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Acta Cryst. (2007). E63, m2006    [ doi:10.1107/S1600536807030528 ]

catena-Poly[[aqua(pyrazine-2-carboxylato)copper(II)]-[mu]-pyrazine-2-carboxylato]

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

Abstract top

The title compound, [Cu(C5H3N2O2)2(H2O)]n, prepared by hydrothermal synthesis, is isostructural with its FeII-, CoII- and NiII-containing analogues. The asymmetric unit contains two bidendate pyrazine-2-carboxylate (pc) anions bonded to Cu in the equatorial plane through one N and one O atom. The Cu atoms are linked into chains by the second N atom of one of the pc anions bonding to an axial site of a neighbouring Cu atom. The slightly distorted octahedral coordination around Cu 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), is isostructural with its FeII, CoII, and NiII analogues [Hao & Liu, (2007); Hao, Mu & Liu, (2007); Gao et al. (2007)]. The CuII atom in (I) 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, Table 1). One pyrazine-2-carboxylate ligand coordinates to a neighboring Cu atom via its second N atom, leading to a polymeic structure with zigzag chains extending parallel to the b axis (Fig. 2). Hydrogen bonding involving the water molecules (Table 2) stablizes the structure.

Related literature top

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

[Prep section states red block crystals were formed, but CIF data tables state blue cube - which is correct?]

Experimental top

A mixture of copper dichloride hexahydrate (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 heated to at 413 K for 2 d, and then cooled to room temperature. Red block-shaped crystals of (I) were obtained in a yield of 36%. Anal. Calc. for C10H8CuN4O5: C 36.62, H 2.44, N 17.09%; Found: C 36.59, H 2.47, N 17.01%.

Refinement top

All H atoms on C atoms were generated geometrically (C—H = 0.93 Å) and refined as riding with Uiso(H) = 1.2Ueq(C). The H atoms of the water molecule were located from difference density maps and were refined with distance restraints of O—H = 0.82 (1) Å and H···H = 1.38 (2) Å and a fixed Uiso(H) of 0.08 Å2.

Computing details top

Data collection: SMART (Bruker, 2001) [Or APEX2?]; 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 (I) showing 30% probability displacement ellipsoids (arbitrary spheres for the H atoms). Atoms labeled with I at the symmetry positions (-x + 1, y - 1/2, -z + 3/2).
catena-Poly[[aqua(pyrazine-2-carboxylato)copper(II)]-µ-pyrazine-2-carboxylato] top
Crystal data top
[Cu(C5H3N2O2)2(H2O)]F(000) = 660
Mr = 327.74Dx = 1.894 Mg m−3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 2460 reflections
a = 7.7379 (5) Åθ = 2.5–27.0°
b = 9.9021 (5) ŵ = 1.93 mm−1
c = 15.002 (1) ÅT = 298 K
V = 1149.48 (12) Å3Cube, blue
Z = 40.10 × 0.10 × 0.10 mm
Data collection top
Bruker APEXII CCD area-detector
diffractometer		2219 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.032
Graphite monochromatorθmax = 27.0°, θmin = 2.5°
φ and ω scansh = −8→9
6840 measured reflectionsk = −12→12
2460 independent reflectionsl = −15→19
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)] = 0.038H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.099 w = 1/[σ2(Fo2) + (0.0666P)2 + 0.3756P]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max = 0.014
2460 reflectionsΔρmax = 1.20 e Å−3
182 parametersΔρmin = −0.36 e Å−3
3 restraintsAbsolute structure: Flack (1983), with 1004 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.49 (2)
Crystal data top
[Cu(C5H3N2O2)2(H2O)]V = 1149.48 (12) Å3
Mr = 327.74Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 7.7379 (5) ŵ = 1.93 mm−1
b = 9.9021 (5) ÅT = 298 K
c = 15.002 (1) Å0.10 × 0.10 × 0.10 mm
Data collection top
Bruker APEXII CCD area-detector
diffractometer		2219 reflections with I > 2σ(I)
6840 measured reflectionsRint = 0.032
2460 independent reflectionsθmax = 27.0°
Refinement top
R[F2 > 2σ(F2)] = 0.038H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.099Δρmax = 1.20 e Å−3
S = 1.01Δρmin = −0.36 e Å−3
2460 reflectionsAbsolute structure: Flack (1983), with 1004 Friedel pairs
182 parametersFlack parameter: 0.49 (2)
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
Cu10.42685 (6)0.63422 (4)0.59076 (3)0.01911 (14)
C10.1940 (5)0.8096 (4)0.6830 (3)0.0259 (5)
C20.3720 (5)0.8540 (4)0.7110 (2)0.0174 (7)
C30.3948 (5)0.9581 (4)0.7733 (3)0.0214 (8)
H30.29811.00260.79550.026*
C40.6843 (6)0.9334 (4)0.7638 (3)0.0243 (9)
H40.79540.95890.78040.029*
C50.6628 (5)0.8307 (4)0.6996 (3)0.0226 (9)
H50.75940.79050.67400.027*
C60.6424 (6)0.4713 (4)0.4810 (3)0.0228 (9)
C70.4616 (5)0.4269 (4)0.4590 (3)0.0232 (9)
C80.4259 (6)0.3353 (4)0.3918 (3)0.0323 (10)
H80.51750.29880.35970.039*
C90.1408 (6)0.3514 (4)0.4213 (3)0.0307 (9)
H90.02680.32690.41010.037*
C100.1755 (6)0.4432 (4)0.4894 (3)0.0271 (9)
H100.08470.47790.52300.033*
N10.5062 (4)0.7910 (3)0.6756 (2)0.0195 (7)
N20.5494 (4)0.9948 (3)0.8012 (2)0.0191 (7)
N30.3352 (4)0.4817 (3)0.5070 (2)0.0197 (7)
N40.2667 (5)0.2974 (4)0.3713 (3)0.0383 (10)
O10.1945 (3)0.7028 (3)0.63112 (18)0.0201 (6)
O20.0686 (3)0.8697 (3)0.70894 (18)0.0259 (5)
O30.6530 (4)0.5644 (3)0.54124 (19)0.0218 (6)
O40.7633 (4)0.4208 (4)0.4411 (3)0.0434 (9)
O50.4184 (4)0.7653 (3)0.48314 (19)0.0274 (6)
H1W0.509 (5)0.793 (6)0.462 (5)0.080*
H2W0.335 (5)0.815 (6)0.475 (5)0.080*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0166 (2)0.0202 (2)0.0205 (2)−0.00007 (19)−0.00077 (19)−0.00039 (19)
C10.0155 (10)0.0306 (12)0.0314 (12)0.0031 (11)−0.0021 (9)−0.0043 (10)
C20.0168 (17)0.0186 (17)0.0168 (17)0.0012 (14)−0.0034 (13)0.0012 (15)
C30.021 (2)0.0237 (18)0.0189 (18)0.0014 (15)0.0012 (16)−0.0043 (15)
C40.019 (2)0.0229 (19)0.031 (2)−0.0010 (17)−0.0004 (17)−0.0052 (17)
C50.0156 (19)0.024 (2)0.029 (2)0.0018 (16)0.0015 (16)−0.0003 (16)
C60.0189 (19)0.024 (2)0.025 (2)−0.0033 (16)0.0005 (16)0.0005 (16)
C70.024 (2)0.0222 (19)0.023 (2)0.0035 (16)0.0005 (16)0.0005 (16)
C80.023 (2)0.037 (2)0.038 (3)0.003 (2)0.002 (2)−0.0162 (17)
C90.0215 (19)0.033 (2)0.038 (2)−0.0013 (18)−0.0046 (18)−0.007 (2)
C100.022 (2)0.027 (2)0.032 (2)0.0010 (17)0.0026 (18)−0.0019 (17)
N10.0169 (15)0.0205 (16)0.0211 (17)0.0013 (13)−0.0001 (13)0.0009 (13)
N20.0184 (17)0.0182 (14)0.0206 (15)0.0002 (14)0.0006 (13)−0.0037 (12)
N30.0185 (16)0.0182 (16)0.0223 (16)0.0007 (13)−0.0003 (14)−0.0014 (13)
N40.031 (2)0.041 (2)0.043 (2)−0.0074 (18)−0.0033 (18)−0.0200 (19)
O10.0146 (13)0.0238 (13)0.0219 (14)0.0003 (11)−0.0022 (11)−0.0039 (11)
O20.0155 (10)0.0306 (12)0.0314 (12)0.0031 (11)−0.0021 (9)−0.0043 (10)
O30.0135 (13)0.0233 (14)0.0286 (15)−0.0016 (11)0.0001 (11)−0.0007 (12)
O40.0217 (17)0.054 (2)0.054 (2)0.0074 (16)0.0067 (15)−0.0191 (17)
O50.0234 (15)0.0304 (15)0.0285 (14)0.0089 (15)0.0052 (14)0.0127 (12)
Geometric parameters (Å, º) top
Cu1—O12.015 (3)C5—H50.9300
Cu1—O32.023 (3)C6—O41.218 (5)
Cu1—O52.073 (3)C6—O31.293 (5)
Cu1—N32.089 (3)C6—C71.503 (6)
Cu1—N12.099 (3)C7—N31.331 (5)
Cu1—N2i2.137 (3)C7—C81.384 (6)
C1—O21.203 (5)C8—N41.324 (6)
C1—O11.313 (5)C8—H80.9300
C1—C21.506 (5)C9—N41.341 (6)
C2—N11.323 (5)C9—C101.394 (6)
C2—C31.402 (5)C9—H90.9300
C3—N21.319 (5)C10—N31.320 (6)
C3—H30.9300C10—H100.9300
C4—N21.332 (5)N2—Cu1ii2.137 (3)
C4—C51.410 (6)O5—H1W0.82 (5)
C4—H40.9300O5—H2W0.82 (5)
C5—N11.324 (5)
O1—Cu1—O3175.85 (12)O4—C6—O3126.0 (4)
O1—Cu1—O589.69 (12)O4—C6—C7119.1 (4)
O3—Cu1—O587.45 (12)O3—C6—C7114.9 (3)
O1—Cu1—N396.98 (12)N3—C7—C8121.0 (4)
O3—Cu1—N379.95 (12)N3—C7—C6116.5 (3)
O5—Cu1—N388.47 (13)C8—C7—C6122.6 (4)
O1—Cu1—N180.18 (12)N4—C8—C7122.8 (4)
O3—Cu1—N1102.86 (13)N4—C8—H8118.6
O5—Cu1—N191.06 (13)C7—C8—H8118.6
N3—Cu1—N1177.12 (14)N4—C9—C10122.0 (4)
O1—Cu1—N2i93.83 (12)N4—C9—H9119.0
O3—Cu1—N2i89.04 (12)C10—C9—H9119.0
O5—Cu1—N2i176.48 (14)N3—C10—C9121.0 (4)
N3—Cu1—N2i91.07 (13)N3—C10—H10119.5
N1—Cu1—N2i89.57 (12)C9—C10—H10119.5
O2—C1—O1126.3 (4)C2—N1—C5118.0 (3)
O2—C1—C2120.2 (4)C2—N1—Cu1111.3 (3)
O1—C1—C2113.5 (3)C5—N1—Cu1130.7 (3)
N1—C2—C3121.0 (3)C3—N2—C4116.8 (3)
N1—C2—C1117.9 (3)C3—N2—Cu1ii119.8 (3)
C3—C2—C1121.1 (3)C4—N2—Cu1ii123.2 (3)
N2—C3—C2121.9 (4)C10—N3—C7117.5 (3)
N2—C3—H3119.1C10—N3—Cu1130.3 (3)
C2—C3—H3119.1C7—N3—Cu1111.8 (3)
N2—C4—C5121.6 (4)C9—N4—C8115.7 (4)
N2—C4—H4119.2C1—O1—Cu1116.9 (2)
C5—C4—H4119.2C6—O3—Cu1116.5 (3)
N1—C5—C4120.5 (4)Cu1—O5—H1W119 (5)
N1—C5—H5119.8Cu1—O5—H2W121 (5)
C4—C5—H5119.8H1W—O5—H2W114 (3)
O2—C1—C2—N1−175.2 (4)C5—C4—N2—Cu1ii172.6 (3)
O1—C1—C2—N15.7 (5)C9—C10—N3—C7−1.8 (6)
O2—C1—C2—C35.3 (6)C9—C10—N3—Cu1170.6 (3)
O1—C1—C2—C3−173.8 (3)C8—C7—N3—C101.5 (6)
N1—C2—C3—N2−2.1 (6)C6—C7—N3—C10−179.4 (4)
C1—C2—C3—N2177.3 (4)C8—C7—N3—Cu1−172.3 (3)
N2—C4—C5—N1−1.0 (6)C6—C7—N3—Cu16.8 (4)
O4—C6—C7—N3177.6 (4)O1—Cu1—N3—C10−1.5 (4)
O3—C6—C7—N3−3.8 (5)O3—Cu1—N3—C10−178.6 (4)
O4—C6—C7—C8−3.3 (6)O5—Cu1—N3—C10−91.0 (4)
O3—C6—C7—C8175.3 (4)N2i—Cu1—N3—C1092.5 (4)
N3—C7—C8—N40.1 (7)O1—Cu1—N3—C7171.3 (3)
C6—C7—C8—N4−179.0 (4)O3—Cu1—N3—C7−5.9 (2)
N4—C9—C10—N30.6 (7)O5—Cu1—N3—C781.8 (3)
C3—C2—N1—C5−1.1 (6)N2i—Cu1—N3—C7−94.7 (3)
C1—C2—N1—C5179.4 (4)C10—C9—N4—C81.0 (7)
C3—C2—N1—Cu1176.9 (3)C7—C8—N4—C9−1.3 (7)
C1—C2—N1—Cu1−2.6 (4)O2—C1—O1—Cu1175.0 (4)
C4—C5—N1—C22.6 (6)C2—C1—O1—Cu1−6.0 (5)
C4—C5—N1—Cu1−175.0 (3)O3—Cu1—O1—C1−133.6 (16)
O1—Cu1—N1—C2−0.4 (2)O5—Cu1—O1—C1−87.4 (3)
O3—Cu1—N1—C2176.7 (3)N3—Cu1—O1—C1−175.8 (3)
O5—Cu1—N1—C289.1 (3)N1—Cu1—O1—C13.8 (3)
N2i—Cu1—N1—C2−94.4 (3)N2i—Cu1—O1—C192.7 (3)
O1—Cu1—N1—C5177.3 (4)O4—C6—O3—Cu1177.0 (4)
O3—Cu1—N1—C5−5.6 (4)C7—C6—O3—Cu1−1.6 (4)
O5—Cu1—N1—C5−93.2 (4)O1—Cu1—O3—C6−38.5 (18)
N2i—Cu1—N1—C583.3 (4)O5—Cu1—O3—C6−84.9 (3)
C2—C3—N2—C43.7 (6)N3—Cu1—O3—C64.0 (3)
C2—C3—N2—Cu1ii−171.3 (3)N1—Cu1—O3—C6−175.4 (3)
C5—C4—N2—C3−2.2 (6)N2i—Cu1—O3—C695.3 (3)
Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) −x+1, y+1/2, −z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5—H2W···O3iii0.82 (5)1.86 (5)2.682 (4)177 (7)
O5—H1W···O1iv0.82 (5)2.01 (4)2.757 (4)153 (7)
Symmetry codes: (iii) x−1/2, −y+3/2, −z+1; (iv) x+1/2, −y+3/2, −z+1.
Selected bond lengths (Å) top
Cu1—O12.015 (3)Cu1—N32.089 (3)
Cu1—O32.023 (3)Cu1—N12.099 (3)
Cu1—O52.073 (3)Cu1—N2i2.137 (3)
Symmetry code: (i) −x+1, y−1/2, −z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5—H2W···O3ii0.82 (5)1.86 (5)2.682 (4)177 (7)
O5—H1W···O1iii0.82 (5)2.01 (4)2.757 (4)153 (7)
Symmetry codes: (ii) x−1/2, −y+3/2, −z+1; (iii) x+1/2, −y+3/2, −z+1.
Acknowledgements top

The authors thank the Natural Science Foundation of China (grant No. 20501017) and Tonghua Teachers' College.

references
References top

Bruker (2001). SMART, SAINT-Plus and SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA. [SMART does not match APEXII diffractometer. Please give correct reference]

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

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

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.