Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807053305/dn2251sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807053305/dn2251Isup2.hkl |
CCDC reference: 667249
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (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
For related literature, see: Gokel et al. (2004); Shan et al. (2001); Starova et al. (2007).
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.
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).
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).
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).
[Zn(C12H6N2O4)(H2O)2] | F(000) = 696 |
Mr = 343.59 | Dx = 1.981 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 1044 reflections |
a = 11.3254 (15) Å | θ = 3.2–25.2° |
b = 7.8829 (10) Å | µ = 2.17 mm−1 |
c = 13.1264 (17) Å | T = 298 K |
β = 100.519 (2)° | Block, colourless |
V = 1152.2 (3) Å3 | 0.28 × 0.22 × 0.19 mm |
Z = 4 |
Bruker APEXII area-detector diffractometer | 1044 independent reflections |
Radiation source: fine-focus sealed tube | 1007 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.039 |
Detector resolution: 0 pixels mm-1 | θmax = 25.2°, θmin = 3.2° |
φ and ω scans | h = −13→11 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | k = −9→9 |
Tmin = 0.572, Tmax = 0.666 | l = −15→15 |
2925 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.128 | H-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 parameters | Δρmax = 0.69 e Å−3 |
0 restraints | Δρmin = −0.60 e Å−3 |
[Zn(C12H6N2O4)(H2O)2] | V = 1152.2 (3) Å3 |
Mr = 343.59 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 11.3254 (15) Å | µ = 2.17 mm−1 |
b = 7.8829 (10) Å | T = 298 K |
c = 13.1264 (17) Å | 0.28 × 0.22 × 0.19 mm |
β = 100.519 (2)° |
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 = 0.666 | Rint = 0.039 |
2925 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.128 | H-atom parameters constrained |
S = 1.17 | w = 1/[σ2(Fo2) + (0.0557P)2 + 12.6528P] where P = (Fo2 + 2Fc2)/3 |
1044 reflections | Δρmax = 0.69 e Å−3 |
96 parameters | Δρmin = −0.60 e Å−3 |
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 | ||
Zn1 | 0.5000 | 0.20313 (9) | 0.2500 | 0.0168 (3) | |
N1 | 0.4346 (3) | 0.4119 (4) | 0.1576 (2) | 0.0076 (7) | |
O1 | 0.3250 (2) | 0.1908 (3) | 0.2842 (2) | 0.0107 (6) | |
H11 | 0.2660 | 0.2311 | 0.2436 | 0.016* | |
H12 | 0.3135 | 0.0913 | 0.3028 | 0.016* | |
O2 | 0.4605 (2) | 1.0082 (3) | 0.1389 (2) | 0.0089 (6) | |
O3 | 0.6348 (2) | 0.8655 (4) | 0.1726 (2) | 0.0116 (6) | |
C1 | 0.3727 (3) | 0.3937 (5) | 0.0605 (3) | 0.0102 (8) | |
H1 | 0.3487 | 0.2856 | 0.0370 | 0.012* | |
C2 | 0.3435 (4) | 0.5300 (5) | −0.0057 (3) | 0.0114 (8) | |
H2 | 0.2948 | 0.5163 | −0.0703 | 0.014* | |
C3 | 0.3891 (3) | 0.6873 (5) | 0.0275 (3) | 0.0093 (8) | |
H3 | 0.3746 | 0.7803 | −0.0166 | 0.011* | |
C4 | 0.4571 (3) | 0.7073 (5) | 0.1272 (3) | 0.0065 (8) | |
C5 | 0.4707 (3) | 0.5671 (5) | 0.1932 (3) | 0.0066 (8) | |
C6 | 0.5228 (4) | 0.8741 (5) | 0.1492 (3) | 0.0079 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.0171 (4) | 0.0127 (4) | 0.0197 (4) | 0.000 | 0.0011 (3) | 0.000 |
N1 | 0.0071 (15) | 0.0062 (16) | 0.0086 (16) | 0.0004 (12) | −0.0008 (13) | −0.0006 (13) |
O1 | 0.0061 (13) | 0.0083 (14) | 0.0173 (15) | 0.0012 (10) | 0.0011 (11) | 0.0034 (11) |
O2 | 0.0103 (13) | 0.0038 (13) | 0.0109 (13) | 0.0012 (10) | −0.0027 (10) | −0.0008 (10) |
O3 | 0.0079 (14) | 0.0081 (14) | 0.0177 (15) | 0.0002 (11) | −0.0009 (11) | 0.0002 (11) |
C1 | 0.0078 (18) | 0.0088 (19) | 0.0131 (19) | −0.0015 (15) | −0.0004 (15) | −0.0030 (16) |
C2 | 0.0103 (19) | 0.013 (2) | 0.0096 (19) | 0.0012 (16) | −0.0013 (15) | −0.0029 (16) |
C3 | 0.0076 (19) | 0.0108 (19) | 0.0085 (19) | 0.0029 (15) | −0.0010 (15) | 0.0000 (15) |
C4 | 0.0056 (18) | 0.0046 (19) | 0.0093 (19) | 0.0019 (14) | 0.0016 (15) | −0.0021 (14) |
C5 | 0.0060 (17) | 0.0063 (18) | 0.007 (2) | 0.0000 (14) | 0.0009 (14) | −0.0020 (15) |
C6 | 0.0134 (19) | 0.0063 (19) | 0.0039 (17) | −0.0016 (15) | 0.0009 (14) | 0.0000 (14) |
Zn1—N1i | 2.098 (3) | O2—Zn1iv | 2.110 (3) |
Zn1—N1 | 2.098 (3) | O3—C6 | 1.252 (5) |
Zn1—O2ii | 2.110 (3) | C1—C2 | 1.383 (6) |
Zn1—O2iii | 2.110 (3) | C1—H1 | 0.9300 |
Zn1—O1 | 2.113 (3) | C2—C3 | 1.383 (6) |
Zn1—O1i | 2.113 (3) | C2—H2 | 0.9300 |
N1—C1 | 1.345 (5) | C3—C4 | 1.401 (6) |
N1—C5 | 1.346 (5) | C3—H3 | 0.9300 |
O1—H11 | 0.8379 | C4—C5 | 1.395 (5) |
O1—H12 | 0.8388 | C4—C6 | 1.513 (5) |
O2—C6 | 1.264 (5) | C5—C5i | 1.519 (7) |
N1i—Zn1—N1 | 76.67 (18) | H11—O1—H12 | 113.1 |
N1i—Zn1—O2ii | 168.29 (12) | C6—O2—Zn1iv | 119.4 (2) |
N1—Zn1—O2ii | 99.41 (12) | N1—C1—C2 | 122.4 (4) |
N1i—Zn1—O2iii | 99.41 (12) | N1—C1—H1 | 118.8 |
N1—Zn1—O2iii | 168.29 (12) | C2—C1—H1 | 118.8 |
O2ii—Zn1—O2iii | 86.50 (15) | C3—C2—C1 | 117.8 (4) |
N1i—Zn1—O1 | 99.16 (12) | C3—C2—H2 | 121.1 |
N1—Zn1—O1 | 85.01 (12) | C1—C2—H2 | 121.1 |
O2ii—Zn1—O1 | 91.41 (11) | C2—C3—C4 | 120.3 (4) |
O2iii—Zn1—O1 | 84.74 (11) | C2—C3—H3 | 119.8 |
N1i—Zn1—O1i | 85.01 (12) | C4—C3—H3 | 119.8 |
N1—Zn1—O1i | 99.16 (12) | C5—C4—C3 | 118.1 (3) |
O2ii—Zn1—O1i | 84.74 (11) | C5—C4—C6 | 125.1 (3) |
O2iii—Zn1—O1i | 91.41 (11) | C3—C4—C6 | 116.3 (3) |
O1—Zn1—O1i | 174.72 (15) | N1—C5—C4 | 120.8 (3) |
C1—N1—C5 | 119.9 (3) | N1—C5—C5i | 113.1 (2) |
C1—N1—Zn1 | 122.2 (3) | C4—C5—C5i | 126.1 (2) |
C5—N1—Zn1 | 117.3 (2) | O3—C6—O2 | 126.3 (4) |
Zn1—O1—H11 | 121.2 | O3—C6—C4 | 116.1 (3) |
Zn1—O1—H12 | 107.9 | O2—C6—C4 | 117.5 (3) |
Symmetry codes: (i) −x+1, y, −z+1/2; (ii) x, y−1, z; (iii) −x+1, y−1, −z+1/2; (iv) x, y+1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H11···O3v | 0.84 | 1.92 | 2.744 (4) | 167 |
O1—H12···O3iii | 0.84 | 1.88 | 2.648 (4) | 151 |
Symmetry codes: (iii) −x+1, y−1, −z+1/2; (v) x−1/2, y−1/2, z. |
Experimental details
Crystal data | |
Chemical formula | [Zn(C12H6N2O4)(H2O)2] |
Mr | 343.59 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 298 |
a, b, c (Å) | 11.3254 (15), 7.8829 (10), 13.1264 (17) |
β (°) | 100.519 (2) |
V (Å3) | 1152.2 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.17 |
Crystal size (mm) | 0.28 × 0.22 × 0.19 |
Data collection | |
Diffractometer | Bruker APEXII area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2004) |
Tmin, Tmax | 0.572, 0.666 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2925, 1044, 1007 |
Rint | 0.039 |
(sin θ/λ)max (Å−1) | 0.599 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.128, 1.17 |
No. of reflections | 1044 |
No. of parameters | 96 |
H-atom treatment | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.0557P)2 + 12.6528P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 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).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H11···O3i | 0.84 | 1.92 | 2.744 (4) | 167.0 |
O1—H12···O3ii | 0.84 | 1.88 | 2.648 (4) | 150.9 |
Symmetry codes: (i) x−1/2, y−1/2, z; (ii) −x+1, y−1, −z+1/2. |
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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).