(3-Acetyl-5-carboxyl-ato-4-methyl-1H-pyrazol-1-ido-κ(2) N (1),O (5))aqua-[(pyridin-2-yl)methanamine-κ(2) N,N']copper(II).

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 mol-ecule in the apical direction. In the crystal, O-H⋯O, N-H⋯O and O-H⋯N hydrogen bonds link the complex mol-ecules into a three-dimensional supra-molecular 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 = 355.84

Triclinic,

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[F 2 > 2σ(F 2)] = 0.027

wR(F 2) = 0.074

S = 1.07

5715 reflections

217 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.72 e Å−3

Δρmin = −0.32 e Å−3

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.

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812044959/xu5636sup1.cif

Click here for additional data file.

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Cu(C7H6N2O3)(C6H8N2)(H2O)]	Z = 2
Mr = 355.84	F(000) = 366
Triclinic, P1	Dx = 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

Nonius KappaCCD diffractometer	5715 independent reflections
Radiation source: fine-focus sealed tube	4833 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromator	Rint = 0.016
Detector resolution: 9 pixels mm-1	θmax = 35.1°, θmin = 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
Tmin = 0.955, Tmax = 0.987	l = −20→21
13527 measured reflections

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(Fo2) + (0.0477P)2] where P = (Fo2 + 2Fc2)/3
5715 reflections	(Δ/σ)max = 0.004
217 parameters	Δρmax = 0.72 e Å−3
0 restraints	Δρmin = −0.32 e Å−3

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.

	x	y	z	Uiso*/Ueq
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)*

	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)

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)

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)

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) ; (ii) ; (iii) .