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Acta Cryst. (2007). E63, m2143    [ doi:10.1107/S1600536807033041 ]

catena-Poly[[aqua(pyrazine-2-carboxylato-[kappa]2N1,O)zinc(II)]-[mu]-pyrazine-2-carboxylato-[kappa]2N1,O:N4]

Y.-X. Gao, L.-B. Wang, Y.-L. Niu and L.-J. Hao

Abstract top

The title compound, [Zn(C5H3N2O2)2(H2O)]n, prepared by hydrothermal synthesis, is isostructural with its FeII, CoII, NiII and CuII analogues. The asymmetric unit contains two bidentate pyrazine-2-carboxylate anions bonded to ZnII in the equatorial plane through one N and one O atom each. The ZnII atoms are linked into a chain by the second N atom of the anion bonding to an axial site of a neighbouring ZnII atom. The slightly distorted octahedral coordination around ZnII is completed by a water molecule, which forms hydrogen bonds to link the chains into a three-dimensional structure. The crystal studied was an inversion twin.

Comment top

The title compound, (I), [Zn(C5H3N2O2)2(H2O)]n, is isostructural with its FeII, CoII, NiII, and CuII analogues (Hao & Liu, 2007; Hao et al., 2007; Gao et al., 2007a,b). The ZnII atoms is coordinated in a bidentate fashion by two O and two N atoms from two independent pyrazine-2-carboxylate anions. The distorted octhedral coordiantion is completed by another N atom from a third pyrazine-2-carboxylate ligand, and by the O atom of a water molecule (Fig. 1). The Zn—N and Zn—O bond lengths are in the range of 2.058 (3)–2.105 (3) and 2.042 (3)–2.073 (3) Å, respectively. One pyrazine-2-carboxylate ligand coordinates to a neighboring ZnII atom via its second N atom, leading to polymeric structure with zigzag chains extending parallel to the b axis (Fig. 2). Hydrogen bonds between the water molecule and the carboxylate groups stabilize the structure. The refined Flack parameter of 0.469 (18) indicates inversion twinning.

Related literature top

For the isostructural FeII, CoII, NiII and CuII analogues, see: Hao & Liu (2007); Hao et al. (2007); Gao et al. (2007a,b).

Experimental top

All chemicals used were purchased from Jinan Henghua Sci & Tec Co. Ltd. A mixture of Zinc(II) acetate dihydrate (0.5 mmol), potassium hydroxide (0.5 mmol), 2-pyrazine caboxylic acid (0.5 mmol), EtOH (8 ml) and H2O (8 ml) in a 25 ml Teflon-lined stainless steel autoclave was kept at 413 K for 2 d, and then cooled to room temperature. Colorless crystals of (I) were obtained in a yield of 36%. Anal. Calc. for C10H8ZnN4O5: C 36.62, H 2.44, N 17.09%; Found: C 36.59, H 2.47, N 17.01%.

Refinement top

C-bound H atoms were generated geometrically (C—H = 0.93 Å) and refined as riding, with Uiso(H) = 1.2Ueq(C). H atoms of the water molecule were located in a difference density map and were refined with distance restraints of O—H = 0.82 (1) and H—H = 1.38 (2) Å.

Computing details top

Data collection: APEX2 (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. A fragment of the structure of the title compound, showing 30% probability displacement ellipsoids. Atoms labeled with I at the symmetry positions (-x + 1, y - 1/2, -z + 3/2).
[Figure 2] Fig. 2. A part of polymeric structure of the title compound.
catena-Poly[aquabis(pyrazine-2-carboxylato-κ2N1,O)zinc(II)]- µ-pyrazine-2-carboxylato-κ3N1,O:N4] top
Crystal data top
[Zn(C5H3N2O2)2(H2O)]F(000) = 664
Mr = 329.57Dx = 1.908 Mg m−3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 2347 reflections
a = 7.8932 (6) Åθ = 2.5–26.7°
b = 9.7615 (10) ŵ = 2.17 mm−1
c = 14.8921 (15) ÅT = 298 K
V = 1147.43 (19) Å3Cube, colorless
Z = 40.10 × 0.10 × 0.10 mm
Data collection top
Bruker APEX II CCD area-detector
diffractometer		2353 independent reflections
Radiation source: fine-focus sealed tube2200 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.027
φ and ω scansθmax = 26.5°, θmin = 2.5°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		h = −8→9
Tmin = 0.812, Tmax = 0.812k = −12→11
6232 measured reflectionsl = −18→9
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.034H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.096 w = 1/[σ2(Fo2) + (0.072P)2 + 0.4177P]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
2353 reflectionsΔρmax = 0.98 e Å−3
188 parametersΔρmin = −0.34 e Å−3
3 restraintsAbsolute structure: Flack (1983), 974 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.469 (18)
Crystal data top
[Zn(C5H3N2O2)2(H2O)]V = 1147.43 (19) Å3
Mr = 329.57Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 7.8932 (6) ŵ = 2.17 mm−1
b = 9.7615 (10) ÅT = 298 K
c = 14.8921 (15) Å0.10 × 0.10 × 0.10 mm
Data collection top
Bruker APEX II CCD area-detector
diffractometer		2353 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		2200 reflections with I > 2σ(I)
Tmin = 0.812, Tmax = 0.812Rint = 0.027
6232 measured reflectionsθmax = 26.5°
Refinement top
R[F2 > 2σ(F2)] = 0.034H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.096Δρmax = 0.98 e Å−3
S = 1.00Δρmin = −0.34 e Å−3
2353 reflectionsAbsolute structure: Flack (1983), 974 Friedel pairs
188 parametersFlack parameter: 0.469 (18)
3 restraints
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
xyzUiso*/Ueq
Zn10.92678 (6)0.86587 (4)0.90927 (3)0.02030 (14)
C10.6936 (5)0.6911 (4)0.8171 (2)0.0175 (7)
C21.1621 (5)0.6694 (4)0.7997 (3)0.0207 (8)
H21.25620.71110.82540.025*
C30.8722 (4)0.6460 (4)0.7893 (2)0.0155 (7)
C41.1047 (5)1.0415 (4)0.7732 (2)0.0182 (8)
H41.19890.99590.79600.022*
C50.8158 (5)1.0668 (4)0.7636 (3)0.0230 (8)
H50.70691.04060.78010.028*
C60.6757 (5)1.0566 (4)1.0101 (3)0.0241 (8)
H60.58731.02110.97600.029*
C70.6414 (5)1.1488 (4)1.0786 (3)0.0278 (8)
H70.52991.17381.09010.033*
C80.9257 (6)1.1651 (4)1.1088 (3)0.0307 (9)
H81.01461.20211.14180.037*
C90.9613 (5)1.0733 (4)1.0410 (3)0.0218 (8)
C101.1434 (5)1.0288 (4)1.0192 (3)0.0214 (8)
H1W1.011 (4)0.703 (6)1.031 (5)0.080*
H2W0.839 (5)0.680 (5)1.015 (5)0.080*
N10.7664 (5)1.2023 (4)1.1284 (3)0.0361 (9)
N20.8349 (4)1.0186 (3)0.9928 (2)0.0183 (6)
N31.0061 (4)0.7089 (3)0.8242 (2)0.0171 (6)
N40.9497 (4)1.0051 (3)0.80119 (19)0.0189 (6)
O11.1531 (3)0.9352 (3)0.95911 (17)0.0196 (5)
O21.2633 (4)1.0798 (4)1.0587 (2)0.0402 (8)
O30.6936 (3)0.7969 (3)0.86870 (17)0.0191 (5)
O40.5686 (3)0.6308 (3)0.79110 (18)0.0275 (6)
O50.9181 (4)0.7349 (3)1.01674 (18)0.0253 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0199 (2)0.0205 (2)0.0205 (2)0.00011 (17)0.00053 (17)−0.00065 (17)
C10.0161 (17)0.0199 (17)0.0166 (17)0.0015 (14)0.0025 (14)0.0033 (14)
C20.0168 (18)0.022 (2)0.0236 (18)0.0008 (15)−0.0016 (15)−0.0049 (15)
C30.0178 (17)0.0162 (16)0.0124 (14)0.0000 (13)0.0005 (12)0.0004 (14)
C40.0180 (19)0.0184 (17)0.0182 (16)−0.0013 (14)−0.0005 (14)0.0040 (14)
C50.0190 (19)0.0247 (19)0.025 (2)−0.0006 (16)−0.0003 (15)0.0044 (16)
C60.0194 (19)0.0221 (19)0.031 (2)−0.0023 (15)−0.0030 (16)−0.0006 (16)
C70.0216 (18)0.028 (2)0.034 (2)0.0025 (16)0.0026 (17)−0.0086 (19)
C80.027 (2)0.032 (2)0.033 (2)−0.002 (2)−0.0027 (19)−0.0137 (16)
C90.021 (2)0.0233 (19)0.0217 (18)−0.0011 (15)−0.0001 (14)0.0029 (15)
C100.0188 (19)0.0220 (19)0.0233 (18)0.0022 (15)0.0001 (15)0.0042 (15)
N10.032 (2)0.037 (2)0.039 (2)0.0051 (17)0.0042 (17)−0.0166 (17)
N20.0179 (15)0.0165 (15)0.0205 (15)0.0002 (12)0.0003 (13)−0.0005 (12)
N30.0175 (14)0.0179 (15)0.0160 (15)−0.0017 (12)0.0005 (12)0.0019 (12)
N40.0208 (16)0.0175 (14)0.0182 (14)0.0007 (13)−0.0019 (13)0.0012 (12)
O10.0165 (12)0.0192 (13)0.0230 (13)0.0023 (10)−0.0012 (11)−0.0033 (11)
O20.0228 (15)0.047 (2)0.051 (2)−0.0052 (14)−0.0092 (14)−0.0173 (16)
O30.0145 (12)0.0234 (14)0.0195 (13)0.0001 (11)0.0021 (10)−0.0048 (11)
O40.0161 (12)0.0330 (14)0.0333 (14)−0.0063 (15)0.0019 (12)−0.0075 (12)
O50.0220 (13)0.0283 (14)0.0255 (13)−0.0088 (13)−0.0038 (13)0.0119 (11)
Geometric parameters (Å, º) top
Zn1—O52.049 (2)C5—N41.339 (5)
Zn1—O12.050 (3)C5—C2ii1.386 (5)
Zn1—O32.051 (3)C5—H50.9300
Zn1—N22.073 (3)C6—N21.335 (5)
Zn1—N32.085 (3)C6—C71.386 (6)
Zn1—N42.114 (3)C6—H60.9300
C1—O41.213 (5)C7—N11.340 (6)
C1—O31.287 (5)C7—H70.9300
C1—C31.534 (5)C8—N11.341 (6)
C2—N31.341 (5)C8—C91.379 (6)
C2—C5i1.386 (5)C8—H80.9300
C2—H20.9300C9—N21.339 (5)
C3—N31.328 (5)C9—C101.537 (5)
C3—C4i1.392 (5)C10—O21.220 (5)
C4—N41.341 (5)C10—O11.281 (5)
C4—C3ii1.392 (5)O5—H1W0.82 (4)
C4—H40.9300O5—H2W0.82 (4)
O5—Zn1—O187.28 (11)N2—C6—C7120.4 (4)
O5—Zn1—O389.72 (11)N2—C6—H6119.8
O1—Zn1—O3175.86 (11)C7—C6—H6119.8
O5—Zn1—N288.17 (12)N1—C7—C6121.1 (4)
O1—Zn1—N281.37 (12)N1—C7—H7119.5
O3—Zn1—N295.68 (12)C6—C7—H7119.5
O5—Zn1—N391.51 (12)N1—C8—C9121.8 (4)
O1—Zn1—N3101.61 (12)N1—C8—H8119.1
O3—Zn1—N381.32 (11)C9—C8—H8119.1
N2—Zn1—N3176.98 (13)N2—C9—C8120.0 (4)
O5—Zn1—N4176.63 (14)N2—C9—C10118.1 (3)
O1—Zn1—N489.35 (12)C8—C9—C10121.9 (4)
O3—Zn1—N493.64 (11)O2—C10—O1125.5 (4)
N2—Zn1—N491.41 (12)O2—C10—C9120.6 (4)
N3—Zn1—N489.09 (11)O1—C10—C9113.9 (3)
O4—C1—O3125.4 (3)C7—N1—C8117.6 (4)
O4—C1—C3121.5 (3)C6—N2—C9119.1 (3)
O3—C1—C3113.1 (3)C6—N2—Zn1130.2 (3)
N3—C2—C5i120.5 (4)C9—N2—Zn1110.3 (3)
N3—C2—H2119.7C3—N3—C2119.5 (3)
C5i—C2—H2119.7C3—N3—Zn1109.8 (2)
N3—C3—C4i119.7 (3)C2—N3—Zn1130.7 (3)
N3—C3—C1119.5 (3)C5—N4—C4118.1 (3)
C4i—C3—C1120.7 (3)C5—N4—Zn1122.7 (3)
N4—C4—C3ii121.4 (3)C4—N4—Zn1119.0 (2)
N4—C4—H4119.3C10—O1—Zn1115.9 (2)
C3ii—C4—H4119.3C1—O3—Zn1116.0 (2)
N4—C5—C2ii120.7 (4)Zn1—O5—H1W114 (5)
N4—C5—H5119.7Zn1—O5—H2W114 (5)
C2ii—C5—H5119.7H1W—O5—H2W116 (3)
Symmetry codes: (i) −x+2, y−1/2, −z+3/2; (ii) −x+2, y+1/2, −z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5—H1W···O3iii0.82 (4)2.08 (4)2.781 (4)144 (7)
O5—H2W···O1iv0.82 (4)1.89 (2)2.695 (4)166 (8)
Symmetry codes: (iii) x+1/2, −y+3/2, −z+2; (iv) x−1/2, −y+3/2, −z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5—H1W···O3i0.82 (4)2.08 (4)2.781 (4)144 (7)
O5—H2W···O1ii0.82 (4)1.89 (2)2.695 (4)166 (8)
Symmetry codes: (i) x+1/2, −y+3/2, −z+2; (ii) x−1/2, −y+3/2, −z+2.
Acknowledgements top

The authors thank the NSFC (grant No. 20501017) and Tonghua Teachers' College.

references
References top

Bruker (2001). APEX2, SAINT-Plus, SHELXTL and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.

Flack, H. D. (1983). Acta Cryst. A39, 876–881.

Gao, Y.-X., Wang, L.-B., Niu, Y.-L. & Hao, L.-J. (2007a). Acta Cryst. E63, m1882–?.

Gao, Y.-X., Wang, L.-B., Niu, Y.-L. & Hao, L.-J. (2007b). Acta Cryst. E63, m2006–?.

Hao, L.-J. & Liu, T.-T. (2007). Acta Cryst. E63, m169–m171.

Hao, L.-J., Mu, C.-H. & Liu, T.-T. (2007). Acta Cryst. E63, m281–m283.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.