Crystal structure of 2-cyano-3,3-bis­(ethyl­sulfan­yl)-N-o-tolyl­acryl­amide

Azzam, R.A.; Elgemeie, G.H.; Ramadan, R.; Jones, P.G.

doi:10.1107/S2056989017005783

Crystal structure of 2-cyano-3,3-bis(ethylsulfanyl)-N-o-tolylacrylamide

R. A. Azzam, G. H. Elgemeie, R. Ramadan and P. G. Jones

In the molecule of the title compound, the central S₂C=C(CN)C moiety is planar (r.m.s. deviation = 0.029 Å). The C=O and C—CN groups are trans to each other across their common C—C bond. In the crystal, one classical and two `weak' hydrogen bonds combine with borderline N

N and S

S contacts to form layers parallel to (10 $\overline{2}$ ).

Keywords: crystal structure; cyanoketene; thioacetal.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989017005783/hg5488sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S2056989017005783/hg5488Isup2.hkl Contains datablock I
	Chemical Markup Language (CML) file https://doi.org/10.1107/S2056989017005783/hg5488Isup3.cml Supplementary material

CCDC reference: 1544524

checkCIF report

Key indicators

Single-crystal X-ray study
T = 100 K
Mean (C-C) = 0.002 Å
Disorder in main residue
R factor = 0.034
wR factor = 0.081
Data-to-parameter ratio = 23.8

checkCIF/PLATON results

No syntax errors found



Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          5 Note
PLAT003_ALERT_2_G Number of Uiso or Uij Restrained non-H Atoms ...          4 Report
PLAT005_ALERT_5_G No Embedded Refinement Details found  in the CIF     Please Do !
PLAT230_ALERT_2_G Hirshfeld Test Diff for    C9     --  C11     ..        6.7 s.u.
PLAT301_ALERT_3_G Main Residue  Disorder ..............(Resd  1)..         10 % Note
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          1 Note
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............         15 Note
PLAT899_ALERT_4_G SHELXL97   is Deprecated and Succeeded by SHELXL       2014 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600        269 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.         13 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   0 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  10 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

Computing details top

Data collection: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); cell refinement: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); data reduction: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

2-Cyano-3,3-bis(ethylsulfanyl)-N-(2-methylphenyl)prop-2-enamide top

Crystal data top

C₁₅H₁₈N₂OS₂	F(000) = 648
M_r = 306.43	D_x = 1.329 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 10087 reflections
a = 9.4104 (4) Å	θ = 2.7–30.4°
b = 12.8350 (4) Å	µ = 0.35 mm⁻¹
c = 13.0774 (5) Å	T = 100 K
β = 104.198 (4)°	Block, pale yellow
V = 1531.28 (10) Å³	0.35 × 0.35 × 0.30 mm
Z = 4

Data collection top

Oxford Diffraction Xcalibur Eos diffractometer	4682 independent reflections
Radiation source: fine-focus sealed X-ray tube	3985 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
Detector resolution: 16.1419 pixels mm^-1	θ_max = 31.2°, θ_min = 2.2°
ω scan	h = −13→13
Absorption correction: multi-scan (CrysAlis PRO; Rigaku Oxford Diffraction, 2015)	k = −18→18
T_min = 0.986, T_max = 1.000	l = −18→18
42164 measured reflections

Refinement top

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.081	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0309P)² + 0.7259P] where P = (F_o² + 2F_c²)/3
4682 reflections	(Δ/σ)_max = 0.001
197 parameters	Δρ_max = 0.37 e Å⁻³
15 restraints	Δρ_min = −0.22 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

7.3265 (0.0012) x + 3.0782 (0.0029) y - 9.8498 (0.0015) z = 0.3852 (0.0018)

* -0.0120 (0.0007) C1 * 0.0262 (0.0010) C8 * 0.0574 (0.0010) C9 * -0.0136 (0.0009) C10 * -0.0055 (0.0004) S1 * -0.0220 (0.0005) S2 * -0.0304 (0.0009) N1 0.0632 (0.0010) O1 0.2839 (0.0014) C11

Rms deviation of fitted atoms = 0.0287

8.1736 (0.0024) x - 6.3013 (0.0055) y - 3.6411 (0.0064) z = 1.1855 (0.0026)

Angle to previous plane (with approximate esd) = 53.30 ( 0.03 )

* -0.0174 (0.0008) C1 * 0.0106 (0.0008) C2 * 0.0039 (0.0009) C3 * -0.0118 (0.0009) C4 * 0.0052 (0.0009) C5 * 0.0095 (0.0008) C6

Rms deviation of fitted atoms = 0.0107

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 > 2sigma(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

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.48134 (12)	0.21516 (9)	0.38738 (9)	0.0144 (2)
C2	0.46128 (12)	0.24547 (9)	0.28216 (9)	0.0156 (2)
C3	0.37643 (14)	0.18128 (10)	0.20464 (9)	0.0206 (2)
H3	0.3601	0.2008	0.1326	0.025*
C4	0.31546 (14)	0.08976 (10)	0.23047 (10)	0.0222 (2)
H4	0.2564	0.0480	0.1765	0.027*
C5	0.34046 (14)	0.05902 (9)	0.33513 (10)	0.0200 (2)
H5	0.3005	−0.0045	0.3529	0.024*
C6	0.42423 (13)	0.12172 (9)	0.41347 (9)	0.0173 (2)
H6	0.4427	0.1008	0.4852	0.021*
C7	0.53257 (14)	0.34242 (10)	0.25430 (10)	0.0214 (2)
H7A	0.4999	0.4026	0.2886	0.032*
H7B	0.5051	0.3522	0.1776	0.032*
H7C	0.6393	0.3357	0.2784	0.032*
C8	0.67932 (12)	0.25551 (9)	0.54338 (9)	0.0148 (2)
C9	0.74786 (13)	0.33969 (9)	0.61750 (9)	0.0157 (2)
C10	0.86223 (13)	0.32278 (9)	0.70449 (9)	0.0156 (2)
C11	0.69858 (13)	0.44369 (9)	0.59035 (9)	0.0176 (2)
S1	0.94594 (3)	0.20139 (2)	0.72800 (2)	0.01904 (8)
C12	1.07266 (14)	0.21116 (10)	0.85705 (10)	0.0222 (2)
H12A	1.1520	0.1594	0.8617	0.027*
H12B	1.1179	0.2813	0.8647	0.027*
C13	1.00032 (18)	0.19311 (12)	0.94728 (11)	0.0324 (3)
H13A	0.9294	0.2489	0.9481	0.049*
H13B	1.0752	0.1930	1.0142	0.049*
H13C	0.9496	0.1258	0.9378	0.049*
S2	0.93498 (3)	0.42489 (2)	0.79137 (2)	0.02058 (8)
C14	0.77925 (19)	0.4973 (2)	0.81670 (17)	0.0211 (6)	0.721 (7)
H14A	0.7472	0.5518	0.7624	0.025*	0.721 (7)
H14B	0.6959	0.4496	0.8145	0.025*	0.721 (7)
C15	0.8290 (3)	0.5466 (2)	0.9252 (2)	0.0234 (5)	0.721 (7)
H15A	0.8431	0.4922	0.9793	0.035*	0.721 (7)
H15B	0.7544	0.5959	0.9358	0.035*	0.721 (7)
H15C	0.9217	0.5836	0.9306	0.035*	0.721 (7)
C14'	0.7812 (5)	0.4548 (6)	0.8430 (5)	0.0206 (13)*	0.279 (7)
H14C	0.6907	0.4573	0.7853	0.025*	0.279 (7)
H14D	0.7689	0.4007	0.8941	0.025*	0.279 (7)
C15'	0.8087 (9)	0.5593 (6)	0.8967 (7)	0.029 (2)*	0.279 (7)
H15D	0.7263	0.5771	0.9269	0.044*	0.279 (7)
H15E	0.8186	0.6125	0.8451	0.044*	0.279 (7)
H15F	0.8991	0.5563	0.9530	0.044*	0.279 (7)
N1	0.55847 (11)	0.28375 (8)	0.46806 (8)	0.0169 (2)
H01	0.5279 (18)	0.3435 (14)	0.4655 (12)	0.026 (4)*
N2	0.65583 (12)	0.52547 (8)	0.56292 (9)	0.0244 (2)
O1	0.73077 (10)	0.16749 (7)	0.55038 (7)	0.01999 (18)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0152 (5)	0.0127 (5)	0.0153 (5)	0.0007 (4)	0.0036 (4)	−0.0020 (4)
C2	0.0157 (5)	0.0146 (5)	0.0170 (5)	0.0021 (4)	0.0048 (4)	0.0008 (4)
C3	0.0233 (6)	0.0228 (6)	0.0149 (5)	0.0019 (5)	0.0032 (4)	−0.0014 (4)
C4	0.0219 (6)	0.0191 (6)	0.0236 (6)	−0.0007 (5)	0.0018 (5)	−0.0073 (5)
C5	0.0205 (6)	0.0130 (5)	0.0272 (6)	−0.0016 (4)	0.0074 (5)	−0.0019 (4)
C6	0.0208 (6)	0.0144 (5)	0.0179 (5)	0.0010 (4)	0.0071 (4)	0.0005 (4)
C7	0.0230 (6)	0.0202 (6)	0.0221 (6)	−0.0010 (5)	0.0075 (5)	0.0048 (5)
C8	0.0166 (5)	0.0134 (5)	0.0153 (5)	−0.0007 (4)	0.0055 (4)	0.0004 (4)
C9	0.0170 (5)	0.0121 (5)	0.0172 (5)	0.0008 (4)	0.0025 (4)	−0.0005 (4)
C10	0.0150 (5)	0.0141 (5)	0.0179 (5)	0.0010 (4)	0.0046 (4)	−0.0003 (4)
C11	0.0173 (5)	0.0155 (5)	0.0175 (5)	−0.0013 (4)	−0.0007 (4)	−0.0032 (4)
S1	0.02006 (15)	0.01621 (14)	0.01943 (14)	0.00640 (11)	0.00213 (11)	−0.00021 (10)
C12	0.0184 (6)	0.0217 (6)	0.0232 (6)	0.0053 (5)	−0.0010 (4)	0.0018 (5)
C13	0.0391 (8)	0.0344 (8)	0.0218 (6)	0.0005 (6)	0.0036 (6)	0.0036 (6)
S2	0.01549 (14)	0.01860 (15)	0.02518 (15)	0.00178 (10)	0.00028 (11)	−0.00709 (11)
C14	0.0192 (9)	0.0211 (12)	0.0238 (9)	0.0043 (7)	0.0069 (6)	−0.0028 (8)
C15	0.0326 (12)	0.0214 (10)	0.0185 (11)	0.0020 (8)	0.0105 (10)	−0.0036 (9)
N1	0.0210 (5)	0.0107 (4)	0.0167 (4)	0.0021 (4)	0.0001 (4)	−0.0014 (4)
N2	0.0239 (6)	0.0151 (5)	0.0278 (5)	−0.0002 (4)	−0.0061 (4)	−0.0021 (4)
O1	0.0224 (4)	0.0132 (4)	0.0227 (4)	0.0037 (3)	0.0025 (3)	−0.0014 (3)

Geometric parameters (Å, º) top

C1—C6	1.3905 (16)	C3—H3	0.9500
C1—C2	1.3975 (15)	C4—H4	0.9500
C1—N1	1.4282 (14)	C5—H5	0.9500
C2—C3	1.3953 (16)	C6—H6	0.9500
C2—C7	1.5004 (16)	C7—H7A	0.9800
C3—C4	1.3850 (18)	C7—H7B	0.9800
C4—C5	1.3879 (18)	C7—H7C	0.9800
C5—C6	1.3865 (17)	C12—H12A	0.9900
C8—O1	1.2236 (14)	C12—H12B	0.9900
C8—N1	1.3585 (15)	C13—H13A	0.9800
C8—C9	1.4888 (16)	C13—H13B	0.9800
C9—C10	1.3781 (16)	C13—H13C	0.9800
C9—C11	1.4290 (16)	C14—H14A	0.9900
C10—S1	1.7390 (12)	C14—H14B	0.9900
C10—S2	1.7594 (12)	C15—H15A	0.9800
C11—N2	1.1496 (16)	C15—H15B	0.9800
S1—C12	1.8162 (13)	C15—H15C	0.9800
C12—C13	1.518 (2)	C14'—H14C	0.9900
S2—C14'	1.783 (5)	C14'—H14D	0.9900
S2—C14	1.8326 (18)	C15'—H15D	0.9800
C14—C15	1.519 (3)	C15'—H15E	0.9800
C14'—C15'	1.507 (9)	C15'—H15F	0.9800
N1—H01	0.817 (17)

C6—C1—C2	120.98 (10)	C2—C7—H7A	109.5
C6—C1—N1	120.49 (10)	C2—C7—H7B	109.5
C2—C1—N1	118.50 (10)	H7A—C7—H7B	109.5
C3—C2—C1	117.77 (11)	C2—C7—H7C	109.5
C3—C2—C7	121.57 (11)	H7A—C7—H7C	109.5
C1—C2—C7	120.63 (10)	H7B—C7—H7C	109.5
C4—C3—C2	121.40 (11)	C13—C12—H12A	108.9
C3—C4—C5	120.10 (11)	S1—C12—H12A	108.9
C6—C5—C4	119.46 (11)	C13—C12—H12B	108.9
C5—C6—C1	120.21 (11)	S1—C12—H12B	108.9
O1—C8—N1	123.11 (11)	H12A—C12—H12B	107.7
O1—C8—C9	121.40 (10)	C12—C13—H13A	109.5
N1—C8—C9	115.49 (10)	C12—C13—H13B	109.5
C10—C9—C11	119.50 (10)	H13A—C13—H13B	109.5
C10—C9—C8	123.30 (10)	C12—C13—H13C	109.5
C11—C9—C8	116.99 (10)	H13A—C13—H13C	109.5
C9—C10—S1	121.02 (9)	H13B—C13—H13C	109.5
C9—C10—S2	121.14 (9)	C15—C14—H14A	110.2
S1—C10—S2	117.75 (7)	S2—C14—H14A	110.2
N2—C11—C9	176.23 (12)	C15—C14—H14B	110.2
C10—S1—C12	105.56 (6)	S2—C14—H14B	110.2
C13—C12—S1	113.23 (10)	H14A—C14—H14B	108.5
C10—S2—C14'	100.46 (17)	C15'—C14'—H14C	110.1
C10—S2—C14	107.01 (7)	S2—C14'—H14C	110.1
C15—C14—S2	107.65 (16)	C15'—C14'—H14D	110.1
C15'—C14'—S2	107.8 (5)	S2—C14'—H14D	110.1
C8—N1—C1	123.68 (10)	H14C—C14'—H14D	108.5
C4—C3—H3	119.3	C14'—C15'—H15D	109.5
C2—C3—H3	119.3	C14'—C15'—H15E	109.5
C3—C4—H4	120.0	H15D—C15'—H15E	109.5
C5—C4—H4	120.0	C14'—C15'—H15F	109.5
C6—C5—H5	120.3	H15D—C15'—H15F	109.5
C4—C5—H5	120.3	H15E—C15'—H15F	109.5
C5—C6—H6	119.9	C8—N1—H01	120.2 (11)
C1—C6—H6	119.9	C1—N1—H01	116.0 (11)

C6—C1—C2—C3	2.91 (17)	C11—C9—C10—S2	7.34 (16)
N1—C1—C2—C3	−175.34 (11)	C8—C9—C10—S2	−178.08 (9)
C6—C1—C2—C7	−175.44 (11)	C9—C10—S1—C12	−173.24 (10)
N1—C1—C2—C7	6.31 (16)	S2—C10—S1—C12	10.20 (9)
C1—C2—C3—C4	−0.85 (18)	C10—S1—C12—C13	83.40 (11)
C7—C2—C3—C4	177.48 (12)	C9—C10—S2—C14'	64.9 (3)
C2—C3—C4—C5	−1.27 (19)	S1—C10—S2—C14'	−118.6 (3)
C3—C4—C5—C6	1.35 (19)	C9—C10—S2—C14	44.96 (14)
C4—C5—C6—C1	0.68 (18)	S1—C10—S2—C14	−138.48 (11)
C2—C1—C6—C5	−2.86 (18)	C10—S2—C14—C15	152.32 (19)
N1—C1—C6—C5	175.35 (11)	C14'—S2—C14—C15	78.5 (5)
O1—C8—C9—C10	−7.09 (18)	C10—S2—C14'—C15'	−164.9 (5)
N1—C8—C9—C10	173.60 (11)	C14—S2—C14'—C15'	−53.9 (6)
O1—C8—C9—C11	167.61 (11)	O1—C8—N1—C1	−1.97 (18)
N1—C8—C9—C11	−11.70 (15)	C9—C8—N1—C1	177.32 (10)
C11—C9—C10—S1	−169.10 (9)	C6—C1—N1—C8	57.60 (16)
C8—C9—C10—S1	5.47 (16)	C2—C1—N1—C8	−124.15 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H01···N2ⁱ	0.817 (17)	2.375 (17)	3.1346 (15)	155.0 (15)
C12—H12A···N2ⁱⁱ	0.99	2.51	3.4628 (16)	160
C5—H5···O1ⁱⁱⁱ	0.95	2.50	3.4110 (15)	161

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, y−1/2, −z+3/2; (iii) −x+1, −y, −z+1.

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Crystal structure of 2-cyano-3,3-bis­(ethyl­sulfan­yl)-N-o-tolyl­acryl­amide

Supporting information

Key indicators

checkCIF/PLATON results

Crystal structure of 2-cyano-3,3-bis(ethylsulfanyl)-N-o-tolylacrylamide