Aqua-bis-(3-chloro-benzoato-κO)bis-(N,N-di-ethyl-nicotinamide-κN)copper(II).

The title compound, [Cu(C7H4ClO2)2(C10H14N2O)2(H2O)], has twofold symmetry with the Cu(II) cation and the O atom of the coordinating water mol-ecule located on the axis. The Cu(II) cation is coordinated by two carboxyl-ate O atoms of chloro-benzoate (CB) anions, two N atoms of N,N-di-ethyl-nicotinamide (DENA) ligands and one water mol-ecule in a distorted N2O3 square-pyramidal geometry. The benzene and pyridine rings are oriented at a dihedral angle of 82.51 (6)°. In the anionic ligand, the carboxyl-ate group is twisted away from the attached benzene ring by 12.85 (11)°. In the crystal, O-H⋯O hydrogen bonds between the coordinating water mol-ecule and the carboxyl group link the complex mol-ecules into supra-molecular chains running along the c-axis direction.

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: Hökelek et al. (1996 ▶, 2009a ▶,b ▶); Hökelek & Necefoğlu (1998 ▶, 2007 ▶); Necefoğlu et al. (2011a ▶,b ▶,c ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

[Cu(C7H4ClO2)2(C10H14N2O)2(H2O)]

M = 749.13

Orthorhombic,

a = 15.9185 (9) Å

b = 19.2366 (11) Å

c = 11.5535 (7) Å

V = 3537.9 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.82 mm−1

T = 296 K

0.35 × 0.20 × 0.15 mm

Data collection

Bruker SMART BREEZE CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2012 ▶) T min = 0.821, T max = 0.884

75834 measured reflections

6232 independent reflections

5189 reflections with I > 2σ(I)

R int = 0.048

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.086

S = 1.06

6232 reflections

224 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.25 e Å−3

Δρmin = −0.39 e Å−3

Absolute structure: Flack (1983 ▶), with no Friedel pairs measured

Flack parameter: 0.027 (10)

Data collection: APEX2 (Bruker, 2012 ▶); cell refinement: SAINT (Bruker, 2012 ▶); 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, 2012 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶) and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813018989/xu5719sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813018989/xu5719Isup2.hkl

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

[Cu(C7H4ClO2)2(C10H14N2O)2(H2O)]	F(000) = 1556
Mr = 749.13	Dx = 1.406 Mg m−3
Orthorhombic, Iba2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: I 2 -2c	Cell parameters from 9278 reflections
a = 15.9185 (9) Å	θ = 2.2–30.7°
b = 19.2366 (11) Å	µ = 0.82 mm−1
c = 11.5535 (7) Å	T = 296 K
V = 3537.9 (4) Å3	Block, blue
Z = 4	0.35 × 0.20 × 0.15 mm

Bruker SMART BREEZE CCD diffractometer	6232 independent reflections
Radiation source: fine-focus sealed tube	5189 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.048
φ and ω scans	θmax = 32.3°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −23→23
Tmin = 0.821, Tmax = 0.884	k = −28→28
75834 measured reflections	l = −17→16

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.032	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.086	w = 1/[σ2(Fo2) + (0.049P)2 + 0.4582P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max = 0.002
6232 reflections	Δρmax = 0.25 e Å−3
224 parameters	Δρmin = −0.39 e Å−3
1 restraint	Absolute structure: Flack (1983), with no Friedel pairs measured
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.027 (10)

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	1.0000	0.5000	0.41873 (3)	0.03000 (6)
Cl1	1.46828 (3)	0.59979 (3)	0.63513 (5)	0.06445 (15)
O1	1.11786 (6)	0.52434 (6)	0.41852 (13)	0.0393 (2)
O2	1.14688 (8)	0.52348 (10)	0.60832 (13)	0.0614 (4)
O3	0.84439 (11)	0.72659 (11)	0.16031 (16)	0.0800 (5)
O4	1.0000	0.5000	0.22505 (18)	0.0538 (6)
H41	1.0395 (19)	0.4937 (15)	0.185 (4)	0.083 (10)*
N1	0.96843 (7)	0.60210 (6)	0.42656 (14)	0.0353 (2)
N2	0.74305 (10)	0.72799 (9)	0.29566 (14)	0.0469 (3)
C1	1.16668 (9)	0.52875 (9)	0.50510 (15)	0.0363 (3)
C2	1.25768 (9)	0.54254 (8)	0.47400 (14)	0.0349 (3)
C3	1.31396 (9)	0.56202 (9)	0.56019 (15)	0.0391 (3)
H3	1.2964	0.5673	0.6364	0.047*
C4	1.39704 (10)	0.57329 (8)	0.52927 (16)	0.0414 (3)
C5	1.42506 (9)	0.56541 (8)	0.4176 (2)	0.0469 (3)
H5	1.4812	0.5729	0.3992	0.056*
C6	1.36773 (12)	0.54600 (10)	0.33236 (19)	0.0514 (4)
H6	1.3857	0.5403	0.2563	0.062*
C7	1.28426 (11)	0.53510 (9)	0.36030 (17)	0.0422 (4)
H7	1.2460	0.5228	0.3030	0.051*
C8	0.90811 (10)	0.62540 (8)	0.35534 (15)	0.0372 (3)
H8	0.8802	0.5936	0.3084	0.045*
C9	0.88569 (10)	0.69476 (8)	0.34881 (14)	0.0398 (3)
C10	0.92796 (12)	0.74174 (8)	0.4190 (2)	0.0510 (4)
H10	0.9146	0.7888	0.4161	0.061*
C11	0.99002 (12)	0.71828 (10)	0.4931 (2)	0.0509 (4)
H11	1.0188	0.7490	0.5409	0.061*
C12	1.00827 (10)	0.64755 (10)	0.49440 (18)	0.0412 (3)
H12	1.0497	0.6314	0.5443	0.049*
C13	0.82193 (13)	0.71794 (10)	0.26044 (15)	0.0462 (4)
C14	0.71426 (12)	0.71772 (12)	0.4142 (2)	0.0551 (4)
H14A	0.6784	0.7563	0.4361	0.066*
H14B	0.7625	0.7177	0.4656	0.066*
C15	0.6667 (2)	0.65112 (17)	0.4298 (3)	0.0907 (8)
H15A	0.6454	0.6486	0.5074	0.136*
H15B	0.7036	0.6125	0.4159	0.136*
H15C	0.6208	0.6496	0.3760	0.136*
C16	0.68061 (14)	0.75374 (11)	0.2115 (2)	0.0546 (5)
H16A	0.6255	0.7363	0.2325	0.066*
H16B	0.6943	0.7358	0.1353	0.066*
C17	0.6778 (2)	0.83180 (13)	0.2067 (3)	0.0864 (9)
H17A	0.6405	0.8462	0.1461	0.130*
H17B	0.7332	0.8495	0.1916	0.130*
H17C	0.6581	0.8496	0.2795	0.130*

	U11	U22	U33	U12	U13	U23
Cu1	0.02380 (9)	0.03532 (10)	0.03087 (11)	0.00119 (8)	0.000	0.000
Cl1	0.0404 (2)	0.0777 (3)	0.0752 (4)	−0.0116 (2)	−0.0184 (2)	0.0065 (3)
O1	0.0265 (4)	0.0465 (5)	0.0449 (5)	−0.0019 (4)	−0.0005 (5)	−0.0018 (7)
O2	0.0334 (6)	0.1087 (12)	0.0420 (7)	−0.0084 (7)	0.0062 (5)	0.0074 (8)
O3	0.0700 (10)	0.1258 (14)	0.0442 (8)	0.0380 (10)	0.0141 (8)	0.0253 (10)
O4	0.0329 (9)	0.1020 (18)	0.0265 (10)	0.0133 (9)	0.000	0.000
N1	0.0290 (5)	0.0383 (5)	0.0385 (7)	0.0010 (4)	0.0002 (6)	−0.0028 (6)
N2	0.0421 (7)	0.0617 (8)	0.0369 (7)	0.0086 (6)	−0.0025 (6)	−0.0013 (7)
C1	0.0271 (6)	0.0404 (8)	0.0414 (8)	0.0011 (5)	0.0034 (5)	0.0022 (6)
C2	0.0259 (6)	0.0380 (7)	0.0408 (8)	0.0008 (5)	0.0023 (6)	0.0036 (6)
C3	0.0304 (6)	0.0462 (8)	0.0409 (8)	−0.0006 (6)	−0.0011 (6)	0.0060 (6)
C4	0.0292 (6)	0.0394 (7)	0.0556 (10)	−0.0005 (6)	−0.0050 (6)	0.0073 (7)
C5	0.0283 (6)	0.0440 (7)	0.0683 (10)	−0.0026 (5)	0.0105 (8)	0.0012 (10)
C6	0.0425 (9)	0.0593 (10)	0.0523 (11)	−0.0073 (7)	0.0181 (8)	−0.0060 (8)
C7	0.0353 (7)	0.0488 (9)	0.0426 (9)	−0.0033 (6)	0.0052 (7)	−0.0042 (7)
C8	0.0340 (7)	0.0392 (7)	0.0385 (8)	0.0023 (5)	−0.0017 (6)	−0.0016 (6)
C9	0.0390 (7)	0.0417 (7)	0.0389 (8)	0.0065 (6)	0.0043 (6)	0.0030 (6)
C10	0.0548 (9)	0.0352 (6)	0.0631 (10)	0.0041 (6)	0.0000 (11)	−0.0029 (10)
C11	0.0458 (9)	0.0426 (9)	0.0643 (12)	−0.0027 (7)	−0.0054 (8)	−0.0141 (8)
C12	0.0339 (7)	0.0463 (8)	0.0435 (9)	0.0026 (6)	−0.0029 (6)	−0.0071 (7)
C13	0.0503 (9)	0.0505 (9)	0.0377 (9)	0.0151 (8)	0.0031 (7)	0.0035 (7)
C14	0.0438 (8)	0.0812 (12)	0.0405 (8)	0.0058 (8)	0.0010 (9)	−0.0060 (12)
C15	0.099 (2)	0.0903 (18)	0.0825 (19)	−0.0149 (15)	0.0178 (19)	0.0077 (18)
C16	0.0501 (10)	0.0630 (11)	0.0508 (10)	0.0082 (8)	−0.0108 (8)	−0.0045 (9)
C17	0.094 (2)	0.0615 (13)	0.104 (2)	0.0226 (13)	−0.0383 (17)	−0.0114 (14)

Cu1—N1	2.0294 (12)	C7—H7	0.9300
Cu1—N1i	2.0294 (12)	C8—H8	0.9300
Cu1—O1	1.9337 (10)	C9—C8	1.383 (2)
Cu1—O1i	1.9337 (10)	C9—C10	1.388 (3)
Cu1—O4	2.238 (2)	C9—C13	1.507 (2)
Cl1—C4	1.7439 (18)	C10—C11	1.383 (3)
O1—C1	1.269 (2)	C10—H10	0.9300
O4—H41	0.79 (4)	C11—H11	0.9300
N1—C8	1.341 (2)	C12—C11	1.391 (3)
N1—C12	1.335 (2)	C12—H12	0.9300
N2—C13	1.334 (2)	C13—O3	1.222 (2)
N2—C14	1.458 (3)	C14—C15	1.499 (4)
N2—C16	1.476 (3)	C14—H14A	0.9700
C1—O2	1.238 (2)	C14—H14B	0.9700
C1—C2	1.516 (2)	C15—H15A	0.9600
C2—C3	1.391 (2)	C15—H15B	0.9600
C2—C7	1.387 (2)	C15—H15C	0.9600
C3—C4	1.387 (2)	C16—C17	1.503 (3)
C3—H3	0.9300	C16—H16A	0.9700
C5—C4	1.373 (3)	C16—H16B	0.9700
C5—C6	1.394 (3)	C17—H17A	0.9600
C5—H5	0.9300	C17—H17B	0.9600
C6—H6	0.9300	C17—H17C	0.9600
C7—C6	1.383 (2)
O1—Cu1—O1i	179.86 (9)	C9—C8—H8	118.6
O1—Cu1—O4	89.93 (5)	C8—C9—C10	118.11 (16)
O1i—Cu1—O4	89.93 (5)	C8—C9—C13	119.75 (16)
O1—Cu1—N1	90.35 (5)	C10—C9—C13	121.96 (15)
O1i—Cu1—N1	89.66 (5)	C9—C10—H10	120.2
O1—Cu1—N1i	89.66 (5)	C11—C10—C9	119.69 (15)
O1i—Cu1—N1i	90.35 (5)	C11—C10—H10	120.2
N1—Cu1—O4	92.55 (5)	C10—C11—C12	118.36 (17)
N1i—Cu1—O4	92.55 (5)	C10—C11—H11	120.8
N1i—Cu1—N1	174.89 (9)	C12—C11—H11	120.8
C1—O1—Cu1	127.53 (12)	N1—C12—C11	122.34 (17)
Cu1—O4—H41	126 (3)	N1—C12—H12	118.8
C8—N1—Cu1	118.25 (11)	C11—C12—H12	118.8
C12—N1—Cu1	122.85 (12)	O3—C13—N2	122.97 (18)
C12—N1—C8	118.79 (13)	O3—C13—C9	118.98 (17)
C13—N2—C14	124.25 (16)	N2—C13—C9	118.05 (16)
C13—N2—C16	118.78 (16)	N2—C14—C15	112.8 (2)
C14—N2—C16	116.93 (15)	N2—C14—H14A	109.0
O1—C1—C2	114.20 (14)	N2—C14—H14B	109.0
O2—C1—O1	126.72 (15)	C15—C14—H14A	109.0
O2—C1—C2	119.08 (15)	C15—C14—H14B	109.0
C3—C2—C1	119.53 (15)	H14A—C14—H14B	107.8
C7—C2—C1	119.85 (14)	C14—C15—H15A	109.5
C7—C2—C3	120.62 (14)	C14—C15—H15B	109.5
C2—C3—H3	120.9	C14—C15—H15C	109.5
C4—C3—C2	118.15 (16)	H15A—C15—H15B	109.5
C4—C3—H3	120.9	H15A—C15—H15C	109.5
C3—C4—Cl1	119.02 (14)	H15B—C15—H15C	109.5
C5—C4—Cl1	118.68 (12)	N2—C16—C17	112.26 (19)
C5—C4—C3	122.30 (16)	N2—C16—H16A	109.2
C4—C5—C6	118.74 (14)	N2—C16—H16B	109.2
C4—C5—H5	120.6	C17—C16—H16A	109.2
C6—C5—H5	120.6	C17—C16—H16B	109.2
C5—C6—H6	119.8	H16A—C16—H16B	107.9
C7—C6—C5	120.31 (18)	C16—C17—H17A	109.5
C7—C6—H6	119.8	C16—C17—H17B	109.5
C2—C7—H7	120.1	C16—C17—H17C	109.5
C6—C7—C2	119.87 (17)	H17A—C17—H17B	109.5
C6—C7—H7	120.1	H17A—C17—H17C	109.5
N1—C8—C9	122.71 (15)	H17B—C17—H17C	109.5
N1—C8—H8	118.6
O4—Cu1—O1—C1	−173.97 (13)	O1—C1—C2—C7	−13.2 (2)
N1—Cu1—O1—C1	93.48 (14)	O2—C1—C2—C3	−12.1 (2)
N1i—Cu1—O1—C1	−81.41 (14)	O2—C1—C2—C7	167.34 (19)
O1—Cu1—N1—C8	133.82 (13)	C1—C2—C3—C4	179.08 (15)
O1i—Cu1—N1—C8	−46.04 (13)	C7—C2—C3—C4	−0.4 (2)
O1—Cu1—N1—C12	−42.21 (15)	C1—C2—C7—C6	−178.40 (16)
O1i—Cu1—N1—C12	137.94 (15)	C3—C2—C7—C6	1.1 (3)
O4—Cu1—N1—C8	43.87 (12)	C2—C3—C4—Cl1	178.47 (12)
O4—Cu1—N1—C12	−132.15 (14)	C2—C3—C4—C5	−0.4 (2)
Cu1—O1—C1—O2	−6.0 (3)	C6—C5—C4—Cl1	−178.34 (14)
Cu1—O1—C1—C2	174.59 (9)	C6—C5—C4—C3	0.6 (3)
Cu1—N1—C8—C9	−175.86 (13)	C4—C5—C6—C7	0.1 (3)
C12—N1—C8—C9	0.3 (3)	C2—C7—C6—C5	−0.9 (3)
Cu1—N1—C12—C11	175.38 (16)	C10—C9—C8—N1	0.2 (3)
C8—N1—C12—C11	−0.6 (3)	C13—C9—C8—N1	175.42 (16)
C14—N2—C13—O3	179.6 (2)	C8—C9—C10—C11	−0.5 (3)
C14—N2—C13—C9	−0.3 (3)	C13—C9—C10—C11	−175.56 (19)
C16—N2—C13—O3	−2.8 (3)	C8—C9—C13—O3	−79.9 (3)
C16—N2—C13—C9	177.28 (16)	C8—C9—C13—N2	100.0 (2)
C13—N2—C14—C15	−102.9 (3)	C10—C9—C13—O3	95.1 (3)
C16—N2—C14—C15	79.5 (3)	C10—C9—C13—N2	−85.0 (2)
C13—N2—C16—C17	−88.5 (3)	C9—C10—C11—C12	0.2 (3)
C14—N2—C16—C17	89.2 (3)	N1—C12—C11—C10	0.4 (3)
O1—C1—C2—C3	167.34 (15)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H41···O2ii	0.79 (4)	1.95 (3)	2.7367 (17)	171 (4)

Table 1

Selected bond lengths (Å)

Cu1—N1	2.0294 (12)
Cu1—O1	1.9337 (10)
Cu1—O4	2.238 (2)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H41⋯O2i	0.79 (4)	1.95 (3)	2.7367 (17)	171 (4)

Symmetry code: (i) .