catena-Poly[[[bis-(nitrato-κO)copper(II)]-bis-[μ-1,3-bis-(imidazol-1-yl)-5-methyl-benzene-κ(2)N(3):N(3')]] dihydrate].

In the title complex, {[Cu(NO(3))(2)(C(13)H(12)N(4))(2)]·2H(2)O}(n), the Cu(II) atom is located on a crystallographic center of symmetry and adopts an N(4)O(2) octa-hedral coordination geometry with four imidazole N atoms in the equatorial sites and two O atoms in the axial sites. The dihedral angles between the central benzene ring and the imidazole rings are 4.93 (11) and 46.08 (12)°. The 1,3-bis-(imidazol-1-yl)-5-methyl-benzene ligand is bis-monodentate, linking symmetry-related Cu(II) atoms into sheets in the bc plane. These sheets are further bridged into a three-dimensional supra-molecular structure by O-H⋯O and C-H⋯O hydrogen bonds.

Related literature

For background to the coordination chemistry of imidazole derivates, see: Huang et al. (2006 ▶); Wang et al. (2008 ▶); Tian et al. (2007 ▶); Jin et al. (2008 ▶). For imidazole ligands bearing rigid spacers, see: Qi et al. (2008 ▶); Li et al. (2007 ▶); Zhang et al. (2008 ▶). For the synthesis, see: Altman & Buchwald (2006 ▶).

Experimental

Crystal data

[Cu(NO3)2(C13H12N4)2]·2H2O

M = 672.12

Monoclinic,

a = 11.585 (4) Å

b = 9.652 (3) Å

c = 15.450 (4) Å

β = 123.604 (17)°

V = 1438.9 (8) Å3

Z = 2

Mo Kα radiation

μ = 0.83 mm−1

T = 293 K

0.22 × 0.20 × 0.18 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T min = 0.839, T max = 0.865

10260 measured reflections

2672 independent reflections

2114 reflections with I > 2σ(I)

R int = 0.039

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.101

S = 1.06

2672 reflections

214 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.43 e Å−3

Δρmin = −0.51 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: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812023628/lr2064sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812023628/lr2064Isup2.hkl

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

[Cu(NO3)2(C13H12N4)2]·2H2O	F(000) = 694
Mr = 672.12	Dx = 1.551 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4382 reflections
a = 11.585 (4) Å	θ = 2.6–26.1°
b = 9.652 (3) Å	µ = 0.83 mm−1
c = 15.450 (4) Å	T = 293 K
β = 123.604 (17)°	Block, blue
V = 1438.9 (8) Å3	0.22 × 0.20 × 0.18 mm
Z = 2

Bruker SMART APEX CCD area-detector diffractometer	2672 independent reflections
Radiation source: sealed tube	2114 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.039
phi and ω scans	θmax = 25.5°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −13→14
Tmin = 0.839, Tmax = 0.865	k = −11→11
10260 measured reflections	l = −18→18

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.0393P)2 + 1.4695P] where P = (Fo2 + 2Fc2)/3
2672 reflections	(Δ/σ)max = 0.002
214 parameters	Δρmax = 0.43 e Å−3
2 restraints	Δρmin = −0.51 e Å−3

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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	0.0000	1.0000	0.5000	0.02941 (15)
N1	0.1444 (2)	0.9308 (2)	0.64001 (17)	0.0311 (5)
N2	0.2629 (2)	0.9008 (2)	0.80892 (16)	0.0283 (5)
N3	0.1879 (2)	1.1172 (2)	1.05555 (16)	0.0310 (5)
N4	0.0729 (2)	1.3057 (2)	1.04231 (17)	0.0333 (5)
N5	0.1839 (3)	0.9479 (3)	0.3683 (2)	0.0465 (6)
O1	0.1000 (3)	0.8849 (3)	0.28647 (19)	0.0649 (7)
O2	0.1663 (2)	0.9523 (3)	0.44070 (18)	0.0589 (6)
O3	0.2867 (4)	1.0002 (4)	0.3790 (3)	0.1209 (15)
O1W	0.5399 (4)	0.9268 (4)	0.3928 (3)	0.0902 (10)
C1	0.2547 (3)	0.8473 (3)	0.6687 (2)	0.0422 (7)
H1	0.2756	0.8095	0.6235	0.051*
C2	0.3288 (3)	0.8274 (3)	0.7721 (2)	0.0432 (7)
H2	0.4089	0.7745	0.8110	0.052*
C3	0.1522 (3)	0.9612 (3)	0.7259 (2)	0.0350 (6)
H3	0.0892	1.0172	0.7290	0.042*
C4	0.3023 (3)	0.9164 (3)	0.91399 (19)	0.0280 (6)
C5	0.4142 (3)	0.8449 (3)	0.9937 (2)	0.0316 (6)
H5	0.4639	0.7847	0.9791	0.038*
C6	0.4530 (3)	0.8625 (3)	1.0961 (2)	0.0309 (6)
C7	0.3782 (3)	0.9530 (3)	1.1169 (2)	0.0310 (6)
H7	0.4033	0.9667	1.1848	0.037*
C8	0.2661 (3)	1.0225 (2)	1.0358 (2)	0.0297 (6)
C9	0.2265 (3)	1.0052 (3)	0.9345 (2)	0.0305 (6)
H9	0.1502	1.0523	0.8808	0.037*
C10	0.5755 (3)	0.7855 (3)	1.1834 (2)	0.0436 (7)
H10A	0.6186	0.8405	1.2455	0.065*
H10B	0.6411	0.7676	1.1652	0.065*
H10C	0.5449	0.6993	1.1951	0.065*
C11	0.1473 (3)	1.2442 (3)	1.0130 (2)	0.0359 (6)
H11	0.1689	1.2832	0.9686	0.043*
C12	0.0659 (3)	1.2134 (3)	1.1069 (2)	0.0372 (6)
H12	0.0194	1.2287	1.1395	0.045*
C13	0.1364 (3)	1.0975 (3)	1.1159 (2)	0.0363 (6)
H13	0.1478	1.0195	1.1553	0.044*
H1WA	0.469 (3)	0.958 (4)	0.393 (3)	0.071 (14)*
H1WB	0.598 (5)	0.964 (5)	0.452 (2)	0.108 (19)*

	U11	U22	U33	U12	U13	U23
Cu1	0.0332 (3)	0.0317 (3)	0.0254 (3)	−0.0040 (2)	0.0176 (2)	−0.00066 (19)
N1	0.0347 (12)	0.0316 (12)	0.0307 (12)	0.0004 (10)	0.0205 (10)	−0.0015 (10)
N2	0.0314 (12)	0.0295 (11)	0.0269 (11)	0.0031 (9)	0.0180 (10)	0.0017 (9)
N3	0.0381 (12)	0.0306 (12)	0.0301 (12)	0.0057 (10)	0.0225 (11)	0.0020 (9)
N4	0.0379 (13)	0.0343 (12)	0.0307 (12)	0.0047 (10)	0.0208 (11)	0.0004 (10)
N5	0.0402 (14)	0.0553 (16)	0.0518 (17)	0.0045 (13)	0.0302 (14)	0.0115 (14)
O1	0.0625 (16)	0.0795 (18)	0.0558 (15)	0.0080 (14)	0.0348 (14)	−0.0128 (14)
O2	0.0598 (15)	0.0764 (16)	0.0548 (15)	0.0019 (12)	0.0408 (13)	−0.0031 (12)
O3	0.087 (2)	0.180 (4)	0.112 (3)	−0.049 (2)	0.066 (2)	0.009 (2)
O1W	0.089 (3)	0.090 (2)	0.088 (3)	−0.026 (2)	0.047 (2)	−0.026 (2)
C1	0.0524 (18)	0.0464 (17)	0.0377 (16)	0.0166 (14)	0.0311 (15)	0.0048 (13)
C2	0.0470 (17)	0.0500 (18)	0.0392 (17)	0.0212 (14)	0.0280 (15)	0.0076 (14)
C3	0.0363 (15)	0.0385 (15)	0.0329 (15)	0.0069 (12)	0.0209 (13)	−0.0012 (12)
C4	0.0312 (13)	0.0284 (13)	0.0277 (13)	−0.0014 (11)	0.0184 (11)	0.0007 (10)
C5	0.0344 (14)	0.0268 (13)	0.0376 (15)	0.0031 (11)	0.0224 (13)	0.0007 (11)
C6	0.0321 (14)	0.0263 (13)	0.0328 (14)	−0.0008 (11)	0.0169 (12)	0.0026 (11)
C7	0.0374 (15)	0.0301 (13)	0.0264 (14)	−0.0017 (11)	0.0182 (12)	0.0015 (11)
C8	0.0355 (14)	0.0277 (14)	0.0315 (14)	0.0009 (11)	0.0221 (12)	0.0001 (10)
C9	0.0315 (13)	0.0314 (13)	0.0287 (14)	0.0056 (11)	0.0169 (11)	0.0045 (11)
C10	0.0428 (17)	0.0446 (17)	0.0368 (16)	0.0118 (14)	0.0179 (14)	0.0093 (13)
C11	0.0491 (17)	0.0350 (15)	0.0331 (15)	0.0073 (13)	0.0287 (14)	0.0060 (12)
C12	0.0446 (16)	0.0406 (16)	0.0371 (16)	0.0016 (13)	0.0294 (14)	0.0000 (12)
C13	0.0504 (17)	0.0342 (15)	0.0360 (15)	0.0020 (12)	0.0312 (14)	0.0049 (12)

Cu1—N1	1.980 (2)	C1—H1	0.9300
Cu1—N1i	1.980 (2)	C2—H2	0.9300
Cu1—N4ii	2.011 (2)	C3—H3	0.9300
Cu1—N4iii	2.011 (2)	C4—C5	1.381 (4)
N1—C3	1.313 (3)	C4—C9	1.383 (4)
N1—C1	1.360 (4)	C5—C6	1.395 (4)
N2—C3	1.345 (3)	C5—H5	0.9300
N2—C2	1.375 (3)	C6—C7	1.388 (4)
N2—C4	1.430 (3)	C6—C10	1.506 (4)
N3—C11	1.346 (3)	C7—C8	1.380 (4)
N3—C13	1.371 (3)	C7—H7	0.9300
N3—C8	1.434 (3)	C8—C9	1.376 (4)
N4—C11	1.316 (3)	C9—H9	0.9300
N4—C12	1.374 (3)	C10—H10A	0.9600
N4—Cu1iv	2.011 (2)	C10—H10B	0.9600
N5—O3	1.217 (4)	C10—H10C	0.9600
N5—O2	1.244 (3)	C11—H11	0.9300
N5—O1	1.246 (4)	C12—C13	1.346 (4)
O1W—H1WA	0.877 (19)	C12—H12	0.9300
O1W—H1WB	0.86 (2)	C13—H13	0.9300
C1—C2	1.344 (4)
N1—Cu1—N1i	180.0	C5—C4—N2	120.8 (2)
N1—Cu1—N4ii	90.60 (9)	C9—C4—N2	118.7 (2)
N1i—Cu1—N4ii	89.40 (9)	C4—C5—C6	120.3 (2)
N1—Cu1—N4iii	89.40 (9)	C4—C5—H5	119.8
N1i—Cu1—N4iii	90.60 (9)	C6—C5—H5	119.8
N4ii—Cu1—N4iii	180.0	C7—C6—C5	119.3 (2)
C3—N1—C1	106.1 (2)	C7—C6—C10	120.2 (2)
C3—N1—Cu1	124.95 (19)	C5—C6—C10	120.5 (2)
C1—N1—Cu1	128.98 (18)	C8—C7—C6	119.3 (2)
C3—N2—C2	106.5 (2)	C8—C7—H7	120.3
C3—N2—C4	125.0 (2)	C6—C7—H7	120.3
C2—N2—C4	128.5 (2)	C9—C8—C7	121.8 (2)
C11—N3—C13	107.0 (2)	C9—C8—N3	117.8 (2)
C11—N3—C8	124.6 (2)	C7—C8—N3	120.3 (2)
C13—N3—C8	128.3 (2)	C8—C9—C4	118.8 (2)
C11—N4—C12	105.7 (2)	C8—C9—H9	120.6
C11—N4—Cu1iv	123.13 (18)	C4—C9—H9	120.6
C12—N4—Cu1iv	131.13 (18)	C6—C10—H10A	109.5
O3—N5—O2	119.9 (3)	C6—C10—H10B	109.5
O3—N5—O1	119.7 (3)	H10A—C10—H10B	109.5
O2—N5—O1	120.3 (3)	C6—C10—H10C	109.5
H1WA—O1W—H1WB	92 (4)	H10A—C10—H10C	109.5
C2—C1—N1	109.8 (2)	H10B—C10—H10C	109.5
C2—C1—H1	125.1	N4—C11—N3	111.2 (2)
N1—C1—H1	125.1	N4—C11—H11	124.4
C1—C2—N2	106.4 (2)	N3—C11—H11	124.4
C1—C2—H2	126.8	C13—C12—N4	109.8 (2)
N2—C2—H2	126.8	C13—C12—H12	125.1
N1—C3—N2	111.3 (2)	N4—C12—H12	125.1
N1—C3—H3	124.4	C12—C13—N3	106.3 (2)
N2—C3—H3	124.4	C12—C13—H13	126.8
C5—C4—C9	120.5 (2)	N3—C13—H13	126.8
N1i—Cu1—N1—C3	−12 (3)	C4—C5—C6—C10	−179.6 (2)
N4ii—Cu1—N1—C3	66.7 (2)	C5—C6—C7—C8	0.7 (4)
N4iii—Cu1—N1—C3	−113.3 (2)	C10—C6—C7—C8	−179.9 (3)
N1i—Cu1—N1—C1	170 (3)	C6—C7—C8—C9	−0.3 (4)
N4ii—Cu1—N1—C1	−111.9 (3)	C6—C7—C8—N3	−179.6 (2)
N4iii—Cu1—N1—C1	68.1 (3)	C11—N3—C8—C9	−44.8 (4)
C3—N1—C1—C2	0.0 (3)	C13—N3—C8—C9	132.7 (3)
Cu1—N1—C1—C2	178.8 (2)	C11—N3—C8—C7	134.5 (3)
N1—C1—C2—N2	0.0 (4)	C13—N3—C8—C7	−48.0 (4)
C3—N2—C2—C1	0.1 (3)	C7—C8—C9—C4	−0.6 (4)
C4—N2—C2—C1	−178.3 (3)	N3—C8—C9—C4	178.7 (2)
C1—N1—C3—N2	0.1 (3)	C5—C4—C9—C8	1.1 (4)
Cu1—N1—C3—N2	−178.82 (17)	N2—C4—C9—C8	−178.6 (2)
C2—N2—C3—N1	−0.1 (3)	C12—N4—C11—N3	0.0 (3)
C4—N2—C3—N1	178.4 (2)	Cu1iv—N4—C11—N3	177.32 (17)
C3—N2—C4—C5	176.8 (2)	C13—N3—C11—N4	−0.2 (3)
C2—N2—C4—C5	−5.1 (4)	C8—N3—C11—N4	177.7 (2)
C3—N2—C4—C9	−3.5 (4)	C11—N4—C12—C13	0.2 (3)
C2—N2—C4—C9	174.6 (3)	Cu1iv—N4—C12—C13	−176.8 (2)
C9—C4—C5—C6	−0.7 (4)	N4—C12—C13—N3	−0.3 (3)
N2—C4—C5—C6	179.0 (2)	C11—N3—C13—C12	0.3 (3)
C4—C5—C6—C7	−0.2 (4)	C8—N3—C13—C12	−177.5 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O3	0.88 (2)	2.04 (2)	2.909 (6)	170 (4)
O1W—H1WB···O3v	0.86 (2)	2.20 (3)	3.020 (5)	159 (5)
O1W—H1WB···O2v	0.86 (2)	2.42 (4)	3.142 (4)	142 (5)
C2—H2···O1Wvi	0.93	2.36	3.230 (5)	156
C3—H3···O1i	0.93	2.27	3.186 (4)	167

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WA⋯O3	0.88 (2)	2.04 (2)	2.909 (6)	170 (4)
O1W—H1WB⋯O3i	0.86 (2)	2.20 (3)	3.020 (5)	159 (5)
O1W—H1WB⋯O2i	0.86 (2)	2.42 (4)	3.142 (4)	142 (5)
C2—H2⋯O1Wii	0.93	2.36	3.230 (5)	156
C3—H3⋯O1iii	0.93	2.27	3.186 (4)	167

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