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In the title complex, [Zn(C12H6N2O4)(H2O)2]n, the Zn atom, located on a twofold axis, is six-coordinated in a distorted octa­hedral arrangement, with two N atoms and two O atoms of two symmetry-related 2,2′-bipyridine-3,3′-dicarboxy­ate (dcbp) ligands located in the equatorial plane, while the two O atoms of the water mol­ecules occupy the axial positions. The dcbp ligand acts as a bridging ligand, linking adjacent Zn ions and forming a one-dimensional infinite chain parallel to the b axis. O—H...O hydrogen bonds involving the coordinated water mol­ecules connect adjacent chains to form layers parallel to the (001) plane.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807053305/dn2251sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807053305/dn2251Isup2.hkl
Contains datablock I

CCDC reference: 667249

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](C-C) = 0.006 Å
  • R factor = 0.042
  • wR factor = 0.128
  • Data-to-parameter ratio = 10.9

checkCIF/PLATON results

No syntax errors found



Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Zn1 (2) 2.05
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 0 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check

Comment top

Transition metal complexes with 2,2'-bipyridine derivatives are suitable models for the study of excited state dynamics. In addition, they are of interest for the development of light-energy conversion devices and optical sensors (Gokel et al., 2004; Shan et al., 2001). One of the simplest carbonyl-containing derivatives of 2,2'-bipyridine is the 3,3'-dicarboxy-2,2'-bipyridine molecule (dcbp). Indeed, the molecule of dcbp has two available centres for complexation: nitrogen atoms of bipyridine fragment and oxygen atoms of the carboxylic groups. The carbonyl groups are capable to form chelates when pyridine rings turn from trans-conformation to cis-conformation (Starova et al., 2007).

The Zn atom, located on a twofold axis, is six-coordinated in a distorted octahedral arrangement, with two N atoms and two O atoms of two symmetry related dcbp ligands are located in the basal plane whereas two O atoms of water molecule occupy the apical positions. The dcbp ligand acts then as a bridging ligand linking adjacent Zn ions and forming a one-dimensional infinite chain parallel to the b axis. O—H···O hydrogen bongs involving the coordinated water molecules connect adjacent chains to form layers parallel to the (0 0 1) plane (Table 1).

Related literature top

For related literature, see: Gokel et al. (2004); Shan et al. (2001); Starova et al. (2007).

Experimental top

ZnSO4(0.016 g, 0.01 mmol), dcbp (0.018 g, 0.012 mmol) and NaOH(0.048 mmol,0.12 mmol), were added in a mixed solvent of ethanol and acetonitrile, the mixture was heated for five hours under reflux. during the process stirring and influx were required. The resultant was then filtered to give a pure solution which was infiltrated by diethyl ether freely in a closed vessel, a weeks later some single crystals of the size suitable for X-Ray diffraction analysis.

Refinement top

All H atoms attached to C were fixed geometrically and treated as riding with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C). H atoms of the coordinated water molecules were located in difference Fourier maps and included in the subsequent refinement as riding on their parent O atoms using restraints (O—H= 0.84 (1)Å and H···H= 1.39 (2) Å) with Uiso(H) = 1.5Ueq(O).

Structure description top

Transition metal complexes with 2,2'-bipyridine derivatives are suitable models for the study of excited state dynamics. In addition, they are of interest for the development of light-energy conversion devices and optical sensors (Gokel et al., 2004; Shan et al., 2001). One of the simplest carbonyl-containing derivatives of 2,2'-bipyridine is the 3,3'-dicarboxy-2,2'-bipyridine molecule (dcbp). Indeed, the molecule of dcbp has two available centres for complexation: nitrogen atoms of bipyridine fragment and oxygen atoms of the carboxylic groups. The carbonyl groups are capable to form chelates when pyridine rings turn from trans-conformation to cis-conformation (Starova et al., 2007).

The Zn atom, located on a twofold axis, is six-coordinated in a distorted octahedral arrangement, with two N atoms and two O atoms of two symmetry related dcbp ligands are located in the basal plane whereas two O atoms of water molecule occupy the apical positions. The dcbp ligand acts then as a bridging ligand linking adjacent Zn ions and forming a one-dimensional infinite chain parallel to the b axis. O—H···O hydrogen bongs involving the coordinated water molecules connect adjacent chains to form layers parallel to the (0 0 1) plane (Table 1).

For related literature, see: Gokel et al. (2004); Shan et al. (2001); Starova et al. (2007).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Bruker, 2004).

Figures top
[Figure 1] Fig. 1. Partial view of the polymeric chain in (I) with the atom-labelling scheme. Displacement ellipsoids are drawn at the 60% probability level. H atoms have been omitted for clarity. [Symmetry codes: (i) 1 - x, y, 1/2 - z; (ii) x, y - 1, z; (iii) 1 - x, y - 1, 1/2 - z; (iv) x, 1 + y, z; (v) 1 - x, 1 + y, 1/2 - z]
catena-Poly[[diaquazinc(II)]-µ-2,2'-bipyridine-3,3'-dicarboxyato- κ4N,N':O,O'] top
Crystal data top
[Zn(C12H6N2O4)(H2O)2]F(000) = 696
Mr = 343.59Dx = 1.981 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 1044 reflections
a = 11.3254 (15) Åθ = 3.2–25.2°
b = 7.8829 (10) ŵ = 2.17 mm1
c = 13.1264 (17) ÅT = 298 K
β = 100.519 (2)°Block, colourless
V = 1152.2 (3) Å30.28 × 0.22 × 0.19 mm
Z = 4
Data collection top
Bruker APEXII area-detector
diffractometer
1044 independent reflections
Radiation source: fine-focus sealed tube1007 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.039
Detector resolution: 0 pixels mm-1θmax = 25.2°, θmin = 3.2°
φ and ω scansh = 1311
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)
k = 99
Tmin = 0.572, Tmax = 0.666l = 1515
2925 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.128H-atom parameters constrained
S = 1.17 w = 1/[σ2(Fo2) + (0.0557P)2 + 12.6528P]
where P = (Fo2 + 2Fc2)/3
1044 reflections(Δ/σ)max < 0.001
96 parametersΔρmax = 0.69 e Å3
0 restraintsΔρmin = 0.60 e Å3
Crystal data top
[Zn(C12H6N2O4)(H2O)2]V = 1152.2 (3) Å3
Mr = 343.59Z = 4
Monoclinic, C2/cMo Kα radiation
a = 11.3254 (15) ŵ = 2.17 mm1
b = 7.8829 (10) ÅT = 298 K
c = 13.1264 (17) Å0.28 × 0.22 × 0.19 mm
β = 100.519 (2)°
Data collection top
Bruker APEXII area-detector
diffractometer
1044 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)
1007 reflections with I > 2σ(I)
Tmin = 0.572, Tmax = 0.666Rint = 0.039
2925 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0420 restraints
wR(F2) = 0.128H-atom parameters constrained
S = 1.17 w = 1/[σ2(Fo2) + (0.0557P)2 + 12.6528P]
where P = (Fo2 + 2Fc2)/3
1044 reflectionsΔρmax = 0.69 e Å3
96 parametersΔρmin = 0.60 e Å3
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
Zn10.50000.20313 (9)0.25000.0168 (3)
N10.4346 (3)0.4119 (4)0.1576 (2)0.0076 (7)
O10.3250 (2)0.1908 (3)0.2842 (2)0.0107 (6)
H110.26600.23110.24360.016*
H120.31350.09130.30280.016*
O20.4605 (2)1.0082 (3)0.1389 (2)0.0089 (6)
O30.6348 (2)0.8655 (4)0.1726 (2)0.0116 (6)
C10.3727 (3)0.3937 (5)0.0605 (3)0.0102 (8)
H10.34870.28560.03700.012*
C20.3435 (4)0.5300 (5)0.0057 (3)0.0114 (8)
H20.29480.51630.07030.014*
C30.3891 (3)0.6873 (5)0.0275 (3)0.0093 (8)
H30.37460.78030.01660.011*
C40.4571 (3)0.7073 (5)0.1272 (3)0.0065 (8)
C50.4707 (3)0.5671 (5)0.1932 (3)0.0066 (8)
C60.5228 (4)0.8741 (5)0.1492 (3)0.0079 (8)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0171 (4)0.0127 (4)0.0197 (4)0.0000.0011 (3)0.000
N10.0071 (15)0.0062 (16)0.0086 (16)0.0004 (12)0.0008 (13)0.0006 (13)
O10.0061 (13)0.0083 (14)0.0173 (15)0.0012 (10)0.0011 (11)0.0034 (11)
O20.0103 (13)0.0038 (13)0.0109 (13)0.0012 (10)0.0027 (10)0.0008 (10)
O30.0079 (14)0.0081 (14)0.0177 (15)0.0002 (11)0.0009 (11)0.0002 (11)
C10.0078 (18)0.0088 (19)0.0131 (19)0.0015 (15)0.0004 (15)0.0030 (16)
C20.0103 (19)0.013 (2)0.0096 (19)0.0012 (16)0.0013 (15)0.0029 (16)
C30.0076 (19)0.0108 (19)0.0085 (19)0.0029 (15)0.0010 (15)0.0000 (15)
C40.0056 (18)0.0046 (19)0.0093 (19)0.0019 (14)0.0016 (15)0.0021 (14)
C50.0060 (17)0.0063 (18)0.007 (2)0.0000 (14)0.0009 (14)0.0020 (15)
C60.0134 (19)0.0063 (19)0.0039 (17)0.0016 (15)0.0009 (14)0.0000 (14)
Geometric parameters (Å, º) top
Zn1—N1i2.098 (3)O2—Zn1iv2.110 (3)
Zn1—N12.098 (3)O3—C61.252 (5)
Zn1—O2ii2.110 (3)C1—C21.383 (6)
Zn1—O2iii2.110 (3)C1—H10.9300
Zn1—O12.113 (3)C2—C31.383 (6)
Zn1—O1i2.113 (3)C2—H20.9300
N1—C11.345 (5)C3—C41.401 (6)
N1—C51.346 (5)C3—H30.9300
O1—H110.8379C4—C51.395 (5)
O1—H120.8388C4—C61.513 (5)
O2—C61.264 (5)C5—C5i1.519 (7)
N1i—Zn1—N176.67 (18)H11—O1—H12113.1
N1i—Zn1—O2ii168.29 (12)C6—O2—Zn1iv119.4 (2)
N1—Zn1—O2ii99.41 (12)N1—C1—C2122.4 (4)
N1i—Zn1—O2iii99.41 (12)N1—C1—H1118.8
N1—Zn1—O2iii168.29 (12)C2—C1—H1118.8
O2ii—Zn1—O2iii86.50 (15)C3—C2—C1117.8 (4)
N1i—Zn1—O199.16 (12)C3—C2—H2121.1
N1—Zn1—O185.01 (12)C1—C2—H2121.1
O2ii—Zn1—O191.41 (11)C2—C3—C4120.3 (4)
O2iii—Zn1—O184.74 (11)C2—C3—H3119.8
N1i—Zn1—O1i85.01 (12)C4—C3—H3119.8
N1—Zn1—O1i99.16 (12)C5—C4—C3118.1 (3)
O2ii—Zn1—O1i84.74 (11)C5—C4—C6125.1 (3)
O2iii—Zn1—O1i91.41 (11)C3—C4—C6116.3 (3)
O1—Zn1—O1i174.72 (15)N1—C5—C4120.8 (3)
C1—N1—C5119.9 (3)N1—C5—C5i113.1 (2)
C1—N1—Zn1122.2 (3)C4—C5—C5i126.1 (2)
C5—N1—Zn1117.3 (2)O3—C6—O2126.3 (4)
Zn1—O1—H11121.2O3—C6—C4116.1 (3)
Zn1—O1—H12107.9O2—C6—C4117.5 (3)
Symmetry codes: (i) x+1, y, z+1/2; (ii) x, y1, z; (iii) x+1, y1, z+1/2; (iv) x, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H11···O3v0.841.922.744 (4)167
O1—H12···O3iii0.841.882.648 (4)151
Symmetry codes: (iii) x+1, y1, z+1/2; (v) x1/2, y1/2, z.

Experimental details

Crystal data
Chemical formula[Zn(C12H6N2O4)(H2O)2]
Mr343.59
Crystal system, space groupMonoclinic, C2/c
Temperature (K)298
a, b, c (Å)11.3254 (15), 7.8829 (10), 13.1264 (17)
β (°) 100.519 (2)
V3)1152.2 (3)
Z4
Radiation typeMo Kα
µ (mm1)2.17
Crystal size (mm)0.28 × 0.22 × 0.19
Data collection
DiffractometerBruker APEXII area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2004)
Tmin, Tmax0.572, 0.666
No. of measured, independent and
observed [I > 2σ(I)] reflections
2925, 1044, 1007
Rint0.039
(sin θ/λ)max1)0.599
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.128, 1.17
No. of reflections1044
No. of parameters96
H-atom treatmentH-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0557P)2 + 12.6528P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å3)0.69, 0.60

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997), SHELXTL (Bruker, 2004).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H11···O3i0.841.922.744 (4)167.0
O1—H12···O3ii0.841.882.648 (4)150.9
Symmetry codes: (i) x1/2, y1/2, z; (ii) x+1, y1, z+1/2.
 

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