supplementary materials


bq2283 scheme

Acta Cryst. (2011). E67, o1046    [ doi:10.1107/S1600536811010373 ]

5-(2-Methoxyphenyl)-1,3,4-thiadiazol-2-yl 2-methoxybenzoate hemihydrate

J. Yao, B. Guo, K. An and J. Guan

Abstract top

In the title compound, C17H14N2O4S·0.5H2O, the molecule, with the exception of the two methoxyphenyl groups, is nearly planar with an r.m.s. deviation of 0.0305 Å. The two 2-methoxyphenyl rings make dihedral angles of 4.1 (3) and 2.3 (3)° with the thiadiazole ring. In the crystal, intermolecular C-H...O and O-H...N hydrogen bonds link the molecules.

Comment top

1,3,4-Thiadiazole derivatives are of great interest because of their chemical and pharmaceutical properties. Some derivatives play a key role in preparing intermediate for anticarcinogen. Recently new derivatives with 1,3,4-thiadiazole nucleus have been synthesized and evaluated for their antiproliferative effect in vitro against the cells of various human tumor cell lines (Matysiak & Opolski, 2006). Some derivatives have effective antibacterial activity. They are of great potential value for killing bacteria (Alireza et al. 2005). In addition, this kind of compounds are known to exhibit diverse biological effects, such as insecticidal activity (Wang et al. 1999).

Herein we report on the crystal structure of the titled compound, (I). The molecular structure of (I) is shown in Fig. 1. The bond lengths (Allen et al. 1987) and angles are within normal ranges. In this structure, there are three rings, ring A (C1/C2/C3/C4/C5/C6), ring B (N1/C7/S/C8/N2) and ring C (C10/C11/C12/C13/C14/C15), all of which are almost planar. Ring B(N1/C7/S/C8/N2) is a planar five-membered ring and the mean deviation from plane is 0.0020 Å. The dihedral angle between ring A and ring B is 4.1 (3)°, ring B and ring C is 2.3 (3)°. In the crystal structure, intermolecular C11—H11···O3 and O1W—H1W···N2 hydrogen bonds (Table 1.) link the molecules to form network structure (Fig. 2), in which they may be effective for the stabilization of the structure.

Related literature top

For general background to 1,3,4-thiadiazole derivatives, see: Matysiak & Opolski (2006). Alireza et al. (2005). Wang et al. (1999). For bond-length data, see: Allen et al. (1987). For the synthesis, see: Kurzer (1971).

Experimental top

3-Methoxy-phthalic anhydride(8 mmol) and 2-(2-methoxyphenyl)-5-hydroxy-1,3,4-thiadiazol(8 mmol) were added in ethanol(50 ml) (Kurzer, 1971). The mixture was refluxed for 5 h. Reactions were monitored by thin-layer chromatography (TLC) with visualization by ultraviolet light and then the solvent was totally evaporated. Then the white power was obtained. The solid was recrystallized from tetrahydrofuran to give the compound (I) (m.p. 520 K). Crystals of (I) suitable for X-ray diffraction were obtained by slow evaporation of a mixed solution of chloroform and tetrahydrofuran.

Refinement top

All H atoms were positioned geometrically, with C—H = 0.96 and 0.93 Å for methyl and aromatic H atoms, respectively and constrained to ride on their parent atoms with Uiso(H) = xUeq(C), where x = 1.5 for methyl H atoms and x =1. 2 for all other H atoms.

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXS97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. A view of the molecular structure of (I). Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. A packing diagram for (I). Dashed lines indicate intermolecular C—H···O and O—H···N hydrogen bonds.
5-(2-Methoxyphenyl)-1,3,4-thiadiazol-2-yl 2-methoxybenzoate hemihydrate top
Crystal data top
C17H14N2O4S·0.5H2OF(000) = 1464
Mr = 356.37Dx = 1.407 Mg m3
Monoclinic, C2/cMelting point: 520 K
Hall symbol: -C 2ycMo Kα radiation, λ = 0.71073 Å
a = 29.858 (6) ÅCell parameters from 25 reflections
b = 14.542 (3) Åθ = 9–13°
c = 7.6710 (15) ŵ = 0.22 mm1
β = 95.19 (3)°T = 293 K
V = 3317.1 (12) Å3Block, colorless
Z = 80.30 × 0.20 × 0.10 mm
Data collection top
Enraf–Nonius CAD-4
diffractometer
1881 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.025
graphiteθmax = 25.4°, θmin = 1.4°
ω/2θ scansh = 035
Absorption correction: ψ scan
(North et al., 1968)
k = 017
Tmin = 0.936, Tmax = 0.978l = 99
3108 measured reflections3 standard reflections every 200 reflections
3050 independent reflections intensity decay: 1%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.063Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.176H atoms treated by a mixture of independent and constrained refinement
S = 1.00 w = 1/[σ2(Fo2) + (0.098P)2]
where P = (Fo2 + 2Fc2)/3
3050 reflections(Δ/σ)max = 0.001
228 parametersΔρmax = 0.41 e Å3
0 restraintsΔρmin = 0.28 e Å3
Crystal data top
C17H14N2O4S·0.5H2OV = 3317.1 (12) Å3
Mr = 356.37Z = 8
Monoclinic, C2/cMo Kα radiation
a = 29.858 (6) ŵ = 0.22 mm1
b = 14.542 (3) ÅT = 293 K
c = 7.6710 (15) Å0.30 × 0.20 × 0.10 mm
β = 95.19 (3)°
Data collection top
Enraf–Nonius CAD-4
diffractometer
1881 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.025
Tmin = 0.936, Tmax = 0.978θmax = 25.4°
3108 measured reflections3 standard reflections every 200 reflections
3050 independent reflections intensity decay: 1%
Refinement top
R[F2 > 2σ(F2)] = 0.063H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.176Δρmax = 0.41 e Å3
S = 1.00Δρmin = 0.28 e Å3
3050 reflectionsAbsolute structure: ?
228 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

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
C10.05152 (13)0.3419 (3)0.6081 (4)0.0711 (11)
H10.02700.31100.64710.085*
C20.04737 (17)0.3882 (4)0.4474 (5)0.0932 (16)
H20.01950.39070.38270.112*
C30.08311 (19)0.4293 (3)0.3852 (5)0.0898 (14)
H30.08000.45700.27550.108*
C40.12303 (15)0.4305 (3)0.4795 (4)0.0698 (11)
H40.14720.46070.43630.084*
C50.12879 (12)0.3875 (2)0.6401 (4)0.0525 (9)
C60.09271 (11)0.3426 (2)0.7089 (4)0.0490 (8)
C70.09536 (10)0.2968 (2)0.8806 (4)0.0441 (7)
C80.10712 (11)0.2309 (3)1.1613 (5)0.0540 (9)
C90.16054 (10)0.2020 (2)1.4126 (4)0.0438 (7)
C100.16644 (9)0.1570 (2)1.5889 (3)0.0385 (7)
C110.20815 (11)0.1655 (2)1.6793 (4)0.0527 (8)
H110.23020.19891.62880.063*
C120.21841 (13)0.1272 (3)1.8389 (5)0.0630 (10)
H120.24690.13501.89660.076*
C130.18718 (14)0.0778 (3)1.9137 (5)0.0707 (11)
H130.19450.05032.02200.085*
C140.14490 (13)0.0674 (2)1.8324 (4)0.0597 (10)
H140.12350.03361.88610.072*
C150.13365 (10)0.1075 (2)1.6690 (4)0.0419 (7)
C160.20649 (14)0.4248 (3)0.6754 (6)0.1006 (16)
H16A0.21140.39350.56870.151*
H16B0.23230.41730.75820.151*
H16C0.20170.48910.65170.151*
C170.05776 (12)0.0530 (3)1.6602 (5)0.0806 (13)
H17A0.06730.00861.68950.121*
H17B0.03100.05101.58110.121*
H17C0.05170.08511.76490.121*
N10.06100 (9)0.2548 (2)0.9303 (3)0.0558 (8)
N20.06703 (10)0.2169 (2)1.0882 (4)0.0720 (9)
O10.16829 (8)0.38751 (17)0.7453 (3)0.0615 (7)
O20.11766 (6)0.19761 (15)1.3039 (3)0.0518 (6)
O30.19112 (7)0.24147 (19)1.3498 (3)0.0691 (8)
O40.09264 (7)0.10003 (17)1.5783 (3)0.0561 (6)
S0.14064 (3)0.29401 (7)1.03358 (11)0.0554 (3)
O1W0.00000.1206 (3)0.25000.1159 (19)
H1W0.019 (3)0.159 (6)0.167 (12)0.40 (7)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.073 (3)0.091 (3)0.048 (2)0.003 (2)0.0013 (19)0.009 (2)
C20.102 (4)0.126 (4)0.048 (2)0.029 (3)0.017 (2)0.006 (3)
C30.134 (4)0.093 (4)0.043 (2)0.019 (3)0.009 (3)0.021 (2)
C40.120 (3)0.055 (2)0.0386 (19)0.004 (2)0.028 (2)0.0050 (17)
C50.077 (2)0.045 (2)0.0388 (17)0.0061 (17)0.0212 (17)0.0022 (15)
C60.058 (2)0.058 (2)0.0316 (15)0.0035 (16)0.0110 (14)0.0026 (15)
C70.0462 (17)0.0501 (19)0.0380 (16)0.0056 (15)0.0142 (13)0.0003 (14)
C80.0469 (19)0.061 (2)0.056 (2)0.0099 (17)0.0134 (16)0.0026 (18)
C90.0421 (16)0.0516 (19)0.0399 (16)0.0055 (15)0.0158 (13)0.0057 (15)
C100.0419 (16)0.0449 (18)0.0302 (14)0.0043 (14)0.0117 (12)0.0022 (13)
C110.0518 (19)0.063 (2)0.0444 (18)0.0056 (17)0.0107 (15)0.0064 (16)
C120.060 (2)0.075 (3)0.053 (2)0.014 (2)0.0012 (18)0.0072 (19)
C130.094 (3)0.069 (3)0.048 (2)0.013 (2)0.001 (2)0.0129 (19)
C140.087 (3)0.052 (2)0.0433 (18)0.007 (2)0.0264 (19)0.0063 (16)
C150.0541 (17)0.0398 (17)0.0337 (15)0.0006 (15)0.0149 (14)0.0012 (13)
C160.099 (3)0.110 (4)0.100 (3)0.052 (3)0.049 (3)0.003 (3)
C170.071 (2)0.099 (3)0.077 (3)0.038 (2)0.031 (2)0.006 (2)
N10.0557 (17)0.074 (2)0.0391 (15)0.0111 (15)0.0085 (13)0.0099 (14)
N20.068 (2)0.090 (3)0.0583 (19)0.0133 (19)0.0061 (16)0.0060 (18)
O10.0687 (16)0.0657 (17)0.0538 (14)0.0200 (13)0.0250 (13)0.0021 (12)
O20.0355 (11)0.0463 (13)0.0756 (16)0.0102 (10)0.0167 (11)0.0032 (12)
O30.0611 (15)0.100 (2)0.0479 (14)0.0212 (14)0.0167 (11)0.0271 (13)
O40.0523 (13)0.0682 (16)0.0502 (13)0.0190 (12)0.0183 (11)0.0020 (11)
S0.0537 (5)0.0621 (6)0.0523 (5)0.0108 (4)0.0158 (4)0.0026 (4)
O1W0.083 (3)0.086 (3)0.187 (6)0.0000.060 (3)0.000
Geometric parameters (Å, °) top
C1—C61.392 (5)C10—C151.401 (4)
C1—C21.401 (5)C11—C121.355 (4)
C1—H10.9300C11—H110.9300
C2—C31.347 (6)C12—C131.346 (5)
C2—H20.9300C12—H120.9300
C3—C41.338 (5)C13—C141.365 (5)
C3—H30.9300C13—H130.9300
C4—C51.378 (5)C14—C151.396 (4)
C4—H40.9300C14—H140.9300
C5—O11.367 (4)C15—O41.357 (4)
C5—C61.403 (4)C16—O11.412 (4)
C6—C71.472 (4)C16—H16A0.9600
C7—N11.282 (4)C16—H16B0.9600
C7—S1.709 (3)C16—H16C0.9600
C8—O21.212 (4)C17—O41.437 (4)
C8—N21.291 (4)C17—H17A0.9600
C8—S1.726 (4)C17—H17B0.9600
C9—O31.214 (3)C17—H17C0.9600
C9—O21.465 (4)N1—N21.328 (4)
C9—C101.499 (4)O1W—H1W1.05 (8)
C10—C111.375 (4)
C6—C1—C2119.2 (4)C10—C11—H11118.7
C6—C1—H1120.4C13—C12—C11119.7 (4)
C2—C1—H1120.4C13—C12—H12120.1
C3—C2—C1121.0 (4)C11—C12—H12120.1
C3—C2—H2119.5C12—C13—C14120.8 (3)
C1—C2—H2119.5C12—C13—H13119.6
C4—C3—C2120.7 (4)C14—C13—H13119.6
C4—C3—H3119.7C13—C14—C15120.1 (3)
C2—C3—H3119.7C13—C14—H14119.9
C3—C4—C5120.7 (4)C15—C14—H14119.9
C3—C4—H4119.6O4—C15—C14124.1 (3)
C5—C4—H4119.6O4—C15—C10116.8 (3)
O1—C5—C4124.0 (3)C14—C15—C10119.2 (3)
O1—C5—C6115.4 (3)O1—C16—H16A109.5
C4—C5—C6120.6 (4)O1—C16—H16B109.5
C1—C6—C5117.7 (3)H16A—C16—H16B109.5
C1—C6—C7117.8 (3)O1—C16—H16C109.5
C5—C6—C7124.5 (3)H16A—C16—H16C109.5
N1—C7—C6120.2 (3)H16B—C16—H16C109.5
N1—C7—S112.9 (2)O4—C17—H17A109.5
C6—C7—S126.9 (2)O4—C17—H17B109.5
O2—C8—N2118.9 (3)H17A—C17—H17B109.5
O2—C8—S127.5 (3)O4—C17—H17C109.5
N2—C8—S113.6 (3)H17A—C17—H17C109.5
O3—C9—O2116.4 (3)H17B—C17—H17C109.5
O3—C9—C10122.2 (3)C7—N1—N2115.0 (3)
O2—C9—C10121.3 (2)C8—N2—N1112.0 (3)
C11—C10—C15117.5 (3)C5—O1—C16117.3 (3)
C11—C10—C9116.3 (3)C8—O2—C9129.7 (3)
C15—C10—C9126.2 (3)C15—O4—C17118.0 (3)
C12—C11—C10122.6 (3)C7—S—C886.50 (16)
C12—C11—H11118.7
C6—C1—C2—C33.4 (7)C13—C14—C15—O4179.4 (3)
C1—C2—C3—C43.2 (8)C13—C14—C15—C100.9 (5)
C2—C3—C4—C51.9 (7)C11—C10—C15—O4179.8 (3)
C3—C4—C5—O1178.6 (4)C9—C10—C15—O40.4 (4)
C3—C4—C5—C60.8 (6)C11—C10—C15—C141.6 (4)
C2—C1—C6—C52.3 (5)C9—C10—C15—C14178.2 (3)
C2—C1—C6—C7177.3 (3)C6—C7—N1—N2179.3 (3)
O1—C5—C6—C1179.0 (3)S—C7—N1—N20.5 (4)
C4—C5—C6—C11.0 (5)O2—C8—N2—N1177.8 (3)
O1—C5—C6—C70.5 (5)S—C8—N2—N10.1 (4)
C4—C5—C6—C7178.4 (3)C7—N1—N2—C80.4 (5)
C1—C6—C7—N12.8 (5)C4—C5—O1—C167.5 (5)
C5—C6—C7—N1177.7 (3)C6—C5—O1—C16174.6 (3)
C1—C6—C7—S175.8 (3)N2—C8—O2—C9179.1 (3)
C5—C6—C7—S3.7 (5)S—C8—O2—C91.8 (5)
O3—C9—C10—C112.2 (5)O3—C9—O2—C83.4 (5)
O2—C9—C10—C11179.9 (3)C10—C9—O2—C8178.8 (3)
O3—C9—C10—C15177.7 (3)C14—C15—O4—C174.1 (5)
O2—C9—C10—C150.1 (5)C10—C15—O4—C17177.4 (3)
C15—C10—C11—C120.9 (5)N1—C7—S—C80.4 (3)
C9—C10—C11—C12179.0 (3)C6—C7—S—C8179.1 (3)
C10—C11—C12—C130.7 (6)O2—C8—S—C7177.3 (4)
C11—C12—C13—C141.4 (6)N2—C8—S—C70.2 (3)
C12—C13—C14—C150.7 (6)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W···N2i1.05 (9)1.81 (9)2.821 (4)159 (7)
C11—H11···O3ii0.932.503.324 (4)148
Symmetry codes: (i) x, y, z−1; (ii) −x+1/2, −y+1/2, −z+3.
Table 1
Hydrogen-bond geometry (Å, °)
top
D—H···AD—HH···AD···AD—H···A
O1W—H1W···N2i1.05 (9)1.81 (9)2.821 (4)159 (7)
C11—H11···O3ii0.932.503.324 (4)148
Symmetry codes: (i) x, y, z−1; (ii) −x+1/2, −y+1/2, −z+3.
Acknowledgements top

The authors would like to thank Professor Hua-qin Wang of Nanjing University, for carrying out the X-ray crystallographic analysis.

references
References top

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