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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807022064/ng2265sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807022064/ng2265Isup2.hkl
Contains datablock I

CCDC reference: 650613

Key indicators

  • Single-crystal X-ray study
  • T = 100 K
  • Mean [sigma](C-C) = 0.002 Å
  • R factor = 0.027
  • wR factor = 0.082
  • Data-to-parameter ratio = 23.8

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.62 Ratio PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 1
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 32.50 From the CIF: _reflns_number_total 3359 Count of symmetry unique reflns 1786 Completeness (_total/calc) 188.07% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 1573 Fraction of Friedel pairs measured 0.881 Are heavy atom types Z>Si present yes PLAT794_ALERT_5_G Check Predicted Bond Valency for Zn1 (2) 2.08 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 2
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 3 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 2 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check

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.

Structure description 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.

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).

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 m3
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 mm1
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)
Graphite monochromatorRint = 0.047
Detector resolution: 8.33 pixels mm-1θmax = 32.5°, θmin = 1.7°
ω scansh = 3535
Absorption correction: multi-scan
(SADABS; Bruker, 2005)
k = 77
Tmin = 0.623, Tmax = 0.874l = 1212
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 Å3
141 parametersΔρmin = 0.70 e Å3
2 restraintsAbsolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methodsAbsolute structure 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 mm1
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 reflections
Refinement top
R[F2 > 2σ(F2)] = 0.027H-atom parameters constrained
wR(F2) = 0.082Δρmax = 0.49 e Å3
S = 1.16Δρmin = 0.70 e Å3
3359 reflectionsAbsolute structure: Flack (1983)
141 parametersAbsolute structure 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)
O1W0.00000.2503 (4)0.2826 (2)0.0169 (3)
H1W10.02700.35320.26510.058 (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)
H5A0.22030.05670.02700.016*
C60.14266 (7)0.0866 (3)0.0522 (2)0.0128 (3)
C70.11221 (7)0.1066 (4)0.0513 (2)0.0136 (3)
H7A0.13400.22400.11700.016*
C80.03036 (6)0.3179 (3)0.1707 (2)0.0127 (3)
C90.05973 (7)0.4942 (4)0.2795 (2)0.0152 (3)
H9A0.09950.49620.27950.018*
N10.05703 (6)0.1304 (3)0.06032 (18)0.0128 (3)
C100.02998 (6)0.6654 (3)0.3870 (3)0.0156 (3)
H10A0.04990.78060.45930.019*
C110.32314 (8)0.0220 (4)0.0525 (3)0.0185 (3)
H11A0.36380.03330.06780.028*
H11B0.31440.02660.06550.028*
H11C0.30930.14510.10020.028*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.01071 (11)0.01086 (11)0.01601 (12)0.0000.0000.00136 (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, º) 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—C1174.80 (12)C2—C1—C6—C7178.82 (16)
O1W—Zn1—O1—C179.74 (15)C5—C6—C7—N1179.40 (17)
N1—Zn1—O1—C116.75 (15)C1—C6—C7—N10.8 (3)
N1i—Zn1—O1—C179.4 (2)N1—C8—C9—C10178.03 (17)
Zn1—O1—C1—C2168.48 (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—Zn111.6 (3)
C6—C1—C2—C30.7 (3)C9—C8—N1—C70.1 (3)
C1—C2—C3—C40.3 (3)C8i—C8—N1—C7178.52 (13)
C11—O2—C4—C59.7 (2)C9—C8—N1—Zn1172.00 (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—O2178.87 (16)O1i—Zn1—N1—C7112.60 (18)
O2—C4—C5—C6179.13 (15)O1W—Zn1—N1—C787.74 (15)
C3—C4—C5—C60.7 (3)N1i—Zn1—N1—C7177.11 (12)
C4—C5—C6—C10.3 (3)O1—Zn1—N1—C8171.21 (12)
C4—C5—C6—C7179.54 (16)O1i—Zn1—N1—C875.55 (19)
O1—C1—C6—C5178.45 (16)O1W—Zn1—N1—C884.12 (11)
C2—C1—C6—C51.0 (2)N1i—Zn1—N1—C811.03 (14)
O1—C1—C6—C71.8 (3)C8—C9—C10—C10i0.5 (2)
Symmetry code: (i) x, y, z.
Hydrogen-bond geometry (Å, º) 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, y1, z; (iii) x+1/2, y, z1/2.

Experimental details

Crystal data
Chemical formula[Zn(C22H18N2O4)(H2O)]
Mr457.79
Crystal system, space groupOrthorhombic, Pmn21
Temperature (K)100
a, b, c (Å)23.3617 (7), 4.9121 (1), 7.9431 (2)
V3)911.51 (4)
Z2
Radiation typeMo Kα
µ (mm1)1.39
Crystal size (mm)0.38 × 0.23 × 0.10
Data collection
DiffractometerBruker SMART APEX2 CCD area-detector
Absorption correctionMulti-scan
(SADABS; Bruker, 2005)
Tmin, Tmax0.623, 0.874
No. of measured, independent and
observed [I > 2σ(I)] reflections
29716, 3359, 3179
Rint0.047
(sin θ/λ)max1)0.756
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.027, 0.082, 1.16
No. of reflections3359
No. of parameters141
No. of restraints2
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.49, 0.70
Absolute structureFlack (1983)
Absolute structure parameter0.012 (10)

Computer programs: APEX2 (Bruker, 2005), APEX2, SAINT (Bruker, 2005), SHELXTL (Sheldrick, 1998), SHELXTL and PLATON (Spek, 2003).

Selected geometric parameters (Å, º) 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—C59.7 (2)C11—O2—C4—C3170.21 (16)
Symmetry code: (i) x, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W1···O1ii0.821.95492.711 (2)153
C7—H7A···O2iii0.9352.56263.358 (2)144
Symmetry codes: (ii) x, y1, z; (iii) x+1/2, y, z1/2.
 

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