Tetra-aqua-bis-[4-(4H-1,2,4-triazol-4-yl)benzoato-κN]copper(II) dihydrate.

In the title compound, [Cu(C(9)H(6)N(3)O(2))(2)(H(2)O)(4)]·2H(2)O, the Cu(II) atom lies on an inversion center and is six-coordinated by two N atoms from two 4-(1,2,4-triazol-4-yl)benzoate ligands and four water mol-ecules in a distorted octa-hedral geometry. In the crystal, inter-molecular O-H⋯O hydrogen bonds lead to a three-dimensional supra-molecular network. Intra-molecular O-H⋯N hydrogen bonds and π-π inter-actions between the benzene rings and between the benzene and triazole rings [centroid-centroid distances = 3.657 (1) and 3.752 (1) Å] are observed.

Related literature

For general background to the structures and applications of inorganic–organic hybrid materials, see: Shi et al. (2009 ▶); Xiao et al. (2006 ▶); Zhang et al. (2004 ▶). For a related structure, see: Wang et al. (2009 ▶).

Experimental

Crystal data

[Cu(C9H6N3O2)2(H2O)4]·2H2O

M = 547.97

Triclinic,

a = 7.3001 (4) Å

b = 7.9904 (5) Å

c = 9.8995 (6) Å

α = 85.343 (1)°

β = 73.243 (1)°

γ = 79.032 (1)°

V = 542.61 (6) Å3

Z = 1

Mo Kα radiation

μ = 1.08 mm−1

T = 293 K

0.24 × 0.22 × 0.19 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.75, T max = 0.83

3001 measured reflections

2102 independent reflections

2025 reflections with I > 2σ(I)

R int = 0.033

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.091

S = 1.12

2102 reflections

178 parameters

7 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.81 e Å−3

Δρmin = −0.69 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and Materials­Studio (Accelrys, 2006 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811018356/hy2429sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811018356/hy2429Isup2.hkl

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

[Cu(C9H6N3O2)2(H2O)4]·2H2O	Z = 1
Mr = 547.97	F(000) = 283
Triclinic, P1	Dx = 1.677 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.3001 (4) Å	Cell parameters from 2131 reflections
b = 7.9904 (5) Å	θ = 1.0–26.0°
c = 9.8995 (6) Å	µ = 1.08 mm−1
α = 85.343 (1)°	T = 293 K
β = 73.243 (1)°	Block, blue
γ = 79.032 (1)°	0.24 × 0.22 × 0.19 mm
V = 542.61 (6) Å3

Bruker APEXII CCD diffractometer	2102 independent reflections
Radiation source: fine-focus sealed tube	2025 reflections with I > 2σ(I)
graphite	Rint = 0.033
φ and ω scans	θmax = 26.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −7→9
Tmin = 0.75, Tmax = 0.83	k = −9→9
3001 measured reflections	l = −10→12

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.091	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ2(Fo2) + (0.048P)2 + 0.4256P] where P = (Fo2 + 2Fc2)/3
2102 reflections	(Δ/σ)max < 0.001
178 parameters	Δρmax = 0.81 e Å−3
7 restraints	Δρmin = −0.69 e Å−3

	x	y	z	Uiso*/Ueq
Cu1	0.0000	0.0000	1.0000	0.01356 (14)
C1	0.4338 (3)	0.8158 (3)	0.2433 (2)	0.0171 (4)
C2	0.3525 (3)	0.6774 (3)	0.3431 (2)	0.0159 (4)
C3	0.3242 (3)	0.5307 (3)	0.2906 (2)	0.0173 (4)
H3	0.3500	0.5208	0.1937	0.021*
C4	0.2582 (3)	0.3996 (3)	0.3803 (2)	0.0177 (4)
H4	0.2397	0.3021	0.3442	0.021*
C5	0.2198 (3)	0.4155 (3)	0.5251 (2)	0.0144 (4)
C6	0.2448 (3)	0.5605 (3)	0.5801 (2)	0.0170 (4)
H6	0.2177	0.5704	0.6771	0.020*
C7	0.3109 (3)	0.6909 (3)	0.4887 (2)	0.0169 (4)
H7	0.3277	0.7889	0.5251	0.020*
C8	0.0901 (3)	0.2734 (3)	0.7605 (2)	0.0158 (4)
H8	0.0776	0.3639	0.8178	0.019*
C9	0.1476 (4)	0.1191 (3)	0.5795 (2)	0.0239 (5)
H9	0.1839	0.0838	0.4868	0.029*
N1	0.1555 (3)	0.2774 (2)	0.61779 (19)	0.0150 (4)
N2	0.0469 (3)	0.1231 (2)	0.80595 (18)	0.0157 (4)
N3	0.0828 (3)	0.0245 (2)	0.6893 (2)	0.0242 (4)
O1	0.4190 (3)	0.9593 (2)	0.29038 (18)	0.0286 (4)
O2	0.5161 (2)	0.7736 (2)	0.11668 (16)	0.0189 (3)
O1W	0.1051 (3)	0.1744 (3)	1.0745 (2)	0.0310 (4)
H1A	0.2286 (18)	0.1646 (15)	1.030 (3)	0.047*
H1B	0.107 (5)	0.146 (5)	1.1613 (17)	0.047*
O2W	−0.3408 (2)	0.1514 (2)	1.09311 (17)	0.0201 (3)
H2A	−0.402 (4)	0.089 (4)	1.152 (3)	0.030*
H2B	−0.384 (4)	0.159 (4)	1.025 (3)	0.030*
O3W	0.2262 (3)	0.5346 (2)	0.94116 (19)	0.0244 (4)
H3A	0.316 (4)	0.450 (3)	0.927 (4)	0.037*
H3B	0.270 (5)	0.624 (3)	0.922 (3)	0.037*

	U11	U22	U33	U12	U13	U23
Cu1	0.0179 (2)	0.0127 (2)	0.0086 (2)	−0.00537 (14)	−0.00024 (14)	0.00153 (13)
C1	0.0141 (10)	0.0192 (11)	0.0151 (10)	−0.0029 (8)	−0.0005 (8)	0.0039 (8)
C2	0.0125 (10)	0.0170 (10)	0.0152 (10)	−0.0019 (8)	−0.0004 (8)	0.0036 (8)
C3	0.0167 (10)	0.0232 (11)	0.0106 (10)	−0.0043 (8)	−0.0016 (8)	0.0008 (8)
C4	0.0188 (11)	0.0197 (11)	0.0147 (10)	−0.0074 (9)	−0.0025 (8)	0.0009 (8)
C5	0.0122 (10)	0.0158 (10)	0.0124 (10)	−0.0023 (8)	−0.0006 (8)	0.0046 (8)
C6	0.0183 (10)	0.0174 (10)	0.0114 (10)	−0.0007 (8)	0.0000 (8)	0.0005 (8)
C7	0.0177 (10)	0.0148 (10)	0.0151 (10)	−0.0018 (8)	−0.0006 (8)	−0.0005 (8)
C8	0.0183 (10)	0.0159 (10)	0.0113 (10)	−0.0039 (8)	−0.0012 (8)	0.0017 (8)
C9	0.0384 (14)	0.0164 (11)	0.0125 (11)	−0.0065 (10)	0.0009 (9)	−0.0004 (8)
N1	0.0163 (9)	0.0143 (9)	0.0115 (8)	−0.0034 (7)	0.0005 (7)	0.0018 (7)
N2	0.0180 (9)	0.0156 (9)	0.0112 (8)	−0.0039 (7)	−0.0002 (7)	0.0001 (7)
N3	0.0397 (12)	0.0175 (10)	0.0119 (9)	−0.0086 (9)	0.0009 (8)	−0.0015 (7)
O1	0.0405 (10)	0.0178 (9)	0.0202 (9)	−0.0109 (7)	0.0064 (7)	−0.0005 (7)
O2	0.0203 (8)	0.0193 (8)	0.0139 (8)	−0.0057 (6)	0.0007 (6)	0.0030 (6)
O1W	0.0343 (10)	0.0347 (10)	0.0231 (9)	−0.0126 (8)	−0.0029 (8)	0.0019 (8)
O2W	0.0225 (9)	0.0205 (8)	0.0166 (8)	−0.0076 (7)	−0.0032 (7)	0.0045 (6)
O3W	0.0219 (9)	0.0178 (8)	0.0303 (9)	−0.0047 (7)	−0.0005 (7)	−0.0028 (7)

Cu1—O1W	1.9937 (19)	C6—H6	0.9300
Cu1—O2W	2.4932 (16)	C7—H7	0.9300
Cu1—N2	2.0535 (18)	C8—N2	1.311 (3)
C1—O1	1.246 (3)	C8—N1	1.354 (3)
C1—O2	1.266 (3)	C8—H8	0.9300
C1—C2	1.512 (3)	C9—N3	1.297 (3)
C2—C3	1.393 (3)	C9—N1	1.366 (3)
C2—C7	1.393 (3)	C9—H9	0.9300
C3—C4	1.383 (3)	N2—N3	1.385 (3)
C3—H3	0.9300	O1W—H1A	0.87 (2)
C4—C5	1.391 (3)	O1W—H1B	0.87 (2)
C4—H4	0.9300	O2W—H2A	0.82 (3)
C5—C6	1.383 (3)	O2W—H2B	0.82 (3)
C5—N1	1.437 (3)	O3W—H3A	0.84 (3)
C6—C7	1.388 (3)	O3W—H3B	0.82 (3)
O1Wi—Cu1—O1W	180.00 (7)	C5—C6—H6	120.4
O1Wi—Cu1—N2	89.17 (8)	C7—C6—H6	120.4
O1W—Cu1—N2	90.83 (8)	C6—C7—C2	121.0 (2)
O1Wi—Cu1—N2i	90.83 (8)	C6—C7—H7	119.5
O2W—Cu1—N2	95.22 (7)	C2—C7—H7	119.5
O2W—Cu1—O1Wi	87.99 (7)	N2—C8—N1	109.97 (19)
O2W—Cu1—N2i	84.78 (7)	N2—C8—H8	125.0
N2—Cu1—N2i	180.0	N1—C8—H8	125.0
O1—C1—O2	125.1 (2)	N3—C9—N1	111.1 (2)
O1—C1—C2	118.90 (19)	N3—C9—H9	124.4
O2—C1—C2	115.97 (19)	N1—C9—H9	124.4
C3—C2—C7	118.7 (2)	C8—N1—C9	104.65 (18)
C3—C2—C1	120.38 (19)	C8—N1—C5	128.54 (18)
C7—C2—C1	120.9 (2)	C9—N1—C5	126.81 (18)
C4—C3—C2	121.1 (2)	C8—N2—N3	107.78 (17)
C4—C3—H3	119.4	C8—N2—Cu1	133.37 (15)
C2—C3—H3	119.4	N3—N2—Cu1	117.25 (13)
C3—C4—C5	119.1 (2)	C9—N3—N2	106.47 (18)
C3—C4—H4	120.5	Cu1—O1W—H1A	107.7 (19)
C5—C4—H4	120.5	Cu1—O1W—H1B	109 (2)
C6—C5—C4	121.0 (2)	H1A—O1W—H1B	102 (3)
C6—C5—N1	120.03 (19)	H2A—O2W—H2B	107 (3)
C4—C5—N1	118.95 (19)	H3A—O3W—H3B	111 (3)
C5—C6—C7	119.2 (2)
O1—C1—C2—C3	164.7 (2)	N3—C9—N1—C8	0.0 (3)
O2—C1—C2—C3	−16.6 (3)	N3—C9—N1—C5	179.9 (2)
O1—C1—C2—C7	−17.6 (3)	C6—C5—N1—C8	8.8 (3)
O2—C1—C2—C7	161.1 (2)	C4—C5—N1—C8	−171.9 (2)
C7—C2—C3—C4	−0.7 (3)	C6—C5—N1—C9	−171.1 (2)
C1—C2—C3—C4	177.1 (2)	C4—C5—N1—C9	8.1 (3)
C2—C3—C4—C5	0.0 (3)	N1—C8—N2—N3	−0.7 (3)
C3—C4—C5—C6	0.6 (3)	N1—C8—N2—Cu1	163.97 (15)
C3—C4—C5—N1	−178.58 (19)	O1Wi—Cu1—N2—C8	167.8 (2)
C4—C5—C6—C7	−0.6 (3)	O1W—Cu1—N2—C8	−12.2 (2)
N1—C5—C6—C7	178.65 (19)	O1Wi—Cu1—N2—N3	−28.63 (17)
C5—C6—C7—C2	−0.2 (3)	O1W—Cu1—N2—N3	151.37 (17)
C3—C2—C7—C6	0.8 (3)	N1—C9—N3—N2	−0.4 (3)
C1—C2—C7—C6	−177.00 (19)	C8—N2—N3—C9	0.7 (3)
N2—C8—N1—C9	0.5 (3)	Cu1—N2—N3—C9	−166.87 (17)
N2—C8—N1—C5	−179.47 (19)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1A···O2ii	0.87 (2)	2.12 (2)	2.948 (3)	158 (2)
O1W—H1B···N3i	0.87 (2)	2.27 (3)	2.873 (3)	126 (3)
O2W—H2A···O1iii	0.82 (3)	1.98 (3)	2.794 (2)	172 (3)
O2W—H2B···O2iv	0.82 (3)	1.91 (3)	2.711 (2)	167 (3)
O3W—H3A···O2ii	0.84 (3)	1.97 (3)	2.789 (2)	167 (3)
O3W—H3B···O2Wv	0.82 (3)	1.94 (3)	2.758 (2)	170 (3)

Table 1

Selected bond lengths (Å)

Cu1—O1W	1.9937 (19)
Cu1—O2W	2.4932 (16)
Cu1—N2	2.0535 (18)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1A⋯O2i	0.87 (2)	2.12 (2)	2.948 (3)	158 (2)
O1W—H1B⋯N3ii	0.87 (2)	2.27 (3)	2.873 (3)	126 (3)
O2W—H2A⋯O1iii	0.82 (3)	1.98 (3)	2.794 (2)	172 (3)
O2W—H2B⋯O2iv	0.82 (3)	1.91 (3)	2.711 (2)	167 (3)
O3W—H3A⋯O2i	0.84 (3)	1.97 (3)	2.789 (2)	167 (3)
O3W—H3B⋯O2Wv	0.82 (3)	1.94 (3)	2.758 (2)	170 (3)

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