catena-Poly[[tetra-aqua-μ-aqua-bis-(μ(4)-pyrimidine-2-carboxyl-ato)tetra-lithium] dichloride].

The asymmetric unit of the title compound, [Li(4)(C(5)H(3)N(2)O(2))(2)(H(2)O)(5)]Cl(2), contains two Li(I) cations, one with a distorted trigonal-bipyramidal and the other with a distorted tetra-hedral coordination geometry. Two symmetry-related asymmetric units constitute a building block of the structure, in which both ligand carboxyl-ate 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 LiI 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 = 434.93

Monoclinic,

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 ▶) 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[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.147

S = 1.02

2819 reflections

152 parameters

4 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.51 e Å−3

Δρmin = −0.36 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.

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812041955/qm2084sup1.cif

Click here for additional data file.

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

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

[Li4(C5H3N2O2)2(H2O)5]Cl2	F(000) = 888
Mr = 434.93	Dx = 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

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

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(Fo2) + (0.0879P)2 + 1.2478P] where P = (Fo2 + 2Fc2)/3
2819 reflections	(Δ/σ)max = 0.004
152 parameters	Δρmax = 0.51 e Å−3
4 restraints	Δρmin = −0.36 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
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)*

	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)

O1—C7	1.247 (2)	Li1—N3iii	2.221 (4)
Li1—O1	2.069 (3)	Li1—Li2iv	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—O22iv	2.623 (7)
C6—C5	1.377 (3)	Li2—Li2i	2.856 (8)
C6—H6	0.9300	Li2—Li2iv	3.183 (11)
C2—C7	1.517 (2)	Li2—Li1iv	3.414 (6)
C4—C5	1.379 (3)	Li2—H222	2.343 (18)
C4—H4	0.9300	O22—Li2iv	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—O22iv	92.4 (2)
C6—N1—Li1	133.22 (14)	O2i—Li2—O22iv	81.1 (2)
C2—N1—Li1	110.62 (14)	O1—Li2—O22iv	76.29 (19)
N1—C6—C5	122.22 (17)	O21—Li2—O22iv	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)	O22iv—Li2—Li2i	106.04 (10)
N3—C4—C5	122.10 (17)	O22—Li2—Li2iv	55.42 (15)
N3—C4—H4	119.0	O2i—Li2—Li2iv	93.4 (2)
C5—C4—H4	119.0	O1—Li2—Li2iv	84.2 (2)
C6—C5—C4	116.98 (18)	O21—Li2—Li2iv	165.6 (3)
C6—C5—H5	121.5	O22iv—Li2—Li2iv	36.95 (15)
C4—C5—H5	121.5	Li2i—Li2—Li2iv	142.6 (2)
O3—Li1—O2iii	103.68 (16)	O22—Li2—Li1iv	82.13 (16)
O3—Li1—O1	91.92 (15)	O2i—Li2—Li1iv	31.87 (10)
O2iii—Li1—O1	107.96 (16)	O1—Li2—Li1iv	139.6 (3)
O3—Li1—N1	127.32 (18)	O21—Li2—Li1iv	126.81 (17)
O2iii—Li1—N1	128.74 (19)	O22iv—Li2—Li1iv	63.32 (13)
O1—Li1—N1	78.11 (12)	Li2i—Li2—Li1iv	111.75 (17)
O3—Li1—N3iii	92.14 (15)	Li2iv—Li2—Li1iv	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—Li2iv	102.75 (17)	O21—Li2—H222	94.7 (9)
O2iii—Li1—Li2iv	30.81 (10)	O22iv—Li2—H222	107.6 (10)
O1—Li1—Li2iv	77.24 (13)	Li2i—Li2—H222	140.1 (7)
N1—Li1—Li2iv	124.23 (17)	Li2iv—Li2—H222	71.8 (9)
N3iii—Li1—Li2iv	109.16 (14)	Li1iv—Li2—H222	102.2 (6)
Li1—O3—H32	129 (3)	Li2—O22—Li2iv	87.6 (2)
Li1—O3—H31	126 (2)	Li2—O22—H221	119 (2)
H32—O3—H31	101 (3)	Li2iv—O22—H221	117 (2)
O1—C7—O2	127.12 (16)	Li2—O22—H222	107.6 (17)
O1—C7—C2	116.22 (14)	Li2iv—O22—H222	135 (3)
O2—C7—C2	116.65 (15)	H221—O22—H222	93 (2)

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···Cl1v	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···Cl1vi	0.86 (4)	2.29 (4)	3.1429 (19)	168 (4)
O21—H211···Cl1vii	0.84 (3)	2.45 (3)	3.288 (2)	175 (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) ; (ii) .

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⋯Cl1iv	0.86 (4)	2.29 (4)	3.1429 (19)	168 (4)
O21—H211⋯Cl1v	0.84 (3)	2.45 (3)	3.288 (2)	175 (3)

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