Piperazine-1,4-diium bis-(2-carb-oxy-1H-pyrazole-4-carboxyl-ate) tetra-hydrate.

The asymmetric unit of the title compound, C(4)H(12)N(2) (2+)·2C(5)H(3)N(2)O(4) (-)·4H(2)O, comprises one-half of a piperazine-1,4-diium cation, which lies on an inversion centre, a 2-carb-oxy-1H-pyrazole-4-carboxyl-ate anion and two water mol-ecules. An extensive network of inter-molecular O-H⋯O, N-H⋯O, N-H⋯N and C-H⋯O hydrogen bonds between the cations, anions and water mol-ecules leads to a three-dimensional supra-molecular framework.

Related literature

For 3,5-pyrazole­dicarb­oxy­lic acid, see: King et al. (2003 ▶); pan class="Gene">Pan et al. (2001 ▶). For reference structural data, see: Li & Su (2007 ▶); Reviriego et al. (2006 ▶).

Experimental

Crystal data

C4H12N2·2C5H3N2O4·4H2O

M = 470.41

Monoclinic,

a = 8.3363 (13) Å

b = 16.246 (3) Å

c = 7.3930 (11) Å

β = 90.812 (3)°

V = 1001.2 (3) Å3

Z = 2

Mo Kα radiation

μ = 0.14 mm−1

T = 291 K

0.15 × 0.14 × 0.12 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T min = 0.980, T max = 0.984

5265 measured reflections

1946 independent reflections

1524 reflections with I > 2σ(I)

R int = 0.051

Refinement

R[F 2 > 2σ(F 2)] = 0.059

wR(F 2) = 0.147

S = 1.10

1946 reflections

169 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.41 e Å−3

Δρmin = −0.23 e Å−3

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681003655X/om2361sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053681003655X/om2361Isup2.hkl

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

C4H12N2·2C5H3N2O4·4H2O	F(000) = 496
Mr = 470.41	Dx = 1.560 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1373 reflections
a = 8.3363 (13) Å	θ = 2.7–24.0°
b = 16.246 (3) Å	µ = 0.14 mm−1
c = 7.3930 (11) Å	T = 291 K
β = 90.812 (3)°	Block, white
V = 1001.2 (3) Å3	0.15 × 0.14 × 0.12 mm
Z = 2

Bruker SMART APEX CCD diffractometer	1946 independent reflections
Radiation source: fine-focus sealed tube	1524 reflections with I > 2σ(I)
graphite	Rint = 0.051
phi and ω scans	θmax = 26.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −10→10
Tmin = 0.980, Tmax = 0.984	k = −13→19
5265 measured reflections	l = −8→9

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.147	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ2(Fo2) + (0.0729P)2] where P = (Fo2 + 2Fc2)/3
1946 reflections	(Δ/σ)max < 0.001
169 parameters	Δρmax = 0.41 e Å−3
0 restraints	Δρmin = −0.23 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
C1	1.1506 (3)	0.78226 (15)	0.2962 (3)	0.0267 (6)
C2	0.9861 (3)	0.77149 (14)	0.2216 (3)	0.0233 (6)
C3	0.8727 (3)	0.82885 (15)	0.1741 (3)	0.0256 (6)
H3	0.8827	0.8858	0.1785	0.031*
C4	0.7391 (3)	0.78344 (14)	0.1178 (3)	0.0226 (5)
C5	0.5785 (3)	0.81182 (15)	0.0528 (3)	0.0246 (6)
C6	0.6653 (4)	0.51108 (17)	−0.0379 (5)	0.0455 (8)
H6A	0.7149	0.4999	0.0790	0.055*
H6B	0.7496	0.5242	−0.1223	0.055*
C7	0.4237 (3)	0.56416 (16)	0.1024 (4)	0.0380 (7)
H7A	0.3509	0.6107	0.1070	0.046*
H7B	0.4666	0.5548	0.2233	0.046*
N1	0.9196 (2)	0.69726 (13)	0.1933 (3)	0.0266 (5)
H1	0.962 (3)	0.6522 (18)	0.220 (4)	0.032*
N2	0.7696 (2)	0.70254 (12)	0.1296 (3)	0.0262 (5)
N3	0.5556 (3)	0.58226 (14)	−0.0224 (3)	0.0399 (7)
H3A	0.604 (4)	0.6268 (19)	0.020 (4)	0.048*
H3B	0.514 (4)	0.5944 (18)	−0.130 (4)	0.048*
O1	1.2097 (2)	0.85001 (11)	0.3144 (3)	0.0454 (6)
O2	1.2193 (2)	0.71272 (11)	0.3390 (3)	0.0360 (5)
H2	1.311 (4)	0.7215 (17)	0.394 (4)	0.043*
O3	0.5431 (2)	0.88609 (10)	0.0779 (3)	0.0360 (5)
O4	0.4901 (2)	0.75870 (11)	−0.0188 (3)	0.0358 (5)
O5	0.0107 (3)	0.53912 (14)	0.2765 (4)	0.0528 (7)
H5A	−0.077 (5)	0.510 (2)	0.316 (5)	0.063*
H5B	0.093 (5)	0.539 (2)	0.346 (5)	0.063*
O6	0.2621 (2)	0.51492 (13)	0.5325 (3)	0.0476 (6)
H6C	0.323 (4)	0.472 (2)	0.486 (5)	0.057*
H6D	0.320 (4)	0.549 (2)	0.556 (5)	0.057*

	U11	U22	U33	U12	U13	U23
C1	0.0215 (13)	0.0285 (14)	0.0299 (15)	0.0002 (11)	−0.0059 (11)	0.0006 (11)
C2	0.0199 (12)	0.0226 (13)	0.0272 (14)	−0.0006 (10)	−0.0039 (10)	0.0002 (10)
C3	0.0205 (13)	0.0193 (12)	0.0369 (15)	−0.0020 (9)	−0.0056 (10)	−0.0016 (10)
C4	0.0189 (12)	0.0203 (12)	0.0286 (14)	0.0011 (10)	−0.0045 (10)	−0.0004 (10)
C5	0.0159 (12)	0.0228 (13)	0.0351 (15)	−0.0025 (10)	−0.0040 (10)	0.0030 (11)
C6	0.0399 (17)	0.0443 (18)	0.052 (2)	−0.0078 (14)	0.0024 (14)	−0.0050 (15)
C7	0.0455 (17)	0.0286 (15)	0.0398 (17)	0.0027 (12)	−0.0021 (14)	−0.0035 (12)
N1	0.0191 (11)	0.0186 (11)	0.0417 (14)	0.0025 (9)	−0.0092 (9)	0.0022 (9)
N2	0.0169 (10)	0.0215 (11)	0.0398 (13)	−0.0001 (8)	−0.0103 (9)	0.0011 (9)
N3	0.0616 (17)	0.0210 (12)	0.0370 (15)	−0.0144 (11)	−0.0069 (12)	−0.0007 (10)
O1	0.0326 (11)	0.0284 (11)	0.0745 (16)	−0.0083 (8)	−0.0248 (10)	0.0010 (10)
O2	0.0195 (9)	0.0284 (10)	0.0597 (14)	−0.0004 (8)	−0.0183 (9)	0.0030 (9)
O3	0.0239 (10)	0.0218 (10)	0.0622 (14)	0.0044 (8)	−0.0093 (9)	−0.0002 (9)
O4	0.0221 (9)	0.0282 (10)	0.0566 (13)	−0.0002 (8)	−0.0167 (9)	−0.0048 (9)
O5	0.0395 (12)	0.0361 (12)	0.0826 (19)	0.0042 (10)	−0.0040 (12)	0.0144 (11)
O6	0.0345 (12)	0.0334 (12)	0.0748 (17)	−0.0035 (9)	−0.0015 (11)	−0.0107 (11)

C1—O1	1.213 (3)	C6—H6B	0.9700
C1—O2	1.304 (3)	C7—N3	1.476 (4)
C1—C2	1.481 (3)	C7—C6i	1.504 (4)
C2—N1	1.342 (3)	C7—H7A	0.9700
C2—C3	1.369 (3)	C7—H7B	0.9700
C3—C4	1.395 (3)	N1—N2	1.333 (3)
C3—H3	0.9300	N1—H1	0.84 (3)
C4—N2	1.341 (3)	N3—H3A	0.88 (3)
C4—C5	1.489 (3)	N3—H3B	0.88 (3)
C5—O4	1.248 (3)	O2—H2	0.87 (3)
C5—O3	1.256 (3)	O5—H5A	0.92 (4)
C6—N3	1.480 (4)	O5—H5B	0.85 (4)
C6—C7i	1.504 (4)	O6—H6C	0.93 (3)
C6—H6A	0.9700	O6—H6D	0.76 (3)
O1—C1—O2	125.7 (2)	H6A—C6—H6B	108.0
O1—C1—C2	121.4 (2)	N3—C7—C6i	109.4 (2)
O2—C1—C2	112.9 (2)	N3—C7—H7A	109.8
N1—C2—C3	106.9 (2)	C6i—C7—H7A	109.8
N1—C2—C1	122.8 (2)	N3—C7—H7B	109.8
C3—C2—C1	130.3 (2)	C6i—C7—H7B	109.8
C2—C3—C4	105.2 (2)	H7A—C7—H7B	108.2
C2—C3—H3	127.4	N2—N1—C2	112.3 (2)
C4—C3—H3	127.4	N2—N1—H1	122.4 (18)
N2—C4—C3	110.4 (2)	C2—N1—H1	125.1 (19)
N2—C4—C5	119.6 (2)	N1—N2—C4	105.21 (19)
C3—C4—C5	130.0 (2)	C7—N3—C6	111.1 (2)
O4—C5—O3	126.1 (2)	C7—N3—H3A	106 (2)
O4—C5—C4	116.5 (2)	C6—N3—H3A	113 (2)
O3—C5—C4	117.5 (2)	C7—N3—H3B	108 (2)
N3—C6—C7i	111.0 (2)	C6—N3—H3B	110 (2)
N3—C6—H6A	109.4	H3A—N3—H3B	108 (3)
C7i—C6—H6A	109.4	C1—O2—H2	110.5 (18)
N3—C6—H6B	109.4	H5A—O5—H5B	117 (3)
C7i—C6—H6B	109.4	H6C—O6—H6D	107 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O5ii	0.84 (3)	1.93 (3)	2.746 (3)	167 (3)
O2—H2···O4iii	0.87 (3)	1.65 (3)	2.520 (2)	175 (3)
N3—H3A···O4	0.88 (3)	2.36 (3)	2.918 (3)	121 (2)
N3—H3A···N2	0.88 (3)	2.01 (3)	2.865 (3)	162 (3)
N3—H3B···O3iv	0.88 (3)	2.20 (3)	2.999 (3)	150 (3)
O5—H5B···O6	0.85 (4)	2.00 (4)	2.831 (3)	166 (3)
O5—H5A···O6v	0.92 (4)	1.96 (4)	2.833 (3)	157 (3)
O6—H6C···O3vi	0.93 (3)	1.85 (3)	2.779 (3)	173 (3)
O6—H6D···O3vii	0.76 (3)	2.14 (3)	2.858 (3)	158 (4)
C6—H6B···O5i	0.97	2.53	3.348 (4)	142
C7—H7A···O1viii	0.97	2.53	3.091 (3)	117

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O5i	0.84 (3)	1.93 (3)	2.746 (3)	167 (3)
O2—H2⋯O4ii	0.87 (3)	1.65 (3)	2.520 (2)	175 (3)
N3—H3A⋯O4	0.88 (3)	2.36 (3)	2.918 (3)	121 (2)
N3—H3A⋯N2	0.88 (3)	2.01 (3)	2.865 (3)	162 (3)
N3—H3B⋯O3iii	0.88 (3)	2.20 (3)	2.999 (3)	150 (3)
O5—H5B⋯O6	0.85 (4)	2.00 (4)	2.831 (3)	166 (3)
O5—H5A⋯O6iv	0.92 (4)	1.96 (4)	2.833 (3)	157 (3)
O6—H6C⋯O3v	0.93 (3)	1.85 (3)	2.779 (3)	173 (3)
O6—H6D⋯O3vi	0.76 (3)	2.14 (3)	2.858 (3)	158 (4)
C6—H6B⋯O5vii	0.97	2.53	3.348 (4)	142
C7—H7A⋯O1viii	0.97	2.53	3.091 (3)	117

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