Diaqua­bis(5-fluoro-2-hydroxy­benzoato-κO1)zinc(II)

Rishmawi, D.; Kelley, J.; Smith, M.D.; Peterson Jr, L.R.; Loye, H.-C. zur

doi:10.1107/S1600536809005716

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 3| March 2009| Page m331

doi:10.1107/S1600536809005716

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Diaquabis(5-fluoro-2-hydroxybenzoato-κO¹)zinc(II)

Diana Rishmawi,^a Jennifer Kelley,^a Mark D. Smith,^b LeRoy Peterson Jr ^a and Hans-Conrad zur Loye ^b ^*

^aChemistry Department, Francis Marion University, Florence, South Carolina 29501, USA, and ^bDepartment of Chemistry and Biochemistry, University of South Carolina, Columbia, South Carolina 29208, USA
^*Correspondence e-mail: lpeterson@fmarion.edu

(Received 9 February 2009; accepted 17 February 2009; online 28 February 2009)

The title compound, [Zn(C₇H₄FO₃)₂(H₂O)₂], is a monomeric Zn^II complex. The Zn^II 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 ); Janiak (2003 ); Mehrotra & Bohra (1983 ); Wasuke et al. (2005 ). For related structures, see: Brownless et al. (1999 ); Wang et al. (2006 ).

Experimental

Crystal data

[Zn(C₇H₄FO₃)₂(H₂O)₂]
M_r = 411.61
Monoclinic, C 2/c
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 ) 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[F² > 2σ(F²)] = 0.035
wR(F²) = 0.081
S = 1.09
1520 reflections
126 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Zn1—O4	1.966 (2)
Zn1—O1	1.9716 (17)

O4—Zn1—O4ⁱ	100.61 (13)
O4—Zn1—O1	121.01 (8)
O4—Zn1—O1ⁱ	94.50 (8)
O1—Zn1—O1ⁱ	124.62 (11)
Symmetry code: (i) $[-x+1, y, -z+{\script{3\over 2}}]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O1	0.803 (18)	1.84 (2)	2.564 (3)	149 (3)
O4—H4A⋯O2ⁱⁱ	0.834 (18)	1.83 (2)	2.641 (3)	162 (3)
O4—H4B⋯O3ⁱⁱⁱ	0.834 (19)	1.89 (2)	2.711 (3)	170 (4)
Symmetry codes: (ii) x, y-1, z; (iii) $[x-{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ .

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

Supporting information

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

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

checkCIF report

Comment top

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 Zn^II atom that lies on a twofold rotation axis, one 5-fsalcyl ligand, and one water molecule. The coordination environment of the Zn^II 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).

Related literature top

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

Experimental top

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.

Computing details top

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

Figures top

	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.

Diaquabis(5-fluoro-2-hydroxybenzoato-κO¹)zinc(II) top

Crystal data top

[Zn(C₇H₄FO₃)₂(H₂O)₂]	F(000) = 832
M_r = 411.61	D_x = 1.837 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2066 reflections
a = 15.3096 (10) Å	θ = 2.7–24.1°
b = 5.4706 (4) Å	µ = 1.72 mm⁻¹
c = 17.7741 (12) Å	T = 150 K
β = 91.674 (1)°	Plate, colorless
V = 1487.99 (18) Å³	0.16 × 0.12 × 0.05 mm
Z = 4

Data collection top

Bruker SMART APEX CCD diffractometer	1520 independent reflections
Radiation source: fine-focus sealed tube	1341 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.053
ϕ and ω scans	θ_max = 26.4°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −18→18
T_min = 0.893, T_max = 1.000	k = −6→6
8435 measured reflections	l = −22→22

Refinement top

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)] = 0.035	Hydrogen site location: mixed
wR(F²) = 0.081	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ²(F_o²) + (0.0397P)² + 0.7409P] where P = (F_o² + 2F_c²)/3
1520 reflections	(Δ/σ)_max < 0.001
126 parameters	Δρ_max = 0.43 e Å⁻³
3 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

[Zn(C₇H₄FO₃)₂(H₂O)₂]	V = 1487.99 (18) Å³
M_r = 411.61	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 15.3096 (10) Å	µ = 1.72 mm⁻¹
b = 5.4706 (4) Å	T = 150 K
c = 17.7741 (12) Å	0.16 × 0.12 × 0.05 mm
β = 91.674 (1)°

Data collection top

Bruker SMART APEX CCD diffractometer	1520 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1341 reflections with I > 2σ(I)
T_min = 0.893, T_max = 1.000	R_int = 0.053
8435 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	3 restraints
wR(F²) = 0.081	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	Δρ_max = 0.43 e Å⁻³
1520 reflections	Δρ_min = −0.27 e Å⁻³
126 parameters

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

	x	y	z	U_iso*/U_eq
Zn1	0.5000	0.08063 (8)	0.7500	0.01954 (15)
C1	0.56321 (16)	0.4151 (5)	0.65619 (14)	0.0204 (5)
C2	0.62447 (16)	0.5945 (5)	0.62352 (14)	0.0199 (5)
C3	0.71316 (16)	0.6031 (5)	0.64632 (14)	0.0191 (5)
C4	0.76803 (16)	0.7820 (5)	0.61874 (14)	0.0221 (6)
H4	0.8278	0.7864	0.6346	0.026*
C5	0.73553 (18)	0.9533 (5)	0.56829 (15)	0.0246 (6)
H5	0.7724	1.0775	0.5495	0.029*
C6	0.64862 (18)	0.9416 (5)	0.54547 (15)	0.0248 (6)
C7	0.59321 (16)	0.7666 (5)	0.57150 (14)	0.0223 (6)
H7	0.5339	0.7624	0.5543	0.027*
O1	0.59620 (11)	0.2481 (3)	0.69963 (10)	0.0233 (4)
O2	0.48283 (11)	0.4310 (3)	0.64435 (11)	0.0265 (4)
F1	0.61747 (11)	1.1088 (3)	0.49488 (10)	0.0391 (5)
O3	0.74885 (12)	0.4400 (4)	0.69676 (11)	0.0266 (4)
H3	0.7120 (18)	0.341 (5)	0.7060 (18)	0.044 (10)*
O4	0.42296 (13)	−0.1489 (4)	0.69475 (13)	0.0305 (5)
H4A	0.437 (2)	−0.271 (5)	0.6700 (16)	0.039 (10)*
H4B	0.3689 (13)	−0.132 (8)	0.691 (2)	0.068 (14)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0113 (2)	0.0184 (2)	0.0290 (3)	0.000	0.00249 (16)	0.000
C1	0.0169 (13)	0.0199 (13)	0.0245 (14)	0.0015 (10)	0.0036 (10)	−0.0063 (11)
C2	0.0174 (12)	0.0209 (13)	0.0214 (13)	−0.0025 (11)	0.0021 (10)	−0.0012 (11)
C3	0.0149 (12)	0.0239 (14)	0.0186 (13)	0.0015 (10)	0.0019 (10)	−0.0007 (11)
C4	0.0118 (12)	0.0293 (15)	0.0252 (14)	−0.0026 (11)	0.0016 (10)	−0.0009 (12)
C5	0.0224 (14)	0.0238 (15)	0.0277 (14)	−0.0068 (11)	0.0065 (11)	0.0003 (12)
C6	0.0233 (14)	0.0255 (15)	0.0256 (14)	0.0021 (12)	0.0000 (11)	0.0056 (12)
C7	0.0151 (13)	0.0263 (14)	0.0253 (14)	−0.0005 (11)	−0.0013 (10)	0.0008 (12)
O1	0.0150 (9)	0.0239 (10)	0.0312 (10)	0.0009 (8)	0.0054 (7)	0.0060 (8)
O2	0.0121 (9)	0.0233 (10)	0.0443 (12)	−0.0014 (8)	0.0025 (8)	−0.0025 (9)
F1	0.0282 (9)	0.0390 (10)	0.0500 (11)	0.0008 (8)	−0.0028 (8)	0.0232 (9)
O3	0.0132 (9)	0.0315 (11)	0.0350 (11)	−0.0020 (8)	−0.0020 (8)	0.0111 (9)
O4	0.0139 (10)	0.0277 (11)	0.0497 (13)	0.0020 (8)	−0.0017 (9)	−0.0155 (10)

Geometric parameters (Å, º) top

Zn1—O4	1.966 (2)	C4—C5	1.380 (4)
Zn1—O4ⁱ	1.966 (2)	C4—H4	0.9500
Zn1—O1	1.9716 (17)	C5—C6	1.381 (4)
Zn1—O1ⁱ	1.9717 (17)	C5—H5	0.9500
C1—O2	1.246 (3)	C6—F1	1.359 (3)
C1—O1	1.289 (3)	C6—C7	1.369 (4)
C1—C2	1.487 (4)	C7—H7	0.9500
C2—C7	1.394 (4)	O3—H3	0.803 (18)
C2—C3	1.406 (4)	O4—H4A	0.834 (18)
C3—O3	1.367 (3)	O4—H4B	0.834 (19)
C3—C4	1.388 (4)

O4—Zn1—O4ⁱ	100.61 (13)	C5—C4—H4	120.1
O4—Zn1—O1	121.01 (8)	C3—C4—H4	120.1
O4ⁱ—Zn1—O1	94.50 (8)	C4—C5—C6	119.0 (2)
O4—Zn1—O1ⁱ	94.50 (8)	C4—C5—H5	120.5
O4ⁱ—Zn1—O1ⁱ	121.01 (8)	C6—C5—H5	120.5
O1—Zn1—O1ⁱ	124.62 (11)	F1—C6—C7	119.0 (2)
O2—C1—O1	121.2 (2)	F1—C6—C5	118.7 (2)
O2—C1—C2	121.3 (2)	C7—C6—C5	122.3 (2)
O1—C1—C2	117.4 (2)	C6—C7—C2	119.5 (2)
C7—C2—C3	118.6 (2)	C6—C7—H7	120.3
C7—C2—C1	119.8 (2)	C2—C7—H7	120.3
C3—C2—C1	121.6 (2)	C1—O1—Zn1	108.44 (15)
O3—C3—C4	117.2 (2)	C3—O3—H3	108 (2)
O3—C3—C2	122.1 (2)	Zn1—O4—H4A	128 (2)
C4—C3—C2	120.7 (2)	Zn1—O4—H4B	123 (3)
C5—C4—C3	119.9 (2)	H4A—O4—H4B	109 (4)

O2—C1—C2—C7	−7.8 (4)	C4—C5—C6—F1	−179.0 (2)
O1—C1—C2—C7	174.9 (2)	C4—C5—C6—C7	0.4 (4)
O2—C1—C2—C3	169.2 (2)	F1—C6—C7—C2	−179.9 (2)
O1—C1—C2—C3	−8.1 (4)	C5—C6—C7—C2	0.7 (4)
C7—C2—C3—O3	−179.6 (2)	C3—C2—C7—C6	−1.5 (4)
C1—C2—C3—O3	3.3 (4)	C1—C2—C7—C6	175.6 (2)
C7—C2—C3—C4	1.2 (4)	O2—C1—O1—Zn1	−8.5 (3)
C1—C2—C3—C4	−175.8 (2)	C2—C1—O1—Zn1	168.89 (17)
O3—C3—C4—C5	−179.3 (2)	O4—Zn1—O1—C1	73.68 (18)
C2—C3—C4—C5	−0.1 (4)	O4ⁱ—Zn1—O1—C1	178.91 (17)
C3—C4—C5—C6	−0.7 (4)	O1ⁱ—Zn1—O1—C1	−48.07 (15)

Symmetry code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O1	0.80 (2)	1.84 (2)	2.564 (3)	149 (3)
O4—H4A···O2ⁱⁱ	0.83 (2)	1.83 (2)	2.641 (3)	162 (3)
O4—H4B···O3ⁱⁱⁱ	0.83 (2)	1.89 (2)	2.711 (3)	170 (4)

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

Experimental details

Crystal data
Chemical formula	[Zn(C₇H₄FO₃)₂(H₂O)₂]
M_r	411.61
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	150
a, b, c (Å)	15.3096 (10), 5.4706 (4), 17.7741 (12)
β (°)	91.674 (1)
V (Å³)	1487.99 (18)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.72
Crystal size (mm)	0.16 × 0.12 × 0.05

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.893, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	8435, 1520, 1341
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.081, 1.09
No. of reflections	1520
No. of parameters	126
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.27

Computer programs: SMART (Bruker, 2007), SAINT-Plus (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Zn1—O4	1.966 (2)	Zn1—O1	1.9716 (17)

O4—Zn1—O4ⁱ	100.61 (13)	O4—Zn1—O1ⁱ	94.50 (8)
O4—Zn1—O1	121.01 (8)	O1—Zn1—O1ⁱ	124.62 (11)

Symmetry code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O1	0.803 (18)	1.84 (2)	2.564 (3)	149 (3)
O4—H4A···O2ⁱⁱ	0.834 (18)	1.83 (2)	2.641 (3)	162 (3)
O4—H4B···O3ⁱⁱⁱ	0.834 (19)	1.89 (2)	2.711 (3)	170 (4)

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

Acknowledgements

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

References

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