Bis(isonicotinamide-κN)bis-(4-methyl-benzoato-κO)copper(II) dihydrate.

In the centrosymmetric title compound, [Cu(C(8)H(7)O(2))(2)(C(6)H(6)N(2)O)(2)]·2H(2)O, the Cu(II) ion is located on a crystallographic inversion center. The asymmetric unit is completed by one 4-methyl-benzoate anion, one isonicotinamide (INA) ligand and one uncoordinated water mol-ecule; all the ligands are monodentate. The two O and the two N atoms around the Cu(II) ion form a slightly distorted square-planar arrangement. The dihedral angle between the carboxyl-ate group and the attached benzene ring is 13.86 (9)°, while the pyridine and benzene rings are oriented at a dihedral angle of 86.08 (5)°. The uncoordinated water mol-ecules are linked to the INA ligands by O-H⋯O hydrogen bonds. In the crystal structure, inter-molecular O-H⋯O, N-H⋯O and C-H⋯O hydrogen bonds link the mol-ecules into a three-dimensional network.

Related literature

For niacin, see: Krishnamachari (1974 ▶) and for N,N-diethyl­nicotinamide, see: Bigoli et al. (1972 ▶). For related structures, see: Hökelek et al. (1996 ▶, 2009a ▶,b ▶,c ▶); Hökelek & Necefoğlu (1998 ▶); Necefoğlu et al. (2010a ▶,b ▶).

Experimental

Crystal data

[Cu(C8H7O2)2(C6H6N2O)2]·2H2O

M = 614.11

Monoclinic,

a = 5.7138 (2) Å

b = 18.9948 (4) Å

c = 11.9671 (3) Å

β = 95.906 (3)°

V = 1291.92 (6) Å3

Z = 2

Mo Kα radiation

μ = 0.91 mm−1

T = 100 K

0.29 × 0.27 × 0.25 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.763, T max = 0.959

11754 measured reflections

3199 independent reflections

2637 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.080

S = 1.08

3199 reflections

204 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.63 e Å−3

Δρmin = −0.51 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 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810028060/su2197sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810028060/su2197Isup2.hkl

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

[Cu(C8H7O2)2(C6H6N2O)2]·2H2O	F(000) = 638
Mr = 614.11	Dx = 1.579 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5200 reflections
a = 5.7138 (2) Å	θ = 2.7–28.2°
b = 18.9948 (4) Å	µ = 0.91 mm−1
c = 11.9671 (3) Å	T = 100 K
β = 95.906 (3)°	Block, violet
V = 1291.92 (6) Å3	0.29 × 0.27 × 0.25 mm
Z = 2

Bruker Kappa APEXII CCD area-detector diffractometer	3199 independent reflections
Radiation source: fine-focus sealed tube	2637 reflections with I > 2σ(I)
graphite	Rint = 0.026
φ and ω scans	θmax = 28.4°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −7→7
Tmin = 0.763, Tmax = 0.959	k = −20→25
11754 measured reflections	l = −16→14

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.080	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ2(Fo2) + (0.0303P)2 + 1.1079P] where P = (Fo2 + 2Fc2)/3
3199 reflections	(Δ/σ)max < 0.001
204 parameters	Δρmax = 0.63 e Å−3
0 restraints	Δρmin = −0.51 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	0.01074 (9)
O1	0.0382 (2)	−0.09651 (7)	−0.17689 (11)	0.0173 (3)
O2	−0.1745 (2)	−0.00164 (6)	−0.14584 (11)	0.0140 (3)
O3	−0.8594 (2)	−0.25069 (7)	0.09449 (12)	0.0191 (3)
O4	−1.1555 (3)	−0.22382 (8)	−0.10917 (14)	0.0184 (3)
H41	−1.077 (5)	−0.2318 (14)	−0.055 (2)	0.027 (7)*
H42	−1.097 (5)	−0.1903 (14)	−0.132 (2)	0.028 (7)*
N1	−0.2249 (3)	−0.07406 (8)	0.05451 (13)	0.0124 (3)
N2	−0.6168 (3)	−0.27723 (9)	0.24930 (14)	0.0158 (3)
H21	−0.707 (4)	−0.3082 (12)	0.2657 (19)	0.016 (6)*
H22	−0.487 (4)	−0.2719 (10)	0.2909 (18)	0.007 (5)*
C1	−0.1300 (3)	−0.05595 (9)	−0.20439 (15)	0.0134 (4)
C2	−0.2973 (3)	−0.06975 (9)	−0.30646 (15)	0.0112 (3)
C3	−0.2437 (3)	−0.11966 (9)	−0.38569 (16)	0.0144 (4)
H3	−0.1009	−0.1435	−0.3763	0.017*
C4	−0.4027 (3)	−0.13357 (9)	−0.47810 (16)	0.0144 (4)
H4	−0.3645	−0.1665	−0.5308	0.017*
C5	−0.6202 (3)	−0.09904 (9)	−0.49401 (15)	0.0132 (4)
C6	−0.6723 (3)	−0.04968 (9)	−0.41381 (16)	0.0136 (4)
H6	−0.8162	−0.0264	−0.4225	0.016*
C7	−0.5137 (3)	−0.03481 (9)	−0.32179 (16)	0.0126 (4)
H7	−0.5510	−0.0013	−0.2697	0.015*
C8	−0.7908 (3)	−0.11485 (10)	−0.59515 (16)	0.0175 (4)
H8A	−0.8165	−0.1647	−0.6006	0.026*
H8B	−0.7274	−0.0984	−0.6616	0.026*
H8C	−0.9374	−0.0915	−0.5878	0.026*
C9	−0.4391 (3)	−0.08763 (10)	0.00027 (16)	0.0143 (4)
H9	−0.4908	−0.0604	−0.0621	0.017*
C10	−0.5851 (3)	−0.14000 (9)	0.03306 (16)	0.0149 (4)
H10	−0.7323	−0.1471	−0.0062	0.018*
C11	−0.5111 (3)	−0.18220 (9)	0.12538 (16)	0.0132 (4)
C12	−0.2892 (3)	−0.16896 (9)	0.18202 (16)	0.0149 (4)
H12	−0.2327	−0.1958	0.2440	0.018*
C13	−0.1551 (3)	−0.11484 (10)	0.14368 (16)	0.0150 (4)
H13	−0.0079	−0.1062	0.1820	0.018*
C14	−0.6762 (3)	−0.24014 (9)	0.15535 (16)	0.0145 (4)

	U11	U22	U33	U12	U13	U23
Cu1	0.01320 (16)	0.01035 (15)	0.00829 (16)	−0.00275 (12)	−0.00076 (11)	−0.00013 (12)
O1	0.0140 (7)	0.0194 (7)	0.0172 (7)	0.0006 (5)	−0.0041 (5)	0.0042 (5)
O2	0.0181 (6)	0.0127 (6)	0.0103 (6)	−0.0040 (5)	−0.0020 (5)	0.0005 (5)
O3	0.0180 (7)	0.0167 (6)	0.0217 (8)	−0.0030 (5)	−0.0025 (6)	0.0026 (6)
O4	0.0205 (8)	0.0147 (7)	0.0189 (8)	−0.0022 (6)	−0.0036 (6)	0.0018 (6)
N1	0.0131 (8)	0.0128 (7)	0.0110 (8)	−0.0015 (6)	−0.0007 (6)	−0.0005 (6)
N2	0.0154 (9)	0.0143 (8)	0.0168 (9)	−0.0034 (6)	−0.0019 (7)	0.0021 (6)
C1	0.0144 (9)	0.0138 (8)	0.0118 (9)	−0.0058 (7)	0.0011 (7)	0.0037 (7)
C2	0.0129 (9)	0.0102 (8)	0.0102 (9)	−0.0029 (6)	−0.0004 (7)	0.0014 (6)
C3	0.0139 (9)	0.0128 (8)	0.0164 (10)	0.0011 (7)	0.0013 (7)	0.0016 (7)
C4	0.0195 (9)	0.0109 (8)	0.0131 (9)	−0.0004 (7)	0.0024 (7)	−0.0036 (7)
C5	0.0163 (9)	0.0117 (8)	0.0110 (9)	−0.0045 (7)	−0.0010 (7)	0.0016 (7)
C6	0.0130 (9)	0.0127 (8)	0.0149 (10)	0.0003 (6)	0.0003 (7)	0.0019 (7)
C7	0.0155 (9)	0.0106 (8)	0.0117 (9)	−0.0016 (6)	0.0014 (7)	−0.0011 (7)
C8	0.0205 (10)	0.0174 (9)	0.0136 (10)	−0.0034 (7)	−0.0032 (8)	−0.0003 (7)
C9	0.0161 (9)	0.0142 (9)	0.0124 (9)	0.0014 (6)	0.0000 (7)	−0.0001 (7)
C10	0.0148 (9)	0.0147 (9)	0.0149 (10)	0.0004 (7)	−0.0004 (7)	−0.0015 (7)
C11	0.0152 (9)	0.0110 (8)	0.0137 (10)	0.0005 (6)	0.0028 (7)	−0.0014 (7)
C12	0.0200 (10)	0.0130 (8)	0.0116 (9)	−0.0013 (7)	0.0012 (7)	0.0014 (7)
C13	0.0149 (9)	0.0164 (9)	0.0131 (9)	−0.0001 (7)	−0.0013 (7)	0.0001 (7)
C14	0.0133 (9)	0.0120 (8)	0.0183 (10)	0.0011 (7)	0.0027 (7)	−0.0012 (7)

Cu1—O2	1.9192 (13)	C4—H4	0.9300
Cu1—O2i	1.9192 (13)	C5—C4	1.401 (3)
Cu1—N1	2.0562 (15)	C5—C6	1.396 (3)
Cu1—N1i	2.0562 (15)	C5—C8	1.504 (3)
O1—C1	1.249 (2)	C6—H6	0.9300
O2—C1	1.287 (2)	C7—C6	1.382 (3)
O3—C14	1.228 (2)	C7—H7	0.9300
O4—H41	0.77 (3)	C8—H8A	0.9600
O4—H42	0.78 (3)	C8—H8B	0.9600
N1—C9	1.350 (2)	C8—H8C	0.9600
N1—C13	1.345 (2)	C9—H9	0.9300
N2—C14	1.341 (2)	C10—C9	1.381 (3)
N2—H21	0.82 (2)	C10—C11	1.395 (3)
N2—H22	0.86 (2)	C10—H10	0.9300
C2—C1	1.495 (3)	C11—C12	1.398 (3)
C2—C3	1.397 (2)	C11—C14	1.516 (2)
C2—C7	1.398 (3)	C12—C13	1.388 (2)
C3—C4	1.383 (3)	C12—H12	0.9300
C3—H3	0.9300	C13—H13	0.9300
O2i—Cu1—O2	180.00 (4)	C7—C6—C5	121.11 (17)
O2—Cu1—N1	89.67 (6)	C7—C6—H6	119.4
O2i—Cu1—N1	90.33 (6)	C2—C7—H7	119.8
O2—Cu1—N1i	90.33 (6)	C6—C7—C2	120.40 (17)
O2i—Cu1—N1i	89.67 (6)	C6—C7—H7	119.8
N1—Cu1—N1i	180.00 (10)	C5—C8—H8A	109.5
C1—O2—Cu1	113.26 (12)	C5—C8—H8B	109.5
H42—O4—H41	103 (3)	C5—C8—H8C	109.5
C9—N1—Cu1	122.91 (12)	H8A—C8—H8B	109.5
C13—N1—Cu1	120.10 (12)	H8A—C8—H8C	109.5
C13—N1—C9	116.85 (16)	H8B—C8—H8C	109.5
C14—N2—H21	117.9 (16)	N1—C9—C10	123.05 (17)
C14—N2—H22	123.8 (14)	N1—C9—H9	118.5
H22—N2—H21	118 (2)	C10—C9—H9	118.5
O1—C1—O2	122.72 (18)	C9—C10—C11	119.75 (17)
O1—C1—C2	121.14 (17)	C9—C10—H10	120.1
O2—C1—C2	116.10 (16)	C11—C10—H10	120.1
C3—C2—C1	120.47 (16)	C10—C11—C12	117.82 (17)
C3—C2—C7	119.07 (17)	C10—C11—C14	117.32 (16)
C7—C2—C1	120.42 (16)	C12—C11—C14	124.85 (17)
C2—C3—H3	120.0	C11—C12—H12	120.7
C4—C3—C2	120.03 (17)	C13—C12—C11	118.51 (17)
C4—C3—H3	120.0	C13—C12—H12	120.7
C3—C4—C5	121.34 (17)	N1—C13—C12	124.04 (17)
C3—C4—H4	119.3	N1—C13—H13	118.0
C5—C4—H4	119.3	C12—C13—H13	118.0
C4—C5—C8	120.56 (16)	O3—C14—N2	122.56 (17)
C6—C5—C4	118.05 (17)	O3—C14—C11	119.40 (17)
C6—C5—C8	121.39 (17)	N2—C14—C11	118.03 (17)
C5—C6—H6	119.4
O2i—Cu1—N1—C9	161.86 (14)	C1—C2—C7—C6	−177.34 (16)
O2—Cu1—N1—C9	−18.14 (14)	C3—C2—C7—C6	0.2 (3)
O2i—Cu1—N1—C13	−22.59 (14)	C2—C3—C4—C5	−0.7 (3)
O2—Cu1—N1—C13	157.41 (14)	C6—C5—C4—C3	0.2 (3)
N1—Cu1—O2—C1	−76.89 (12)	C8—C5—C4—C3	179.96 (17)
N1i—Cu1—O2—C1	103.11 (12)	C4—C5—C6—C7	0.5 (3)
Cu1—O2—C1—O1	−11.8 (2)	C8—C5—C6—C7	−179.23 (16)
Cu1—O2—C1—C2	166.15 (11)	C2—C7—C6—C5	−0.7 (3)
Cu1—N1—C9—C10	176.28 (14)	C11—C10—C9—N1	−0.8 (3)
C13—N1—C9—C10	0.6 (3)	C9—C10—C11—C12	0.5 (3)
Cu1—N1—C13—C12	−175.86 (14)	C9—C10—C11—C14	−178.32 (16)
C9—N1—C13—C12	0.0 (3)	C10—C11—C12—C13	0.0 (3)
C3—C2—C1—O1	−13.1 (3)	C14—C11—C12—C13	178.73 (17)
C7—C2—C1—O1	164.51 (16)	C10—C11—C14—O3	4.5 (2)
C3—C2—C1—O2	169.00 (16)	C10—C11—C14—N2	−174.41 (17)
C7—C2—C1—O2	−13.4 (2)	C12—C11—C14—O3	−174.24 (18)
C7—C2—C3—C4	0.5 (3)	C12—C11—C14—N2	6.9 (3)
C1—C2—C3—C4	178.05 (16)	C11—C12—C13—N1	−0.3 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···O1ii	0.82 (2)	2.46 (2)	3.283 (2)	177 (2)
N2—H22···O4iii	0.86 (2)	2.14 (2)	2.983 (2)	171 (2)
O4—H41···O3	0.77 (3)	2.10 (3)	2.866 (2)	178 (3)
O4—H42···O1iv	0.78 (3)	2.04 (3)	2.813 (2)	173 (3)
C3—H3···O3v	0.93	2.48	3.324 (2)	151
C10—H10···O1iv	0.93	2.50	3.242 (2)	137
C12—H12···O4iii	0.93	2.34	3.253 (2)	169

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H21⋯O1i	0.82 (2)	2.46 (2)	3.283 (2)	177 (2)
N2—H22⋯O4ii	0.86 (2)	2.14 (2)	2.983 (2)	171 (2)
O4—H41⋯O3	0.77 (3)	2.10 (3)	2.866 (2)	178 (3)
O4—H42⋯O1iii	0.78 (3)	2.04 (3)	2.813 (2)	173 (3)
C3—H3⋯O3iv	0.93	2.48	3.324 (2)	151
C10—H10⋯O1iii	0.93	2.50	3.242 (2)	137
C12—H12⋯O4ii	0.93	2.34	3.253 (2)	169

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