metal-organic compounds
Aquabis(3′-hydroxy-2,2′-bipyridine-3-olato-κ2N,N′)zinc(II)
aDepartment of Chemistry and Chemical Engineering, Institute of Materials Chemistry, Binzhou University, Binzhou 256603, People's Republic of China, and bDepartment of Chemistry, Shandong Normal University, Jinan 250014, People's Republic of China
*Correspondence e-mail: zhangshiguo1970@yahoo.com.cn
In the title complex, [Zn(C10H7N2O2)2(H2O)], the ZnII ion and water O atom are located on a crystallographic twofold rotation axis and the metal atom assumes a distorted trigonal-bipyramidal ZnN4O coordination geometry. An intramolecular O—H⋯O hydrogen bond occurs within the ligand and intermolecular O—H⋯O hydrogen bonds involving the water molecule result in a sheet structure in the In addition, a short C—O⋯π contact between the O atom of the deprotonated hydroxyl group and a nearby pyridine ring [O⋯Cg = 3.977 (2) Å, where Cg is the centroid of the pyridine ring] is observed.
Related literature
For related structures, see: Cargill Thompson et al. (1996); Stephenson & Hardie (2007).
Experimental
Crystal data
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Refinement
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Data collection: SMART (Bruker, 1997); cell SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.
Supporting information
10.1107/S1600536808024495/hb2736sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808024495/hb2736Isup2.hkl
A 10-ml H2O solution of ZnCl2 (0.1214 g, 0.891 mmol) was added to a 10-ml hot ethanol solution containing 2,2'-bipyridine-3,3'-diol (0.1664 g, 0.884 mmol), and the mixed solution was stirred for a few minutes. Yellow blocks of (I) were obtained after the solution had been allowed to stand at room temperature for two weeks.
The water H atom was located in a difference Fourier map and refined as riding in its as found relative position with Uiso(H) = 1.5Ueq(O). The other H atoms geometrically placed (C—H = 0.93-0.96Å, O—H = 0.82Å) and refined as riding with with Uiso = Uiso = 1.2Ueq(C) or 1.5Ueq(methyl C, O).
Data collection: SMART (Bruker, 1997); cell
SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and local programs.[Zn(C10H7N2O2)2(H2O)] | F(000) = 936 |
Mr = 457.74 | Dx = 1.657 Mg m−3 |
Orthorhombic, Pbcn | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2n 2ab | Cell parameters from 2299 reflections |
a = 13.931 (2) Å | θ = 2.7–24.6° |
b = 9.1685 (16) Å | µ = 1.38 mm−1 |
c = 14.364 (3) Å | T = 298 K |
V = 1834.7 (6) Å3 | Block, yellow |
Z = 4 | 0.40 × 0.21 × 0.20 mm |
Bruker SMART APEX CCD diffractometer | 1621 independent reflections |
Radiation source: fine-focus sealed tube | 1293 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.035 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.7° |
Absorption correction: multi-scan (SADABS; Bruker, 1997) | h = −15→16 |
Tmin = 0.608, Tmax = 0.770 | k = −9→10 |
8883 measured reflections | l = −17→17 |
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)] = 0.030 | Hydrogen site location: difmap and geom |
wR(F2) = 0.083 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0435P)2 + 0.4048P] where P = (Fo2 + 2Fc2)/3 |
1621 reflections | (Δ/σ)max < 0.001 |
137 parameters | Δρmax = 0.24 e Å−3 |
0 restraints | Δρmin = −0.22 e Å−3 |
[Zn(C10H7N2O2)2(H2O)] | V = 1834.7 (6) Å3 |
Mr = 457.74 | Z = 4 |
Orthorhombic, Pbcn | Mo Kα radiation |
a = 13.931 (2) Å | µ = 1.38 mm−1 |
b = 9.1685 (16) Å | T = 298 K |
c = 14.364 (3) Å | 0.40 × 0.21 × 0.20 mm |
Bruker SMART APEX CCD diffractometer | 1621 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1997) | 1293 reflections with I > 2σ(I) |
Tmin = 0.608, Tmax = 0.770 | Rint = 0.035 |
8883 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.083 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.24 e Å−3 |
1621 reflections | Δρmin = −0.22 e Å−3 |
137 parameters |
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 | ||
C1 | 0.18495 (17) | −0.0831 (3) | 0.84200 (18) | 0.0497 (6) | |
H8A | 0.1443 | −0.1318 | 0.8829 | 0.060* | |
C2 | 0.28226 (18) | −0.0979 (3) | 0.85235 (18) | 0.0505 (6) | |
H7 | 0.3078 | −0.1560 | 0.8993 | 0.061* | |
C3 | 0.34041 (17) | −0.0251 (3) | 0.7919 (2) | 0.0484 (6) | |
H6A | 0.4066 | −0.0346 | 0.7980 | 0.058* | |
C4 | 0.30414 (16) | 0.0627 (3) | 0.72164 (17) | 0.0405 (6) | |
C5 | 0.20250 (14) | 0.0718 (2) | 0.71420 (15) | 0.0328 (5) | |
C6 | 0.14629 (15) | 0.1528 (2) | 0.64177 (14) | 0.0335 (5) | |
C7 | 0.18121 (17) | 0.2589 (3) | 0.57966 (15) | 0.0433 (6) | |
C8 | 0.1158 (2) | 0.3273 (3) | 0.52075 (16) | 0.0532 (7) | |
H4 | 0.1371 | 0.4013 | 0.4816 | 0.064* | |
C9 | 0.0216 (2) | 0.2884 (3) | 0.51908 (18) | 0.0530 (7) | |
H3 | −0.0212 | 0.3329 | 0.4783 | 0.064* | |
C10 | −0.00846 (16) | 0.1818 (3) | 0.57930 (17) | 0.0482 (6) | |
H2 | −0.0724 | 0.1528 | 0.5782 | 0.058* | |
N1 | 0.14707 (14) | −0.00122 (19) | 0.77522 (15) | 0.0401 (5) | |
N2 | 0.05150 (12) | 0.11824 (19) | 0.63953 (12) | 0.0379 (5) | |
O1 | 0.27183 (13) | 0.3017 (2) | 0.57387 (13) | 0.0673 (6) | |
H5 | 0.3044 | 0.2553 | 0.6111 | 0.101* | |
O2 | 0.36348 (11) | 0.1306 (2) | 0.66513 (12) | 0.0574 (5) | |
O3 | 0.0000 | −0.2225 (3) | 0.7500 | 0.0640 (8) | |
H1 | −0.0443 | −0.2657 | 0.7730 | 0.096* | |
Zn1 | 0.0000 | −0.00413 (4) | 0.7500 | 0.03787 (16) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0382 (14) | 0.0538 (16) | 0.0571 (16) | −0.0007 (11) | −0.0022 (12) | 0.0162 (12) |
C2 | 0.0420 (14) | 0.0485 (15) | 0.0610 (16) | 0.0054 (11) | −0.0147 (12) | 0.0037 (12) |
C3 | 0.0248 (12) | 0.0561 (16) | 0.0644 (16) | 0.0022 (11) | −0.0092 (13) | −0.0119 (13) |
C4 | 0.0291 (12) | 0.0451 (13) | 0.0474 (13) | −0.0045 (11) | 0.0016 (11) | −0.0133 (11) |
C5 | 0.0264 (11) | 0.0330 (12) | 0.0389 (12) | −0.0026 (9) | 0.0007 (9) | −0.0086 (10) |
C6 | 0.0311 (12) | 0.0340 (11) | 0.0353 (11) | 0.0003 (9) | 0.0039 (9) | −0.0069 (9) |
C7 | 0.0451 (14) | 0.0455 (14) | 0.0393 (13) | −0.0082 (11) | 0.0066 (11) | −0.0059 (11) |
C8 | 0.0669 (19) | 0.0496 (16) | 0.0432 (14) | −0.0014 (13) | 0.0054 (13) | 0.0075 (12) |
C9 | 0.0555 (16) | 0.0570 (17) | 0.0464 (15) | 0.0136 (14) | −0.0026 (12) | 0.0049 (13) |
C10 | 0.0356 (14) | 0.0567 (16) | 0.0525 (15) | 0.0114 (11) | −0.0028 (11) | 0.0013 (13) |
N1 | 0.0276 (11) | 0.0446 (12) | 0.0482 (11) | 0.0002 (8) | 0.0001 (9) | 0.0067 (9) |
N2 | 0.0272 (10) | 0.0421 (11) | 0.0444 (11) | 0.0025 (8) | 0.0014 (8) | 0.0001 (8) |
O1 | 0.0538 (12) | 0.0821 (14) | 0.0661 (12) | −0.0260 (10) | 0.0022 (9) | 0.0184 (11) |
O2 | 0.0277 (9) | 0.0776 (13) | 0.0669 (11) | −0.0141 (8) | 0.0075 (8) | −0.0009 (10) |
O3 | 0.0353 (14) | 0.0391 (14) | 0.118 (2) | 0.000 | 0.0278 (13) | 0.000 |
Zn1 | 0.0232 (2) | 0.0418 (3) | 0.0487 (3) | 0.000 | 0.00383 (15) | 0.000 |
C1—N1 | 1.328 (3) | C7—C8 | 1.392 (3) |
C1—C2 | 1.370 (3) | C8—C9 | 1.361 (4) |
C1—H8A | 0.9300 | C8—H4 | 0.9300 |
C2—C3 | 1.362 (4) | C9—C10 | 1.371 (4) |
C2—H7 | 0.9300 | C9—H3 | 0.9300 |
C3—C4 | 1.386 (4) | C10—N2 | 1.336 (3) |
C3—H6A | 0.9300 | C10—H2 | 0.9300 |
C4—O2 | 1.315 (3) | O1—H5 | 0.8200 |
C4—C5 | 1.422 (3) | O3—H1 | 0.8042 |
C5—N1 | 1.346 (3) | Zn1—N1 | 2.081 (2) |
C5—C6 | 1.499 (3) | Zn1—N2 | 2.0716 (18) |
C6—N2 | 1.359 (3) | Zn1—N2i | 2.0716 (18) |
C6—C7 | 1.407 (3) | Zn1—N1i | 2.081 (2) |
C7—O1 | 1.324 (3) | O3—Zn1 | 2.002 (2) |
N1—C1—C2 | 121.8 (2) | C8—C9—C10 | 118.0 (2) |
N1—C1—H8A | 119.1 | C8—C9—H3 | 121.0 |
C2—C1—H8A | 119.1 | C10—C9—H3 | 121.0 |
C3—C2—C1 | 118.1 (2) | N2—C10—C9 | 121.9 (2) |
C3—C2—H7 | 121.0 | N2—C10—H2 | 119.0 |
C1—C2—H7 | 121.0 | C9—C10—H2 | 119.0 |
C2—C3—C4 | 122.1 (2) | C1—N1—C5 | 121.6 (2) |
C2—C3—H6A | 118.9 | C1—N1—Zn1 | 120.67 (16) |
C4—C3—H6A | 118.9 | C5—N1—Zn1 | 117.24 (15) |
O2—C4—C3 | 119.7 (2) | C10—N2—C6 | 121.4 (2) |
O2—C4—C5 | 123.5 (2) | C10—N2—Zn1 | 121.03 (15) |
C3—C4—C5 | 116.8 (2) | C6—N2—Zn1 | 116.41 (14) |
N1—C5—C4 | 119.5 (2) | C7—O1—H5 | 109.5 |
N1—C5—C6 | 113.49 (18) | Zn1—O3—H1 | 119.5 |
C4—C5—C6 | 126.9 (2) | O3—Zn1—N2 | 122.79 (5) |
N2—C6—C7 | 118.8 (2) | O3—Zn1—N2i | 122.79 (5) |
N2—C6—C5 | 114.11 (18) | N2—Zn1—N2i | 114.42 (10) |
C7—C6—C5 | 127.03 (19) | O3—Zn1—N1 | 90.73 (5) |
O1—C7—C8 | 116.9 (2) | N2—Zn1—N1 | 77.61 (7) |
O1—C7—C6 | 125.0 (2) | N2i—Zn1—N1 | 101.58 (7) |
C8—C7—C6 | 118.1 (2) | O3—Zn1—N1i | 90.73 (5) |
C9—C8—C7 | 121.6 (2) | N2—Zn1—N1i | 101.58 (7) |
C9—C8—H4 | 119.2 | N2i—Zn1—N1i | 77.61 (7) |
C7—C8—H4 | 119.2 | N1—Zn1—N1i | 178.53 (10) |
N1—C1—C2—C3 | 0.3 (4) | C4—C5—N1—Zn1 | −172.45 (15) |
C1—C2—C3—C4 | 0.3 (4) | C6—C5—N1—Zn1 | 5.8 (2) |
C2—C3—C4—O2 | −180.0 (2) | C9—C10—N2—C6 | −2.3 (4) |
C2—C3—C4—C5 | −1.0 (4) | C9—C10—N2—Zn1 | 165.07 (19) |
O2—C4—C5—N1 | −179.9 (2) | C7—C6—N2—C10 | 0.6 (3) |
C3—C4—C5—N1 | 1.2 (3) | C5—C6—N2—C10 | 179.53 (19) |
O2—C4—C5—C6 | 2.1 (4) | C7—C6—N2—Zn1 | −167.35 (15) |
C3—C4—C5—C6 | −176.8 (2) | C5—C6—N2—Zn1 | 11.6 (2) |
N1—C5—C6—N2 | −11.3 (3) | C10—N2—Zn1—O3 | 102.57 (17) |
C4—C5—C6—N2 | 166.8 (2) | C6—N2—Zn1—O3 | −89.42 (15) |
N1—C5—C6—C7 | 167.5 (2) | C10—N2—Zn1—N2i | −77.43 (17) |
C4—C5—C6—C7 | −14.4 (3) | C6—N2—Zn1—N2i | 90.58 (15) |
N2—C6—C7—O1 | −179.3 (2) | C10—N2—Zn1—N1 | −174.67 (19) |
C5—C6—C7—O1 | 1.9 (4) | C6—N2—Zn1—N1 | −6.65 (14) |
N2—C6—C7—C8 | 2.2 (3) | C10—N2—Zn1—N1i | 4.08 (19) |
C5—C6—C7—C8 | −176.6 (2) | C6—N2—Zn1—N1i | 172.10 (14) |
O1—C7—C8—C9 | 178.0 (2) | C1—N1—Zn1—O3 | −48.31 (19) |
C6—C7—C8—C9 | −3.4 (4) | C5—N1—Zn1—O3 | 123.54 (16) |
C7—C8—C9—C10 | 1.8 (4) | C1—N1—Zn1—N2 | −171.8 (2) |
C8—C9—C10—N2 | 1.1 (4) | C5—N1—Zn1—N2 | 0.05 (16) |
C2—C1—N1—C5 | −0.1 (4) | C1—N1—Zn1—N2i | 75.4 (2) |
C2—C1—N1—Zn1 | 171.39 (19) | C5—N1—Zn1—N2i | −112.72 (16) |
C4—C5—N1—C1 | −0.7 (3) | C1—N1—Zn1—N1i | 131.69 (18) |
C6—C5—N1—C1 | 177.6 (2) | C5—N1—Zn1—N1i | −56.46 (16) |
Symmetry code: (i) −x, y, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H5···O2 | 0.82 | 1.61 | 2.410 (3) | 165 |
O3—H1···O2ii | 0.80 | 1.83 | 2.630 (2) | 174 |
Symmetry code: (ii) x−1/2, y−1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | [Zn(C10H7N2O2)2(H2O)] |
Mr | 457.74 |
Crystal system, space group | Orthorhombic, Pbcn |
Temperature (K) | 298 |
a, b, c (Å) | 13.931 (2), 9.1685 (16), 14.364 (3) |
V (Å3) | 1834.7 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.38 |
Crystal size (mm) | 0.40 × 0.21 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1997) |
Tmin, Tmax | 0.608, 0.770 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8883, 1621, 1293 |
Rint | 0.035 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.083, 1.05 |
No. of reflections | 1621 |
No. of parameters | 137 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.24, −0.22 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXTL (Sheldrick, 2008) and local programs.
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H5···O2 | 0.82 | 1.61 | 2.410 (3) | 165 |
O3—H1···O2i | 0.80 | 1.83 | 2.630 (2) | 174 |
Symmetry code: (i) x−1/2, y−1/2, −z+3/2. |
Acknowledgements
The authors thank the Natural Science Foundation of Shandong Province of China (Grant No. Y2007B26).
References
Bruker (1997). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cargill Thompson, A. M. W., Jeffery, J. C., Liard, D. J. & Ward, M. D. (1996). J. Chem. Soc. Dalton Trans. pp. 879–884. CrossRef Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stephenson, M. D. & Hardie, M. J. (2007). CrystEngComm. 9, 496–502. Web of Science CSD CrossRef CAS Google Scholar
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2,2'-Bipyridine-3,3'-diol (bpd) has the potential to be a useful multi-dentate ligand and may act as a bridging ligand due to coordination of its N and O atoms. A few multi-nuclear complexes have been synthesized with mono-deprotonated bpd as a bridging ligand (Cargill Thompson et al. 1996; Stephenson & Hardie, 2007). We attempted to prepare a similar compound, but instead we obtained the mono-nuclear title complex, (I), (Fig. 1) and report its structure herein.
The Zn1 atom in (I) lies in a twofold axis and is in a distorted trigonal bipyramidal geometry (Table 1). The dihedral angle between the N1 and N2 ring mean planes is 13.08 (12)°. An intramolecular O—H···O hydrogen bond between O atom of deprotonated hydroxyl and hydroxyl group (Table 2) occcurs within the ligand. The water molecule (O atom site symmetry 2) makes an intermolecular O—H···.O hydrogen bond to result in a supramolecular sheet structure in the ab plane (Fig. 2). In addition to the hydrogen bonds there is weak interaction between C—O bond and pyridine ring and the relevant distances are as follows: C4—O2···Cg1i = 3.977 (2) Å and C4—O2···Cg1iperp = 3.635 Å [Cg1 is the centroid of N1/C1—C5 ring, C4—O2···Cg1iperp is the perpendicular distance from O2 atom to ring Cg1i; symmetry code: (i) 1/2-x, 1/2+y, z].