supplementary materials


cv5400 scheme

Acta Cryst. (2013). E69, o714    [ doi:10.1107/S1600536813009239 ]

(3-Chlorophenyl)[(E)-2-(1,3-dithiolan-2-ylidene)hydrazinylidene]methyl 3-chlorobenzoate

L. Yin

Abstract top

In the title compound, C17H12Cl2N2O2S2, the dithiacyclopentane ring has an envelope conformation with one of the methylene C atoms as the flap. The chlorophenyl rings make a dihedral angle of 82.63 (7)°. In the crystal, [pi]-[pi] interactions between the benzene rings of neighbouring molecules [centroid-centroid distance = 3.547 (2) Å] link the molecules into inversion dimers. Weak non-classical C-H...X (X = O, N, Cl) interactions further consolidate the packing, forming a layer structure parallel to (110).

Comment top

Many dithiolan heterocyclic compounds have been widely used as potent and broad-spectrum fungicides (Tanaka et al., 1976; Wang et al., 1994). In order to search for new heterocylic compounds with higher biological activities, we synthesized the (E)-((1,3-dithiolan-2-yl)diazenyl)(3-chlorophenyl)methyl 3-chlorobenzoate (I) and described its structure here.

In (I) (Fig. 1), the dithiacyclopentane ring has an envelope conformation with C16 atom as a flap. Two chlorophenyl rings (C1—C6 and C9—C14) in the molecule form a dihedral angle of 82.63 (7)°. All bond lengths and angles are normal and in a good agreement with those reported previously for related compounds (Yin, 2013)

In the crystal, π-π interactions between the benzene rings from two neighbouring molecules [centroid-centroid distance of 3.547 (2) Å] link the latters into centrosymmetric dimer, and weak non-classical C—H···X (X=O, N, Cl) interactions (Table 1) consolidate further the packing.

Related literature top

For applications of heterocyclic dithiolane compounds, see: Tanaka et al. (1976); Wang et al. (1994). For the crystal structure of (E)-[2-(1,3-dithiolan-2-ylidene)hydrazinylidene](3-fluorophenyl)methyl 3-fluorobenzoate, see: Yin (2013).

Experimental top

1.34 g (10 mmol) of (1,3-dithiolan-2-ylidene)hydrazine and 20 mmol triethylamine was dissolved in 15 ml of dichloromethane and stirred at room temperature, 3.50 g (20 mmol) 3-chlorobenzoyl chloride was added dropwise to the mixture. The reaction mixture was stirred vigorously at 0 centigrade for 4 h. The reaction mixture was poured into 200 ml of water and extracted with three 50-ml portions of dichloromethane. The combined extracts were washed with saturated brine, dried over anhydrous sodium sulfate and evaporated on a rotary evaporator to afford the crude product, which was purified by column chromatography to yield the pure product as colorless crystals. Single crystals suitable for X-ray diffraction were obtained through slow evaporation of a solution of the pure title compound in ethanol.

Refinement top

All H atoms bonded on carbon were found on difference maps, with C–H = 0.93 or 0.97 Å, and included in the final cycles of refinement using a riding model, with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: CrystalClear-SM Expert (Rigaku/MSC, 2009); cell refinement: CrystalClear-SM Expert (Rigaku/MSC, 2009); data reduction: CrystalClear-SM Expert (Rigaku/MSC, 2009); 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: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. View of the title compound showing the atomic numbering and 50% probability displacement ellipsoids.
(3-Chlorophenyl)[(E)-2-(1,3-dithiolan-2-ylidene)hydrazinylidene]methyl 3-chlorobenzoate top
Crystal data top
C17H12Cl2N2O2S2Z = 2
Mr = 411.31F(000) = 420
Triclinic, P1Dx = 1.585 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.960 (5) ÅCell parameters from 3010 reflections
b = 9.944 (6) Åθ = 2.1–27.9°
c = 11.128 (6) ŵ = 0.63 mm1
α = 104.174 (8)°T = 113 K
β = 111.041 (7)°Block, colourless
γ = 99.410 (2)°0.34 × 0.25 × 0.20 mm
V = 861.9 (8) Å3
Data collection top
Rigaku Saturn CCD area-detector
diffractometer
4080 independent reflections
Radiation source: rotating anode3115 reflections with I > 2σ(I)
Multilayer monochromatorRint = 0.034
Detector resolution: 14.63 pixels mm-1θmax = 27.9°, θmin = 2.1°
ω and φ scansh = 1111
Absorption correction: multi-scan
(CrystalClear-SM Expert; Rigaku/MSC, 2009)
k = 1313
Tmin = 0.884, Tmax = 0.884l = 1414
11088 measured reflections
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)] = 0.030Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.074H-atom parameters constrained
S = 0.95 w = 1/[σ2(Fo2) + (0.0343P)2]
where P = (Fo2 + 2Fc2)/3
4080 reflections(Δ/σ)max = 0.001
226 parametersΔρmax = 0.46 e Å3
0 restraintsΔρmin = 0.22 e Å3
Crystal data top
C17H12Cl2N2O2S2γ = 99.410 (2)°
Mr = 411.31V = 861.9 (8) Å3
Triclinic, P1Z = 2
a = 8.960 (5) ÅMo Kα radiation
b = 9.944 (6) ŵ = 0.63 mm1
c = 11.128 (6) ÅT = 113 K
α = 104.174 (8)°0.34 × 0.25 × 0.20 mm
β = 111.041 (7)°
Data collection top
Rigaku Saturn CCD area-detector
diffractometer
4080 independent reflections
Absorption correction: multi-scan
(CrystalClear-SM Expert; Rigaku/MSC, 2009)
3115 reflections with I > 2σ(I)
Tmin = 0.884, Tmax = 0.884Rint = 0.034
11088 measured reflectionsθmax = 27.9°
Refinement top
R[F2 > 2σ(F2)] = 0.030H-atom parameters constrained
wR(F2) = 0.074Δρmax = 0.46 e Å3
S = 0.95Δρmin = 0.22 e Å3
4080 reflectionsAbsolute structure: ?
226 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
S10.30877 (5)0.64714 (4)0.23284 (4)0.02513 (11)
S20.09584 (5)0.34521 (4)0.09623 (4)0.02211 (11)
Cl10.52910 (5)0.06840 (4)0.12078 (4)0.03188 (12)
Cl20.10357 (5)1.00841 (4)0.89309 (4)0.02569 (11)
O10.11886 (13)0.59701 (10)0.42806 (10)0.0180 (2)
O20.27715 (13)0.66856 (11)0.26079 (10)0.0234 (3)
N10.07149 (15)0.43373 (13)0.26298 (12)0.0168 (3)
N20.05526 (15)0.55241 (13)0.28369 (13)0.0203 (3)
C10.3769 (2)0.38581 (18)0.40729 (17)0.0269 (4)
H1B0.34380.48070.46990.032*
C20.5067 (2)0.2817 (2)0.39886 (19)0.0356 (4)
H2B0.56290.30600.45550.043*
C30.5555 (2)0.1434 (2)0.30938 (18)0.0320 (4)
H3A0.64540.07250.30340.038*
C40.47179 (19)0.10906 (17)0.22822 (15)0.0222 (4)
C50.34232 (18)0.21123 (16)0.23301 (14)0.0180 (3)
H5A0.28720.18630.17560.022*
C60.29455 (18)0.35118 (16)0.32354 (15)0.0173 (3)
C70.15643 (18)0.46156 (15)0.33172 (14)0.0163 (3)
C80.19326 (17)0.69437 (16)0.37966 (15)0.0167 (3)
C90.15680 (17)0.82978 (15)0.49075 (14)0.0156 (3)
C100.05798 (17)0.84909 (15)0.62690 (15)0.0162 (3)
H10A0.01680.77340.65230.019*
C110.02184 (18)0.98142 (16)0.72356 (14)0.0172 (3)
C120.08166 (18)1.09324 (16)0.68971 (15)0.0193 (3)
H12A0.05401.18350.75800.023*
C130.18269 (19)1.07119 (16)0.55451 (16)0.0213 (3)
H13A0.22651.14620.53000.026*
C140.21989 (18)0.94018 (16)0.45513 (16)0.0195 (3)
H14A0.28850.92570.36260.023*
C150.13750 (18)0.51590 (16)0.21249 (15)0.0172 (3)
C160.31996 (19)0.54981 (17)0.07793 (15)0.0225 (4)
H16A0.23930.56640.00130.027*
H16B0.43310.58320.08300.027*
C170.27909 (19)0.39074 (17)0.06257 (16)0.0246 (4)
H17A0.37440.37030.12780.030*
H17B0.25680.33190.03100.030*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0235 (2)0.0184 (2)0.0313 (2)0.00078 (17)0.01585 (19)0.00201 (18)
S20.0228 (2)0.0166 (2)0.0255 (2)0.00214 (17)0.01373 (18)0.00125 (17)
Cl10.0338 (2)0.0226 (2)0.0255 (2)0.00746 (19)0.00331 (19)0.00860 (18)
Cl20.0353 (2)0.0202 (2)0.0180 (2)0.00879 (18)0.00931 (17)0.00234 (16)
O10.0231 (6)0.0137 (5)0.0157 (5)0.0080 (5)0.0067 (4)0.0024 (4)
O20.0237 (6)0.0210 (6)0.0187 (6)0.0067 (5)0.0025 (5)0.0042 (5)
N10.0171 (6)0.0139 (6)0.0194 (6)0.0033 (5)0.0083 (5)0.0053 (5)
N20.0192 (7)0.0143 (7)0.0258 (7)0.0013 (5)0.0111 (6)0.0037 (6)
C10.0310 (10)0.0262 (9)0.0335 (9)0.0128 (8)0.0210 (8)0.0116 (8)
C20.0345 (10)0.0436 (11)0.0494 (12)0.0182 (9)0.0324 (10)0.0225 (10)
C30.0201 (9)0.0381 (11)0.0453 (11)0.0056 (8)0.0169 (8)0.0231 (9)
C40.0191 (8)0.0230 (9)0.0210 (8)0.0025 (7)0.0033 (7)0.0111 (7)
C50.0162 (8)0.0217 (8)0.0170 (7)0.0044 (7)0.0066 (6)0.0087 (7)
C60.0166 (7)0.0220 (8)0.0177 (8)0.0089 (7)0.0080 (6)0.0100 (6)
C70.0192 (8)0.0147 (8)0.0138 (7)0.0068 (6)0.0050 (6)0.0042 (6)
C80.0135 (7)0.0167 (8)0.0221 (8)0.0047 (6)0.0093 (6)0.0071 (6)
C90.0130 (7)0.0135 (7)0.0205 (8)0.0028 (6)0.0086 (6)0.0039 (6)
C100.0160 (7)0.0138 (7)0.0218 (8)0.0050 (6)0.0106 (6)0.0061 (6)
C110.0170 (8)0.0174 (8)0.0190 (8)0.0036 (6)0.0105 (6)0.0051 (6)
C120.0208 (8)0.0132 (8)0.0260 (8)0.0044 (6)0.0143 (7)0.0030 (6)
C130.0214 (8)0.0162 (8)0.0305 (9)0.0086 (7)0.0126 (7)0.0098 (7)
C140.0172 (8)0.0205 (8)0.0208 (8)0.0060 (7)0.0072 (6)0.0074 (7)
C150.0177 (8)0.0140 (7)0.0192 (8)0.0045 (6)0.0067 (6)0.0060 (6)
C160.0186 (8)0.0263 (9)0.0236 (8)0.0035 (7)0.0109 (7)0.0084 (7)
C170.0228 (9)0.0259 (9)0.0257 (9)0.0050 (7)0.0139 (7)0.0047 (7)
Geometric parameters (Å, º) top
S1—C151.7493 (17)C5—C61.394 (2)
S1—C161.8048 (18)C5—H5A0.9500
S2—C151.7507 (17)C6—C71.473 (2)
S2—C171.8228 (18)C8—C91.483 (2)
Cl1—C41.7427 (18)C9—C141.392 (2)
Cl2—C111.7393 (17)C9—C101.398 (2)
O1—C81.3713 (17)C10—C111.382 (2)
O1—C71.4008 (17)C10—H10A0.9500
O2—C81.1989 (18)C11—C121.386 (2)
N1—C71.2744 (19)C12—C131.388 (2)
N1—N21.4058 (18)C12—H12A0.9500
N2—C151.2917 (19)C13—C141.385 (2)
C1—C21.383 (2)C13—H13A0.9500
C1—C61.397 (2)C14—H14A0.9500
C1—H1B0.9500C16—C171.516 (2)
C2—C31.376 (3)C16—H16A0.9900
C2—H2B0.9500C16—H16B0.9900
C3—C41.384 (2)C17—H17A0.9900
C3—H3A0.9500C17—H17B0.9900
C4—C51.387 (2)
C15—S1—C1694.86 (8)C10—C9—C8121.62 (13)
C15—S2—C1795.15 (7)C11—C10—C9118.14 (13)
C8—O1—C7115.97 (11)C11—C10—H10A120.9
C7—N1—N2114.80 (13)C9—C10—H10A120.9
C15—N2—N1111.40 (13)C10—C11—C12122.18 (14)
C2—C1—C6119.91 (16)C10—C11—Cl2118.80 (11)
C2—C1—H1B120.0C12—C11—Cl2119.01 (12)
C6—C1—H1B120.0C11—C12—C13118.94 (14)
C3—C2—C1120.83 (16)C11—C12—H12A120.5
C3—C2—H2B119.6C13—C12—H12A120.5
C1—C2—H2B119.6C14—C13—C12120.22 (14)
C2—C3—C4119.02 (16)C14—C13—H13A119.9
C2—C3—H3A120.5C12—C13—H13A119.9
C4—C3—H3A120.5C13—C14—C9120.04 (14)
C3—C4—C5121.63 (16)C13—C14—H14A120.0
C3—C4—Cl1118.48 (13)C9—C14—H14A120.0
C5—C4—Cl1119.87 (13)N2—C15—S1118.01 (12)
C4—C5—C6118.83 (15)N2—C15—S2126.35 (12)
C4—C5—H5A120.6S1—C15—S2115.64 (9)
C6—C5—H5A120.6C17—C16—S1107.62 (11)
C5—C6—C1119.77 (14)C17—C16—H16A110.2
C5—C6—C7120.01 (13)S1—C16—H16A110.2
C1—C6—C7120.21 (14)C17—C16—H16B110.2
N1—C7—O1122.71 (13)S1—C16—H16B110.2
N1—C7—C6122.70 (14)H16A—C16—H16B108.5
O1—C7—C6114.45 (13)C16—C17—S2108.49 (11)
O2—C8—O1122.10 (14)C16—C17—H17A110.0
O2—C8—C9125.99 (14)S2—C17—H17A110.0
O1—C8—C9111.91 (12)C16—C17—H17B110.0
C14—C9—C10120.46 (13)S2—C17—H17B110.0
C14—C9—C8117.88 (13)H17A—C17—H17B108.4
C7—N1—N2—C15179.07 (13)O1—C8—C9—C14177.72 (12)
C6—C1—C2—C30.5 (3)O2—C8—C9—C10179.57 (14)
C1—C2—C3—C40.5 (3)O1—C8—C9—C100.29 (19)
C2—C3—C4—C51.3 (2)C14—C9—C10—C111.6 (2)
C2—C3—C4—Cl1177.27 (12)C8—C9—C10—C11176.34 (13)
C3—C4—C5—C60.9 (2)C9—C10—C11—C120.7 (2)
Cl1—C4—C5—C6177.58 (10)C9—C10—C11—Cl2179.01 (11)
C4—C5—C6—C10.1 (2)C10—C11—C12—C130.7 (2)
C4—C5—C6—C7179.44 (13)Cl2—C11—C12—C13179.55 (11)
C2—C1—C6—C50.8 (2)C11—C12—C13—C141.3 (2)
C2—C1—C6—C7179.86 (14)C12—C13—C14—C90.4 (2)
N2—N1—C7—O14.57 (19)C10—C9—C14—C131.1 (2)
N2—N1—C7—C6179.94 (12)C8—C9—C14—C13176.96 (13)
C8—O1—C7—N189.63 (17)N1—N2—C15—S1176.17 (9)
C8—O1—C7—C694.53 (15)N1—N2—C15—S23.35 (19)
C5—C6—C7—N13.2 (2)C16—S1—C15—N2163.32 (12)
C1—C6—C7—N1176.16 (14)C16—S1—C15—S217.11 (9)
C5—C6—C7—O1179.00 (11)C17—S2—C15—N2174.68 (14)
C1—C6—C7—O10.33 (19)C17—S2—C15—S14.84 (9)
C7—O1—C8—O24.5 (2)C15—S1—C16—C1737.74 (12)
C7—O1—C8—C9175.41 (12)S1—C16—C17—S245.83 (13)
O2—C8—C9—C142.4 (2)C15—S2—C17—C1630.73 (12)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C10—H10A···N1i0.952.593.534 (2)173
C14—H14A···Cl1ii0.952.803.727 (2)165
C16—H16B···O2iii0.992.483.274 (3)137
Symmetry codes: (i) x, y+1, z+1; (ii) x, y+1, z; (iii) x+1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C10—H10A···N1i0.952.593.534 (2)172.9
C14—H14A···Cl1ii0.952.803.727 (2)165.1
C16—H16B···O2iii0.992.483.274 (3)137.1
Symmetry codes: (i) x, y+1, z+1; (ii) x, y+1, z; (iii) x+1, y, z.
references
References top

Rigaku/MSC (2009). CrystalClear-SM Expert. Rigaku/MSC, The Woodlands, Texas, USA.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Tanaka, H., Araki, F., Harada, T. & Kurono, H. (1976). Jpn Patent No. 51151326A.

Wang, Y., Li, Z. H. & Gao, N. (1994). Yaoxue Xuebao, 29, 78–80.

Yin, L. (2013). Acta Cryst. E69, o571.