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Acta Cryst. (2007). E63, m1633-m1634    [ doi:10.1107/S1600536807022064 ]

Aqua{4,4'-dimethoxy-2,2'-[1,2-phenylenebis(nitrilomethylidyne)]diphenolato-[kappa]4O,O',N,N'}zinc(II)

N. E. Eltayeb, S. G. Teoh, S. Chantrapromma, H.-K. Fun and K. Ibrahim

Abstract top

In the title compound, [Zn(C22H18N2O4)(H2O)], the ZnII center, on a crystallographic mirror plane, is in a five-coordinate N2O3 environment that is approximately square pyramidal, with the N2O2 tetradentate Schiff base ligand as the basal plane and the water molecule in the apical position. Intermolecular O-H...O and weak C-H...O interactions link the molecules into chains along [010]. These chains are further interconnected in a zigzag manner into a three-dimensional network.

Comment top

It is well known that zinc complexes with Schiff-bases are active in biological systems and show very good activity against the leukemic cell (Tarafder et al., 2002). Recently, we reported the crystal structure of {2,2'-[1,2-phenylenebis(nitrilomethylidyne)]diphenolato- κ4O,N,N',O'}(pyridine-κN)zinc(II) (Eltayeb et al., 2007). Herein, we report the crystal structure of (I).

In (I), the Zn1 and O1W atoms lie on a mirror plane and the asymmetric unit therefore contains only half of the molecule. The tetradentate Schiff-base ligand is almost planar with a maximum deviation from the C1–C10/O1–O2/N1 plane of 0.053 (3) Å for atom N1. The methoxy group is slightly twisted from the C1–C10/O1–O2/N1 mean plane as indicated by the torsion angle C11/O2/C4/C5 of -9.6 (2)°. The ligand is coordinated to Zn1 as a tetradentate ligand via through two N and two O donor atoms, resulting in a square-pyramidal ZnII center whose fifth (axial) position is occupied by a water molecule (Fig. 1). The four atoms N1, O1, N1i and O1i [i = -x, y, z] form the basal plane, and the ZnII is displaced 0.044 (7) Å out of this mean basal plane towards the axial water molecule. Bond lengths and angles observed in the structure are normal (Allen et al., 1987).

In the crystal of (I) in Fig. 2, the water molecule is involved in an intermolecular O—H···O hydrogen bond [O1W—H1W···O1; symmetry code x, -1 + y, +z] and the ligand is involved in weak C—H···O intermolecular interaction [C7—H7A···O2; symmetry code 1/2 - x, -y, -1/2 + z] (Table 2). The molcecules are linked into chains along the b axis. These chains are further interconnected in a zig-zag manner into a three-dimensional network.

Related literature top

For related literature on values of bond lengths and angles, see: Allen et al. (1987). For related structures, see, for example: Humphrey et al. (1999); Eltayeb, Teoh, Ng et al. (2007); Eltayeb, Teoh, Fun et al. (2007). For related literature, see: Tarafder et al. (2002).

Experimental top

The title compound (I) was synthesized by adding 5-methoxy-2-hydroxybenzaldehyde (0.610 g, 4 mmol) to a solution of o-phenylenediamine (0.216 g, 2 mmol) in ethanol 95% (20 ml). The mixture was refluxed with stirring for half an hour. Zinc chloride (0.272 g, 2 mmol) in ethanol (10 ml) was then added, followed by triethylamine (0.5 ml,3.6 mmol). The mixture was stirred at room temperature for two h. An orange-red precipitate was obtained; this was washed by about 5 ml e thanol, dried, and then washed by copious amount of diethyl ether. This precipitate was then dissolved in 25 ml of pyridine. Red single crystals were formed after two months.

Refinement top

The water hydrogen atoms were located in a difference map and were restrained with an O1W—H distance of 0.82 Å. All other H atoms were positioned geometrically and allowed to ride on their parent atoms with C—H distances in the range 0.93–0.96 Å. The Uiso values were constrained to be 1.5Ueq of the carrier atom for methyl H atoms and 1.2Ueq for the remaining H atoms. A rotating group model was used for the methyl groups; 1573 Friedel pairs were used to determine the absolute structure.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 1998); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. The asymmetric unit of (I), showing 50% probability displacement ellipsoids and the atomic numbering.
[Figure 2] Fig. 2. The crystal packing of (I), viewed along the b axis. Hydrogen bonds are shown as dash lines.
Aqua{4,4'-dimethoxy-2,2'-[1,2-phenylenebis(nitrilomethylidyne)]diphenolato- κ4O,O',N,N'}zinc(II) top
Crystal data top
[Zn(C22H18N2O4)(H2O)]F(000) = 472
Mr = 457.79Dx = 1.668 Mg m−3
Orthorhombic, Pmn21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac -2Cell parameters from 3359 reflections
a = 23.3617 (7) Åθ = 1.7–32.5°
b = 4.9121 (1) ŵ = 1.39 mm−1
c = 7.9431 (2) ÅT = 100 K
V = 911.51 (4) Å3Plate, red
Z = 20.38 × 0.23 × 0.10 mm
Data collection top
Bruker SMART APEX2 CCD area-detector
diffractometer		3359 independent reflections
Radiation source: fine-focus sealed tube3179 reflections with I > 2σ(I)
graphiteRint = 0.047
Detector resolution: 8.33 pixels mm-1θmax = 32.5°, θmin = 1.7°
ω scansh = −35→35
Absorption correction: multi-scan
(SADABS; Bruker, 2005)		k = −7→7
Tmin = 0.623, Tmax = 0.874l = −12→12
29716 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.027H-atom parameters constrained
wR(F2) = 0.082 w = 1/[σ2(Fo2) + (0.0476P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.16(Δ/σ)max < 0.001
3359 reflectionsΔρmax = 0.49 e Å−3
141 parametersΔρmin = −0.70 e Å−3
2 restraintsAbsolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.012 (10)
Crystal data top
[Zn(C22H18N2O4)(H2O)]V = 911.51 (4) Å3
Mr = 457.79Z = 2
Orthorhombic, Pmn21Mo Kα radiation
a = 23.3617 (7) ŵ = 1.39 mm−1
b = 4.9121 (1) ÅT = 100 K
c = 7.9431 (2) Å0.38 × 0.23 × 0.10 mm
Data collection top
Bruker SMART APEX2 CCD area-detector
diffractometer		3359 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2005)		3179 reflections with I > 2σ(I)
Tmin = 0.623, Tmax = 0.874Rint = 0.047
29716 measured reflectionsθmax = 32.5°
Refinement top
R[F2 > 2σ(F2)] = 0.027H-atom parameters constrained
wR(F2) = 0.082Δρmax = 0.49 e Å−3
S = 1.16Δρmin = −0.70 e Å−3
3359 reflectionsAbsolute structure: Flack (1983)
141 parametersFlack parameter: 0.012 (10)
2 restraints
Special details top

Experimental. The low-temparture data was collected with the Oxford Cyrosystem Cobra low-temperature attachment.

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
Zn10.00000.05705 (5)0.10449 (4)0.01253 (7)
O10.06065 (5)0.3095 (3)0.17986 (17)0.0153 (2)
O20.29634 (5)0.2460 (3)0.13415 (15)0.0170 (3)
O1W0.0000−0.2503 (4)0.2826 (2)0.0169 (3)
H1W10.0270−0.35320.26510.058 (11)*
C10.11623 (7)0.2828 (4)0.1586 (2)0.0133 (3)
C20.15306 (8)0.4597 (3)0.2488 (2)0.0146 (3)
H2A0.13690.59130.31840.017*
C30.21158 (8)0.4445 (3)0.2376 (2)0.0148 (3)
H3A0.23430.56490.29850.018*
C40.23727 (7)0.2473 (4)0.1342 (2)0.0143 (3)
C50.20328 (7)0.0725 (3)0.0424 (2)0.0133 (3)
H5A0.2203−0.0567−0.02700.016*
C60.14266 (7)0.0866 (3)0.0522 (2)0.0128 (3)
C70.11221 (7)−0.1066 (4)−0.0513 (2)0.0136 (3)
H7A0.1340−0.2240−0.11700.016*
C80.03036 (6)−0.3179 (3)−0.1707 (2)0.0127 (3)
C90.05973 (7)−0.4942 (4)−0.2795 (2)0.0152 (3)
H9A0.0995−0.4962−0.27950.018*
N10.05703 (6)−0.1304 (3)−0.06032 (18)0.0128 (3)
C100.02998 (6)−0.6654 (3)−0.3870 (3)0.0156 (3)
H10A0.0499−0.7806−0.45930.019*
C110.32314 (8)0.0220 (4)0.0525 (3)0.0185 (3)
H11A0.36380.03330.06780.028*
H11B0.31440.0266−0.06550.028*
H11C0.3093−0.14510.10020.028*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.01071 (11)0.01086 (11)0.01601 (12)0.0000.000−0.00136 (12)
O10.0101 (5)0.0129 (5)0.0231 (6)−0.0003 (4)−0.0004 (4)−0.0032 (5)
O20.0102 (5)0.0185 (6)0.0223 (8)−0.0005 (4)−0.0013 (4)−0.0038 (5)
O1W0.0191 (8)0.0129 (8)0.0188 (8)0.0000.0000.0001 (7)
C10.0123 (7)0.0122 (7)0.0154 (7)0.0004 (5)−0.0006 (5)0.0012 (5)
C20.0133 (7)0.0113 (7)0.0191 (8)0.0007 (5)−0.0001 (6)−0.0014 (6)
C30.0134 (7)0.0130 (8)0.0179 (8)−0.0021 (5)−0.0013 (6)−0.0006 (6)
C40.0116 (6)0.0137 (7)0.0176 (10)0.0004 (5)−0.0010 (5)0.0009 (5)
C50.0102 (6)0.0136 (7)0.0161 (7)0.0003 (5)0.0010 (5)−0.0003 (6)
C60.0110 (7)0.0129 (7)0.0144 (6)−0.0008 (5)−0.0011 (5)0.0005 (5)
C70.0122 (7)0.0147 (7)0.0140 (7)−0.0005 (5)0.0010 (6)−0.0007 (5)
C80.0122 (7)0.0118 (7)0.0141 (7)−0.0010 (5)−0.0001 (5)0.0001 (6)
C90.0118 (7)0.0176 (7)0.0161 (8)0.0010 (6)0.0004 (6)−0.0017 (6)
N10.0122 (6)0.0116 (6)0.0147 (6)−0.0009 (5)−0.0006 (5)−0.0014 (5)
C100.0148 (6)0.0149 (6)0.0170 (7)0.0013 (5)0.0014 (8)−0.0040 (8)
C110.0133 (7)0.0178 (8)0.0244 (9)0.0005 (6)0.0002 (6)−0.0018 (6)
Geometric parameters (Å, °) top
Zn1—O11.9758 (12)C5—C61.420 (2)
Zn1—O1i1.9758 (12)C5—H5A0.9300
Zn1—O1W2.069 (2)C6—C71.443 (2)
Zn1—N12.0825 (14)C7—N11.296 (2)
Zn1—N1i2.0826 (14)C7—H7A0.9300
O1—C11.316 (2)C8—C91.403 (2)
O2—C41.3800 (19)C8—N11.416 (2)
O2—C111.422 (2)C8—C8i1.419 (3)
O1W—H1W10.8200C9—C101.385 (3)
C1—C21.417 (2)C9—H9A0.9300
C1—C61.423 (2)C10—C10i1.401 (3)
C2—C31.372 (2)C10—H10A0.9300
C2—H2A0.9300C11—H11A0.9600
C3—C41.404 (2)C11—H11B0.9600
C3—H3A0.9300C11—H11C0.9600
C4—C51.379 (2)
O1—Zn1—O1i91.64 (7)C4—C5—H5A119.5
O1—Zn1—O1W104.52 (6)C6—C5—H5A119.5
O1i—Zn1—O1W104.52 (6)C5—C6—C1119.90 (15)
O1—Zn1—N190.52 (6)C5—C6—C7115.35 (15)
O1i—Zn1—N1157.94 (6)C1—C6—C7124.75 (16)
O1W—Zn1—N196.16 (6)N1—C7—C6125.52 (16)
O1—Zn1—N1i157.94 (6)N1—C7—H7A117.2
O1i—Zn1—N1i90.52 (6)C6—C7—H7A117.2
O1W—Zn1—N1i96.16 (6)C9—C8—N1124.60 (14)
N1—Zn1—N1i79.56 (8)C9—C8—C8i119.28 (10)
C1—O1—Zn1127.32 (11)N1—C8—C8i116.10 (8)
C4—O2—C11116.36 (14)C10—C9—C8120.61 (15)
Zn1—O1W—H1W1109.5C10—C9—H9A119.7
O1—C1—C2118.24 (16)C8—C9—H9A119.7
O1—C1—C6124.88 (16)C7—N1—C8122.04 (15)
C2—C1—C6116.87 (15)C7—N1—Zn1124.16 (12)
C3—C2—C1122.59 (16)C8—N1—Zn1113.29 (10)
C3—C2—H2A118.7C9—C10—C10i120.11 (10)
C1—C2—H2A118.7C9—C10—H10A119.9
C2—C3—C4120.10 (16)C10i—C10—H10A119.9
C2—C3—H3A119.9O2—C11—H11A109.5
C4—C3—H3A119.9O2—C11—H11B109.5
C5—C4—O2124.95 (15)H11A—C11—H11B109.5
C5—C4—C3119.53 (15)O2—C11—H11C109.5
O2—C4—C3115.52 (15)H11A—C11—H11C109.5
C4—C5—C6120.99 (16)H11B—C11—H11C109.5
O1i—Zn1—O1—C1−174.80 (12)C2—C1—C6—C7−178.82 (16)
O1W—Zn1—O1—C179.74 (15)C5—C6—C7—N1179.40 (17)
N1—Zn1—O1—C1−16.75 (15)C1—C6—C7—N1−0.8 (3)
N1i—Zn1—O1—C1−79.4 (2)N1—C8—C9—C10−178.03 (17)
Zn1—O1—C1—C2−168.48 (12)C8i—C8—C9—C100.5 (2)
Zn1—O1—C1—C610.9 (3)C6—C7—N1—C8177.22 (16)
O1—C1—C2—C3178.75 (17)C6—C7—N1—Zn1−11.6 (3)
C6—C1—C2—C3−0.7 (3)C9—C8—N1—C70.1 (3)
C1—C2—C3—C4−0.3 (3)C8i—C8—N1—C7−178.52 (13)
C11—O2—C4—C5−9.7 (2)C9—C8—N1—Zn1−172.00 (14)
C11—O2—C4—C3170.21 (16)C8i—C8—N1—Zn19.43 (12)
C2—C3—C4—C51.0 (3)O1—Zn1—N1—C716.93 (15)
C2—C3—C4—O2−178.87 (16)O1i—Zn1—N1—C7112.60 (18)
O2—C4—C5—C6179.13 (15)O1W—Zn1—N1—C7−87.74 (15)
C3—C4—C5—C6−0.7 (3)N1i—Zn1—N1—C7177.11 (12)
C4—C5—C6—C1−0.3 (3)O1—Zn1—N1—C8−171.21 (12)
C4—C5—C6—C7179.54 (16)O1i—Zn1—N1—C8−75.55 (19)
O1—C1—C6—C5−178.45 (16)O1W—Zn1—N1—C884.12 (11)
C2—C1—C6—C51.0 (2)N1i—Zn1—N1—C8−11.03 (14)
O1—C1—C6—C71.8 (3)C8—C9—C10—C10i−0.5 (2)
Symmetry codes: (i) −x, y, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W1···O1ii0.821.962.711 (2)153
C7—H7A···O2iii0.942.563.358 (2)144
Symmetry codes: (ii) x, y−1, z; (iii) −x+1/2, −y, z−1/2.
Table 1
Selected geometric parameters (Å, °) top
Zn1—O11.9758 (12)Zn1—N12.0825 (14)
Zn1—O1W2.069 (2)
O1—Zn1—O1i91.64 (7)O1—Zn1—N190.52 (6)
O1—Zn1—O1W104.52 (6)O1W—Zn1—N196.16 (6)
C11—O2—C4—C5−9.7 (2)C11—O2—C4—C3170.21 (16)
Symmetry codes: (i) −x, y, z.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W1···O1ii0.821.962.711 (2)153
C7—H7A···O2iii0.942.563.358 (2)144
Symmetry codes: (ii) x, y−1, z; (iii) −x+1/2, −y, z−1/2.
Acknowledgements top

The authors thank the Malaysian Government, Ministry of Science Technology and Innovation, Malaysia (MOSTI) and Universiti Sains Malaysia for the research grants and facilities. International University of Africa (Sudan) is acknowledged for providing study leave to NEE. The authors also thank Universiti Sains Malaysia for the Fundamental Research Grant Scheme (FRGS) grant No. 203/PFIZIK/671064.

references
References top

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–S19.

Bruker (2005). APEX2 (Version 1.27), SAINT (Version 7.12A) and SADABS (Version 2004/1). Bruker AXS Inc., Madison, Wisconsin, USA.

Eltayeb, N. E., Teoh, S. G., Fun, H.-K., Ibrahim, K. & Rosli, M. M. (2007). Acta Cryst. E63, m1182–m1184.

Eltayeb, N. E., Teoh, S. G., Ng, S.-L., Fun, H.-K. & Ibrahim, K. (2007). Acta Cryst. E63, m1284–m1285.

Flack, H. D. (1983). Acta Cryst. A39, 876–881.

Humphrey, E. R., Mann, K. L. V., Reeves, Z. R., Behrendt, A., Jeffery, J. C., Maher, J. P., McCleverty, J. A. & Ward, M. D. (1999). New J. Chem. 23, 417–423.

Sheldrick, G. M. (1998). SHELXTL. Version 5.1. Bruker AXS Inc., Madison, Wisconsin, USA.

Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.

Tarafder, M. T. H., Chew, K.-B., Crouse, K. A., Ali, A. M., Yamin, B. M. & Fun, H.-K. (2002). Polyhedron, 21, 2683–2690.