Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807038536/ng2303sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807038536/ng2303Isup2.hkl |
CCDC reference: 660069
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean (C-C) = 0.003 Å
- R factor = 0.037
- wR factor = 0.076
- Data-to-parameter ratio = 18.1
checkCIF/PLATON results
No syntax errors found
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 = 4 PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 2
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Zn1 (2) 2.02
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 1 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 1 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 normal values of bond lengths, see Allen et al. (1987). For related structures see, for example, Chaudhuri et al. (2007); Eltayeb et al. (2007a,b,c). For literature on the biological activities of related compounds, see: Assaf & Chung (1984); Berg & Shi (1996); Tarafder et al. (2002).
The title compound (I) was synthesized by adding 3-methyl-2-hydroxybenzaldehyde (0.544 g, 4 mmol) into 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 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, which was washed by about 5 ml e thanol, dried, and then washed by copious amounts of diethyl ether. The precipitate was dissolved in 20 ml of chloroform and single crystals of the title compound were formed after one day of slow evaporation of chloroform at room temperature.
The water H atoms were located in a difference map and isotropically refined. The remainning H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H distances in the range 0.93–0.98 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.
Zinc is an essential element for the normal function of most biological systems. ZnII chelate complexes are studied as models for hydrolytically active enzymes. It also 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 ZnII complexes with Schiff bases are biologically active and show very good cytotoxicity against the leukemic cell (Tarafder et al., 2002). The coordination number of ZnII in the catalytic sites is often lower than six, even though water molecule or hydroxide ion is bound to the metal as an additional ligand. Since our previous investigations (Eltayeb et al., 2007a,b,c) have shown the possibility of formation of a five coordination environment with tetradentate Schiff base ligand, we have extend our synthesis to the title complex and its crystal structure is reported.
The title complex molecule (Fig. 1) is characterized by an approxmately square pyramidal ZnII coordination, with the tetradentate Schiff base ligand in the basal plane (N1, N2, O1 and O2) and a water molecule in the apical site. The Zn atom is almost in the same plane of this basal plane, as indicated by the displacement of 0.0098 Å out of this basal donor atoms in the direction of the apical water molecule. Bond lengths and angles in this Schiff base ligand are very similar to those reported for the other ZnII complexes with Schiff base ligands (Eltayeb et al., 2007a,b,c). The Zn1—N1 and Zn1—N2 distances of 2.0818 (19) Å and 2.0708 (18) Å, respectively lie in the same range as the other five coordination ZnII complexes of Schiff base ligands (Chaudhuri et al., 2007; Eltayeb et al., 2007,b,c). However, the Zn1—O1 and Zn1—O2 distances of 2.0036 (15) Å and 2.0027 (15) Å, respectively, are longer than those observed in other closely related structures (Eltayeb et al., 2007a,b,c) where the Zn—O distances are in the range of 1.9326 (17)–1.9798 (13) Å. Bond angles around Zn1 are in agreement with the values found for similar ZnII complexes (Eltayeb et al., 2007a,b,c). Evidently, changing the substitutional groups on the Schiff base ligands has no effect on the coordination of the tetradentate Schiff base ligands. Bond lengths and angles observed in the structure are normal (Allen et al., 1987).
In the crystal packing (Fig. 2), the water molecule is involved in intermolecular O—H···O hydrogen bonds [O1W—H2WA···O1 and O1W—H1WA···O2; symmetry code 1 - x, -y, 2 - z] and the chloroform molecule is involved in a weak C—H···O intermolecular interaction [C23—H23···O1W; symmetry code 1 - x, -y, 2 - z] (Table 2). The molcecules are linked into one-dimension chains along the a axis. These chains form molecular sheets parallel to the ac plane. The crystal is stabilized by intermolecular O—H···O hydrogen bonds and weak C—H···O interaction.
For normal values of bond lengths, see Allen et al. (1987). For related structures see, for example, Chaudhuri et al. (2007); Eltayeb et al. (2007a,b,c). For literature on the biological activities of related compounds, see: Assaf & Chung (1984); Berg & Shi (1996); Tarafder et al. (2002).
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).
[Zn(C22H18N2O2)(H2O)]·CHCl3 | Z = 2 |
Mr = 545.16 | F(000) = 556 |
Triclinic, P1 | Dx = 1.607 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.0115 (1) Å | Cell parameters from 5412 reflections |
b = 10.7771 (2) Å | θ = 2.4–28.0° |
c = 12.9018 (2) Å | µ = 1.48 mm−1 |
α = 94.338 (1)° | T = 100 K |
β = 103.963 (1)° | Block, yellow |
γ = 109.851 (1)° | 0.32 × 0.21 × 0.15 mm |
V = 1126.55 (3) Å3 |
Bruker SMART APEXII CCD area-detector diffractometer | 5412 independent reflections |
Radiation source: fine-focus sealed tube | 4243 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.043 |
Detector resolution: 8.33 pixels mm-1 | θmax = 28.0°, θmin = 2.4° |
ω scans | h = −11→11 |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | k = −14→13 |
Tmin = 0.651, Tmax = 0.810 | l = −16→17 |
19823 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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.077 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0279P)2 + 0.4583P] where P = (Fo2 + 2Fc2)/3 |
5412 reflections | (Δ/σ)max = 0.001 |
299 parameters | Δρmax = 0.38 e Å−3 |
0 restraints | Δρmin = −0.41 e Å−3 |
[Zn(C22H18N2O2)(H2O)]·CHCl3 | γ = 109.851 (1)° |
Mr = 545.16 | V = 1126.55 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.0115 (1) Å | Mo Kα radiation |
b = 10.7771 (2) Å | µ = 1.48 mm−1 |
c = 12.9018 (2) Å | T = 100 K |
α = 94.338 (1)° | 0.32 × 0.21 × 0.15 mm |
β = 103.963 (1)° |
Bruker SMART APEXII CCD area-detector diffractometer | 5412 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | 4243 reflections with I > 2σ(I) |
Tmin = 0.651, Tmax = 0.810 | Rint = 0.043 |
19823 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.077 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.38 e Å−3 |
5412 reflections | Δρmin = −0.41 e Å−3 |
299 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 | 0.27559 (3) | −0.00780 (3) | 0.88420 (2) | 0.01584 (8) | |
O1 | 0.46560 (18) | 0.16671 (15) | 0.91153 (12) | 0.0174 (3) | |
O2 | 0.26547 (18) | −0.00680 (15) | 1.03761 (12) | 0.0177 (3) | |
O1W | 0.4145 (2) | −0.12826 (17) | 0.89043 (14) | 0.0170 (4) | |
N1 | 0.2252 (2) | −0.00472 (18) | 0.71842 (15) | 0.0168 (4) | |
N2 | 0.0356 (2) | −0.14449 (18) | 0.83007 (15) | 0.0159 (4) | |
C1 | 0.5332 (3) | 0.2309 (2) | 0.84187 (18) | 0.0161 (5) | |
C2 | 0.6815 (3) | 0.3463 (2) | 0.88245 (19) | 0.0176 (5) | |
C3 | 0.7567 (3) | 0.4130 (2) | 0.81148 (19) | 0.0207 (5) | |
H3A | 0.8538 | 0.4873 | 0.8393 | 0.025* | |
C4 | 0.6930 (3) | 0.3738 (2) | 0.6991 (2) | 0.0220 (5) | |
H4A | 0.7474 | 0.4201 | 0.6529 | 0.026* | |
C5 | 0.5491 (3) | 0.2659 (2) | 0.65847 (19) | 0.0198 (5) | |
H5A | 0.5049 | 0.2399 | 0.5837 | 0.024* | |
C6 | 0.4655 (3) | 0.1926 (2) | 0.72707 (18) | 0.0172 (5) | |
C7 | 0.3160 (3) | 0.0813 (2) | 0.67323 (19) | 0.0172 (5) | |
H7A | 0.2809 | 0.0700 | 0.5980 | 0.021* | |
C8 | 0.0777 (3) | −0.1091 (2) | 0.65642 (18) | 0.0166 (5) | |
C9 | 0.0306 (3) | −0.1450 (2) | 0.54369 (19) | 0.0213 (5) | |
H9A | 0.0992 | −0.0992 | 0.5043 | 0.026* | |
C10 | −0.1162 (3) | −0.2473 (2) | 0.4902 (2) | 0.0224 (5) | |
H10A | −0.1463 | −0.2702 | 0.4151 | 0.027* | |
C11 | −0.2193 (3) | −0.3164 (2) | 0.54805 (19) | 0.0207 (5) | |
H11A | −0.3190 | −0.3848 | 0.5117 | 0.025* | |
C12 | −0.1739 (3) | −0.2836 (2) | 0.65921 (19) | 0.0194 (5) | |
H12A | −0.2434 | −0.3308 | 0.6975 | 0.023* | |
C13 | −0.0256 (3) | −0.1810 (2) | 0.71564 (18) | 0.0153 (5) | |
C14 | −0.0571 (3) | −0.1917 (2) | 0.89165 (19) | 0.0179 (5) | |
H14A | −0.1656 | −0.2469 | 0.8568 | 0.022* | |
C15 | −0.0096 (3) | −0.1677 (2) | 1.00789 (18) | 0.0171 (5) | |
C16 | −0.1320 (3) | −0.2383 (2) | 1.0558 (2) | 0.0217 (5) | |
H16A | −0.2348 | −0.2944 | 1.0112 | 0.026* | |
C17 | −0.1034 (3) | −0.2266 (2) | 1.1652 (2) | 0.0224 (5) | |
H17A | −0.1839 | −0.2762 | 1.1951 | 0.027* | |
C18 | 0.0503 (3) | −0.1379 (2) | 1.2319 (2) | 0.0222 (5) | |
H18A | 0.0701 | −0.1288 | 1.3068 | 0.027* | |
C19 | 0.1727 (3) | −0.0639 (2) | 1.19001 (18) | 0.0181 (5) | |
C20 | 0.1462 (3) | −0.0785 (2) | 1.07590 (18) | 0.0161 (5) | |
C21 | 0.7545 (3) | 0.3909 (2) | 1.00306 (19) | 0.0225 (5) | |
H21A | 0.8440 | 0.4758 | 1.0177 | 0.034* | |
H21B | 0.7945 | 0.3258 | 1.0336 | 0.034* | |
H21C | 0.6718 | 0.3995 | 1.0348 | 0.034* | |
C22 | 0.3308 (3) | 0.0367 (2) | 1.26331 (19) | 0.0216 (5) | |
H22A | 0.3276 | 0.0380 | 1.3372 | 0.032* | |
H22B | 0.3450 | 0.1238 | 1.2449 | 0.032* | |
H22C | 0.4210 | 0.0127 | 1.2548 | 0.032* | |
H2WA | 0.417 (3) | −0.158 (3) | 0.946 (2) | 0.027 (8)* | |
H1WA | 0.507 (4) | −0.083 (3) | 0.891 (2) | 0.036 (9)* | |
C23 | 0.3000 (3) | 0.6266 (2) | 0.7042 (2) | 0.0232 (5) | |
H23A | 0.3319 | 0.7066 | 0.7586 | 0.028* | |
Cl1 | 0.43406 (7) | 0.54081 (6) | 0.74705 (6) | 0.03189 (16) | |
Cl2 | 0.09640 (7) | 0.52333 (7) | 0.69353 (6) | 0.03265 (16) | |
Cl3 | 0.31570 (9) | 0.67676 (7) | 0.57947 (5) | 0.03654 (17) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.01532 (13) | 0.01675 (14) | 0.01440 (15) | 0.00447 (10) | 0.00455 (10) | 0.00246 (11) |
O1 | 0.0177 (8) | 0.0168 (8) | 0.0156 (8) | 0.0039 (6) | 0.0044 (7) | 0.0038 (7) |
O2 | 0.0170 (8) | 0.0203 (8) | 0.0161 (8) | 0.0057 (7) | 0.0068 (7) | 0.0034 (7) |
O1W | 0.0169 (9) | 0.0177 (9) | 0.0154 (9) | 0.0046 (7) | 0.0049 (7) | 0.0034 (7) |
N1 | 0.0147 (9) | 0.0157 (10) | 0.0186 (10) | 0.0043 (8) | 0.0043 (8) | 0.0029 (8) |
N2 | 0.0165 (9) | 0.0163 (10) | 0.0154 (10) | 0.0071 (8) | 0.0039 (8) | 0.0022 (8) |
C1 | 0.0155 (11) | 0.0156 (11) | 0.0203 (12) | 0.0088 (9) | 0.0051 (9) | 0.0059 (10) |
C2 | 0.0157 (11) | 0.0166 (12) | 0.0213 (13) | 0.0074 (9) | 0.0044 (10) | 0.0030 (10) |
C3 | 0.0167 (11) | 0.0167 (12) | 0.0262 (14) | 0.0040 (9) | 0.0051 (10) | 0.0033 (10) |
C4 | 0.0214 (12) | 0.0215 (13) | 0.0241 (14) | 0.0056 (10) | 0.0100 (11) | 0.0094 (11) |
C5 | 0.0236 (12) | 0.0228 (13) | 0.0154 (12) | 0.0099 (10) | 0.0070 (10) | 0.0065 (10) |
C6 | 0.0165 (11) | 0.0172 (12) | 0.0190 (12) | 0.0076 (9) | 0.0048 (10) | 0.0050 (10) |
C7 | 0.0186 (11) | 0.0192 (12) | 0.0149 (12) | 0.0088 (10) | 0.0039 (9) | 0.0035 (10) |
C8 | 0.0160 (11) | 0.0169 (12) | 0.0168 (12) | 0.0075 (9) | 0.0025 (9) | 0.0020 (10) |
C9 | 0.0244 (12) | 0.0208 (13) | 0.0190 (13) | 0.0072 (10) | 0.0080 (10) | 0.0051 (10) |
C10 | 0.0276 (13) | 0.0216 (13) | 0.0161 (13) | 0.0107 (11) | 0.0014 (10) | −0.0004 (10) |
C11 | 0.0156 (11) | 0.0177 (12) | 0.0225 (13) | 0.0043 (9) | −0.0014 (10) | −0.0023 (10) |
C12 | 0.0191 (11) | 0.0178 (12) | 0.0213 (13) | 0.0072 (10) | 0.0057 (10) | 0.0025 (10) |
C13 | 0.0165 (11) | 0.0153 (11) | 0.0155 (12) | 0.0090 (9) | 0.0027 (9) | 0.0030 (9) |
C14 | 0.0154 (11) | 0.0156 (12) | 0.0225 (13) | 0.0056 (9) | 0.0048 (10) | 0.0034 (10) |
C15 | 0.0185 (11) | 0.0182 (12) | 0.0180 (12) | 0.0091 (9) | 0.0067 (10) | 0.0060 (10) |
C16 | 0.0203 (12) | 0.0201 (12) | 0.0277 (14) | 0.0081 (10) | 0.0098 (11) | 0.0076 (11) |
C17 | 0.0264 (13) | 0.0220 (13) | 0.0246 (14) | 0.0092 (11) | 0.0153 (11) | 0.0104 (11) |
C18 | 0.0313 (13) | 0.0251 (13) | 0.0162 (13) | 0.0143 (11) | 0.0109 (11) | 0.0060 (10) |
C19 | 0.0223 (12) | 0.0182 (12) | 0.0180 (12) | 0.0117 (10) | 0.0068 (10) | 0.0047 (10) |
C20 | 0.0173 (11) | 0.0147 (11) | 0.0212 (13) | 0.0101 (9) | 0.0076 (10) | 0.0047 (10) |
C21 | 0.0217 (12) | 0.0178 (12) | 0.0220 (13) | 0.0021 (10) | 0.0040 (10) | 0.0005 (10) |
C22 | 0.0252 (13) | 0.0257 (13) | 0.0166 (13) | 0.0115 (11) | 0.0077 (10) | 0.0036 (10) |
C23 | 0.0235 (12) | 0.0231 (13) | 0.0229 (14) | 0.0086 (10) | 0.0078 (11) | 0.0006 (11) |
Cl1 | 0.0218 (3) | 0.0304 (4) | 0.0445 (4) | 0.0107 (3) | 0.0100 (3) | 0.0058 (3) |
Cl2 | 0.0204 (3) | 0.0332 (4) | 0.0433 (4) | 0.0078 (3) | 0.0118 (3) | 0.0018 (3) |
Cl3 | 0.0461 (4) | 0.0358 (4) | 0.0268 (4) | 0.0111 (3) | 0.0145 (3) | 0.0053 (3) |
Zn1—O2 | 2.0027 (15) | C10—C11 | 1.387 (3) |
Zn1—O1 | 2.0036 (15) | C10—H10A | 0.9300 |
Zn1—N2 | 2.0708 (18) | C11—C12 | 1.375 (3) |
Zn1—O1W | 2.0810 (16) | C11—H11A | 0.9300 |
Zn1—N1 | 2.0818 (19) | C12—C13 | 1.394 (3) |
O1—C1 | 1.315 (3) | C12—H12A | 0.9300 |
O2—C20 | 1.322 (2) | C14—C15 | 1.434 (3) |
O1W—H2WA | 0.80 (3) | C14—H14A | 0.9300 |
O1W—H1WA | 0.81 (3) | C15—C16 | 1.417 (3) |
N1—C7 | 1.291 (3) | C15—C20 | 1.423 (3) |
N1—C8 | 1.417 (3) | C16—C17 | 1.360 (3) |
N2—C14 | 1.296 (3) | C16—H16A | 0.9300 |
N2—C13 | 1.418 (3) | C17—C18 | 1.405 (3) |
C1—C6 | 1.427 (3) | C17—H17A | 0.9300 |
C1—C2 | 1.429 (3) | C18—C19 | 1.379 (3) |
C2—C3 | 1.372 (3) | C18—H18A | 0.9300 |
C2—C21 | 1.504 (3) | C19—C20 | 1.421 (3) |
C3—C4 | 1.397 (3) | C19—C22 | 1.498 (3) |
C3—H3A | 0.9300 | C21—H21A | 0.9600 |
C4—C5 | 1.365 (3) | C21—H21B | 0.9600 |
C4—H4A | 0.9300 | C21—H21C | 0.9600 |
C5—C6 | 1.413 (3) | C22—H22A | 0.9600 |
C5—H5A | 0.9300 | C22—H22B | 0.9600 |
C6—C7 | 1.436 (3) | C22—H22C | 0.9600 |
C7—H7A | 0.9300 | C23—Cl2 | 1.758 (2) |
C8—C9 | 1.397 (3) | C23—Cl3 | 1.759 (2) |
C8—C13 | 1.412 (3) | C23—Cl1 | 1.771 (2) |
C9—C10 | 1.377 (3) | C23—H23A | 0.9800 |
C9—H9A | 0.9300 | ||
O2—Zn1—O1 | 96.84 (6) | C11—C10—H10A | 119.9 |
O2—Zn1—N2 | 89.99 (7) | C12—C11—C10 | 119.9 (2) |
O1—Zn1—N2 | 158.92 (7) | C12—C11—H11A | 120.1 |
O2—Zn1—O1W | 95.73 (7) | C10—C11—H11A | 120.1 |
O1—Zn1—O1W | 95.93 (7) | C11—C12—C13 | 121.2 (2) |
N2—Zn1—O1W | 103.23 (7) | C11—C12—H12A | 119.4 |
O2—Zn1—N1 | 164.74 (7) | C13—C12—H12A | 119.4 |
O1—Zn1—N1 | 89.63 (7) | C12—C13—C8 | 118.8 (2) |
N2—Zn1—N1 | 79.38 (7) | C12—C13—N2 | 125.3 (2) |
O1W—Zn1—N1 | 97.34 (7) | C8—C13—N2 | 115.88 (19) |
C1—O1—Zn1 | 129.18 (14) | N2—C14—C15 | 126.8 (2) |
C20—O2—Zn1 | 129.59 (14) | N2—C14—H14A | 116.6 |
Zn1—O1W—H2WA | 107.6 (19) | C15—C14—H14A | 116.6 |
Zn1—O1W—H1WA | 109 (2) | C16—C15—C20 | 119.2 (2) |
H2WA—O1W—H1WA | 109 (3) | C16—C15—C14 | 115.5 (2) |
C7—N1—C8 | 121.5 (2) | C20—C15—C14 | 125.2 (2) |
C7—N1—Zn1 | 125.23 (16) | C17—C16—C15 | 121.9 (2) |
C8—N1—Zn1 | 113.26 (14) | C17—C16—H16A | 119.1 |
C14—N2—C13 | 120.93 (19) | C15—C16—H16A | 119.1 |
C14—N2—Zn1 | 125.15 (16) | C16—C17—C18 | 118.6 (2) |
C13—N2—Zn1 | 113.89 (13) | C16—C17—H17A | 120.7 |
O1—C1—C6 | 123.6 (2) | C18—C17—H17A | 120.7 |
O1—C1—C2 | 118.7 (2) | C19—C18—C17 | 122.1 (2) |
C6—C1—C2 | 117.7 (2) | C19—C18—H18A | 118.9 |
C3—C2—C1 | 119.8 (2) | C17—C18—H18A | 118.9 |
C3—C2—C21 | 121.1 (2) | C18—C19—C20 | 119.8 (2) |
C1—C2—C21 | 119.1 (2) | C18—C19—C22 | 120.7 (2) |
C2—C3—C4 | 122.6 (2) | C20—C19—C22 | 119.5 (2) |
C2—C3—H3A | 118.7 | O2—C20—C19 | 118.7 (2) |
C4—C3—H3A | 118.7 | O2—C20—C15 | 123.0 (2) |
C5—C4—C3 | 118.6 (2) | C19—C20—C15 | 118.3 (2) |
C5—C4—H4A | 120.7 | C2—C21—H21A | 109.5 |
C3—C4—H4A | 120.7 | C2—C21—H21B | 109.5 |
C4—C5—C6 | 121.7 (2) | H21A—C21—H21B | 109.5 |
C4—C5—H5A | 119.1 | C2—C21—H21C | 109.5 |
C6—C5—H5A | 119.1 | H21A—C21—H21C | 109.5 |
C5—C6—C1 | 119.5 (2) | H21B—C21—H21C | 109.5 |
C5—C6—C7 | 115.7 (2) | C19—C22—H22A | 109.5 |
C1—C6—C7 | 124.8 (2) | C19—C22—H22B | 109.5 |
N1—C7—C6 | 126.7 (2) | H22A—C22—H22B | 109.5 |
N1—C7—H7A | 116.6 | C19—C22—H22C | 109.5 |
C6—C7—H7A | 116.6 | H22A—C22—H22C | 109.5 |
C9—C8—C13 | 119.2 (2) | H22B—C22—H22C | 109.5 |
C9—C8—N1 | 124.8 (2) | Cl2—C23—Cl3 | 110.58 (13) |
C13—C8—N1 | 115.96 (19) | Cl2—C23—Cl1 | 109.94 (13) |
C10—C9—C8 | 120.7 (2) | Cl3—C23—Cl1 | 110.28 (12) |
C10—C9—H9A | 119.7 | Cl2—C23—H23A | 108.7 |
C8—C9—H9A | 119.7 | Cl3—C23—H23A | 108.7 |
C9—C10—C11 | 120.2 (2) | Cl1—C23—H23A | 108.7 |
C9—C10—H10A | 119.9 | ||
O2—Zn1—O1—C1 | −176.55 (17) | C5—C6—C7—N1 | 175.1 (2) |
N2—Zn1—O1—C1 | −68.4 (3) | C1—C6—C7—N1 | −4.0 (4) |
O1W—Zn1—O1—C1 | 86.93 (17) | C7—N1—C8—C9 | 12.0 (3) |
N1—Zn1—O1—C1 | −10.41 (17) | Zn1—N1—C8—C9 | −167.72 (18) |
O1—Zn1—O2—C20 | 163.81 (17) | C7—N1—C8—C13 | −168.7 (2) |
N2—Zn1—O2—C20 | 3.80 (18) | Zn1—N1—C8—C13 | 11.6 (2) |
O1W—Zn1—O2—C20 | −99.50 (18) | C13—C8—C9—C10 | 1.3 (3) |
N1—Zn1—O2—C20 | 49.3 (3) | N1—C8—C9—C10 | −179.4 (2) |
O2—Zn1—N1—C7 | 122.3 (3) | C8—C9—C10—C11 | −0.1 (4) |
O1—Zn1—N1—C7 | 6.87 (18) | C9—C10—C11—C12 | −0.8 (4) |
N2—Zn1—N1—C7 | 168.79 (19) | C10—C11—C12—C13 | 0.4 (3) |
O1W—Zn1—N1—C7 | −89.06 (18) | C11—C12—C13—C8 | 0.8 (3) |
O2—Zn1—N1—C8 | −58.0 (3) | C11—C12—C13—N2 | −176.6 (2) |
O1—Zn1—N1—C8 | −173.39 (15) | C9—C8—C13—C12 | −1.7 (3) |
N2—Zn1—N1—C8 | −11.48 (14) | N1—C8—C13—C12 | 179.02 (19) |
O1W—Zn1—N1—C8 | 90.68 (15) | C9—C8—C13—N2 | 176.00 (19) |
O2—Zn1—N2—C14 | 1.06 (18) | N1—C8—C13—N2 | −3.3 (3) |
O1—Zn1—N2—C14 | −108.3 (2) | C14—N2—C13—C12 | −11.3 (3) |
O1W—Zn1—N2—C14 | 96.94 (18) | Zn1—N2—C13—C12 | 170.87 (17) |
N1—Zn1—N2—C14 | −167.93 (19) | C14—N2—C13—C8 | 171.2 (2) |
O2—Zn1—N2—C13 | 178.78 (14) | Zn1—N2—C13—C8 | −6.6 (2) |
O1—Zn1—N2—C13 | 69.5 (2) | C13—N2—C14—C15 | 177.3 (2) |
O1W—Zn1—N2—C13 | −85.34 (15) | Zn1—N2—C14—C15 | −5.1 (3) |
N1—Zn1—N2—C13 | 9.79 (14) | N2—C14—C15—C16 | −176.2 (2) |
Zn1—O1—C1—C6 | 8.5 (3) | N2—C14—C15—C20 | 5.1 (4) |
Zn1—O1—C1—C2 | −172.26 (14) | C20—C15—C16—C17 | −2.0 (3) |
O1—C1—C2—C3 | 178.4 (2) | C14—C15—C16—C17 | 179.1 (2) |
C6—C1—C2—C3 | −2.3 (3) | C15—C16—C17—C18 | 2.3 (4) |
O1—C1—C2—C21 | −0.4 (3) | C16—C17—C18—C19 | −0.6 (4) |
C6—C1—C2—C21 | 178.9 (2) | C17—C18—C19—C20 | −1.3 (3) |
C1—C2—C3—C4 | 0.8 (3) | C17—C18—C19—C22 | 175.7 (2) |
C21—C2—C3—C4 | 179.5 (2) | Zn1—O2—C20—C19 | 176.74 (14) |
C2—C3—C4—C5 | 1.0 (4) | Zn1—O2—C20—C15 | −4.8 (3) |
C3—C4—C5—C6 | −1.0 (3) | C18—C19—C20—O2 | −179.9 (2) |
C4—C5—C6—C1 | −0.6 (3) | C22—C19—C20—O2 | 3.1 (3) |
C4—C5—C6—C7 | −179.8 (2) | C18—C19—C20—C15 | 1.6 (3) |
O1—C1—C6—C5 | −178.50 (19) | C22—C19—C20—C15 | −175.5 (2) |
C2—C1—C6—C5 | 2.3 (3) | C16—C15—C20—O2 | −178.5 (2) |
O1—C1—C6—C7 | 0.6 (3) | C14—C15—C20—O2 | 0.3 (3) |
C2—C1—C6—C7 | −178.7 (2) | C16—C15—C20—C19 | 0.0 (3) |
C8—N1—C7—C6 | 178.6 (2) | C14—C15—C20—C19 | 178.7 (2) |
Zn1—N1—C7—C6 | −1.7 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H2WA···O1i | 0.81 (3) | 1.91 (3) | 2.646 (2) | 151 (3) |
O1W—H1WA···O2i | 0.81 (4) | 1.90 (3) | 2.636 (3) | 152 (3) |
C23—H23A···O1Wii | 0.98 | 2.16 | 3.132 (3) | 174 |
Symmetry codes: (i) −x+1, −y, −z+2; (ii) x, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | [Zn(C22H18N2O2)(H2O)]·CHCl3 |
Mr | 545.16 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 100 |
a, b, c (Å) | 9.0115 (1), 10.7771 (2), 12.9018 (2) |
α, β, γ (°) | 94.338 (1), 103.963 (1), 109.851 (1) |
V (Å3) | 1126.55 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.48 |
Crystal size (mm) | 0.32 × 0.21 × 0.15 |
Data collection | |
Diffractometer | Bruker SMART APEXII CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2005) |
Tmin, Tmax | 0.651, 0.810 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19823, 5412, 4243 |
Rint | 0.043 |
(sin θ/λ)max (Å−1) | 0.661 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.077, 1.03 |
No. of reflections | 5412 |
No. of parameters | 299 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.38, −0.41 |
Computer programs: APEX2 (Bruker, 2005), APEX2, SAINT (Bruker, 2005), SHELXTL (Sheldrick, 1998), SHELXTL and PLATON (Spek, 2003).
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H2WA···O1i | 0.81 (3) | 1.91 (3) | 2.646 (2) | 151 (3) |
O1W—H1WA···O2i | 0.81 (4) | 1.90 (3) | 2.636 (3) | 152 (3) |
C23—H23A···O1Wii | 0.98 | 2.1554 | 3.132 (3) | 174 |
Symmetry codes: (i) −x+1, −y, −z+2; (ii) x, y+1, z. |
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Zinc is an essential element for the normal function of most biological systems. ZnII chelate complexes are studied as models for hydrolytically active enzymes. It also 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 ZnII complexes with Schiff bases are biologically active and show very good cytotoxicity against the leukemic cell (Tarafder et al., 2002). The coordination number of ZnII in the catalytic sites is often lower than six, even though water molecule or hydroxide ion is bound to the metal as an additional ligand. Since our previous investigations (Eltayeb et al., 2007a,b,c) have shown the possibility of formation of a five coordination environment with tetradentate Schiff base ligand, we have extend our synthesis to the title complex and its crystal structure is reported.
The title complex molecule (Fig. 1) is characterized by an approxmately square pyramidal ZnII coordination, with the tetradentate Schiff base ligand in the basal plane (N1, N2, O1 and O2) and a water molecule in the apical site. The Zn atom is almost in the same plane of this basal plane, as indicated by the displacement of 0.0098 Å out of this basal donor atoms in the direction of the apical water molecule. Bond lengths and angles in this Schiff base ligand are very similar to those reported for the other ZnII complexes with Schiff base ligands (Eltayeb et al., 2007a,b,c). The Zn1—N1 and Zn1—N2 distances of 2.0818 (19) Å and 2.0708 (18) Å, respectively lie in the same range as the other five coordination ZnII complexes of Schiff base ligands (Chaudhuri et al., 2007; Eltayeb et al., 2007,b,c). However, the Zn1—O1 and Zn1—O2 distances of 2.0036 (15) Å and 2.0027 (15) Å, respectively, are longer than those observed in other closely related structures (Eltayeb et al., 2007a,b,c) where the Zn—O distances are in the range of 1.9326 (17)–1.9798 (13) Å. Bond angles around Zn1 are in agreement with the values found for similar ZnII complexes (Eltayeb et al., 2007a,b,c). Evidently, changing the substitutional groups on the Schiff base ligands has no effect on the coordination of the tetradentate Schiff base ligands. Bond lengths and angles observed in the structure are normal (Allen et al., 1987).
In the crystal packing (Fig. 2), the water molecule is involved in intermolecular O—H···O hydrogen bonds [O1W—H2WA···O1 and O1W—H1WA···O2; symmetry code 1 - x, -y, 2 - z] and the chloroform molecule is involved in a weak C—H···O intermolecular interaction [C23—H23···O1W; symmetry code 1 - x, -y, 2 - z] (Table 2). The molcecules are linked into one-dimension chains along the a axis. These chains form molecular sheets parallel to the ac plane. The crystal is stabilized by intermolecular O—H···O hydrogen bonds and weak C—H···O interaction.