catena-Poly[[di-aqua-bis-(μ3-5-carboxyl-ato-1H-pyrazole-3-carb-oxy-lic acid-κ(3) O (3):O (3);O (5))dilithium(I)] monohydrate].

The basic structural unit of the title polymeric ribbon, {[Li2(C5H3N2O2)2(H2O)2]·H2O} n , is a centrosymmetric dinuclear complex in which the two Li(I) ions are bridged by two carboxyl-ato O atoms, to generate a centrosymmetric Li2O2 core. These are connected into a chain along [01-1] by carboxylic acid-carbonyl-O bonds. The tetra-hedral coordination of the Li(I) cation is completed by an aqua ligand. The carboxylic acid is involved in an intra-ribbon hydrogen bond. A solvate water molecule showing positional (50:50) disorder is observed. Polymeric ribbons along [01-1] are connected by O-H⋯O, N-H⋯O and O-H⋯N hydrogen bonds into a three-dimensional architecture.

Related literature

For the structure of the pyrazole-3,5-di­carb­oxy­lic acid hydrate, see: Ching et al. (2000 ▶).

Experimental

Crystal data

[Li2(C5H3N2O2)2(H2O)2]·H2O

M = 378.12

Triclinic,

a = 7.2610 (15) Å

b = 7.5835 (15) Å

c = 8.5751 (17) Å

α = 68.38 (3)°

β = 89.07 (3)°

γ = 63.66 (3)°

V = 387.19 (13) Å3

Z = 1

Mo Kα radiation

μ = 0.15 mm−1

T = 293 K

0.32 × 0.19 × 0.15 mm

Data collection

Kuma KM-4 four-circle diffractometer

Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008 ▶) T min = 0.963, T max = 0.983

2319 measured reflections

2139 independent reflections

1631 reflections with I > 2σ(I)

R int = 0.051

3 standard reflections every 200 reflections intensity decay: 3.2%

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.139

S = 1.04

2139 reflections

148 parameters

4 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.36 e Å−3

Δρmin = −0.43 e Å−3

Data collection: KM-4 Software (Kuma, 1996 ▶); cell refinement: KM-4 Software; data reduction: DATAPROC (Kuma, 2001 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536813026408/kp2459sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813026408/kp2459Isup2.hkl

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

[Li2(C5H3N2O2)2(H2O)2]·H2O	Z = 1
Mr = 378.12	F(000) = 194
Triclinic, P1	Dx = 1.622 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.2610 (15) Å	Cell parameters from 25 reflections
b = 7.5835 (15) Å	θ = 6–15°
c = 8.5751 (17) Å	µ = 0.15 mm−1
α = 68.38 (3)°	T = 293 K
β = 89.07 (3)°	Blocks, colourless
γ = 63.66 (3)°	0.32 × 0.19 × 0.15 mm
V = 387.19 (13) Å3

Kuma KM-4 four-circle diffractometer	1631 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.051
Graphite monochromator	θmax = 30.1°, θmin = 2.6°
profile data from ω/2θ scan	h = −9→9
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008)	k = 0→9
Tmin = 0.963, Tmax = 0.983	l = −11→11
2319 measured reflections	3 standard reflections every 200 reflections
2139 independent reflections	intensity decay: 3.2%

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.139	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0979P)2 + 0.0513P] where P = (Fo2 + 2Fc2)/3
2139 reflections	(Δ/σ)max < 0.001
148 parameters	Δρmax = 0.36 e Å−3
4 restraints	Δρmin = −0.43 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	Occ. (<1)
O1	0.31476 (15)	0.19235 (16)	0.41828 (13)	0.0317 (3)
O3	−0.04302 (15)	1.06450 (16)	−0.29666 (13)	0.0330 (3)
H3	−0.0066	1.1326	−0.3779	0.050*
N2	−0.12574 (16)	0.83399 (17)	−0.01238 (13)	0.0229 (2)
O4	0.30113 (16)	0.84618 (17)	−0.21398 (14)	0.0352 (3)
O2	−0.02499 (16)	0.33302 (17)	0.43139 (13)	0.0361 (3)
N1	−0.11472 (16)	0.68180 (16)	0.13403 (13)	0.0219 (2)
C5	0.08191 (17)	0.51952 (18)	0.19965 (15)	0.0208 (3)
C4	0.20777 (18)	0.56837 (19)	0.08850 (15)	0.0236 (3)
H4	0.3512	0.4884	0.0977	0.028*
C3	0.07157 (18)	0.76495 (18)	−0.04109 (14)	0.0209 (3)
C7	0.12037 (19)	0.8962 (2)	−0.19328 (15)	0.0230 (3)
C6	0.12709 (19)	0.33371 (19)	0.36231 (15)	0.0218 (3)
Li1	0.4462 (4)	−0.0115 (4)	0.6522 (3)	0.0310 (5)
O5	0.50246 (15)	0.15574 (18)	0.75835 (14)	0.0331 (3)
O6	0.4576 (4)	0.5520 (4)	0.5472 (4)	0.0493 (6)	0.50
H1	−0.225 (4)	0.700 (4)	0.173 (3)	0.046 (6)*
H52	0.531 (5)	0.254 (4)	0.683 (4)	0.070 (8)*
H51	0.630 (5)	0.063 (5)	0.832 (4)	0.078 (9)*
H62	0.328 (4)	0.602 (6)	0.559 (9)	0.14 (3)*	0.50
H61	0.508 (15)	0.57 (3)	0.624 (19)	0.38 (11)*	0.50

	U11	U22	U33	U12	U13	U23
O1	0.0179 (4)	0.0260 (5)	0.0233 (4)	0.0000 (4)	0.0017 (3)	0.0056 (4)
O3	0.0216 (5)	0.0280 (5)	0.0247 (5)	−0.0075 (4)	0.0030 (4)	0.0095 (4)
N2	0.0175 (5)	0.0181 (5)	0.0188 (5)	−0.0056 (4)	0.0027 (3)	0.0038 (4)
O4	0.0215 (5)	0.0304 (5)	0.0329 (5)	−0.0091 (4)	0.0097 (4)	0.0044 (4)
O2	0.0212 (5)	0.0292 (5)	0.0296 (5)	−0.0066 (4)	0.0068 (4)	0.0106 (4)
N1	0.0148 (5)	0.0178 (5)	0.0188 (5)	−0.0047 (4)	0.0032 (3)	0.0034 (4)
C5	0.0156 (5)	0.0166 (5)	0.0182 (5)	−0.0050 (4)	0.0025 (4)	0.0019 (4)
C4	0.0150 (5)	0.0183 (5)	0.0218 (5)	−0.0034 (4)	0.0040 (4)	0.0023 (4)
C3	0.0173 (5)	0.0175 (5)	0.0178 (5)	−0.0067 (4)	0.0038 (4)	0.0014 (4)
C7	0.0210 (6)	0.0189 (5)	0.0195 (5)	−0.0082 (4)	0.0047 (4)	0.0006 (4)
C6	0.0172 (5)	0.0173 (5)	0.0177 (5)	−0.0048 (4)	0.0018 (4)	0.0022 (4)
Li1	0.0219 (10)	0.0268 (11)	0.0278 (11)	−0.0074 (9)	0.0077 (8)	0.0006 (9)
O5	0.0173 (4)	0.0320 (5)	0.0309 (5)	−0.0070 (4)	0.0031 (4)	0.0012 (4)
O6	0.0359 (13)	0.0414 (14)	0.0517 (15)	−0.0200 (11)	0.0027 (10)	0.0030 (11)

O1—C6	1.2578 (16)	C5—C6	1.4816 (17)
O1—Li1i	1.929 (3)	C4—C3	1.3935 (17)
Li1—O1	1.948 (3)	C4—H4	0.9300
O3—C7	1.2958 (17)	C3—C7	1.4698 (16)
O3—H3	0.8200	Li1—O4iii	1.910 (3)
N2—N1	1.3298 (14)	Li1—O1i	1.930 (3)
N2—C3	1.3436 (16)	Li1—O5	1.981 (3)
O4—C7	1.2240 (16)	Li1—Li1i	2.679 (5)
O4—Li1ii	1.910 (3)	O5—H52	0.89 (3)
O2—C6	1.2458 (15)	O5—H51	0.93 (3)
N1—C5	1.3513 (16)	O6—O6iv	1.296 (6)
N1—H1	0.84 (2)	O6—H62	0.87 (2)
C5—C4	1.3758 (16)	O6—H61	0.86 (2)
C6—O1—Li1i	141.01 (13)	O3—C7—C3	113.68 (11)
C6—O1—Li1	128.30 (12)	O2—C6—O1	126.09 (12)
Li1i—O1—Li1	87.41 (12)	O2—C6—C5	116.69 (11)
C7—O3—H3	109.5	O1—C6—C5	117.22 (12)
N1—N2—C3	104.63 (10)	O4iii—Li1—O1i	114.50 (14)
C7—O4—Li1ii	136.31 (12)	O4iii—Li1—O1	118.27 (14)
N2—N1—C5	112.49 (10)	O1i—Li1—O1	92.59 (12)
N2—N1—H1	117.8 (16)	O4iii—Li1—O5	111.34 (13)
C5—N1—H1	129.7 (16)	O1i—Li1—O5	114.31 (14)
N1—C5—C4	106.99 (10)	O1—Li1—O5	104.38 (13)
N1—C5—C6	120.84 (11)	O4iii—Li1—Li1i	130.02 (19)
C4—C5—C6	132.17 (11)	O1i—Li1—Li1i	46.58 (9)
C5—C4—C3	104.29 (10)	O1—Li1—Li1i	46.02 (8)
C5—C4—H4	127.9	O5—Li1—Li1i	118.50 (16)
C3—C4—H4	127.9	Li1—O5—H52	111.3 (17)
N2—C3—C4	111.59 (11)	Li1—O5—H51	106.9 (16)
N2—C3—C7	120.02 (11)	H52—O5—H51	101 (2)
C4—C3—C7	128.37 (11)	O6iv—O6—H62	126 (6)
O4—C7—O3	125.27 (12)	O6iv—O6—H61	133 (7)
O4—C7—C3	121.04 (12)	H62—O6—H61	100 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2ii	0.82	1.73	2.5159 (16)	160
N1—H1···O5v	0.84 (2)	2.02 (2)	2.8233 (17)	161 (2)
O5—H52···O6	0.89 (3)	1.94 (3)	2.749 (3)	150 (3)
O5—H52···O6iv	0.89 (3)	2.01 (3)	2.851 (3)	157 (3)
O5—H51···N2vi	0.93 (3)	1.89 (3)	2.810 (2)	169 (3)
O5—H51···O3vi	0.93 (3)	2.60 (3)	3.1235 (16)	116 (2)
O6—H62···O2v	0.87 (2)	2.03 (3)	2.886 (3)	167 (7)

Table 1

Selected bond lengths (Å)

Li1—O1	1.948 (3)
Li1—O4i	1.910 (3)
Li1—O1ii	1.930 (3)
Li1—O5	1.981 (3)

Symmetry codes: (i) ; (ii) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O2iii	0.82	1.73	2.5159 (16)	160
N1—H1⋯O5iv	0.84 (2)	2.02 (2)	2.8233 (17)	161 (2)
O5—H52⋯O6	0.89 (3)	1.94 (3)	2.749 (3)	150 (3)
O5—H52⋯O6v	0.89 (3)	2.01 (3)	2.851 (3)	157 (3)
O5—H51⋯N2vi	0.93 (3)	1.89 (3)	2.810 (2)	169 (3)
O5—H51⋯O3vi	0.93 (3)	2.60 (3)	3.1235 (16)	116 (2)
O6—H62⋯O2iv	0.87 (2)	2.03 (3)	2.886 (3)	167 (7)

Symmetry codes: (iii) ; (iv) ; (v) ; (vi) .