Aqua-bis-(3,5-dimethyl-1H-pyrazole-κN)(oxydiacetato-κO,O',O'')copper(II) dihydrate.

In the title compound, [Cu(C(4)H(4)O(5))(C(5)H(8)N(2))(2)(H(2)O)]·2H(2)O, the Cu(II) cation assumes a distorted octa-hedral coordination geometry formed by two 3,5-dimethyl-1H-pyrazole ligands, one oxydiacetate (ODA) dianion and one coordinated water mol-ecule. The tridentate ODA ligand chelates to the Cu cation in a facial configuration with a longer Cu-O bond [2.597 (3) Å], and both chelating rings display envelope conformations. In the mol-ecule, the two pyrazole rings are twisted with respect to each other at a dihedral angle of 57.5 (3)°. Extensive inter-molecular O-H⋯O and N-H⋯O hydrogen bonding is present in the crystal structure.

Related literature

For background to pyrazole compounds, see: Haanstra et al. (1990 ▶); Mukherjee (2000 ▶). For the structure of a related n class="Chemical">ODA complex, see: Wu et al. (2003 ▶).

Experimental

Crystal data

[Cu(C4H4O5)(C5n class="Species">H8N2)2(H2O)]·2H2O

M = 441.93

Triclinic,

a = 7.5502 (12) Å

b = 10.6264 (17) Å

c = 12.687 (2) Å

α = 92.219 (2)°

β = 104.880 (2)°

γ = 93.769 (2)°

V = 980.0 (3) Å3

Z = 2

Mo Kα radiation

μ = 1.16 mm−1

T = 295 K

0.25 × 0.19 × 0.15 mm

Data collection

Bruker SMART 1000 diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.767, T max = 0.840

5085 measured reflections

3389 independent reflections

2663 reflections with I > 2σ(I)

R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.051

wR(F 2) = 0.133

S = 1.05

3389 reflections

244 parameters

H-atom parameters constrained

Δρmax = 0.97 e Å−3

Δρmin = −0.64 e Å−3

Data collection: SMART (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAIn class="Chemical">NT; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811015169/xu5195sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811015169/xu5195Isup2.hkl

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

[Cu(C4H4O5)(C5H8N2)2(H2O)]·2H2O	Z = 2
Mr = 441.93	F(000) = 462
Triclinic, P1	Dx = 1.498 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.5502 (12) Å	Cell parameters from 2650 reflections
b = 10.6264 (17) Å	θ = 2.0–25.0°
c = 12.687 (2) Å	µ = 1.16 mm−1
α = 92.219 (2)°	T = 295 K
β = 104.880 (2)°	Prism, blue
γ = 93.769 (2)°	0.25 × 0.19 × 0.15 mm
V = 980.0 (3) Å3

Bruker SMART 1000 diffractometer	3389 independent reflections
Radiation source: fine-focus sealed tube	2663 reflections with I > 2σ(I)
graphite	Rint = 0.023
ω scans	θmax = 25.0°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −8→8
Tmin = 0.767, Tmax = 0.840	k = −10→12
5085 measured reflections	l = −15→12

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.133	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0597P)2 + 1.5674P] where P = (Fo2 + 2Fc2)/3
3389 reflections	(Δ/σ)max < 0.001
244 parameters	Δρmax = 0.97 e Å−3
0 restraints	Δρmin = −0.64 e Å−3

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.

	x	y	z	Uiso*/Ueq
Cu	0.03356 (7)	0.40147 (5)	0.29056 (4)	0.02518 (19)
O1	0.2664 (4)	0.5043 (3)	0.4150 (2)	0.0366 (8)
H1A	0.3378	0.5675	0.4096	0.055*
H1B	0.2773	0.4952	0.4826	0.055*
O31	−0.1202 (4)	0.5234 (3)	0.3466 (2)	0.0273 (7)
O32	−0.3929 (4)	0.5595 (3)	0.3709 (2)	0.0426 (9)
O33	0.0910 (4)	0.5157 (3)	0.1841 (2)	0.0346 (7)
O34	0.0182 (5)	0.6530 (3)	0.0567 (3)	0.0453 (9)
O35	−0.2706 (4)	0.4198 (3)	0.1414 (2)	0.0373 (8)
N11	0.1915 (5)	0.2768 (3)	0.2429 (3)	0.0283 (8)
N12	0.1713 (5)	0.2466 (4)	0.1347 (3)	0.0334 (9)
H12A	0.1038	0.2781	0.0888	0.040*
N21	−0.0679 (5)	0.2709 (3)	0.3726 (3)	0.0291 (8)
N22	−0.0561 (5)	0.2859 (3)	0.4817 (3)	0.0305 (9)
H22A	−0.0139	0.3484	0.5105	0.037*
C11	0.2563 (7)	0.1441 (4)	0.1202 (4)	0.0381 (12)
C12	0.3380 (7)	0.1053 (5)	0.2215 (4)	0.0395 (12)
H12	0.4079	0.0362	0.2375	0.047*
C13	0.2950 (6)	0.1905 (4)	0.2959 (4)	0.0324 (10)
C14	0.2536 (9)	0.0916 (6)	0.0080 (4)	0.0608 (17)
H14A	0.1822	0.1420	−0.0459	0.091*
H14B	0.1998	0.0062	−0.0022	0.091*
H14C	0.3770	0.0932	0.0005	0.091*
C15	0.3537 (8)	0.1923 (5)	0.4175 (4)	0.0482 (14)
H15A	0.3035	0.2616	0.4476	0.072*
H15B	0.4854	0.2020	0.4417	0.072*
H15C	0.3099	0.1144	0.4414	0.072*
C21	−0.1237 (7)	0.1816 (4)	0.5189 (4)	0.0326 (10)
C22	−0.1789 (7)	0.0966 (4)	0.4317 (4)	0.0379 (12)
H22	−0.2307	0.0148	0.4321	0.046*
C23	−0.1438 (6)	0.1538 (4)	0.3425 (4)	0.0299 (10)
C24	−0.1240 (9)	0.1774 (6)	0.6367 (4)	0.0567 (16)
H24A	−0.0728	0.2569	0.6743	0.085*
H24B	−0.0514	0.1112	0.6692	0.085*
H24C	−0.2478	0.1614	0.6422	0.085*
C25	−0.1799 (7)	0.1017 (5)	0.2272 (4)	0.0418 (12)
H25A	−0.1402	0.1643	0.1838	0.063*
H25B	−0.3091	0.0794	0.1984	0.063*
H25C	−0.1135	0.0280	0.2253	0.063*
C31	−0.2937 (6)	0.5131 (4)	0.3171 (3)	0.0293 (10)
C32	−0.3894 (6)	0.4403 (5)	0.2100 (4)	0.0374 (11)
H32A	−0.4406	0.3592	0.2257	0.045*
H32B	−0.4904	0.4865	0.1712	0.045*
C33	−0.2287 (7)	0.5301 (5)	0.0895 (4)	0.0425 (13)
H33A	−0.2890	0.5996	0.1134	0.051*
H33B	−0.2789	0.5156	0.0112	0.051*
C34	−0.0253 (7)	0.5683 (4)	0.1126 (3)	0.0328 (11)
O1W	0.3682 (9)	0.7458 (7)	0.0748 (6)	0.147 (3)
H1WA	0.2788	0.6940	0.0771	0.221*
H1WB	0.3837	0.7389	0.0109	0.221*
O2W	0.4093 (11)	0.1824 (6)	0.7222 (6)	0.155 (3)
H2WA	0.3974	0.2410	0.6778	0.232*
H2WB	0.4868	0.2111	0.7836	0.232*

	U11	U22	U33	U12	U13	U23
Cu	0.0271 (3)	0.0284 (3)	0.0217 (3)	0.0038 (2)	0.0086 (2)	0.0027 (2)
O1	0.0293 (18)	0.049 (2)	0.0288 (16)	−0.0038 (15)	0.0052 (14)	−0.0014 (15)
O31	0.0236 (17)	0.0296 (16)	0.0273 (15)	0.0019 (13)	0.0050 (13)	−0.0020 (13)
O32	0.0310 (19)	0.067 (2)	0.0319 (17)	0.0094 (17)	0.0119 (15)	−0.0013 (16)
O33	0.0377 (19)	0.0389 (19)	0.0288 (16)	0.0048 (15)	0.0104 (14)	0.0091 (14)
O34	0.058 (2)	0.045 (2)	0.0338 (18)	0.0047 (18)	0.0123 (17)	0.0152 (16)
O35	0.039 (2)	0.044 (2)	0.0291 (16)	−0.0013 (16)	0.0119 (14)	−0.0023 (14)
N11	0.031 (2)	0.033 (2)	0.0234 (18)	0.0047 (17)	0.0108 (16)	0.0030 (15)
N12	0.039 (2)	0.038 (2)	0.0264 (19)	0.0089 (18)	0.0127 (17)	0.0060 (17)
N21	0.033 (2)	0.034 (2)	0.0227 (18)	0.0052 (17)	0.0113 (16)	0.0016 (16)
N22	0.038 (2)	0.028 (2)	0.0274 (19)	0.0005 (17)	0.0130 (17)	−0.0018 (15)
C11	0.043 (3)	0.034 (3)	0.041 (3)	0.008 (2)	0.019 (2)	−0.002 (2)
C12	0.039 (3)	0.037 (3)	0.049 (3)	0.012 (2)	0.019 (2)	0.006 (2)
C13	0.030 (3)	0.036 (3)	0.035 (2)	0.007 (2)	0.013 (2)	0.007 (2)
C14	0.083 (5)	0.059 (4)	0.047 (3)	0.018 (3)	0.026 (3)	−0.009 (3)
C15	0.051 (3)	0.057 (3)	0.038 (3)	0.023 (3)	0.008 (2)	0.012 (2)
C21	0.037 (3)	0.033 (3)	0.033 (2)	0.006 (2)	0.015 (2)	0.009 (2)
C22	0.048 (3)	0.028 (3)	0.040 (3)	−0.004 (2)	0.018 (2)	0.003 (2)
C23	0.027 (2)	0.029 (2)	0.035 (2)	0.0009 (19)	0.0103 (19)	−0.0027 (19)
C24	0.081 (5)	0.057 (4)	0.038 (3)	−0.002 (3)	0.026 (3)	0.011 (3)
C25	0.043 (3)	0.042 (3)	0.038 (3)	−0.005 (2)	0.012 (2)	−0.009 (2)
C31	0.028 (3)	0.037 (3)	0.023 (2)	0.005 (2)	0.0072 (19)	0.0093 (19)
C32	0.028 (3)	0.055 (3)	0.029 (2)	−0.003 (2)	0.009 (2)	−0.003 (2)
C33	0.041 (3)	0.058 (3)	0.031 (2)	0.014 (3)	0.009 (2)	0.012 (2)
C34	0.044 (3)	0.036 (3)	0.020 (2)	0.006 (2)	0.011 (2)	−0.002 (2)
O1W	0.111 (5)	0.152 (6)	0.182 (7)	−0.049 (5)	0.062 (5)	−0.026 (5)
O2W	0.176 (8)	0.094 (5)	0.180 (7)	−0.003 (5)	0.022 (6)	0.031 (5)

Cu—O33	1.960 (3)	C14—H14B	0.9600
Cu—N21	1.995 (4)	C14—H14C	0.9600
Cu—N11	2.015 (3)	C15—H15A	0.9600
Cu—O31	2.020 (3)	C15—H15B	0.9600
Cu—O1	2.228 (3)	C15—H15C	0.9600
O1—H1A	0.8500	C21—C22	1.360 (6)
O1—H1B	0.8500	C21—C24	1.498 (6)
O31—C31	1.263 (5)	C22—C23	1.381 (6)
O32—C31	1.246 (5)	C22—H22	0.9300
O33—C34	1.266 (5)	C23—C25	1.495 (6)
O34—C34	1.245 (5)	C24—H24A	0.9600
O35—C32	1.421 (5)	C24—H24B	0.9600
O35—C33	1.424 (6)	C24—H24C	0.9600
N11—C13	1.332 (5)	C25—H25A	0.9600
N11—N12	1.364 (5)	C25—H25B	0.9600
N12—C11	1.329 (6)	C25—H25C	0.9600
N12—H12A	0.7732	C31—C32	1.519 (6)
N21—C23	1.334 (6)	C32—H32A	0.9700
N21—N22	1.366 (5)	C32—H32B	0.9700
N22—C21	1.342 (6)	C33—C34	1.512 (7)
N22—H22A	0.7550	C33—H33A	0.9700
C11—C12	1.367 (7)	C33—H33B	0.9700
C11—C14	1.503 (6)	O1W—H1WA	0.8499
C12—C13	1.395 (6)	O1W—H1WB	0.8500
C12—H12	0.9300	O2W—H2WA	0.8499
C13—C15	1.491 (6)	O2W—H2WB	0.8748
C14—H14A	0.9600
O33—Cu—N21	168.02 (14)	H15A—C15—H15B	109.5
O33—Cu—N11	88.43 (13)	C13—C15—H15C	109.5
N21—Cu—N11	91.13 (14)	H15A—C15—H15C	109.5
O33—Cu—O31	94.10 (12)	H15B—C15—H15C	109.5
N21—Cu—O31	86.76 (13)	N22—C21—C22	106.1 (4)
N11—Cu—O31	176.92 (12)	N22—C21—C24	120.3 (4)
O33—Cu—O1	87.35 (12)	C22—C21—C24	133.6 (5)
N21—Cu—O1	104.62 (13)	C21—C22—C23	107.5 (4)
N11—Cu—O1	94.36 (13)	C21—C22—H22	126.2
O31—Cu—O1	84.00 (12)	C23—C22—H22	126.2
Cu—O1—H1A	130.6	N21—C23—C22	109.6 (4)
Cu—O1—H1B	120.0	N21—C23—C25	121.4 (4)
H1A—O1—H1B	107.7	C22—C23—C25	129.0 (4)
C31—O31—Cu	122.4 (3)	C21—C24—H24A	109.5
C34—O33—Cu	125.6 (3)	C21—C24—H24B	109.5
C32—O35—C33	113.1 (4)	H24A—C24—H24B	109.5
C13—N11—N12	105.3 (3)	C21—C24—H24C	109.5
C13—N11—Cu	132.4 (3)	H24A—C24—H24C	109.5
N12—N11—Cu	120.7 (3)	H24B—C24—H24C	109.5
C11—N12—N11	111.5 (4)	C23—C25—H25A	109.5
C11—N12—H12A	124.7	C23—C25—H25B	109.5
N11—N12—H12A	122.8	H25A—C25—H25B	109.5
C23—N21—N22	105.4 (3)	C23—C25—H25C	109.5
C23—N21—Cu	131.4 (3)	H25A—C25—H25C	109.5
N22—N21—Cu	123.0 (3)	H25B—C25—H25C	109.5
C21—N22—N21	111.4 (4)	O32—C31—O31	123.9 (4)
C21—N22—H22A	131.2	O32—C31—C32	117.4 (4)
N21—N22—H22A	117.3	O31—C31—C32	118.8 (4)
N12—C11—C12	107.3 (4)	O35—C32—C31	113.2 (4)
N12—C11—C14	121.6 (4)	O35—C32—H32A	108.9
C12—C11—C14	131.1 (5)	C31—C32—H32A	108.9
C11—C12—C13	105.8 (4)	O35—C32—H32B	108.9
C11—C12—H12	127.1	C31—C32—H32B	108.9
C13—C12—H12	127.1	H32A—C32—H32B	107.7
N11—C13—C12	110.1 (4)	O35—C33—C34	114.0 (4)
N11—C13—C15	122.3 (4)	O35—C33—H33A	108.8
C12—C13—C15	127.6 (4)	C34—C33—H33A	108.8
C11—C14—H14A	109.5	O35—C33—H33B	108.8
C11—C14—H14B	109.5	C34—C33—H33B	108.8
H14A—C14—H14B	109.5	H33A—C33—H33B	107.7
C11—C14—H14C	109.5	O34—C34—O33	123.1 (5)
H14A—C14—H14C	109.5	O34—C34—C33	115.8 (4)
H14B—C14—H14C	109.5	O33—C34—C33	121.1 (4)
C13—C15—H15A	109.5	H1WA—O1W—H1WB	107.7
C13—C15—H15B	109.5	H2WA—O2W—H2WB	108.2

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O32i	0.85	2.21	2.798 (5)	126
O1—H1B···O32ii	0.85	1.97	2.764 (5)	156
O1W—H1WA···O34	0.85	1.93	2.707 (8)	151
O1W—H1WB···O35iii	0.85	2.45	3.097 (8)	133
O2W—H2WA···O32ii	0.85	2.23	3.024 (8)	156
O2W—H2WB···O1Wiv	0.88	1.87	2.741 (10)	171
N12—H12A···O34iii	0.77	2.03	2.773 (5)	163
N22—H22A···O31ii	0.75	2.20	2.904 (5)	155

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O32i	0.85	2.21	2.798 (5)	126
O1—H1B⋯O32ii	0.85	1.97	2.764 (5)	156
O1W—H1WA⋯O34	0.85	1.93	2.707 (8)	151
O1W—H1WB⋯O35iii	0.85	2.45	3.097 (8)	133
O2W—H2WA⋯O32ii	0.85	2.23	3.024 (8)	156
O2W—H2WB⋯O1Wiv	0.88	1.87	2.741 (10)	171
N12—H12A⋯O34iii	0.77	2.03	2.773 (5)	163
N22—H22A⋯O31ii	0.75	2.20	2.904 (5)	155

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .