Bis[bis­(1H-pyrazol-1-yl)methane-κ2N2,N2′](formato-κ2O,O′)copper(II) perchlorate

Zhao, C.-J.; Zhang, R.-F.

doi:10.1107/S1600536811039675

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page m1486

doi:10.1107/S1600536811039675

Open

access

Bis[bis(1H-pyrazol-1-yl)methane-κ²N²,N^2′](formato-κ²O,O′)copper(II) perchlorate

Cai-Juan Zhao ^a and Rui-Feng Zhang ^a ^*

^aSchool of Chemistry & Material Science, Shanxi Normal University, Linfen 041004, People's Republic of China
^*Correspondence e-mail: sxsdzrf@yahoo.com.cn

(Received 29 August 2011; accepted 27 September 2011; online 5 October 2011)

In the crystal structure of the title compound, [Cu(HCO₂)(C₇H₈N₄)₂]ClO₄, the Cu^II ion is octahedrally coordinated by one bidentate formate ion and two bidentate bis(1H-pyrazol-1-yl)methane ligands. There are C—H⋯O hydrogen bonds and π–π interactions [centroid–centroid distance = 3.487 (3) Å] in the crystal structure. The perchlorate anion is disordered over two positions with an occupancy ratio of 0.628 (9):0.372 (9).

Related literature

For applications of coordination polymers, see: Kitagawa et al. (2004 ); Robson (2000 ). For synthesis of the bis(pyrazol-1-yl)methane ligand, see: Elguero et al. (1982 ).

Experimental

Crystal data

[Cu(CHO₂)(C₇H₈N₄)₂]ClO₄
M_r = 504.36
Monoclinic, P 2₁ /n
a = 11.0458 (19) Å
b = 14.816 (3) Å
c = 12.273 (2) Å
β = 99.031 (3)°
V = 1983.6 (6) Å³
Z = 4
Mo Kα radiation
μ = 1.29 mm⁻¹
T = 294 K
0.22 × 0.20 × 0.16 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.768, T_max = 1.000
9920 measured reflections
3439 independent reflections
2334 reflections with I > 2σ(I)
R_int = 0.037

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.165
S = 1.02
3439 reflections
318 parameters
122 restraints
H-atom parameters constrained
Δρ_max = 1.07 e Å⁻³
Δρ_min = −0.62 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13⋯O2ⁱ	0.93	2.66	3.424 (7)	140
C4—H4B⋯O4ⁱⁱ	0.97	2.37	3.343 (14)	176
C4—H4B⋯O4′ⁱⁱ	0.97	2.66	3.580 (12)	159
C11—H11B⋯O5ⁱⁱⁱ	0.97	2.60	3.525 (17)	161
C11—H11B⋯O5′ⁱⁱⁱ	0.97	2.32	3.286 (9)	176
C12—H12⋯O3ⁱⁱⁱ	0.93	2.49	3.220 (14)	136
C12—H12⋯O3′ⁱⁱⁱ	0.93	2.30	3.195 (10)	161
Symmetry codes: (i) -x+1, -y, -z+1; (ii) -x+1, -y+1, -z; (iii) -x+1, -y+1, -z+1.

Data collection: SMART-NT (Bruker, 1998 ); cell refinement: SAINT-NT (Bruker, 1998); data reduction: SAINT-NT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811039675/jh2326sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811039675/jh2326Isup2.hkl

checkCIF report

Comment top

Coordination polymers have received significant attention in recent years, primarily due to their potential applications in many areas such as catalysis, molecular adsorption, magnetism properties and non-linear optics (Kitagawa et al., 2004; Robson, 2000). We report herein the structure of the title compound, namely [Cu(L₁)₂(HCO₂)]ClO₄ (L₁ = bis(pyrazol-1-yl)methane). The title compound crystallizes in monoclinic space group P2₁/n. The asymmetrical unit of the unit cell contains one Cu^II ion, one formic acid and two ligand L₁ (as shown in Fig. 1). The Cu ion is octahedrally coordinated to two oxygen atoms from one formate ion and four nitrogen atoms from two L₁ ligands. In the crystal structure, intermolecular C—H···O hydrogen bonds link the molecules into a three-dimensional network (Fig. 2), and π-π interactions between two pyrazole rings (centroid-centroid distance is 3.487 Å) consolidate the crystal packing.

Related literature top

For applications of coordination polymers, see: Kitagawa et al. (2004); Robson (2000). For synthesis of the bis(pyrazol-1-yl)methane ligand, see: Elguero et al. (1982).

Experimental top

The ligand L₁ was synthesized according to literature (Elguero et al., 1982). The title compound was prepared by adding 5 ml methanol solution of copper(II) perchlorate (0.3 mmol) to 10 ml aqueous solution of L₁ (0.5 mmol) and formic acid (0.3 mmol). The mixture was stirred for half an hour and filtered. The filtrate was slowly evaporated at room temperature to yield blue cubic crystals suitable for X-ray analysis. Analysis calculated for C₁₅H₁₇ClCuN₈: C 35.69, H 3.37, N 22.21%; found: C 33.21, H 3.09, N 24.03%.

Computing details top

Data collection: SMART-NT (Bruker, 1998); cell refinement: SAINT-NT (Bruker, 1998); data reduction: SAINT-NT (Bruker, 1998); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 30% probability level. (Hydrogen atoms and the perchlorate ion are omitted for clarity.)
	Fig. 2. The packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

Bis[bis(1H-pyrazol-1-yl)methane-κ²N²,N^2'](formato- κ²O,O')copper(II) perchlorate top

Crystal data top

[Cu(CHO₂)(C₇H₈N₄)₂]ClO₄	F(000) = 1028
M_r = 504.36	D_x = 1.689 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 11.0458 (19) Å	Cell parameters from 3002 reflections
b = 14.816 (3) Å	θ = 2.2–25.4°
c = 12.273 (2) Å	µ = 1.29 mm⁻¹
β = 99.031 (3)°	T = 294 K
V = 1983.6 (6) Å³	Cubic, blue
Z = 4	0.22 × 0.20 × 0.16 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	3439 independent reflections
Radiation source: fine-focus sealed tube	2334 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→13
T_min = 0.768, T_max = 1.000	k = −17→16
9920 measured reflections	l = −14→14

Refinement top

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)] = 0.052	H-atom parameters constrained
wR(F²) = 0.165	w = 1/[σ²(F_o²) + (0.099P)² + 1.4485P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.001
3439 reflections	Δρ_max = 1.07 e Å⁻³
318 parameters	Δρ_min = −0.62 e Å⁻³
122 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0099 (12)

Crystal data top

[Cu(CHO₂)(C₇H₈N₄)₂]ClO₄	V = 1983.6 (6) Å³
M_r = 504.36	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 11.0458 (19) Å	µ = 1.29 mm⁻¹
b = 14.816 (3) Å	T = 294 K
c = 12.273 (2) Å	0.22 × 0.20 × 0.16 mm
β = 99.031 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3439 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2334 reflections with I > 2σ(I)
T_min = 0.768, T_max = 1.000	R_int = 0.037
9920 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	122 restraints
wR(F²) = 0.165	H-atom parameters constrained
S = 1.02	Δρ_max = 1.07 e Å⁻³
3439 reflections	Δρ_min = −0.62 e Å⁻³
318 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cu1	0.51417 (5)	0.18886 (4)	0.24183 (4)	0.0406 (3)
O1	0.4358 (5)	0.0590 (4)	0.1916 (4)	0.0968 (16)
O2	0.5977 (5)	0.0465 (4)	0.2919 (4)	0.0984 (16)
N1	0.6033 (4)	0.1867 (3)	0.1089 (3)	0.0448 (9)
N2	0.5865 (3)	0.2511 (3)	0.0313 (3)	0.0431 (9)
N3	0.4141 (3)	0.3339 (2)	0.0709 (3)	0.0410 (9)
N4	0.3848 (3)	0.2847 (3)	0.1554 (3)	0.0451 (10)
N5	0.6403 (3)	0.2826 (3)	0.3261 (3)	0.0427 (9)
N6	0.6134 (3)	0.3316 (2)	0.4117 (3)	0.0388 (9)
N7	0.4428 (3)	0.2470 (2)	0.4540 (3)	0.0405 (9)
N8	0.4262 (4)	0.1837 (2)	0.3739 (3)	0.0457 (9)
C1	0.6507 (5)	0.1161 (3)	0.0628 (4)	0.0550 (13)
H1	0.6716	0.0613	0.0978	0.066*
C2	0.6644 (5)	0.1366 (4)	−0.0450 (4)	0.0559 (13)
H2	0.6959	0.0993	−0.0946	0.067*
C3	0.6224 (4)	0.2217 (4)	−0.0628 (4)	0.0504 (12)
H3	0.6188	0.2543	−0.1281	0.060*
C4	0.5405 (4)	0.3388 (3)	0.0552 (4)	0.0435 (11)
H4A	0.5896	0.3628	0.1213	0.052*
H4B	0.5478	0.3796	−0.0053	0.052*
C5	0.3162 (5)	0.3769 (3)	0.0150 (4)	0.0504 (12)
H5	0.3156	0.4142	−0.0460	0.061*
C6	0.2190 (5)	0.3555 (4)	0.0647 (5)	0.0593 (14)
H6	0.1385	0.3750	0.0451	0.071*
C7	0.2642 (4)	0.2986 (4)	0.1508 (4)	0.0532 (13)
H7	0.2170	0.2732	0.1993	0.064*
C8	0.7606 (5)	0.2959 (3)	0.3287 (4)	0.0518 (13)
H8	0.8065	0.2702	0.2793	0.062*
C9	0.8077 (5)	0.3525 (4)	0.4143 (5)	0.0570 (13)
H9	0.8884	0.3718	0.4326	0.068*
C10	0.7118 (4)	0.3739 (3)	0.4658 (4)	0.0496 (12)
H10	0.7140	0.4109	0.5272	0.059*
C11	0.4874 (4)	0.3361 (3)	0.4292 (4)	0.0417 (10)
H11A	0.4371	0.3598	0.3635	0.050*
H11B	0.4808	0.3767	0.4899	0.050*
C12	0.4066 (4)	0.2174 (4)	0.5466 (4)	0.0522 (13)
H12	0.4091	0.2498	0.6118	0.063*
C13	0.3656 (5)	0.1318 (4)	0.5284 (4)	0.0574 (14)
H13	0.3350	0.0940	0.5781	0.069*
C14	0.3787 (5)	0.1122 (3)	0.4204 (4)	0.0513 (12)
H14	0.3577	0.0576	0.3851	0.062*
C15	0.5126 (7)	0.0079 (4)	0.2389 (5)	0.0663 (18)
H15	0.5063	−0.0547	0.2345	0.080*
Cl1	0.48695 (14)	0.56011 (9)	0.25933 (10)	0.0592 (4)
O3	0.4395 (14)	0.6517 (6)	0.2731 (10)	0.094 (5)	0.372 (9)
O4	0.4250 (15)	0.5272 (9)	0.1570 (8)	0.110 (6)	0.372 (9)
O5	0.4583 (17)	0.5091 (9)	0.3505 (10)	0.145 (7)	0.372 (9)
O6	0.6157 (8)	0.5647 (14)	0.2589 (18)	0.267 (14)	0.372 (9)
O3'	0.5275 (10)	0.6523 (5)	0.2451 (7)	0.125 (4)	0.628 (9)
O4'	0.5199 (12)	0.5081 (7)	0.1726 (8)	0.147 (4)	0.628 (9)
O5'	0.5488 (9)	0.5305 (5)	0.3645 (5)	0.094 (3)	0.628 (9)
O6'	0.3574 (7)	0.5562 (10)	0.2584 (13)	0.259 (9)	0.628 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0503 (4)	0.0379 (4)	0.0332 (4)	−0.0003 (2)	0.0051 (2)	0.0002 (2)
O1	0.109 (4)	0.118 (4)	0.067 (3)	−0.004 (3)	0.023 (3)	−0.008 (3)
O2	0.108 (4)	0.127 (5)	0.063 (3)	−0.003 (3)	0.021 (3)	0.007 (3)
N1	0.053 (2)	0.044 (2)	0.037 (2)	0.0068 (18)	0.0069 (18)	0.0010 (18)
N2	0.044 (2)	0.048 (2)	0.038 (2)	0.0015 (17)	0.0081 (17)	0.0010 (18)
N3	0.042 (2)	0.039 (2)	0.040 (2)	0.0013 (16)	0.0004 (17)	−0.0036 (17)
N4	0.044 (2)	0.055 (2)	0.036 (2)	−0.0080 (18)	0.0048 (18)	0.0002 (18)
N5	0.044 (2)	0.046 (2)	0.038 (2)	0.0073 (17)	0.0067 (17)	0.0045 (17)
N6	0.041 (2)	0.039 (2)	0.0358 (19)	−0.0028 (16)	0.0023 (17)	−0.0004 (16)
N7	0.041 (2)	0.042 (2)	0.040 (2)	−0.0030 (16)	0.0080 (17)	−0.0003 (17)
N8	0.052 (2)	0.041 (2)	0.044 (2)	−0.0103 (18)	0.0100 (18)	0.0011 (18)
C1	0.057 (3)	0.050 (3)	0.060 (3)	0.008 (2)	0.014 (3)	−0.005 (2)
C2	0.052 (3)	0.066 (4)	0.052 (3)	−0.004 (3)	0.016 (2)	−0.016 (3)
C3	0.051 (3)	0.064 (3)	0.038 (2)	−0.002 (2)	0.011 (2)	−0.002 (2)
C4	0.047 (3)	0.040 (3)	0.043 (2)	−0.001 (2)	0.004 (2)	0.005 (2)
C5	0.056 (3)	0.042 (3)	0.049 (3)	0.006 (2)	−0.006 (2)	−0.003 (2)
C6	0.040 (3)	0.057 (3)	0.075 (4)	0.011 (2)	−0.008 (3)	−0.016 (3)
C7	0.041 (3)	0.064 (3)	0.056 (3)	−0.003 (2)	0.009 (2)	−0.015 (3)
C8	0.048 (3)	0.055 (3)	0.055 (3)	0.005 (2)	0.014 (2)	0.016 (2)
C9	0.043 (3)	0.057 (3)	0.068 (3)	−0.009 (2)	−0.003 (3)	0.018 (3)
C10	0.051 (3)	0.039 (3)	0.055 (3)	−0.008 (2)	−0.005 (2)	0.003 (2)
C11	0.042 (2)	0.040 (3)	0.043 (2)	0.0008 (19)	0.007 (2)	−0.004 (2)
C12	0.045 (3)	0.074 (4)	0.039 (3)	0.001 (2)	0.012 (2)	0.004 (2)
C13	0.054 (3)	0.070 (4)	0.052 (3)	0.002 (3)	0.017 (3)	0.018 (3)
C14	0.056 (3)	0.043 (3)	0.057 (3)	−0.007 (2)	0.015 (2)	0.002 (2)
C15	0.111 (6)	0.027 (3)	0.067 (4)	−0.004 (3)	0.032 (4)	−0.001 (3)
Cl1	0.0867 (10)	0.0433 (8)	0.0434 (7)	0.0043 (6)	−0.0028 (7)	−0.0003 (5)
O3	0.114 (9)	0.069 (7)	0.095 (8)	0.029 (6)	0.004 (7)	−0.013 (6)
O4	0.136 (10)	0.099 (8)	0.087 (8)	−0.010 (7)	−0.006 (7)	−0.005 (7)
O5	0.145 (7)	0.145 (7)	0.144 (7)	−0.0001 (11)	0.0230 (16)	0.0005 (11)
O6	0.267 (14)	0.267 (14)	0.267 (14)	0.0001 (11)	0.042 (2)	0.0000 (11)
O3'	0.156 (8)	0.089 (6)	0.121 (7)	−0.025 (5)	−0.004 (6)	0.010 (5)
O4'	0.167 (8)	0.148 (8)	0.137 (7)	−0.020 (6)	0.057 (6)	−0.036 (6)
O5'	0.130 (6)	0.074 (5)	0.070 (4)	−0.004 (4)	−0.011 (4)	0.026 (4)
O6'	0.216 (11)	0.289 (13)	0.272 (13)	0.000 (9)	0.038 (9)	−0.026 (9)

Geometric parameters (Å, º) top

Cu1—N8	2.018 (4)	C4—H4A	0.9700
Cu1—N1	2.034 (4)	C4—H4B	0.9700
Cu1—N5	2.119 (4)	C5—C6	1.353 (7)
Cu1—O1	2.160 (5)	C5—H5	0.9300
Cu1—N4	2.169 (4)	C6—C7	1.383 (8)
Cu1—O2	2.345 (6)	C6—H6	0.9300
O1—C15	1.215 (7)	C7—H7	0.9300
O2—C15	1.201 (7)	C8—C9	1.380 (8)
N1—C1	1.334 (6)	C8—H8	0.9300
N1—N2	1.340 (5)	C9—C10	1.354 (8)
N2—C3	1.350 (6)	C9—H9	0.9300
N2—C4	1.443 (6)	C10—H10	0.9300
N3—C5	1.346 (6)	C11—H11A	0.9700
N3—N4	1.347 (5)	C11—H11B	0.9700
N3—C4	1.441 (6)	C12—C13	1.353 (8)
N4—C7	1.340 (6)	C12—H12	0.9300
N5—C8	1.339 (6)	C13—C14	1.388 (7)
N5—N6	1.347 (5)	C13—H13	0.9300
N6—C10	1.338 (6)	C14—H14	0.9300
N6—C11	1.442 (6)	C15—H15	0.9300
N7—C12	1.338 (6)	Cl1—O4'	1.408 (6)
N7—N8	1.350 (5)	Cl1—O4	1.419 (7)
N7—C11	1.458 (6)	Cl1—O6	1.425 (8)
N8—C14	1.347 (6)	Cl1—O5	1.427 (8)
C1—C2	1.388 (7)	Cl1—O6'	1.431 (7)
C1—H1	0.9300	Cl1—O5'	1.432 (5)
C2—C3	1.351 (7)	Cl1—O3'	1.456 (6)
C2—H2	0.9300	Cl1—O3	1.473 (7)
C3—H3	0.9300

N8—Cu1—N1	176.90 (16)	C5—C6—H6	127.2
N8—Cu1—N5	89.75 (15)	C7—C6—H6	127.2
N1—Cu1—N5	92.19 (15)	N4—C7—C6	111.3 (5)
N8—Cu1—O1	88.46 (16)	N4—C7—H7	124.4
N1—Cu1—O1	88.83 (17)	C6—C7—H7	124.4
N5—Cu1—O1	157.97 (19)	N5—C8—C9	111.2 (5)
N8—Cu1—N4	93.12 (15)	N5—C8—H8	124.4
N1—Cu1—N4	89.00 (15)	C9—C8—H8	124.4
N5—Cu1—N4	98.13 (16)	C10—C9—C8	105.6 (4)
O1—Cu1—N4	103.89 (19)	C10—C9—H9	127.2
N8—Cu1—O2	88.52 (16)	C8—C9—H9	127.2
N1—Cu1—O2	88.64 (16)	N6—C10—C9	107.0 (5)
N5—Cu1—O2	105.09 (18)	N6—C10—H10	126.5
O1—Cu1—O2	52.9 (2)	C9—C10—H10	126.5
N4—Cu1—O2	156.73 (18)	N6—C11—N7	110.8 (3)
C15—O1—Cu1	101.5 (4)	N6—C11—H11A	109.5
C15—O2—Cu1	92.5 (4)	N7—C11—H11A	109.5
C1—N1—N2	106.0 (4)	N6—C11—H11B	109.5
C1—N1—Cu1	128.6 (3)	N7—C11—H11B	109.5
N2—N1—Cu1	121.9 (3)	H11A—C11—H11B	108.1
N1—N2—C3	110.7 (4)	N7—C12—C13	107.7 (4)
N1—N2—C4	120.7 (4)	N7—C12—H12	126.2
C3—N2—C4	128.6 (4)	C13—C12—H12	126.2
C5—N3—N4	112.2 (4)	C12—C13—C14	105.7 (4)
C5—N3—C4	128.7 (4)	C12—C13—H13	127.1
N4—N3—C4	119.0 (4)	C14—C13—H13	127.1
C7—N4—N3	104.0 (4)	N8—C14—C13	110.3 (5)
C7—N4—Cu1	134.0 (3)	N8—C14—H14	124.9
N3—N4—Cu1	120.7 (3)	C13—C14—H14	124.9
C8—N5—N6	104.0 (4)	O2—C15—O1	113.0 (6)
C8—N5—Cu1	133.0 (3)	O2—C15—H15	123.5
N6—N5—Cu1	121.7 (3)	O1—C15—H15	123.5
C10—N6—N5	112.2 (4)	O4'—Cl1—O4	44.7 (6)
C10—N6—C11	129.2 (4)	O4'—Cl1—O6	69.3 (8)
N5—N6—C11	118.5 (4)	O4—Cl1—O6	110.9 (7)
C12—N7—N8	111.5 (4)	O4'—Cl1—O5	114.8 (9)
C12—N7—C11	129.0 (4)	O4—Cl1—O5	112.1 (7)
N8—N7—C11	119.3 (3)	O6—Cl1—O5	111.9 (7)
C14—N8—N7	104.8 (4)	O4'—Cl1—O6'	110.4 (6)
C14—N8—Cu1	129.7 (3)	O4—Cl1—O6'	68.7 (7)
N7—N8—Cu1	122.0 (3)	O6—Cl1—O6'	179.2 (9)
N1—C1—C2	109.9 (5)	O5—Cl1—O6'	68.9 (8)
N1—C1—H1	125.0	O4'—Cl1—O5'	111.8 (6)
C2—C1—H1	125.0	O4—Cl1—O5'	142.0 (7)
C3—C2—C1	105.8 (4)	O6—Cl1—O5'	71.5 (8)
C3—C2—H2	127.1	O5—Cl1—O5'	42.6 (7)
C1—C2—H2	127.1	O6'—Cl1—O5'	109.3 (6)
N2—C3—C2	107.5 (4)	O4'—Cl1—O3'	107.6 (5)
N2—C3—H3	126.2	O4—Cl1—O3'	109.3 (7)
C2—C3—H3	126.2	O6—Cl1—O3'	68.2 (9)
N3—C4—N2	111.2 (4)	O5—Cl1—O3'	134.5 (8)
N3—C4—H4A	109.4	O6'—Cl1—O3'	111.3 (6)
N2—C4—H4A	109.4	O5'—Cl1—O3'	106.4 (4)
N3—C4—H4B	109.4	O4'—Cl1—O3	136.9 (7)
N2—C4—H4B	109.4	O4—Cl1—O3	106.7 (6)
H4A—C4—H4B	108.0	O6—Cl1—O3	109.2 (7)
N3—C5—C6	106.9 (5)	O5—Cl1—O3	105.7 (6)
N3—C5—H5	126.6	O6'—Cl1—O3	70.4 (8)
C6—C5—H5	126.6	O5'—Cl1—O3	107.8 (6)
C5—C6—C7	105.7 (4)	O3'—Cl1—O3	43.3 (7)

N8—Cu1—O1—C15	−89.2 (4)	C8—N5—N6—C11	176.7 (4)
N1—Cu1—O1—C15	89.3 (4)	Cu1—N5—N6—C11	−14.9 (5)
N5—Cu1—O1—C15	−3.7 (7)	C12—N7—N8—C14	−0.6 (5)
N4—Cu1—O1—C15	178.0 (4)	C11—N7—N8—C14	−176.6 (4)
O2—Cu1—O1—C15	0.1 (3)	C12—N7—N8—Cu1	−161.4 (3)
N8—Cu1—O2—C15	89.1 (4)	C11—N7—N8—Cu1	22.6 (5)
N1—Cu1—O2—C15	−89.7 (4)	N1—Cu1—N8—C14	−10 (3)
N5—Cu1—O2—C15	178.4 (3)	N5—Cu1—N8—C14	−139.0 (5)
O1—Cu1—O2—C15	−0.1 (3)	O1—Cu1—N8—C14	19.0 (5)
N4—Cu1—O2—C15	−5.4 (6)	N4—Cu1—N8—C14	122.8 (4)
N8—Cu1—N1—C1	−6 (3)	O2—Cu1—N8—C14	−33.9 (5)
N5—Cu1—N1—C1	123.0 (4)	N1—Cu1—N8—N7	145 (3)
O1—Cu1—N1—C1	−35.0 (5)	N5—Cu1—N8—N7	16.5 (4)
N4—Cu1—N1—C1	−138.9 (4)	O1—Cu1—N8—N7	174.6 (4)
O2—Cu1—N1—C1	17.9 (5)	N4—Cu1—N8—N7	−81.6 (4)
N8—Cu1—N1—N2	150 (3)	O2—Cu1—N8—N7	121.6 (4)
N5—Cu1—N1—N2	−81.0 (3)	N2—N1—C1—C2	0.2 (6)
O1—Cu1—N1—N2	121.0 (4)	Cu1—N1—C1—C2	159.2 (4)
N4—Cu1—N1—N2	17.1 (3)	N1—C1—C2—C3	−0.6 (6)
O2—Cu1—N1—N2	174.0 (4)	N1—N2—C3—C2	−0.6 (5)
C1—N1—N2—C3	0.2 (5)	C4—N2—C3—C2	176.9 (4)
Cu1—N1—N2—C3	−160.5 (3)	C1—C2—C3—N2	0.7 (6)
C1—N1—N2—C4	−177.5 (4)	C5—N3—C4—N2	−121.3 (5)
Cu1—N1—N2—C4	21.8 (5)	N4—N3—C4—N2	62.9 (5)
C5—N3—N4—C7	−0.1 (5)	N1—N2—C4—N3	−69.0 (5)
C4—N3—N4—C7	176.3 (4)	C3—N2—C4—N3	113.8 (5)
C5—N3—N4—Cu1	168.7 (3)	N4—N3—C5—C6	0.2 (5)
C4—N3—N4—Cu1	−14.9 (5)	C4—N3—C5—C6	−175.9 (4)
N8—Cu1—N4—C7	−33.5 (4)	N3—C5—C6—C7	−0.1 (6)
N1—Cu1—N4—C7	144.3 (4)	N3—N4—C7—C6	0.0 (5)
N5—Cu1—N4—C7	−123.7 (4)	Cu1—N4—C7—C6	−166.6 (4)
O1—Cu1—N4—C7	55.7 (5)	C5—C6—C7—N4	0.1 (6)
O2—Cu1—N4—C7	60.1 (6)	N6—N5—C8—C9	−0.3 (5)
N8—Cu1—N4—N3	161.7 (3)	Cu1—N5—C8—C9	−166.8 (3)
N1—Cu1—N4—N3	−20.6 (3)	N5—C8—C9—C10	0.4 (6)
N5—Cu1—N4—N3	71.5 (3)	N5—N6—C10—C9	0.1 (5)
O1—Cu1—N4—N3	−109.1 (3)	C11—N6—C10—C9	−176.0 (4)
O2—Cu1—N4—N3	−104.8 (4)	C8—C9—C10—N6	−0.3 (5)
N8—Cu1—N5—C8	143.9 (4)	C10—N6—C11—N7	−120.8 (5)
N1—Cu1—N5—C8	−33.7 (4)	N5—N6—C11—N7	63.2 (5)
O1—Cu1—N5—C8	58.6 (6)	C12—N7—C11—N6	115.5 (5)
N4—Cu1—N5—C8	−123.0 (4)	N8—N7—C11—N6	−69.2 (5)
O2—Cu1—N5—C8	55.5 (4)	N8—N7—C12—C13	0.5 (6)
N8—Cu1—N5—N6	−20.7 (3)	C11—N7—C12—C13	176.1 (4)
N1—Cu1—N5—N6	161.7 (3)	N7—C12—C13—C14	−0.3 (6)
O1—Cu1—N5—N6	−106.0 (5)	N7—N8—C14—C13	0.4 (6)
N4—Cu1—N5—N6	72.4 (3)	Cu1—N8—C14—C13	159.1 (4)
O2—Cu1—N5—N6	−109.1 (3)	C12—C13—C14—N8	0.0 (6)
C8—N5—N6—C10	0.1 (5)	Cu1—O2—C15—O1	0.2 (5)
Cu1—N5—N6—C10	168.5 (3)	Cu1—O1—C15—O2	−0.2 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···O2ⁱ	0.93	2.66	3.424 (7)	140
C4—H4B···O4ⁱⁱ	0.97	2.37	3.343 (14)	176
C4—H4B···O4′ⁱⁱ	0.97	2.66	3.580 (12)	159
C11—H11B···O5ⁱⁱⁱ	0.97	2.60	3.525 (17)	161
C11—H11B···O5′ⁱⁱⁱ	0.97	2.32	3.286 (9)	176
C12—H12···O3ⁱⁱⁱ	0.93	2.49	3.220 (14)	136
C12—H12···O3′ⁱⁱⁱ	0.93	2.30	3.195 (10)	161

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

Experimental details

Crystal data
Chemical formula	[Cu(CHO₂)(C₇H₈N₄)₂]ClO₄
M_r	504.36
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	294
a, b, c (Å)	11.0458 (19), 14.816 (3), 12.273 (2)
β (°)	99.031 (3)
V (Å³)	1983.6 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.29
Crystal size (mm)	0.22 × 0.20 × 0.16

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.768, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	9920, 3439, 2334
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.165, 1.02
No. of reflections	3439
No. of parameters	318
No. of restraints	122
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.07, −0.62

Computer programs: SMART-NT (Bruker, 1998), SAINT-NT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···O2ⁱ	0.93	2.66	3.424 (7)	140.3
C4—H4B···O4ⁱⁱ	0.97	2.37	3.343 (14)	176.2
C4—H4B···O4'ⁱⁱ	0.97	2.66	3.580 (12)	159.1
C11—H11B···O5ⁱⁱⁱ	0.97	2.60	3.525 (17)	160.5
C11—H11B···O5'ⁱⁱⁱ	0.97	2.32	3.286 (9)	175.9
C12—H12···O3ⁱⁱⁱ	0.93	2.49	3.220 (14)	135.9
C12—H12···O3'ⁱⁱⁱ	0.93	2.30	3.195 (10)	161.2

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

Acknowledgements

This work was supported financially by the Natural Science Foundation of Shanxi Normal University (ZR1012) and the Research Fund for the Doctoral Program of Shanxi Normal University (No. 833114).

References

Bruker, (1998). SMART-NT and SAINT-NT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Elguero, J., Ochoa, C., Julia, S., Sala, P., Mazo, J. & Sancho, M. (1982). J. Heterocycl. Chem. 19, 1141–1145. Google Scholar
Kitagawa, S., Kitaura, R. & Noro, S. (2004). Angew. Chem. Int. Ed. 43, 2334–2375. Web of Science CrossRef CAS Google Scholar
Robson, R. (2000). J. Chem. Soc. Dalton Trans. pp. 3735–3744. Web of Science CrossRef Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.