μ-α-Methyl­glutarato-bis­{aqua­[bis­(2-pyridylcarbon­yl)aminato]copper(II)} trihydrate

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

doi:10.1107/S1600536808034570

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 11| November 2008| Pages m1471-m1472

doi:10.1107/S1600536808034570

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μ-α-Methylglutarato-bis{aqua[bis(2-pyridylcarbonyl)aminato]copper(II)} trihydrate

Hong-Zhen Xie,^a ^* Wei-Juan Pan,^a Wei Xu ^a and Jian-Li Lin ^a

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

(Received 24 June 2008; accepted 23 October 2008; online 31 October 2008)

In the title compound, [Cu₂(C₁₂H₈N₃O₂)₂(C₆H₈O₄)(H₂O)₂]·3H₂O, both crystallographically independent Cu atoms are in similar distorted square-pyramidal coordination environments. The dinuclear complex molecules are assembled into one-dimensional supramolecular chains extending in the [100] direction by hydrogen bonds. Interchain hydrogen bonds further link these chains into layers perpendicular to [001].

Related literature

For general background, see: Kajiwara et al. (2002 ); Kamiyama et al. (2000 ); Kooijman et al. (2006 ); Lescouezec et al. (2005 ); Ohkoshi & Hashimoto (1999 ); Ohkoshi et al. (1998 ); Smolin & Rapoport (1959 ); Toma et al. (2005 ); Yamamoto et al. (1998 ); Zheng et al. (2006 ). For related structures, see: Wei et al. (2002 ).

Experimental

Crystal data

[Cu₂(C₁₂H₈N₃O₂)₂(C₆H₈O₄)(H₂O)₂]·3H₂O
M_r = 813.71
Orthorhombic, P b c n
a = 7.2712 (15) Å
b = 26.910 (5) Å
c = 34.207 (7) Å
V = 6693 (2) Å³
Z = 8
Mo Kα radiation
μ = 1.35 mm⁻¹
T = 293 (2) K
0.31 × 0.28 × 0.18 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.502, T_max = 0.547 (expected range = 0.720–0.785)
55287 measured reflections
7670 independent reflections
5714 reflections with I > 2σ(I)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.108
S = 1.05
7670 reflections
461 parameters
H-atom parameters constrained
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3A⋯O5ⁱ	0.89	2.06	2.835 (4)	144
O3—H3B⋯O12ⁱ	0.82	1.94	2.740 (4)	164
O6—H6A⋯O8ⁱ	0.80	2.04	2.819 (4)	165
O6—H6B⋯O1ⁱⁱ	0.82	2.00	2.822 (4)	179
O11—H11A⋯O13	0.962	1.94	2.808 (4)	150
O11—H11B⋯O2ⁱⁱⁱ	0.910	2.17	2.968 (4)	146
O11—H11B⋯O1ⁱⁱⁱ	0.910	2.41	3.129 (4)	136
O12—H12A⋯O10^iv	0.88	2.09	2.907 (4)	154
O12—H12B⋯O9^v	0.88	2.10	2.935 (4)	159
O12—H12B⋯O10^v	0.88	2.53	3.108 (4)	124
O13—H13B⋯O7^vi	0.820	2.13	2.933 (4)	168
Symmetry codes: (i) x+1, y, z; (ii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, z]$ ; (iii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (iv) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (v) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (vi) x-1, y, z.

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808034570/cs2084sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808034570/cs2084Isup2.hkl

checkCIF report

Comment top

Chemistry of multi-metal-centered complexes attracted much attention because they often show interesting properties induced by direct and indirect M—M interactions such as magnetism (Ohkoshi & Hashimoto, 1999), conductivity (Yamamoto et al., 1998) and photoactivity (Ohkoshi, et al., 1998). Generally, the utilization of multidentate O– and N-donor ligands is an effective strategy to construct this kind of complex molecules. Hence, bpca (bis(2-pyridylcarbonyl)aminato) ligand is often used to prepare polynuclear complexes, (Lescouezec et al., 2005; Kamiyama et al., 2000; Kooijman et al., 2006; Kajiwara et al., 2002). However, investigations of the combination of bpca and dicarboxylate anions to design polynuclear ligands is limited. A novel dinuclear complex [Cu₂(C₁₀H₈N₃O₂)₂(C₆H₈O₄)(H₂O)₂].3H₂O was conceived as described.

Tptz (2,4,6-Tripyridyl-1,3,5-triazine) will only hydrolyse in the presence of concentrated mineral acids and temperatures above 150°C (Smolin & Rapoport, 1959) or in the presence of Cu²⁺ ions under mild conditions (Toma et al., 2005). In absence of any acids reaction of tptz and Cu²⁺ produced [Cu(bpca)(tca)].2H₂O (tca: 2-pyridinecarboxylate) (Zheng et al., 2006). In the title compound tptz undergoes hydrolysis in the presence of α-methylglutaric acid.

The title crystal structure contains solvate water molecules and the dinuclear [Cu₂(C₁₀H₈N₃O₂)₂(C₆H₈O₄) (H₂O)₂] complex (Fig 1). Both Cu atoms within the complex appear in similar square pyramidal coordination environments with the three N atoms of a bis(2-pyridylcarbonyl)amine (bpca) ligand and one O atoms of the α-methylglutarato ligand situtated at basal corners and one O atoms from the aqua ligand at apical position with normal Cu—N and Cu—O bond lengths (Wei et al., 2002). The Cu—O bond 2.273 (2) Å and 2.272 (2) Å is slightly longer than that of basal ones which vary from 1.939 (2) Å to 2.015 (2) Å. Through intermolecular hydrogen bonds between the uncoordinated carboxylate O atoms and coordinated aqua ligand [O3—O5ⁱ= 2.835 (2) Å and O6—O8ⁱ= 2.819 (2) Å; symmetry code: (i) x + 1, y, z], respectively, the dinuclear complex molecules [Cu₂(C₁₀H₈N₃O₂)₂(C₆H₈O₄)(H₂O)₂] are assembled into infinite chains extending in the [100] directions. The resulting chains are further interlinked into two-dimensional layers, perpendicular to the [001] direction, by interchain hydrogen bonds between the O1 of a bpca ligand and O6 of an aqua ligand (Fig. 2). The two-dimensional layers are stacked parallel and the solvate water molecules are sandwiched between them. Extensive hydrogen bonding exist between the included water molecules and the carbonyl O atoms of α-methylglutarato ligands or between the carboxylate O atoms of the α-methylglutarato ligand (Table 1).

Related literature top

For general background, see: Kajiwara et al. (2002); Kamiyama et al. (2000); Kooijman et al. (2006); Lescouezec et al. (2005); Ohkoshi & Hashimoto (1999); Ohkoshi et al. (1998); Smolin & Rapoport (1959); Toma et al. (2005); Yamamoto et al. (1998); Zheng et al. (2006). For related structures, see: Wei et al. (2002).

Experimental top

Addition of 2.0 ml (1.0 M) NaOH to a stirred aqueous solution of CuCl₂.2H₂O (0.172 g, 1.0 mmol) yielded a blue precipitate. After centrifugation, the blue precipitate was subsequently added to a strirred solution of tptz (0.312 g, 1.0 mmol) and α-methylglutaric acid (0.146 g, 1.0 mmol) in 20 ml CH₃OH–H₂O (1:1 v/v). The resulting blue solution (pH = 6.13) was kept at room temperature and slow solvent evaporation afforded blue crystals (yield: 45% based on the initial CuCl₂.2H₂O input).

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. ORTEP view of the title complex with displacement ellipsoids drawn at the 45% probability level, H atoms omitted for visibility.
	Fig. 2. Two-dimensional supramolecular layer in the crystal perpendicular to the [001]direction with H-atoms omitted, broken lines indicate H-bridges.

µ-α-Methylglutarato-bis{aqua[bis(2-pyridylcarbonyl)aminato]copper(II)} trihydrate top

Crystal data top

[Cu₂(C₁₂H₈N₃O₂)₂(C₆H₈O₄)(H₂O)₂]·3H₂O	F(000) = 3344
M_r = 813.71	D_x = 1.615 Mg m⁻³
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 37378 reflections
a = 7.2712 (15) Å	θ = 3.0–27.5°
b = 26.910 (5) Å	µ = 1.35 mm⁻¹
c = 34.207 (7) Å	T = 293 K
V = 6693 (2) Å³	Prism, blue
Z = 8	0.31 × 0.28 × 0.18 mm

Data collection top

Rigaku R-AXIS RAPID diffractometer	7670 independent reflections
Radiation source: fine-focus sealed tube	5714 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.045
Detector resolution: 0 pixels mm^-1	θ_max = 27.5°, θ_min = 3.0°
ω scans	h = −9→9
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −34→34
T_min = 0.502, T_max = 0.547	l = −37→44
55287 measured reflections

Refinement top

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.108	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0539P)² + 2.9935P] where P = (F_o² + 2F_c²)/3
7670 reflections	(Δ/σ)_max = 0.001
461 parameters	Δρ_max = 0.48 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

[Cu₂(C₁₂H₈N₃O₂)₂(C₆H₈O₄)(H₂O)₂]·3H₂O	V = 6693 (2) Å³
M_r = 813.71	Z = 8
Orthorhombic, Pbcn	Mo Kα radiation
a = 7.2712 (15) Å	µ = 1.35 mm⁻¹
b = 26.910 (5) Å	T = 293 K
c = 34.207 (7) Å	0.31 × 0.28 × 0.18 mm

Data collection top

Rigaku R-AXIS RAPID diffractometer	7670 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	5714 reflections with I > 2σ(I)
T_min = 0.502, T_max = 0.547	R_int = 0.045
55287 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.108	H-atom parameters constrained
S = 1.05	Δρ_max = 0.48 e Å⁻³
7670 reflections	Δρ_min = −0.26 e Å⁻³
461 parameters

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

	x	y	z	U_iso*/U_eq
Cu1	0.54934 (4)	0.175121 (11)	0.399089 (8)	0.03535 (9)
Cu2	0.53997 (4)	0.428788 (12)	0.359585 (9)	0.03870 (10)
N1	0.6355 (3)	0.39906 (8)	0.30992 (6)	0.0419 (5)
N2	0.5980 (3)	0.49025 (8)	0.33255 (6)	0.0419 (5)
N3	0.4645 (3)	0.47635 (8)	0.40161 (6)	0.0407 (5)
N4	0.6124 (3)	0.22696 (8)	0.43940 (6)	0.0390 (5)
N5	0.5884 (3)	0.13085 (8)	0.44302 (6)	0.0406 (5)
N6	0.4822 (3)	0.11127 (8)	0.37233 (6)	0.0373 (5)
O1	0.6058 (3)	0.57559 (7)	0.34103 (6)	0.0569 (5)
O2	0.7173 (4)	0.51996 (9)	0.27399 (6)	0.0710 (7)
O3	0.8095 (3)	0.40705 (9)	0.38851 (6)	0.0580 (5)
H3A	0.9077	0.3911	0.3792	0.070*
H3B	0.8148	0.4194	0.4104	0.070*
O4	0.4229 (2)	0.36961 (7)	0.38088 (6)	0.0455 (4)
O5	0.1669 (3)	0.40030 (7)	0.35585 (6)	0.0520 (5)
O6	0.8389 (3)	0.17044 (8)	0.37424 (7)	0.0631 (6)
H6A	0.9344	0.1804	0.3830	0.076*
H6B	0.8544	0.1431	0.3642	0.076*
O7	0.4551 (2)	0.22091 (7)	0.35979 (5)	0.0422 (4)
O8	0.1987 (3)	0.20334 (8)	0.39062 (6)	0.0545 (5)
O9	0.6702 (4)	0.13072 (8)	0.50887 (6)	0.0742 (7)
O10	0.6010 (3)	0.04711 (7)	0.45907 (6)	0.0548 (5)
O11	−0.1837 (5)	0.12871 (10)	0.26137 (10)	0.1035 (10)
H11B	−0.1864	0.1000	0.2754	0.124*
H11A	−0.2408	0.1608	0.2588	0.124*
O12	−0.1091 (4)	0.43917 (9)	0.46254 (6)	0.0694 (6)
H12A	−0.0701	0.4702	0.4636	0.083*
H12B	−0.0190	0.4245	0.4753	0.083*
O13	−0.3775 (4)	0.21512 (10)	0.28183 (7)	0.0788 (7)
H13A	−0.4803	0.2103	0.2712	0.095*
H13B	−0.4091	0.2186	0.3047	0.095*
C1	0.6535 (4)	0.35111 (11)	0.30126 (9)	0.0494 (7)
H1	0.6177	0.3276	0.3197	0.059*
C2	0.7233 (4)	0.33506 (13)	0.26606 (9)	0.0587 (8)
H2	0.7339	0.3013	0.2606	0.070*
C3	0.7770 (5)	0.37017 (14)	0.23906 (9)	0.0634 (9)
H3	0.8245	0.3603	0.2150	0.076*
C4	0.7601 (4)	0.41966 (13)	0.24782 (8)	0.0560 (8)
H4	0.7956	0.4437	0.2298	0.067*
C5	0.6896 (4)	0.43331 (11)	0.28384 (7)	0.0427 (6)
C6	0.6701 (4)	0.48686 (11)	0.29562 (8)	0.0461 (6)
C7	0.5733 (3)	0.53352 (10)	0.35210 (8)	0.0424 (6)
C8	0.4951 (3)	0.52436 (10)	0.39251 (8)	0.0405 (6)
C9	0.4558 (4)	0.56223 (12)	0.41808 (9)	0.0536 (7)
H9	0.4785	0.5951	0.4113	0.064*
C10	0.3814 (5)	0.55019 (13)	0.45422 (9)	0.0592 (8)
H10	0.3533	0.5751	0.4721	0.071*
C11	0.3496 (4)	0.50144 (13)	0.46335 (8)	0.0569 (8)
H11	0.2997	0.4928	0.4875	0.068*
C12	0.3924 (4)	0.46541 (12)	0.43645 (8)	0.0498 (7)
H12	0.3705	0.4323	0.4427	0.060*
C13	0.2503 (4)	0.36850 (9)	0.37466 (7)	0.0383 (6)
C14	0.1458 (4)	0.32513 (10)	0.39196 (8)	0.0464 (6)
H14A	0.0544	0.3376	0.4101	0.056*
H14B	0.2305	0.3043	0.4065	0.056*
C15	0.0508 (4)	0.29403 (10)	0.36086 (9)	0.0495 (7)
H15A	−0.0378	0.2722	0.3733	0.059*
H15B	−0.0155	0.3158	0.3432	0.059*
C16	0.1865 (4)	0.26321 (11)	0.33775 (8)	0.0454 (6)
H16	0.2791	0.2855	0.3266	0.054*
C17	0.2841 (4)	0.22620 (10)	0.36493 (7)	0.0401 (6)
C18	0.0964 (5)	0.23415 (14)	0.30441 (10)	0.0677 (9)
H18A	0.1890	0.2161	0.2903	0.081*
H18B	0.0355	0.2568	0.2870	0.081*
H18C	0.0083	0.2112	0.3150	0.081*
C19	0.6176 (4)	0.27655 (10)	0.43521 (8)	0.0469 (6)
H19	0.5975	0.2902	0.4106	0.056*
C20	0.6518 (5)	0.30785 (11)	0.46620 (10)	0.0591 (8)
H20	0.6551	0.3421	0.4625	0.071*
C21	0.6809 (5)	0.28799 (12)	0.50268 (9)	0.0613 (8)
H21	0.7008	0.3085	0.5241	0.074*
C22	0.6800 (4)	0.23712 (12)	0.50692 (8)	0.0546 (7)
H22	0.7025	0.2229	0.5312	0.065*
C23	0.6456 (4)	0.20759 (10)	0.47502 (7)	0.0428 (6)
C24	0.6377 (4)	0.15139 (10)	0.47802 (8)	0.0459 (6)
C25	0.5724 (3)	0.08108 (10)	0.43633 (8)	0.0392 (6)
C26	0.5099 (3)	0.07091 (9)	0.39491 (7)	0.0362 (5)
C27	0.4783 (4)	0.02377 (10)	0.38124 (8)	0.0446 (6)
H27	0.4976	−0.0036	0.3973	0.054*
C28	0.4175 (4)	0.01755 (11)	0.34332 (9)	0.0503 (7)
H28	0.3970	−0.0142	0.3334	0.060*
C29	0.3879 (4)	0.05820 (11)	0.32057 (9)	0.0518 (7)
H29	0.3450	0.0547	0.2951	0.062*
C30	0.4223 (4)	0.10465 (10)	0.33579 (8)	0.0460 (6)
H30	0.4032	0.1324	0.3201	0.055*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.04081 (18)	0.03272 (16)	0.03252 (16)	0.00093 (12)	−0.00488 (13)	0.00500 (12)
Cu2	0.03813 (18)	0.03853 (18)	0.03945 (17)	−0.00216 (13)	0.00413 (13)	0.00180 (13)
N1	0.0352 (11)	0.0474 (13)	0.0429 (12)	−0.0011 (10)	−0.0028 (9)	−0.0040 (10)
N2	0.0423 (12)	0.0409 (12)	0.0424 (11)	−0.0042 (10)	0.0038 (10)	0.0018 (10)
N3	0.0343 (11)	0.0438 (12)	0.0441 (12)	0.0003 (9)	0.0023 (9)	0.0013 (10)
N4	0.0388 (11)	0.0392 (11)	0.0390 (11)	−0.0006 (9)	−0.0043 (9)	0.0026 (9)
N5	0.0498 (13)	0.0361 (11)	0.0358 (11)	−0.0021 (9)	−0.0064 (10)	0.0069 (9)
N6	0.0378 (11)	0.0363 (11)	0.0378 (11)	−0.0002 (9)	−0.0003 (9)	0.0045 (9)
O1	0.0696 (14)	0.0403 (11)	0.0607 (12)	−0.0068 (10)	0.0064 (11)	0.0039 (9)
O2	0.0964 (18)	0.0621 (14)	0.0544 (12)	−0.0039 (13)	0.0194 (13)	0.0150 (11)
O3	0.0429 (11)	0.0751 (14)	0.0562 (12)	0.0099 (10)	−0.0059 (9)	−0.0121 (11)
O4	0.0365 (10)	0.0407 (10)	0.0594 (12)	0.0002 (8)	0.0034 (9)	0.0073 (9)
O5	0.0456 (11)	0.0405 (10)	0.0699 (13)	0.0011 (9)	−0.0042 (10)	0.0123 (9)
O6	0.0454 (12)	0.0494 (12)	0.0944 (17)	−0.0048 (9)	0.0140 (12)	−0.0135 (11)
O7	0.0443 (10)	0.0427 (10)	0.0395 (9)	0.0084 (8)	−0.0055 (8)	0.0053 (8)
O8	0.0469 (11)	0.0563 (12)	0.0601 (12)	0.0039 (10)	−0.0005 (10)	0.0112 (10)
O9	0.120 (2)	0.0585 (13)	0.0436 (11)	−0.0118 (14)	−0.0271 (13)	0.0149 (10)
O10	0.0743 (14)	0.0414 (11)	0.0487 (11)	−0.0025 (10)	−0.0117 (10)	0.0150 (9)
O11	0.128 (3)	0.0629 (17)	0.120 (2)	0.0112 (17)	0.010 (2)	0.0282 (16)
O12	0.0928 (18)	0.0621 (14)	0.0531 (12)	0.0024 (13)	−0.0098 (12)	−0.0001 (11)
O13	0.0754 (16)	0.100 (2)	0.0607 (14)	−0.0013 (15)	0.0081 (12)	0.0096 (14)
C1	0.0420 (15)	0.0497 (16)	0.0565 (16)	−0.0013 (13)	−0.0056 (13)	−0.0061 (13)
C2	0.0512 (17)	0.063 (2)	0.0615 (19)	0.0038 (15)	−0.0064 (15)	−0.0207 (16)
C3	0.0538 (18)	0.086 (3)	0.0502 (17)	0.0043 (17)	−0.0012 (15)	−0.0222 (17)
C4	0.0498 (16)	0.080 (2)	0.0383 (14)	−0.0017 (16)	0.0020 (13)	−0.0009 (15)
C5	0.0353 (13)	0.0568 (16)	0.0360 (12)	−0.0018 (12)	−0.0035 (11)	0.0009 (12)
C6	0.0408 (14)	0.0555 (17)	0.0421 (14)	−0.0031 (12)	0.0004 (12)	0.0079 (13)
C7	0.0344 (13)	0.0439 (15)	0.0489 (15)	−0.0047 (11)	0.0003 (11)	0.0006 (12)
C8	0.0312 (12)	0.0464 (15)	0.0440 (14)	−0.0023 (11)	−0.0009 (10)	−0.0019 (12)
C9	0.0493 (17)	0.0514 (17)	0.0601 (18)	−0.0007 (13)	0.0030 (14)	−0.0114 (14)
C10	0.0567 (18)	0.068 (2)	0.0533 (17)	0.0021 (16)	0.0031 (15)	−0.0180 (16)
C11	0.0513 (17)	0.079 (2)	0.0404 (14)	0.0042 (16)	0.0073 (13)	−0.0023 (15)
C12	0.0474 (15)	0.0566 (17)	0.0455 (15)	0.0016 (13)	0.0048 (13)	0.0056 (13)
C13	0.0440 (14)	0.0319 (13)	0.0388 (13)	0.0017 (11)	0.0061 (11)	−0.0013 (10)
C14	0.0473 (15)	0.0421 (15)	0.0496 (15)	−0.0018 (12)	0.0071 (13)	0.0056 (12)
C15	0.0400 (15)	0.0373 (14)	0.071 (2)	−0.0006 (12)	−0.0042 (14)	0.0079 (13)
C16	0.0416 (14)	0.0508 (16)	0.0438 (14)	−0.0005 (12)	−0.0076 (12)	0.0048 (12)
C17	0.0474 (15)	0.0376 (13)	0.0354 (12)	0.0008 (12)	−0.0051 (12)	−0.0009 (11)
C18	0.075 (2)	0.076 (2)	0.0524 (18)	−0.0053 (19)	−0.0135 (17)	0.0037 (17)
C19	0.0488 (15)	0.0430 (15)	0.0490 (15)	0.0003 (12)	−0.0070 (13)	0.0048 (12)
C20	0.066 (2)	0.0412 (16)	0.070 (2)	−0.0052 (14)	−0.0114 (17)	−0.0046 (14)
C21	0.071 (2)	0.0567 (19)	0.0564 (18)	−0.0087 (16)	−0.0156 (16)	−0.0119 (15)
C22	0.0607 (19)	0.0628 (19)	0.0402 (14)	−0.0070 (15)	−0.0134 (14)	−0.0012 (13)
C23	0.0436 (15)	0.0456 (15)	0.0391 (13)	−0.0039 (12)	−0.0060 (11)	0.0033 (11)
C24	0.0533 (16)	0.0468 (15)	0.0377 (13)	−0.0045 (13)	−0.0078 (12)	0.0079 (12)
C25	0.0361 (13)	0.0393 (13)	0.0421 (13)	−0.0007 (10)	0.0002 (11)	0.0078 (11)
C26	0.0307 (12)	0.0380 (13)	0.0400 (13)	−0.0010 (10)	0.0047 (10)	0.0047 (11)
C27	0.0493 (15)	0.0344 (13)	0.0502 (15)	−0.0023 (12)	0.0051 (13)	0.0052 (12)
C28	0.0556 (17)	0.0411 (15)	0.0541 (16)	−0.0073 (13)	0.0039 (14)	−0.0068 (13)
C29	0.0605 (18)	0.0534 (17)	0.0417 (14)	−0.0065 (14)	−0.0039 (14)	−0.0052 (13)
C30	0.0586 (17)	0.0401 (14)	0.0392 (14)	−0.0010 (13)	−0.0059 (12)	0.0041 (12)

Geometric parameters (Å, º) top

Cu1—N5	1.939 (2)	C3—H3	0.9300
Cu1—O7	1.9479 (17)	C4—C5	1.384 (4)
Cu1—N6	2.007 (2)	C4—H4	0.9300
Cu1—N4	2.014 (2)	C5—C6	1.503 (4)
Cu1—O6	2.274 (2)	C7—C8	1.515 (4)
Cu2—N2	1.941 (2)	C8—C9	1.373 (4)
Cu2—O4	1.9470 (19)	C9—C10	1.388 (4)
Cu2—N3	2.001 (2)	C9—H9	0.9300
Cu2—N1	2.002 (2)	C10—C11	1.368 (5)
Cu2—O3	2.272 (2)	C10—H10	0.9300
N1—C1	1.330 (4)	C11—C12	1.373 (4)
N1—C5	1.342 (3)	C11—H11	0.9300
N2—C7	1.355 (3)	C12—H12	0.9300
N2—C6	1.371 (3)	C13—C14	1.513 (4)
N3—C12	1.335 (3)	C14—C15	1.520 (4)
N3—C8	1.347 (4)	C14—H14A	0.9700
N4—C19	1.342 (3)	C14—H14B	0.9700
N4—C23	1.347 (3)	C15—C16	1.512 (4)
N5—C25	1.364 (3)	C15—H15A	0.9700
N5—C24	1.366 (3)	C15—H15B	0.9700
N6—C30	1.336 (3)	C16—C18	1.530 (4)
N6—C26	1.348 (3)	C16—C17	1.536 (4)
O1—C7	1.217 (3)	C16—H16	0.9800
O2—C6	1.208 (3)	C18—H18A	0.9600
O3—H3A	0.8924	C18—H18B	0.9600
O3—H3B	0.8203	C18—H18C	0.9600
O4—C13	1.274 (3)	C19—C20	1.376 (4)
O5—C13	1.230 (3)	C19—H19	0.9300
O6—H6A	0.8019	C20—C21	1.374 (4)
O6—H6B	0.8200	C20—H20	0.9300
O7—C17	1.264 (3)	C21—C22	1.377 (4)
O8—C17	1.239 (3)	C21—H21	0.9300
O9—C24	1.216 (3)	C22—C23	1.373 (4)
O10—C25	1.218 (3)	C22—H22	0.9300
O11—H11B	0.9101	C23—C24	1.517 (4)
O11—H11A	0.9623	C25—C26	1.513 (4)
O12—H12A	0.8813	C26—C27	1.371 (4)
O12—H12B	0.8800	C27—C28	1.380 (4)
O13—H13A	0.8412	C27—H27	0.9300
O13—H13B	0.8222	C28—C29	1.360 (4)
C1—C2	1.376 (4)	C28—H28	0.9300
C1—H1	0.9300	C29—C30	1.377 (4)
C2—C3	1.378 (5)	C29—H29	0.9300
C2—H2	0.9300	C30—H30	0.9300
C3—C4	1.370 (5)

N5—Cu1—O7	167.20 (9)	C11—C10—C9	119.5 (3)
N5—Cu1—N6	82.13 (9)	C11—C10—H10	120.2
O7—Cu1—N6	98.13 (8)	C9—C10—H10	120.2
N5—Cu1—N4	82.04 (9)	C10—C11—C12	119.1 (3)
O7—Cu1—N4	96.56 (8)	C10—C11—H11	120.5
N6—Cu1—N4	163.82 (8)	C12—C11—H11	120.5
N5—Cu1—O6	96.91 (9)	N3—C12—C11	122.1 (3)
O7—Cu1—O6	95.88 (8)	N3—C12—H12	118.9
N6—Cu1—O6	90.41 (8)	C11—C12—H12	118.9
N4—Cu1—O6	94.80 (8)	O5—C13—O4	123.8 (2)
N2—Cu2—O4	165.95 (9)	O5—C13—C14	119.6 (2)
N2—Cu2—N3	81.77 (9)	O4—C13—C14	116.6 (2)
O4—Cu2—N3	97.74 (9)	C13—C14—C15	112.3 (2)
N2—Cu2—N1	82.00 (9)	C13—C14—H14A	109.1
O4—Cu2—N1	98.17 (9)	C15—C14—H14A	109.1
N3—Cu2—N1	163.76 (9)	C13—C14—H14B	109.1
N2—Cu2—O3	103.84 (9)	C15—C14—H14B	109.1
O4—Cu2—O3	90.20 (8)	H14A—C14—H14B	107.9
N3—Cu2—O3	95.07 (8)	C16—C15—C14	111.8 (2)
N1—Cu2—O3	88.13 (8)	C16—C15—H15A	109.3
C1—N1—C5	119.3 (2)	C14—C15—H15A	109.3
C1—N1—Cu2	127.6 (2)	C16—C15—H15B	109.3
C5—N1—Cu2	113.05 (18)	C14—C15—H15B	109.3
C7—N2—C6	124.2 (2)	H15A—C15—H15B	107.9
C7—N2—Cu2	117.93 (17)	C15—C16—C18	113.0 (3)
C6—N2—Cu2	117.74 (18)	C15—C16—C17	109.9 (2)
C12—N3—C8	118.8 (2)	C18—C16—C17	108.5 (2)
C12—N3—Cu2	127.4 (2)	C15—C16—H16	108.4
C8—N3—Cu2	113.71 (17)	C18—C16—H16	108.4
C19—N4—C23	118.4 (2)	C17—C16—H16	108.4
C19—N4—Cu1	128.44 (18)	O8—C17—O7	122.4 (2)
C23—N4—Cu1	113.08 (17)	O8—C17—C16	121.3 (2)
C25—N5—C24	124.5 (2)	O7—C17—C16	116.3 (2)
C25—N5—Cu1	117.44 (17)	C16—C18—H18A	109.5
C24—N5—Cu1	117.98 (17)	C16—C18—H18B	109.5
C30—N6—C26	118.5 (2)	H18A—C18—H18B	109.5
C30—N6—Cu1	128.33 (18)	C16—C18—H18C	109.5
C26—N6—Cu1	113.10 (17)	H18A—C18—H18C	109.5
Cu2—O3—H3A	131.2	H18B—C18—H18C	109.5
Cu2—O3—H3B	109.5	N4—C19—C20	122.1 (3)
H3A—O3—H3B	118.9	N4—C19—H19	119.0
C13—O4—Cu2	112.80 (16)	C20—C19—H19	119.0
Cu1—O6—H6A	130.1	C21—C20—C19	119.3 (3)
Cu1—O6—H6B	109.5	C21—C20—H20	120.4
H6A—O6—H6B	109.6	C19—C20—H20	120.4
C17—O7—Cu1	108.74 (16)	C20—C21—C22	118.8 (3)
H11B—O11—H11A	143.2	C20—C21—H21	120.6
H12A—O12—H12B	99.4	C22—C21—H21	120.6
H13A—O13—H13B	100.4	C23—C22—C21	119.5 (3)
N1—C1—C2	122.4 (3)	C23—C22—H22	120.2
N1—C1—H1	118.8	C21—C22—H22	120.2
C2—C1—H1	118.8	N4—C23—C22	121.9 (3)
C1—C2—C3	118.4 (3)	N4—C23—C24	116.1 (2)
C1—C2—H2	120.8	C22—C23—C24	122.0 (2)
C3—C2—H2	120.8	O9—C24—N5	128.8 (3)
C4—C3—C2	119.6 (3)	O9—C24—C23	120.5 (3)
C4—C3—H3	120.2	N5—C24—C23	110.7 (2)
C2—C3—H3	120.2	O10—C25—N5	128.0 (3)
C3—C4—C5	119.0 (3)	O10—C25—C26	120.9 (2)
C3—C4—H4	120.5	N5—C25—C26	111.1 (2)
C5—C4—H4	120.5	N6—C26—C27	121.7 (2)
N1—C5—C4	121.2 (3)	N6—C26—C25	115.8 (2)
N1—C5—C6	116.9 (2)	C27—C26—C25	122.5 (2)
C4—C5—C6	121.9 (3)	C26—C27—C28	119.1 (3)
O2—C6—N2	128.6 (3)	C26—C27—H27	120.5
O2—C6—C5	121.1 (3)	C28—C27—H27	120.5
N2—C6—C5	110.3 (2)	C29—C28—C27	119.4 (3)
O1—C7—N2	128.3 (3)	C29—C28—H28	120.3
O1—C7—C8	120.5 (3)	C27—C28—H28	120.3
N2—C7—C8	111.1 (2)	C28—C29—C30	119.0 (3)
N3—C8—C9	122.0 (3)	C28—C29—H29	120.5
N3—C8—C7	115.4 (2)	C30—C29—H29	120.5
C9—C8—C7	122.6 (3)	N6—C30—C29	122.3 (3)
C8—C9—C10	118.4 (3)	N6—C30—H30	118.9
C8—C9—H9	120.8	C29—C30—H30	118.9
C10—C9—H9	120.8

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O5ⁱ	0.89	2.06	2.835 (4)	144
O3—H3B···O12ⁱ	0.82	1.94	2.740 (4)	164
O6—H6A···O8ⁱ	0.80	2.04	2.819 (4)	165
O6—H6B···O1ⁱⁱ	0.82	2.00	2.822 (4)	179
O11—H11A···O13	0.962	1.94	2.808 (4)	150
O11—H11B···O2ⁱⁱⁱ	0.910	2.17	2.968 (4)	146
O11—H11B···O1ⁱⁱⁱ	0.910	2.41	3.129 (4)	136
O12—H12A···O10^iv	0.88	2.09	2.907 (4)	154
O12—H12B···O9^v	0.88	2.10	2.935 (4)	159
O12—H12B···O10^v	0.88	2.53	3.108 (4)	124
O13—H13B···O7^vi	0.820	2.13	2.933 (4)	168

Symmetry codes: (i) x+1, y, z; (ii) −x+3/2, y−1/2, z; (iii) −x+1/2, y−1/2, z; (iv) −x+1/2, y+1/2, z; (v) x−1/2, −y+1/2, −z+1; (vi) x−1, y, z.

Experimental details

Crystal data
Chemical formula	[Cu₂(C₁₂H₈N₃O₂)₂(C₆H₈O₄)(H₂O)₂]·3H₂O
M_r	813.71
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	293
a, b, c (Å)	7.2712 (15), 26.910 (5), 34.207 (7)
V (Å³)	6693 (2)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	1.35
Crystal size (mm)	0.31 × 0.28 × 0.18

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.502, 0.547
No. of measured, independent and observed [I > 2σ(I)] reflections	55287, 7670, 5714
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.108, 1.05
No. of reflections	7670
No. of parameters	461
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.48, −0.26

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPII (Johnson, 1976).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O5ⁱ	0.892	2.06	2.835 (4)	144
O3—H3B···O12ⁱ	0.820	1.94	2.740 (4)	164
O6—H6A···O8ⁱ	0.802	2.04	2.819 (4)	165
O6—H6B···O1ⁱⁱ	0.820	2.00	2.822 (4)	179
O11—H11A···O13	0.962	1.94	2.808 (4)	150
O11—H11B···O2ⁱⁱⁱ	0.910	2.17	2.968 (4)	146
O11—H11B···O1ⁱⁱⁱ	0.910	2.41	3.129 (4)	136
O12—H12A···O10^iv	0.881	2.09	2.907 (4)	154
O12—H12B···O9^v	0.880	2.10	2.935 (4)	159
O12—H12B···O10^v	0.880	2.53	3.108 (4)	124
O13—H13B···O7^vi	0.820	2.13	2.933 (4)	168

Symmetry codes: (i) x+1, y, z; (ii) −x+3/2, y−1/2, z; (iii) −x+1/2, y−1/2, z; (iv) −x+1/2, y+1/2, z; (v) x−1/2, −y+1/2, −z+1; (vi) x−1, y, z.

Acknowledgements

The project was supported by 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. 2006 A610061) and the Ningbo University Foundation (008–460452 and 008–460453), and sponsored by the K. C. Wong Magna Fund of Ningbo University.

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Volume 64| Part 11| November 2008| Pages m1471-m1472

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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

μ-α-Methyl­glutarato-bis­­{aqua­[bis­­(2-pyridylcarbon­yl)aminato]copper(II)} trihydrate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

μ-α-Methylglutarato-bis{aqua[bis(2-pyridylcarbonyl)aminato]copper(II)} trihydrate