(Benzo­yl)[2-(cyano­imino)-1,3-thia­zolidin-2-yl]methyl acetate

The title compound, C₁₄H₁₃N₃O₃S, has been synthesized as a potent fungicidal agent. The 1,3-thia­zolidine ring is approximately planar and makes a dihedral angle of 84.9 (2)° with the phenyl ring. There are weak intra­molecular C—H...O and C—H...N hydrogen bonds, which stabilize the mol­ecular structure.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.043
• wR factor = 0.119
• Data-to-parameter ratio = 13.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    N2     -   C14     ..       6.92 su
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C9

Alert level G
PLAT793_ALERT_1_G Check the Absolute Configuration of C8     = ...          R

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 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
   2 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
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Recently, compounds containing 2-cyanoimino-thiazolidine group have attracted much interest because they exhibit diverse biological activities, such as antiulcer, vasodilator, antihypertensive and insecticidal activities (Ezer et al., 1984; Shiokawa et al., 1990; Ogawa et al., 1992; Zhang et al., 2000). They are widely applied in the fields of medication and plant protection (Yoneda et al., 2001; Schmuck, 2001; Ford & Casida, 2006). For example, the chloronicotinyl insecticide Thiacloprid has high insecticidal activity with a favorable ecobiological profile and safety to bees, it is very useful in horticulture as well as in modern crop protection systems (Brackmann et al., 2005; Mota-Sanchez et al., 2006). In a search for more biologically active 2-cyanoimino-thiazolidine derivatives, the title compound was synthesized and its crystal structure was determined (Fig. 1). The molecule is non-planar, the benzene ring and the 1,3-thiazolidine ring making a dihedral of 84.9 (2) °.

Related literature

For related literature, see: Brackmann et al. (2005); Ezer et al. (1984); Ford & Casida (2006); Liu et al. (2006); Mota-Sanchez et al. (2006); Ogawa et al. (1992); Schmuck (2001); Shiokawa et al. (1990); Yoneda et al. (2001); Zhang et al. (2000).

S2. Experimental

[3-(2-Oxo-2-phenylethyl)thiazolidin-2-ylideneamino]formonitrile (Liu et al., 2006; 5 mmol) was dissolved in acetic acid (20 ml), and sodium acetate (6 mmol) was added. Then bromine (6 mmol) was dropwise added with stirring at 343 K, the reaction was maintained for about 3 h, until the mixture was turned into light yellow. Then water (50 ml) and chloroform (40 ml) were added. The organic layer was washed with saturated brine (3 × 30 ml), the combined organic layer was dried over anhydrous Na₂SO₄. After removal of the solvent, the residue was separated by column chromatography on silica gel, with petroleum ether/ethyl acetate (2:1 v/v) as eluent, and recrystallized from ethyl acetate to give a colorless crystal (yield 65%).

S3. Refinement

H atoms were placed in calculated positions (C—H = 0.93–0.97 Å) and were refined as riding, with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for publication: SHELXTL (Bruker, 1999).

Figures

Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level.

(Benzoyl)[2-(cyanoimino)-1,3-thiazolidin-2-yl]methyl acetate

Crystal data

C14H13N3O3S	F(000) = 632
Mr = 303.33	Dx = 1.356 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2292 reflections
a = 8.4679 (19) Å	θ = 2.6–25.4°
b = 8.713 (2) Å	µ = 0.23 mm^−1
c = 20.147 (5) Å	T = 294 K
β = 91.565 (4)°	Monoclinic, colorless
V = 1486.0 (6) Å^3	0.22 × 0.18 × 0.12 mm
Z = 4

Data collection

Bruker SMART 1000 diffractometer	2620 independent reflections
Radiation source: fine-focus sealed tube	1807 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
φ and ω scans	θmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→10
Tmin = 0.951, Tmax = 0.963	k = −10→10
7441 measured reflections	l = −23→20

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.119	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0469P)^2 + 0.8973P] where P = (Fo^2 + 2Fc^2)/3
2620 reflections	(Δ/σ)max = 0.001
191 parameters	Δρmax = 0.38 e Å^−3
0 restraints	Δρmin = −0.30 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
S1	0.48762 (9)	0.77682 (9)	0.05323 (4)	0.0621 (3)
O1	0.0277 (2)	1.0382 (2)	0.23069 (9)	0.0649 (6)
O3	0.0994 (4)	1.2840 (3)	0.05419 (12)	0.1099 (10)
N1	0.2699 (2)	0.9246 (2)	0.11271 (9)	0.0397 (5)
N2	0.2269 (3)	0.9170 (3)	−0.00064 (10)	0.0523 (6)
N3	0.3142 (4)	0.8453 (4)	−0.11270 (13)	0.0963 (10)
C1	−0.0593 (3)	0.7490 (3)	0.10658 (12)	0.0450 (6)
H1	−0.0287	0.8022	0.0690	0.054*
C2	−0.1267 (3)	0.6056 (3)	0.10017 (14)	0.0545 (7)
H2	−0.1413	0.5623	0.0583	0.065*
C3	−0.1727 (3)	0.5259 (3)	0.15584 (15)	0.0590 (7)
H3	−0.2163	0.4283	0.1515	0.071*
C4	−0.1537 (3)	0.5914 (3)	0.21766 (14)	0.0558 (7)
H4	−0.1869	0.5388	0.2550	0.067*
C5	−0.0863 (3)	0.7335 (3)	0.22468 (12)	0.0476 (6)
H5	−0.0732	0.7765	0.2667	0.057*
C6	−0.0370 (3)	0.8143 (3)	0.16918 (11)	0.0383 (6)
C7	0.0381 (3)	0.9666 (3)	0.17954 (11)	0.0408 (6)
C8	0.1404 (3)	1.0279 (3)	0.12343 (12)	0.0411 (6)
H8	0.0763	1.0392	0.0825	0.049*
O2	0.2034 (2)	1.1730 (2)	0.14353 (9)	0.0576 (5)
C9	0.1813 (3)	1.2918 (3)	0.10238 (14)	0.0537 (7)
C10	0.2675 (4)	1.4304 (3)	0.12631 (18)	0.0838 (10)
H10A	0.2424	1.5155	0.0976	0.126*
H10B	0.3791	1.4114	0.1262	0.126*
H10C	0.2367	1.4541	0.1707	0.126*
C11	0.3752 (3)	0.8805 (4)	0.16776 (13)	0.0665 (9)
H11A	0.3194	0.8153	0.1983	0.080*
H11B	0.4108	0.9713	0.1917	0.080*
C12	0.5133 (3)	0.7969 (4)	0.14161 (14)	0.0631 (8)
H12A	0.5217	0.6964	0.1621	0.076*
H12B	0.6096	0.8532	0.1520	0.076*
C13	0.3130 (3)	0.8817 (3)	0.05162 (12)	0.0409 (6)
C14	0.2788 (4)	0.8745 (3)	−0.05949 (15)	0.0638 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0543 (4)	0.0690 (5)	0.0636 (5)	0.0039 (4)	0.0152 (3)	−0.0048 (4)
O1	0.0687 (13)	0.0744 (14)	0.0521 (11)	−0.0061 (10)	0.0119 (9)	−0.0255 (10)
O3	0.199 (3)	0.0569 (14)	0.0711 (16)	−0.0233 (17)	−0.0545 (18)	0.0135 (12)
N1	0.0361 (10)	0.0495 (13)	0.0335 (11)	−0.0032 (9)	0.0015 (8)	0.0027 (9)
N2	0.0626 (14)	0.0613 (15)	0.0329 (12)	−0.0084 (11)	0.0015 (10)	−0.0033 (10)
N3	0.151 (3)	0.094 (2)	0.0454 (16)	−0.030 (2)	0.0220 (17)	−0.0161 (15)
C1	0.0454 (14)	0.0501 (16)	0.0398 (14)	−0.0043 (12)	0.0062 (11)	0.0022 (11)
C2	0.0575 (17)	0.0517 (17)	0.0543 (16)	−0.0074 (14)	0.0049 (13)	−0.0062 (13)
C3	0.0544 (17)	0.0488 (17)	0.074 (2)	−0.0090 (13)	0.0055 (14)	0.0084 (15)
C4	0.0463 (15)	0.0654 (19)	0.0559 (18)	−0.0030 (14)	0.0057 (13)	0.0208 (14)
C5	0.0379 (13)	0.0680 (18)	0.0372 (13)	0.0017 (13)	0.0044 (10)	0.0049 (12)
C6	0.0303 (11)	0.0488 (15)	0.0359 (13)	0.0020 (11)	0.0022 (10)	0.0015 (11)
C7	0.0377 (13)	0.0492 (15)	0.0354 (13)	0.0044 (11)	−0.0008 (10)	−0.0028 (12)
C8	0.0453 (14)	0.0374 (14)	0.0401 (13)	−0.0044 (11)	−0.0068 (11)	−0.0006 (11)
O2	0.0730 (12)	0.0415 (11)	0.0570 (12)	−0.0124 (9)	−0.0203 (9)	0.0054 (9)
C9	0.0671 (18)	0.0477 (17)	0.0462 (16)	−0.0078 (14)	0.0018 (13)	0.0003 (13)
C10	0.098 (3)	0.0502 (19)	0.102 (3)	−0.0221 (18)	−0.015 (2)	0.0055 (18)
C11	0.0541 (17)	0.098 (2)	0.0466 (16)	0.0191 (16)	−0.0078 (13)	−0.0024 (16)
C12	0.0464 (16)	0.078 (2)	0.0654 (19)	0.0064 (15)	0.0018 (13)	0.0114 (16)
C13	0.0435 (13)	0.0403 (14)	0.0391 (14)	−0.0138 (11)	0.0066 (11)	0.0010 (11)
C14	0.085 (2)	0.0584 (19)	0.0480 (18)	−0.0203 (16)	0.0042 (15)	−0.0025 (14)

Geometric parameters (Å, º)

S1—C13	1.738 (3)	C4—H4	0.9300
S1—C12	1.796 (3)	C5—C6	1.395 (3)
O1—C7	1.210 (3)	C5—H5	0.9300
O3—C9	1.179 (3)	C6—C7	1.484 (3)
N1—C13	1.346 (3)	C7—C8	1.538 (3)
N1—C8	1.439 (3)	C8—O2	1.427 (3)
N1—C11	1.456 (3)	C8—H8	0.9800
N2—C13	1.301 (3)	O2—C9	1.336 (3)
N2—C14	1.328 (3)	C9—C10	1.485 (4)
N3—C14	1.149 (4)	C10—H10A	0.9600
C1—C2	1.378 (4)	C10—H10B	0.9600
C1—C6	1.392 (3)	C10—H10C	0.9600
C1—H1	0.9300	C11—C12	1.487 (4)
C2—C3	1.384 (4)	C11—H11A	0.9700
C2—H2	0.9300	C11—H11B	0.9700
C3—C4	1.376 (4)	C12—H12A	0.9700
C3—H3	0.9300	C12—H12B	0.9700
C4—C5	1.369 (4)
C13—S1—C12	92.71 (12)	O2—C8—H8	110.1
C13—N1—C8	122.5 (2)	N1—C8—H8	110.1
C13—N1—C11	116.6 (2)	C7—C8—H8	110.1
C8—N1—C11	120.26 (19)	C9—O2—C8	117.73 (19)
C13—N2—C14	117.7 (2)	O3—C9—O2	122.4 (3)
C2—C1—C6	120.1 (2)	O3—C9—C10	125.9 (3)
C2—C1—H1	120.0	O2—C9—C10	111.7 (2)
C6—C1—H1	120.0	C9—C10—H10A	109.5
C1—C2—C3	120.3 (3)	C9—C10—H10B	109.5
C1—C2—H2	119.9	H10A—C10—H10B	109.5
C3—C2—H2	119.9	C9—C10—H10C	109.5
C4—C3—C2	119.8 (3)	H10A—C10—H10C	109.5
C4—C3—H3	120.1	H10B—C10—H10C	109.5
C2—C3—H3	120.1	N1—C11—C12	109.3 (2)
C5—C4—C3	120.5 (2)	N1—C11—H11A	109.8
C5—C4—H4	119.8	C12—C11—H11A	109.8
C3—C4—H4	119.8	N1—C11—H11B	109.8
C4—C5—C6	120.4 (2)	C12—C11—H11B	109.8
C4—C5—H5	119.8	H11A—C11—H11B	108.3
C6—C5—H5	119.8	C11—C12—S1	108.89 (19)
C1—C6—C5	119.0 (2)	C11—C12—H12A	109.9
C1—C6—C7	122.7 (2)	S1—C12—H12A	109.9
C5—C6—C7	118.4 (2)	C11—C12—H12B	109.9
O1—C7—C6	122.7 (2)	S1—C12—H12B	109.9
O1—C7—C8	120.2 (2)	H12A—C12—H12B	108.3
C6—C7—C8	117.1 (2)	N2—C13—N1	120.9 (2)
O2—C8—N1	108.44 (19)	N2—C13—S1	126.66 (19)
O2—C8—C7	108.22 (19)	N1—C13—S1	112.39 (18)
N1—C8—C7	109.86 (19)	N3—C14—N2	174.3 (4)
C6—C1—C2—C3	0.1 (4)	O1—C7—C8—N1	115.7 (2)
C1—C2—C3—C4	1.2 (4)	C6—C7—C8—N1	−60.7 (3)
C2—C3—C4—C5	−1.5 (4)	N1—C8—O2—C9	113.8 (2)
C3—C4—C5—C6	0.5 (4)	C7—C8—O2—C9	−127.1 (2)
C2—C1—C6—C5	−1.1 (4)	C8—O2—C9—O3	7.7 (4)
C2—C1—C6—C7	178.6 (2)	C8—O2—C9—C10	−173.9 (2)
C4—C5—C6—C1	0.8 (3)	C13—N1—C11—C12	1.0 (4)
C4—C5—C6—C7	−178.9 (2)	C8—N1—C11—C12	−170.1 (2)
C1—C6—C7—O1	163.7 (2)	N1—C11—C12—S1	−2.8 (3)
C5—C6—C7—O1	−16.7 (3)	C13—S1—C12—C11	3.1 (2)
C1—C6—C7—C8	−20.0 (3)	C14—N2—C13—N1	178.2 (2)
C5—C6—C7—C8	159.7 (2)	C14—N2—C13—S1	−2.7 (3)
C13—N1—C8—O2	−106.5 (2)	C8—N1—C13—N2	−8.6 (3)
C11—N1—C8—O2	64.1 (3)	C11—N1—C13—N2	−179.5 (2)
C13—N1—C8—C7	135.4 (2)	C8—N1—C13—S1	172.23 (17)
C11—N1—C8—C7	−54.0 (3)	C11—N1—C13—S1	1.4 (3)
O1—C7—C8—O2	−2.5 (3)	C12—S1—C13—N2	178.3 (2)
C6—C7—C8—O2	−178.97 (18)	C12—S1—C13—N1	−2.61 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···O3	0.98	2.22	2.649 (4)	105
C8—H8···N2	0.98	2.38	2.796 (3)	105