(Formato-κO)bis­(1,10-phenanthroline-κ2N,N′)copper(II) formate hexa­hydrate

Xu, W.; Lin, J.-L.; Xie, H.-Z.; Zhang, M.

doi:10.1107/S1600536808035320

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 64| Part 12| December 2008| Page m1496

doi:10.1107/S1600536808035320

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(Formato-κO)bis(1,10-phenanthroline-κ²N,N′)copper(II) formate hexahydrate

Wei Xu,^a ^* Jian-Li Lin,^a Hong-Zhen Xie ^a and Ming Zhang ^a

^aState Key Laboratory Base of Novel Functional Materials & Preparation Science, Faculty of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211, People's Republic of China
^*Correspondence e-mail: zhengyueqing@nbu.edu.cn

(Received 30 September 2008; accepted 29 October 2008; online 8 November 2008)

In the title compound, [Cu(CHO₂)(C₁₂H₈N₂)₂]CHO₂·6H₂O, the Cu atom is coordinated in a distorted trigonal-bipyramidal fashion by an O atom of the formate ligand and four N atoms of two phenanthroline ligands with Cu—O and Cu—N distances of 2.020 (3) and 1.978 (3)–2.177 (3) Å, respectively. Hydrogen bonding O—H⋯O between water molecules and between water anions as well as π–π interactions [centroid–centroid distances between phen rings = 3.38 (7) and 3.40 (5) Å] are responsible for the supramolecular assembly.

Related literature

For backgorund on the utilization of formic acid for the rational design and synthesis of coordination polymers and the potential applications of these compounds, see: Dybtsev et al. (2003 ); Manson et al. (2003 ); Wang et al. (2005 , 2006 ).

Experimental

Crystal data

[Cu(CHO₂)(C₁₂H₈N₂)₂]CHO₂·6H₂O
M_r = 622.09
Monoclinic, P 2₁ /n
a = 14.765 (3) Å
b = 12.764 (3) Å
c = 15.513 (3) Å
β = 109.76 (3)°
V = 2751.4 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.86 mm⁻¹
T = 295 (2) K
0.43 × 0.29 × 0.22 mm

Data collection

Bruker P4 diffractometer
Absorption correction: ψ scan (XSCANS; Siemens, 1996 ) T_min = 0.740, T_max = 0.819
5942 measured reflections
4812 independent reflections
3341 reflections with I > 2σ(I)
R_int = 0.068
3 standard reflections every 97 reflections intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.163
S = 1.11
4812 reflections
372 parameters
H-atom parameters constrained
Δρ_max = 0.67 e Å⁻³
Δρ_min = −0.76 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5A⋯O8	0.82	2.10	2.874 (5)	160
O5—H5B⋯O4ⁱ	0.73	2.10	2.808 (6)	164
O6—H6A⋯O3	0.74	2.16	2.870 (5)	163
O6—H6B⋯O10	0.85	2.03	2.810 (5)	153
O7—H7A⋯O4	0.90	1.95	2.799 (5)	158
O7—H7B⋯O6ⁱⁱ	0.73	2.08	2.794 (6)	165
O8—H8A⋯O3	0.82	2.12	2.879 (5)	154
O8—H8B⋯O7ⁱ	0.76	2.20	2.876 (6)	148
O9—H9A⋯O2ⁱⁱⁱ	0.75	2.05	2.754 (5)	157
O9—H9B⋯O10^iv	0.83	2.09	2.827 (6)	148
O10—H10A⋯O5	0.85	2.03	2.798 (6)	149
O10—H10B⋯O9	0.82	2.01	2.832 (6)	179
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x, -y+1, -z; (iii) -x+1, -y+1, -z; (iv) -x, -y+2, -z.

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: XSCANS; 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808035320/pk2125sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808035320/pk2125Isup2.hkl

checkCIF report

Comment top

In recent years, interest in the utilization of formic acid for the rational design and synthesis of coordination polymers has been growing rapidly due to their potential applications and intriguing architectures (Dybtsev, et al., 2003; Manson, et al., 2003; Wang, et al., 2005; Wang, et al., 2006). In the present contribution, we report a new copper complex, [Cu(phen)₂(HCOO)](HCOO).6H₂O, resulting from self-assembly of Cu²⁺ ions, phenanthroline and formic acid.

The asymmetric unit of the title compound consists of one [Cu(phen)₂(HCOO)]⁺ complex cation, one formate anion and six water molecules. As illustrated in Fig. 1, the Cu atom is penta-coordinated by four N atoms of two different bidentate chelating phen ligands and one O atom of the formate ligand. The coordination polyhedra is a trigonal bipyramid with d(Cu—O) = 2.020 (3) Å and d(Cu—N) = 1.978 (3)–2.177 (3) Å. The phenanthroline ring systems are each nearly planar and the dihedral angle between the two phen planes is 56.69 (5)°. The complex cations are arranged in such a way that non-symmetry related phen planes of neighboring complexes are oriented parallel to each other with phen-to-phen separations of about 3.38 (7) and 3.40 (5) Å. Such π-π stacking interactions assemble the complex cations into two-dimensional layers parallel to (001) (Fig. 2). The six crystallographically distinct H₂O molecules and the non-coordinating formate anions are held together by hydrogen bonds (d(O···O) = 2.794 (6)–2.879 (5) Å; <O—H···O = 148–179°) to generate two-dimensional water-anionic layers parallel to (100) (Fig. 3). Through the hydrogen bonding interactions (O9···O2), the [Cu(phen)₂(HCOO)]⁺ complex cationic layers are assembled into a three-dimensional network with the H₂O molecules.

Related literature top

For backgorund on the utilization of formic acid for the rational design and synthesis of coordination polymers and the potential applications of these compounds, see: Dybtsev et al. (2003); Manson et al. (2003); Wang et al. (2005, 2006).

Experimental top

Addition of 2.0 ml (1.0 M) NaOH to a stirred aqueous solution of 0.171 g (1.00 mmol) CuCl₂.2H₂O in 5.0 ml H₂O gave a blue precipitate, which was then separated by centrifugation, followed by washing with double-distilled water until no detectable Cl^- anions were present in the supernatant. The precipitate was added to a stirred ethanolic aqueous solution of 0.398 g (2.00 mmol) phenanthroline monohydrate in 20 ml EtOH/H₂O (v/v = 1:1). To the mixture was added 2.0 ml (1.0 M) HCOOH and the blue suspension was further stirred for ca 1 h. After filtration, the filtrate (pH = 5.56) was allowed to stand at room temperature. Slow evaporation for several days gave blue block crystals (yield 32%, based on the initial CuCl₂.2H₂O input).

Computing details top

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS (Siemens, 1996); data reduction: XSCANS (Siemens, 1996); 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: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title complex showing 40% probability displacement ellipsoids.
	Fig. 2. Supramolecular assembly of the [Cu(phen)₂(HCOO)]⁺ complex cations based on π-π stacking interactions.
	Fig. 3. The two-dimensional water-formate anion layers.

(Formato-κO)bis(1,10-phenanthroline-κ²N,N')copper(II) formate hexahydrate top

Crystal data top

[Cu(CHO₂)(C₁₂H₈N₂)₂]CHO₂·6H₂O	F(000) = 1292
M_r = 622.09	D_x = 1.502 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 14.765 (3) Å	θ = 5.0–12.5°
b = 12.764 (3) Å	µ = 0.86 mm⁻¹
c = 15.513 (3) Å	T = 295 K
β = 109.76 (3)°	Block, blue
V = 2751.4 (11) Å³	0.43 × 0.29 × 0.22 mm
Z = 4

Data collection top

Bruker P4 diffractometer	3341 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.068
Graphite monochromator	θ_max = 25.0°, θ_min = 1.7°
θ/2θ scans	h = −1→17
Absorption correction: ψ scan (XSCANS; Siemens, 1996)	k = −1→15
T_min = 0.740, T_max = 0.819	l = −18→17
5942 measured reflections	3 standard reflections every 97 reflections
4812 independent reflections	intensity decay: none

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)] = 0.053	H-atom parameters constrained
wR(F²) = 0.163	w = 1/[σ²(F_o²) + (0.0836P)² + 2.1346P] where P = (F_o² + 2F_c²)/3
S = 1.11	(Δ/σ)_max < 0.001
4812 reflections	Δρ_max = 0.67 e Å⁻³
372 parameters	Δρ_min = −0.76 e Å⁻³
0 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: 0.0091 (10)

Crystal data top

[Cu(CHO₂)(C₁₂H₈N₂)₂]CHO₂·6H₂O	V = 2751.4 (11) Å³
M_r = 622.09	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 14.765 (3) Å	µ = 0.86 mm⁻¹
b = 12.764 (3) Å	T = 295 K
c = 15.513 (3) Å	0.43 × 0.29 × 0.22 mm
β = 109.76 (3)°

Data collection top

Bruker P4 diffractometer	3341 reflections with I > 2σ(I)
Absorption correction: ψ scan (XSCANS; Siemens, 1996)	R_int = 0.068
T_min = 0.740, T_max = 0.819	3 standard reflections every 97 reflections
5942 measured reflections	intensity decay: none
4812 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.163	H-atom parameters constrained
S = 1.11	Δρ_max = 0.67 e Å⁻³
4812 reflections	Δρ_min = −0.76 e Å⁻³
372 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
Cu	0.64373 (3)	0.25126 (4)	0.01020 (3)	0.0379 (2)
N1	0.7686 (2)	0.3308 (2)	0.0792 (2)	0.0375 (7)
N2	0.6376 (2)	0.2407 (2)	0.1353 (2)	0.0396 (7)
C1	0.8348 (3)	0.3739 (3)	0.0496 (3)	0.0478 (10)
H1A	0.8252	0.3736	−0.0129	0.057*
C2	0.9184 (3)	0.4195 (3)	0.1096 (3)	0.0563 (11)
H2A	0.9643	0.4471	0.0871	0.068*
C3	0.9326 (3)	0.4234 (3)	0.2005 (3)	0.0558 (11)
H3A	0.9881	0.4540	0.2405	0.067*
C4	0.8635 (3)	0.3813 (3)	0.2342 (3)	0.0436 (9)
C5	0.8705 (4)	0.3821 (4)	0.3286 (3)	0.0580 (12)
H5C	0.9246	0.4112	0.3719	0.070*
C6	0.8005 (3)	0.3416 (4)	0.3557 (3)	0.0558 (11)
H6C	0.8056	0.3460	0.4171	0.067*
C7	0.7191 (3)	0.2924 (3)	0.2925 (2)	0.0447 (9)
C8	0.6439 (4)	0.2461 (4)	0.3157 (3)	0.0568 (12)
H8C	0.6446	0.2481	0.3758	0.068*
C9	0.5702 (4)	0.1984 (4)	0.2498 (3)	0.0592 (12)
H9C	0.5209	0.1667	0.2650	0.071*
C10	0.5685 (3)	0.1968 (4)	0.1599 (3)	0.0531 (10)
H10C	0.5174	0.1642	0.1155	0.064*
C11	0.7114 (3)	0.2880 (3)	0.2003 (2)	0.0359 (8)
C12	0.7831 (3)	0.3341 (3)	0.1702 (2)	0.0357 (8)
N3	0.5138 (2)	0.3447 (2)	−0.0467 (2)	0.0414 (7)
N4	0.6447 (2)	0.2693 (2)	−0.1166 (2)	0.0393 (7)
C13	0.4500 (3)	0.3792 (3)	−0.0117 (3)	0.0532 (10)
H13A	0.4635	0.3737	0.0512	0.064*
C14	0.3627 (3)	0.4240 (4)	−0.0651 (4)	0.0647 (13)
H14A	0.3186	0.4462	−0.0381	0.078*
C15	0.3430 (4)	0.4348 (3)	−0.1563 (4)	0.0661 (13)
H15A	0.2851	0.4648	−0.1922	0.079*
C16	0.4094 (3)	0.4007 (3)	−0.1966 (3)	0.0526 (11)
C17	0.3954 (4)	0.4059 (4)	−0.2923 (3)	0.0679 (15)
H17A	0.3393	0.4362	−0.3316	0.081*
C18	0.4601 (4)	0.3687 (4)	−0.3271 (3)	0.0656 (14)
H18A	0.4480	0.3730	−0.3898	0.079*
C19	0.5478 (3)	0.3223 (3)	−0.2694 (3)	0.0514 (11)
C20	0.6173 (4)	0.2797 (4)	−0.3019 (3)	0.0608 (13)
H20A	0.6090	0.2827	−0.3640	0.073*
C21	0.6962 (4)	0.2345 (3)	−0.2430 (3)	0.0596 (13)
H21A	0.7426	0.2059	−0.2643	0.072*
C22	0.7083 (4)	0.2306 (3)	−0.1504 (3)	0.0520 (11)
H22A	0.7635	0.1994	−0.1106	0.062*
C23	0.5649 (3)	0.3155 (3)	−0.1749 (2)	0.0392 (9)
C24	0.4947 (3)	0.3552 (3)	−0.1378 (2)	0.0384 (8)
C25	0.6441 (4)	0.0437 (3)	−0.0195 (3)	0.0552 (11)
H25	0.6237	−0.0242	−0.0378	0.066*
O1	0.5806 (2)	0.1097 (2)	−0.02386 (19)	0.0543 (7)
O2	0.7306 (2)	0.0600 (3)	0.0067 (2)	0.0683 (9)
C26	0.1997 (4)	0.5352 (4)	0.2316 (3)	0.0618 (12)
H26	0.2453	0.5124	0.2859	0.074*
O3	0.1314 (3)	0.5838 (3)	0.2400 (3)	0.0798 (10)
O4	0.2164 (3)	0.5125 (3)	0.1609 (2)	0.0796 (11)
O5	0.1030 (3)	0.9175 (3)	0.3028 (3)	0.0833 (11)
O6	0.0247 (3)	0.6818 (3)	0.0693 (2)	0.0770 (10)
O7	0.1697 (3)	0.3535 (3)	0.0289 (2)	0.0729 (10)
O8	0.1647 (3)	0.7213 (3)	0.3948 (2)	0.0719 (9)
O9	0.1259 (3)	1.0518 (3)	0.0279 (2)	0.0885 (12)
O10	0.0479 (3)	0.8961 (3)	0.1125 (3)	0.0831 (11)
H5A	0.1169	0.8562	0.3155	0.100*
H5B	0.1448	0.9521	0.3137	0.100*
H6A	0.0482	0.6457	0.1074	0.100*
H6B	0.0514	0.7399	0.0896	0.100*
H7A	0.1700	0.4114	0.0616	0.100*
H7B	0.1178	0.3552	0.0052	0.100*
H8A	0.1746	0.6809	0.3576	0.100*
H8B	0.2154	0.7354	0.4264	0.100*
H9A	0.1669	1.0365	0.0126	0.100*
H9B	0.0905	1.0691	−0.0241	0.100*
H10A	0.0478	0.9198	0.1640	0.100*
H10B	0.0707	0.9418	0.0885	0.100*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu	0.0408 (3)	0.0447 (3)	0.0282 (3)	−0.0022 (2)	0.0116 (2)	0.00049 (18)
N1	0.0403 (17)	0.0364 (16)	0.0372 (16)	0.0011 (14)	0.0149 (13)	0.0014 (13)
N2	0.0380 (17)	0.0473 (18)	0.0350 (16)	−0.0030 (14)	0.0141 (13)	0.0018 (13)
C1	0.054 (2)	0.045 (2)	0.049 (2)	−0.0029 (19)	0.0223 (19)	0.0063 (18)
C2	0.048 (2)	0.050 (2)	0.076 (3)	−0.005 (2)	0.028 (2)	0.004 (2)
C3	0.043 (2)	0.047 (2)	0.072 (3)	−0.0049 (19)	0.010 (2)	−0.008 (2)
C4	0.041 (2)	0.036 (2)	0.048 (2)	0.0021 (17)	0.0074 (18)	−0.0051 (17)
C5	0.065 (3)	0.054 (3)	0.040 (2)	0.007 (2)	−0.003 (2)	−0.0094 (19)
C6	0.070 (3)	0.060 (3)	0.032 (2)	0.006 (2)	0.011 (2)	−0.0045 (19)
C7	0.057 (2)	0.046 (2)	0.0314 (19)	0.0104 (19)	0.0154 (18)	0.0028 (17)
C8	0.071 (3)	0.069 (3)	0.040 (2)	0.007 (2)	0.032 (2)	0.009 (2)
C9	0.067 (3)	0.069 (3)	0.052 (3)	−0.008 (2)	0.034 (2)	0.010 (2)
C10	0.050 (2)	0.064 (3)	0.048 (2)	−0.010 (2)	0.021 (2)	0.001 (2)
C11	0.039 (2)	0.0367 (18)	0.0308 (18)	0.0066 (16)	0.0103 (16)	0.0029 (15)
C12	0.039 (2)	0.0308 (17)	0.0362 (18)	0.0061 (16)	0.0116 (16)	0.0012 (15)
N3	0.0456 (18)	0.0380 (17)	0.0403 (17)	0.0032 (14)	0.0142 (15)	0.0006 (13)
N4	0.0449 (18)	0.0409 (17)	0.0354 (16)	−0.0010 (14)	0.0181 (14)	0.0006 (13)
C13	0.058 (3)	0.047 (2)	0.060 (3)	0.002 (2)	0.027 (2)	−0.005 (2)
C14	0.054 (3)	0.051 (3)	0.095 (4)	0.007 (2)	0.033 (3)	−0.010 (3)
C15	0.055 (3)	0.041 (2)	0.091 (4)	0.006 (2)	0.009 (3)	0.007 (2)
C16	0.051 (2)	0.033 (2)	0.061 (3)	−0.0014 (18)	0.003 (2)	0.0078 (19)
C17	0.080 (4)	0.045 (3)	0.051 (3)	−0.003 (2)	−0.012 (3)	0.018 (2)
C18	0.091 (4)	0.056 (3)	0.035 (2)	−0.015 (3)	0.002 (2)	0.009 (2)
C19	0.079 (3)	0.041 (2)	0.0320 (19)	−0.018 (2)	0.015 (2)	−0.0006 (17)
C20	0.103 (4)	0.051 (2)	0.036 (2)	−0.023 (3)	0.033 (3)	−0.0063 (19)
C21	0.094 (4)	0.047 (2)	0.059 (3)	−0.007 (2)	0.053 (3)	−0.009 (2)
C22	0.068 (3)	0.047 (2)	0.052 (2)	−0.001 (2)	0.036 (2)	−0.0015 (19)
C23	0.052 (2)	0.0323 (19)	0.0311 (18)	−0.0075 (17)	0.0105 (17)	−0.0003 (15)
C24	0.041 (2)	0.0306 (18)	0.0382 (19)	−0.0027 (15)	0.0070 (16)	0.0032 (15)
C25	0.075 (3)	0.037 (2)	0.042 (2)	−0.004 (2)	0.006 (2)	0.0013 (18)
O1	0.0549 (17)	0.0500 (17)	0.0495 (16)	−0.0009 (15)	0.0064 (13)	0.0002 (13)
O2	0.061 (2)	0.076 (2)	0.0609 (19)	0.0112 (18)	0.0103 (16)	0.0038 (17)
C26	0.074 (3)	0.047 (2)	0.058 (3)	−0.002 (2)	0.015 (2)	−0.002 (2)
O3	0.065 (2)	0.074 (2)	0.103 (3)	0.0053 (19)	0.031 (2)	−0.007 (2)
O4	0.116 (3)	0.060 (2)	0.061 (2)	0.001 (2)	0.027 (2)	−0.0082 (16)
O5	0.089 (3)	0.075 (2)	0.090 (3)	0.017 (2)	0.036 (2)	0.018 (2)
O6	0.078 (2)	0.086 (3)	0.064 (2)	0.004 (2)	0.0206 (18)	−0.0112 (19)
O7	0.080 (2)	0.076 (2)	0.0580 (19)	0.0064 (19)	0.0182 (17)	−0.0100 (17)
O8	0.075 (2)	0.075 (2)	0.072 (2)	−0.0008 (18)	0.0341 (19)	0.0044 (18)
O9	0.085 (3)	0.108 (3)	0.067 (2)	0.016 (2)	0.0197 (19)	−0.012 (2)
O10	0.094 (3)	0.075 (2)	0.076 (2)	0.009 (2)	0.023 (2)	0.0016 (19)

Geometric parameters (Å, º) top

Cu—N2	1.978 (3)	C14—H14A	0.9300
Cu—N4	1.986 (3)	C15—C16	1.400 (7)
Cu—O1	2.020 (3)	C15—H15A	0.9300
Cu—N1	2.059 (3)	C16—C24	1.407 (5)
Cu—N3	2.177 (3)	C16—C17	1.430 (7)
N1—C1	1.332 (5)	C17—C18	1.333 (7)
N1—C12	1.356 (5)	C17—H17A	0.9300
N2—C10	1.327 (5)	C18—C19	1.430 (7)
N2—C11	1.352 (5)	C18—H18A	0.9300
C1—C2	1.397 (6)	C19—C20	1.398 (7)
C1—H1A	0.9300	C19—C23	1.403 (5)
C2—C3	1.355 (6)	C20—C21	1.343 (7)
C2—H2A	0.9300	C20—H20A	0.9300
C3—C4	1.402 (6)	C21—C22	1.388 (6)
C3—H3A	0.9300	C21—H21A	0.9300
C4—C12	1.399 (5)	C22—H22A	0.9300
C4—C5	1.432 (6)	C23—C24	1.437 (5)
C5—C6	1.345 (6)	C25—O2	1.220 (5)
C5—H5C	0.9300	C25—O1	1.245 (5)
C6—C7	1.415 (6)	C25—H25	0.9300
C6—H6C	0.9300	C26—O3	1.228 (6)
C7—C11	1.396 (5)	C26—O4	1.237 (6)
C7—C8	1.409 (6)	C26—H26	0.9300
C8—C9	1.360 (7)	O5—H5A	0.8162
C8—H8C	0.9300	O5—H5B	0.7309
C9—C10	1.386 (6)	O6—H6A	0.7368
C9—H9C	0.9300	O6—H6B	0.8486
C10—H10C	0.9300	O7—H7A	0.8961
C11—C12	1.421 (5)	O7—H7B	0.7303
N3—C13	1.311 (5)	O8—H8A	0.8225
N3—C24	1.352 (5)	O8—H8B	0.7656
N4—C22	1.316 (5)	O9—H9A	0.7471
N4—C23	1.353 (5)	O9—H9B	0.8279
C13—C14	1.397 (6)	O10—H10A	0.8544
C13—H13A	0.9300	O10—H10B	0.8217
C14—C15	1.351 (7)

N2—Cu—N4	176.56 (12)	C24—N3—Cu	108.7 (2)
N2—Cu—O1	91.46 (12)	C22—N4—C23	118.4 (3)
N4—Cu—O1	90.09 (12)	C22—N4—Cu	126.6 (3)
N2—Cu—N1	81.60 (12)	C23—N4—Cu	114.6 (2)
N4—Cu—N1	98.78 (12)	N3—C13—C14	122.7 (4)
O1—Cu—N1	146.07 (12)	N3—C13—H13A	118.7
N2—Cu—N3	96.24 (12)	C14—C13—H13A	118.7
N4—Cu—N3	80.52 (12)	C15—C14—C13	119.4 (4)
O1—Cu—N3	96.83 (12)	C15—C14—H14A	120.3
N1—Cu—N3	116.87 (12)	C13—C14—H14A	120.3
C1—N1—C12	118.0 (3)	C14—C15—C16	120.1 (4)
C1—N1—Cu	131.1 (3)	C14—C15—H15A	120.0
C12—N1—Cu	110.8 (2)	C16—C15—H15A	120.0
C10—N2—C11	118.6 (3)	C15—C16—C24	116.6 (4)
C10—N2—Cu	127.2 (3)	C15—C16—C17	125.0 (4)
C11—N2—Cu	114.1 (2)	C24—C16—C17	118.4 (4)
N1—C1—C2	121.9 (4)	C18—C17—C16	122.1 (4)
N1—C1—H1A	119.0	C18—C17—H17A	118.9
C2—C1—H1A	119.0	C16—C17—H17A	118.9
C3—C2—C1	120.0 (4)	C17—C18—C19	121.0 (4)
C3—C2—H2A	120.0	C17—C18—H18A	119.5
C1—C2—H2A	120.0	C19—C18—H18A	119.5
C2—C3—C4	119.8 (4)	C20—C19—C23	117.3 (4)
C2—C3—H3A	120.1	C20—C19—C18	123.7 (4)
C4—C3—H3A	120.1	C23—C19—C18	119.0 (4)
C12—C4—C3	116.8 (4)	C21—C20—C19	119.7 (4)
C12—C4—C5	118.7 (4)	C21—C20—H20A	120.2
C3—C4—C5	124.6 (4)	C19—C20—H20A	120.2
C6—C5—C4	121.3 (4)	C20—C21—C22	119.9 (4)
C6—C5—H5C	119.3	C20—C21—H21A	120.1
C4—C5—H5C	119.3	C22—C21—H21A	120.1
C5—C6—C7	121.0 (4)	N4—C22—C21	122.6 (5)
C5—C6—H6C	119.5	N4—C22—H22A	118.7
C7—C6—H6C	119.5	C21—C22—H22A	118.7
C11—C7—C8	116.5 (4)	N4—C23—C19	122.2 (4)
C11—C7—C6	119.0 (4)	N4—C23—C24	118.0 (3)
C8—C7—C6	124.6 (4)	C19—C23—C24	119.8 (4)
C9—C8—C7	119.8 (4)	N3—C24—C16	122.9 (4)
C9—C8—H8C	120.1	N3—C24—C23	117.4 (3)
C7—C8—H8C	120.1	C16—C24—C23	119.7 (4)
C8—C9—C10	120.0 (4)	O2—C25—O1	125.9 (4)
C8—C9—H9C	120.0	O2—C25—H25	117.0
C10—C9—H9C	120.0	O1—C25—H25	117.0
N2—C10—C9	121.9 (4)	C25—O1—Cu	108.6 (3)
N2—C10—H10C	119.1	O3—C26—O4	129.0 (5)
C9—C10—H10C	119.1	O3—C26—H26	115.5
N2—C11—C7	123.3 (4)	O4—C26—H26	115.5
N2—C11—C12	116.2 (3)	H5A—O5—H5B	113.5
C7—C11—C12	120.5 (4)	H6A—O6—H6B	102.5
N1—C12—C4	123.4 (3)	H7A—O7—H7B	93.7
N1—C12—C11	117.2 (3)	H8A—O8—H8B	103.3
C4—C12—C11	119.5 (3)	H9A—O9—H9B	94.2
C13—N3—C24	118.3 (3)	H10A—O10—H10B	107.7
C13—N3—Cu	132.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O8	0.82	2.10	2.874 (5)	160
O5—H5B···O4ⁱ	0.73	2.10	2.808 (6)	164
O6—H6A···O3	0.74	2.16	2.870 (5)	163
O6—H6B···O10	0.85	2.03	2.810 (5)	153
O7—H7A···O4	0.90	1.95	2.799 (5)	158
O7—H7B···O6ⁱⁱ	0.73	2.08	2.794 (6)	165
O8—H8A···O3	0.82	2.12	2.879 (5)	154
O8—H8B···O7ⁱ	0.76	2.20	2.876 (6)	148
O9—H9A···O2ⁱⁱⁱ	0.75	2.05	2.754 (5)	157
O9—H9B···O10^iv	0.83	2.09	2.827 (6)	148
O10—H10A···O5	0.85	2.03	2.798 (6)	149
O10—H10B···O9	0.82	2.01	2.832 (6)	179

Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) −x, −y+1, −z; (iii) −x+1, −y+1, −z; (iv) −x, −y+2, −z.

Experimental details

Crystal data
Chemical formula	[Cu(CHO₂)(C₁₂H₈N₂)₂]CHO₂·6H₂O
M_r	622.09
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	295
a, b, c (Å)	14.765 (3), 12.764 (3), 15.513 (3)
β (°)	109.76 (3)
V (Å³)	2751.4 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.86
Crystal size (mm)	0.43 × 0.29 × 0.22

Data collection
Diffractometer	Bruker P4 diffractometer
Absorption correction	ψ scan (XSCANS; Siemens, 1996)
T_min, T_max	0.740, 0.819
No. of measured, independent and observed [I > 2σ(I)] reflections	5942, 4812, 3341
R_int	0.068
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.163, 1.11
No. of reflections	4812
No. of parameters	372
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.67, −0.76

Computer programs: XSCANS (Siemens, 1996), 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
O5—H5A···O8	0.82	2.10	2.874 (5)	160
O5—H5B···O4ⁱ	0.73	2.10	2.808 (6)	164
O6—H6A···O3	0.74	2.16	2.870 (5)	163
O6—H6B···O10	0.85	2.03	2.810 (5)	153
O7—H7A···O4	0.90	1.95	2.799 (5)	158
O7—H7B···O6ⁱⁱ	0.73	2.08	2.794 (6)	165
O8—H8A···O3	0.82	2.12	2.879 (5)	154
O8—H8B···O7ⁱ	0.76	2.20	2.876 (6)	148
O9—H9A···O2ⁱⁱⁱ	0.75	2.05	2.754 (5)	157
O9—H9B···O10^iv	0.83	2.09	2.827 (6)	148
O10—H10A···O5	0.85	2.03	2.798 (6)	149
O10—H10B···O9	0.82	2.01	2.832 (6)	179

Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) −x, −y+1, −z; (iii) −x+1, −y+1, −z; (iv) −x, −y+2, −z.

Acknowledgements

This project was sponsored by the K. C. Wong Magna Fund of Ningbo University, the Expert Project of Key Basic Research of the Ministry of Science and Technology of China (grant No. 2003CCA00800), the Ningbo Municipal Natural Science Foundation (grant No. 2006A610061), the Newer Training Program Foundation for Talents of the Science and Technology Department of Zhejiang Province (grant No. 2007R40G2070020) and the Scientific Research Fund of Ningbo University (XYL08012).

References

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