Crystal structure of ethyl 3-anilino-2-{[bis­(methyl­sulfan­yl)methyl­idene]amino}-3-oxopropano­ate

The mol­ecular conformation of the title compound, C₁₄H₁₈N₂O₃S₂, is stabilized by intra­molecular N—H...N and C—H...O hydrogen bonds. The crystal packing is characterized by a series of C—H...O hydrogen bonds, resulting in a three-dimensional network.

Key indicators

• Single-crystal X-ray study
• T = 145 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.039
• wR factor = 0.101
• Data-to-parameter ratio = 18.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT480_ALERT_4_C Long H...A H-Bond Reported H10B   ..  O3      ..       2.65 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H11A   ..  O2      ..       2.64 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H13B   ..  O1      ..       2.63 Ang.
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          8 Why ?

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF     Please Do !
PLAT793_ALERT_4_G The Model has Chirality at C8      .............          S Verify
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          1 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600        643 Note

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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 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
   5 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

Quinoline fused five-membered heterocyclic compounds have been the subject of sustained interest because many of them have cytotoxic properties. Thus, they are potential antitumor agents (Adams et al., 2002). We have reported the synthesis and cytotoxic activity of several thiazolo[5,4-b]quinoline (TQ) derivatives (Rodríguez-Loaiza et al., 2004; Loza-Mejía et al., 2008; Loza-Mejía et al., 2009.). During a study on the synthesis of new oxazolo[5,4-b]quinoline derivatives, which can be considered as analogues of TQ, the preparation of a key intermediate was tried by using a procedure previously reported by our group.

In the title compound, the asymmetric unit consist of one molecule of the ethyl-2-{[bis(methylsulfanyl)methylidene]amino}-3-oxo-3-(phenylamino)-propanoate (Fig. 1). The planes formed by phenyl ring C1/C6 (equation plane: 6.499 (4) x + 3.679 (6) y - 5.701 (6) z = 0.613 (6)) and the N1—C7/O1—C8 group (equation plane: 6.941 (4) x + 3.217 (7) y - 4.499 (8) z = 1.040 (4)) are almost coplanar with a dihedral angle between them of 7.64 (11)°; of the same way the dihedral angle of 8.34 (9)° between planes formed by N1—C7/O1—C8 and S1—C12/N2—S2 (equation plane: 7.465 (2) x + 2.049 (5) y - 4.965 (2) z = 0.633 (9)) evidence the coplanarity. On the other hand, the plane formed by C8—C9/O2—O3 (equation plane: - 3.115 (6) x + 8.551 (3) y + 1.760 (9) z = 3.314 (1)) shows a behavior near to orthogonality with the other planes.

In the crystal structure there are intermolecular C—H···O contacts (Table 1) connecting the molecules to a three-dimensional network.

Related literature

For the synthesis and cytotoxic activity of thiazolo[5,4-b]quinoline derivatives, see: Rodríguez-Loaiza et al. (2004); Loza-Mejía et al. (2008, 2009); Adams et al. (2002).

S2. Experimental

Ethyl {[bis(methylsulfanyl)methylidene]amino}acetate was reacted with phenyl isocyanate at low temperature (-75°) under basic conditions, in order to obtain the oxazole derivative which is a intermediate suitable for the formation of the oxazolo[5,4-b]quinoline system. Surprisingly, this reaction gave in a high yield a different crystal intermediate, whose structure was characterized by IR, NMR and X-ray studies. Yield: 66.7%. Colorless crystals; mp: 103°C; IR (νmax, cm^-1): 3283 (–NH amidic); 2982, 2930, 2891 (–CH aliph.); 1733 (C=O ester); 1687 (C=O amidic); 1H NMR (400 MHz, DMSO-d ₆): d 1.17 (t, J = 7.1 Hz, 3H) –CH₃; 2.46 (s, 3H) –SCH₃; 2.59 (s, 3H) –SCH₃; 4.14 (q, J = 7.1, 2H) –CH₂; 5.00 (s, 1H) –CH; 7.07 (t, J = 7.8 Hz, 1H) –H4; 7.31 (d, J = 7.8 Hz, 2H) –H3, –H5; 7.61 (d, J = 8.4 Hz, 2H) –H2, –H6; 9.97 (s, 1H) –NH–; ¹³C NMR (101 MHz, DMSO– d ₆): d 14.42, 14.98, 15.26, 61.69, 69.68, 120.03, 124.33, 129.20, 138.74, 165.34, 167.06.

S3. Refinement

The H atom of the amine group (N1/H1F) was located in a difference map and refined isotropically with U_iso(H) = 1.2U_eq(N). The N-H distance was restrained to 0.92 (2)Å. H atoms attached to C atoms were placed in geometrically idealized positions and refined as riding on their parent atoms, with C—H = 0.95–0.99 Å and with U_iso(H) = 1.2U_eq(C), for aromatic and methylene groups and U_iso(H) = 1.5U_eq(C) for methyl groups.

Computing details

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis CCD (Agilent, 2012); data reduction: CrysAlis RED (Agilent, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as circles of arbitrary size.
	Fig. 2. Crystal packing with intermolecular interactions of type C—H···O forming a three-dimensional network.

Ethyl 3-anilino-2-{[bis(methylsulfanyl)methylidene]amino}-3-oxopropanoate

Crystal data

C14H18N2O3S2	Z = 2
Mr = 326.42	F(000) = 344
Triclinic, P1	Dx = 1.38 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.5298 (11) Å	Cell parameters from 2290 reflections
b = 9.1422 (16) Å	θ = 3.6–29.4°
c = 11.0268 (13) Å	µ = 0.35 mm^−1
α = 101.377 (12)°	T = 145 K
β = 102.102 (10)°	Block, colourless
γ = 104.457 (13)°	0.6 × 0.5 × 0.35 mm
V = 785.3 (2) Å^3

Data collection

Agilent Xcalibur Atlas Gemini diffractometer	3625 independent reflections
Graphite monochromator	3022 reflections with I > 2σ(I)
Detector resolution: 10.4685 pixels mm^-1	Rint = 0.028
ω scans	θmax = 29.4°, θmin = 3.6°
Absorption correction: analytical (CrysAlis RED; Agilent, 2012)	h = −11→11
Tmin = 0.87, Tmax = 0.922	k = −9→11
5879 measured reflections	l = −15→14

Refinement

Refinement on F^2	H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0448P)^2 + 0.1551P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.039	(Δ/σ)max < 0.001
wR(F^2) = 0.101	Δρmax = 0.34 e Å^−3
S = 1.05	Δρmin = −0.36 e Å^−3
3625 reflections	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
197 parameters	Extinction coefficient: 0.033 (3)
1 restraint

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.22485 (19)	0.68715 (19)	0.59186 (14)	0.0184 (3)
C2	0.1478 (2)	0.8032 (2)	0.57936 (16)	0.0216 (4)
H2	0.0786	0.7997	0.4985	0.026*
C3	0.1738 (2)	0.9243 (2)	0.68710 (16)	0.0260 (4)
H3	0.1217	1.0038	0.6792	0.031*
C4	0.2741 (2)	0.9311 (2)	0.80562 (17)	0.0289 (4)
H4	0.2909	1.0146	0.8784	0.035*
C5	0.3498 (2)	0.8150 (2)	0.81709 (16)	0.0276 (4)
H5	0.4188	0.819	0.8981	0.033*
C6	0.3254 (2)	0.6930 (2)	0.71085 (16)	0.0241 (4)
H6	0.3773	0.6135	0.7193	0.029*
C7	0.13582 (19)	0.5349 (2)	0.36177 (15)	0.0194 (3)
C8	0.1513 (2)	0.38584 (19)	0.27795 (14)	0.0187 (3)
H8	0.0362	0.3141	0.2294	0.022*
C9	0.24576 (19)	0.43850 (19)	0.18264 (15)	0.0188 (3)
C10	0.2175 (2)	0.4733 (2)	−0.02788 (15)	0.0244 (4)
H10A	0.3176	0.5663	0.0132	0.029*
H10B	0.1363	0.5023	−0.0897	0.029*
C11	0.2686 (2)	0.3427 (2)	−0.09767 (18)	0.0325 (4)
H11A	0.315	0.3746	−0.1659	0.049*
H11B	0.1701	0.2496	−0.1356	0.049*
H11C	0.3541	0.3186	−0.0372	0.049*
C12	0.2467 (2)	0.1698 (2)	0.31142 (14)	0.0195 (3)
C13	0.2088 (2)	−0.1139 (2)	0.13307 (17)	0.0294 (4)
H13A	0.1576	−0.18	0.0448	0.044*
H13B	0.1628	−0.1673	0.1925	0.044*
H13C	0.3309	−0.0944	0.1545	0.044*
C14	0.4017 (3)	0.2120 (2)	0.56368 (16)	0.0317 (4)
H14A	0.4778	0.3092	0.5589	0.048*
H14B	0.4595	0.1723	0.6305	0.048*
H14C	0.3018	0.2324	0.5847	0.048*
N1	0.20693 (17)	0.56002 (17)	0.48823 (12)	0.0200 (3)
N2	0.23886 (17)	0.30580 (16)	0.35854 (12)	0.0200 (3)
O1	0.06584 (17)	0.61847 (16)	0.31231 (11)	0.0308 (3)
O2	0.39713 (14)	0.48975 (15)	0.20888 (11)	0.0265 (3)
O3	0.14030 (13)	0.42455 (14)	0.07059 (10)	0.0217 (3)
S1	0.16283 (5)	0.06980 (5)	0.14655 (4)	0.02388 (13)
S2	0.33924 (6)	0.06874 (5)	0.41135 (4)	0.02561 (14)
H1F	0.254 (2)	0.487 (2)	0.5037 (18)	0.031*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0190 (7)	0.0190 (9)	0.0168 (7)	0.0042 (6)	0.0079 (6)	0.0029 (6)
C2	0.0246 (8)	0.0205 (9)	0.0218 (8)	0.0075 (7)	0.0089 (7)	0.0064 (7)
C3	0.0335 (9)	0.0187 (9)	0.0300 (9)	0.0100 (7)	0.0155 (8)	0.0061 (7)
C4	0.0343 (9)	0.0227 (10)	0.0251 (9)	0.0037 (8)	0.0121 (8)	−0.0017 (7)
C5	0.0272 (9)	0.0317 (11)	0.0187 (8)	0.0059 (8)	0.0030 (7)	0.0024 (7)
C6	0.0243 (8)	0.0268 (10)	0.0220 (8)	0.0095 (7)	0.0061 (7)	0.0059 (7)
C7	0.0205 (7)	0.0190 (9)	0.0189 (7)	0.0062 (6)	0.0062 (7)	0.0044 (6)
C8	0.0210 (7)	0.0178 (8)	0.0165 (7)	0.0065 (6)	0.0035 (6)	0.0040 (6)
C9	0.0217 (8)	0.0162 (8)	0.0182 (7)	0.0080 (6)	0.0036 (7)	0.0025 (6)
C10	0.0272 (8)	0.0315 (10)	0.0191 (8)	0.0124 (7)	0.0075 (7)	0.0113 (7)
C11	0.0356 (10)	0.0377 (12)	0.0288 (9)	0.0133 (9)	0.0161 (8)	0.0086 (8)
C12	0.0212 (7)	0.0201 (9)	0.0177 (7)	0.0057 (6)	0.0062 (7)	0.0055 (6)
C13	0.0382 (10)	0.0196 (9)	0.0280 (9)	0.0107 (8)	0.0077 (8)	−0.0001 (7)
C14	0.0426 (10)	0.0306 (11)	0.0177 (8)	0.0121 (9)	−0.0001 (8)	0.0043 (7)
N1	0.0251 (7)	0.0197 (8)	0.0175 (6)	0.0116 (6)	0.0057 (6)	0.0040 (5)
N2	0.0243 (7)	0.0189 (7)	0.0173 (6)	0.0082 (6)	0.0048 (6)	0.0049 (5)
O1	0.0461 (7)	0.0291 (7)	0.0208 (6)	0.0229 (6)	0.0034 (6)	0.0061 (5)
O2	0.0202 (6)	0.0324 (8)	0.0245 (6)	0.0052 (5)	0.0029 (5)	0.0092 (5)
O3	0.0208 (6)	0.0300 (7)	0.0153 (5)	0.0094 (5)	0.0038 (5)	0.0072 (5)
S1	0.0304 (2)	0.0213 (2)	0.0173 (2)	0.00912 (18)	0.00318 (17)	0.00107 (16)
S2	0.0351 (3)	0.0212 (2)	0.0211 (2)	0.01201 (19)	0.00365 (19)	0.00657 (17)

Geometric parameters (Å, º)

C1—C6	1.392 (2)	C10—O3	1.4683 (19)
C1—C2	1.395 (2)	C10—C11	1.498 (3)
C1—N1	1.412 (2)	C10—H10A	0.99
C2—C3	1.390 (2)	C10—H10B	0.99
C2—H2	0.95	C11—H11A	0.98
C3—C4	1.384 (3)	C11—H11B	0.98
C3—H3	0.95	C11—H11C	0.98
C4—C5	1.386 (3)	C12—N2	1.273 (2)
C4—H4	0.95	C12—S2	1.7587 (17)
C5—C6	1.388 (2)	C12—S1	1.7678 (16)
C5—H5	0.95	C13—S1	1.8035 (19)
C6—H6	0.95	C13—H13A	0.98
C7—O1	1.2217 (19)	C13—H13B	0.98
C7—N1	1.347 (2)	C13—H13C	0.98
C7—C8	1.541 (2)	C14—S2	1.7968 (18)
C8—N2	1.461 (2)	C14—H14A	0.98
C8—C9	1.532 (2)	C14—H14B	0.98
C8—H8	1	C14—H14C	0.98
C9—O2	1.2075 (19)	N1—H1F	0.889 (15)
C9—O3	1.3292 (18)
C6—C1—C2	120.11 (15)	C11—C10—H10A	109.6
C6—C1—N1	116.63 (15)	O3—C10—H10B	109.6
C2—C1—N1	123.25 (14)	C11—C10—H10B	109.6
C3—C2—C1	118.97 (16)	H10A—C10—H10B	108.2
C3—C2—H2	120.5	C10—C11—H11A	109.5
C1—C2—H2	120.5	C10—C11—H11B	109.5
C4—C3—C2	121.22 (17)	H11A—C11—H11B	109.5
C4—C3—H3	119.4	C10—C11—H11C	109.5
C2—C3—H3	119.4	H11A—C11—H11C	109.5
C3—C4—C5	119.36 (16)	H11B—C11—H11C	109.5
C3—C4—H4	120.3	N2—C12—S2	120.47 (12)
C5—C4—H4	120.3	N2—C12—S1	123.28 (12)
C4—C5—C6	120.39 (16)	S2—C12—S1	116.23 (10)
C4—C5—H5	119.8	S1—C13—H13A	109.5
C6—C5—H5	119.8	S1—C13—H13B	109.5
C5—C6—C1	119.94 (17)	H13A—C13—H13B	109.5
C5—C6—H6	120	S1—C13—H13C	109.5
C1—C6—H6	120	H13A—C13—H13C	109.5
O1—C7—N1	126.13 (16)	H13B—C13—H13C	109.5
O1—C7—C8	120.39 (14)	S2—C14—H14A	109.5
N1—C7—C8	113.48 (14)	S2—C14—H14B	109.5
N2—C8—C9	112.30 (13)	H14A—C14—H14B	109.5
N2—C8—C7	110.24 (12)	S2—C14—H14C	109.5
C9—C8—C7	106.50 (13)	H14A—C14—H14C	109.5
N2—C8—H8	109.2	H14B—C14—H14C	109.5
C9—C8—H8	109.2	C7—N1—C1	129.37 (14)
C7—C8—H8	109.2	C7—N1—H1F	111.8 (13)
O2—C9—O3	125.06 (15)	C1—N1—H1F	118.7 (13)
O2—C9—C8	123.37 (14)	C12—N2—C8	120.84 (13)
O3—C9—C8	111.54 (13)	C9—O3—C10	116.15 (12)
O3—C10—C11	110.09 (15)	C12—S1—C13	104.78 (8)
O3—C10—H10A	109.6	C12—S2—C14	99.96 (8)
C6—C1—C2—C3	0.3 (2)	O1—C7—N1—C1	−2.9 (3)
N1—C1—C2—C3	−179.69 (15)	C8—C7—N1—C1	176.35 (15)
C1—C2—C3—C4	−0.1 (3)	C6—C1—N1—C7	−171.05 (16)
C2—C3—C4—C5	−0.1 (3)	C2—C1—N1—C7	8.9 (3)
C3—C4—C5—C6	0.0 (3)	S2—C12—N2—C8	−175.45 (11)
C4—C5—C6—C1	0.2 (3)	S1—C12—N2—C8	2.8 (2)
C2—C1—C6—C5	−0.4 (2)	C9—C8—N2—C12	−70.50 (19)
N1—C1—C6—C5	179.60 (15)	C7—C8—N2—C12	170.92 (14)
O1—C7—C8—N2	−179.82 (15)	O2—C9—O3—C10	1.2 (2)
N1—C7—C8—N2	0.92 (19)	C8—C9—O3—C10	179.46 (13)
O1—C7—C8—C9	58.11 (19)	C11—C10—O3—C9	83.60 (18)
N1—C7—C8—C9	−121.15 (14)	N2—C12—S1—C13	179.81 (14)
N2—C8—C9—O2	−38.3 (2)	S2—C12—S1—C13	−1.86 (12)
C7—C8—C9—O2	82.41 (19)	N2—C12—S2—C14	−1.14 (16)
N2—C8—C9—O3	143.40 (13)	S1—C12—S2—C14	−179.52 (10)
C7—C8—C9—O3	−95.84 (15)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1F···N2	0.889 (15)	2.019 (18)	2.586 (2)	120.5 (15)
C2—H2···O1	0.95	2.33	2.932 (2)	121
C6—H6···O2^i	0.95	2.4	3.295 (2)	156
C10—H10B···O1^ii	0.99	2.53	3.340 (2)	138
C10—H10B···O3^ii	0.99	2.65	3.377 (2)	131
C11—H11A···O2^iii	0.98	2.64	3.465 (2)	141
C13—H13B···O1^iv	0.98	2.63	3.579 (2)	162

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