(3-Acetyl-5-carboxyl­ato-4-methyl-1H-pyrazol-1-ido-κ2N1,O5)aqua­[(pyridin-2-yl)methanamine-κ2N,N′]copper(II)

Malinkin, S.; Pavlenko, V.A.; Gumienna-Kontecka, E.; Prisyazhnaya, E.V.; Iskenderov, T.S.

doi:10.1107/S1600536812044959

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 12| December 2012| Pages m1455-m1456

doi:10.1107/S1600536812044959

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(3-Acetyl-5-carboxylato-4-methyl-1H-pyrazol-1-ido-κ²N¹,O⁵)aqua[(pyridin-2-yl)methanamine-κ²N,N′]copper(II)

Sergey Malinkin,^a ^* Vadim A. Pavlenko,^a Elzbieta Gumienna-Kontecka,^b Elena V. Prisyazhnaya ^c and Turganbay S. Iskenderov ^a

^aDepartment of Chemistry, Kyiv National Taras Shevchenko University, Volodymyrska Str. 64, 01601 Kiev, Ukraine, ^bFaculty of Chemistry, University of Wrocław, F. Joliot-Curie Str. 14, 50-383, Wrocław, Poland, and ^cDepartment of Chemistry, Kyiv National University of Construction and Architecture, Povitroflotsky Avenue 31, 03680 Kiev, Ukraine
^*Correspondence e-mail: malinachem@mail.ru

(Received 18 October 2012; accepted 30 October 2012; online 3 November 2012)

In the title compound, [Cu(C₇H₆N₂O₃)(C₆H₈N₂)(H₂O)], the Cu^II ion is in a distorted square-pyramidal N₃O₂ environment formed by two bidentate chelating ligands in the equatorial coordination sites and one water molecule in the apical direction. In the crystal, O—H⋯O, N—H⋯O and O—H⋯N hydrogen bonds link the complex molecules into a three-dimensional supramolecular network.

Related literature

For applications of related pyrazoles, see: Sachse et al. (2008 ); Penkova et al. (2009 ). For synthetic and structural studies of 3,5-disubstituted 1H-pyrazoles and their metal complexes, see: Malinkin et al. (2011 , 2012 ). For related structures, see: Fritsky et al. (2004 ); Kanderal et al. (2005 ); Krämer & Fritsky (2000 ); Moroz et al. (2010 ); Sliva et al. (1997 ); Wörl et al. (2005a ,b ).

Experimental

Crystal data

[Cu(C₇H₆N₂O₃)(C₆H₈N₂)(H₂O)]
M_r = 355.84
Triclinic, $[P \overline 1]$
a = 7.3063 (2) Å
b = 8.3258 (5) Å
c = 13.1260 (7) Å
α = 90.695 (6)°
β = 105.935 (4)°
γ = 110.232 (4)°
V = 715.32 (6) Å³
Z = 2
Mo Kα radiation
μ = 1.55 mm⁻¹
T = 120 K
0.36 × 0.23 × 0.13 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997 ) T_min = 0.955, T_max = 0.987
13527 measured reflections
5715 independent reflections
4833 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.074
S = 1.07
5715 reflections
217 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.72 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—N1	1.9451 (9)
Cu1—N3	1.9973 (9)
Cu1—N4	2.0048 (10)
Cu1—O1	1.9874 (8)
Cu1—O4	2.3492 (8)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H1O4⋯O2ⁱ	0.78 (2)	1.90 (2)	2.6782 (11)	176 (2)
O4—H2O4⋯N2ⁱⁱ	0.717 (18)	2.049 (18)	2.7581 (12)	169.7 (19)
N4—H1N4⋯O4ⁱⁱ	0.849 (17)	2.055 (17)	2.8542 (12)	156.6 (16)
N4—H2N4⋯O1ⁱⁱⁱ	0.84 (2)	2.50 (2)	3.1017 (13)	128.6 (16)
Symmetry codes: (i) -x+2, -y+1, -z; (ii) -x+1, -y, -z; (iii) -x+1, -y+1, -z.

Data collection: COLLECT (Nonius, 2000 ); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SIR2004 (Burla et al., 2005 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: DIAMOND (Brandenburg, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812044959/xu5636sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812044959/xu5636Isup2.hkl

checkCIF report

Comment top

Pyrazole–derived ligands are widely used in molecular magnetism, bioinorganic modelling and supramolecular chemistry due to their bridging nature and possibility for easy functionalization (Sachse et al., 2008; Penkova et al., 2009). Although usually this family of ligands is used for preparation of polynuclear complexes and coordination polymers, the mononuclear complexes based on pyrazole ligands can also represent an evident interest, especially as building block for preparation of polynuclear species. Herein we report the molecular and crystal structures of the title compound (Fig. 1) obtained in the framework of our synthetic and structural study of unsymmetrical 3,5-disubstituted pyrazolate ligands (Malinkin et al., 2011, 2012).

The title compound, [Cu(C₆H₆N₂O₃)(C₆H₈N₂)(H₂O)] is a mononuclear mixed ligand complex, in which Cu^II ion is in distorted square-pyramidal environment formed by two bidentate (N, O) and (N, N) chelating ligands occupying four equatorial coordination sites and by the apically coordinated water molecule. While 2-aminomethylpyridine acts as a neutral ligand, the (3-acetyl-5-carboxylate)pyrazole ligand is a doubly charged acidoligand exhibiting its traditional (N, O)-chelating binding mode. The equatorial Cu—N and Cu—O bond lengths are in the range 1.9451 (9)–2.0048 (10) Å, whereas the apical Cu—O contact with water molecule is longer (2.3492 (8) Å). The coordination bond lengths Cu—N and Cu—O are typical for square-pyramidal Cu(II) complexes with the amine, deprotonated pyrazolate and carboxylate donors (Sliva et al., 1997; Kanderal et al., 2005). The bite angles around the central atom deviate from an ideal square-planar configuration [e.g. N1—Cu1—O2 = 82.74 (3)°], which is a consequence of the formation of five-membered chelate rings.

The C—N and C—C bond lengths in the pyridine rings are normal for 2-substituted pyridine derivatives (Krämer et al., 2000; Moroz et al., 2010). The C—C, C—N and N—N bond lengths in the pyrazole ring have their typical values (Sachse et al., 2008; Penkova et al., 2009). The C—O bond lengths in the deprotonated carboxylic groups differs significantly (1.2376 (13) and 1.2917 (13)) which is typical for monodentately coordinated carboxylates (Fritsky et al., 2004; Wörl et al., 2005a,b).

Numerous intermolecular O—H···O, N—H···O and O—H···N H-bonds in which the water molecules and the amine groups act as donors while the carboxylic groups, the water oxygen and the pyrazole nitrogen atoms act as acceptors unite the complex molecules in three-dimensional H-bonded network (Fig. 2).

Related literature top

For applications of related pyrazoles, see: Sachse et al. (2008); Penkova et al. (2009). For synthetic and structural studies of 3,5-disubstituted 1H-pyrazoles and their metal complexes, see: Malinkin et al. (2011, 2012). For related structures, see: Fritsky et al. (2004); Kanderal et al. (2005); Krämer & Fritsky (2000); Moroz et al. (2010); Sliva et al. (1997); Wörl et al. (2005a,b).

Experimental top

To the solution of [Cu₄(KA)₄(H₂O)₄] x 4H₂O (Malinkin et al., 2011) (0.100 g, 0.078 mmol) in methanol (8 ml), 2-aminomethylpyridine (0.042 g, 0.391 mmol) was added. The reaction mixture was stirred upon ambient temperature for 10 minutes. Blue crystals suitable for X-ray diffraction were formed upon slow diffusion of diethyl ester into methanolic solution in 24 h (yield 0.028 g, 20%). Elemental analysis calc. (%) for C₁₃H₁₈CuN₄O₄: C 43.63; H 5.07; N 15.66; found: C 44.11; H 5.40; N 15.43.

Computing details top

Data collection: COLLECT (Nonius, 2000); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the title compound, with displacement ellipsoids shown at the 50% probability level. H atoms are drawn as spheres of arbitrary radii.
	Fig. 2. Crystal packing of the title compound. Hydrogen bonds are indicated by dashed lines. H atoms not involved in H-bonds are omitted for clarity. Symmetry codes: (i) -1 + x, -1 + y, z; (ii) 1 - x, 1 - y, -z; (iii) -x, -y, -z; (iv) -1 + x, y, z.

(3-Acetyl-5-carboxylato-4-methyl-1H-pyrazol-1-ido- κ²N¹,O⁵)aqua[(pyridin-2-yl)methanamine- κ²N,N']copper(II) top

Crystal data top

[Cu(C₇H₆N₂O₃)(C₆H₈N₂)(H₂O)]	Z = 2
M_r = 355.84	F(000) = 366
Triclinic, P1	D_x = 1.652 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.3063 (2) Å	Cell parameters from 2567 reflections
b = 8.3258 (5) Å	θ = 3.0–28.5°
c = 13.1260 (7) Å	µ = 1.55 mm⁻¹
α = 90.695 (6)°	T = 120 K
β = 105.935 (4)°	Block, blue
γ = 110.232 (4)°	0.36 × 0.23 × 0.13 mm
V = 715.32 (6) Å³

Data collection top

Nonius KappaCCD diffractometer	5715 independent reflections
Radiation source: fine-focus sealed tube	4833 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromator	R_int = 0.016
Detector resolution: 9 pixels mm^-1	θ_max = 35.1°, θ_min = 2.9°
ϕ scans and ω scans with κ offset	h = −11→9
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)	k = −13→13
T_min = 0.955, T_max = 0.987	l = −20→21
13527 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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.074	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0477P)²] where P = (F_o² + 2F_c²)/3
5715 reflections	(Δ/σ)_max = 0.004
217 parameters	Δρ_max = 0.72 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

[Cu(C₇H₆N₂O₃)(C₆H₈N₂)(H₂O)]	γ = 110.232 (4)°
M_r = 355.84	V = 715.32 (6) Å³
Triclinic, P1	Z = 2
a = 7.3063 (2) Å	Mo Kα radiation
b = 8.3258 (5) Å	µ = 1.55 mm⁻¹
c = 13.1260 (7) Å	T = 120 K
α = 90.695 (6)°	0.36 × 0.23 × 0.13 mm
β = 105.935 (4)°

Data collection top

Nonius KappaCCD diffractometer	5715 independent reflections
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)	4833 reflections with I > 2σ(I)
T_min = 0.955, T_max = 0.987	R_int = 0.016
13527 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	0 restraints
wR(F²) = 0.074	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.72 e Å⁻³
5715 reflections	Δρ_min = −0.32 e Å⁻³
217 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	0.545220 (19)	0.299111 (15)	0.020497 (9)	0.01226 (4)
O1	0.74298 (12)	0.49534 (9)	−0.02392 (6)	0.01456 (14)
O2	0.85228 (12)	0.57781 (10)	−0.16483 (6)	0.01670 (15)
O3	0.22559 (13)	−0.03669 (11)	−0.47062 (6)	0.01945 (16)
O4	0.79221 (13)	0.17036 (10)	0.06402 (6)	0.01427 (14)
N1	0.45340 (14)	0.21529 (11)	−0.13062 (7)	0.01267 (15)
N2	0.30428 (14)	0.08145 (11)	−0.19556 (7)	0.01319 (16)
N3	0.63606 (14)	0.39053 (11)	0.17463 (7)	0.01323 (15)
N4	0.29685 (15)	0.14866 (12)	0.05729 (7)	0.01486 (16)
C1	0.73803 (15)	0.47312 (13)	−0.12234 (8)	0.01244 (17)
C2	0.57544 (15)	0.31343 (12)	−0.18524 (8)	0.01178 (17)
C3	0.50547 (16)	0.24117 (13)	−0.29113 (8)	0.01245 (17)
C4	0.33336 (16)	0.09471 (13)	−0.29373 (8)	0.01263 (17)
C5	0.19154 (17)	−0.03454 (13)	−0.38437 (8)	0.01427 (18)
C6	0.00133 (18)	−0.16234 (15)	−0.36737 (9)	0.0198 (2)
H6A	−0.0784	−0.2390	−0.4318	0.030*
H6B	−0.0776	−0.1019	−0.3486	0.030*
H6C	0.0386	−0.2276	−0.3108	0.030*
C7	0.58880 (17)	0.30559 (15)	−0.38093 (9)	0.0172 (2)
H7A	0.7016	0.4131	−0.3560	0.026*
H7B	0.4839	0.3224	−0.4374	0.026*
H7C	0.6345	0.2227	−0.4070	0.026*
C8	0.79957 (17)	0.53218 (14)	0.22340 (9)	0.01563 (18)
H8	0.8738	0.6015	0.1826	0.019*
C9	0.86018 (18)	0.57730 (15)	0.33271 (9)	0.0189 (2)
H9	0.9714	0.6771	0.3649	0.023*
C10	0.75138 (19)	0.47038 (16)	0.39326 (9)	0.0204 (2)
H10	0.7917	0.4959	0.4670	0.024*
C11	0.58221 (19)	0.32535 (15)	0.34283 (9)	0.0187 (2)
H11	0.5067	0.2531	0.3821	0.022*
C12	0.52770 (17)	0.28997 (14)	0.23287 (8)	0.01449 (18)
C13	0.34690 (17)	0.13433 (14)	0.17266 (9)	0.01577 (19)
H13A	0.3780	0.0310	0.1864	0.019*
H13B	0.2302	0.1252	0.1970	0.019*
H1N4	0.236 (3)	0.048 (2)	0.0232 (14)	0.025 (4)*
H2O4	0.773 (3)	0.114 (2)	0.1040 (14)	0.024 (4)*
H2N4	0.207 (3)	0.194 (3)	0.0389 (16)	0.040 (5)*
H1O4	0.895 (3)	0.247 (3)	0.0914 (17)	0.041 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.01549 (7)	0.00997 (6)	0.00858 (6)	0.00179 (4)	0.00302 (4)	−0.00059 (4)
O1	0.0177 (4)	0.0105 (3)	0.0116 (3)	0.0019 (3)	0.0025 (3)	0.0001 (2)
O2	0.0156 (4)	0.0145 (3)	0.0161 (4)	0.0008 (3)	0.0045 (3)	0.0034 (3)
O3	0.0233 (4)	0.0230 (4)	0.0110 (3)	0.0081 (3)	0.0041 (3)	−0.0014 (3)
O4	0.0171 (4)	0.0098 (3)	0.0128 (3)	0.0018 (3)	0.0037 (3)	0.0014 (2)
N1	0.0140 (4)	0.0102 (4)	0.0107 (4)	0.0014 (3)	0.0029 (3)	0.0003 (3)
N2	0.0157 (4)	0.0109 (4)	0.0094 (4)	0.0016 (3)	0.0023 (3)	−0.0001 (3)
N3	0.0147 (4)	0.0134 (4)	0.0118 (4)	0.0059 (3)	0.0033 (3)	−0.0005 (3)
N4	0.0167 (4)	0.0139 (4)	0.0116 (4)	0.0033 (3)	0.0037 (3)	−0.0019 (3)
C1	0.0123 (4)	0.0106 (4)	0.0132 (4)	0.0039 (3)	0.0022 (3)	0.0015 (3)
C2	0.0128 (4)	0.0099 (4)	0.0110 (4)	0.0026 (3)	0.0030 (3)	0.0010 (3)
C3	0.0137 (4)	0.0133 (4)	0.0102 (4)	0.0047 (3)	0.0037 (3)	0.0015 (3)
C4	0.0155 (4)	0.0120 (4)	0.0097 (4)	0.0041 (3)	0.0036 (3)	0.0014 (3)
C5	0.0168 (5)	0.0124 (4)	0.0122 (4)	0.0055 (3)	0.0019 (4)	−0.0002 (3)
C6	0.0207 (5)	0.0167 (5)	0.0146 (5)	0.0008 (4)	0.0015 (4)	−0.0017 (3)
C7	0.0186 (5)	0.0204 (5)	0.0125 (4)	0.0050 (4)	0.0070 (4)	0.0023 (3)
C8	0.0142 (4)	0.0163 (5)	0.0149 (5)	0.0055 (4)	0.0021 (4)	−0.0029 (3)
C9	0.0171 (5)	0.0204 (5)	0.0164 (5)	0.0074 (4)	0.0001 (4)	−0.0055 (4)
C10	0.0227 (5)	0.0260 (6)	0.0117 (5)	0.0112 (4)	0.0012 (4)	−0.0034 (4)
C11	0.0230 (5)	0.0229 (5)	0.0117 (5)	0.0097 (4)	0.0057 (4)	0.0009 (4)
C12	0.0182 (5)	0.0156 (4)	0.0119 (4)	0.0087 (4)	0.0047 (4)	0.0005 (3)
C13	0.0191 (5)	0.0152 (4)	0.0133 (4)	0.0055 (4)	0.0062 (4)	0.0017 (3)

Geometric parameters (Å, º) top

Cu1—N1	1.9451 (9)	C3—C7	1.4937 (15)
Cu1—N3	1.9973 (9)	C4—C5	1.4724 (15)
Cu1—N4	2.0048 (10)	C5—C6	1.5055 (16)
Cu1—O1	1.9874 (8)	C6—H6A	0.9600
Cu1—O4	2.3492 (8)	C6—H6B	0.9600
O1—C1	1.2917 (13)	C6—H6C	0.9600
O2—C1	1.2376 (13)	C7—H7A	0.9600
O3—C5	1.2252 (13)	C7—H7B	0.9600
O4—H2O4	0.717 (18)	C7—H7C	0.9600
O4—H1O4	0.78 (2)	C8—C9	1.3852 (15)
N1—N2	1.3351 (12)	C8—H8	0.9300
N1—C2	1.3558 (13)	C9—C10	1.3895 (18)
N2—C4	1.3622 (13)	C9—H9	0.9300
N3—C12	1.3422 (14)	C10—C11	1.3868 (17)
N3—C8	1.3473 (14)	C10—H10	0.9300
N4—C13	1.4736 (14)	C11—C12	1.3862 (15)
N4—H1N4	0.849 (17)	C11—H11	0.9300
N4—H2N4	0.84 (2)	C12—C13	1.5056 (15)
C1—C2	1.4842 (14)	C13—H13A	0.9700
C2—C3	1.3899 (14)	C13—H13B	0.9700
C3—C4	1.4087 (14)

N1—Cu1—O1	82.74 (3)	C3—C4—C5	129.26 (9)
N1—Cu1—N3	178.33 (4)	O3—C5—C4	121.35 (10)
O1—Cu1—N3	96.71 (3)	O3—C5—C6	121.30 (10)
N1—Cu1—N4	97.67 (4)	C4—C5—C6	117.34 (9)
O1—Cu1—N4	162.48 (4)	C5—C6—H6A	109.5
N3—Cu1—N4	82.38 (4)	C5—C6—H6B	109.5
N1—Cu1—O4	94.29 (3)	H6A—C6—H6B	109.5
O1—Cu1—O4	88.99 (3)	C5—C6—H6C	109.5
N3—Cu1—O4	87.27 (3)	H6A—C6—H6C	109.5
N4—Cu1—O4	108.40 (4)	H6B—C6—H6C	109.5
C1—O1—Cu1	113.96 (6)	C3—C7—H7A	109.5
Cu1—O4—H2O4	109.7 (14)	C3—C7—H7B	109.5
Cu1—O4—H1O4	104.8 (15)	H7A—C7—H7B	109.5
H2O4—O4—H1O4	106 (2)	C3—C7—H7C	109.5
N2—N1—C2	110.24 (8)	H7A—C7—H7C	109.5
N2—N1—Cu1	136.81 (7)	H7B—C7—H7C	109.5
C2—N1—Cu1	112.89 (7)	N3—C8—C9	121.77 (11)
N1—N2—C4	106.46 (8)	N3—C8—H8	119.1
C12—N3—C8	119.53 (9)	C9—C8—H8	119.1
C12—N3—Cu1	114.19 (7)	C8—C9—C10	118.62 (11)
C8—N3—Cu1	126.10 (8)	C8—C9—H9	120.7
C13—N4—Cu1	110.41 (7)	C10—C9—H9	120.7
C13—N4—H1N4	109.1 (12)	C9—C10—C11	119.49 (10)
Cu1—N4—H1N4	116.1 (11)	C9—C10—H10	120.3
C13—N4—H2N4	110.5 (13)	C11—C10—H10	120.3
Cu1—N4—H2N4	107.6 (13)	C12—C11—C10	118.78 (11)
H1N4—N4—H2N4	102.8 (17)	C12—C11—H11	120.6
O2—C1—O1	124.10 (9)	C10—C11—H11	120.6
O2—C1—C2	120.82 (9)	N3—C12—C11	121.76 (10)
O1—C1—C2	115.01 (9)	N3—C12—C13	116.41 (9)
N1—C2—C3	109.44 (9)	C11—C12—C13	121.81 (10)
N1—C2—C1	114.77 (8)	N4—C13—C12	110.16 (9)
C3—C2—C1	135.63 (9)	N4—C13—H13A	109.6
C2—C3—C4	103.02 (9)	C12—C13—H13A	109.6
C2—C3—C7	128.53 (10)	N4—C13—H13B	109.6
C4—C3—C7	128.43 (9)	C12—C13—H13B	109.6
N2—C4—C3	110.82 (9)	H13A—C13—H13B	108.1
N2—C4—C5	119.92 (9)

N1—Cu1—O1—C1	−6.64 (7)	O2—C1—C2—N1	−176.16 (10)
N3—Cu1—O1—C1	174.95 (7)	O1—C1—C2—N1	1.03 (13)
N4—Cu1—O1—C1	−99.11 (13)	O2—C1—C2—C3	−1.25 (19)
O4—Cu1—O1—C1	87.82 (7)	O1—C1—C2—C3	175.94 (11)
O1—Cu1—N1—N2	−176.05 (11)	N1—C2—C3—C4	0.34 (11)
N3—Cu1—N1—N2	−105.3 (12)	C1—C2—C3—C4	−174.76 (11)
N4—Cu1—N1—N2	−13.71 (11)	N1—C2—C3—C7	178.83 (10)
O4—Cu1—N1—N2	95.53 (11)	C1—C2—C3—C7	3.7 (2)
O1—Cu1—N1—C2	7.03 (7)	N1—N2—C4—C3	−0.11 (12)
N3—Cu1—N1—C2	77.8 (12)	N1—N2—C4—C5	−179.58 (9)
N4—Cu1—N1—C2	169.36 (7)	C2—C3—C4—N2	−0.14 (12)
O4—Cu1—N1—C2	−81.40 (7)	C7—C3—C4—N2	−178.64 (10)
C2—N1—N2—C4	0.33 (12)	C2—C3—C4—C5	179.26 (10)
Cu1—N1—N2—C4	−176.65 (8)	C7—C3—C4—C5	0.77 (19)
N1—Cu1—N3—C12	107.5 (12)	N2—C4—C5—O3	−172.17 (10)
O1—Cu1—N3—C12	178.03 (7)	C3—C4—C5—O3	8.47 (18)
N4—Cu1—N3—C12	15.67 (8)	N2—C4—C5—C6	8.75 (15)
O4—Cu1—N3—C12	−93.31 (8)	C3—C4—C5—C6	−170.61 (11)
N1—Cu1—N3—C8	−77.6 (12)	C12—N3—C8—C9	0.21 (16)
O1—Cu1—N3—C8	−7.01 (9)	Cu1—N3—C8—C9	−174.50 (8)
N4—Cu1—N3—C8	−169.37 (9)	N3—C8—C9—C10	1.62 (17)
O4—Cu1—N3—C8	81.65 (9)	C8—C9—C10—C11	−2.07 (18)
N1—Cu1—N4—C13	158.90 (7)	C9—C10—C11—C12	0.76 (18)
O1—Cu1—N4—C13	−110.94 (12)	C8—N3—C12—C11	−1.61 (16)
N3—Cu1—N4—C13	−22.79 (7)	Cu1—N3—C12—C11	173.71 (8)
O4—Cu1—N4—C13	61.76 (8)	C8—N3—C12—C13	179.85 (9)
Cu1—O1—C1—O2	−178.07 (8)	Cu1—N3—C12—C13	−4.84 (12)
Cu1—O1—C1—C2	4.84 (11)	C10—C11—C12—N3	1.12 (17)
N2—N1—C2—C3	−0.44 (12)	C10—C11—C12—C13	179.58 (10)
Cu1—N1—C2—C3	177.32 (7)	Cu1—N4—C13—C12	25.68 (10)
N2—N1—C2—C1	175.79 (8)	N3—C12—C13—N4	−14.04 (13)
Cu1—N1—C2—C1	−6.45 (11)	C11—C12—C13—N4	167.42 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H1O4···O2ⁱ	0.78 (2)	1.90 (2)	2.6782 (11)	176 (2)
O4—H2O4···N2ⁱⁱ	0.717 (18)	2.049 (18)	2.7581 (12)	169.7 (19)
N4—H1N4···O4ⁱⁱ	0.849 (17)	2.055 (17)	2.8542 (12)	156.6 (16)
N4—H2N4···O1ⁱⁱⁱ	0.84 (2)	2.50 (2)	3.1017 (13)	128.6 (16)

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

Experimental details

Crystal data
Chemical formula	[Cu(C₇H₆N₂O₃)(C₆H₈N₂)(H₂O)]
M_r	355.84
Crystal system, space group	Triclinic, P1
Temperature (K)	120
a, b, c (Å)	7.3063 (2), 8.3258 (5), 13.1260 (7)
α, β, γ (°)	90.695 (6), 105.935 (4), 110.232 (4)
V (Å³)	715.32 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.55
Crystal size (mm)	0.36 × 0.23 × 0.13

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)
T_min, T_max	0.955, 0.987
No. of measured, independent and observed [I > 2σ(I)] reflections	13527, 5715, 4833
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.810

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.074, 1.07
No. of reflections	5715
No. of parameters	217
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.72, −0.32

Computer programs: COLLECT (Nonius, 2000), DENZO/SCALEPACK (Otwinowski & Minor, 1997), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2009).

Selected bond lengths (Å) top

Cu1—N1	1.9451 (9)	Cu1—O1	1.9874 (8)
Cu1—N3	1.9973 (9)	Cu1—O4	2.3492 (8)
Cu1—N4	2.0048 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H1O4···O2ⁱ	0.78 (2)	1.90 (2)	2.6782 (11)	176 (2)
O4—H2O4···N2ⁱⁱ	0.717 (18)	2.049 (18)	2.7581 (12)	169.7 (19)
N4—H1N4···O4ⁱⁱ	0.849 (17)	2.055 (17)	2.8542 (12)	156.6 (16)
N4—H2N4···O1ⁱⁱⁱ	0.84 (2)	2.50 (2)	3.1017 (13)	128.6 (16)

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

Acknowledgements

Financial support from the State Fund for Fundamental Researches of Ukraine (grant No. F40.3/041) and the Swedish Institute (Visby Program) is gratefully acknowledged.

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