catena-Poly[[di­aqua­bis­(μ3-5-carboxyl­ato-1H-pyrazole-3-carb­oxy­lic acid-κ3O3:O3;O5)dilithium(I)] monohydrate]

Starosta, W.; Leciejewicz, J.

doi:10.1107/S1600536813026408

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 11| November 2013| Pages m593-m594

doi:10.1107/S1600536813026408

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catena-Poly[[diaquabis(μ₃-5-carboxylato-1H-pyrazole-3-carboxylic acid-κ³O³:O³;O⁵)dilithium(I)] monohydrate]

Wojciech Starosta ^a and Janusz Leciejewicz ^a ^*

^aInstitute of Nuclear Chemistry and Technology, ul.Dorodna 16, 03-195 Warszawa, Poland
^*Correspondence e-mail: j.leciejewicz@ichtj.waw.pl

(Received 10 September 2013; accepted 24 September 2013; online 12 October 2013)

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 carboxylato O atoms, to generate a centrosymmetric Li₂O₂ core. These are connected into a chain along [01-1] by carboxylic acid–carbonyl-O bonds. The tetrahedral 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.

CCDC reference: 962945

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_r = 378.12
Triclinic, $[P \overline 1]$
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 $[Oxford Diffraction (2008). CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ) 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[F² > 2σ(F²)] = 0.048
wR(F²) = 0.139
S = 1.04
2139 reflections
148 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.43 e Å⁻³

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) x, y-1, z+1; (ii) -x+1, -y, -z+1.

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⋯O5^iv	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⋯O6^v	0.89 (3)	2.01 (3)	2.851 (3)	157 (3)
O5—H51⋯N2^vi	0.93 (3)	1.89 (3)	2.810 (2)	169 (3)
O5—H51⋯O3^vi	0.93 (3)	2.60 (3)	3.1235 (16)	116 (2)
O6—H62⋯O2^iv	0.87 (2)	2.03 (3)	2.886 (3)	167 (7)
Symmetry codes: (iii) x, y+1, z-1; (iv) -x, -y+1, -z+1; (v) -x+1, -y+1, -z+1; (vi) x+1, y-1, z+1.

Data collection: KM-4 Software (Kuma, 1996 $[Kuma (1996). KM-4 Software. Kuma Diffraction Ltd, Wrocław, Poland.]$ ); cell refinement: KM-4 Software; data reduction: DATAPROC (Kuma, 2001 $[Kuma (2001). DATAPROC. Kuma Diffraction Ltd, Wrocław, Poland.]$ ); 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.

Supporting information

CCDC reference: 962945

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536813026408/kp2459sup1.cif

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

checkCIF report

Comment top

The structural unit of the title complex is a centrosymmetric dinuclear moiety composed of two Li^I ions bridged by two bidentate carboxylato O atoms, each donated by a symmetry related ligand (Fig. 1). The ligand acts in µ₃ bridging mode since apart from the bidentate O1 atom, the O4 atom of its second carboxylate group is chelated to a Li^(vi) ion in the adjacent dimer. In this way a Li^I ion is coordinated by the bridging O1 and O1⁽ⁱⁱ⁾ atoms, the O4⁽ⁱ⁾ from the adjacent dimer and an aqua O5 atom resulting in a distorted tetrahedral geometry. The Li—O bond distances (Table 1) which fall in the range between 1.930 (2) Å and 1.980 (3) Å are typical of Li^I complexes with carboxylate and water ligands. The pyrazole ring is planar with r.m.s. of 0.0009 (1) Å; the carboxylate group C6/O1/O2 and C7/O3/O4 make with it dihedral angles of 2.4 (1)° and 5.5 (1)°, respectively. The carboxylate O2 atom is chelating inactive, the O3 remains protonated and participates as a donor in the short hydrogen bond of 2.516 (2) Å to O2^vi in an adjacent dimer. Bond distances and bond angles within the pyrazole ring do not differ from those reported in the structure of the parent acid (Ching et al., 2000). The plane of the Li1,O1,Li⁽ⁱⁱ⁾,O1⁽ⁱⁱ⁾ dimer core makes a dihedral angle of 36.1° with the ligand plane. The dimeric units linked by carboxylate O4 atoms form molecular ribbons . A solvate water molecule O6 with 50% site occupancy is present in the asymmetric cell resulting in one molecule per a dimer. Moreover, this water molecule shows 0.5/0.5 positional disorder. The ribbons are held together by a system of hydrogen bonds involving coordinated and crystal water molecules the carboxylate/carboxylato groups and pyrazole N ring atoms (Fig. 2, Table 2).

Related literature top

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

Experimental top

1 mmol of pyrazole-3,5-dicarboxylic acid hydrate and ca2 mmol s of lithium hydroxide dissolved in 50 mL of hot, doubly distilled water were boiled under reflux with stirring for six hours and then left to crystallize at room temperature. Colourless single-crystal blocks with two differet shapes deposited after a week. One of the crystals was selected, washed with cold ethanol and dried in the air.

Computing details top

Data collection: KM-4 Software (Kuma, 1996); cell refinement: KM-4 Software (Kuma, 1996); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. A fragment of a molecular ribbon showing a dinuclear structural building unit of the title complex with atom labelling scheme and 50% probability displacement ellipsoids. Symmetry code: (i) x, y - 1,z + 1; (ii) -x + 1, -y, -z + 1; (iii): -x + 1, -y + 1, -z.
	Fig. 2. The packing of molecular ribbons via hydrogen bonds viewed along their propagation direction.

catena-Poly[[diaquabis(µ₃-5-carboxylato-1H-pyrazole-3-carboxylic acid-κ³O³:O³;O⁵)dilithium(I)] monohydrate] top

Crystal data top

[Li₂(C₅H₃N₂O₂)₂(H₂O)₂]·H₂O	Z = 1
M_r = 378.12	F(000) = 194
Triclinic, P1	D_x = 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

Data collection top

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

Refinement top

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(F_o²) + (0.0979P)² + 0.0513P] where P = (F_o² + 2F_c²)/3
2139 reflections	(Δ/σ)_max < 0.001
148 parameters	Δρ_max = 0.36 e Å⁻³
4 restraints	Δρ_min = −0.43 e Å⁻³

Crystal data top

[Li₂(C₅H₃N₂O₂)₂(H₂O)₂]·H₂O	γ = 63.66 (3)°
M_r = 378.12	V = 387.19 (13) Å³
Triclinic, P1	Z = 1
a = 7.2610 (15) Å	Mo Kα radiation
b = 7.5835 (15) Å	µ = 0.15 mm⁻¹
c = 8.5751 (17) Å	T = 293 K
α = 68.38 (3)°	0.32 × 0.19 × 0.15 mm
β = 89.07 (3)°

Data collection top

Kuma KM-4 four-circle diffractometer	1631 reflections with I > 2σ(I)
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008)	R_int = 0.051
T_min = 0.963, T_max = 0.983	3 standard reflections every 200 reflections
2319 measured reflections	intensity decay: 3.2%
2139 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	4 restraints
wR(F²) = 0.139	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.36 e Å⁻³
2139 reflections	Δρ_min = −0.43 e Å⁻³
148 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	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

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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—O6^iv	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)	O6^iv—O6—H62	126 (6)
O4—C7—O3	125.27 (12)	O6^iv—O6—H61	133 (7)
O4—C7—C3	121.04 (12)	H62—O6—H61	100 (3)

Symmetry codes: (i) −x+1, −y, −z+1; (ii) x, y+1, z−1; (iii) x, y−1, z+1; (iv) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

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···O5^v	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···O6^iv	0.89 (3)	2.01 (3)	2.851 (3)	157 (3)
O5—H51···N2^vi	0.93 (3)	1.89 (3)	2.810 (2)	169 (3)
O5—H51···O3^vi	0.93 (3)	2.60 (3)	3.1235 (16)	116 (2)
O6—H62···O2^v	0.87 (2)	2.03 (3)	2.886 (3)	167 (7)

Symmetry codes: (ii) x, y+1, z−1; (iv) −x+1, −y+1, −z+1; (v) −x, −y+1, −z+1; (vi) x+1, y−1, z+1.

Selected bond lengths (Å) top

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

Symmetry codes: (i) x, y−1, z+1; (ii) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2ⁱⁱⁱ	0.82	1.73	2.5159 (16)	159.5
N1—H1···O5^iv	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···O6^v	0.89 (3)	2.01 (3)	2.851 (3)	157 (3)
O5—H51···N2^vi	0.93 (3)	1.89 (3)	2.810 (2)	169 (3)
O5—H51···O3^vi	0.93 (3)	2.60 (3)	3.1235 (16)	116 (2)
O6—H62···O2^iv	0.87 (2)	2.03 (3)	2.886 (3)	167 (7)

Symmetry codes: (iii) x, y+1, z−1; (iv) −x, −y+1, −z+1; (v) −x+1, −y+1, −z+1; (vi) x+1, y−1, z+1.

References

Ching, N., Pan, L., Huang, X. & Li, J. (2000). Acta Cryst. C56, 1124–1125. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Kuma (1996). KM-4 Software. Kuma Diffraction Ltd, Wrocław, Poland. Google Scholar
Kuma (2001). DATAPROC. Kuma Diffraction Ltd, Wrocław, Poland. Google Scholar
Oxford Diffraction (2008). CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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