Poly[μ2-aqua-μ2-(pyrazine-2-carboxyl­ato)-lithium]

Starosta, W.; Leciejewicz, J.

doi:10.1107/S1600536812024683

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 7| July 2012| Pages m933-m934

https://doi.org/10.1107/S1600536812024683

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Poly[μ₂-aqua-μ₂-(pyrazine-2-carboxylato)-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 23 May 2012; accepted 30 May 2012; online 16 June 2012)

The structure of the title compound, [Li(C₅H₃N₂O₂)(H₂O)]_n, contains an Li^I ion with a distorted trigonal–bipyramidal coordination environment involving the N and O atoms of pyrazine-2-carboxylate ligands with a bridging carboxylate group, and two aqua O atoms also in a bridging mode. The symmetry-related Li^I ions bridged by a carboxylate O atom and a coordinating water O atom form an Li₂O₂ unit with an Li⋯Li distance of 3.052 (4) Å, which generates molecular ribbons propagating in the c-axis direction. The ribbons are held together by a network of O—H⋯O hydrogen bonds in which the coordinating water molecules act as donors and the carboxylate O atoms as acceptors.

Related literature

For the crystal structure of an Li^I complex with a 3-aminopyrazine-2-carboxylate ligand, see: Starosta & Leciejewicz, (2010 ) and for the crystal structure of an Li^I complex with a 5-methylpyrazine-2-carboxylate ligand, see: Starosta & Leciejewicz, (2011a ). The structures of complexes with pyridazine-3-carboxylate and pyridazine-4-carboxylate ligands were reported by Starosta & Leciejewicz, (2011b ,c ). The structure of a complex with a pyrimidine-2-carboxylate ligand was also determined (Starosta & Leciejewicz, 2011d ).

Experimental

Crystal data

[Li(C₅H₃N₂O₂)(H₂O)]
M_r = 148.05
Orthorhombic, P c a 2₁
a = 24.433 (5) Å
b = 4.7861 (10) Å
c = 5.6385 (11) Å
V = 659.4 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 293 K
0.35 × 0.18 × 0.13 mm

Data collection

Kuma KM-4 four-cricle diffractometer
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.972, T_max = 0.995
1586 measured reflections
1056 independent reflections
813 reflections with I > 2σ(I)
R_int = 0.078
3 standard reflections every 200 reflections intensity decay: 4.4%

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.116
S = 1.09
1056 reflections
108 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Selected bond lengths (Å)

Li1—O1	2.080 (6)
Li1—N1	2.190 (6)
Li1—O3	2.013 (6)
Li1—O3ⁱ	2.032 (5)
Li1—O1ⁱ	2.237 (6)
Symmetry code: (i) $[-x+{\script{1\over 2}}, y, z+{\script{1\over 2}}]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H31⋯O1ⁱⁱ	0.83 (5)	1.96 (5)	2.786 (3)	176 (5)
O3—H32⋯O2ⁱⁱⁱ	0.94 (4)	1.75 (4)	2.672 (3)	167 (4)
Symmetry codes: (ii) x, y-1, z; (iii) $[-x+{\script{1\over 2}}, y-1, z+{\script{1\over 2}}]$ .

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: https://doi.org/10.1107/S1600536812024683/kp2421sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812024683/kp2421Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812024683/kp2421Isup3.cml

checkCIF report

Comment top

The structure of the title complex is built of Li^I ions, each coordinated by ligand with N1,O1 where O atom acts as bidentate and bridging to symmetry related Li1 and Li1ⁱ ions, whereas the O2 atom remains chelating inactive. The metal ions are also bridged by coordinated water O3 atom forming a Li1—O1—Li1ⁱ—O3—Li1 connectivity with Li1—Li1ⁱ distance of 3.052 (4) Å, (Fig.1). The observed bonding pathways –Li—O_carb—Li- and –Li—O_aqua—Li- give rise to molecular ribbon which propagates in the unit cell c direction (Fig. 2). The Li1 coordination polyhedron is distorted trigonal bipyramid (Fig. 1, Table 1) with an equatorial plane composed of O1, N1ⁱ and O3ⁱ; the Li1 ion is 0.0405 (2) Å out of the plane, O1 and O3 atoms are at the axial positions. The pyrazine ring is planar with r.m.s. of 0.0019 (1) Å; the dihedral angle between the pyrazine and the carboxylato group (C7/O1/O2) is 12.3 (1)°. Hydrogen bonds are realised through coordinated aqua O3 and carboxylato O2 atoms (Table 2, Fig. 2). Weak C—H···N interactions of 3.518 (5) Å and 3.651 (5) Å are observed. The structures of Li^I complexes with diazine monocarboxylate ligands show a variety of polymeric patterns. The structure of a complex with 3-aminopyrazine-2-carboxylato ligand shows a catenated pattern (Starosta & Leciejewicz, 2010) while the structure of a complex with 5-methylpyrazine-2-carboxylato ligand is composed of molecular columns (Starosta & Leciejewicz, 2011a). Molecular layers were reported in the structure of a complex with pyrimidine-2-carboxylato and nitrato ligands (Starosta & Leciejewicz, 2011d) and in the structure of a complex with pyridazine-4-carboxylato ligand (Starosta & Leciejewicz, 2011c). On the other hand, the structure of a complex with pyridazine-3-carboxylato ligand is built of monomeric molecules (Starosta & Leciejewicz, 2011b).

Related literature top

For the crystal structure of an Li^I complex with a 3-aminopyrazine-2-carboxylate ligand, see: Starosta & Leciejewicz, (2010) and for the crystal structure of an Li^I complex with a 5-methylpyrazine-2-carboxylate ligand, see: Starosta & Leciejewicz, (2011a). The structures of complexes with pyridazine-3-carboxylate and pyridazine-4-carboxylate ligands were reported by Starosta & Leciejewicz, (2011b,c). The structure of a complex with a pyrimidine-2-carboxylate ligand was also determined (Starosta & Leciejewicz, 2011d).

Experimental top

50 mL of a solution containing 1 mmol of LiNO₃ and an excess of pyrazine-2-carboxylic acid dihydrate to mantain pH ca 5.1 was boiled under reflux with stirring for 10 h, then left to crystallise at room temperature. After a couple of days single-crystal blocks of the title compound were detected among polycrystalline material. They were washed with methanol and dried in the air.

Structure description top

# Used for convenience to store draft or replaced versions # of the abstract, comment etc. # Its contents will not be output

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. Two structural units of the title compound with atom labelling scheme and 50% probability displacement ellipsoids. Symmetry code: (i) -x + 1/2, y, z - 1/2; (ii) -x + 1/2, y, z + 1/2.
	Fig. 2. Packing diagram of the structure viewed along the c axis.

Poly[µ₂-aqua-µ₂-(pyrazine-2-carboxylato)-lithium] top

Crystal data top

[Li(C₅H₃N₂O₂)(H₂O)]	F(000) = 304
M_r = 148.05	D_x = 1.491 Mg m⁻³
Orthorhombic, Pca2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 25 reflections
a = 24.433 (5) Å	θ = 6–15°
b = 4.7861 (10) Å	µ = 0.12 mm⁻¹
c = 5.6385 (11) Å	T = 293 K
V = 659.4 (2) Å³	Blocks, colourless
Z = 4	0.35 × 0.18 × 0.13 mm

Data collection top

Kuma KM-4 four-cricle diffractometer	813 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.078
Graphite monochromator	θ_max = 30.1°, θ_min = 1.7°
profile data from ω/2θ scans	h = −27→34
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008)	k = 0→6
T_min = 0.972, T_max = 0.995	l = 0→7
1586 measured reflections	3 standard reflections every 200 reflections
1056 independent reflections	intensity decay: 4.4%

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.116	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ²(F_o²) + (0.0244P)² + 0.4211P] where P = (F_o² + 2F_c²)/3
1056 reflections	(Δ/σ)_max < 0.001
108 parameters	Δρ_max = 0.31 e Å⁻³
1 restraint	Δρ_min = −0.30 e Å⁻³

Crystal data top

[Li(C₅H₃N₂O₂)(H₂O)]	V = 659.4 (2) Å³
M_r = 148.05	Z = 4
Orthorhombic, Pca2₁	Mo Kα radiation
a = 24.433 (5) Å	µ = 0.12 mm⁻¹
b = 4.7861 (10) Å	T = 293 K
c = 5.6385 (11) Å	0.35 × 0.18 × 0.13 mm

Data collection top

Kuma KM-4 four-cricle diffractometer	813 reflections with I > 2σ(I)
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008)	R_int = 0.078
T_min = 0.972, T_max = 0.995	3 standard reflections every 200 reflections
1586 measured reflections	intensity decay: 4.4%
1056 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	1 restraint
wR(F²) = 0.116	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	Δρ_max = 0.31 e Å⁻³
1056 reflections	Δρ_min = −0.30 e Å⁻³
108 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
O1	0.28627 (9)	1.1874 (4)	0.7415 (4)	0.0324 (4)
O2	0.35150 (10)	1.3781 (5)	0.5168 (5)	0.0480 (7)
N1	0.36091 (10)	0.8665 (5)	0.9601 (5)	0.0320 (5)
C2	0.37639 (11)	1.0110 (5)	0.7680 (5)	0.0258 (5)
C7	0.33500 (11)	1.2093 (5)	0.6658 (5)	0.0281 (5)
C5	0.44910 (14)	0.6601 (7)	0.9486 (7)	0.0453 (8)
H5	0.4735	0.5346	1.0167	0.054*
N2	0.46487 (12)	0.8025 (6)	0.7586 (6)	0.0462 (7)
C6	0.39802 (14)	0.6901 (7)	1.0492 (6)	0.0414 (7)
H6	0.3892	0.5851	1.1825	0.050*
C3	0.42814 (12)	0.9788 (7)	0.6705 (6)	0.0364 (6)
H3	0.4375	1.0848	0.5383	0.044*
Li1	0.2739 (2)	0.9324 (11)	1.0354 (10)	0.0338 (10)
O3	0.22904 (9)	0.6809 (4)	0.8254 (4)	0.0282 (4)
H31	0.247 (3)	0.538 (8)	0.796 (9)	0.051 (11)*
H32	0.1986 (18)	0.599 (8)	0.901 (7)	0.046 (11)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0283 (8)	0.0332 (9)	0.0358 (10)	0.0041 (8)	0.0052 (9)	0.0123 (10)
O2	0.0369 (11)	0.0567 (13)	0.0504 (15)	0.0051 (10)	0.0081 (11)	0.0333 (12)
N1	0.0324 (12)	0.0371 (11)	0.0265 (11)	0.0009 (10)	0.0033 (11)	0.0109 (10)
C2	0.0244 (10)	0.0276 (10)	0.0254 (11)	−0.0016 (10)	0.0010 (10)	0.0055 (10)
C7	0.0288 (11)	0.0282 (11)	0.0274 (12)	0.0006 (10)	0.0000 (11)	0.0069 (12)
C5	0.0361 (16)	0.0481 (17)	0.0517 (19)	0.0118 (14)	−0.0062 (17)	0.0153 (16)
N2	0.0333 (13)	0.0540 (16)	0.0514 (17)	0.0105 (12)	0.0064 (13)	0.0105 (16)
C6	0.0388 (16)	0.0493 (17)	0.0362 (15)	0.0036 (13)	−0.0019 (14)	0.0205 (15)
C3	0.0311 (13)	0.0433 (15)	0.0347 (14)	0.0014 (12)	0.0098 (13)	0.0093 (14)
Li1	0.036 (3)	0.040 (2)	0.026 (2)	−0.002 (2)	0.001 (2)	0.007 (2)
O3	0.0328 (9)	0.0287 (9)	0.0230 (8)	−0.0004 (8)	0.0014 (8)	0.0075 (9)

Geometric parameters (Å, º) top

O1—C7	1.269 (4)	N2—C3	1.328 (4)
Li1—O1	2.080 (6)	C6—H6	0.9300
O1—Li1ⁱ	2.237 (6)	C3—H3	0.9300
O2—C7	1.233 (4)	Li1—O3	2.013 (6)
N1—C6	1.337 (4)	Li1—O3ⁱⁱ	2.032 (5)
N1—C2	1.340 (4)	Li1—O1ⁱⁱ	2.237 (6)
Li1—N1	2.190 (6)	Li1—Li1ⁱ	3.052 (4)
C2—C3	1.387 (4)	Li1—Li1ⁱⁱ	3.052 (4)
C2—C7	1.502 (4)	O3—Li1ⁱ	2.032 (5)
C5—N2	1.327 (5)	O3—H31	0.83 (5)
C5—C6	1.379 (5)	O3—H32	0.94 (4)
C5—H5	0.9300

C7—O1—Li1	116.9 (2)	O3—Li1—N1	109.2 (3)
C7—O1—Li1ⁱ	119.2 (2)	O3ⁱⁱ—Li1—N1	96.0 (2)
Li1—O1—Li1ⁱ	89.92 (19)	O1—Li1—N1	77.8 (2)
C6—N1—C2	116.0 (3)	O3—Li1—O1ⁱⁱ	105.9 (3)
C6—N1—Li1	132.6 (3)	O3ⁱⁱ—Li1—O1ⁱⁱ	83.2 (2)
C2—N1—Li1	110.9 (2)	O1—Li1—O1ⁱⁱ	100.9 (2)
N1—C2—C3	121.4 (3)	N1—Li1—O1ⁱⁱ	144.8 (3)
N1—C2—C7	116.5 (2)	O3—Li1—Li1ⁱ	41.25 (17)
C3—C2—C7	122.1 (2)	O3ⁱⁱ—Li1—Li1ⁱ	136.9 (2)
O2—C7—O1	126.1 (3)	O1—Li1—Li1ⁱ	47.12 (13)
O2—C7—C2	117.1 (3)	N1—Li1—Li1ⁱ	101.1 (2)
O1—C7—C2	116.8 (2)	O1ⁱⁱ—Li1—Li1ⁱ	103.2 (3)
N2—C5—C6	122.8 (3)	O3—Li1—Li1ⁱⁱ	109.5 (3)
N2—C5—H5	118.6	O3ⁱⁱ—Li1—Li1ⁱⁱ	40.79 (14)
C6—C5—H5	118.6	O1—Li1—Li1ⁱⁱ	142.33 (19)
C5—N2—C3	115.6 (3)	N1—Li1—Li1ⁱⁱ	123.4 (3)
N1—C6—C5	121.7 (3)	O1ⁱⁱ—Li1—Li1ⁱⁱ	42.96 (17)
N1—C6—H6	119.2	Li1ⁱ—Li1—Li1ⁱⁱ	135.0 (4)
C5—C6—H6	119.2	Li1—O3—Li1ⁱ	98.0 (2)
N2—C3—C2	122.5 (3)	Li1—O3—H31	109 (4)
N2—C3—H3	118.7	Li1ⁱ—O3—H31	110 (3)
C2—C3—H3	118.7	Li1—O3—H32	114 (3)
O3—Li1—O3ⁱⁱ	95.7 (2)	Li1ⁱ—O3—H32	126 (2)
O3—Li1—O1	87.8 (2)	H31—O3—H32	100 (4)
O3ⁱⁱ—Li1—O1	173.7 (3)

Symmetry codes: (i) −x+1/2, y, z−1/2; (ii) −x+1/2, y, z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H31···O1ⁱⁱⁱ	0.83 (5)	1.96 (5)	2.786 (3)	176 (5)
O3—H32···O2^iv	0.94 (4)	1.75 (4)	2.672 (3)	167 (4)

Symmetry codes: (iii) x, y−1, z; (iv) −x+1/2, y−1, z+1/2.

Experimental details

Crystal data
Chemical formula	[Li(C₅H₃N₂O₂)(H₂O)]
M_r	148.05
Crystal system, space group	Orthorhombic, Pca2₁
Temperature (K)	293
a, b, c (Å)	24.433 (5), 4.7861 (10), 5.6385 (11)
V (Å³)	659.4 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.35 × 0.18 × 0.13

Data collection
Diffractometer	Kuma KM-4 four-cricle
Absorption correction	Analytical (CrysAlis RED; Oxford Diffraction, 2008)
T_min, T_max	0.972, 0.995
No. of measured, independent and observed [I > 2σ(I)] reflections	1586, 1056, 813
R_int	0.078
(sin θ/λ)_max (Å⁻¹)	0.705

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.116, 1.09
No. of reflections	1056
No. of parameters	108
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.30

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—O1	2.080 (6)	Li1—O3ⁱ	2.032 (5)
Li1—N1	2.190 (6)	Li1—O1ⁱ	2.237 (6)
Li1—O3	2.013 (6)

Symmetry code: (i) −x+1/2, y, z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H31···O1ⁱⁱ	0.83 (5)	1.96 (5)	2.786 (3)	176 (5)
O3—H32···O2ⁱⁱⁱ	0.94 (4)	1.75 (4)	2.672 (3)	167 (4)

Symmetry codes: (ii) x, y−1, z; (iii) −x+1/2, y−1, z+1/2.

References

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
Starosta, W. & Leciejewicz, J. (2010). Acta Cryst. E66, m744–m745. Web of Science CSD CrossRef IUCr Journals Google Scholar
Starosta, W. & Leciejewicz, J. (2011a). Acta Cryst. E67, m1000–m1001. Web of Science CSD CrossRef IUCr Journals Google Scholar
Starosta, W. & Leciejewicz, J. (2011b). Acta Cryst. E67, m202. Web of Science CSD CrossRef IUCr Journals Google Scholar
Starosta, W. & Leciejewicz, J. (2011c). Acta Cryst. E67, m425–m426. Web of Science CSD CrossRef IUCr Journals Google Scholar
Starosta, W. & Leciejewicz, J. (2011d). Acta Cryst. E67, m818. Web of Science CSD CrossRef IUCr Journals Google Scholar

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Volume 68| Part 7| July 2012| Pages m933-m934

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