trans,trans,trans-Diaqua­bis(nicotin­amide-κN)bis­(2-nitro­benzoato-κO)copper(II)

Abstract

The water-coordinated metal atom in the title compound, [Cu(C₇H₄NO₄)₂(C₆H₆N₂O)₂(H₂O)₂], lies on a center of inversion in an all-trans octa­hedral environment with slight distortions. The mol­ecule inter­acts with adjacent mol­ecules through O—H⋯O and N—H⋯O hydrogen bonds, forming a layered network parallel to (010).

Related literature

There are recent examples of diaquadi(aryl­carboxyl­ato)di(nicotinamide)metal(II) compounds, see: Hökelek & Necefoğlu (2007a ▶,b ▶); Hökelek et al. (2007 ▶); Koksharova et al. (2006 ▶); Şahin et al. (2007a ▶, 2007b ▶); Stachova et al. (2006 ▶); Çaylak et al. (2007 ▶); Zhang et al. (2009 ▶).

Experimental

Crystal data

• [Cu(C₇H₄NO₄)₂(C₆H₆N₂O)₂(H₂O)₂]

• M _r = 676.05

• Monoclinic,

• a = 7.9582 (3) Å

• b = 18.7044 (6) Å

• c = 9.8573 (2) Å

• β = 104.012 (2)°

• V = 1423.63 (8) ų

• Z = 2

• Mo Kα radiation

• μ = 0.84 mm⁻¹

• T = 295 K

• 0.45 × 0.20 × 0.16 mm

Data collection

• Bruker SMART area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.557, T _max = 0.877

• 7295 measured reflections

• 2507 independent reflections

• 2069 reflections with I > 2σ(I)

• R _int = 0.036

Refinement

• R[F ² > 2σ(F ²)] = 0.048

• wR(F ²) = 0.111

• S = 1.12

• 2507 reflections

• 229 parameters

• 4 restraints

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.31 e Å⁻³

• Δρ_min = −0.46 e Å⁻³

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2009 ▶).

Supplementary Material

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

Table 1. Selected bond lengths (Å).

Cu1—O1	1.995 (2)
Cu1—N2	2.006 (3)
Cu1—O1w	2.537 (3)

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1w—H11⋯O2i	0.85 (4)	1.92 (2)	2.726 (4)	159 (4)
O1w—H12⋯O5ii	0.85 (4)	2.11 (2)	2.934 (2)	165 (3)
N3—H32⋯O2iii	0.85 (4)	2.15 (2)	2.929 (4)	152 (4)
N3—H31⋯O5iv	0.85 (4)	2.11 (2)	2.926 (4)	161 (4)

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

supplementary crystallographic information

Experimental

A water/methanol (1:1 v/v) solution (3 ml) of copper nitrate trihydrate (0.174 g, 0.6 mmol) was added to a water/methanol (1:1 v/v) solution (3 ml) of 2-nitrobenzoic acid (0.100 g, 0.6 mmol), sodium hydroxide (0.024 g 0.6 mmol) and nicotinamide (0.073 g, 0.6 mmol). Blue block were obtained after several days (yield: 40%). CH&N elemental analysis: calc. for C₂₆H₂₄CuN₆O_12: C 46.19, H 3.59,N 12.43%; found: C 46.37, H 3.41, N 12.60%.

Refinement

Carbon-bound H atoms were placed in calculated positions and were allowed to ride on the parent atoms. The oxygen-bound ones were located in a difference Fourier map, and were refined with distance restraints N–H, O–H = 0.85±0.01 Å; an additional H···H 1.39 + 0.01 Å restraint was used. Their displacement parameters were freely refined.

Figures

Fig. 1.

Thermal ellipsoid plot of Cu(H2O)2(C7H4NO4)2(C6H6N2O)2; displacement ellipsoids are drawn at the 50% probabability level, and H atoms as spheres of arbitrary radii.

Crystal data

[Cu(C7H4NO4)2(C6H6N2O)2(H2O)2]	F(000) = 694
Mr = 676.05	Dx = 1.577 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3858 reflections
a = 7.9582 (3) Å	θ = 2.2–25.0°
b = 18.7044 (6) Å	µ = 0.84 mm−1
c = 9.8573 (2) Å	T = 295 K
β = 104.012 (2)°	Block, blue
V = 1423.63 (8) Å3	0.45 × 0.20 × 0.16 mm
Z = 2

Data collection

Bruker SMART area-detector diffractometer	2507 independent reflections
Radiation source: medium-focus sealed tube	2069 reflections with I > 2σ(I)
graphite	Rint = 0.036
φ and ω scans	θmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.557, Tmax = 0.877	k = −14→22
7295 measured reflections	l = −11→11

Refinement

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ2(Fo2) + (0.0395P)2 + 1.8061P] where P = (Fo2 + 2Fc2)/3
2507 reflections	(Δ/σ)max = 0.001
229 parameters	Δρmax = 0.31 e Å−3
4 restraints	Δρmin = −0.46 e Å−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.5000	0.5000	0.5000	0.02960 (19)
O1	0.6141 (3)	0.41263 (12)	0.4483 (2)	0.0329 (5)
O2	0.3896 (3)	0.37179 (15)	0.2856 (3)	0.0531 (7)
O3	0.3215 (5)	0.2416 (3)	0.0916 (5)	0.1123 (16)
O4	0.3942 (5)	0.2153 (2)	0.3108 (5)	0.1137 (16)
O5	0.0632 (4)	0.49124 (18)	0.8331 (3)	0.0642 (9)
O1W	0.8082 (4)	0.54476 (16)	0.5876 (3)	0.0493 (7)
H11	0.772 (6)	0.5753 (19)	0.637 (4)	0.067 (15)*
H12	0.883 (5)	0.522 (2)	0.647 (4)	0.073 (16)*
N1	0.4256 (5)	0.2375 (2)	0.2043 (5)	0.0624 (10)
N2	0.4917 (3)	0.45491 (14)	0.6829 (3)	0.0290 (6)
N3	0.1614 (5)	0.4274 (2)	1.0283 (3)	0.0539 (9)
H31	0.081 (4)	0.442 (2)	1.065 (4)	0.069 (14)*
H32	0.241 (4)	0.403 (2)	1.082 (4)	0.075 (16)*
C1	0.6639 (4)	0.32322 (17)	0.2924 (3)	0.0297 (7)
C2	0.6033 (5)	0.26281 (19)	0.2137 (4)	0.0372 (8)
C3	0.7038 (6)	0.2231 (2)	0.1461 (4)	0.0496 (10)
H3	0.6578	0.1835	0.0929	0.057 (12)*
C4	0.8740 (6)	0.2428 (2)	0.1585 (4)	0.0552 (11)
H4	0.9433	0.2170	0.1125	0.065 (13)*
C5	0.9406 (5)	0.3009 (2)	0.2392 (4)	0.0503 (10)
H5	1.0561	0.3135	0.2495	0.067 (14)*
C6	0.8366 (4)	0.3409 (2)	0.3053 (4)	0.0395 (8)
H6	0.8834	0.3801	0.3591	0.038 (10)*
C7	0.5449 (4)	0.37176 (17)	0.3480 (3)	0.0289 (7)
C8	0.3508 (4)	0.46333 (17)	0.7327 (3)	0.0306 (7)
H8	0.2571	0.4882	0.6785	0.029 (9)*
C9	0.3378 (4)	0.43678 (18)	0.8613 (3)	0.0304 (7)
C10	0.4781 (5)	0.3999 (2)	0.9403 (4)	0.0434 (9)
H10	0.4747	0.3819	1.0276	0.048 (11)*
C11	0.6240 (5)	0.3899 (2)	0.8889 (4)	0.0461 (10)
H11A	0.7186	0.3644	0.9402	0.062 (13)*
C12	0.6259 (4)	0.41833 (19)	0.7608 (4)	0.0364 (8)
H12A	0.7241	0.4120	0.7268	0.032 (9)*
C13	0.1760 (5)	0.4530 (2)	0.9067 (4)	0.0419 (9)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cu1	0.0375 (3)	0.0296 (3)	0.0256 (3)	0.0041 (3)	0.0153 (2)	0.0014 (2)
O1	0.0378 (13)	0.0332 (12)	0.0292 (12)	0.0057 (10)	0.0110 (10)	−0.0034 (10)
O2	0.0318 (14)	0.0677 (19)	0.0557 (17)	0.0093 (13)	0.0028 (12)	−0.0203 (14)
O3	0.061 (2)	0.178 (5)	0.091 (3)	−0.027 (3)	0.006 (2)	−0.071 (3)
O4	0.094 (3)	0.118 (4)	0.140 (4)	−0.030 (3)	0.049 (3)	0.048 (3)
O5	0.0489 (16)	0.107 (3)	0.0436 (15)	0.0375 (17)	0.0254 (13)	0.0285 (16)
O1W	0.0454 (16)	0.0586 (19)	0.0407 (16)	0.0032 (14)	0.0045 (13)	−0.0056 (14)
N1	0.060 (2)	0.051 (2)	0.079 (3)	−0.0141 (19)	0.023 (2)	−0.022 (2)
N2	0.0302 (14)	0.0338 (15)	0.0250 (14)	0.0037 (12)	0.0104 (11)	−0.0004 (12)
N3	0.046 (2)	0.084 (3)	0.039 (2)	0.020 (2)	0.0237 (17)	0.0225 (18)
C1	0.0332 (18)	0.0310 (17)	0.0259 (17)	0.0033 (14)	0.0089 (14)	0.0021 (14)
C2	0.040 (2)	0.0354 (19)	0.037 (2)	0.0021 (16)	0.0110 (16)	0.0003 (16)
C3	0.066 (3)	0.037 (2)	0.046 (2)	0.007 (2)	0.014 (2)	−0.0094 (18)
C4	0.069 (3)	0.054 (3)	0.050 (3)	0.025 (2)	0.027 (2)	0.003 (2)
C5	0.041 (2)	0.052 (2)	0.062 (3)	0.0077 (19)	0.0224 (19)	0.005 (2)
C6	0.036 (2)	0.037 (2)	0.045 (2)	0.0019 (16)	0.0094 (16)	−0.0030 (17)
C7	0.0341 (18)	0.0287 (17)	0.0254 (17)	0.0025 (14)	0.0104 (14)	0.0028 (14)
C8	0.0326 (18)	0.0327 (18)	0.0270 (17)	0.0055 (15)	0.0082 (14)	0.0006 (14)
C9	0.0335 (18)	0.0333 (18)	0.0269 (17)	0.0033 (14)	0.0123 (14)	0.0022 (14)
C10	0.050 (2)	0.054 (2)	0.0303 (18)	0.0127 (19)	0.0168 (17)	0.0124 (17)
C11	0.043 (2)	0.056 (2)	0.042 (2)	0.0189 (19)	0.0159 (18)	0.0153 (18)
C12	0.0342 (19)	0.041 (2)	0.038 (2)	0.0087 (16)	0.0168 (16)	0.0057 (16)
C13	0.042 (2)	0.053 (2)	0.0347 (19)	0.0079 (18)	0.0167 (17)	0.0081 (17)

Geometric parameters (Å, °)

Cu1—O1i	1.995 (2)	C1—C6	1.389 (5)
Cu1—O1	1.995 (2)	C1—C7	1.507 (4)
Cu1—N2i	2.006 (3)	C2—C3	1.377 (5)
Cu1—N2	2.006 (3)	C3—C4	1.380 (6)
Cu1—O1w	2.537 (3)	C3—H3	0.9300
O1—C7	1.266 (4)	C4—C5	1.375 (6)
O2—C7	1.240 (4)	C4—H4	0.9300
O3—N1	1.216 (5)	C5—C6	1.389 (5)
O4—N1	1.210 (5)	C5—H5	0.9300
O5—C13	1.237 (4)	C6—H6	0.9300
O1W—H11	0.85 (4)	C8—C9	1.389 (4)
O1W—H12	0.85 (4)	C8—H8	0.9300
N1—C2	1.472 (5)	C9—C10	1.381 (5)
N2—C8	1.337 (4)	C9—C13	1.493 (5)
N2—C12	1.342 (4)	C10—C11	1.387 (5)
N3—C13	1.322 (5)	C10—H10	0.9300
N3—H31	0.85 (4)	C11—C12	1.374 (5)
N3—H32	0.85 (4)	C11—H11A	0.9300
C1—C2	1.389 (5)	C12—H12A	0.9300
O1i—Cu1—O1	180.000 (1)	C4—C3—H3	120.5
O1i—Cu1—N2i	90.07 (10)	C5—C4—C3	119.7 (4)
O1—Cu1—N2i	89.93 (10)	C5—C4—H4	120.1
O1i—Cu1—N2	89.93 (10)	C3—C4—H4	120.1
O1—Cu1—N2	90.07 (10)	C4—C5—C6	120.4 (4)
N2i—Cu1—N2	180.00 (14)	C4—C5—H5	119.8
O1i—Cu1—O1W	96.04 (9)	C6—C5—H5	119.8
O1—Cu1—O1W	83.96 (9)	C5—C6—C1	121.2 (4)
N2i—Cu1—O1W	85.84 (10)	C5—C6—H6	119.4
N2—Cu1—O1W	94.16 (10)	C1—C6—H6	119.4
C7—O1—Cu1	123.7 (2)	O2—C7—O1	125.5 (3)
Cu1—O1W—H11	89 (3)	O2—C7—C1	117.3 (3)
Cu1—O1W—H12	122 (3)	O1—C7—C1	117.1 (3)
H11—O1W—H12	103 (4)	N2—C8—C9	123.2 (3)
O4—N1—O3	125.1 (4)	N2—C8—H8	118.4
O4—N1—C2	116.9 (4)	C9—C8—H8	118.4
O3—N1—C2	117.9 (4)	C10—C9—C8	117.7 (3)
C8—N2—C12	118.1 (3)	C10—C9—C13	124.8 (3)
C8—N2—Cu1	119.6 (2)	C8—C9—C13	117.5 (3)
C12—N2—Cu1	122.3 (2)	C9—C10—C11	119.7 (3)
C13—N3—H31	120 (3)	C9—C10—H10	120.2
C13—N3—H32	123 (3)	C11—C10—H10	120.2
H31—N3—H32	115 (4)	C12—C11—C10	118.7 (3)
C2—C1—C6	116.5 (3)	C12—C11—H11A	120.7
C2—C1—C7	122.0 (3)	C10—C11—H11A	120.7
C6—C1—C7	121.2 (3)	N2—C12—C11	122.6 (3)
C3—C2—C1	123.1 (3)	N2—C12—H12A	118.7
C3—C2—N1	117.2 (3)	C11—C12—H12A	118.7
C1—C2—N1	119.7 (3)	O5—C13—N3	122.1 (3)
C2—C3—C4	119.0 (4)	O5—C13—C9	119.9 (3)
C2—C3—H3	120.5	N3—C13—C9	118.0 (3)
N2i—Cu1—O1—C7	−65.5 (2)	C2—C1—C6—C5	1.7 (5)
N2—Cu1—O1—C7	114.5 (2)	C7—C1—C6—C5	−171.9 (3)
O1W—Cu1—O1—C7	−151.3 (2)	Cu1—O1—C7—O2	−14.1 (5)
O1i—Cu1—N2—C8	40.3 (2)	Cu1—O1—C7—C1	160.6 (2)
O1—Cu1—N2—C8	−139.7 (2)	C2—C1—C7—O2	−24.1 (5)
O1W—Cu1—N2—C8	136.3 (2)	C6—C1—C7—O2	149.2 (3)
O1i—Cu1—N2—C12	−137.2 (3)	C2—C1—C7—O1	160.7 (3)
O1—Cu1—N2—C12	42.8 (3)	C6—C1—C7—O1	−26.0 (4)
O1W—Cu1—N2—C12	−41.1 (3)	C12—N2—C8—C9	0.7 (5)
C6—C1—C2—C3	−2.6 (5)	Cu1—N2—C8—C9	−176.9 (2)
C7—C1—C2—C3	171.0 (3)	N2—C8—C9—C10	−0.1 (5)
C6—C1—C2—N1	175.3 (3)	N2—C8—C9—C13	177.3 (3)
C7—C1—C2—N1	−11.1 (5)	C8—C9—C10—C11	−0.8 (6)
O4—N1—C2—C3	111.8 (5)	C13—C9—C10—C11	−178.0 (4)
O3—N1—C2—C3	−69.5 (5)	C9—C10—C11—C12	1.2 (6)
O4—N1—C2—C1	−66.2 (5)	C8—N2—C12—C11	−0.4 (5)
O3—N1—C2—C1	112.5 (4)	Cu1—N2—C12—C11	177.2 (3)
C1—C2—C3—C4	1.3 (6)	C10—C11—C12—N2	−0.6 (6)
N1—C2—C3—C4	−176.6 (4)	C10—C9—C13—O5	174.3 (4)
C2—C3—C4—C5	0.9 (6)	C8—C9—C13—O5	−2.9 (5)
C3—C4—C5—C6	−1.6 (6)	C10—C9—C13—N3	−3.5 (6)
C4—C5—C6—C1	0.3 (6)	C8—C9—C13—N3	179.3 (4)

Symmetry codes: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O1w—H11···O2i	0.85 (4)	1.92 (2)	2.726 (4)	159 (4)
O1w—H12···O5ii	0.85 (4)	2.11 (2)	2.934 (2)	165 (3)
N3—H32···O2iii	0.85 (4)	2.15 (2)	2.929 (4)	152 (4)
N3—H31···O5iv	0.85 (4)	2.11 (2)	2.926 (4)	161 (4)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1, y, z; (iii) x, y, z+1; (iv) −x, −y+1, −z+2.