Poly[bis-(μ(2)-pyrimidine-2-carboxyl-ato-κO,N:O',N')calcium].

In the crystal structure of the title polymeric complex, [Ca(C(5)H(3)N(2)O(2))(2)](n), the Ca(II) cation has site symmetry m2 and is N,O-chelated by four pyrimidine-2-carboxyl-ate anions in a square-anti-prismatic geometry. The planar pyrimidine-2-carboxyl-ate anion is located on a crystallographic special position, three C atoms have site symmetry 2mm, while the carboxyl O atom, the pyrimidine N atom and the other C atom have site symmetry m. Each pyrimidine-2--carboxyl-ate anion bridges two Ca(II) cations, forming polymeric sheets extending parallel to (001). π-π stacking exists between parallel pyrimidine rings [centroid-centroid distance = 3.6436 (6) Å] of adjacent polymeric sheets. Weak C-H⋯O hydrogen bonding is also observed between these sheets.

Related literature

For general background, see: Deisenhofer & Michel (1989 ▶); Pan & Xu (2004 ▶); Li et al. (2005 ▶). For polymeric structures of metal complexes with the pyrimidine-2-carboxyl­ate ligand, see: Rodríguez-Diéguez et al. (2007 ▶, 2008 ▶); Zhang et al. (2008a ▶,b ▶); Sava et al. (2008 ▶). For mononuclear metal complexes of pyrimidine-2-carboxyl­ate, see: Antolić et al. (2000 ▶); Zhang et al. (2008 ▶); Xu et al. (2008 ▶). For Ca—N and Ca—O bond distances in N,O-chelated complexes, see: Starosta & Leciejewicz (2004 ▶).

Experimental

Crystal data

[Ca(C5H3N2O2)2]

M = 286.27

Tetragonal,

a = 6.5312 (12) Å

c = 25.734 (3) Å

V = 1097.7 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.59 mm−1

T = 294 K

0.22 × 0.20 × 0.14 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.85, T max = 0.92

3191 measured reflections

375 independent reflections

364 reflections with I > 2σ(I)

R int = 0.016

Refinement

R[F 2 > 2σ(F 2)] = 0.025

wR(F 2) = 0.068

S = 1.13

375 reflections

34 parameters

H-atom parameters constrained

Δρmax = 0.22 e Å−3

Δρmin = −0.17 e Å−3

Data collection: PROCESS-AUTO (Rigaku, 1998 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809025537/hk2721sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809025537/hk2721Isup2.hkl

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

[Ca(C5H3N2O2)2]	Dx = 1.732 Mg m−3
Mr = 286.27	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I41/amd	Cell parameters from 1086 reflections
Hall symbol: -I 4bd 2	θ = 3.2–25.0°
a = 6.5312 (12) Å	µ = 0.59 mm−1
c = 25.734 (3) Å	T = 294 K
V = 1097.7 (3) Å3	Block, colorless
Z = 4	0.22 × 0.20 × 0.14 mm
F(000) = 584

Rigaku R-AXIS RAPID IP diffractometer	375 independent reflections
Radiation source: fine-focus sealed tube	364 reflections with I > 2σ(I)
graphite	Rint = 0.016
ω scans	θmax = 27.5°, θmin = 3.2°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −8→8
Tmin = 0.85, Tmax = 0.92	k = −7→8
3191 measured reflections	l = −14→33

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)] = 0.025	H-atom parameters constrained
wR(F2) = 0.068	w = 1/[σ2(Fo2) + (0.0407P)2 + 0.7773P] where P = (Fo2 + 2Fc2)/3
S = 1.13	(Δ/σ)max < 0.001
375 reflections	Δρmax = 0.22 e Å−3
34 parameters	Δρmin = −0.17 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: 0.071 (5)

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
Ca	0.5000	0.7500	0.3750	0.0164 (3)
N1	0.5000	0.4327 (2)	0.30820 (5)	0.0226 (4)
O1	0.5000	0.41994 (18)	0.41274 (4)	0.0292 (4)
C1	0.5000	0.2500	0.39085 (8)	0.0197 (5)
C2	0.5000	0.2500	0.33146 (8)	0.0188 (5)
C3	0.5000	0.4306 (3)	0.25605 (6)	0.0299 (4)
H3	0.5000	0.5542	0.2381	0.036*
C4	0.5000	0.2500	0.22845 (10)	0.0319 (6)
H4	0.5000	0.2500	0.1923	0.038*

	U11	U22	U33	U12	U13	U23
Ca	0.0152 (3)	0.0152 (3)	0.0189 (4)	0.000	0.000	0.000
N1	0.0254 (7)	0.0209 (7)	0.0215 (7)	0.000	0.000	0.0026 (5)
O1	0.0499 (8)	0.0169 (6)	0.0209 (6)	0.000	0.000	−0.0015 (4)
C1	0.0224 (10)	0.0181 (10)	0.0186 (10)	0.000	0.000	0.000
C2	0.0170 (9)	0.0201 (10)	0.0193 (10)	0.000	0.000	0.000
C3	0.0345 (9)	0.0326 (9)	0.0226 (8)	0.000	0.000	0.0072 (7)
C4	0.0337 (13)	0.0438 (15)	0.0184 (10)	0.000	0.000	0.000

Ca—O1i	2.3644 (12)	N1—C3	1.342 (2)
Ca—O1ii	2.3644 (11)	O1—C1	1.2447 (15)
Ca—O1	2.3644 (11)	C1—O1iv	1.2447 (15)
Ca—O1iii	2.3644 (12)	C1—C2	1.528 (3)
Ca—N1iii	2.6923 (14)	C2—N1iv	1.3350 (16)
Ca—N1	2.6923 (13)	C3—C4	1.377 (2)
Ca—N1ii	2.6923 (13)	C3—H3	0.9300
Ca—N1i	2.6923 (14)	C4—C3iv	1.377 (2)
N1—C2	1.3350 (16)	C4—H4	0.9300
O1i—Ca—O1ii	99.72 (2)	O1ii—Ca—N1i	74.795 (18)
O1i—Ca—O1	99.72 (2)	O1—Ca—N1i	74.795 (18)
O1ii—Ca—O1	131.49 (5)	O1iii—Ca—N1i	164.58 (4)
O1i—Ca—O1iii	131.49 (5)	N1iii—Ca—N1i	100.65 (6)
O1ii—Ca—O1iii	99.72 (2)	N1—Ca—N1i	114.05 (3)
O1—Ca—O1iii	99.72 (2)	N1ii—Ca—N1i	114.05 (3)
O1i—Ca—N1iii	164.58 (4)	C2—N1—C3	116.03 (15)
O1ii—Ca—N1iii	74.795 (18)	C2—N1—Ca	113.69 (10)
O1—Ca—N1iii	74.795 (18)	C3—N1—Ca	130.28 (11)
O1iii—Ca—N1iii	63.93 (4)	C1—O1—Ca	128.83 (11)
O1i—Ca—N1	74.796 (18)	O1—C1—O1iv	126.2 (2)
O1ii—Ca—N1	164.58 (4)	O1—C1—C2	116.91 (10)
O1—Ca—N1	63.93 (4)	O1iv—C1—C2	116.91 (10)
O1iii—Ca—N1	74.796 (18)	N1iv—C2—N1	126.74 (19)
N1iii—Ca—N1	114.05 (3)	N1iv—C2—C1	116.63 (10)
O1i—Ca—N1ii	74.796 (18)	N1—C2—C1	116.63 (10)
O1ii—Ca—N1ii	63.93 (4)	N1—C3—C4	121.66 (16)
O1—Ca—N1ii	164.58 (4)	N1—C3—H3	119.2
O1iii—Ca—N1ii	74.796 (18)	C4—C3—H3	119.2
N1iii—Ca—N1ii	114.05 (3)	C3—C4—C3iv	117.9 (2)
N1—Ca—N1ii	100.65 (5)	C3—C4—H4	121.1
O1i—Ca—N1i	63.93 (4)	C3iv—C4—H4	121.1

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O1v	0.93	2.57	3.3689 (19)	144

Table 1

Selected bond lengths (Å)

Ca—O1	2.3644 (11)
Ca—N1	2.6923 (13)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O1i	0.93	2.57	3.3689 (19)	144

Symmetry code: (i) .