Bis(μ(3)-pyrimidine-4-carboxyl-ato)bis-(μ(2)-pyrimidine-4-carboxyl-ato)tetra-kis-(aqua-lithium).

The asymmetric unit of the title compound, [Li(4)(C(5)H(3)N(2)O(2))(4)(H(2)O)(4)], contains two symmetry-independent Li(I) ions, two symmetry-independent ligands and two symmetry-independent coordinated water mol-ecules. They form a dinuclear unit in which the two Li(I) ions are bridged by two carboxyl-ate O atoms from the two ligands. Two dinuclear units related by an inversion centre form the tetra-meric mol-ecule. One of the Li(I) ions shows a distorted tetra-hedral coordination geometry, the other a distorted trigonal-bipyramidal environment. The tetra-mers are held together by hydrogen bonds in which coordinated water mol-ecules act as donors, and the carboxyl-ate O atoms act as acceptors. A hydrogen bond between coordinated water molecule as donor and a ring N atom as acceptor is also observed.

Related literature

For the crystal structures of four 3d metal complexes with pyrimidine-4-carboxyl­ate and aqua ligands, see: Aakeröy et al. (2006 ▶). For the structure of an ionic LiI complex with pyridazine-3,6-dicarboxyl­ate and water ligands, see: Starosta & Leciejewicz (2012 ▶).

Experimental

Crystal data

[Li4(C5H3N2O2)4(H2O)4]

M = 592.20

Triclinic,

a = 7.2750 (15) Å

b = 7.9108 (16) Å

c = 12.966 (3) Å

α = 77.91 (3)°

β = 84.59 (3)°

γ = 67.23 (3)°

V = 672.7 (2) Å3

Z = 1

Mo Kα radiation

μ = 0.12 mm−1

T = 293 K

0.24 × 0.20 × 0.08 mm

Data collection

Kuma KM-4 four-cricle diffractometer

Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008 ▶) T min = 0.982, T max = 0.991

4167 measured reflections

3874 independent reflections

2417 reflections with I > 2σ(I)

R int = 0.048

3 standard reflections every 200 reflections intensity decay: 2.8%

Refinement

R[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.164

S = 1.07

3874 reflections

216 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.50 e Å−3

Δρmin = −0.43 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.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681203142X/kp2430sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681203142X/kp2430Isup2.hkl

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

[Li4(C5H3N2O2)4(H2O)4]	Z = 1
Mr = 592.20	F(000) = 304
Triclinic, P1	Dx = 1.462 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.2750 (15) Å	Cell parameters from 25 reflections
b = 7.9108 (16) Å	θ = 6–15°
c = 12.966 (3) Å	µ = 0.12 mm−1
α = 77.91 (3)°	T = 293 K
β = 84.59 (3)°	Plate, colourless
γ = 67.23 (3)°	0.24 × 0.20 × 0.08 mm
V = 672.7 (2) Å3

Kuma KM-4 four-cricle diffractometer	2417 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.048
Graphite monochromator	θmax = 30.1°, θmin = 1.6°
profile data from ω/2θ scans	h = 0→9
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008)	k = −10→10
Tmin = 0.982, Tmax = 0.991	l = −18→18
4167 measured reflections	3 standard reflections every 200 reflections
3874 independent reflections	intensity decay: 2.8%

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.044	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.164	w = 1/[σ2(Fo2) + (0.1119P)2] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max < 0.001
3874 reflections	Δρmax = 0.50 e Å−3
216 parameters	Δρmin = −0.43 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.045 (10)

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
O11	0.88666 (17)	0.45353 (18)	0.30827 (9)	0.0367 (3)
O22	0.58826 (18)	0.34392 (18)	0.40929 (9)	0.0388 (3)
O1	0.95392 (19)	0.29323 (18)	0.55962 (10)	0.0375 (3)
O12	1.12854 (18)	0.55986 (19)	0.25411 (10)	0.0399 (3)
C14	1.0751 (2)	0.3590 (2)	0.15808 (11)	0.0271 (3)
C17	1.0257 (2)	0.4686 (2)	0.24760 (11)	0.0271 (3)
N13	0.9603 (2)	0.2639 (2)	0.15315 (11)	0.0384 (3)
N11	1.1556 (3)	0.1439 (3)	0.00732 (13)	0.0535 (5)
C15	1.2310 (3)	0.3528 (3)	0.08744 (12)	0.0363 (4)
H15	1.3087	0.4217	0.0893	0.044*
C12	1.0059 (3)	0.1634 (3)	0.07720 (16)	0.0536 (5)
H12	0.9239	0.0998	0.0724	0.064*
C16	1.2665 (3)	0.2393 (3)	0.01366 (14)	0.0458 (5)
H16	1.3732	0.2302	−0.0334	0.055*
Li1	0.7612 (4)	0.4527 (4)	0.4490 (2)	0.0339 (6)
Li2	0.7150 (4)	0.3328 (4)	0.2642 (2)	0.0371 (6)
N23	0.6007 (2)	0.10648 (19)	0.28871 (10)	0.0326 (3)
C27	0.4559 (2)	0.27807 (19)	0.43070 (11)	0.0253 (3)
C24	0.4582 (2)	0.14055 (19)	0.36333 (11)	0.0249 (3)
C25	0.3226 (2)	0.0542 (2)	0.37941 (12)	0.0313 (3)
H25	0.2217	0.0804	0.4303	0.038*
C22	0.6095 (3)	−0.0203 (3)	0.23334 (14)	0.0415 (4)
H22	0.7098	−0.0463	0.1822	0.050*
O21	0.32633 (17)	0.31149 (16)	0.50106 (9)	0.0336 (3)
N21	0.4884 (2)	−0.1138 (2)	0.24405 (12)	0.0405 (4)
C26	0.3446 (3)	−0.0731 (2)	0.31605 (14)	0.0383 (4)
H26	0.2546	−0.1326	0.3244	0.046*
O2	0.5018 (2)	0.55144 (19)	0.18214 (11)	0.0402 (3)
H1	0.922 (4)	0.340 (3)	0.614 (2)	0.055 (7)*
H3	0.378 (4)	0.549 (4)	0.208 (2)	0.068 (8)*
H2	1.071 (5)	0.274 (4)	0.531 (2)	0.080 (9)*
H4	0.505 (5)	0.649 (5)	0.189 (3)	0.085 (10)*

	U11	U22	U33	U12	U13	U23
O11	0.0329 (6)	0.0583 (7)	0.0359 (6)	−0.0296 (5)	0.0146 (4)	−0.0274 (5)
O22	0.0413 (6)	0.0582 (8)	0.0401 (6)	−0.0374 (6)	0.0153 (5)	−0.0283 (5)
O1	0.0344 (6)	0.0499 (7)	0.0410 (6)	−0.0248 (5)	0.0082 (5)	−0.0217 (5)
O12	0.0398 (6)	0.0590 (7)	0.0429 (6)	−0.0357 (6)	0.0152 (5)	−0.0297 (6)
C14	0.0279 (7)	0.0358 (7)	0.0252 (6)	−0.0174 (6)	0.0055 (5)	−0.0138 (5)
C17	0.0252 (6)	0.0375 (7)	0.0259 (6)	−0.0167 (6)	0.0040 (5)	−0.0138 (5)
N13	0.0384 (7)	0.0538 (8)	0.0413 (7)	−0.0309 (7)	0.0145 (6)	−0.0278 (6)
N11	0.0659 (11)	0.0736 (11)	0.0482 (9)	−0.0461 (10)	0.0266 (8)	−0.0421 (8)
C15	0.0386 (8)	0.0528 (10)	0.0323 (7)	−0.0300 (7)	0.0132 (6)	−0.0202 (7)
C12	0.0612 (12)	0.0773 (13)	0.0555 (11)	−0.0511 (11)	0.0262 (9)	−0.0457 (10)
C16	0.0511 (10)	0.0667 (12)	0.0372 (8)	−0.0364 (10)	0.0230 (8)	−0.0293 (8)
Li1	0.0348 (13)	0.0468 (15)	0.0335 (13)	−0.0252 (12)	0.0086 (10)	−0.0205 (11)
Li2	0.0364 (14)	0.0545 (16)	0.0374 (13)	−0.0302 (13)	0.0131 (11)	−0.0254 (12)
N23	0.0345 (7)	0.0371 (7)	0.0376 (7)	−0.0215 (5)	0.0107 (5)	−0.0206 (5)
C27	0.0252 (6)	0.0305 (7)	0.0256 (6)	−0.0141 (5)	0.0016 (5)	−0.0107 (5)
C24	0.0258 (7)	0.0260 (6)	0.0278 (6)	−0.0132 (5)	0.0013 (5)	−0.0094 (5)
C25	0.0307 (7)	0.0335 (7)	0.0376 (8)	−0.0196 (6)	0.0069 (6)	−0.0119 (6)
C22	0.0487 (10)	0.0469 (9)	0.0451 (9)	−0.0298 (8)	0.0187 (8)	−0.0286 (8)
O21	0.0311 (6)	0.0429 (6)	0.0360 (6)	−0.0193 (5)	0.0110 (4)	−0.0213 (5)
N21	0.0517 (9)	0.0387 (8)	0.0460 (8)	−0.0280 (7)	0.0072 (7)	−0.0212 (6)
C26	0.0469 (9)	0.0379 (8)	0.0448 (9)	−0.0297 (7)	0.0034 (7)	−0.0142 (7)
O2	0.0412 (7)	0.0468 (7)	0.0485 (7)	−0.0290 (6)	0.0118 (5)	−0.0239 (5)

O11—C17	1.2491 (18)	N11—C12	1.332 (2)
Li1—O11	1.961 (3)	C15—C16	1.386 (2)
Li1—O22	1.932 (3)	C15—H15	0.9300
Li1—O21i	1.953 (3)	C12—H12	0.9300
Li1—O1	1.967 (3)	C16—H16	0.9300
Li2—O11	2.021 (3)	N23—C22	1.3299 (19)
Li2—O22	2.020 (3)	N23—C24	1.3370 (18)
Li2—N13	2.155 (3)	C27—O21	1.2395 (17)
Li2—O2	1.998 (4)	C27—C24	1.5257 (18)
Li2—N23	2.205 (3)	C24—C25	1.3803 (19)
O22—C27	1.2463 (17)	C25—C26	1.383 (2)
O1—H1	0.83 (3)	C25—H25	0.9300
O1—H2	0.87 (3)	C22—N21	1.335 (2)
O12—C17	1.2425 (18)	C22—H22	0.9300
C14—N13	1.3354 (18)	O21—Li1i	1.953 (3)
C14—C15	1.381 (2)	N21—C26	1.323 (2)
C14—C17	1.5263 (19)	C26—H26	0.9300
N13—C12	1.332 (2)	O2—H3	0.93 (3)
N11—C16	1.318 (2)	O2—H4	0.81 (4)
C17—O11—Li1	149.71 (13)	O2—Li2—O22	98.68 (14)
C17—O11—Li2	117.79 (12)	O2—Li2—O11	102.08 (15)
Li1—O11—Li2	91.26 (11)	O22—Li2—O11	86.21 (11)
C27—O22—Li1	151.27 (13)	O2—Li2—N13	103.79 (15)
C27—O22—Li2	116.48 (12)	O22—Li2—N13	155.06 (18)
Li1—O22—Li2	92.15 (11)	O11—Li2—N13	78.69 (10)
Li1—O1—H1	108.4 (17)	O2—Li2—N23	104.14 (13)
Li1—O1—H2	106 (2)	O22—Li2—N23	77.76 (10)
H1—O1—H2	121 (3)	O11—Li2—N23	150.98 (18)
N13—C14—C15	121.20 (13)	N13—Li2—N23	106.61 (13)
N13—C14—C17	115.74 (12)	C22—N23—C24	116.37 (13)
C15—C14—C17	123.04 (13)	C22—N23—Li2	134.44 (13)
O12—C17—O11	126.77 (13)	C24—N23—Li2	107.11 (11)
O12—C17—C14	117.50 (12)	O21—C27—O22	126.68 (13)
O11—C17—C14	115.71 (13)	O21—C27—C24	117.70 (12)
C12—N13—C14	116.22 (14)	O22—C27—C24	115.61 (12)
C12—N13—Li2	133.18 (14)	N23—C24—C25	121.87 (13)
C14—N13—Li2	110.24 (12)	N23—C24—C27	116.20 (12)
C16—N11—C12	115.34 (15)	C25—C24—C27	121.93 (13)
C14—C15—C16	117.12 (15)	C24—C25—C26	116.60 (14)
C14—C15—H15	121.4	C24—C25—H25	121.7
C16—C15—H15	121.4	C26—C25—H25	121.7
N11—C12—N13	127.28 (16)	N23—C22—N21	126.36 (15)
N11—C12—H12	116.4	N23—C22—H22	116.8
N13—C12—H12	116.4	N21—C22—H22	116.8
N11—C16—C15	122.80 (15)	C27—O21—Li1i	120.24 (12)
N11—C16—H16	118.6	C26—N21—C22	116.08 (13)
C15—C16—H16	118.6	N21—C26—C25	122.67 (14)
O22—Li1—O21i	125.60 (16)	N21—C26—H26	118.7
O22—Li1—O11	90.34 (12)	C25—C26—H26	118.7
O21i—Li1—O11	115.37 (15)	Li2—O2—H3	108.4 (17)
O22—Li1—O1	115.40 (15)	Li2—O2—H4	112 (2)
O21i—Li1—O1	99.05 (12)	H3—O2—H4	108 (3)
O11—Li1—O1	111.64 (15)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O12ii	0.83 (3)	1.98 (3)	2.8120 (18)	175 (2)
O2—H3···O12iii	0.93 (3)	1.84 (3)	2.7671 (18)	177 (3)
O1—H2···O21iv	0.87 (3)	1.98 (3)	2.7941 (18)	155 (3)
O2—H4···N21v	0.81 (4)	2.10 (4)	2.8881 (19)	166 (3)

Table 1

Selected bond lengths (Å)

Li1—O11	1.961 (3)
Li1—O22	1.932 (3)
Li1—O21i	1.953 (3)
Li1—O1	1.967 (3)
Li2—O11	2.021 (3)
Li2—O22	2.020 (3)
Li2—N13	2.155 (3)
Li2—O2	1.998 (4)
Li2—N23	2.205 (3)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O12ii	0.83 (3)	1.98 (3)	2.8120 (18)	175 (2)
O2—H3⋯O12iii	0.93 (3)	1.84 (3)	2.7671 (18)	177 (3)
O1—H2⋯O21iv	0.87 (3)	1.98 (3)	2.7941 (18)	155 (3)
O2—H4⋯N21v	0.81 (4)	2.10 (4)	2.8881 (19)	166 (3)

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