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Acta Crystallogr Sect E Struct Rep Online. 2009 March 1; 65(Pt 3): m331.
Published online 2009 February 28. doi:  10.1107/S1600536809005716
PMCID: PMC2968431

Diaqua­bis(5-fluoro-2-hydroxy­benzoato-κO 1)zinc(II)

Abstract

The title compound, [Zn(C7H4FO3)2(H2O)2], is a monomeric ZnII complex. The ZnII atom, which lies on a twofold rotation axis, is situated in a distorted tetra­hedral environment composed of two monodentate carboxlyate O atoms and two water O atoms. O—H(...)O hydrogen bonds link these units, forming sheets that are stacked along the c axis.

Related literature

For general background, see: Ellsworth & zur Loye (2008 [triangle]); Janiak (2003 [triangle]); Mehrotra & Bohra (1983 [triangle]); Wasuke et al. (2005 [triangle]). For related structures, see: Brownless et al. (1999 [triangle]); Wang et al. (2006 [triangle]).

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Object name is e-65-0m331-scheme1.jpg

Experimental

Crystal data

  • [Zn(C7H4FO3)2(H2O)2]
  • M r = 411.61
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0m331-efi2.jpg
  • a = 15.3096 (10) Å
  • b = 5.4706 (4) Å
  • c = 17.7741 (12) Å
  • β = 91.674 (1)°
  • V = 1487.99 (18) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 1.72 mm−1
  • T = 150 K
  • 0.16 × 0.12 × 0.05 mm

Data collection

  • Bruker SMART APEX CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2001 [triangle]) T min = 0.893, T max = 1.000 (expected range = 0.820–0.918)
  • 8435 measured reflections
  • 1520 independent reflections
  • 1341 reflections with I > 2σ(I)
  • R int = 0.053

Refinement

  • R[F 2 > 2σ(F 2)] = 0.035
  • wR(F 2) = 0.081
  • S = 1.09
  • 1520 reflections
  • 126 parameters
  • 3 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.43 e Å−3
  • Δρmin = −0.27 e Å−3

Data collection: SMART (Bruker, 2007 [triangle]); cell refinement: SAINT-Plus (Bruker, 2007 [triangle]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: DIAMOND (Brandenburg, 1999 [triangle]); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 [triangle]).

Table 1
Selected geometric parameters (Å, °)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809005716/hy2183sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809005716/hy2183Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

Financial support from the National Science Foundation, awards CHE-0714555 and CHE-0714439, is gratefully acknowledged.

supplementary crystallographic information

Comment

Metal carboxylate complexes have long been an extensively studied class of compounds (Mehrotra & Bohra, 1983), and in recent years they have become a major focus of study due to their potentally useful properties (Janiak, 2003; Wasuke et al., 2005). As a continuation of our own studies (Ellsworth & zur Loye, 2008), we report here the crystal structure of the title compound.

The structure of the title compound is built from the monomeric complex of formula Zn(5-fsalcyl)2(H2O)2 (Fig. 1) (5-fsalcyl = 5-fluorosalicylate). The asymmetric unit consists of one ZnII atom that lies on a twofold rotation axis, one 5-fsalcyl ligand, and one water molecule. The coordination environment of the ZnII atom is that of a distorted tetrahedron consisting of two equivalent O atoms from two monodentate carboxylates, and two equivalent O atoms from two water molecules. All four Zn—O bond distances fall within the normal range, with an average length of 1.969 (2) Å. It is worth noting that for the carboxylate O2 atom, the Zn···O2 distance of 2.692 (2)Å falls outside the range considered normal for a Zn—O coordination bond (Wang et al., 2006).

Due to its monodentate binding mode, the 5-fsalcyl carboxylate group adopts a highly asymmetrical configuration. This is manifested in a C1—O1 distance [1.289 (3) Å] for the coordinating O atom that is noticeably longer than the C1—O2 distance [1.246 (3) Å] corresponding to the noncoordinating O atom. In addition, the carboxylate group of the 5-fsalcyl ligand is twisted with a dihedral angle of 9.7 (2) ° with respect to the phenyl ring. As is typical for salicylates, the hydroxyl group of 5-fsalcyl is internally hydrogen bonded to its carboxylate O1 that is located on the same side of the ligand (Brownless et al., 1999).

The monomeric units are hydrogen bonded into chains that are themselves hydrogen bonded into sheets that are stacked along the c axis (Fig. 2).

Experimental

All chemicals and solvents were purchased from commercial sources and used without further purification. 5-Fluorosalicylic acid (3 mmol) was added to 100 ml of water and subsequently brought to pH 6.5 by the addition of 3M NaOH with constant stirring. To this solution was added 10 ml of a 0.10 M solution of Zn(NO3)2.6H2O. Single crystals of the title compound were formed in four weeks after complete evaporation of the solution under ambient conditions.

Refinement

H atoms bonded to C atoms were positioned geometrically and refined as riding atoms. O-bound H atoms were located in a difference Fourier map and refined isotropically, with their O—H distances restrained to 0.84 (2) Å.

Figures

Fig. 1.
Molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bonds are represented by dashed lines. [Symmetry code: (i) -x+1, y, -z+3/2.]
Fig. 2.
View of the crystal packing in the title compound. All H atoms except for those of water and the hydroxyl group are omitted for clarity. Hydrogen bonds are represented by dashed lines.

Crystal data

[Zn(C7H4FO3)2(H2O)2]F(000) = 832
Mr = 411.61Dx = 1.837 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 2066 reflections
a = 15.3096 (10) Åθ = 2.7–24.1°
b = 5.4706 (4) ŵ = 1.72 mm1
c = 17.7741 (12) ÅT = 150 K
β = 91.674 (1)°Plate, colorless
V = 1487.99 (18) Å30.16 × 0.12 × 0.05 mm
Z = 4

Data collection

Bruker SMART APEX CCD diffractometer1520 independent reflections
Radiation source: fine-focus sealed tube1341 reflections with I > 2σ(I)
graphiteRint = 0.053
[var phi] and ω scansθmax = 26.4°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2001)h = −18→18
Tmin = 0.893, Tmax = 1.000k = −6→6
8435 measured reflectionsl = −22→22

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.035Hydrogen site location: mixed
wR(F2) = 0.081H atoms treated by a mixture of independent and constrained refinement
S = 1.09w = 1/[σ2(Fo2) + (0.0397P)2 + 0.7409P] where P = (Fo2 + 2Fc2)/3
1520 reflections(Δ/σ)max < 0.001
126 parametersΔρmax = 0.43 e Å3
3 restraintsΔρmin = −0.27 e Å3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Zn10.50000.08063 (8)0.75000.01954 (15)
C10.56321 (16)0.4151 (5)0.65619 (14)0.0204 (5)
C20.62447 (16)0.5945 (5)0.62352 (14)0.0199 (5)
C30.71316 (16)0.6031 (5)0.64632 (14)0.0191 (5)
C40.76803 (16)0.7820 (5)0.61874 (14)0.0221 (6)
H40.82780.78640.63460.026*
C50.73553 (18)0.9533 (5)0.56829 (15)0.0246 (6)
H50.77241.07750.54950.029*
C60.64862 (18)0.9416 (5)0.54547 (15)0.0248 (6)
C70.59321 (16)0.7666 (5)0.57150 (14)0.0223 (6)
H70.53390.76240.55430.027*
O10.59620 (11)0.2481 (3)0.69963 (10)0.0233 (4)
O20.48283 (11)0.4310 (3)0.64435 (11)0.0265 (4)
F10.61747 (11)1.1088 (3)0.49488 (10)0.0391 (5)
O30.74885 (12)0.4400 (4)0.69676 (11)0.0266 (4)
H30.7120 (18)0.341 (5)0.7060 (18)0.044 (10)*
O40.42296 (13)−0.1489 (4)0.69475 (13)0.0305 (5)
H4A0.437 (2)−0.271 (5)0.6700 (16)0.039 (10)*
H4B0.3689 (13)−0.132 (8)0.691 (2)0.068 (14)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Zn10.0113 (2)0.0184 (2)0.0290 (3)0.0000.00249 (16)0.000
C10.0169 (13)0.0199 (13)0.0245 (14)0.0015 (10)0.0036 (10)−0.0063 (11)
C20.0174 (12)0.0209 (13)0.0214 (13)−0.0025 (11)0.0021 (10)−0.0012 (11)
C30.0149 (12)0.0239 (14)0.0186 (13)0.0015 (10)0.0019 (10)−0.0007 (11)
C40.0118 (12)0.0293 (15)0.0252 (14)−0.0026 (11)0.0016 (10)−0.0009 (12)
C50.0224 (14)0.0238 (15)0.0277 (14)−0.0068 (11)0.0065 (11)0.0003 (12)
C60.0233 (14)0.0255 (15)0.0256 (14)0.0021 (12)0.0000 (11)0.0056 (12)
C70.0151 (13)0.0263 (14)0.0253 (14)−0.0005 (11)−0.0013 (10)0.0008 (12)
O10.0150 (9)0.0239 (10)0.0312 (10)0.0009 (8)0.0054 (7)0.0060 (8)
O20.0121 (9)0.0233 (10)0.0443 (12)−0.0014 (8)0.0025 (8)−0.0025 (9)
F10.0282 (9)0.0390 (10)0.0500 (11)0.0008 (8)−0.0028 (8)0.0232 (9)
O30.0132 (9)0.0315 (11)0.0350 (11)−0.0020 (8)−0.0020 (8)0.0111 (9)
O40.0139 (10)0.0277 (11)0.0497 (13)0.0020 (8)−0.0017 (9)−0.0155 (10)

Geometric parameters (Å, °)

Zn1—O41.966 (2)C4—C51.380 (4)
Zn1—O4i1.966 (2)C4—H40.9500
Zn1—O11.9716 (17)C5—C61.381 (4)
Zn1—O1i1.9717 (17)C5—H50.9500
C1—O21.246 (3)C6—F11.359 (3)
C1—O11.289 (3)C6—C71.369 (4)
C1—C21.487 (4)C7—H70.9500
C2—C71.394 (4)O3—H30.803 (18)
C2—C31.406 (4)O4—H4A0.834 (18)
C3—O31.367 (3)O4—H4B0.834 (19)
C3—C41.388 (4)
O4—Zn1—O4i100.61 (13)C5—C4—H4120.1
O4—Zn1—O1121.01 (8)C3—C4—H4120.1
O4i—Zn1—O194.50 (8)C4—C5—C6119.0 (2)
O4—Zn1—O1i94.50 (8)C4—C5—H5120.5
O4i—Zn1—O1i121.01 (8)C6—C5—H5120.5
O1—Zn1—O1i124.62 (11)F1—C6—C7119.0 (2)
O2—C1—O1121.2 (2)F1—C6—C5118.7 (2)
O2—C1—C2121.3 (2)C7—C6—C5122.3 (2)
O1—C1—C2117.4 (2)C6—C7—C2119.5 (2)
C7—C2—C3118.6 (2)C6—C7—H7120.3
C7—C2—C1119.8 (2)C2—C7—H7120.3
C3—C2—C1121.6 (2)C1—O1—Zn1108.44 (15)
O3—C3—C4117.2 (2)C3—O3—H3108 (2)
O3—C3—C2122.1 (2)Zn1—O4—H4A128 (2)
C4—C3—C2120.7 (2)Zn1—O4—H4B123 (3)
C5—C4—C3119.9 (2)H4A—O4—H4B109 (4)
O2—C1—C2—C7−7.8 (4)C4—C5—C6—F1−179.0 (2)
O1—C1—C2—C7174.9 (2)C4—C5—C6—C70.4 (4)
O2—C1—C2—C3169.2 (2)F1—C6—C7—C2−179.9 (2)
O1—C1—C2—C3−8.1 (4)C5—C6—C7—C20.7 (4)
C7—C2—C3—O3−179.6 (2)C3—C2—C7—C6−1.5 (4)
C1—C2—C3—O33.3 (4)C1—C2—C7—C6175.6 (2)
C7—C2—C3—C41.2 (4)O2—C1—O1—Zn1−8.5 (3)
C1—C2—C3—C4−175.8 (2)C2—C1—O1—Zn1168.89 (17)
O3—C3—C4—C5−179.3 (2)O4—Zn1—O1—C173.68 (18)
C2—C3—C4—C5−0.1 (4)O4i—Zn1—O1—C1178.91 (17)
C3—C4—C5—C6−0.7 (4)O1i—Zn1—O1—C1−48.07 (15)

Symmetry codes: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O3—H3···O10.80 (2)1.84 (2)2.564 (3)149 (3)
O4—H4A···O2ii0.83 (2)1.83 (2)2.641 (3)162 (3)
O4—H4B···O3iii0.83 (2)1.89 (2)2.711 (3)170 (4)

Symmetry codes: (ii) x, y−1, z; (iii) x−1/2, y−1/2, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HY2183).

References

  • Brandenburg, K. (1999). DIAMOND Crystal Impact GbR, Bonn, Germany.
  • Brownless, J. B., Edwards, D. A. & Mahon, M. F. (1999). Inorg. Chim. Acta, 287, 89–94.
  • Bruker (2001). SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2007). SMART and SAINT-Plus Bruker AXS Inc., Madison, Wisconsin, USA.
  • Ellsworth, J. M. & zur Loye, H.-C. (2008). Dalton Trans. pp. 5823–5835. [PubMed]
  • Janiak, C. (2003). Dalton Trans. pp. 2781–2804.
  • Mehrotra, R. C. & Bohra, R. (1983). In Metal Carboxylates London: Academic Press.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Wang, Z., Zhang, H., Chen, Y., Huang, C., Sun, R., Cao, Y. & Yu, X. (2006). J. Solid State Chem.179, 1536–1544.
  • Wasuke, M., Tomohiko, S., Tesushi, O., Chika, N. K. & Tohru, T. (2005). J. Solid State Chem.178, 2555–2573.

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