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

In the title complex, [Cu(C(8)H(5)O(3))(2)(C(6)H(6)N(2)O)(2)(H(2)O)(2)], the Cu(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 in an elongated distorted octa-hedral geometry. The dihedral angle between the carboxyl-ate group and the adjacent benzene ring is 23.00 (10)°, while the pyridine ring and the benzene ring are oriented at a dihedral angle of 85.34 (4)°. An intra-molecular O-H⋯O hydrogen bond occurs between coordinating water mol-ecule and the carboxyl-ate group. 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. 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

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

M = 642.08

Triclinic,

a = 7.8175 (2) Å

b = 9.6539 (3) Å

c = 9.8361 (3) Å

α = 77.053 (3)°

β = 74.041 (2)°

γ = 87.295 (3)°

V = 695.49 (4) Å3

Z = 1

Mo Kα radiation

μ = 0.85 mm−1

T = 100 K

0.32 × 0.28 × 0.14 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.762, T max = 0.888

12850 measured reflections

3482 independent reflections

3325 reflections with I > 2σ(I)

R int = 0.025

Refinement

R[F 2 > 2σ(F 2)] = 0.025

wR(F 2) = 0.066

S = 1.09

3482 reflections

216 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.40 e Å−3

Δρmin = −0.39 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/S1600536812028814/xu5579sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812028814/xu5579Isup2.hkl

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

[Cu(C8H5O3)2(C6H6N2O)2(H2O)2]	Z = 1
Mr = 642.08	F(000) = 331
Triclinic, P1	Dx = 1.533 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.8175 (2) Å	Cell parameters from 8185 reflections
b = 9.6539 (3) Å	θ = 2.7–28.4°
c = 9.8361 (3) Å	µ = 0.85 mm−1
α = 77.053 (3)°	T = 100 K
β = 74.041 (2)°	Block, blue
γ = 87.295 (3)°	0.32 × 0.28 × 0.14 mm
V = 695.49 (4) Å3

Bruker Kappa APEXII CCD area-detector diffractometer	3482 independent reflections
Radiation source: fine-focus sealed tube	3325 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
φ and ω scans	θmax = 28.4°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −10→9
Tmin = 0.762, Tmax = 0.888	k = −12→12
12850 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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.066	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ2(Fo2) + (0.0239P)2 + 0.4466P] where P = (Fo2 + 2Fc2)/3
3482 reflections	(Δ/σ)max < 0.001
216 parameters	Δρmax = 0.40 e Å−3
0 restraints	Δρmin = −0.39 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
Cu1	0.0000	0.0000	0.0000	0.01041 (7)
O1	0.11157 (12)	0.17792 (10)	0.00993 (10)	0.01370 (18)
O2	−0.11627 (12)	0.27371 (10)	0.15230 (11)	0.0162 (2)
O3	0.49068 (16)	0.66970 (15)	0.32698 (17)	0.0416 (4)
O4	−0.42482 (13)	−0.00030 (11)	−0.33929 (11)	0.0183 (2)
O5	0.29806 (13)	−0.08287 (11)	−0.07100 (11)	0.0174 (2)
H51	0.377 (3)	−0.044 (2)	−0.139 (2)	0.031 (5)*
H52	0.261 (3)	−0.152 (3)	−0.099 (3)	0.045 (6)*
N1	−0.00062 (14)	0.08754 (11)	−0.20468 (12)	0.0117 (2)
N2	−0.32207 (17)	0.13253 (14)	−0.56511 (13)	0.0173 (2)
H21	−0.241 (3)	0.185 (2)	−0.629 (2)	0.024 (5)*
H22	−0.409 (3)	0.102 (2)	−0.592 (2)	0.034 (5)*
C1	0.04545 (17)	0.26238 (13)	0.09204 (14)	0.0119 (2)
C2	0.17587 (17)	0.35192 (13)	0.12491 (14)	0.0119 (2)
C3	0.35050 (17)	0.30847 (14)	0.11108 (15)	0.0146 (2)
H3	0.3910	0.2305	0.0710	0.018*
C4	0.46457 (18)	0.38186 (15)	0.15737 (16)	0.0171 (3)
H4	0.5811	0.3522	0.1494	0.021*
C5	0.40476 (18)	0.49929 (15)	0.21546 (16)	0.0172 (3)
C6	0.23127 (18)	0.54629 (15)	0.22500 (16)	0.0187 (3)
H6	0.1925	0.6268	0.2612	0.022*
C7	0.11731 (18)	0.47245 (14)	0.18029 (15)	0.0161 (3)
H7	0.0013	0.5030	0.1871	0.019*
C8	0.5289 (2)	0.57274 (18)	0.26668 (19)	0.0270 (3)
H8	0.651 (3)	0.5350 (19)	0.252 (2)	0.024 (5)*
C9	−0.14085 (17)	0.06582 (13)	−0.25139 (14)	0.0120 (2)
H9	−0.2365	0.0117	−0.1864	0.014*
C10	−0.14972 (17)	0.12042 (13)	−0.39217 (14)	0.0121 (2)
C11	−0.00706 (18)	0.20287 (15)	−0.48827 (15)	0.0166 (3)
H11	−0.0085	0.2413	−0.5835	0.020*
C12	0.13731 (18)	0.22679 (15)	−0.43983 (15)	0.0178 (3)
H12	0.2335	0.2823	−0.5020	0.021*
C13	0.13671 (17)	0.16727 (14)	−0.29819 (15)	0.0144 (2)
H13	0.2344	0.1828	−0.2665	0.017*
C14	−0.31061 (17)	0.08129 (14)	−0.43099 (14)	0.0137 (2)

	U11	U22	U33	U12	U13	U23
Cu1	0.01132 (11)	0.01179 (11)	0.00973 (11)	−0.00110 (8)	−0.00490 (8)	−0.00287 (8)
O1	0.0137 (4)	0.0152 (4)	0.0136 (4)	−0.0023 (3)	−0.0042 (3)	−0.0049 (4)
O2	0.0112 (4)	0.0197 (5)	0.0182 (5)	−0.0017 (4)	−0.0034 (4)	−0.0059 (4)
O3	0.0244 (6)	0.0474 (8)	0.0666 (10)	−0.0024 (5)	−0.0109 (6)	−0.0415 (7)
O4	0.0175 (5)	0.0246 (5)	0.0135 (5)	−0.0075 (4)	−0.0063 (4)	−0.0014 (4)
O5	0.0135 (5)	0.0208 (5)	0.0182 (5)	−0.0008 (4)	−0.0026 (4)	−0.0066 (4)
N1	0.0113 (5)	0.0128 (5)	0.0120 (5)	−0.0008 (4)	−0.0039 (4)	−0.0034 (4)
N2	0.0172 (6)	0.0236 (6)	0.0122 (6)	−0.0057 (5)	−0.0068 (4)	−0.0017 (5)
C1	0.0134 (6)	0.0119 (6)	0.0108 (6)	−0.0016 (4)	−0.0056 (4)	0.0001 (4)
C2	0.0126 (6)	0.0120 (6)	0.0109 (6)	−0.0022 (4)	−0.0035 (4)	−0.0014 (4)
C3	0.0139 (6)	0.0129 (6)	0.0180 (6)	0.0005 (5)	−0.0043 (5)	−0.0057 (5)
C4	0.0114 (6)	0.0179 (6)	0.0236 (7)	0.0001 (5)	−0.0058 (5)	−0.0067 (5)
C5	0.0144 (6)	0.0176 (6)	0.0215 (7)	−0.0033 (5)	−0.0049 (5)	−0.0072 (5)
C6	0.0163 (6)	0.0155 (6)	0.0264 (7)	−0.0004 (5)	−0.0041 (5)	−0.0109 (5)
C7	0.0120 (6)	0.0156 (6)	0.0217 (7)	0.0016 (5)	−0.0051 (5)	−0.0056 (5)
C8	0.0162 (7)	0.0316 (8)	0.0393 (9)	−0.0031 (6)	−0.0078 (6)	−0.0194 (7)
C9	0.0116 (5)	0.0131 (6)	0.0120 (6)	−0.0011 (4)	−0.0038 (4)	−0.0031 (5)
C10	0.0129 (6)	0.0130 (6)	0.0120 (6)	0.0001 (4)	−0.0049 (5)	−0.0041 (5)
C11	0.0184 (6)	0.0198 (6)	0.0110 (6)	−0.0030 (5)	−0.0044 (5)	−0.0011 (5)
C12	0.0149 (6)	0.0213 (7)	0.0154 (6)	−0.0060 (5)	−0.0018 (5)	−0.0015 (5)
C13	0.0121 (6)	0.0162 (6)	0.0160 (6)	−0.0016 (5)	−0.0044 (5)	−0.0048 (5)
C14	0.0143 (6)	0.0156 (6)	0.0134 (6)	0.0001 (5)	−0.0058 (5)	−0.0054 (5)

Cu1—O1	1.9960 (9)	C3—H3	0.9300
Cu1—O1i	1.9960 (9)	C4—C5	1.3869 (19)
Cu1—O5	2.3951 (10)	C4—H4	0.9300
Cu1—O5i	2.3951 (10)	C5—C8	1.4807 (19)
Cu1—N1	2.0025 (11)	C6—C5	1.3947 (19)
Cu1—N1i	2.0025 (11)	C6—H6	0.9300
O1—C1	1.2689 (16)	C7—C2	1.3989 (18)
O2—C1	1.2512 (16)	C7—C6	1.3824 (19)
O3—C8	1.201 (2)	C7—H7	0.9300
O4—C14	1.2395 (16)	C8—H8	0.990 (19)
O5—H51	0.80 (2)	C9—H9	0.9300
O5—H52	0.87 (2)	C10—C9	1.3864 (18)
N1—C9	1.3411 (16)	C10—C11	1.3921 (18)
N1—C13	1.3449 (16)	C10—C14	1.4981 (17)
N2—C14	1.3272 (17)	C11—C12	1.3870 (19)
N2—H21	0.85 (2)	C11—H11	0.9300
N2—H22	0.87 (2)	C12—H12	0.9300
C1—C2	1.5103 (17)	C13—C12	1.3816 (19)
C3—C2	1.3883 (18)	C13—H13	0.9300
C3—C4	1.3899 (18)
O1—Cu1—O1i	180.00 (5)	C3—C4—H4	120.0
O1—Cu1—O5	85.74 (4)	C5—C4—C3	120.09 (12)
O1i—Cu1—O5	94.26 (4)	C5—C4—H4	120.0
O1—Cu1—O5i	94.26 (4)	C4—C5—C6	120.31 (12)
O1i—Cu1—O5i	85.74 (4)	C4—C5—C8	118.53 (13)
O1—Cu1—N1	89.34 (4)	C6—C5—C8	121.16 (13)
O1i—Cu1—N1	90.66 (4)	C5—C6—H6	120.2
O1—Cu1—N1i	90.66 (4)	C7—C6—C5	119.57 (12)
O1i—Cu1—N1i	89.34 (4)	C7—C6—H6	120.2
O5i—Cu1—O5	180.00 (2)	C2—C7—H7	119.9
N1—Cu1—O5	92.97 (4)	C6—C7—C2	120.25 (12)
N1i—Cu1—O5	87.03 (4)	C6—C7—H7	119.9
N1—Cu1—O5i	87.03 (4)	O3—C8—C5	125.09 (15)
N1i—Cu1—O5i	92.97 (4)	O3—C8—H8	118.9 (11)
N1i—Cu1—N1	180.0	C5—C8—H8	116.0 (11)
C1—O1—Cu1	127.13 (8)	N1—C9—C10	122.97 (12)
Cu1—O5—H51	126.3 (15)	N1—C9—H9	118.5
Cu1—O5—H52	90.8 (15)	C10—C9—H9	118.5
H51—O5—H52	105 (2)	C9—C10—C11	118.17 (12)
C9—N1—Cu1	119.55 (9)	C9—C10—C14	117.06 (11)
C9—N1—C13	118.50 (11)	C11—C10—C14	124.72 (12)
C13—N1—Cu1	121.95 (9)	C10—C11—H11	120.5
C14—N2—H21	122.1 (13)	C12—C11—C10	118.98 (12)
C14—N2—H22	118.5 (14)	C12—C11—H11	120.5
H21—N2—H22	118.9 (19)	C11—C12—H12	120.4
O1—C1—C2	116.43 (11)	C13—C12—C11	119.29 (12)
O2—C1—O1	126.00 (12)	C13—C12—H12	120.4
O2—C1—C2	117.50 (11)	N1—C13—C12	122.08 (12)
C3—C2—C1	119.97 (11)	N1—C13—H13	119.0
C3—C2—C7	119.90 (12)	C12—C13—H13	119.0
C7—C2—C1	119.93 (11)	O4—C14—N2	122.45 (12)
C2—C3—C4	119.81 (12)	O4—C14—C10	119.40 (12)
C2—C3—H3	120.1	N2—C14—C10	118.11 (12)
C4—C3—H3	120.1
O5—Cu1—O1—C1	−150.51 (11)	C4—C3—C2—C1	−172.50 (12)
O5i—Cu1—O1—C1	29.49 (11)	C4—C3—C2—C7	2.4 (2)
N1—Cu1—O1—C1	116.46 (11)	C2—C3—C4—C5	−0.8 (2)
N1i—Cu1—O1—C1	−63.54 (11)	C3—C4—C5—C6	−1.4 (2)
O1—Cu1—N1—C9	−140.43 (10)	C3—C4—C5—C8	178.62 (14)
O1i—Cu1—N1—C9	39.57 (10)	C4—C5—C8—O3	−175.17 (18)
O1—Cu1—N1—C13	40.10 (10)	C6—C5—C8—O3	4.8 (3)
O1i—Cu1—N1—C13	−139.90 (10)	C7—C6—C5—C4	2.0 (2)
O5—Cu1—N1—C9	133.87 (10)	C7—C6—C5—C8	−177.98 (14)
O5i—Cu1—N1—C9	−46.13 (10)	C6—C7—C2—C1	173.14 (13)
O5—Cu1—N1—C13	−45.60 (10)	C6—C7—C2—C3	−1.8 (2)
O5i—Cu1—N1—C13	134.40 (10)	C2—C7—C6—C5	−0.4 (2)
Cu1—O1—C1—O2	−21.17 (19)	C11—C10—C9—N1	−0.81 (19)
Cu1—O1—C1—C2	155.74 (8)	C14—C10—C9—N1	176.96 (11)
Cu1—N1—C9—C10	−178.70 (9)	C9—C10—C11—C12	0.1 (2)
C13—N1—C9—C10	0.79 (19)	C14—C10—C11—C12	−177.50 (12)
Cu1—N1—C13—C12	179.43 (10)	C9—C10—C14—O4	−2.22 (18)
C9—N1—C13—C12	−0.05 (19)	C9—C10—C14—N2	179.90 (12)
O1—C1—C2—C3	−22.27 (18)	C11—C10—C14—O4	175.39 (13)
O1—C1—C2—C7	162.83 (12)	C11—C10—C14—N2	−2.5 (2)
O2—C1—C2—C3	154.91 (12)	C10—C11—C12—C13	0.6 (2)
O2—C1—C2—C7	−19.98 (18)	N1—C13—C12—C11	−0.6 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···O2ii	0.85 (2)	2.100 (19)	2.8675 (16)	150 (2)
N2—H22···O4iii	0.88 (2)	2.00 (2)	2.8685 (17)	169 (2)
O5—H51···O4iv	0.81 (2)	2.11 (2)	2.8930 (15)	162 (2)
O5—H52···O2i	0.87 (3)	1.91 (3)	2.7542 (15)	163 (2)
C4—H4···O2iv	0.93	2.46	3.3824 (18)	175
C13—H13···O3v	0.93	2.49	3.290 (2)	144
C6—H6···Cgvi	0.93	2.75	3.656 (2)	166

Table 1

Selected bond lengths (Å)

Cu1—O1	1.9960 (9)
Cu1—O5	2.3951 (10)
Cu1—N1	2.0025 (11)

Table 2

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	0.85 (2)	2.100 (19)	2.8675 (16)	150 (2)
N2—H22⋯O4ii	0.88 (2)	2.00 (2)	2.8685 (17)	169 (2)
O5—H51⋯O4iii	0.81 (2)	2.11 (2)	2.8930 (15)	162 (2)
O5—H52⋯O2iv	0.87 (3)	1.91 (3)	2.7542 (15)	163 (2)
C4—H4⋯O2iii	0.93	2.46	3.3824 (18)	175
C13—H13⋯O3v	0.93	2.49	3.290 (2)	144
C6—H6⋯Cg vi	0.93	2.75	3.656 (2)	166

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