catena-Poly[[tetra­aqua-μ-aqua-bis­(μ4-pyrimidine-2-carboxyl­ato)tetra­lithium] dichloride]

Starosta, W.; Leciejewicz, J.

doi:10.1107/S1600536812041955

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 11| November 2012| Pages m1369-m1370

doi:10.1107/S1600536812041955

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catena-Poly[[tetraaqua-μ-aqua-bis(μ₄-pyrimidine-2-carboxylato)tetralithium] dichloride]

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 27 September 2012; accepted 7 October 2012; online 20 October 2012)

The asymmetric unit of the title compound, [Li₄(C₅H₃N₂O₂)₂(H₂O)₅]Cl₂, contains two Li^I cations, one with a distorted trigonal–bipyramidal and the other with a distorted tetrahedral coordination geometry. Two symmetry-related asymmetric units constitute a building block of the structure, in which both ligand carboxylate O atoms are bidentate and bridge the metal ions, forming a divalent cation. Charge balance is maintained by two chloride anions. The building blocks, bridged by Li^I cations, form cationic ribbons with chloride anions in the space between them. The ribbons propagate in [010] and are held together by a network of weak O—H⋯O hydrogen bonds which operate in the space between adjacent ribbons.

Related literature

For the structure of a Li complex with pyrimidine-2-carboxylate and nitrate ligands, see: Starosta & Leciejewicz (2011 ). The structure of a Li^I complex with pyrimidine-4-carboxylate and water ligands was reported recently by Starosta & Leciejewicz (2012 ).

Experimental

Crystal data

[Li₄(C₅H₃N₂O₂)₂(H₂O)₅]Cl₂
M_r = 434.93
Monoclinic, C 2/c
a = 22.084 (4) Å
b = 8.0773 (16) Å
c = 10.814 (2) Å
β = 94.08 (3)°
V = 1924.1 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.39 mm⁻¹
T = 293 K
0.37 × 0.24 × 0.18 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 = 0.917, T_max = 0.935
2964 measured reflections
2819 independent reflections
1781 reflections with I > 2σ(I)
R_int = 0.029
3 standard reflections every 200 reflections intensity decay: 2.3%

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.147
S = 1.02
2819 reflections
152 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Table 1
Selected bond lengths (Å)

Li1—O1	2.069 (3)
Li1—N1	2.175 (4)
Li1—O3	1.987 (4)
Li1—O2ⁱ	2.029 (4)
Li1—N3ⁱ	2.221 (4)
Li2—O21	2.140 (6)
Li2—O22	1.915 (4)
Li2—O2ⁱⁱ	1.968 (4)
Li2—O1	1.993 (4)
Symmetry codes: (i) $[x, -y+2, z+{\script{1\over 2}}]$ ; (ii) $[-x, y, -z+{\script{1\over 2}}]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O22—H222⋯O3	0.89 (2)	2.16 (3)	2.841 (3)	133 (3)
O22—H221⋯Cl1ⁱⁱⁱ	0.87 (2)	2.36 (2)	3.212 (2)	167 (3)
O3—H31⋯Cl1	0.83 (4)	2.35 (4)	3.1381 (19)	158 (3)
O3—H32⋯Cl1^iv	0.86 (4)	2.29 (4)	3.1429 (19)	168 (4)
O21—H211⋯Cl1^v	0.84 (3)	2.45 (3)	3.288 (2)	175 (3)
Symmetry codes: (iii) $[-x, y, -z+{\script{3\over 2}}]$ ; (iv) $[x, -y+1, z-{\script{1\over 2}}]$ ; (v) -x, -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

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812041955/qm2084sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812041955/qm2084Isup2.hkl

checkCIF report

Comment top

The asymmetric cell of the title compound contains two symmetry independent Li^I ions, one deprotonated pyramidine-2-carboxylatato ligand molecule, three symmetry independent water molecules which are coordinated to metal ions and one chloride anion. The latter maintains charge balance in the cell. Two symmetry related cells form a molecular moiety which can be visualized as a building unit of the structure (Fig. 1).The ligand bridges Li ions in a µ₄ mode using both its carboxylate O atoms which act as bidentate. Ligand bonding groups N1,O1 and N3,O2 chelate Li1 and Liⁱⁱ ions; the O1 and O2 atoms are also bonded to Li2 and Li2ⁱ ions, respectively. Since the Li1 and Li1ⁱⁱ ions are also coordinated by bonding groups from adjacent symmetry related ligands, a –Li1ⁱⁱ—O2—O1—Li1—O2ⁱⁱⁱO1ⁱⁱⁱ—Li1ⁱⁱⁱ– bridging pathway is formed. Apart from two N,O bonding groups, Li1 coordination is completed by an aqua O3 atom. On the other hand, pairs of adjacent symmetry related Li2 and Li2ⁱ ions are bridged by an aqua O21 atom while the other coordinated to them aqua O22 and O22ⁱ atoms are not bridging. Symmetry code: ⁱ -x, y, -z + 1/2; ⁱⁱ x, -y + 2, z - 1/2; ⁱⁱⁱ x, -y + 2, z + 1/2. Adjacent moieties linked along the Li1 bridging pathway form a cationic ribbon propagating in the unit cell b direction (Fig. 2). Chloride anions are located in the space between adjacent ribbons. Fig. 1 shows, that a ribbon can be visualized as built of centro-symmetric molecular clusters in which Li ions form a tetrameric entities additionally connected by Li2—O21—Li2ⁱ bridges. The Li1 ion exhibits a distorted trigonal bipyramidal coordination environment in which O1, O3 and N3ⁱⁱⁱ atoms form an equatorial plane with a Li1 ion 0.0619 (2) Å out of it; N1 and O2ⁱⁱⁱ atoms are at apical positions. The coordination of the Li2 ion is strongly distorted tetrahedral. The Li—O and Li—N bond distances (Table 1) are close to those reported in the structures of a Li complex with the title and nitrate ligands (Starosta & Leciejewicz, 2011) and pyrimidine-4-carboxylate and water ligands (Starosta & Leciejewicz, 2012). The pyrimidine ring is planar with r.m.s. of 0.0071 (1) Å; the C7/O1/O2 makes with it a dihedral angle of 5.8 (1)°. Weak hydrogen bonds in which water O atoms are as donors and chloride anions act as acceptors operate between adjacent ribbons (Table 2).

Related literature top

For the structure of a Li complex with pyrimidine-2-carboxylate and nitrate ligands, see: Starosta & Leciejewicz (2011). The structure of a Li^I complex with pyrimidine-4-carboxylate and water ligands was reported recently by Starosta & Leciejewicz (2012).

Experimental top

1 mmol of methyl pyrimidine-2-carboxylate and ca2 mmol s of lithium hydroxide dissolved in 50 ml of hot, doubly distilled water were boiled under reflux with stirring for twenty hours. After evaporation to dryness at room temperature the polycrystalline material was dissolved in 50 ml of water. The solution was titrated with 1 N HCl until the pH reached 6.0 and then stirred for 3 h at ca 320 K. Left to crystallize at room temperature, colourless single-crystal blocks deposited after a week. They were washed with cold methanol 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 cationic ribbon of the title compound with atom labelling scheme and 50% probability displacement ellipsoids. Symmetry code: ⁱ -x, y, -z + 1/2; ⁱⁱ x, -y + 2, z - 1/2; ⁱⁱⁱ x, -y + 2, z + 1/2; ^iv -x, -y + 2, z + 1.
	Fig. 2. The alignment of cationic ribbons and chloride anions in the structure of the title compound viewed along the unit cell b direction.

catena-Poly[[tetraaqua-µ-aqua-bis(µ₄-pyrimidine-2-carboxylato)tetralithium] dichloride] top

Crystal data top

[Li₄(C₅H₃N₂O₂)₂(H₂O)₅]Cl₂	F(000) = 888
M_r = 434.93	D_x = 1.501 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 25 reflections
a = 22.084 (4) Å	θ = 6–15°
b = 8.0773 (16) Å	µ = 0.39 mm⁻¹
c = 10.814 (2) Å	T = 293 K
β = 94.08 (3)°	Block, colourless
V = 1924.1 (7) Å³	0.37 × 0.24 × 0.18 mm
Z = 4

Data collection top

Kuma KM4 four-circle diffractometer	1781 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.029
Graphite monochromator	θ_max = 30.1°, θ_min = 1.9°
profile data from ω/2θ scans	h = −31→31
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008)	k = −11→0
T_min = 0.917, T_max = 0.935	l = 0→15
2964 measured reflections	3 standard reflections every 200 reflections
2819 independent reflections	intensity decay: 2.3%

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.147	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0879P)² + 1.2478P] where P = (F_o² + 2F_c²)/3
2819 reflections	(Δ/σ)_max = 0.004
152 parameters	Δρ_max = 0.51 e Å⁻³
4 restraints	Δρ_min = −0.36 e Å⁻³

Crystal data top

[Li₄(C₅H₃N₂O₂)₂(H₂O)₅]Cl₂	V = 1924.1 (7) Å³
M_r = 434.93	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 22.084 (4) Å	µ = 0.39 mm⁻¹
b = 8.0773 (16) Å	T = 293 K
c = 10.814 (2) Å	0.37 × 0.24 × 0.18 mm
β = 94.08 (3)°

Data collection top

Kuma KM4 four-circle diffractometer	1781 reflections with I > 2σ(I)
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008)	R_int = 0.029
T_min = 0.917, T_max = 0.935	3 standard reflections every 200 reflections
2964 measured reflections	intensity decay: 2.3%
2819 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	4 restraints
wR(F²) = 0.147	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.51 e Å⁻³
2819 reflections	Δρ_min = −0.36 e Å⁻³
152 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	0.08301 (6)	0.92604 (19)	0.37614 (11)	0.0321 (3)
O2	0.08768 (6)	0.96441 (19)	0.17202 (11)	0.0319 (3)
N3	0.20103 (7)	1.0854 (2)	0.20733 (13)	0.0277 (3)
N1	0.19897 (7)	1.0170 (2)	0.42115 (13)	0.0277 (3)
C6	0.25599 (9)	1.0720 (3)	0.43984 (17)	0.0326 (4)
H6	0.2752	1.0657	0.5191	0.039*
C2	0.17410 (7)	1.0274 (2)	0.30494 (14)	0.0232 (3)
C4	0.25768 (9)	1.1411 (3)	0.22901 (18)	0.0332 (4)
H4	0.2778	1.1836	0.1634	0.040*
C5	0.28729 (9)	1.1378 (3)	0.3457 (2)	0.0353 (4)
H5	0.3266	1.1781	0.3601	0.042*
Li1	0.13426 (15)	0.9162 (5)	0.5437 (3)	0.0323 (7)
O3	0.11355 (9)	0.6795 (2)	0.56747 (16)	0.0469 (4)
C7	0.10916 (8)	0.9673 (2)	0.28238 (14)	0.0239 (3)
O21	0.0000	0.6868 (4)	0.2500	0.0527 (6)
Li2	−0.00573 (17)	0.8841 (8)	0.3807 (4)	0.0590 (13)
Cl1	0.10829 (3)	0.57231 (8)	0.84542 (5)	0.04391 (17)
H211	−0.0286 (13)	0.622 (4)	0.230 (3)	0.064 (10)*
H32	0.1130 (18)	0.599 (5)	0.515 (4)	0.086 (12)*
H31	0.1170 (14)	0.627 (4)	0.634 (3)	0.065 (9)*
O22	−0.00669 (8)	0.8066 (3)	0.54795 (18)	0.0618 (6)
H221	−0.0386 (10)	0.754 (4)	0.570 (3)	0.075 (10)*
H222	0.0166 (14)	0.717 (4)	0.555 (3)	0.120 (17)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0302 (6)	0.0478 (8)	0.0185 (6)	−0.0032 (6)	0.0031 (5)	0.0039 (5)
O2	0.0313 (6)	0.0472 (8)	0.0164 (5)	−0.0051 (6)	−0.0040 (4)	0.0036 (5)
N3	0.0316 (7)	0.0335 (8)	0.0181 (6)	−0.0022 (6)	0.0028 (5)	0.0009 (6)
N1	0.0312 (7)	0.0352 (8)	0.0165 (6)	−0.0006 (6)	−0.0012 (5)	0.0012 (6)
C6	0.0330 (8)	0.0390 (10)	0.0245 (8)	−0.0006 (8)	−0.0062 (6)	−0.0016 (7)
C2	0.0291 (8)	0.0258 (8)	0.0148 (6)	0.0024 (6)	0.0012 (5)	0.0000 (6)
C4	0.0354 (9)	0.0361 (10)	0.0289 (9)	−0.0051 (8)	0.0075 (7)	0.0008 (7)
C5	0.0289 (9)	0.0392 (10)	0.0373 (10)	−0.0036 (8)	−0.0006 (7)	−0.0014 (8)
Li1	0.0376 (16)	0.0420 (18)	0.0173 (13)	0.0004 (14)	0.0020 (11)	−0.0006 (12)
O3	0.0754 (12)	0.0358 (8)	0.0277 (7)	0.0017 (8)	−0.0090 (7)	0.0005 (7)
C7	0.0258 (7)	0.0285 (8)	0.0171 (7)	0.0017 (6)	0.0006 (5)	0.0009 (6)
O21	0.0337 (11)	0.0675 (17)	0.0551 (15)	0.000	−0.0086 (10)	0.000
Li2	0.0301 (17)	0.116 (4)	0.0305 (18)	0.009 (2)	0.0030 (14)	0.018 (2)
Cl1	0.0420 (3)	0.0553 (3)	0.0345 (3)	−0.0001 (2)	0.00346 (19)	0.0087 (2)
O22	0.0349 (8)	0.0967 (16)	0.0550 (11)	0.0101 (10)	0.0123 (7)	0.0338 (11)

Geometric parameters (Å, º) top

O1—C7	1.247 (2)	Li1—N3ⁱⁱⁱ	2.221 (4)
Li1—O1	2.069 (3)	Li1—Li2^iv	3.414 (6)
O2—C7	1.2528 (19)	O3—H32	0.86 (4)
O2—Li2ⁱ	1.968 (4)	O3—H31	0.83 (4)
O2—Li1ⁱⁱ	2.029 (4)	Li2—O21	2.140 (6)
N3—C2	1.333 (2)	O21—Li2ⁱ	2.140 (6)
N3—C4	1.335 (2)	O21—H211	0.84 (3)
N3—Li1ⁱⁱ	2.221 (4)	Li2—O22	1.915 (4)
N1—C6	1.337 (2)	Li2—O2ⁱ	1.968 (4)
N1—C2	1.338 (2)	Li2—O1	1.993 (4)
Li1—N1	2.175 (4)	Li2—O22^iv	2.623 (7)
C6—C5	1.377 (3)	Li2—Li2ⁱ	2.856 (8)
C6—H6	0.9300	Li2—Li2^iv	3.183 (11)
C2—C7	1.517 (2)	Li2—Li1^iv	3.414 (6)
C4—C5	1.379 (3)	Li2—H222	2.343 (18)
C4—H4	0.9300	O22—Li2^iv	2.623 (7)
C5—H5	0.9300	O22—H221	0.868 (18)
Li1—O3	1.987 (4)	O22—H222	0.891 (18)
Li1—O2ⁱⁱⁱ	2.029 (4)

C7—O1—Li2	125.36 (16)	Li2—O21—Li2ⁱ	83.7 (3)
C7—O1—Li1	117.79 (15)	Li2—O21—H211	124 (2)
Li2—O1—Li1	116.70 (16)	Li2ⁱ—O21—H211	112 (2)
C7—O2—Li2ⁱ	124.07 (17)	O22—Li2—O2ⁱ	108.02 (19)
C7—O2—Li1ⁱⁱ	117.82 (15)	O22—Li2—O1	98.98 (19)
Li2ⁱ—O2—Li1ⁱⁱ	117.32 (18)	O2ⁱ—Li2—O1	145.3 (3)
C2—N3—C4	116.42 (15)	O22—Li2—O21	112.7 (3)
C2—N3—Li1ⁱⁱ	108.69 (14)	O2ⁱ—Li2—O21	98.6 (2)
C4—N3—Li1ⁱⁱ	134.65 (15)	O1—Li2—O21	90.32 (18)
C6—N1—C2	116.14 (15)	O22—Li2—O22^iv	92.4 (2)
C6—N1—Li1	133.22 (14)	O2ⁱ—Li2—O22^iv	81.1 (2)
C2—N1—Li1	110.62 (14)	O1—Li2—O22^iv	76.29 (19)
N1—C6—C5	122.22 (17)	O21—Li2—O22^iv	153.3 (2)
N1—C6—H6	118.9	O22—Li2—Li2ⁱ	160.4 (2)
C5—C6—H6	118.9	O2ⁱ—Li2—Li2ⁱ	81.81 (19)
N3—C2—N1	126.11 (16)	O1—Li2—Li2ⁱ	79.56 (18)
N3—C2—C7	117.06 (14)	O21—Li2—Li2ⁱ	48.13 (14)
N1—C2—C7	116.82 (15)	O22^iv—Li2—Li2ⁱ	106.04 (10)
N3—C4—C5	122.10 (17)	O22—Li2—Li2^iv	55.42 (15)
N3—C4—H4	119.0	O2ⁱ—Li2—Li2^iv	93.4 (2)
C5—C4—H4	119.0	O1—Li2—Li2^iv	84.2 (2)
C6—C5—C4	116.98 (18)	O21—Li2—Li2^iv	165.6 (3)
C6—C5—H5	121.5	O22^iv—Li2—Li2^iv	36.95 (15)
C4—C5—H5	121.5	Li2ⁱ—Li2—Li2^iv	142.6 (2)
O3—Li1—O2ⁱⁱⁱ	103.68 (16)	O22—Li2—Li1^iv	82.13 (16)
O3—Li1—O1	91.92 (15)	O2ⁱ—Li2—Li1^iv	31.87 (10)
O2ⁱⁱⁱ—Li1—O1	107.96 (16)	O1—Li2—Li1^iv	139.6 (3)
O3—Li1—N1	127.32 (18)	O21—Li2—Li1^iv	126.81 (17)
O2ⁱⁱⁱ—Li1—N1	128.74 (19)	O22^iv—Li2—Li1^iv	63.32 (13)
O1—Li1—N1	78.11 (12)	Li2ⁱ—Li2—Li1^iv	111.75 (17)
O3—Li1—N3ⁱⁱⁱ	92.14 (15)	Li2^iv—Li2—Li1^iv	63.10 (15)
O2ⁱⁱⁱ—Li1—N3ⁱⁱⁱ	78.36 (12)	O22—Li2—H222	21.2 (6)
O1—Li1—N3ⁱⁱⁱ	171.42 (18)	O2ⁱ—Li2—H222	124.0 (7)
N1—Li1—N3ⁱⁱⁱ	93.42 (14)	O1—Li2—H222	88.1 (8)
O3—Li1—Li2^iv	102.75 (17)	O21—Li2—H222	94.7 (9)
O2ⁱⁱⁱ—Li1—Li2^iv	30.81 (10)	O22^iv—Li2—H222	107.6 (10)
O1—Li1—Li2^iv	77.24 (13)	Li2ⁱ—Li2—H222	140.1 (7)
N1—Li1—Li2^iv	124.23 (17)	Li2^iv—Li2—H222	71.8 (9)
N3ⁱⁱⁱ—Li1—Li2^iv	109.16 (14)	Li1^iv—Li2—H222	102.2 (6)
Li1—O3—H32	129 (3)	Li2—O22—Li2^iv	87.6 (2)
Li1—O3—H31	126 (2)	Li2—O22—H221	119 (2)
H32—O3—H31	101 (3)	Li2^iv—O22—H221	117 (2)
O1—C7—O2	127.12 (16)	Li2—O22—H222	107.6 (17)
O1—C7—C2	116.22 (14)	Li2^iv—O22—H222	135 (3)
O2—C7—C2	116.65 (15)	H221—O22—H222	93 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O22—H222···O3	0.89 (2)	2.16 (3)	2.841 (3)	133 (3)
O22—H221···Cl1^v	0.87 (2)	2.36 (2)	3.212 (2)	167 (3)
O3—H31···Cl1	0.83 (4)	2.35 (4)	3.1381 (19)	158 (3)
O3—H32···Cl1^vi	0.86 (4)	2.29 (4)	3.1429 (19)	168 (4)
O21—H211···Cl1^vii	0.84 (3)	2.45 (3)	3.288 (2)	175 (3)

Symmetry codes: (v) −x, y, −z+3/2; (vi) x, −y+1, z−1/2; (vii) −x, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	[Li₄(C₅H₃N₂O₂)₂(H₂O)₅]Cl₂
M_r	434.93
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	22.084 (4), 8.0773 (16), 10.814 (2)
β (°)	94.08 (3)
V (Å³)	1924.1 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.39
Crystal size (mm)	0.37 × 0.24 × 0.18

Data collection
Diffractometer	Kuma KM4 four-circle diffractometer
Absorption correction	Analytical (CrysAlis RED; Oxford Diffraction, 2008)
T_min, T_max	0.917, 0.935
No. of measured, independent and observed [I > 2σ(I)] reflections	2964, 2819, 1781
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.705

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.147, 1.02
No. of reflections	2819
No. of parameters	152
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.51, −0.36

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	2.069 (3)	Li2—O21	2.140 (6)
Li1—N1	2.175 (4)	Li2—O22	1.915 (4)
Li1—O3	1.987 (4)	Li2—O2ⁱⁱ	1.968 (4)
Li1—O2ⁱ	2.029 (4)	Li2—O1	1.993 (4)
Li1—N3ⁱ	2.221 (4)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O22—H222···O3	0.891 (18)	2.16 (3)	2.841 (3)	133 (3)
O22—H221···Cl1ⁱⁱⁱ	0.868 (18)	2.36 (2)	3.212 (2)	167 (3)
O3—H31···Cl1	0.83 (4)	2.35 (4)	3.1381 (19)	158 (3)
O3—H32···Cl1^iv	0.86 (4)	2.29 (4)	3.1429 (19)	168 (4)
O21—H211···Cl1^v	0.84 (3)	2.45 (3)	3.288 (2)	175 (3)

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

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. (2011). Acta Cryst. E67, m818. Web of Science CSD CrossRef IUCr Journals Google Scholar
Starosta, W. & Leciejewicz, J. (2012). Acta Cryst. E68, m1065–m1066. CSD CrossRef CAS IUCr Journals Google Scholar

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