Poly[di-methyl-ammonium [(μ2-benzene-1,2-di-carboxyl-ato-κ(2) O (1):O (3))[μ2-3-(pyri-din-4-yl)-1H-pyrazol-1-ido-κ(2) N (1):N (3)]cuprate(II)]].

In the title complex, {(C2H8N)[Cu(C8H4O4)(C8H6N3)]} n , there are two Cu(II) cations (each located on a centre of inversion), one benzene-1,2-di-carboxyl-ate dianion, one 3-(pyridin-4-yl)-1H-pyrazol-1-ide anion and one di-methyl-ammonium cation in the asymmetric unit. The di-methyl-ammonium cation was highly disordered and was treated with the SQUEEZE routine in PLATON [Spek (2009 ▶). Acta Cryst. D65, 148-155]; the crystallographic data takes into account the presence of the cation. Each Cu(II) cation exhibits a square-planar coordination geometry. A benzene-1,2-di-carboxyl-ate dianion bridges two Cu(II) cations, building a linear chain along [001]. The chains are connected by 3-(pyridin-4-yl)-1H-pyrazol-1-ide anions, constructing a layer parallel to (101). The layers are assembled into a three-dimensional supra-molecular network through C-H⋯π inter-actions.

Related literature

For background to complexes derived from 4-(1H-pyrazol-3-yl)pyridine, see: Davies et al. (2005 ▶); Tan et al. (2011 ▶); For background to complexes derived from benzene-1,2-di­carb­oxy­lic acid, see: Guo (2010 ▶); Yan et al. (2012 ▶).

Experimental

Crystal data

(C2H8N)[Cu(C8H4O4)(C8H6N3)]

M = 417.91

Triclinic,

a = 8.0978 (16) Å

b = 9.7244 (19) Å

c = 11.694 (2) Å

α = 89.26 (3)°

β = 89.12 (3)°

γ = 89.64 (3)°

V = 920.7 (3) Å3

Z = 2

Mo Kα radiation

μ = 1.22 mm−1

T = 293 K

0.24 × 0.22 × 0.21 mm

Data collection

Rigaku SCXmini diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.759, T max = 0.784

8051 measured reflections

3236 independent reflections

2486 reflections with I > 2σ(I)

R int = 0.044

Refinement

R[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 0.124

S = 1.06

3236 reflections

220 parameters

H-atom parameters constrained

Δρmax = 0.50 e Å−3

Δρmin = −0.30 e Å−3

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPII (Johnson, 1976 ▶) and DIAMOND (Brandenburg, 1999 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813016334/tk5232sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813016334/tk5232Isup2.hkl

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

(C2H8N)[Cu(C8H4O4)(C8H6N3)]	Z = 2
Mr = 417.91	F(000) = 430
Triclinic, P1	Dx = 1.507 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.0978 (16) Å	Cell parameters from 8598 reflections
b = 9.7244 (19) Å	θ = 3.0–27.6°
c = 11.694 (2) Å	µ = 1.22 mm−1
α = 89.26 (3)°	T = 293 K
β = 89.12 (3)°	Block, blue
γ = 89.64 (3)°	0.24 × 0.22 × 0.21 mm
V = 920.7 (3) Å3

Rigaku SCXmini diffractometer	3236 independent reflections
Radiation source: fine-focus sealed tube	2486 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.044
ω scans	θmax = 25.0°, θmin = 3.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −9→9
Tmin = 0.759, Tmax = 0.784	k = −11→11
8051 measured reflections	l = −13→13

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.124	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0557P)2 + 0.9233P] where P = (Fo2 + 2Fc2)/3
3236 reflections	(Δ/σ)max < 0.001
220 parameters	Δρmax = 0.50 e Å−3
0 restraints	Δρmin = −0.30 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	1.0000	0.5000	0.5000	0.0276 (2)
Cu2	1.0000	0.5000	0.0000	0.0269 (2)
O1	0.9981 (3)	0.6272 (3)	0.3683 (2)	0.0309 (6)
O2	0.8655 (4)	0.7485 (3)	0.4981 (3)	0.0519 (9)
O3	0.8239 (3)	0.5948 (3)	0.1664 (2)	0.0329 (6)
O4	1.0087 (3)	0.6914 (3)	0.0509 (2)	0.0318 (6)
N1	0.1845 (4)	0.4575 (3)	0.1055 (3)	0.0304 (8)
N2	0.7841 (4)	0.4230 (3)	0.4546 (3)	0.0310 (8)
N3	0.7012 (4)	0.4575 (3)	0.3568 (3)	0.0284 (7)
C1	0.9180 (5)	0.7341 (4)	0.3997 (3)	0.0320 (9)
C2	0.8933 (5)	0.8487 (4)	0.3141 (3)	0.0299 (9)
C3	0.8962 (5)	0.8307 (4)	0.1954 (3)	0.0287 (9)
C4	0.9107 (5)	0.6958 (4)	0.1364 (3)	0.0270 (8)
C5	0.8805 (5)	0.9467 (4)	0.1244 (4)	0.0387 (10)
H5	0.8842	0.9362	0.0455	0.046*
C6	0.8600 (6)	1.0754 (5)	0.1688 (4)	0.0504 (12)
H6	0.8488	1.1511	0.1200	0.061*
C7	0.8559 (7)	1.0929 (5)	0.2847 (4)	0.0539 (13)
H7	0.8424	1.1803	0.3150	0.065*
C8	0.8719 (6)	0.9800 (5)	0.3561 (4)	0.0445 (11)
H8	0.8683	0.9924	0.4349	0.053*
C9	0.6856 (5)	0.3392 (4)	0.5137 (3)	0.0349 (10)
H9	0.7116	0.2992	0.5839	0.042*
C10	0.5388 (5)	0.3190 (4)	0.4571 (3)	0.0357 (10)
H10	0.4502	0.2649	0.4812	0.043*
C11	0.5517 (5)	0.3955 (4)	0.3579 (3)	0.0287 (9)
C12	0.4293 (4)	0.4167 (4)	0.2673 (3)	0.0283 (9)
C13	0.2849 (5)	0.3433 (5)	0.2711 (4)	0.0451 (12)
H13	0.2666	0.2781	0.3287	0.054*
C14	0.1682 (5)	0.3670 (5)	0.1896 (4)	0.0447 (12)
H14	0.0715	0.3160	0.1939	0.054*
C15	0.3227 (6)	0.5277 (6)	0.1017 (4)	0.0567 (14)
H15	0.3367	0.5935	0.0440	0.068*
C16	0.4478 (6)	0.5087 (5)	0.1790 (4)	0.0566 (15)
H16	0.5450	0.5587	0.1710	0.068*

	U11	U22	U33	U12	U13	U23
Cu1	0.0263 (4)	0.0308 (4)	0.0260 (4)	−0.0010 (3)	−0.0127 (3)	0.0035 (3)
Cu2	0.0247 (4)	0.0338 (4)	0.0226 (3)	−0.0005 (3)	−0.0098 (3)	−0.0011 (3)
O1	0.0306 (14)	0.0326 (16)	0.0298 (14)	0.0011 (12)	−0.0102 (12)	0.0046 (12)
O2	0.068 (2)	0.055 (2)	0.0314 (17)	0.0063 (17)	0.0068 (16)	0.0069 (15)
O3	0.0355 (15)	0.0350 (16)	0.0283 (14)	−0.0081 (12)	−0.0066 (12)	0.0024 (12)
O4	0.0318 (15)	0.0367 (16)	0.0271 (14)	−0.0033 (12)	−0.0019 (12)	−0.0018 (12)
N1	0.0264 (17)	0.038 (2)	0.0272 (17)	−0.0013 (14)	−0.0066 (14)	0.0004 (15)
N2	0.0301 (18)	0.037 (2)	0.0261 (17)	−0.0010 (15)	−0.0137 (14)	0.0061 (15)
N3	0.0259 (17)	0.0328 (19)	0.0269 (17)	0.0009 (14)	−0.0125 (14)	0.0000 (14)
C1	0.033 (2)	0.037 (2)	0.027 (2)	−0.0043 (18)	−0.0089 (18)	0.0011 (18)
C2	0.033 (2)	0.029 (2)	0.028 (2)	0.0001 (17)	−0.0050 (17)	0.0006 (17)
C3	0.027 (2)	0.032 (2)	0.027 (2)	0.0014 (16)	−0.0038 (16)	0.0019 (17)
C4	0.0250 (19)	0.032 (2)	0.024 (2)	0.0002 (17)	−0.0112 (17)	0.0000 (16)
C5	0.045 (3)	0.042 (3)	0.029 (2)	0.001 (2)	−0.0041 (19)	0.0073 (19)
C6	0.070 (3)	0.029 (3)	0.052 (3)	0.006 (2)	0.000 (3)	0.010 (2)
C7	0.081 (4)	0.027 (2)	0.054 (3)	0.007 (2)	−0.001 (3)	−0.004 (2)
C8	0.059 (3)	0.041 (3)	0.033 (2)	0.000 (2)	−0.005 (2)	−0.006 (2)
C9	0.036 (2)	0.041 (3)	0.028 (2)	−0.0007 (19)	−0.0116 (18)	0.0113 (18)
C10	0.027 (2)	0.047 (3)	0.033 (2)	−0.0069 (18)	−0.0058 (18)	0.0040 (19)
C11	0.024 (2)	0.032 (2)	0.030 (2)	−0.0009 (16)	−0.0063 (17)	−0.0014 (17)
C12	0.024 (2)	0.036 (2)	0.0245 (19)	−0.0001 (16)	−0.0068 (16)	−0.0030 (17)
C13	0.039 (3)	0.062 (3)	0.034 (2)	−0.014 (2)	−0.011 (2)	0.019 (2)
C14	0.031 (2)	0.062 (3)	0.041 (3)	−0.016 (2)	−0.013 (2)	0.015 (2)
C15	0.038 (3)	0.076 (4)	0.056 (3)	−0.016 (2)	−0.024 (2)	0.036 (3)
C16	0.033 (2)	0.073 (4)	0.064 (3)	−0.025 (2)	−0.027 (2)	0.036 (3)

Cu1—O1	1.963 (3)	C3—C4	1.494 (5)
Cu1—O1i	1.963 (3)	C5—C6	1.370 (6)
Cu1—N2i	1.989 (3)	C5—H5	0.9300
Cu1—N2	1.989 (3)	C6—C7	1.368 (7)
Cu2—O4	1.964 (3)	C6—H6	0.9300
Cu2—O4ii	1.964 (3)	C7—C8	1.378 (6)
Cu2—N1iii	1.990 (3)	C7—H7	0.9300
Cu2—N1iv	1.990 (3)	C8—H8	0.9300
O1—C1	1.276 (5)	C9—C10	1.387 (6)
O2—C1	1.230 (5)	C9—H9	0.9300
O3—C4	1.254 (4)	C10—C11	1.373 (5)
O4—C4	1.268 (4)	C10—H10	0.9300
N1—C15	1.315 (5)	C11—C12	1.474 (5)
N1—C14	1.317 (5)	C12—C16	1.365 (6)
N1—Cu2v	1.990 (3)	C12—C13	1.373 (6)
N2—C9	1.324 (5)	C13—C14	1.369 (6)
N2—N3	1.372 (4)	C13—H13	0.9300
N3—C11	1.355 (5)	C14—H14	0.9300
C1—C2	1.503 (5)	C15—C16	1.378 (6)
C2—C8	1.384 (6)	C15—H15	0.9300
C2—C3	1.400 (5)	C16—H16	0.9300
C3—C5	1.399 (5)
O1—Cu1—O1i	180.000 (1)	C3—C5—H5	119.3
O1—Cu1—N2i	89.29 (12)	C7—C6—C5	120.1 (4)
O1i—Cu1—N2i	90.71 (12)	C7—C6—H6	119.9
O1—Cu1—N2	90.71 (12)	C5—C6—H6	119.9
O1i—Cu1—N2	89.29 (12)	C6—C7—C8	119.4 (4)
N2i—Cu1—N2	180.00 (17)	C6—C7—H7	120.3
O4—Cu2—O4ii	180.00 (14)	C8—C7—H7	120.3
O4—Cu2—N1iii	88.12 (12)	C7—C8—C2	121.9 (4)
O4ii—Cu2—N1iii	91.88 (12)	C7—C8—H8	119.1
O4—Cu2—N1iv	91.88 (12)	C2—C8—H8	119.1
O4ii—Cu2—N1iv	88.12 (12)	N2—C9—C10	111.0 (3)
N1iii—Cu2—N1iv	180.00 (19)	N2—C9—H9	124.5
C1—O1—Cu1	106.8 (2)	C10—C9—H9	124.5
C4—O4—Cu2	104.6 (2)	C11—C10—C9	105.5 (3)
C15—N1—C14	116.5 (3)	C11—C10—H10	127.3
C15—N1—Cu2v	121.6 (3)	C9—C10—H10	127.3
C14—N1—Cu2v	121.6 (3)	N3—C11—C10	107.7 (3)
C9—N2—N3	106.2 (3)	N3—C11—C12	123.1 (3)
C9—N2—Cu1	128.4 (3)	C10—C11—C12	129.1 (3)
N3—N2—Cu1	125.2 (2)	C16—C12—C13	116.6 (4)
C11—N3—N2	109.6 (3)	C16—C12—C11	123.9 (3)
O2—C1—O1	122.5 (4)	C13—C12—C11	119.5 (3)
O2—C1—C2	119.0 (4)	C14—C13—C12	119.5 (4)
O1—C1—C2	118.5 (3)	C14—C13—H13	120.2
C8—C2—C3	118.7 (4)	C12—C13—H13	120.2
C8—C2—C1	117.3 (4)	N1—C14—C13	124.0 (4)
C3—C2—C1	124.0 (3)	N1—C14—H14	118.0
C5—C3—C2	118.6 (4)	C13—C14—H14	118.0
C5—C3—C4	116.0 (3)	N1—C15—C16	123.3 (4)
C2—C3—C4	125.4 (3)	N1—C15—H15	118.4
O3—C4—O4	122.1 (4)	C16—C15—H15	118.4
O3—C4—C3	121.5 (3)	C12—C16—C15	120.1 (4)
O4—C4—C3	116.3 (3)	C12—C16—H16	120.0
C6—C5—C3	121.3 (4)	C15—C16—H16	120.0
C6—C5—H5	119.3

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···Cg1vi	0.93	2.85	3.698 (5)	152

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the N2,N3,C9–C11 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7⋯Cg1i	0.93	2.85	3.698 (5)	152

Symmetry code: (i) .