Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807052713/sj2387sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807052713/sj2387Isup2.hkl |
CCDC reference: 667235
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean (C-C) = 0.004 Å
- R factor = 0.039
- wR factor = 0.088
- Data-to-parameter ratio = 13.5
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT417_ALERT_2_B Short Inter D-H..H-D H4B .. H4B .. 1.17 Ang.
Alert level C PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 100 Deg. PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 = 5 PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 8
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Zn1 (2) 2.09 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 1
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 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 1 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
For bond-length data, see Allen et al. (1987). For related structures, see for example: Chaudhuri et al. (2007); Eltayeb et al. (2007a,b,c,d). For background information on the biological activity of zinc and its complexes, see for example: Assaf & Chung (1984); Berg & Shi (1996); Tarafder et al. (2002).
The title compound (I) was synthesized by adding 2,4-dihydroxybenzaldehyde (0.552 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 an hour. Then zinc chloride (0.272 g, 2 mmol) in ethanol (10 ml) was added, followed by triethylamine (0.5 ml, 3.6 mmol). The mixture was stirred at room temperature for two hours. A yellow precipitate was obtained, washed with about 5 ml e thanol, dried, and then with copious amounts of diethyl ether. This precipitate was dissolved in 20 ml of acetone and, after evaporation of the acetone, the powder obtained was dissolved in diethyl ether. Single crystals of the title compound suitable for x-ray structure determination were formed after several days of slow evaporation of the diethyl ether at room temperature.
The H atom (H1W3) was located from the difference map and was refined isotropically. The remaining H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H distances of 0.93 Å and an O—H distance of 0.85 Å and the Uiso values were constrained to be 1.2Ueq(C) and 1.5Ueq(O). The highest residual electron density peak is located 0.94 Å from O4W and the deepest hole is located 0.87 Å from Zn1.
Zinc is an element attracting strong interests in biology, medicine, materials, and catalysis. It plays important roles in various biological systems such as neurotransmission, signal transduction, and gene expression (Assaf & Chung, 1984; Berg & Shi, 1996). It is well known that zinc complexes with Schiff-bases are biologically active and show very good cytotoxicity against the leukemic cell (Tarafder et al., 2002). Since our previous investigations (Eltayeb et al., 2007a, b, c, d) show the possibility of generating five coordinate zinc complexes using tetradentate Schiff base ligands, we have extended our synthesis to the title complex and report its crystal structure here.
In the title complex (Fig. 1), ZnII coordinates with the tetradentate Schiff base ligand in the basal plane (N1, N2, O1 and O2) and a water molecule in the apical site. The ZnII center lies slightly above the N2O2 plane in a geometry that is roughly square pyramidal, with the Zn in the Zn—N2O2 plane being tilted 0.01190 Å towards the axial water molecule. This geometry has been observed for similar Schiff base ligand ZnII complexes (Eltayeb et al., 2007a, b, c, d). The dihedral angles between the two benzene rings (C1–C6) and (C15–C20) and the central benzene ring (C8–C13) are 12.64 (14)° and 17.25 (14) °, respectively. The Zn1—N1 and Zn1—N2 distances of 2.069 (2) Å and 2.075 (2) Å and bond angles around Zn1 are in agreement with the values found for similar ZnII complexes (Eltayeb et al., 2007a, b, c, d). However, the Zn1—O1 and Zn1—O2 distances, 1.9905 (19) and 2.001 (2) Å, respectively are slightly shorter than those observed in a closely related structure (Eltayeb ey al., 2007 d) where the Zn—O distances are in the range 2.0027 (15)–2.0036 (15) Å. All water molecules are involved in intermolecular O—H···O hydrogen bonds. Bond lengths and angles observed in the structure are normal (Allen et al., 1987).
In the crystal packing (Fig. 2), O—H···O hydrogen bonds (Table 1) link the molecules into sheets parallel to the ab plane.
For bond-length data, see Allen et al. (1987). For related structures, see for example: Chaudhuri et al. (2007); Eltayeb et al. (2007a,b,c,d). For background information on the biological activity of zinc and its complexes, see for example: Assaf & Chung (1984); Berg & Shi (1996); Tarafder et al. (2002).
Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 1998); program(s) used to refine structure: SHELXTL (Sheldrick, 1998); molecular graphics: SHELXTL (Sheldrick, 1998); software used to prepare material for publication: SHELXTL (Sheldrick, 1998) and PLATON (Spek, 2003).
[Zn(C20H14N2O4)(H2O)]·3H2O | Z = 2 |
Mr = 483.77 | F(000) = 500 |
Triclinic, P1 | Dx = 1.641 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 4.7462 (1) Å | Cell parameters from 3830 reflections |
b = 13.9290 (2) Å | θ = 1.9–26.0° |
c = 15.1128 (2) Å | µ = 1.31 mm−1 |
α = 82.147 (1)° | T = 100 K |
β = 82.367 (1)° | Needle, brown |
γ = 85.640 (1)° | 0.45 × 0.44 × 0.06 mm |
V = 979.26 (3) Å3 |
Bruker SMART APEXII CCD area-detector diffractometer | 3830 independent reflections |
Radiation source: fine-focus sealed tube | 3151 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.042 |
Detector resolution: 8.33 pixels mm-1 | θmax = 26.0°, θmin = 1.9° |
ω scans | h = −5→5 |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | k = −17→17 |
Tmin = 0.591, Tmax = 0.928 | l = −18→18 |
13930 measured reflections |
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)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.088 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0324P)2 + 1.1626P] where P = (Fo2 + 2Fc2)/3 |
3830 reflections | (Δ/σ)max = 0.001 |
283 parameters | Δρmax = 0.40 e Å−3 |
1 restraint | Δρmin = −0.49 e Å−3 |
[Zn(C20H14N2O4)(H2O)]·3H2O | γ = 85.640 (1)° |
Mr = 483.77 | V = 979.26 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 4.7462 (1) Å | Mo Kα radiation |
b = 13.9290 (2) Å | µ = 1.31 mm−1 |
c = 15.1128 (2) Å | T = 100 K |
α = 82.147 (1)° | 0.45 × 0.44 × 0.06 mm |
β = 82.367 (1)° |
Bruker SMART APEXII CCD area-detector diffractometer | 3830 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | 3151 reflections with I > 2σ(I) |
Tmin = 0.591, Tmax = 0.928 | Rint = 0.042 |
13930 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 1 restraint |
wR(F2) = 0.088 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.40 e Å−3 |
3830 reflections | Δρmin = −0.49 e Å−3 |
283 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Zn1 | 0.30697 (8) | 0.72049 (2) | 0.26300 (2) | 0.01785 (11) | |
O1 | 0.5818 (5) | 0.60560 (14) | 0.28209 (13) | 0.0254 (5) | |
O2 | 0.4864 (4) | 0.79828 (13) | 0.33907 (13) | 0.0212 (5) | |
O3 | 1.0486 (5) | 0.29375 (14) | 0.25981 (14) | 0.0261 (5) | |
H3A | 1.1055 | 0.3046 | 0.3062 | 0.039* | |
O4 | 0.8766 (5) | 1.06174 (14) | 0.43613 (13) | 0.0246 (5) | |
H4B | 0.9353 | 1.0162 | 0.4706 | 0.037* | |
N1 | 0.1980 (5) | 0.66784 (16) | 0.15136 (15) | 0.0185 (5) | |
N2 | 0.1532 (5) | 0.84744 (16) | 0.19188 (15) | 0.0169 (5) | |
C1 | 0.6230 (6) | 0.5270 (2) | 0.24088 (18) | 0.0189 (6) | |
C2 | 0.8138 (7) | 0.4521 (2) | 0.27199 (19) | 0.0212 (6) | |
H2A | 0.9083 | 0.4593 | 0.3206 | 0.025* | |
C3 | 0.8651 (7) | 0.3675 (2) | 0.23203 (19) | 0.0206 (6) | |
C4 | 0.7266 (7) | 0.3553 (2) | 0.1590 (2) | 0.0256 (7) | |
H4A | 0.7608 | 0.2989 | 0.1318 | 0.031* | |
C5 | 0.5405 (7) | 0.4273 (2) | 0.1279 (2) | 0.0249 (7) | |
H5A | 0.4477 | 0.4185 | 0.0794 | 0.030* | |
C6 | 0.4823 (6) | 0.5148 (2) | 0.16609 (18) | 0.0186 (6) | |
C7 | 0.2848 (7) | 0.5843 (2) | 0.12562 (19) | 0.0209 (7) | |
H7A | 0.2113 | 0.5680 | 0.0759 | 0.025* | |
C8 | 0.0170 (6) | 0.7336 (2) | 0.10196 (18) | 0.0171 (6) | |
C9 | −0.1341 (7) | 0.7108 (2) | 0.03546 (19) | 0.0212 (7) | |
H9A | −0.1256 | 0.6472 | 0.0226 | 0.025* | |
C10 | −0.2963 (7) | 0.7814 (2) | −0.01161 (19) | 0.0229 (7) | |
H10A | −0.3921 | 0.7658 | −0.0570 | 0.027* | |
C11 | −0.3156 (7) | 0.8755 (2) | 0.00914 (19) | 0.0226 (7) | |
H11A | −0.4263 | 0.9228 | −0.0223 | 0.027* | |
C12 | −0.1730 (7) | 0.9001 (2) | 0.07570 (18) | 0.0210 (6) | |
H12A | −0.1896 | 0.9636 | 0.0891 | 0.025* | |
C13 | −0.0037 (6) | 0.8303 (2) | 0.12306 (18) | 0.0170 (6) | |
C14 | 0.2075 (6) | 0.9345 (2) | 0.20311 (18) | 0.0188 (6) | |
H14A | 0.1272 | 0.9853 | 0.1662 | 0.023* | |
C15 | 0.3774 (6) | 0.96045 (19) | 0.26622 (18) | 0.0171 (6) | |
C16 | 0.4182 (7) | 1.0602 (2) | 0.26370 (19) | 0.0213 (7) | |
H16A | 0.3286 | 1.1045 | 0.2230 | 0.026* | |
C17 | 0.5840 (7) | 1.0945 (2) | 0.3185 (2) | 0.0246 (7) | |
H17A | 0.6095 | 1.1606 | 0.3144 | 0.030* | |
C18 | 0.7142 (6) | 1.0281 (2) | 0.38088 (18) | 0.0189 (6) | |
C19 | 0.6798 (6) | 0.9299 (2) | 0.38556 (18) | 0.0188 (6) | |
H19A | 0.7697 | 0.8869 | 0.4271 | 0.023* | |
C20 | 0.5135 (6) | 0.89341 (19) | 0.32953 (18) | 0.0165 (6) | |
O1W | −0.0108 (5) | 0.67205 (17) | 0.35940 (14) | 0.0328 (6) | |
H2W1 | −0.1094 | 0.6304 | 0.3435 | 0.049* | |
H1W1 | −0.1175 | 0.7232 | 0.3651 | 0.049* | |
O2W | 0.2688 (6) | 0.50060 (16) | 0.45460 (16) | 0.0441 (7) | |
H1W2 | 0.3130 | 0.5479 | 0.4146 | 0.066* | |
H2W2 | 0.2341 | 0.5225 | 0.5050 | 0.066* | |
O3W | 0.2523 (5) | 0.31908 (15) | 0.41217 (14) | 0.0268 (5) | |
H2W3 | 0.2690 | 0.3772 | 0.4216 | 0.040* | |
H1W3 | 0.400 (6) | 0.289 (2) | 0.429 (2) | 0.040* | |
O4W | 0.2536 (5) | 0.75935 (14) | 0.51765 (13) | 0.0250 (5) | |
H1W4 | 0.2389 | 0.8198 | 0.5220 | 0.037* | |
H2W4 | 0.3054 | 0.7527 | 0.4627 | 0.037* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.0192 (2) | 0.01691 (18) | 0.01923 (18) | −0.00110 (14) | −0.00642 (14) | −0.00494 (12) |
O1 | 0.0318 (13) | 0.0187 (10) | 0.0301 (11) | 0.0039 (10) | −0.0159 (10) | −0.0103 (9) |
O2 | 0.0263 (12) | 0.0143 (10) | 0.0257 (10) | −0.0019 (9) | −0.0108 (10) | −0.0045 (8) |
O3 | 0.0284 (13) | 0.0196 (11) | 0.0317 (11) | 0.0047 (10) | −0.0092 (10) | −0.0064 (9) |
O4 | 0.0263 (13) | 0.0205 (11) | 0.0310 (11) | −0.0017 (10) | −0.0142 (10) | −0.0074 (9) |
N1 | 0.0186 (14) | 0.0172 (12) | 0.0208 (12) | −0.0036 (11) | −0.0041 (11) | −0.0035 (10) |
N2 | 0.0152 (13) | 0.0186 (12) | 0.0192 (12) | −0.0008 (10) | −0.0063 (10) | −0.0064 (9) |
C1 | 0.0182 (16) | 0.0177 (14) | 0.0208 (14) | −0.0032 (13) | −0.0006 (13) | −0.0033 (11) |
C2 | 0.0222 (17) | 0.0214 (15) | 0.0218 (14) | −0.0029 (13) | −0.0070 (13) | −0.0045 (12) |
C3 | 0.0193 (16) | 0.0156 (14) | 0.0250 (15) | −0.0007 (13) | 0.0023 (13) | −0.0010 (11) |
C4 | 0.0306 (19) | 0.0208 (15) | 0.0277 (16) | −0.0002 (14) | −0.0037 (15) | −0.0116 (12) |
C5 | 0.0272 (18) | 0.0268 (16) | 0.0234 (15) | −0.0002 (14) | −0.0074 (14) | −0.0088 (13) |
C6 | 0.0175 (16) | 0.0190 (14) | 0.0200 (14) | −0.0028 (13) | −0.0022 (13) | −0.0041 (11) |
C7 | 0.0224 (17) | 0.0219 (15) | 0.0211 (14) | −0.0056 (13) | −0.0060 (13) | −0.0070 (12) |
C8 | 0.0141 (15) | 0.0207 (14) | 0.0169 (13) | −0.0032 (12) | −0.0020 (12) | −0.0022 (11) |
C9 | 0.0227 (17) | 0.0186 (14) | 0.0236 (15) | −0.0048 (13) | −0.0046 (13) | −0.0037 (12) |
C10 | 0.0211 (17) | 0.0291 (16) | 0.0204 (14) | −0.0040 (14) | −0.0068 (13) | −0.0047 (12) |
C11 | 0.0216 (17) | 0.0257 (16) | 0.0204 (14) | 0.0006 (14) | −0.0051 (13) | −0.0017 (12) |
C12 | 0.0203 (17) | 0.0226 (15) | 0.0206 (14) | −0.0014 (13) | −0.0021 (13) | −0.0047 (12) |
C13 | 0.0140 (15) | 0.0211 (14) | 0.0160 (13) | −0.0038 (12) | −0.0009 (12) | −0.0027 (11) |
C14 | 0.0176 (16) | 0.0192 (14) | 0.0192 (14) | 0.0015 (13) | −0.0028 (13) | −0.0023 (11) |
C15 | 0.0167 (16) | 0.0174 (14) | 0.0175 (13) | −0.0021 (12) | −0.0002 (12) | −0.0042 (11) |
C16 | 0.0245 (17) | 0.0172 (14) | 0.0228 (15) | 0.0003 (13) | −0.0086 (13) | −0.0005 (12) |
C17 | 0.0326 (19) | 0.0144 (14) | 0.0294 (16) | −0.0029 (14) | −0.0104 (15) | −0.0043 (12) |
C18 | 0.0169 (16) | 0.0195 (14) | 0.0221 (14) | −0.0038 (13) | −0.0040 (13) | −0.0066 (12) |
C19 | 0.0185 (16) | 0.0177 (14) | 0.0215 (14) | 0.0010 (13) | −0.0069 (13) | −0.0033 (11) |
C20 | 0.0152 (15) | 0.0145 (13) | 0.0206 (14) | −0.0002 (12) | −0.0013 (12) | −0.0060 (11) |
O1W | 0.0326 (14) | 0.0409 (13) | 0.0280 (12) | −0.0171 (11) | 0.0019 (11) | −0.0126 (10) |
O2W | 0.070 (2) | 0.0225 (12) | 0.0439 (14) | 0.0046 (13) | −0.0254 (14) | −0.0063 (10) |
O3W | 0.0268 (13) | 0.0195 (11) | 0.0361 (12) | 0.0014 (10) | −0.0103 (11) | −0.0053 (9) |
O4W | 0.0329 (13) | 0.0201 (10) | 0.0241 (11) | −0.0022 (10) | −0.0083 (10) | −0.0053 (8) |
Zn1—O2 | 1.9905 (19) | C9—C10 | 1.380 (4) |
Zn1—O1 | 2.001 (2) | C9—H9A | 0.9300 |
Zn1—O1W | 2.038 (2) | C10—C11 | 1.382 (4) |
Zn1—N1 | 2.069 (2) | C10—H10A | 0.9300 |
Zn1—N2 | 2.075 (2) | C11—C12 | 1.378 (4) |
O1—C1 | 1.322 (3) | C11—H11A | 0.9300 |
O2—C20 | 1.327 (3) | C12—C13 | 1.396 (4) |
O3—C3 | 1.354 (3) | C12—H12A | 0.9300 |
O3—H3A | 0.8200 | C14—C15 | 1.426 (4) |
O4—C18 | 1.358 (3) | C14—H14A | 0.9300 |
O4—H4B | 0.8200 | C15—C16 | 1.412 (4) |
N1—C7 | 1.298 (3) | C15—C20 | 1.426 (4) |
N1—C8 | 1.414 (4) | C16—C17 | 1.368 (4) |
N2—C14 | 1.296 (3) | C16—H16A | 0.9300 |
N2—C13 | 1.412 (3) | C17—C18 | 1.398 (4) |
C1—C2 | 1.402 (4) | C17—H17A | 0.9300 |
C1—C6 | 1.422 (4) | C18—C19 | 1.381 (4) |
C2—C3 | 1.387 (4) | C19—C20 | 1.399 (4) |
C2—H2A | 0.9300 | C19—H19A | 0.9300 |
C3—C4 | 1.393 (4) | O1W—H2W1 | 0.8501 |
C4—C5 | 1.361 (4) | O1W—H1W1 | 0.8500 |
C4—H4A | 0.9300 | O2W—H1W2 | 0.8498 |
C5—C6 | 1.411 (4) | O2W—H2W2 | 0.8499 |
C5—H5A | 0.9300 | O3W—H2W3 | 0.8516 |
C6—C7 | 1.429 (4) | O3W—H1W3 | 0.838 (18) |
C7—H7A | 0.9300 | O4W—H1W4 | 0.8499 |
C8—C9 | 1.392 (4) | O4W—H2W4 | 0.8499 |
C8—C13 | 1.419 (4) | ||
O2—Zn1—O1 | 93.81 (8) | N1—C8—C13 | 115.4 (2) |
O2—Zn1—O1W | 96.57 (8) | C10—C9—C8 | 120.9 (3) |
O1—Zn1—O1W | 97.05 (10) | C10—C9—H9A | 119.6 |
O2—Zn1—N1 | 161.27 (9) | C8—C9—H9A | 119.6 |
O1—Zn1—N1 | 89.57 (8) | C9—C10—C11 | 119.6 (3) |
O1W—Zn1—N1 | 101.29 (9) | C9—C10—H10A | 120.2 |
O2—Zn1—N2 | 90.02 (8) | C11—C10—H10A | 120.2 |
O1—Zn1—N2 | 154.17 (9) | C12—C11—C10 | 120.9 (3) |
O1W—Zn1—N2 | 107.88 (10) | C12—C11—H11A | 119.5 |
N1—Zn1—N2 | 79.23 (9) | C10—C11—H11A | 119.5 |
C1—O1—Zn1 | 129.69 (18) | C11—C12—C13 | 120.4 (3) |
C20—O2—Zn1 | 129.08 (17) | C11—C12—H12A | 119.8 |
C3—O3—H3A | 109.5 | C13—C12—H12A | 119.8 |
C18—O4—H4B | 109.5 | C12—C13—N2 | 125.2 (3) |
C7—N1—C8 | 121.3 (2) | C12—C13—C8 | 118.9 (3) |
C7—N1—Zn1 | 125.6 (2) | N2—C13—C8 | 115.9 (2) |
C8—N1—Zn1 | 113.17 (17) | N2—C14—C15 | 126.8 (3) |
C14—N2—C13 | 121.7 (2) | N2—C14—H14A | 116.6 |
C14—N2—Zn1 | 125.19 (19) | C15—C14—H14A | 116.6 |
C13—N2—Zn1 | 112.96 (17) | C16—C15—C20 | 118.0 (3) |
O1—C1—C2 | 118.8 (2) | C16—C15—C14 | 117.0 (3) |
O1—C1—C6 | 122.9 (3) | C20—C15—C14 | 125.0 (3) |
C2—C1—C6 | 118.3 (2) | C17—C16—C15 | 122.8 (3) |
C3—C2—C1 | 121.6 (3) | C17—C16—H16A | 118.6 |
C3—C2—H2A | 119.2 | C15—C16—H16A | 118.6 |
C1—C2—H2A | 119.2 | C16—C17—C18 | 118.6 (3) |
O3—C3—C2 | 123.4 (3) | C16—C17—H17A | 120.7 |
O3—C3—C4 | 116.5 (2) | C18—C17—H17A | 120.7 |
C2—C3—C4 | 120.1 (3) | O4—C18—C19 | 120.6 (3) |
C5—C4—C3 | 119.1 (3) | O4—C18—C17 | 118.9 (2) |
C5—C4—H4A | 120.5 | C19—C18—C17 | 120.4 (3) |
C3—C4—H4A | 120.5 | C18—C19—C20 | 121.8 (3) |
C4—C5—C6 | 122.8 (3) | C18—C19—H19A | 119.1 |
C4—C5—H5A | 118.6 | C20—C19—H19A | 119.1 |
C6—C5—H5A | 118.6 | O2—C20—C19 | 118.3 (2) |
C5—C6—C1 | 118.1 (3) | O2—C20—C15 | 123.4 (2) |
C5—C6—C7 | 116.6 (2) | C19—C20—C15 | 118.3 (2) |
C1—C6—C7 | 125.3 (3) | Zn1—O1W—H2W1 | 113.9 |
N1—C7—C6 | 126.4 (3) | Zn1—O1W—H1W1 | 102.4 |
N1—C7—H7A | 116.8 | H2W1—O1W—H1W1 | 107.7 |
C6—C7—H7A | 116.8 | H1W2—O2W—H2W2 | 107.7 |
C9—C8—N1 | 125.3 (3) | H2W3—O3W—H1W3 | 103.5 |
C9—C8—C13 | 119.2 (3) | H1W4—O4W—H2W4 | 107.7 |
O2—Zn1—O1—C1 | −169.1 (2) | C5—C6—C7—N1 | 178.5 (3) |
O1W—Zn1—O1—C1 | 93.8 (3) | C1—C6—C7—N1 | −1.6 (5) |
N1—Zn1—O1—C1 | −7.6 (3) | C7—N1—C8—C9 | 14.6 (4) |
N2—Zn1—O1—C1 | −71.2 (3) | Zn1—N1—C8—C9 | −166.5 (2) |
O1—Zn1—O2—C20 | 146.0 (2) | C7—N1—C8—C13 | −164.6 (3) |
O1W—Zn1—O2—C20 | −116.5 (2) | Zn1—N1—C8—C13 | 14.4 (3) |
N1—Zn1—O2—C20 | 46.0 (4) | N1—C8—C9—C10 | −177.3 (3) |
N2—Zn1—O2—C20 | −8.5 (2) | C13—C8—C9—C10 | 1.8 (4) |
O2—Zn1—N1—C7 | 107.0 (3) | C8—C9—C10—C11 | −1.8 (5) |
O1—Zn1—N1—C7 | 6.4 (3) | C9—C10—C11—C12 | 0.6 (5) |
O1W—Zn1—N1—C7 | −90.7 (3) | C10—C11—C12—C13 | 0.6 (5) |
N2—Zn1—N1—C7 | 163.0 (3) | C11—C12—C13—N2 | 179.5 (3) |
O2—Zn1—N1—C8 | −71.9 (4) | C11—C12—C13—C8 | −0.5 (4) |
O1—Zn1—N1—C8 | −172.57 (19) | C14—N2—C13—C12 | −16.6 (4) |
O1W—Zn1—N1—C8 | 90.3 (2) | Zn1—N2—C13—C12 | 167.9 (2) |
N2—Zn1—N1—C8 | −15.98 (19) | C14—N2—C13—C8 | 163.4 (3) |
O2—Zn1—N2—C14 | 4.4 (2) | Zn1—N2—C13—C8 | −12.1 (3) |
O1—Zn1—N2—C14 | −94.4 (3) | C9—C8—C13—C12 | −0.7 (4) |
O1W—Zn1—N2—C14 | 101.3 (2) | N1—C8—C13—C12 | 178.5 (3) |
N1—Zn1—N2—C14 | −160.2 (3) | C9—C8—C13—N2 | 179.3 (3) |
O2—Zn1—N2—C13 | 179.72 (19) | N1—C8—C13—N2 | −1.5 (4) |
O1—Zn1—N2—C13 | 80.9 (3) | C13—N2—C14—C15 | −175.9 (3) |
O1W—Zn1—N2—C13 | −83.36 (19) | Zn1—N2—C14—C15 | −0.9 (4) |
N1—Zn1—N2—C13 | 15.15 (19) | N2—C14—C15—C16 | 177.1 (3) |
Zn1—O1—C1—C2 | −174.6 (2) | N2—C14—C15—C20 | −1.2 (5) |
Zn1—O1—C1—C6 | 5.5 (4) | C20—C15—C16—C17 | 0.7 (5) |
O1—C1—C2—C3 | 179.6 (3) | C14—C15—C16—C17 | −177.8 (3) |
C6—C1—C2—C3 | −0.4 (4) | C15—C16—C17—C18 | −1.2 (5) |
C1—C2—C3—O3 | 179.7 (3) | C16—C17—C18—O4 | −179.3 (3) |
C1—C2—C3—C4 | 0.2 (5) | C16—C17—C18—C19 | 1.2 (5) |
O3—C3—C4—C5 | −179.7 (3) | O4—C18—C19—C20 | 179.9 (3) |
C2—C3—C4—C5 | −0.2 (5) | C17—C18—C19—C20 | −0.6 (5) |
C3—C4—C5—C6 | 0.5 (5) | Zn1—O2—C20—C19 | −172.2 (2) |
C4—C5—C6—C1 | −0.7 (5) | Zn1—O2—C20—C15 | 9.0 (4) |
C4—C5—C6—C7 | 179.2 (3) | C18—C19—C20—O2 | −178.8 (3) |
O1—C1—C6—C5 | −179.4 (3) | C18—C19—C20—C15 | 0.0 (4) |
C2—C1—C6—C5 | 0.6 (4) | C16—C15—C20—O2 | 178.8 (3) |
O1—C1—C6—C7 | 0.7 (5) | C14—C15—C20—O2 | −2.9 (5) |
C2—C1—C6—C7 | −179.3 (3) | C16—C15—C20—C19 | 0.0 (4) |
C8—N1—C7—C6 | 175.4 (3) | C14—C15—C20—C19 | 178.3 (3) |
Zn1—N1—C7—C6 | −3.4 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3A···O3Wi | 0.82 | 1.87 | 2.688 (3) | 175 |
O4—H4B···O4ii | 0.82 | 1.93 | 2.728 (3) | 164 |
O1W—H1W1···O2iii | 0.85 | 2.14 | 2.879 (3) | 146 |
O2W—H1W2···O1 | 0.85 | 2.31 | 3.066 (3) | 149 |
O2W—H1W2···O1W | 0.85 | 2.36 | 2.936 (3) | 125 |
O3W—H1W3···O4Wiv | 0.85 (2) | 1.95 (2) | 2.788 (3) | 169 (3) |
O4W—H1W4···O4v | 0.85 | 1.87 | 2.685 (3) | 161 |
O1W—H2W1···O1iii | 0.85 | 1.91 | 2.670 (3) | 148 |
O2W—H2W2···O2Wvi | 0.85 | 2.42 | 2.732 (4) | 103 |
O3W—H2W3···O2W | 0.85 | 1.85 | 2.701 (3) | 173 |
O4W—H2W4···O2 | 0.85 | 1.99 | 2.774 (3) | 153 |
Symmetry codes: (i) x+1, y, z; (ii) −x+2, −y+2, −z+1; (iii) x−1, y, z; (iv) −x+1, −y+1, −z+1; (v) −x+1, −y+2, −z+1; (vi) −x, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Zn(C20H14N2O4)(H2O)]·3H2O |
Mr | 483.77 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 100 |
a, b, c (Å) | 4.7462 (1), 13.9290 (2), 15.1128 (2) |
α, β, γ (°) | 82.147 (1), 82.367 (1), 85.640 (1) |
V (Å3) | 979.26 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.31 |
Crystal size (mm) | 0.45 × 0.44 × 0.06 |
Data collection | |
Diffractometer | Bruker SMART APEXII CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2005) |
Tmin, Tmax | 0.591, 0.928 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13930, 3830, 3151 |
Rint | 0.042 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.088, 1.03 |
No. of reflections | 3830 |
No. of parameters | 283 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.40, −0.49 |
Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 1998) and PLATON (Spek, 2003).
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3A···O3Wi | 0.82 | 1.8700 | 2.688 (3) | 175 |
O4—H4B···O4ii | 0.82 | 1.9316 | 2.728 (3) | 164 |
O1W—H1W1···O2iii | 0.85 | 2.1372 | 2.879 (3) | 146 |
O2W—H1W2···O1 | 0.85 | 2.3068 | 3.066 (3) | 149 |
O2W—H1W2···O1W | 0.85 | 2.3644 | 2.936 (3) | 125 |
O3W—H1W3···O4Wiv | 0.85 (2) | 1.95 (2) | 2.788 (3) | 169 (3) |
O4W—H1W4···O4v | 0.85 | 1.8652 | 2.685 (3) | 161 |
O1W—H2W1···O1iii | 0.85 | 1.9117 | 2.670 (3) | 148 |
O2W—H2W2···O2Wvi | 0.85 | 2.4185 | 2.732 (4) | 103 |
O3W—H2W3···O2W | 0.85 | 1.8539 | 2.701 (3) | 173 |
O4W—H2W4···O2 | 0.85 | 1.9911 | 2.774 (3) | 153 |
Symmetry codes: (i) x+1, y, z; (ii) −x+2, −y+2, −z+1; (iii) x−1, y, z; (iv) −x+1, −y+1, −z+1; (v) −x+1, −y+2, −z+1; (vi) −x, −y+1, −z+1. |
Subscribe to Acta Crystallographica Section E: Crystallographic Communications
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- If you have already subscribed, you may need to register
Zinc is an element attracting strong interests in biology, medicine, materials, and catalysis. It plays important roles in various biological systems such as neurotransmission, signal transduction, and gene expression (Assaf & Chung, 1984; Berg & Shi, 1996). It is well known that zinc complexes with Schiff-bases are biologically active and show very good cytotoxicity against the leukemic cell (Tarafder et al., 2002). Since our previous investigations (Eltayeb et al., 2007a, b, c, d) show the possibility of generating five coordinate zinc complexes using tetradentate Schiff base ligands, we have extended our synthesis to the title complex and report its crystal structure here.
In the title complex (Fig. 1), ZnII coordinates with the tetradentate Schiff base ligand in the basal plane (N1, N2, O1 and O2) and a water molecule in the apical site. The ZnII center lies slightly above the N2O2 plane in a geometry that is roughly square pyramidal, with the Zn in the Zn—N2O2 plane being tilted 0.01190 Å towards the axial water molecule. This geometry has been observed for similar Schiff base ligand ZnII complexes (Eltayeb et al., 2007a, b, c, d). The dihedral angles between the two benzene rings (C1–C6) and (C15–C20) and the central benzene ring (C8–C13) are 12.64 (14)° and 17.25 (14) °, respectively. The Zn1—N1 and Zn1—N2 distances of 2.069 (2) Å and 2.075 (2) Å and bond angles around Zn1 are in agreement with the values found for similar ZnII complexes (Eltayeb et al., 2007a, b, c, d). However, the Zn1—O1 and Zn1—O2 distances, 1.9905 (19) and 2.001 (2) Å, respectively are slightly shorter than those observed in a closely related structure (Eltayeb ey al., 2007 d) where the Zn—O distances are in the range 2.0027 (15)–2.0036 (15) Å. All water molecules are involved in intermolecular O—H···O hydrogen bonds. Bond lengths and angles observed in the structure are normal (Allen et al., 1987).
In the crystal packing (Fig. 2), O—H···O hydrogen bonds (Table 1) link the molecules into sheets parallel to the ab plane.