06886 (12)	−0.25570 (13)	0.0130 (2)
H9	−0.2389	0.0133	−0.1891	0.016*
C10	−0.15532 (16)	0.12280 (12)	−0.39347 (13)	0.0128 (2)
C11	−0.01388 (18)	0.20716 (14)	−0.49194 (14)	0.0174 (2)
H11	−0.0172	0.2454	−0.5852	0.021*
C12	0.13220 (18)	0.23343 (14)	−0.44905 (14)	0.0188 (3)
H12	0.2279	0.2900	−0.5130	0.023*
C13	0.13331 (16)	0.17428 (13)	−0.30981 (14)	0.0152 (2)
H13	0.2319	0.1916	−0.2817	0.018*
C14	−0.31771 (16)	0.08278 (12)	−0.42778 (13)	0.0138 (2)

	U11	U22	U33	U12	U13	U23
Co1	0.00908 (11)	0.01327 (11)	0.01077 (12)	−0.00042 (8)	−0.00433 (8)	−0.00344 (8)
O1	0.0133 (4)	0.0159 (4)	0.0150 (4)	−0.0020 (3)	−0.0039 (3)	−0.0047 (3)
O2	0.0111 (4)	0.0182 (4)	0.0186 (4)	−0.0011 (3)	−0.0045 (3)	−0.0052 (3)
O3	0.0230 (6)	0.0454 (7)	0.0642 (9)	−0.0011 (5)	−0.0124 (6)	−0.0386 (7)
O4	0.0163 (4)	0.0237 (5)	0.0137 (4)	−0.0062 (3)	−0.0062 (3)	−0.0015 (3)
O5	0.0115 (4)	0.0177 (4)	0.0162 (4)	−0.0009 (3)	−0.0036 (4)	−0.0048 (4)
N1	0.0123 (5)	0.0144 (5)	0.0136 (5)	−0.0006 (4)	−0.0053 (4)	−0.0036 (4)
N2	0.0176 (5)	0.0237 (6)	0.0132 (5)	−0.0058 (4)	−0.0077 (4)	−0.0014 (4)
C1	0.0131 (5)	0.0124 (5)	0.0116 (5)	−0.0020 (4)	−0.0058 (4)	0.0006 (4)
C2	0.0119 (5)	0.0136 (5)	0.0122 (5)	−0.0022 (4)	−0.0043 (4)	−0.0011 (4)
C3	0.0116 (5)	0.0168 (6)	0.0225 (6)	0.0009 (4)	−0.0050 (5)	−0.0058 (5)
C4	0.0150 (6)	0.0163 (6)	0.0276 (7)	0.0000 (5)	−0.0046 (5)	−0.0104 (5)
C5	0.0141 (6)	0.0180 (6)	0.0202 (6)	−0.0027 (4)	−0.0052 (5)	−0.0060 (5)
C6	0.0115 (5)	0.0179 (6)	0.0217 (6)	0.0008 (4)	−0.0064 (5)	−0.0051 (5)
C7	0.0138 (6)	0.0132 (5)	0.0184 (6)	0.0005 (4)	−0.0049 (5)	−0.0044 (4)
C8	0.0157 (6)	0.0299 (7)	0.0362 (8)	−0.0023 (5)	−0.0087 (6)	−0.0159 (6)
C9	0.0121 (5)	0.0142 (5)	0.0136 (6)	−0.0012 (4)	−0.0049 (4)	−0.0029 (4)
C10	0.0126 (5)	0.0144 (5)	0.0129 (5)	0.0001 (4)	−0.0054 (4)	−0.0042 (4)
C11	0.0181 (6)	0.0221 (6)	0.0119 (6)	−0.0033 (5)	−0.0055 (5)	−0.0009 (5)
C12	0.0157 (6)	0.0222 (6)	0.0167 (6)	−0.0058 (5)	−0.0038 (5)	−0.0004 (5)
C13	0.0119 (5)	0.0178 (6)	0.0167 (6)	−0.0018 (4)	−0.0050 (5)	−0.0041 (5)
C14	0.0139 (5)	0.0160 (5)	0.0138 (6)	0.0001 (4)	−0.0060 (4)	−0.0050 (4)

Co1—O1	2.0864 (8)	C3—C4	1.3819 (17)
Co1—O1i	2.0864 (8)	C3—H3	0.9300
Co1—O5	2.1254 (9)	C4—H4	0.9300
Co1—O5i	2.1254 (9)	C5—C4	1.3932 (18)
Co1—N1	2.1276 (10)	C5—C8	1.4804 (18)
Co1—N1i	2.1276 (10)	C6—C5	1.3884 (17)
O1—C1	1.2610 (14)	C6—C7	1.3907 (17)
O2—C1	1.2608 (15)	C6—H6	0.9300
O3—C8	1.2014 (18)	C7—H7	0.9300
O4—C14	1.2391 (15)	C8—H8	0.973 (18)
O5—H51	0.81 (2)	C9—H9	0.9300
O5—H52	0.86 (2)	C10—C9	1.3858 (17)
N1—C9	1.3415 (15)	C10—C11	1.3904 (17)
N1—C13	1.3433 (15)	C10—C14	1.5005 (16)
N2—C14	1.3267 (16)	C11—C12	1.3873 (18)
N2—H21	0.870 (19)	C11—H11	0.9300
N2—H22	0.861 (19)	C12—H12	0.9300
C1—C2	1.5090 (16)	C13—C12	1.3828 (18)
C2—C3	1.3990 (17)	C13—H13	0.9300
C2—C7	1.3903 (17)
O1i—Co1—O1	180.00 (2)	C3—C4—C5	119.70 (11)
O1—Co1—O5	87.96 (3)	C3—C4—H4	120.1
O1i—Co1—O5	92.04 (3)	C5—C4—H4	120.1
O1—Co1—O5i	92.04 (3)	C4—C5—C8	121.27 (12)
O1i—Co1—O5i	87.96 (3)	C6—C5—C4	120.33 (11)
O1—Co1—N1	89.61 (4)	C6—C5—C8	118.41 (12)
O1i—Co1—N1	90.39 (4)	C5—C6—C7	120.04 (11)
O1—Co1—N1i	90.39 (4)	C5—C6—H6	120.0
O1i—Co1—N1i	89.61 (4)	C7—C6—H6	120.0
O5i—Co1—O5	180.0	C2—C7—C6	119.75 (11)
O5—Co1—N1	92.20 (4)	C2—C7—H7	120.1
O5i—Co1—N1	87.80 (4)	C6—C7—H7	120.1
O5—Co1—N1i	87.80 (4)	O3—C8—C5	124.84 (13)
O5i—Co1—N1i	92.20 (4)	O3—C8—H8	120.3 (10)
N1—Co1—N1i	180.00 (6)	C5—C8—H8	114.8 (10)
C1—O1—Co1	127.04 (8)	N1—C9—C10	123.26 (11)
Co1—O5—H51	124.5 (13)	N1—C9—H9	118.4
Co1—O5—H52	98.6 (14)	C10—C9—H9	118.4
H52—O5—H51	104.8 (18)	C9—C10—C11	118.10 (11)
C9—N1—Co1	119.37 (8)	C9—C10—C14	117.60 (11)
C9—N1—C13	118.05 (11)	C11—C10—C14	124.27 (11)
C13—N1—Co1	122.58 (8)	C10—C11—H11	120.5
C14—N2—H21	123.1 (12)	C12—C11—C10	119.07 (12)
C14—N2—H22	117.7 (12)	C12—C11—H11	120.5
H21—N2—H22	118.5 (17)	C11—C12—H12	120.5
O1—C1—C2	117.52 (10)	C13—C12—C11	119.01 (12)
O2—C1—O1	125.58 (11)	C13—C12—H12	120.5
O2—C1—C2	116.84 (10)	N1—C13—C12	122.50 (11)
C3—C2—C1	120.06 (11)	N1—C13—H13	118.7
C7—C2—C1	119.83 (11)	C12—C13—H13	118.7
C7—C2—C3	119.96 (11)	O4—C14—N2	122.48 (11)
C2—C3—H3	119.9	O4—C14—C10	119.74 (11)
C4—C3—C2	120.18 (11)	N2—C14—C10	117.73 (11)
C4—C3—H3	119.9
O5—Co1—O1—C1	−153.43 (10)	C1—C2—C3—C4	173.96 (12)
O5i—Co1—O1—C1	26.57 (10)	C7—C2—C3—C4	−1.47 (19)
N1—Co1—O1—C1	114.35 (10)	C1—C2—C7—C6	−173.32 (11)
N1i—Co1—O1—C1	−65.65 (10)	C3—C2—C7—C6	2.12 (19)
O1—Co1—N1—C9	−143.16 (9)	C2—C3—C4—C5	−0.5 (2)
O1i—Co1—N1—C9	36.84 (9)	C6—C5—C4—C3	1.9 (2)
O1—Co1—N1—C13	37.41 (9)	C8—C5—C4—C3	−178.06 (13)
O1i—Co1—N1—C13	−142.59 (9)	C4—C5—C8—O3	4.7 (3)
O5—Co1—N1—C9	128.90 (9)	C6—C5—C8—O3	−175.19 (16)
O5i—Co1—N1—C9	−51.10 (9)	C7—C6—C5—C4	−1.2 (2)
O5—Co1—N1—C13	−50.53 (10)	C7—C6—C5—C8	178.71 (13)
O5i—Co1—N1—C13	129.47 (10)	C5—C6—C7—C2	−0.78 (19)
Co1—O1—C1—O2	−20.75 (17)	C11—C10—C9—N1	−0.79 (18)
Co1—O1—C1—C2	156.34 (8)	C14—C10—C9—N1	177.53 (11)
Co1—N1—C9—C10	−178.76 (9)	C9—C10—C11—C12	0.23 (18)
C13—N1—C9—C10	0.70 (18)	C14—C10—C11—C12	−177.97 (12)
Co1—N1—C13—C12	179.38 (9)	C9—C10—C14—O4	−1.39 (17)
C9—N1—C13—C12	−0.06 (18)	C9—C10—C14—N2	−179.18 (11)
O1—C1—C2—C3	161.25 (11)	C11—C10—C14—O4	176.81 (12)
O1—C1—C2—C7	−23.31 (17)	C11—C10—C14—N2	−0.97 (18)
O2—C1—C2—C3	−21.40 (17)	C10—C11—C12—C13	0.35 (19)
O2—C1—C2—C7	154.03 (12)	N1—C13—C12—C11	−0.5 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···O2ii	0.87 (2)	2.078 (19)	2.8834 (15)	153 (2)
N2—H22···O4iii	0.86 (2)	2.04 (2)	2.8908 (16)	167 (2)
O5—H51···O4iv	0.81 (2)	2.08 (2)	2.8583 (13)	162.3 (19)
O5—H52···O2i	0.87 (2)	1.83 (2)	2.6774 (14)	164 (2)
C6—H6···O2iv	0.93	2.39	3.3123 (17)	172
C13—H13···O3v	0.93	2.47	3.3120 (18)	150
C4—H4···Cgvi	0.93	2.72	3.6338 (14)	167

Table 1

Hydrogen-bond geometry (Å, °)

Cg is the centroid of the pyridine ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H21⋯O2i	0.87 (2)	2.078 (19)	2.8834 (15)	153 (2)
N2—H22⋯O4ii	0.86 (2)	2.04 (2)	2.8908 (16)	167 (2)
O5—H51⋯O4iii	0.81 (2)	2.08 (2)	2.8583 (13)	162.3 (19)
O5—H52⋯O2iv	0.87 (2)	1.83 (2)	2.6774 (14)	164 (2)
C6—H6⋯O2iii	0.93	2.39	3.3123 (17)	172
C13—H13⋯O3v	0.93	2.47	3.3120 (18)	150
C4—H4⋯Cg vi	0.93	2.72	3.6338 (14)	167

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