2-(2-Fluoro-5-methyl­phen­yl)-2-oxo-1-(1H-1,2,4-triazol-1-yl)ethyl morpholine-4-carbodithio­ate

Zhang, S.-S.; Wan, J.; Li, C.-L.; Li, X.-M.; Ouyang, P.-K.

doi:10.1107/S1600536805042029

2-(2-Fluoro-5-methylphenyl)-2-oxo-1-(1H-1,2,4-triazol-1-yl)ethyl morpholine-4-carbodithioate

S.-S. Zhang, J. Wan, C.-L. Li, X.-M. Li and P.-K. Ouyang

In the title compound, C₁₆H₁₇FN₄O₂S₂, molecules are linked into ribbons parallel to the b axis by C—H

O and C—H

N hydrogen bonds. The packing is further stabilized by π–π interactions involving the fluoromethylphenyl rings into two-dimensional layers in the bc plane.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805042029/sj6189sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536805042029/sj6189Isup2.hkl Contains datablock I

CCDC reference: 296671

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.004 Å
R factor = 0.054
wR factor = 0.138
Data-to-parameter ratio = 15.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.97
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature .        293 K
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          5
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety        C16

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   6 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   3 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
   1 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

We have recently reported the structure of 2-(4-chlorophenyl)-2-oxo-1-(1H-1,2,4-triazol-1-ylmethyl)ethyl morpholine-4-carbodithioate, (II) (Wang et al., 2005). As part of our ongoing studies of triazole compounds, the title compound, (I), has been synthesized and its structure is reported here (Fig. 1 and Table 1).

The bond lengths and angles in (I) are within normal ranges (Allen et al., 1987), and are comparable to the corresponding values in (II). The dihedral angle between the C1–C6 and N2–N4/C14/C15 rings is 79.0 (2)°. The morpholine moiety adopts a chair conformation, and atom S2 is synperiplanar with respect to C8, with the C8—S1—C9—S2 torsion angle being −7.4 (2)°. In the crystal structure, molecules are linked into ribbons parallel to the b axis (Fig. 2) by C12—H12B···O2 and C13—H13A···N4 hydrogen bonds (Table 2). π–π stacking interactions involving the C1–C6 benzene rings [Cg···Cg(1 − x, 1 − y, 1 − z) = 3.652 Å] further stabilize the packing, forming two-dimensional layers along the bc plane.

Experimental top

The title compound was prepared by the method of Wan et al. (2005). Single crystals suitable for an X-ray diffraction study were obtained by slow evaporation of an ethyl acetate–alcohol (1:1 v/v) solution over a period of one week.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 2003).

Figures top

	Fig. 1. The structure of the (I), showing 50% probability displacement ellipsoids and the atom-numbering scheme.
	Fig. 2. A view down the a axis, showing the ribbons along the b axis and π–π interactions. Hydrogen bonds are indicated by dashed lines.

2-(2-Fluoro-5-methylphenyl)-2-oxo-1-(1H-1,2,4-triazol-1-yl)ethyl morpholine-4-carbodithioate top

Crystal data top

C₁₆H₁₇FN₄O₂S₂	Z = 2
M_r = 380.46	F(000) = 396
Triclinic, P1	D_x = 1.437 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.7311 (13) Å	Cell parameters from 1446 reflections
b = 7.7910 (15) Å	θ = 2.3–25.9°
c = 18.107 (4) Å	µ = 0.33 mm⁻¹
α = 98.200 (3)°	T = 293 K
β = 92.649 (4)°	Plate, colourless
γ = 109.900 (3)°	0.29 × 0.21 × 0.09 mm
V = 879.1 (3) Å³

Data collection top

Siemens SMART 1000 CCD area-detector diffractometer	3385 independent reflections
Radiation source: fine-focus sealed tube	2534 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.014
Detector resolution: 8.33 pixels mm^-1	θ_max = 26.0°, θ_min = 2.3°
ω scans	h = −8→7
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −9→9
T_min = 0.910, T_max = 0.971	l = −16→22
4955 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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.138	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0636P)² + 0.3536P] where P = (F_o² + 2F_c²)/3
3385 reflections	(Δ/σ)_max < 0.001
226 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₁₆H₁₇FN₄O₂S₂	γ = 109.900 (3)°
M_r = 380.46	V = 879.1 (3) Å³
Triclinic, P1	Z = 2
a = 6.7311 (13) Å	Mo Kα radiation
b = 7.7910 (15) Å	µ = 0.33 mm⁻¹
c = 18.107 (4) Å	T = 293 K
α = 98.200 (3)°	0.29 × 0.21 × 0.09 mm
β = 92.649 (4)°

Data collection top

Siemens SMART 1000 CCD area-detector diffractometer	3385 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2534 reflections with I > 2σ(I)
T_min = 0.910, T_max = 0.971	R_int = 0.014
4955 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	0 restraints
wR(F²) = 0.138	H-atom parameters constrained
S = 1.06	Δρ_max = 0.33 e Å⁻³
3385 reflections	Δρ_min = −0.18 e Å⁻³
226 parameters

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

	x	y	z	U_iso*/U_eq
S1	0.17311 (13)	0.60830 (11)	0.24119 (4)	0.0525 (2)
S2	0.39342 (16)	0.41709 (12)	0.13363 (4)	0.0658 (3)
F1	0.6179 (3)	0.5610 (3)	0.32055 (10)	0.0689 (5)
O1	0.0206 (3)	0.4158 (4)	0.39562 (11)	0.0704 (7)
O2	0.1976 (4)	0.9085 (3)	0.00547 (13)	0.0714 (7)
N1	0.2772 (4)	0.7009 (3)	0.11157 (12)	0.0440 (6)
N2	−0.0098 (4)	0.2475 (3)	0.25445 (12)	0.0468 (6)
N3	−0.0062 (4)	0.0810 (4)	0.26668 (18)	0.0681 (8)
N4	−0.3260 (5)	0.0512 (5)	0.21260 (18)	0.0834 (10)
C1	0.5869 (5)	0.6355 (4)	0.38979 (17)	0.0491 (7)
C2	0.7643 (5)	0.7462 (4)	0.4363 (2)	0.0616 (9)
H2A	0.8988	0.7686	0.4203	0.074*
C3	0.7403 (5)	0.8238 (4)	0.50711 (19)	0.0607 (8)
H3B	0.8604	0.8978	0.5390	0.073*
C4	0.5407 (5)	0.7942 (4)	0.53199 (16)	0.0501 (7)
C5	0.3666 (5)	0.6785 (4)	0.48332 (15)	0.0454 (7)
H5A	0.2320	0.6546	0.4994	0.054*
C6	0.3834 (4)	0.5962 (4)	0.41141 (15)	0.0420 (6)
C7	0.1833 (4)	0.4699 (4)	0.36642 (15)	0.0444 (6)
C8	0.1770 (4)	0.4112 (4)	0.28149 (14)	0.0424 (6)
H8A	0.3056	0.3846	0.2702	0.051*
C9	0.2876 (4)	0.5796 (4)	0.15465 (14)	0.0414 (6)
C10	0.3925 (5)	0.7235 (5)	0.04465 (16)	0.0543 (8)
H10A	0.4244	0.6126	0.0281	0.065*
H10B	0.5260	0.8266	0.0571	0.065*
C11	0.2647 (6)	0.7582 (5)	−0.01740 (17)	0.0650 (9)
H11A	0.3494	0.7834	−0.0591	0.078*
H11B	0.1412	0.6478	−0.0346	0.078*
C12	0.0693 (5)	0.8718 (5)	0.06493 (19)	0.0630 (9)
H12A	−0.0534	0.7603	0.0484	0.076*
H12B	0.0187	0.9735	0.0788	0.076*
C13	0.1891 (5)	0.8476 (4)	0.13196 (17)	0.0526 (7)
H13A	0.3034	0.9630	0.1518	0.063*
H13B	0.0948	0.8157	0.1707	0.063*
C14	−0.2013 (6)	0.2258 (6)	0.22357 (19)	0.0699 (10)
H14A	−0.2419	0.3219	0.2113	0.084*
C15	−0.1994 (6)	−0.0296 (5)	0.2400 (2)	0.0760 (11)
H15A	−0.2452	−0.1564	0.2402	0.091*
C16	0.5139 (6)	0.8809 (5)	0.60898 (18)	0.0685 (9)
H16A	0.3656	0.8439	0.6159	0.103*
H16B	0.5732	1.0133	0.6139	0.103*
H16C	0.5860	0.8407	0.6462	0.103*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0777 (6)	0.0581 (5)	0.0397 (4)	0.0414 (4)	0.0207 (4)	0.0175 (3)
S2	0.1061 (7)	0.0742 (6)	0.0501 (5)	0.0653 (5)	0.0306 (4)	0.0240 (4)
F1	0.0544 (11)	0.0767 (13)	0.0656 (12)	0.0141 (9)	0.0227 (9)	−0.0027 (10)
O1	0.0449 (12)	0.1072 (19)	0.0414 (12)	0.0070 (12)	0.0093 (10)	0.0034 (12)
O2	0.0913 (17)	0.0882 (16)	0.0655 (15)	0.0566 (15)	0.0233 (13)	0.0433 (13)
N1	0.0538 (14)	0.0537 (13)	0.0369 (12)	0.0307 (12)	0.0106 (10)	0.0151 (10)
N2	0.0467 (14)	0.0558 (14)	0.0389 (12)	0.0200 (12)	0.0038 (10)	0.0067 (11)
N3	0.0604 (18)	0.0506 (15)	0.092 (2)	0.0181 (14)	0.0080 (15)	0.0122 (15)
N4	0.064 (2)	0.091 (2)	0.073 (2)	0.0088 (19)	−0.0084 (16)	−0.0050 (18)
C1	0.0500 (18)	0.0456 (15)	0.0513 (17)	0.0147 (14)	0.0103 (14)	0.0109 (13)
C2	0.0418 (17)	0.0533 (18)	0.080 (2)	0.0038 (15)	0.0117 (16)	0.0107 (17)
C3	0.054 (2)	0.0511 (18)	0.063 (2)	0.0029 (15)	−0.0052 (16)	0.0082 (16)
C4	0.0581 (19)	0.0458 (15)	0.0456 (16)	0.0144 (14)	0.0021 (14)	0.0159 (13)
C5	0.0492 (16)	0.0480 (15)	0.0426 (15)	0.0174 (13)	0.0084 (13)	0.0175 (13)
C6	0.0449 (16)	0.0424 (14)	0.0419 (15)	0.0158 (12)	0.0077 (12)	0.0155 (12)
C7	0.0438 (16)	0.0530 (16)	0.0395 (14)	0.0180 (13)	0.0090 (12)	0.0139 (12)
C8	0.0491 (16)	0.0470 (15)	0.0370 (14)	0.0222 (13)	0.0083 (12)	0.0117 (12)
C9	0.0484 (16)	0.0472 (15)	0.0358 (14)	0.0244 (13)	0.0071 (12)	0.0099 (12)
C10	0.069 (2)	0.0667 (19)	0.0454 (16)	0.0393 (16)	0.0204 (14)	0.0228 (14)
C11	0.087 (2)	0.075 (2)	0.0453 (17)	0.039 (2)	0.0123 (17)	0.0229 (16)
C12	0.063 (2)	0.081 (2)	0.066 (2)	0.0426 (18)	0.0148 (16)	0.0334 (18)
C13	0.067 (2)	0.0559 (17)	0.0526 (17)	0.0393 (16)	0.0133 (15)	0.0181 (14)
C14	0.064 (2)	0.088 (3)	0.056 (2)	0.028 (2)	−0.0060 (17)	0.0069 (18)
C15	0.067 (2)	0.060 (2)	0.084 (3)	0.006 (2)	0.019 (2)	−0.005 (2)
C16	0.085 (3)	0.065 (2)	0.0462 (18)	0.0162 (19)	−0.0002 (17)	0.0058 (16)

Geometric parameters (Å, º) top

S1—C9	1.797 (3)	C4—C5	1.386 (4)
S1—C8	1.799 (3)	C4—C16	1.506 (4)
S2—C9	1.660 (3)	C5—C6	1.394 (4)
F1—C1	1.361 (3)	C5—H5A	0.9300
O1—C7	1.208 (3)	C6—C7	1.488 (4)
O2—C11	1.409 (4)	C7—C8	1.535 (4)
O2—C12	1.411 (4)	C8—H8A	0.9800
N1—C9	1.326 (3)	C10—C11	1.494 (4)
N1—C13	1.468 (3)	C10—H10A	0.9700
N1—C10	1.469 (3)	C10—H10B	0.9700
N2—C14	1.327 (4)	C11—H11A	0.9700
N2—N3	1.355 (3)	C11—H11B	0.9700
N2—C8	1.457 (4)	C12—C13	1.496 (4)
N3—C15	1.314 (4)	C12—H12A	0.9700
N4—C14	1.314 (5)	C12—H12B	0.9700
N4—C15	1.336 (5)	C13—H13A	0.9700
C1—C2	1.370 (4)	C13—H13B	0.9700
C1—C6	1.386 (4)	C14—H14A	0.9300
C2—C3	1.379 (5)	C15—H15A	0.9300
C2—H2A	0.9300	C16—H16A	0.9600
C3—C4	1.391 (4)	C16—H16B	0.9600
C3—H3B	0.9300	C16—H16C	0.9600

C9—S1—C8	102.84 (12)	N1—C9—S1	112.52 (19)
C11—O2—C12	109.9 (2)	S2—C9—S1	122.11 (15)
C9—N1—C13	124.7 (2)	N1—C10—C11	111.0 (2)
C9—N1—C10	121.5 (2)	N1—C10—H10A	109.4
C13—N1—C10	112.7 (2)	C11—C10—H10A	109.4
C14—N2—N3	109.1 (3)	N1—C10—H10B	109.4
C14—N2—C8	132.4 (3)	C11—C10—H10B	109.4
N3—N2—C8	118.3 (2)	H10A—C10—H10B	108.0
C15—N3—N2	101.8 (3)	O2—C11—C10	112.0 (3)
C14—N4—C15	101.9 (3)	O2—C11—H11A	109.2
F1—C1—C2	117.0 (3)	C10—C11—H11A	109.2
F1—C1—C6	120.3 (3)	O2—C11—H11B	109.2
C2—C1—C6	122.6 (3)	C10—C11—H11B	109.2
C1—C2—C3	118.9 (3)	H11A—C11—H11B	107.9
C1—C2—H2A	120.5	O2—C12—C13	111.5 (2)
C3—C2—H2A	120.5	O2—C12—H12A	109.3
C2—C3—C4	121.6 (3)	C13—C12—H12A	109.3
C2—C3—H3B	119.2	O2—C12—H12B	109.3
C4—C3—H3B	119.2	C13—C12—H12B	109.3
C5—C4—C3	117.1 (3)	H12A—C12—H12B	108.0
C5—C4—C16	121.1 (3)	N1—C13—C12	110.4 (3)
C3—C4—C16	121.7 (3)	N1—C13—H13A	109.6
C4—C5—C6	123.2 (3)	C12—C13—H13A	109.6
C4—C5—H5A	118.4	N1—C13—H13B	109.6
C6—C5—H5A	118.4	C12—C13—H13B	109.6
C1—C6—C5	116.5 (3)	H13A—C13—H13B	108.1
C1—C6—C7	126.3 (3)	N4—C14—N2	111.2 (3)
C5—C6—C7	117.2 (2)	N4—C14—H14A	124.4
O1—C7—C6	120.6 (2)	N2—C14—H14A	124.4
O1—C7—C8	118.5 (2)	N3—C15—N4	115.9 (3)
C6—C7—C8	120.8 (2)	N3—C15—H15A	122.0
N2—C8—C7	110.2 (2)	N4—C15—H15A	122.0
N2—C8—S1	112.22 (18)	C4—C16—H16A	109.5
C7—C8—S1	105.23 (18)	C4—C16—H16B	109.5
N2—C8—H8A	109.7	H16A—C16—H16B	109.5
C7—C8—H8A	109.7	C4—C16—H16C	109.5
S1—C8—H8A	109.7	H16A—C16—H16C	109.5
N1—C9—S2	125.4 (2)	H16B—C16—H16C	109.5

C14—N2—N3—C15	1.2 (4)	C6—C7—C8—N2	162.3 (2)
C8—N2—N3—C15	176.2 (3)	O1—C7—C8—S1	101.2 (3)
F1—C1—C2—C3	−179.7 (3)	C6—C7—C8—S1	−76.5 (3)
C6—C1—C2—C3	−0.8 (5)	C9—S1—C8—N2	−85.9 (2)
C1—C2—C3—C4	−0.8 (5)	C9—S1—C8—C7	154.19 (18)
C2—C3—C4—C5	1.9 (5)	C13—N1—C9—S2	−178.0 (2)
C2—C3—C4—C16	−179.2 (3)	C10—N1—C9—S2	−10.4 (4)
C3—C4—C5—C6	−1.5 (4)	C13—N1—C9—S1	1.9 (4)
C16—C4—C5—C6	179.5 (3)	C10—N1—C9—S1	169.4 (2)
F1—C1—C6—C5	180.0 (2)	C8—S1—C9—N1	172.7 (2)
C2—C1—C6—C5	1.1 (4)	C8—S1—C9—S2	−7.4 (2)
F1—C1—C6—C7	2.4 (4)	C9—N1—C10—C11	142.5 (3)
C2—C1—C6—C7	−176.5 (3)	C13—N1—C10—C11	−48.6 (4)
C4—C5—C6—C1	0.1 (4)	C12—O2—C11—C10	−60.4 (4)
C4—C5—C6—C7	177.9 (2)	N1—C10—C11—O2	53.9 (4)
C1—C6—C7—O1	164.7 (3)	C11—O2—C12—C13	61.6 (4)
C5—C6—C7—O1	−12.9 (4)	C9—N1—C13—C12	−142.0 (3)
C1—C6—C7—C8	−17.6 (4)	C10—N1—C13—C12	49.5 (3)
C5—C6—C7—C8	164.8 (2)	O2—C12—C13—N1	−56.0 (4)
C14—N2—C8—C7	96.0 (4)	C15—N4—C14—N2	1.2 (4)
N3—N2—C8—C7	−77.5 (3)	N3—N2—C14—N4	−1.6 (4)
C14—N2—C8—S1	−20.9 (4)	C8—N2—C14—N4	−175.5 (3)
N3—N2—C8—S1	165.6 (2)	N2—N3—C15—N4	−0.6 (4)
O1—C7—C8—N2	−20.0 (4)	C14—N4—C15—N3	−0.3 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12B···O2ⁱ	0.97	2.53	3.207 (4)	127
C13—H13A···N4ⁱⁱ	0.97	2.50	3.267 (5)	135

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

Experimental details

Crystal data
Chemical formula	C₁₆H₁₇FN₄O₂S₂
M_r	380.46
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	6.7311 (13), 7.7910 (15), 18.107 (4)
α, β, γ (°)	98.200 (3), 92.649 (4), 109.900 (3)
V (Å³)	879.1 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.33
Crystal size (mm)	0.29 × 0.21 × 0.09

Data collection
Diffractometer	Siemens SMART 1000 CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.910, 0.971
No. of measured, independent and observed [I > 2σ(I)] reflections	4955, 3385, 2534
R_int	0.014
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.138, 1.06
No. of reflections	3385
No. of parameters	226
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.18

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 2003).

Selected geometric parameters (Å, º) top

S1—C9	1.797 (3)	F1—C1	1.361 (3)
S1—C8	1.799 (3)	O1—C7	1.208 (3)
S2—C9	1.660 (3)

N2—C8—C7	110.2 (2)	C7—C8—S1	105.23 (18)
N2—C8—S1	112.22 (18)