Tri­aqua­(pyrazole-4-carboxyl­ato-κN1)lithium

Starosta, W.; Leciejewicz, J.

doi:10.1107/S160053681301831X

metal-organic compounds

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Volume 69| Part 8| August 2013| Page m438

doi:10.1107/S160053681301831X

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Triaqua(pyrazole-4-carboxylato-κN¹)lithium

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 25 June 2013; accepted 2 July 2013; online 6 July 2013)

In the monomeric title complex, [Li(C₄H₃N₂O₂)(H₂O)₃], the Li⁺ cation is coordinated by a pyrazole N atom and three water molecules in a distorted tetrahedral geometry. The carboxylate group is deprotonated. The complex molecules are involved in O—H⋯O and N—H⋯O hydrogen bonding, forming layers stacked along the b axis.

Related literature

For the structure of pyrazole-4-carboxylic acid, see: Foces-Foces et al. (2001 ).

Experimental

Crystal data

[Li(C₄H₃N₂O₂)(H₂O)₃]
M_r = 172.07
Orthorhombic, P n a 2₁
a = 7.2817 (15) Å
b = 6.9635 (14) Å
c = 15.186 (3) Å
V = 770.0 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 293 K
0.25 × 0.18 × 0.12 mm

Data collection

Kuma KM4 four-circle diffractometer
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis RED. Oxford Diffraction Ltd., Yarnton, England.]$ ) T_min = 0.967, T_max = 0.983
1161 measured reflections
1161 independent reflections
901 reflections with I > 2σ(I)
3 standard reflections every 200 reflections intensity decay: 5.9%

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.119
S = 1.01
1161 reflections
133 parameters
7 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.44 e Å⁻³

Table 1
Selected bond lengths (Å)

Li1—N2	2.053 (5)
Li1—O3	1.905 (5)
Li1—O5	1.909 (4)
Li1—O4	1.960 (5)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H32⋯O1ⁱ	0.84 (2)	1.87 (3)	2.666 (3)	159 (4)
O4—H41⋯O2ⁱⁱ	0.81 (2)	1.88 (2)	2.684 (2)	171 (4)
O5—H52⋯O2ⁱⁱⁱ	0.80 (2)	2.04 (3)	2.813 (3)	163 (5)
O4—H42⋯O2^iv	0.84 (2)	1.94 (2)	2.770 (3)	174 (4)
O3—H31⋯O4^v	0.82 (2)	2.05 (3)	2.820 (3)	156 (4)
O5—H51⋯O3^vi	0.83 (2)	1.98 (2)	2.804 (3)	172 (4)
N1—H1⋯O1ⁱ	0.86	1.96	2.776 (3)	159
Symmetry codes: (i) x-1, y, z; (ii) $[-x+1, -y+1, z-{\script{1\over 2}}]$ ; (iii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iv) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (v) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z]$ ; (vi) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z]$ .

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

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681301831X/kp2455sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681301831X/kp2455Isup2.hkl

checkCIF report

Comment top

The orthorhombic structure of the title compound is composed of dicrete mononuclear molecules in which Li¹⁺ is coordinated by the non-protonated hetero-ring N atom of the ligand molecule and three aqua O atoms at the apices of distorted tetrahedron. The observed Li—O and Li—N bond distances and bond angles reveal usual values (Table 2). The carboxylic group is deprotonated. It makes a dihedral angle of 10.7 (2)° with the almost planar [r.m.s.0.0014 (1) Å] pyrazole ring. Bond distances and bond angles within the latter are close to those observed in the structure of the parent acid (Foces-Foces et al., 2001). Complex molecules form layers parallel to the unit cell ac plane (Fig.2) and are stacked along the b axis (Fig.3). Coordinated water molecules are active as donors and acceptors in an extended hydrogen bond system in which carboxylate O atoms are as acceptors (Table 3). The protonated hetero-ring N atom is as a donor and a carboxylate O atom scts as an acceptor is also observed.

Related literature top

For the structure of pyrazole-4-carboxylic acid, see: Foces-Foces et al. (2001).

Experimental top

The compound was synthetized using 1 mmol of LiOH (Aldrich) and a small excess over 1 mmol of pyrazole-4-carboxylic acid (Aldrich) dissolved in 50 mL of doubly distilled water. The solution was refluxed with stirring for 5 h and then left to crystallize at room temperature. Colourless single-crystal blocks deposited after a week. They were 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 molecule of the title complex with atom labelling scheme and 50% probability displacement ellipsoids.
	Fig. 2. A single molecular layer viewed along the b axis.
	Fig. 3. Molecular layers as viewed along the a direction.

Triaqua(pyrazole-4-carboxylato-κN¹)lithium top

Crystal data top

[Li(C₄H₃N₂O₂)(H₂O)₃]	F(000) = 360
M_r = 172.07	D_x = 1.484 Mg m⁻³
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 25 reflections
a = 7.2817 (15) Å	θ = 6–15°
b = 6.9635 (14) Å	µ = 0.13 mm⁻¹
c = 15.186 (3) Å	T = 293 K
V = 770.0 (3) Å³	Block, colourless
Z = 4	0.25 × 0.18 × 0.12 mm

Data collection top

Kuma KM4 four-circle diffractometer	901 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.000
Graphite monochromator	θ_max = 30.1°, θ_min = 2.7°
profile data from ω/2θ scan	h = 0→10
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008)	k = 0→9
T_min = 0.967, T_max = 0.983	l = 0→21
1161 measured reflections	3 standard reflections every 200 reflections
1161 independent reflections	intensity decay: 5.9%

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.119	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ²(F_o²) + (0.0972P)²] where P = (F_o² + 2F_c²)/3
1161 reflections	(Δ/σ)_max < 0.001
133 parameters	Δρ_max = 0.34 e Å⁻³
7 restraints	Δρ_min = −0.44 e Å⁻³

Crystal data top

[Li(C₄H₃N₂O₂)(H₂O)₃]	V = 770.0 (3) Å³
M_r = 172.07	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 7.2817 (15) Å	µ = 0.13 mm⁻¹
b = 6.9635 (14) Å	T = 293 K
c = 15.186 (3) Å	0.25 × 0.18 × 0.12 mm

Data collection top

Kuma KM4 four-circle diffractometer	901 reflections with I > 2σ(I)
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008)	R_int = 0.000
T_min = 0.967, T_max = 0.983	3 standard reflections every 200 reflections
1161 measured reflections	intensity decay: 5.9%
1161 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	7 restraints
wR(F²) = 0.119	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.34 e Å⁻³
1161 reflections	Δρ_min = −0.44 e Å⁻³
133 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
O2	0.5914 (2)	0.4578 (3)	0.32056 (11)	0.0290 (4)
O1	0.7088 (2)	0.5037 (3)	0.18706 (12)	0.0332 (4)
N2	0.1533 (3)	0.4966 (3)	0.10494 (15)	0.0333 (5)
C4	0.3883 (2)	0.4946 (3)	0.20198 (14)	0.0217 (4)
N1	0.0900 (2)	0.5047 (3)	0.18846 (14)	0.0287 (4)
H1	−0.0246	0.5103	0.2019	0.034*
C6	0.5766 (3)	0.4856 (3)	0.23794 (14)	0.0214 (4)
C3	0.3351 (3)	0.4911 (4)	0.11354 (15)	0.0335 (5)
H3	0.4167	0.4856	0.0665	0.040*
C5	0.2250 (3)	0.5030 (3)	0.24788 (17)	0.0281 (4)
H5	0.2115	0.5067	0.3088	0.034*
Li1	0.0107 (6)	0.4846 (6)	−0.0115 (3)	0.0300 (8)
O4	0.1074 (2)	0.6710 (3)	−0.09637 (13)	0.0299 (4)
O3	−0.2382 (2)	0.5471 (3)	0.01447 (13)	0.0319 (4)
O5	0.0491 (3)	0.2401 (3)	−0.06531 (17)	0.0444 (5)
H51	0.121 (4)	0.161 (4)	−0.043 (3)	0.044 (10)*
H31	−0.277 (5)	0.650 (4)	−0.005 (3)	0.044 (10)*
H42	0.043 (4)	0.751 (4)	−0.123 (2)	0.039 (9)*
H52	−0.007 (5)	0.177 (7)	−0.100 (3)	0.073 (14)*
H41	0.192 (4)	0.631 (5)	−0.126 (2)	0.040 (8)*
H32	−0.275 (6)	0.554 (7)	0.0665 (16)	0.055 (12)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O2	0.0241 (7)	0.0453 (9)	0.0177 (6)	0.0001 (6)	−0.0027 (6)	0.0022 (6)
O1	0.0169 (7)	0.0595 (11)	0.0230 (8)	0.0000 (6)	0.0001 (6)	0.0051 (7)
N2	0.0198 (8)	0.0599 (13)	0.0203 (8)	0.0004 (8)	−0.0028 (8)	0.0006 (8)
C4	0.0149 (7)	0.0327 (10)	0.0176 (9)	0.0008 (6)	−0.0011 (7)	0.0013 (7)
N1	0.0162 (7)	0.0465 (11)	0.0236 (10)	0.0002 (6)	−0.0010 (7)	0.0021 (7)
C6	0.0160 (7)	0.0279 (8)	0.0203 (9)	0.0007 (6)	−0.0023 (7)	0.0007 (7)
C3	0.0186 (9)	0.0639 (15)	0.0180 (11)	0.0019 (9)	−0.0011 (8)	0.0004 (10)
C5	0.0175 (8)	0.0458 (12)	0.0210 (9)	0.0004 (8)	−0.0010 (8)	0.0012 (8)
Li1	0.0259 (15)	0.0370 (18)	0.0270 (18)	0.0004 (14)	0.0000 (16)	0.0022 (15)
O4	0.0282 (7)	0.0381 (9)	0.0235 (6)	0.0039 (6)	0.0062 (7)	0.0043 (6)
O3	0.0277 (7)	0.0433 (9)	0.0248 (8)	0.0045 (6)	0.0015 (6)	0.0026 (8)
O5	0.0602 (13)	0.0355 (9)	0.0376 (9)	0.0057 (9)	−0.0118 (10)	−0.0080 (8)

Geometric parameters (Å, º) top

O2—C6	1.274 (3)	C5—H5	0.9300
O1—C6	1.240 (3)	Li1—O3	1.905 (5)
N2—C3	1.331 (3)	Li1—O5	1.909 (4)
N2—N1	1.350 (3)	Li1—O4	1.960 (5)
Li1—N2	2.053 (5)	O4—H42	0.835 (19)
C4—C5	1.379 (3)	O4—H41	0.813 (19)
C4—C3	1.398 (3)	O3—H31	0.823 (19)
C4—C6	1.478 (3)	O3—H32	0.84 (2)
N1—C5	1.334 (3)	O5—H51	0.829 (19)
N1—H1	0.8600	O5—H52	0.80 (2)
C3—H3	0.9300

C3—N2—N1	104.39 (18)	C4—C5—H5	126.5
C3—N2—Li1	125.9 (2)	O3—Li1—O5	115.6 (2)
N1—N2—Li1	129.66 (19)	O3—Li1—O4	109.1 (2)
C5—C4—C3	104.33 (18)	O5—Li1—O4	104.9 (2)
C5—C4—C6	128.0 (2)	O3—Li1—N2	107.0 (2)
C3—C4—C6	127.69 (19)	O5—Li1—N2	109.3 (2)
C5—N1—N2	112.55 (18)	O4—Li1—N2	110.9 (2)
C5—N1—H1	123.7	Li1—O4—H42	124 (2)
N2—N1—H1	123.7	Li1—O4—H41	114 (3)
O1—C6—O2	124.3 (2)	H42—O4—H41	112 (4)
O1—C6—C4	119.05 (19)	Li1—O3—H31	117 (3)
O2—C6—C4	116.66 (19)	Li1—O3—H32	121 (3)
N2—C3—C4	111.67 (19)	H31—O3—H32	100 (4)
N2—C3—H3	124.2	Li1—O5—H51	121 (3)
C4—C3—H3	124.2	Li1—O5—H52	134 (4)
N1—C5—C4	107.1 (2)	H51—O5—H52	103 (5)
N1—C5—H5	126.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H32···O1ⁱ	0.84 (2)	1.87 (3)	2.666 (3)	159 (4)
O4—H41···O2ⁱⁱ	0.81 (2)	1.88 (2)	2.684 (2)	171 (4)
O5—H52···O2ⁱⁱⁱ	0.80 (2)	2.04 (3)	2.813 (3)	163 (5)
O4—H42···O2^iv	0.84 (2)	1.94 (2)	2.770 (3)	174 (4)
O3—H31···O4^v	0.82 (2)	2.05 (3)	2.820 (3)	156 (4)
O5—H51···O3^vi	0.83 (2)	1.98 (2)	2.804 (3)	172 (4)
N1—H1···O1ⁱ	0.86	1.96	2.776 (3)	159

Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+1, z−1/2; (iii) −x+1/2, y−1/2, z−1/2; (iv) −x+1/2, y+1/2, z−1/2; (v) x−1/2, −y+3/2, z; (vi) x+1/2, −y+1/2, z.

Experimental details

Crystal data
Chemical formula	[Li(C₄H₃N₂O₂)(H₂O)₃]
M_r	172.07
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	293
a, b, c (Å)	7.2817 (15), 6.9635 (14), 15.186 (3)
V (Å³)	770.0 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.25 × 0.18 × 0.12

Data collection
Diffractometer	Kuma KM4 four-circle diffractometer
Absorption correction	Analytical (CrysAlis RED; Oxford Diffraction, 2008)
T_min, T_max	0.967, 0.983
No. of measured, independent and observed [I > 2σ(I)] reflections	1161, 1161, 901
R_int	0.000
(sin θ/λ)_max (Å⁻¹)	0.705

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.119, 1.01
No. of reflections	1161
No. of parameters	133
No. of restraints	7
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.44

Computer programs: KM-4 Software (Kuma, 1996), DATAPROC (Kuma, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Li1—N2	2.053 (5)	Li1—O5	1.909 (4)
Li1—O3	1.905 (5)	Li1—O4	1.960 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H32···O1ⁱ	0.84 (2)	1.87 (3)	2.666 (3)	159 (4)
O4—H41···O2ⁱⁱ	0.813 (19)	1.88 (2)	2.684 (2)	171 (4)
O5—H52···O2ⁱⁱⁱ	0.80 (2)	2.04 (3)	2.813 (3)	163 (5)
O4—H42···O2^iv	0.835 (19)	1.938 (19)	2.770 (3)	174 (4)
O3—H31···O4^v	0.823 (19)	2.05 (3)	2.820 (3)	156 (4)
O5—H51···O3^vi	0.829 (19)	1.98 (2)	2.804 (3)	172 (4)
N1—H1···O1ⁱ	0.86	1.96	2.776 (3)	159.3

Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+1, z−1/2; (iii) −x+1/2, y−1/2, z−1/2; (iv) −x+1/2, y+1/2, z−1/2; (v) x−1/2, −y+3/2, z; (vi) x+1/2, −y+1/2, z.

References

Foces-Foces, G., Echevarria, A., Jagerovic, N., Alkorta, I., Elguero, L., Langer, U., Klein, O., Minguet-Banvehi, M. & Limbach, H.-H. (2001). J. Am. Chem. Soc. 123, 7898–7906. Web of Science PubMed CAS 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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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 8| August 2013| Page m438

doi:10.1107/S160053681301831X

Open

access