Aqua­[6-carboxyl­ato-N′-(pyridin-2-yl­methyl­idene)pyridine-2-carbohydrazidato]copper(II) trihydrate

Huang, Y.-M.; Wu, W.-S.; Wang, X.-Y.

doi:10.1107/S1600536812021447

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page m783

doi:10.1107/S1600536812021447

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Aqua[6-carboxylato-N′-(pyridin-2-ylmethylidene)pyridine-2-carbohydrazidato]copper(II) trihydrate

Yu-Min Huang,^a Wen-Shi Wu ^a ^* and Xin-Yu Wang ^a

^aCollege of Materials Science and Engineering, Huaqiao University, Xiamen, Fujian 361021, People's Republic of China
^*Correspondence e-mail: wws@hqu.edu.cn

(Received 16 April 2012; accepted 11 May 2012; online 19 May 2012)

In the title compound, [Cu(C₁₃H₈N₄O₃)(H₂O)]·3H₂O, the complex molecule, except for the aqua ligand, is essentially planar [r.m.s. deviation = 0.034 (2) Å]. The coordination polyhedron of the Cu²⁺ cation is a square-pyramid, with the aqua ligand at the apex. The compound exhibits a three-dimensional structure, which is is stabilized by O—H⋯O and O—-H⋯N hydrogen bonds and π–π interactions [centroid–centroid distance = 2.987 (3) Å].

Related literature

For the synthesis, see: Wu et al. (2007 ). For a related structure, see: Cheng et al. (2007 ).

Experimental

Crystal data

[Cu(C₁₃H₈N₄O₃)(H₂O)]·3H₂O
M_r = 403.85
Triclinic, $[P \overline 1]$
a = 7.1646 (16) Å
b = 9.369 (2) Å
c = 12.647 (3) Å
α = 75.313 (4)°
β = 78.864 (4)°
γ = 74.155 (4)°
V = 783.0 (3) Å³
Z = 2
Mo Kα radiation
μ = 1.44 mm⁻¹
T = 173 K
0.46 × 0.25 × 0.20 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.655, T_max = 0.749
4689 measured reflections
3903 independent reflections
3270 reflections with I > 2σ(I)
R_int = 0.017

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.097
S = 1.09
3903 reflections
259 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.87 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4B⋯O1ⁱ	0.70 (3)	2.04 (3)	2.718 (2)	165 (3)
O7—H7B⋯O6ⁱⁱ	0.72 (3)	2.09 (3)	2.796 (3)	167 (3)
O6—H6A⋯O3ⁱⁱⁱ	0.74 (3)	1.94 (3)	2.675 (3)	176 (3)
O5—H5B⋯O4	0.72 (3)	2.07 (3)	2.788 (3)	173 (3)
O4—H4A⋯N3^iv	0.70 (4)	2.20 (4)	2.878 (2)	163 (3)
O4—H4A⋯O1^iv	0.70 (4)	2.56 (3)	3.053 (2)	129 (3)
O5—H5A⋯O7	0.65 (3)	2.10 (4)	2.742 (3)	168 (4)
O7—H7A⋯O6^v	0.86 (4)	1.95 (4)	2.803 (3)	175 (3)
O6—H6B⋯O5	0.78 (4)	1.94 (4)	2.718 (3)	178 (3)
Symmetry codes: (i) x+1, y, z; (ii) -x+1, -y+1, -z; (iii) -x+1, -y+2, -z; (iv) -x, -y+1, -z+1; (v) x-1, y, z.

Data collection: SMART (Bruker, 1999 ); cell refinement: SAINT (Bruker, 1999); 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812021447/hg5211sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812021447/hg5211Isup2.hkl

checkCIF report

Comment top

In the title compound, [(C₁₃H₈N₄O₃)(H₂O)Cu].3H₂O (I), the Cu(II) ion is 5-coordinated by two nitrogen from two pyridine rings of the same molecule, one nitrogen from the hydrazine, one carboxyl oxygen, and an oxygen atom from H₂O. They form a rectangular pyramid. N1, N2, N4, O2 from the bottom side (Rms=0.0039 (7) Å), The distances of Cu and O4 to the plane are 0.1446 (8)Å and 2.477 (2)Å. The Cu—O bond lengths Cu—O2 and Cu—O4 are 2.008 (2) Å and 2.338 (2) Å , the bond lengths of two pyridine ring nitrogens with Cu are 1.940 (2) Å and 1.932 (2) Å, which are a little shorter then the normal value(1.99 Å). The distance of Cu—N2 is 1.942 (2) Å. The structure of the title compound shown in Fig 1. Except for the H₂O molecules and the Cu atom , the complex molecule is essentially planar, the r.m.s. deviation from planarity being 0.034 (2) Å. It exhibits a three-dimensional structure which is stabilized by hydrogen bonds, van der Waals forces and π–π interactions [the distance between the layers is 0.987 (3) Å]. The O—H···N, O—H···O hydrogen bonds are detailed in Fig 2 and Table 1.

Related literature top

For the synthesis, see: Wu et al. (2007). For a related structure, see: Cheng et al. (2007).

Experimental top

Concentrated H₂SO₄ (2 mL)was added slowly with stirring to a solution of pyridine-2,6-dicarboxylic acid in ethanol. The solution was left to reflux for 24 h, yielding a white precipitate of ethylpyridine-2,6-dicarboxylate. This was dissolved in ethanol, then the hydrazine hydrate was slowly added with continuous stirring and the mixture was refluxed over a period of 6 h, yielding awhite crystalline solid of pyridine-2-carbohydrazide-6-carboxyl acid.

The synthesis of N²-(pyridin-2-ylmethylidene)-pyridine-2-carbohydrazide methylformamide -6-carboxylic acid was carried out in accord with the method of Cheng et al. , (2007). To a suspension of pyridine-2-carbohydrazide-6-carboxyl acid (5.43 g, 30 mmol) in absolute ethanol(50 ml), a solution of pyridine-2-aldehyde (6.43 g, 60 mmol) in the same solvent(20 ml) was added at 353 K. The mixture was left to react at refluxing for 8 h. The yellowish product was filtered, washed with hot ethanol(20 ml) three times and dried in vacuo.

The title compound (I) was synthesized according to the method of Wu et al., (2004). The N²-(pyridin-2-ylmethylidene)-pyridine-2-carbohydrazide methylformamide -6-carboxylic acid (0.03 g,0.1 mmol) dissolved in DMF(10 ml), then CuBr₂(0.02 g, 0.1 mmol) in DMF(10 ml) was added slowly. Black crystals of the title complex precipitated after a few weeks of slow evaporation of the DMF solution at room temperature. Elemental analysis: caculated for C₁₃H₁₀CuN₄O₄.3H₂O:C 38.61%, H 3.96%, N 13.86% ; found: C 38.70%, H 3.83%, N 13.95%. Mp: 645 K.

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); 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 molecular structure (at 30% probability) of the title compound.
	Fig. 2. Packing diagram of the title complex, showing hydrogen bonds as dashed lines.

Aqua[6-carboxylato-N'-(pyridin-2-ylmethylidene)pyridine-2- carbohydrazidato]copper(II) trihydrate top

Crystal data top

[Cu(C₁₃H₈N₄O₃)(H₂O)]·3H₂O	Z = 2
M_r = 403.85	F(000) = 414.0
Triclinic, P1	D_x = 1.713 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.1646 (16) Å	Cell parameters from 4689 reflections
b = 9.369 (2) Å	θ = 2.3–28.3°
c = 12.647 (3) Å	µ = 1.44 mm⁻¹
α = 75.313 (4)°	T = 173 K
β = 78.864 (4)°	Prism, black
γ = 74.155 (4)°	0.46 × 0.25 × 0.20 mm
V = 783.0 (3) Å³

Data collection top

Bruker SMART CCD diffractometer	3903 independent reflections
Radiation source: fine-focus sealed tube	3270 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.017
ω scans	θ_max = 28.3°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→5
T_min = 0.655, T_max = 0.749	k = −12→11
4689 measured reflections	l = −16→15

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.097	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ²(F_o²) + (0.060P)² + 0.2857P] where P = (F_o² + 2F_c²)/3
3903 reflections	(Δ/σ)_max = 0.001
259 parameters	Δρ_max = 0.87 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

[Cu(C₁₃H₈N₄O₃)(H₂O)]·3H₂O	γ = 74.155 (4)°
M_r = 403.85	V = 783.0 (3) Å³
Triclinic, P1	Z = 2
a = 7.1646 (16) Å	Mo Kα radiation
b = 9.369 (2) Å	µ = 1.44 mm⁻¹
c = 12.647 (3) Å	T = 173 K
α = 75.313 (4)°	0.46 × 0.25 × 0.20 mm
β = 78.864 (4)°

Data collection top

Bruker SMART CCD diffractometer	3903 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3270 reflections with I > 2σ(I)
T_min = 0.655, T_max = 0.749	R_int = 0.017
4689 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.097	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	Δρ_max = 0.87 e Å⁻³
3903 reflections	Δρ_min = −0.34 e Å⁻³
259 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Cu1	0.09853 (3)	0.81795 (2)	0.437142 (18)	0.02327 (10)
N1	−0.0413 (2)	0.87989 (18)	0.31321 (14)	0.0236 (3)
N2	−0.1026 (2)	0.70465 (19)	0.49414 (14)	0.0248 (3)
N3	−0.1258 (2)	0.60892 (19)	0.59384 (14)	0.0262 (3)
N4	0.2029 (2)	0.77149 (19)	0.57510 (14)	0.0243 (3)
O1	−0.3452 (2)	0.63031 (17)	0.43908 (13)	0.0302 (3)
O2	0.2363 (2)	0.97722 (17)	0.34524 (13)	0.0316 (3)
O3	0.2579 (3)	1.1266 (2)	0.17829 (15)	0.0430 (4)
C1	−0.1882 (3)	0.8163 (2)	0.31567 (17)	0.0243 (4)
C2	−0.2883 (3)	0.8560 (2)	0.22629 (18)	0.0293 (4)
H2B	−0.3903	0.8123	0.2263	0.035*
C3	−0.2335 (3)	0.9632 (3)	0.13589 (18)	0.0331 (4)
H3B	−0.3000	0.9923	0.0747	0.040*
C4	−0.0801 (3)	1.0273 (2)	0.13613 (18)	0.0307 (4)
H4	−0.0429	1.0991	0.0758	0.037*
C5	0.0152 (3)	0.9817 (2)	0.22791 (17)	0.0261 (4)
C6	−0.2228 (3)	0.7064 (2)	0.42312 (16)	0.0242 (4)
C7	−0.0134 (3)	0.5975 (2)	0.66471 (17)	0.0274 (4)
H7	−0.0378	0.5299	0.7307	0.049 (8)*
C8	0.1460 (3)	0.6693 (2)	0.66302 (17)	0.0263 (4)
C9	0.2380 (3)	0.6271 (3)	0.75670 (18)	0.0324 (4)
H9A	0.1984	0.5561	0.8168	0.039*
C10	0.3894 (3)	0.6908 (3)	0.7609 (2)	0.0357 (5)
H10A	0.4529	0.6620	0.8232	0.043*
C11	0.4442 (3)	0.7971 (3)	0.67170 (19)	0.0325 (5)
H11A	0.5433	0.8431	0.6730	0.039*
C12	0.3489 (3)	0.8337 (2)	0.58068 (18)	0.0287 (4)
H12A	0.3869	0.9046	0.5200	0.034*
C13	0.1842 (3)	1.0349 (2)	0.25009 (18)	0.0287 (4)
O4	0.3293 (2)	0.63057 (18)	0.35862 (13)	0.0264 (3)
O5	0.3746 (3)	0.7227 (2)	0.12947 (18)	0.0412 (4)
O6	0.7331 (3)	0.6617 (2)	0.00850 (16)	0.0414 (4)
O7	0.1112 (3)	0.6122 (3)	0.06140 (17)	0.0461 (4)
H4B	0.416 (5)	0.615 (3)	0.381 (2)	0.033 (8)*
H7B	0.158 (5)	0.537 (4)	0.052 (3)	0.045 (9)*
H6A	0.733 (4)	0.723 (3)	−0.041 (3)	0.033 (7)*
H5B	0.371 (5)	0.693 (4)	0.188 (3)	0.043 (9)*
H4A	0.291 (5)	0.566 (4)	0.381 (3)	0.045 (9)*
H5A	0.303 (5)	0.707 (4)	0.113 (3)	0.044 (10)*
H7A	−0.003 (6)	0.632 (4)	0.042 (3)	0.061 (10)*
H6B	0.632 (5)	0.680 (4)	0.044 (3)	0.048 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.02030 (15)	0.02569 (15)	0.02592 (15)	−0.00806 (10)	−0.00475 (9)	−0.00513 (10)
N1	0.0186 (7)	0.0252 (8)	0.0273 (8)	−0.0051 (6)	−0.0031 (6)	−0.0063 (6)
N2	0.0209 (8)	0.0282 (8)	0.0262 (8)	−0.0069 (6)	−0.0017 (6)	−0.0071 (6)
N3	0.0225 (8)	0.0269 (8)	0.0289 (8)	−0.0070 (6)	−0.0001 (6)	−0.0067 (6)
N4	0.0208 (8)	0.0287 (8)	0.0266 (8)	−0.0066 (6)	−0.0026 (6)	−0.0109 (6)
O1	0.0236 (7)	0.0330 (7)	0.0377 (8)	−0.0116 (6)	−0.0048 (6)	−0.0083 (6)
O2	0.0299 (8)	0.0300 (7)	0.0377 (8)	−0.0133 (6)	−0.0068 (6)	−0.0039 (6)
O3	0.0413 (9)	0.0402 (9)	0.0452 (10)	−0.0197 (8)	−0.0075 (8)	0.0071 (7)
C1	0.0200 (9)	0.0239 (9)	0.0292 (9)	−0.0023 (7)	−0.0033 (7)	−0.0088 (7)
C2	0.0251 (10)	0.0328 (10)	0.0336 (10)	−0.0056 (8)	−0.0074 (8)	−0.0123 (8)
C3	0.0342 (11)	0.0352 (11)	0.0297 (10)	−0.0021 (9)	−0.0108 (8)	−0.0083 (8)
C4	0.0317 (10)	0.0303 (10)	0.0274 (9)	−0.0041 (8)	−0.0022 (8)	−0.0058 (8)
C5	0.0243 (9)	0.0220 (9)	0.0303 (9)	−0.0035 (7)	−0.0018 (7)	−0.0062 (7)
C6	0.0187 (8)	0.0250 (9)	0.0290 (9)	−0.0039 (7)	−0.0005 (7)	−0.0093 (7)
C7	0.0278 (10)	0.0276 (9)	0.0260 (9)	−0.0082 (8)	−0.0006 (7)	−0.0044 (7)
C8	0.0240 (9)	0.0270 (9)	0.0286 (9)	−0.0033 (7)	−0.0029 (7)	−0.0108 (7)
C9	0.0335 (11)	0.0349 (11)	0.0286 (10)	−0.0062 (9)	−0.0065 (8)	−0.0067 (8)
C10	0.0309 (11)	0.0435 (12)	0.0375 (11)	−0.0035 (9)	−0.0125 (9)	−0.0167 (10)
C11	0.0236 (10)	0.0387 (11)	0.0405 (12)	−0.0045 (8)	−0.0061 (8)	−0.0197 (9)
C12	0.0229 (9)	0.0324 (10)	0.0346 (10)	−0.0076 (8)	−0.0026 (8)	−0.0138 (8)
C13	0.0240 (9)	0.0249 (9)	0.0368 (11)	−0.0071 (7)	−0.0034 (8)	−0.0048 (8)
O4	0.0221 (7)	0.0270 (8)	0.0315 (7)	−0.0078 (6)	−0.0043 (6)	−0.0059 (6)
O5	0.0384 (10)	0.0548 (11)	0.0350 (10)	−0.0198 (8)	−0.0031 (8)	−0.0091 (8)
O6	0.0392 (10)	0.0409 (10)	0.0341 (9)	−0.0032 (8)	−0.0033 (8)	0.0018 (8)
O7	0.0441 (11)	0.0474 (11)	0.0530 (11)	−0.0105 (9)	−0.0160 (9)	−0.0150 (9)

Geometric parameters (Å, º) top

Cu1—N1	1.9042 (17)	C4—C5	1.375 (3)
Cu1—N4	1.9325 (17)	C4—H4	0.9300
Cu1—N2	1.9415 (17)	C5—C13	1.525 (3)
Cu1—O2	2.0084 (15)	C7—C8	1.470 (3)
Cu1—O4	2.3379 (15)	C7—H7	0.9300
N1—C5	1.326 (3)	C8—C9	1.384 (3)
N1—C1	1.336 (2)	C9—C10	1.388 (3)
N2—C6	1.353 (3)	C9—H9A	0.9300
N2—N3	1.360 (2)	C10—C11	1.376 (4)
N3—C7	1.283 (3)	C10—H10A	0.9300
N4—C12	1.349 (3)	C11—C12	1.373 (3)
N4—C8	1.348 (3)	C11—H11A	0.9300
O1—C6	1.232 (2)	C12—H12A	0.9300
O2—C13	1.270 (3)	O4—H4B	0.70 (3)
O3—C13	1.228 (3)	O4—H4A	0.70 (4)
C1—C2	1.373 (3)	O5—H5B	0.72 (3)
C1—C6	1.506 (3)	O5—H5A	0.65 (3)
C2—C3	1.389 (3)	O6—H6A	0.74 (3)
C2—H2B	0.9300	O6—H6B	0.78 (4)
C3—C4	1.389 (3)	O7—H7B	0.72 (3)
C3—H3B	0.9300	O7—H7A	0.86 (4)

N1—Cu1—N4	170.94 (7)	N1—C5—C4	119.82 (19)
N1—Cu1—N2	80.89 (7)	N1—C5—C13	111.31 (18)
N4—Cu1—N2	95.11 (7)	C4—C5—C13	128.86 (19)
N1—Cu1—O2	80.84 (7)	O1—C6—N2	127.17 (19)
N4—Cu1—O2	101.87 (7)	O1—C6—C1	121.94 (18)
N2—Cu1—O2	160.31 (7)	N2—C6—C1	110.88 (16)
N1—Cu1—O4	91.72 (6)	N3—C7—C8	133.21 (19)
N4—Cu1—O4	96.87 (6)	N3—C7—H7	113.4
N2—Cu1—O4	97.22 (7)	C8—C7—H7	113.4
O2—Cu1—O4	90.63 (6)	N4—C8—C9	120.50 (19)
C5—N1—C1	123.44 (18)	N4—C8—C7	122.52 (18)
C5—N1—Cu1	118.13 (14)	C9—C8—C7	116.98 (19)
C1—N1—Cu1	118.41 (14)	C8—C9—C10	120.0 (2)
C6—N2—N3	114.57 (16)	C8—C9—H9A	120.0
C6—N2—Cu1	117.02 (13)	C10—C9—H9A	120.0
N3—N2—Cu1	127.98 (13)	C11—C10—C9	119.1 (2)
C7—N3—N2	118.37 (17)	C11—C10—H10A	120.4
C12—N4—C8	118.86 (18)	C9—C10—H10A	120.4
C12—N4—Cu1	118.88 (14)	C12—C11—C10	118.3 (2)
C8—N4—Cu1	122.02 (14)	C12—C11—H11A	120.8
C13—O2—Cu1	114.80 (13)	C10—C11—H11A	120.8
N1—C1—C2	119.63 (19)	N4—C12—C11	123.1 (2)
N1—C1—C6	112.24 (17)	N4—C12—H12A	118.4
C2—C1—C6	128.12 (19)	C11—C12—H12A	118.4
C1—C2—C3	118.32 (19)	O3—C13—O2	125.5 (2)
C1—C2—H2B	120.8	O3—C13—C5	119.8 (2)
C3—C2—H2B	120.8	O2—C13—C5	114.64 (18)
C2—C3—C4	120.6 (2)	Cu1—O4—H4B	108 (2)
C2—C3—H3B	119.7	Cu1—O4—H4A	103 (3)
C4—C3—H3B	119.7	H4B—O4—H4A	106 (3)
C5—C4—C3	118.2 (2)	H5B—O5—H5A	108 (4)
C5—C4—H4	120.9	H6A—O6—H6B	107 (3)
C3—C4—H4	120.9	H7B—O7—H7A	105 (3)

N4—Cu1—N1—C5	112.0 (4)	C1—C2—C3—C4	0.4 (3)
N2—Cu1—N1—C5	176.41 (15)	C2—C3—C4—C5	0.0 (3)
O2—Cu1—N1—C5	3.82 (14)	C1—N1—C5—C4	0.4 (3)
O4—Cu1—N1—C5	−86.55 (15)	Cu1—N1—C5—C4	178.88 (15)
N4—Cu1—N1—C1	−69.4 (4)	C1—N1—C5—C13	179.22 (17)
N2—Cu1—N1—C1	−5.02 (14)	Cu1—N1—C5—C13	−2.3 (2)
O2—Cu1—N1—C1	−177.62 (15)	C3—C4—C5—N1	−0.5 (3)
O4—Cu1—N1—C1	92.02 (15)	C3—C4—C5—C13	−179.05 (19)
N1—Cu1—N2—C6	7.05 (14)	N3—N2—C6—O1	−1.1 (3)
N4—Cu1—N2—C6	178.85 (14)	Cu1—N2—C6—O1	171.93 (16)
O2—Cu1—N2—C6	29.2 (3)	N3—N2—C6—C1	179.46 (15)
O4—Cu1—N2—C6	−83.54 (14)	Cu1—N2—C6—C1	−7.5 (2)
N1—Cu1—N2—N3	179.04 (16)	N1—C1—C6—O1	−176.13 (17)
N4—Cu1—N2—N3	−9.16 (16)	C2—C1—C6—O1	4.7 (3)
O2—Cu1—N2—N3	−158.79 (17)	N1—C1—C6—N2	3.3 (2)
O4—Cu1—N2—N3	88.45 (16)	C2—C1—C6—N2	−175.89 (18)
C6—N2—N3—C7	178.04 (17)	N2—N3—C7—C8	0.1 (3)
Cu1—N2—N3—C7	5.9 (3)	C12—N4—C8—C9	−1.0 (3)
N1—Cu1—N4—C12	−113.4 (4)	Cu1—N4—C8—C9	173.31 (15)
N2—Cu1—N4—C12	−176.78 (15)	C12—N4—C8—C7	179.16 (18)
O2—Cu1—N4—C12	−6.80 (16)	Cu1—N4—C8—C7	−6.5 (3)
O4—Cu1—N4—C12	85.30 (15)	N3—C7—C8—N4	0.5 (4)
N1—Cu1—N4—C8	72.3 (4)	N3—C7—C8—C9	−179.4 (2)
N2—Cu1—N4—C8	8.91 (16)	N4—C8—C9—C10	0.4 (3)
O2—Cu1—N4—C8	178.88 (15)	C7—C8—C9—C10	−179.80 (19)
O4—Cu1—N4—C8	−89.02 (15)	C8—C9—C10—C11	0.9 (3)
N1—Cu1—O2—C13	−4.88 (15)	C9—C10—C11—C12	−1.4 (3)
N4—Cu1—O2—C13	−176.09 (14)	C8—N4—C12—C11	0.5 (3)
N2—Cu1—O2—C13	−27.1 (3)	Cu1—N4—C12—C11	−174.03 (15)
O4—Cu1—O2—C13	86.76 (15)	C10—C11—C12—N4	0.7 (3)
C5—N1—C1—C2	0.1 (3)	Cu1—O2—C13—O3	−175.11 (19)
Cu1—N1—C1—C2	−178.37 (14)	Cu1—O2—C13—C5	4.9 (2)
C5—N1—C1—C6	−179.18 (17)	N1—C5—C13—O3	178.1 (2)
Cu1—N1—C1—C6	2.3 (2)	C4—C5—C13—O3	−3.2 (3)
N1—C1—C2—C3	−0.5 (3)	N1—C5—C13—O2	−1.9 (3)
C6—C1—C2—C3	178.64 (18)	C4—C5—C13—O2	176.8 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4B···O1ⁱ	0.70 (3)	2.04 (3)	2.718 (2)	165 (3)
O7—H7B···O6ⁱⁱ	0.72 (3)	2.09 (3)	2.796 (3)	167 (3)
O6—H6A···O3ⁱⁱⁱ	0.74 (3)	1.94 (3)	2.675 (3)	176 (3)
O5—H5B···O4	0.72 (3)	2.07 (3)	2.788 (3)	173 (3)
O4—H4A···N3^iv	0.70 (4)	2.20 (4)	2.878 (2)	163 (3)
O4—H4A···O1^iv	0.70 (4)	2.56 (3)	3.053 (2)	129 (3)
O5—H5A···O7	0.65 (3)	2.10 (4)	2.742 (3)	168 (4)
O7—H7A···O6^v	0.86 (4)	1.95 (4)	2.803 (3)	175 (3)
O6—H6B···O5	0.78 (4)	1.94 (4)	2.718 (3)	178 (3)

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

Experimental details

Crystal data
Chemical formula	[Cu(C₁₃H₈N₄O₃)(H₂O)]·3H₂O
M_r	403.85
Crystal system, space group	Triclinic, P1
Temperature (K)	173
a, b, c (Å)	7.1646 (16), 9.369 (2), 12.647 (3)
α, β, γ (°)	75.313 (4), 78.864 (4), 74.155 (4)
V (Å³)	783.0 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.44
Crystal size (mm)	0.46 × 0.25 × 0.20

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.655, 0.749
No. of measured, independent and observed [I > 2σ(I)] reflections	4689, 3903, 3270
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.097, 1.09
No. of reflections	3903
No. of parameters	259
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.87, −0.34

Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), 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
O4—H4B···O1ⁱ	0.70 (3)	2.04 (3)	2.718 (2)	165 (3)
O7—H7B···O6ⁱⁱ	0.72 (3)	2.09 (3)	2.796 (3)	167 (3)
O6—H6A···O3ⁱⁱⁱ	0.74 (3)	1.94 (3)	2.675 (3)	176 (3)
O5—H5B···O4	0.72 (3)	2.07 (3)	2.788 (3)	173 (3)
O4—H4A···N3^iv	0.70 (4)	2.20 (4)	2.878 (2)	163 (3)
O4—H4A···O1^iv	0.70 (4)	2.56 (3)	3.053 (2)	129 (3)
O5—H5A···O7	0.65 (3)	2.10 (4)	2.742 (3)	168 (4)
O7—H7A···O6^v	0.86 (4)	1.95 (4)	2.803 (3)	175 (3)
O6—H6B···O5	0.78 (4)	1.94 (4)	2.718 (3)	178 (3)

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

Acknowledgements

We are grateful for financial support from the National Science Foundation of Fujian Province of China (No. 2010J01288) and the Fundamental Research Funds for the Central Universities (No. JB-JC1003). We also thank Dr Zhan-bin Wei (Department of Chemistry, Xiamen University) for the data collection.

References

Bruker (1999). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cheng, C.-X., Liu, H.-W., Luo, F.-H., Cao, M.-N. & Hu, Z.-Q. (2007). Acta Cryst. E63, o2899. Web of Science CSD CrossRef IUCr Journals 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
Wu, W. S., Wu, D. S., Cheng, W. D., Zhang, H. & Dai, J. C. (2007). Cryst. Growth Des. 7, 2316–2323. Web of Science CSD CrossRef CAS Google Scholar

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Volume 68| Part 6| June 2012| Page m783

doi:10.1107/S1600536812021447

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

Aqua­[6-carboxyl­ato-N′-(pyridin-2-yl­methyl­­idene)pyridine-2-carbohydrazidato]copper(II) trihydrate

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

Aqua[6-carboxylato-N′-(pyridin-2-ylmethylidene)pyridine-2-carbohydrazidato]copper(II) trihydrate