Tetra-kis(μ-4-methyl-benzoato-κO:O')bis-[(isonicotinamide-κN)copper(II)].

In the title centrosymmetric binuclear complex, [Cu(2)(C(8)H(7)O(2))(4)(C(6)H(6)N(2)O)(2)], the Cu atoms [Cu⋯Cu = 2.6375 (6) Å] are bridged by four 4-methyl-benzoate (PMB) ligands. The four nearest O atoms around each Cu(II) ion form a distorted square-planar arrangement, and the distorted square-pyramidal coordination is completed by the pyridine N atom of the isonicotinamide (INA) ligand. Each Cu(II) ion is displaced by 0.2633 (1) Å from the plane of the four O atoms, with an average Cu-O distance of 1.974 (2) Å. The dihedral angles between carboxyl-ate groups and the adjacent benzene rings are 7.88 (19) and 9.68 (10)°, while the benzene rings are oriented at a dihedral angle of 85.90 (9)°. The pyridine ring is oriented at dihedral angles of 8.59 (7) and 83.89 (9)° with respect to the benzene rings. In the crystal structure, inter-molecular N-H⋯O hydrogen bonds link the mol-ecules into a three-dimensional network. π-π contacts between the benzene rings and between the pyridine and benzene rings, [centroid-centroid distances = 3.563 (2) and 3.484 (2) Å, respectively] may further stabilize the crystal structure.

Related literature

For niacin, see: Krishnamachari (1974 ▶), and for the nicotinic acid derivative N,N-diethyl­nicotinamide, see: Bigoli et al. (1972 ▶). For related structures, see: Hökelek et al. (1995 ▶, 2009a ▶,b ▶,c ▶); Speier & Fulop (1989 ▶); Usubaliev et al. (1980 ▶).

Experimental

Crystal data

[Cu2(C8H7O2)4(C6H6N2O)2]

M = 911.88

Monoclinic,

a = 11.2305 (2) Å

b = 23.4691 (4) Å

c = 8.0087 (1) Å

β = 102.128 (1)°

V = 2063.74 (6) Å3

Z = 2

Mo Kα radiation

μ = 1.10 mm−1

T = 101 K

0.30 × 0.24 × 0.14 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.735, T max = 0.862

20056 measured reflections

5101 independent reflections

3629 reflections with I > 2σ(I)

R int = 0.062

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.087

S = 1.01

5101 reflections

281 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.47 e Å−3

Δρmin = −0.70 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 datablocks I, global. DOI: 10.1107/S1600536810006513/xu2729sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810006513/xu2729Isup2.hkl

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

[Cu2(C8H7O2)4(C6H6N2O)2]	F(000) = 940
Mr = 911.88	Dx = 1.467 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3119 reflections
a = 11.2305 (2) Å	θ = 2.5–25.4°
b = 23.4691 (4) Å	µ = 1.10 mm−1
c = 8.0087 (1) Å	T = 101 K
β = 102.128 (1)°	Block, green
V = 2063.74 (6) Å3	0.30 × 0.24 × 0.14 mm
Z = 2

Bruker Kappa APEXII CCD area-detector diffractometer	5101 independent reflections
Radiation source: fine-focus sealed tube	3629 reflections with I > 2σ(I)
graphite	Rint = 0.062
φ and ω scans	θmax = 28.3°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −14→11
Tmin = 0.735, Tmax = 0.862	k = −31→31
20056 measured reflections	l = −10→10

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.087	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ2(Fo2) + (0.0224P)2 + 2.5778P] where P = (Fo2 + 2Fc2)/3
5101 reflections	(Δ/σ)max = 0.001
281 parameters	Δρmax = 0.47 e Å−3
0 restraints	Δρmin = −0.70 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 > 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.

	x	y	z	Uiso*/Ueq
Cu1	0.95060 (3)	0.966319 (13)	1.09852 (4)	0.01099 (9)
O1	0.81764 (18)	0.95045 (8)	0.9002 (2)	0.0191 (4)
O2	0.90275 (17)	1.00855 (8)	0.7371 (2)	0.0168 (4)
O3	1.04702 (19)	0.90818 (8)	1.0089 (2)	0.0203 (4)
O4	0.86037 (17)	1.03478 (8)	1.1481 (2)	0.0180 (4)
O5	0.70039 (18)	0.75397 (8)	1.5592 (2)	0.0183 (4)
N1	0.8976 (2)	0.90548 (9)	1.2719 (3)	0.0139 (5)
N2	0.7819 (3)	0.81071 (11)	1.7825 (3)	0.0200 (6)
H2A	0.752 (3)	0.7887 (13)	1.854 (4)	0.022 (8)*
H2B	0.818 (3)	0.8419 (16)	1.818 (4)	0.047 (12)*
C1	0.8203 (3)	0.97549 (10)	0.7606 (3)	0.0130 (5)
C2	0.7165 (2)	0.96483 (11)	0.6131 (3)	0.0122 (5)
C3	0.6147 (2)	0.93399 (11)	0.6322 (3)	0.0138 (6)
H3	0.6095	0.9196	0.7413	0.017*
C4	0.5205 (3)	0.92415 (11)	0.4928 (3)	0.0148 (6)
H4	0.4508	0.9034	0.5077	0.018*
C5	0.5265 (3)	0.94428 (11)	0.3308 (3)	0.0147 (6)
C6	0.6286 (3)	0.97476 (11)	0.3131 (3)	0.0159 (6)
H6	0.6344	0.9885	0.2035	0.019*
C7	0.7225 (2)	0.98563 (10)	0.4518 (3)	0.0128 (5)
H7	0.7911	1.0072	0.4371	0.015*
C8	0.4259 (3)	0.93213 (12)	0.1789 (3)	0.0221 (6)
H8A	0.3516	0.9219	0.2179	0.033*
H8B	0.4498	0.9005	0.1132	0.033*
H8C	0.4106	0.9661	0.1064	0.033*
C9	1.1213 (2)	0.91754 (11)	0.9141 (3)	0.0133 (5)
C10	1.1926 (3)	0.86716 (11)	0.8745 (3)	0.0142 (6)
C11	1.1638 (3)	0.81263 (11)	0.9227 (3)	0.0188 (6)
H11	1.0971	0.8075	0.9770	0.023*
C12	1.2313 (3)	0.76602 (12)	0.8923 (3)	0.0224 (7)
H12	1.2090	0.7291	0.9232	0.027*
C13	1.3314 (3)	0.77232 (12)	0.8172 (3)	0.0206 (6)
C14	1.3589 (3)	0.82663 (12)	0.7674 (3)	0.0203 (6)
H14	1.4264	0.8318	0.7146	0.024*
C15	1.2897 (3)	0.87351 (11)	0.7932 (3)	0.0176 (6)
H15	1.3087	0.9101	0.7552	0.021*
C16	1.4105 (3)	0.72204 (13)	0.7957 (4)	0.0284 (7)
H16A	1.3606	0.6874	0.7780	0.043*
H16B	1.4748	0.7177	0.8985	0.043*
H16C	1.4473	0.7283	0.6967	0.043*
C17	0.7944 (2)	0.87572 (10)	1.2239 (3)	0.0134 (5)
H17	0.7501	0.8796	1.1096	0.016*
C18	0.7487 (2)	0.83964 (11)	1.3316 (3)	0.0124 (5)
H18	0.6757	0.8188	1.2916	0.015*
C19	0.8121 (2)	0.83446 (10)	1.4999 (3)	0.0127 (5)
C20	0.9206 (3)	0.86403 (11)	1.5496 (3)	0.0170 (6)
H20	0.9674	0.8604	1.6626	0.020*
C21	0.9600 (3)	0.89878 (11)	1.4330 (3)	0.0152 (6)
H21	1.0346	0.9188	1.4683	0.018*
C22	0.7601 (3)	0.79620 (11)	1.6172 (3)	0.0142 (6)

	U11	U22	U33	U12	U13	U23
Cu1	0.01279 (18)	0.01089 (15)	0.00968 (13)	−0.00136 (15)	0.00323 (11)	0.00055 (13)
O1	0.0192 (11)	0.0233 (11)	0.0133 (9)	−0.0080 (9)	0.0000 (8)	0.0042 (7)
O2	0.0154 (11)	0.0202 (10)	0.0137 (8)	−0.0071 (8)	0.0003 (7)	0.0035 (7)
O3	0.0299 (13)	0.0129 (9)	0.0236 (10)	0.0023 (9)	0.0177 (9)	0.0009 (8)
O4	0.0208 (11)	0.0142 (9)	0.0221 (9)	0.0023 (9)	0.0116 (8)	0.0033 (8)
O5	0.0255 (12)	0.0147 (10)	0.0160 (9)	−0.0046 (9)	0.0077 (8)	0.0016 (7)
N1	0.0156 (13)	0.0140 (11)	0.0130 (10)	0.0012 (10)	0.0050 (9)	0.0011 (8)
N2	0.0348 (17)	0.0132 (12)	0.0140 (11)	−0.0057 (12)	0.0094 (11)	0.0010 (9)
C1	0.0174 (15)	0.0085 (13)	0.0143 (11)	0.0016 (11)	0.0058 (10)	−0.0026 (9)
C2	0.0137 (14)	0.0096 (11)	0.0128 (11)	0.0027 (11)	0.0018 (9)	−0.0023 (10)
C3	0.0153 (16)	0.0133 (13)	0.0141 (12)	0.0024 (11)	0.0061 (10)	0.0007 (10)
C4	0.0127 (15)	0.0136 (13)	0.0179 (12)	−0.0008 (11)	0.0028 (11)	−0.0016 (10)
C5	0.0161 (16)	0.0110 (12)	0.0162 (12)	0.0039 (11)	0.0011 (10)	−0.0026 (10)
C6	0.0218 (16)	0.0124 (13)	0.0138 (11)	0.0015 (11)	0.0045 (11)	0.0006 (10)
C7	0.0144 (15)	0.0103 (12)	0.0150 (12)	0.0002 (11)	0.0062 (10)	0.0001 (9)
C8	0.0226 (18)	0.0209 (15)	0.0198 (13)	−0.0015 (13)	−0.0026 (12)	−0.0029 (11)
C9	0.0125 (15)	0.0159 (13)	0.0099 (11)	−0.0029 (11)	−0.0013 (10)	−0.0023 (9)
C10	0.0161 (16)	0.0154 (13)	0.0104 (11)	0.0002 (11)	0.0013 (10)	−0.0003 (10)
C11	0.0192 (17)	0.0180 (14)	0.0195 (13)	−0.0011 (12)	0.0049 (11)	0.0025 (11)
C12	0.0265 (19)	0.0149 (14)	0.0241 (14)	0.0034 (13)	0.0017 (12)	0.0022 (11)
C13	0.0245 (18)	0.0209 (15)	0.0149 (13)	0.0078 (13)	0.0009 (11)	−0.0017 (11)
C14	0.0202 (17)	0.0247 (16)	0.0171 (13)	0.0041 (13)	0.0063 (11)	−0.0008 (11)
C15	0.0222 (17)	0.0136 (13)	0.0160 (12)	0.0004 (12)	0.0016 (11)	0.0003 (10)
C16	0.036 (2)	0.0219 (16)	0.0264 (15)	0.0131 (14)	0.0043 (14)	0.0000 (12)
C17	0.0183 (16)	0.0113 (12)	0.0110 (11)	0.0004 (11)	0.0036 (10)	−0.0014 (9)
C18	0.0138 (15)	0.0112 (12)	0.0130 (11)	−0.0006 (11)	0.0049 (10)	−0.0026 (10)
C19	0.0177 (16)	0.0093 (12)	0.0127 (11)	0.0007 (11)	0.0065 (10)	−0.0005 (9)
C20	0.0202 (17)	0.0189 (14)	0.0108 (11)	−0.0003 (12)	0.0003 (10)	0.0026 (10)
C21	0.0140 (15)	0.0152 (13)	0.0160 (12)	−0.0036 (11)	0.0026 (10)	0.0002 (10)
C22	0.0186 (16)	0.0134 (13)	0.0118 (12)	0.0009 (12)	0.0060 (11)	0.0033 (10)

Cu1—Cu1i	2.6375 (6)	C8—H8A	0.9800
Cu1—O1	1.9733 (18)	C8—H8B	0.9800
Cu1—O2i	1.9703 (18)	C8—H8C	0.9800
Cu1—O3	1.9687 (18)	C9—O4i	1.259 (3)
Cu1—O4	1.9836 (18)	C9—C10	1.499 (4)
Cu1—N1	2.161 (2)	C10—C11	1.394 (4)
O1—C1	1.269 (3)	C10—C15	1.390 (4)
O2—Cu1i	1.9703 (18)	C11—C12	1.381 (4)
O2—C1	1.252 (3)	C11—H11	0.9500
O3—C9	1.259 (3)	C12—C13	1.389 (4)
O4—C9i	1.259 (3)	C12—H12	0.9500
O5—C22	1.232 (3)	C13—C14	1.389 (4)
N1—C17	1.338 (3)	C13—C16	1.508 (4)
N1—C21	1.342 (3)	C14—C15	1.387 (4)
N2—C22	1.339 (3)	C14—H14	0.9500
N2—H2A	0.89 (3)	C15—H15	0.9500
N2—H2B	0.85 (4)	C16—H16A	0.9800
C1—C2	1.497 (3)	C16—H16B	0.9800
C2—C3	1.388 (4)	C16—H16C	0.9800
C2—C7	1.397 (3)	C17—C18	1.382 (3)
C3—C4	1.387 (4)	C17—H17	0.9500
C3—H3	0.9500	C18—C19	1.391 (3)
C4—C5	1.395 (3)	C18—H18	0.9500
C4—H4	0.9500	C19—C20	1.387 (4)
C5—C6	1.384 (4)	C19—C22	1.503 (3)
C5—C8	1.503 (4)	C20—C21	1.381 (3)
C6—C7	1.385 (4)	C20—H20	0.9500
C6—H6	0.9500	C21—H21	0.9500
C7—H7	0.9500
O1—Cu1—Cu1i	88.51 (5)	H8A—C8—H8B	109.5
O1—Cu1—O4	88.96 (8)	H8A—C8—H8C	109.5
O1—Cu1—N1	97.37 (8)	H8B—C8—H8C	109.5
O2i—Cu1—Cu1i	79.79 (5)	O3—C9—O4i	125.3 (2)
O2i—Cu1—O1	168.28 (7)	O3—C9—C10	116.2 (2)
O2i—Cu1—O4	90.82 (8)	O4i—C9—C10	118.6 (2)
O2i—Cu1—N1	94.19 (8)	C11—C10—C9	120.0 (2)
O3—Cu1—Cu1i	82.21 (5)	C15—C10—C9	121.4 (2)
O3—Cu1—O1	87.53 (8)	C15—C10—C11	118.6 (3)
O3—Cu1—O2i	90.25 (8)	C10—C11—H11	119.6
O3—Cu1—O4	167.82 (7)	C12—C11—C10	120.7 (3)
O3—Cu1—N1	91.34 (8)	C12—C11—H11	119.6
O4—Cu1—Cu1i	86.04 (5)	C11—C12—C13	121.1 (3)
O4—Cu1—N1	100.68 (8)	C11—C12—H12	119.5
N1—Cu1—Cu1i	171.10 (6)	C13—C12—H12	119.5
C1—O1—Cu1	117.87 (17)	C12—C13—C16	121.0 (3)
C1—O2—Cu1i	128.72 (16)	C14—C13—C12	118.1 (3)
C9—O3—Cu1	125.69 (17)	C14—C13—C16	120.9 (3)
C9i—O4—Cu1	120.50 (17)	C13—C14—H14	119.3
C17—N1—Cu1	119.94 (16)	C15—C14—C13	121.3 (3)
C17—N1—C21	117.5 (2)	C15—C14—H14	119.3
C21—N1—Cu1	122.42 (18)	C10—C15—H15	119.9
C22—N2—H2A	118 (2)	C14—C15—C10	120.2 (3)
C22—N2—H2B	121 (2)	C14—C15—H15	119.9
H2A—N2—H2B	120 (3)	C13—C16—H16A	109.5
O1—C1—C2	117.3 (2)	C13—C16—H16B	109.5
O2—C1—O1	125.1 (2)	C13—C16—H16C	109.5
O2—C1—C2	117.6 (2)	H16A—C16—H16B	109.5
C3—C2—C1	121.6 (2)	H16A—C16—H16C	109.5
C3—C2—C7	119.1 (2)	H16B—C16—H16C	109.5
C7—C2—C1	119.4 (2)	N1—C17—C18	123.6 (2)
C2—C3—H3	119.9	N1—C17—H17	118.2
C4—C3—C2	120.3 (2)	C18—C17—H17	118.2
C4—C3—H3	119.9	C17—C18—C19	118.5 (2)
C3—C4—C5	121.0 (3)	C17—C18—H18	120.7
C3—C4—H4	119.5	C19—C18—H18	120.7
C5—C4—H4	119.5	C18—C19—C22	118.1 (2)
C4—C5—C8	120.9 (3)	C20—C19—C18	118.3 (2)
C6—C5—C4	118.2 (2)	C20—C19—C22	123.6 (2)
C6—C5—C8	120.9 (2)	C19—C20—H20	120.4
C5—C6—C7	121.4 (2)	C21—C20—C19	119.3 (2)
C5—C6—H6	119.3	C21—C20—H20	120.4
C7—C6—H6	119.3	N1—C21—C20	122.8 (3)
C2—C7—H7	120.0	N1—C21—H21	118.6
C6—C7—C2	120.0 (2)	C20—C21—H21	118.6
C6—C7—H7	120.0	O5—C22—N2	123.4 (2)
C5—C8—H8A	109.5	O5—C22—C19	119.8 (2)
C5—C8—H8B	109.5	N2—C22—C19	116.9 (2)
C5—C8—H8C	109.5
Cu1i—Cu1—O1—C1	−1.45 (18)	O2—C1—C2—C7	8.2 (4)
O2i—Cu1—O1—C1	−4.4 (5)	C1—C2—C3—C4	−179.2 (2)
O3—Cu1—O1—C1	−83.72 (19)	C7—C2—C3—C4	−0.1 (4)
O4—Cu1—O1—C1	84.61 (19)	C1—C2—C7—C6	178.2 (2)
N1—Cu1—O1—C1	−174.75 (19)	C3—C2—C7—C6	−0.9 (4)
Cu1i—Cu1—O3—C9	5.3 (2)	C2—C3—C4—C5	0.8 (4)
O1—Cu1—O3—C9	94.1 (2)	C3—C4—C5—C6	−0.5 (4)
O2i—Cu1—O3—C9	−74.4 (2)	C3—C4—C5—C8	178.2 (2)
O4—Cu1—O3—C9	20.7 (5)	C4—C5—C6—C7	−0.5 (4)
N1—Cu1—O3—C9	−168.6 (2)	C8—C5—C6—C7	−179.2 (2)
Cu1i—Cu1—O4—C9i	−2.61 (18)	C5—C6—C7—C2	1.2 (4)
O1—Cu1—O4—C9i	−91.19 (19)	O3—C9—C10—C11	8.4 (4)
O2i—Cu1—O4—C9i	77.09 (19)	O3—C9—C10—C15	−170.2 (2)
O3—Cu1—O4—C9i	−17.9 (5)	O4i—C9—C10—C11	−171.8 (2)
N1—Cu1—O4—C9i	171.51 (19)	O4i—C9—C10—C15	9.6 (4)
O1—Cu1—N1—C17	−4.4 (2)	C9—C10—C11—C12	−177.8 (2)
O1—Cu1—N1—C21	−179.6 (2)	C15—C10—C11—C12	0.8 (4)
O2i—Cu1—N1—C17	177.58 (19)	C9—C10—C15—C14	176.1 (2)
O2i—Cu1—N1—C21	2.4 (2)	C11—C10—C15—C14	−2.6 (4)
O3—Cu1—N1—C17	−92.1 (2)	C10—C11—C12—C13	1.7 (4)
O3—Cu1—N1—C21	92.7 (2)	C11—C12—C13—C14	−2.5 (4)
O4—Cu1—N1—C17	85.95 (19)	C11—C12—C13—C16	175.5 (3)
O4—Cu1—N1—C21	−89.3 (2)	C12—C13—C14—C15	0.8 (4)
Cu1—O1—C1—O2	2.0 (3)	C16—C13—C14—C15	−177.3 (3)
Cu1—O1—C1—C2	−177.69 (16)	C13—C14—C15—C10	1.8 (4)
Cu1i—O2—C1—O1	−1.3 (4)	N1—C17—C18—C19	1.0 (4)
Cu1i—O2—C1—C2	178.39 (16)	C17—C18—C19—C20	−2.6 (4)
Cu1—O3—C9—O4i	−5.1 (4)	C17—C18—C19—C22	178.6 (2)
Cu1—O3—C9—C10	174.71 (16)	C18—C19—C20—C21	2.1 (4)
Cu1—N1—C17—C18	−174.35 (19)	C22—C19—C20—C21	−179.1 (2)
C21—N1—C17—C18	1.1 (4)	C18—C19—C22—O5	30.9 (4)
Cu1—N1—C21—C20	173.7 (2)	C18—C19—C22—N2	−148.8 (3)
C17—N1—C21—C20	−1.6 (4)	C20—C19—C22—O5	−147.9 (3)
O1—C1—C2—C3	7.0 (4)	C20—C19—C22—N2	32.4 (4)
O1—C1—C2—C7	−172.1 (2)	C19—C20—C21—N1	0.1 (4)
O2—C1—C2—C3	−172.7 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O5ii	0.89 (3)	2.11 (3)	2.984 (3)	169 (3)

Table 1

Selected bond lengths (Å)

Cu1—O1	1.9733 (18)
Cu1—O2i	1.9703 (18)
Cu1—O3	1.9687 (18)
Cu1—O4	1.9836 (18)
Cu1—N1	2.161 (2)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O5ii	0.89 (3)	2.11 (3)	2.984 (3)	169 (3)

Symmetry code: (ii) .