Dipyridinium diaqua-bis-(pyrazole-3,5-di-carboxyl-ato-κ(2) N,O)cuprate(II) dihydrate.

In the mononuclear title salt, (C5H6N)2[Cu(C5H2N2O4)2(H2O)2]·2H2O, the Cu(II) ion is located on an inversion centre and is coordinated by two chelating pyrazole-3,5-dicarboxyl-ate anions and two water mol-ecules, forming a Jahn-Teller-distorted CuN2O4 octa-hedron. O-H⋯O and N-H⋯O hydrogen bonds are formed between water mol-ecules, complex anions and the pyridine counter-cations, leading to the formation of layers parallel to (100). The layers are held together by weak C-H⋯O hydrogen bonds.

Related literature

For more information on ligands derived from pyrazole-3,5-dicarb­oxy­lic acid, see: King et al. (2004 ▶). For the bond-valence method, see: Brown (2002 ▶).

Experimental

Crystal data

(C5H6N)2[Cu(C5H2N2O4)2(H2O)2]·2H2O

M = 603.99

Monoclinic,

a = 9.3531 (4) Å

b = 7.3521 (1) Å

c = 17.9903 (7) Å

β = 95.600 (2)°

V = 1231.20 (7) Å3

Z = 2

Mo Kα radiation

μ = 0.96 mm−1

T = 273 K

0.34 × 0.18 × 0.06 mm

Data collection

Bruker SMART CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.735, T max = 0.944

3386 measured reflections

2106 independent reflections

1802 reflections with I > 2σ(I)

R int = 0.038

Refinement

R[F 2 > 2σ(F 2)] = 0.075

wR(F 2) = 0.154

S = 1.26

2106 reflections

193 parameters

5 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.50 e Å−3

Δρmin = −0.41 e Å−3

Data collection: SMART (Siemens, 1998 ▶); cell refinement: SAINT (Siemens, 1998 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: WinGX (Farrugia, 2012 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812046508/wm2698sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812046508/wm2698Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536812046508/wm2698Isup4.cdx

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

(C5H6N)2[Cu(C5H2N2O4)2(H2O)2]·2H2O	F(000) = 622
Mr = 603.99	Dx = 1.629 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1917 reflections
a = 9.3531 (4) Å	θ = 2.2–25.0°
b = 7.3521 (1) Å	µ = 0.96 mm−1
c = 17.9903 (7) Å	T = 273 K
β = 95.600 (2)°	Prism, blue
V = 1231.20 (7) Å3	0.34 × 0.18 × 0.06 mm
Z = 2

Bruker SMART CCD diffractometer	2106 independent reflections
Radiation source: fine-focus sealed tube	1802 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.038
phi and ω scans	θmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→9
Tmin = 0.735, Tmax = 0.944	k = −8→7
3386 measured reflections	l = −21→10

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)] = 0.075	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.154	H atoms treated by a mixture of independent and constrained refinement
S = 1.26	w = 1/[σ2(Fo2) + (0.0117P)2 + 6.7689P] where P = (Fo2 + 2Fc2)/3
2106 reflections	(Δ/σ)max < 0.001
193 parameters	Δρmax = 0.50 e Å−3
5 restraints	Δρmin = −0.41 e Å−3

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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 > σ(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	0.5000	0.5000	0.5000	0.0307 (3)
O1	0.3159 (5)	1.0520 (5)	0.7574 (2)	0.0340 (10)
O3	0.7070 (4)	0.9725 (6)	0.5173 (2)	0.0334 (10)
N1	0.3911 (5)	0.6681 (6)	0.6461 (2)	0.0253 (11)
H1	0.3367	0.5826	0.6599	0.030*
O4	0.6331 (4)	0.6957 (5)	0.4799 (2)	0.0303 (10)
N2	0.4725 (5)	0.6559 (6)	0.5890 (2)	0.0250 (10)
C2	0.4060 (6)	0.8331 (8)	0.6791 (3)	0.0238 (12)
O2	0.2622 (5)	0.7604 (6)	0.7754 (2)	0.0405 (11)
C1	0.3205 (6)	0.8838 (8)	0.7425 (3)	0.0265 (13)
C4	0.5402 (6)	0.8162 (7)	0.5856 (3)	0.0220 (12)
O5	0.2915 (6)	0.6726 (6)	0.4319 (3)	0.0425 (11)
H3A	0.290 (8)	0.779 (4)	0.444 (4)	0.051*
H3B	0.287 (8)	0.679 (10)	0.3864 (12)	0.051*
C5	0.6349 (6)	0.8345 (7)	0.5240 (3)	0.0221 (12)
C3	0.5020 (6)	0.9310 (8)	0.6420 (3)	0.0270 (13)
H2	0.5345	1.0487	0.6523	0.032*
O6	0.7456 (6)	0.6665 (6)	0.3457 (3)	0.0482 (13)
H4A	0.719 (8)	0.703 (10)	0.385 (2)	0.058*
H4B	0.709 (8)	0.739 (9)	0.315 (3)	0.058*
N3	1.1229 (6)	0.2882 (8)	0.3354 (3)	0.0381 (13)
H5	1.185 (6)	0.350 (8)	0.313 (3)	0.046*
C9	1.0145 (7)	0.0054 (11)	0.3514 (4)	0.0479 (17)
H9	1.0028	−0.1166	0.3385	0.057*
C10	1.1080 (7)	0.1140 (9)	0.3174 (4)	0.0408 (16)
H10	1.1615	0.0649	0.2814	0.049*
C7	0.9545 (8)	0.2621 (13)	0.4227 (4)	0.056 (2)
H7	0.9016	0.3144	0.4583	0.067*
C8	0.9389 (7)	0.0817 (11)	0.4047 (4)	0.0496 (19)
H8	0.8760	0.0102	0.4291	0.059*
C6	1.0501 (8)	0.3639 (11)	0.3870 (4)	0.0512 (19)
H6	1.0637	0.4862	0.3989	0.061*

	U11	U22	U33	U12	U13	U23
Cu1	0.0437 (6)	0.0249 (5)	0.0268 (5)	−0.0106 (5)	0.0198 (4)	−0.0103 (5)
O1	0.042 (3)	0.029 (2)	0.033 (2)	0.0026 (19)	0.018 (2)	−0.0069 (18)
O3	0.038 (2)	0.031 (2)	0.034 (2)	−0.009 (2)	0.0175 (19)	−0.0081 (19)
N1	0.030 (3)	0.024 (2)	0.024 (2)	−0.001 (2)	0.013 (2)	−0.002 (2)
O4	0.040 (2)	0.027 (2)	0.027 (2)	−0.0115 (18)	0.0212 (19)	−0.0082 (17)
N2	0.031 (3)	0.024 (2)	0.021 (2)	−0.001 (2)	0.012 (2)	−0.001 (2)
C2	0.027 (3)	0.027 (3)	0.018 (3)	0.002 (2)	0.004 (2)	−0.003 (2)
O2	0.059 (3)	0.034 (2)	0.032 (2)	−0.004 (2)	0.024 (2)	0.002 (2)
C1	0.027 (3)	0.034 (3)	0.020 (3)	0.008 (3)	0.004 (2)	−0.007 (3)
C4	0.026 (3)	0.021 (3)	0.019 (3)	−0.004 (2)	0.004 (2)	−0.005 (2)
O5	0.068 (3)	0.030 (2)	0.030 (2)	−0.004 (2)	0.006 (2)	−0.002 (2)
C5	0.021 (3)	0.025 (3)	0.021 (3)	−0.001 (2)	0.003 (2)	−0.001 (2)
C3	0.028 (3)	0.025 (3)	0.029 (3)	−0.004 (2)	0.009 (3)	−0.004 (2)
O6	0.078 (4)	0.030 (3)	0.042 (3)	−0.004 (2)	0.037 (3)	−0.005 (2)
N3	0.037 (3)	0.046 (3)	0.033 (3)	−0.009 (3)	0.012 (2)	0.009 (3)
C9	0.045 (4)	0.049 (4)	0.050 (4)	−0.009 (4)	0.002 (3)	0.012 (4)
C10	0.042 (4)	0.046 (4)	0.035 (4)	0.000 (3)	0.008 (3)	0.001 (3)
C7	0.039 (4)	0.092 (6)	0.040 (4)	−0.002 (4)	0.019 (3)	−0.016 (4)
C8	0.037 (4)	0.076 (5)	0.035 (4)	−0.020 (4)	0.000 (3)	0.018 (4)
C6	0.051 (4)	0.051 (4)	0.054 (4)	−0.006 (4)	0.018 (4)	−0.013 (4)

Cu1—O4	1.959 (4)	O5—H3A	0.82 (2)
Cu1—O4i	1.959 (4)	O5—H3B	0.82 (2)
Cu1—N2	2.006 (4)	C3—H2	0.9300
Cu1—N2i	2.006 (4)	O6—H4A	0.82 (2)
Cu1—O5	2.539 (5)	O6—H4B	0.82 (2)
Cu1—O5i	2.539 (5)	N3—C10	1.325 (9)
O1—C1	1.267 (7)	N3—C6	1.325 (8)
O3—C5	1.230 (6)	N3—H5	0.87 (2)
N1—N2	1.341 (6)	C9—C8	1.367 (10)
N1—C2	1.351 (7)	C9—C10	1.371 (9)
N1—H1	0.8600	C9—H9	0.9300
O4—C5	1.292 (6)	C10—H10	0.9300
N2—C4	1.342 (7)	C7—C8	1.369 (11)
C2—C3	1.374 (8)	C7—C6	1.373 (10)
C2—C1	1.502 (7)	C7—H7	0.9300
O2—C1	1.239 (7)	C8—H8	0.9300
C4—C3	1.393 (7)	C6—H6	0.9300
C4—C5	1.491 (7)
O4—Cu1—O4i	179.999 (1)	H3A—O5—H3B	102 (7)
O4—Cu1—N2	81.99 (16)	O3—C5—O4	124.5 (5)
O4i—Cu1—N2	98.01 (16)	O3—C5—C4	121.2 (5)
O4—Cu1—N2i	98.01 (16)	O4—C5—C4	114.3 (5)
O4i—Cu1—N2i	81.99 (16)	C2—C3—C4	105.2 (5)
N2—Cu1—N2i	179.999 (1)	C2—C3—H2	127.4
O4—Cu1—O5	90.92 (17)	C4—C3—H2	127.4
O4i—Cu1—O5	89.08 (17)	H4A—O6—H4B	103 (7)
N2—Cu1—O5	86.97 (17)	C10—N3—C6	121.9 (6)
N2i—Cu1—O5	93.03 (17)	C10—N3—H5	117 (5)
N2—N1—C2	110.8 (4)	C6—N3—H5	121 (5)
N2—N1—H1	124.6	C8—C9—C10	118.0 (7)
C2—N1—H1	124.6	C8—C9—H9	121.0
C5—O4—Cu1	116.0 (3)	C10—C9—H9	121.0
N1—N2—C4	106.3 (4)	N3—C10—C9	120.7 (7)
N1—N2—Cu1	141.0 (4)	N3—C10—H10	119.6
C4—N2—Cu1	111.6 (3)	C9—C10—H10	119.6
N1—C2—C3	107.6 (5)	C8—C7—C6	118.5 (7)
N1—C2—C1	121.1 (5)	C8—C7—H7	120.8
C3—C2—C1	131.3 (5)	C6—C7—H7	120.8
O2—C1—O1	126.0 (5)	C9—C8—C7	120.8 (7)
O2—C1—C2	118.2 (5)	C9—C8—H8	119.6
O1—C1—C2	115.8 (5)	C7—C8—H8	119.6
N2—C4—C3	110.1 (5)	N3—C6—C7	120.1 (7)
N2—C4—C5	115.5 (4)	N3—C6—H6	120.0
C3—C4—C5	134.4 (5)	C7—C6—H6	120.0
N2—Cu1—O4—C5	−5.9 (4)	Cu1—N2—C4—C5	−7.8 (6)
N2i—Cu1—O4—C5	174.1 (4)	Cu1—O4—C5—O3	−176.5 (4)
C2—N1—N2—C4	−0.1 (6)	Cu1—O4—C5—C4	3.3 (6)
C2—N1—N2—Cu1	−166.3 (5)	N2—C4—C5—O3	−176.9 (5)
O4—Cu1—N2—N1	173.2 (6)	C3—C4—C5—O3	4.2 (10)
O4i—Cu1—N2—N1	−6.8 (6)	N2—C4—C5—O4	3.3 (7)
O4—Cu1—N2—C4	7.4 (4)	C3—C4—C5—O4	−175.6 (6)
O4i—Cu1—N2—C4	−172.6 (4)	N1—C2—C3—C4	0.8 (6)
N2—N1—C2—C3	−0.5 (6)	C1—C2—C3—C4	−176.5 (6)
N2—N1—C2—C1	177.2 (5)	N2—C4—C3—C2	−0.9 (7)
N1—C2—C1—O2	16.6 (8)	C5—C4—C3—C2	178.0 (6)
C3—C2—C1—O2	−166.4 (6)	C6—N3—C10—C9	0.7 (11)
N1—C2—C1—O1	−163.7 (5)	C8—C9—C10—N3	−0.8 (10)
C3—C2—C1—O1	13.3 (9)	C10—C9—C8—C7	1.1 (11)
N1—N2—C4—C3	0.6 (6)	C6—C7—C8—C9	−1.3 (11)
Cu1—N2—C4—C3	171.3 (4)	C10—N3—C6—C7	−0.9 (11)
N1—N2—C4—C5	−178.5 (5)	C8—C7—C6—N3	1.1 (12)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O6i	0.86	1.99	2.783 (6)	154
O5—H3A···O3ii	0.81 (4)	1.95 (4)	2.764 (6)	175 (8)
O5—H3B···O2iii	0.82 (2)	2.04 (3)	2.845 (6)	170 (7)
O6—H4A···O4	0.82 (5)	1.96 (5)	2.735 (7)	159 (7)
O6—H4B···O1ii	0.82 (6)	2.01 (6)	2.801 (6)	162 (7)
N3—H5···O1iv	0.87 (6)	1.81 (6)	2.665 (7)	171 (6)
C6—H6···O5v	0.93	2.55	3.247 (9)	132
C8—H8···O3vi	0.93	2.36	3.211 (8)	151
C10—H10···O2vii	0.93	2.58	3.231 (8)	128

Cu1—O4	1.959 (4)
Cu1—N2	2.006 (4)
Cu1—O5	2.539 (5)

O4—Cu1—N2	81.99 (16)
O4—Cu1—O5	90.92 (17)
N2—Cu1—O5	86.97 (17)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O6i	0.86	1.99	2.783 (6)	154
O5—H3A⋯O3ii	0.81 (4)	1.95 (4)	2.764 (6)	175 (8)
O5—H3B⋯O2iii	0.82 (2)	2.04 (3)	2.845 (6)	170 (7)
O6—H4A⋯O4	0.82 (5)	1.96 (5)	2.735 (7)	159 (7)
O6—H4B⋯O1ii	0.82 (6)	2.01 (6)	2.801 (6)	162 (7)
N3—H5⋯O1iv	0.87 (6)	1.81 (6)	2.665 (7)	171 (6)
C6—H6⋯O5v	0.93	2.55	3.247 (9)	132
C8—H8⋯O3vi	0.93	2.36	3.211 (8)	151
C10—H10⋯O2vii	0.93	2.58	3.231 (8)	128

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .