


Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536810029879/ng5002sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536810029879/ng5002Isup2.hkl |
CCDC reference: 788517
Key indicators
- Single-crystal X-ray study
- T = 113 K
- Mean
(C-C) = 0.003 Å
- R factor = 0.046
- wR factor = 0.113
- Data-to-parameter ratio = 19.5
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C10 PLAT034_ALERT_1_C No Flack Parameter Given. Z .GT. Si, NonCentro . ?
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 27.87 From the CIF: _reflns_number_total 3019 Count of symmetry unique reflns 1783 Completeness (_total/calc) 169.32% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 1236 Fraction of Friedel pairs measured 0.693 Are heavy atom types Z>Si present yes PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 19 C9 -N2 -C12 -N3 18.00 0.00 1.555 1.555 1.555 1.555 PLAT791_ALERT_4_G Note: The Model has Chirality at C7 (Verify) R
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 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 0 ALERT type 3 Indicator that the structure quality may be low 3 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
(Z)-(thiazolidin-2-ylideneamino)formonitrile 1.27 g (10.0 mmol) and potassium carbonate (10.0 mmol) were dissolved in N,N-dimethylformamide(DMF) (15 ml) which was stirred 0.5 h at room temperature. Then 1-chloro-4-(1-chloroethyl)benzene 1.75 g (10.0 mmol) was added dropwising within 2 h at 283 K. The mixture was stirred for 8 h at 428 K. Upon cooling at room temperature. Then water (20 ml) was added. The mixture was extracted with CH2Cl2 (15 ml) and the organic layer was washed with water and dried over anhydrous sodium sulfate. The excess CH2Cl2 was removed on a water vacuum pump to obtain the oily product. Crystallized from methanol to afford the title compound 2.0 g (76% yield) (Jeschke, et al., 2002.). Single crystals suitable for X-ray measurement were obtained by recrystallization from the mixture of acetone and methanol at room temperature.
All C-bound H atoms were placed in calculated positions, with C—H = 0.93–0.98 Å, and included in the final cycles of refinement using a riding model, with Uiso(H) = 1.2Ueq(C) for the aryl and 1.5 Ueq(C) for methyl H atoms. Friedel pairs = 6200.
Recently, compounds containing the 2-(thiazolidin-2-ylidene)malononitrile group have attracted much interest because its containing a thiazole ring system are well known as efficient insecticide in pesticides, and have good plant-growth regulatory activity for a wide variety of crops e.g. thiacloprid (Hense et al., 2002). A new compound, (I), which containing thiazole ring has higher insecticide activity. We report here the crystal structure and synthesis of (I).
In (I) (Fig. 1), the bond lengths and angles are normal and in a agreement with those common to a previously reported structure (Cunico, et al., 2007). The thiazole ring is in and envelope conformation with the –CH2– group bonded to the S atom forming the flap. The carbon-nitrogen double bond of the molecule is trans. Flack x parameter = -0.0865 (with e.s.d. 0.0872) (Flack, 1983). The crystal structure involves C—H···S intermolecular hydrogen bonds.
For the biological activity of thiazole componds, see: Hense et al. (2002). For a related structure, see: Cunico, et al. (2007). For the synthesis, see: Jeschke et al. (2002).
Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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).
![]() | Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 40% probability level. |
C12H12ClN3S | F(000) = 552 |
Mr = 265.76 | Dx = 1.397 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 193 reflections |
a = 5.8850 (12) Å | θ = 1.4–27.9° |
b = 7.5965 (15) Å | µ = 0.45 mm−1 |
c = 28.273 (6) Å | T = 113 K |
V = 1264.0 (4) Å3 | Block, white |
Z = 4 | 0.14 × 0.12 × 0.10 mm |
Rigaku Saturn diffractometer | 3019 independent reflections |
Radiation source: rotating anode | 2640 reflections with I > 2σ(I) |
Confocal monochromator | Rint = 0.062 |
ω scans | θmax = 27.9°, θmin = 1.4° |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | h = −7→7 |
Tmin = 0.940, Tmax = 0.957 | k = −9→8 |
9219 measured reflections | l = −29→37 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.046 | H-atom parameters constrained |
wR(F2) = 0.113 | w = 1/[σ2(Fo2) + (0.0534P)2 + 0.0295P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max = 0.001 |
3019 reflections | Δρmax = 0.38 e Å−3 |
155 parameters | Δρmin = −0.34 e Å−3 |
0 restraints | Absolute structure: Flack (1983), 6200 Friedel pairs |
Primary atom site location: structure-invariant direct methods |
C12H12ClN3S | V = 1264.0 (4) Å3 |
Mr = 265.76 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 5.8850 (12) Å | µ = 0.45 mm−1 |
b = 7.5965 (15) Å | T = 113 K |
c = 28.273 (6) Å | 0.14 × 0.12 × 0.10 mm |
Rigaku Saturn diffractometer | 3019 independent reflections |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | 2640 reflections with I > 2σ(I) |
Tmin = 0.940, Tmax = 0.957 | Rint = 0.062 |
9219 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.113 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.38 e Å−3 |
3019 reflections | Δρmin = −0.34 e Å−3 |
155 parameters | Absolute structure: Flack (1983), 6200 Friedel pairs |
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 | ||
Cl1 | 0.31420 (16) | −0.62970 (7) | 0.98241 (2) | 0.0438 (2) | |
S1 | 0.18444 (12) | 0.16944 (8) | 0.77090 (2) | 0.03081 (17) | |
N2 | 0.2773 (4) | 0.3380 (3) | 0.85392 (7) | 0.0279 (4) | |
C9 | 0.3024 (4) | 0.1982 (3) | 0.82718 (8) | 0.0238 (5) | |
C1 | 0.2990 (4) | −0.1331 (3) | 0.93777 (8) | 0.0267 (5) | |
H1 | 0.2024 | −0.0368 | 0.9407 | 0.032* | |
N1 | 0.4250 (4) | 0.0594 (2) | 0.84129 (6) | 0.0255 (5) | |
C6 | 0.4992 (4) | −0.1158 (3) | 0.91192 (8) | 0.0242 (5) | |
C7 | 0.5466 (4) | 0.0572 (3) | 0.88698 (8) | 0.0257 (5) | |
H7 | 0.4806 | 0.1507 | 0.9065 | 0.031* | |
C8 | 0.7950 (5) | 0.1029 (4) | 0.87970 (9) | 0.0369 (6) | |
H8A | 0.8064 | 0.2125 | 0.8630 | 0.055* | |
H8B | 0.8672 | 0.0117 | 0.8616 | 0.055* | |
H8C | 0.8686 | 0.1135 | 0.9099 | 0.055* | |
C12 | 0.1462 (5) | 0.4672 (3) | 0.83801 (8) | 0.0294 (6) | |
C2 | 0.2409 (4) | −0.2905 (3) | 0.95914 (8) | 0.0288 (5) | |
H2 | 0.1055 | −0.3011 | 0.9759 | 0.035* | |
C4 | 0.5886 (5) | −0.4192 (3) | 0.93042 (9) | 0.0316 (6) | |
H4 | 0.6860 | −0.5152 | 0.9284 | 0.038* | |
C3 | 0.3874 (5) | −0.4315 (3) | 0.95515 (8) | 0.0285 (5) | |
N3 | 0.0347 (5) | 0.5868 (3) | 0.82737 (8) | 0.0414 (6) | |
C5 | 0.6432 (5) | −0.2610 (3) | 0.90865 (8) | 0.0292 (6) | |
H5 | 0.7778 | −0.2518 | 0.8916 | 0.035* | |
C11 | 0.4588 (7) | −0.0759 (4) | 0.80600 (9) | 0.0479 (8) | |
H11A | 0.6166 | −0.0769 | 0.7961 | 0.058* | |
H11B | 0.4235 | −0.1901 | 0.8195 | 0.058* | |
C10 | 0.3144 (8) | −0.0437 (4) | 0.76555 (12) | 0.0648 (12) | |
H10A | 0.1977 | −0.1336 | 0.7638 | 0.078* | |
H10B | 0.4039 | −0.0488 | 0.7368 | 0.078* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0702 (5) | 0.0288 (3) | 0.0324 (4) | −0.0048 (3) | 0.0066 (4) | 0.0021 (3) |
S1 | 0.0384 (4) | 0.0355 (3) | 0.0185 (3) | −0.0011 (3) | −0.0028 (3) | 0.0002 (2) |
N2 | 0.0319 (11) | 0.0266 (9) | 0.0252 (11) | −0.0013 (9) | −0.0015 (9) | −0.0014 (8) |
C9 | 0.0227 (11) | 0.0302 (11) | 0.0186 (11) | −0.0047 (10) | 0.0030 (10) | 0.0020 (8) |
C1 | 0.0253 (12) | 0.0304 (11) | 0.0246 (12) | 0.0062 (11) | 0.0008 (10) | 0.0000 (9) |
N1 | 0.0305 (11) | 0.0255 (10) | 0.0204 (11) | 0.0005 (9) | −0.0029 (9) | −0.0032 (8) |
C6 | 0.0232 (11) | 0.0293 (11) | 0.0201 (12) | −0.0007 (9) | −0.0038 (9) | −0.0022 (9) |
C7 | 0.0267 (12) | 0.0289 (12) | 0.0215 (13) | −0.0010 (10) | −0.0029 (10) | −0.0016 (9) |
C8 | 0.0319 (14) | 0.0419 (14) | 0.0368 (16) | −0.0080 (13) | −0.0029 (12) | 0.0067 (12) |
C12 | 0.0371 (15) | 0.0332 (12) | 0.0179 (12) | −0.0011 (11) | 0.0008 (10) | −0.0010 (9) |
C2 | 0.0284 (13) | 0.0332 (12) | 0.0249 (13) | −0.0021 (10) | 0.0014 (10) | −0.0010 (10) |
C4 | 0.0376 (14) | 0.0252 (11) | 0.0319 (14) | 0.0079 (11) | −0.0017 (11) | −0.0064 (10) |
C3 | 0.0386 (14) | 0.0260 (11) | 0.0210 (13) | −0.0031 (11) | −0.0019 (10) | −0.0016 (10) |
N3 | 0.0575 (17) | 0.0394 (12) | 0.0273 (13) | 0.0087 (12) | −0.0025 (11) | −0.0006 (10) |
C5 | 0.0296 (14) | 0.0329 (11) | 0.0252 (14) | 0.0034 (11) | 0.0024 (10) | −0.0026 (10) |
C11 | 0.069 (2) | 0.0489 (16) | 0.0254 (15) | 0.0203 (17) | −0.0048 (14) | −0.0132 (13) |
C10 | 0.097 (3) | 0.0508 (18) | 0.046 (2) | 0.027 (2) | −0.038 (2) | −0.0243 (14) |
Cl1—C3 | 1.746 (2) | C8—H8A | 0.9600 |
S1—C9 | 1.750 (2) | C8—H8B | 0.9600 |
S1—C10 | 1.797 (3) | C8—H8C | 0.9600 |
N2—C9 | 1.311 (3) | C12—N3 | 1.161 (3) |
N2—C12 | 1.327 (3) | C2—C3 | 1.380 (4) |
C9—N1 | 1.338 (3) | C2—H2 | 0.9300 |
C1—C2 | 1.383 (3) | C4—C3 | 1.378 (4) |
C1—C6 | 1.393 (3) | C4—C5 | 1.388 (3) |
C1—H1 | 0.9300 | C4—H4 | 0.9300 |
N1—C11 | 1.446 (3) | C5—H5 | 0.9300 |
N1—C7 | 1.477 (3) | C11—C10 | 1.446 (4) |
C6—C5 | 1.394 (3) | C11—H11A | 0.9700 |
C6—C7 | 1.517 (3) | C11—H11B | 0.9700 |
C7—C8 | 1.516 (4) | C10—H10A | 0.9700 |
C7—H7 | 0.9800 | C10—H10B | 0.9700 |
C9—S1—C10 | 91.16 (13) | N3—C12—N2 | 174.7 (3) |
C9—N2—C12 | 118.0 (2) | C3—C2—C1 | 118.8 (2) |
N2—C9—N1 | 121.8 (2) | C3—C2—H2 | 120.6 |
N2—C9—S1 | 125.49 (18) | C1—C2—H2 | 120.6 |
N1—C9—S1 | 112.73 (17) | C3—C4—C5 | 118.9 (2) |
C2—C1—C6 | 121.3 (2) | C3—C4—H4 | 120.6 |
C2—C1—H1 | 119.3 | C5—C4—H4 | 120.6 |
C6—C1—H1 | 119.3 | C4—C3—C2 | 121.7 (2) |
C9—N1—C11 | 115.4 (2) | C4—C3—Cl1 | 119.64 (19) |
C9—N1—C7 | 122.06 (19) | C2—C3—Cl1 | 118.6 (2) |
C11—N1—C7 | 121.9 (2) | C4—C5—C6 | 121.0 (2) |
C1—C6—C5 | 118.3 (2) | C4—C5—H5 | 119.5 |
C1—C6—C7 | 118.8 (2) | C6—C5—H5 | 119.5 |
C5—C6—C7 | 122.9 (2) | C10—C11—N1 | 110.1 (2) |
N1—C7—C8 | 110.2 (2) | C10—C11—H11A | 109.6 |
N1—C7—C6 | 109.10 (19) | N1—C11—H11A | 109.6 |
C8—C7—C6 | 116.0 (2) | C10—C11—H11B | 109.6 |
N1—C7—H7 | 107.0 | N1—C11—H11B | 109.6 |
C8—C7—H7 | 107.0 | H11A—C11—H11B | 108.1 |
C6—C7—H7 | 107.0 | C11—C10—S1 | 109.6 (2) |
C7—C8—H8A | 109.5 | C11—C10—H10A | 109.7 |
C7—C8—H8B | 109.5 | S1—C10—H10A | 109.7 |
H8A—C8—H8B | 109.5 | C11—C10—H10B | 109.7 |
C7—C8—H8C | 109.5 | S1—C10—H10B | 109.7 |
H8A—C8—H8C | 109.5 | H10A—C10—H10B | 108.2 |
H8B—C8—H8C | 109.5 | ||
C12—N2—C9—N1 | −177.6 (2) | C1—C6—C7—C8 | 152.3 (2) |
C12—N2—C9—S1 | 2.1 (3) | C5—C6—C7—C8 | −30.3 (3) |
C10—S1—C9—N2 | 179.1 (3) | C9—N2—C12—N3 | 177 (100) |
C10—S1—C9—N1 | −1.1 (2) | C6—C1—C2—C3 | 1.1 (4) |
N2—C9—N1—C11 | −173.2 (2) | C5—C4—C3—C2 | −0.6 (4) |
S1—C9—N1—C11 | 7.0 (3) | C5—C4—C3—Cl1 | 179.5 (2) |
N2—C9—N1—C7 | −2.4 (4) | C1—C2—C3—C4 | −0.2 (4) |
S1—C9—N1—C7 | 177.89 (18) | C1—C2—C3—Cl1 | 179.7 (2) |
C2—C1—C6—C5 | −1.1 (4) | C3—C4—C5—C6 | 0.6 (4) |
C2—C1—C6—C7 | 176.5 (2) | C1—C6—C5—C4 | 0.2 (4) |
C9—N1—C7—C8 | −98.3 (3) | C7—C6—C5—C4 | −177.3 (2) |
C11—N1—C7—C8 | 72.0 (3) | C9—N1—C11—C10 | −10.7 (4) |
C9—N1—C7—C6 | 133.2 (2) | C7—N1—C11—C10 | 178.5 (3) |
C11—N1—C7—C6 | −56.5 (3) | N1—C11—C10—S1 | 9.2 (4) |
C1—C6—C7—N1 | −82.5 (3) | C9—S1—C10—C11 | −4.8 (3) |
C5—C6—C7—N1 | 94.9 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C10—H10A···S1i | 0.97 | 2.87 | 3.799 (4) | 160 |
Symmetry code: (i) −x, y−1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | C12H12ClN3S |
Mr | 265.76 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 113 |
a, b, c (Å) | 5.8850 (12), 7.5965 (15), 28.273 (6) |
V (Å3) | 1264.0 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.45 |
Crystal size (mm) | 0.14 × 0.12 × 0.10 |
Data collection | |
Diffractometer | Rigaku Saturn |
Absorption correction | Multi-scan (CrystalClear; Rigaku, 2005) |
Tmin, Tmax | 0.940, 0.957 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9219, 3019, 2640 |
Rint | 0.062 |
(sin θ/λ)max (Å−1) | 0.658 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.113, 1.06 |
No. of reflections | 3019 |
No. of parameters | 155 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.38, −0.34 |
Absolute structure | Flack (1983), 6200 Friedel pairs |
Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
C10—H10A···S1i | 0.97 | 2.87 | 3.799 (4) | 159.8 |
Symmetry code: (i) −x, y−1/2, −z+3/2. |
Recently, compounds containing the 2-(thiazolidin-2-ylidene)malononitrile group have attracted much interest because its containing a thiazole ring system are well known as efficient insecticide in pesticides, and have good plant-growth regulatory activity for a wide variety of crops e.g. thiacloprid (Hense et al., 2002). A new compound, (I), which containing thiazole ring has higher insecticide activity. We report here the crystal structure and synthesis of (I).
In (I) (Fig. 1), the bond lengths and angles are normal and in a agreement with those common to a previously reported structure (Cunico, et al., 2007). The thiazole ring is in and envelope conformation with the –CH2– group bonded to the S atom forming the flap. The carbon-nitrogen double bond of the molecule is trans. Flack x parameter = -0.0865 (with e.s.d. 0.0872) (Flack, 1983). The crystal structure involves C—H···S intermolecular hydrogen bonds.