4-Allyl-3-[(5-methyl-2-oxo-1,3-benzoxazol-3-yl)meth­yl]-1H-1,2,4-triazole-5(4H)-thione

In the mol­ecular structure of the title compound, C₁₄H₁₄N₄O₂S, the benzoxazoline group is essentially planar, with a maximum deviation of 0.0358 (2) Å. N—H...S and C—H...S hydrogen bonds are primary inter­actions n the crystal structure. π–π Stacking inter­actions are present between the oxazoline ring systems, which are aligned in a parallel manner. The closest inter­action has a perpendicular separation of 3.4 Å.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• Disorder in main residue
• R factor = 0.042
• wR factor = 0.123
• Data-to-parameter ratio = 13.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size .......       0.66 mm
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.18 Ratio
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C12
PLAT301_ALERT_3_C Main Residue  Disorder .........................       5.00 Perc.

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K

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

   2 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
   2 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

---

S1. Comment

In the title compound, (I) (Fig. 1), the benzoxazoline ring system is essentially planar, with a maximum deviation from the mean plane of the nine-membered ring of -0.0358 (2) Å for atom C8. The C—N bond distances and angles are in agreement with values in our related structure, 3-[4-(2-chlorophenyl)piperazinomethyl]-5-methyl-1-benzoxazolin-2(3H)-one (Koysal et al., 2003). The dihedral angle between the triazole and benzoxazoline ring systems is 68.62 (8)°. The anisotropic displacement parameters of allyl group atoms C13 and C14 are larger than those of the other atoms, suggesting that this group could be affected by high thermal motion.

The structure of compound (I) contains two intermolecular contacts, N3—H3···S1ⁱ and C14A—H14C···S1ⁱⁱ (Table 2). The adjacent S atom forms intermolecular hydrogen bonds linking the molecules into a three-dimensional network generating graph set R²₂(8) (Bernstein et al., 1995).

π–π stacking interactions are present in (I), with the oxazoline ring systems aligned in a parallel manner. The closest interaction with a perpendicular seperation is 3.4 Å.

Related literature

The synthesis of the title compound was published by Salgın et al. (2007). In the title compound, the benzoxazoline ring system is essentially planar, with a maximum deviation from the mean plane of the nine-membered ring of -0.0358 (2) Å for atom C8. The C—N bond distances and angles in the title compound are in agreement with values in our related structure (Koysal et al., 2003).

For related literature, see: Bernstein et al. (1995).

S2. Experimental

The synthesis of the title compound and related derivatives was published by Salgın et al. (2007).

S3. Refinement

In compound (I), atom C14 of the allyl group is disordered over two positions, with site occupancies of 0.64 (2) and 0.36 (2). The atomic displacement parameters are only slightly larger than those of the other atoms. The missing H atom in the allyl group could not be determined, either by fixing or by Fourier map, because disordered atom C14 atom is unexpectedly close to C13. N-bound atom N3 was located in a difference map and refined freely. The remaining H atoms were located geometrically and refined using a riding model, with C—H = 0.93 Å for aromatic H, 0.97 Å for CH₂ and 0.96 Å for methyl H, and with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: WinGX (Farrugia, 1999) and PARST (Nardelli, 1995).

Figures

	Fig. 1. The structure of compound (I), showing 50% probability displacement ellipsoids and the atom-numbering scheme.
	Fig. 2. A view of the C—H···S interactions between the molecules, down the c axis. Hydrogen bonds are indicated by dashed lines.

4-Allyl-3-[(5-methyl-2-oxo-1,3-benzoxazol-3-yl)methyl]-1H-1,2,4- triazole-5(4H)-thione

Crystal data

C14H13N4O2S	F(000) = 1256
Mr = 301.34	Dx = 1.375 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 28896 reflections
a = 7.2848 (3) Å	θ = 2.0–27.2°
b = 19.9139 (7) Å	µ = 0.23 mm^−1
c = 20.0634 (10) Å	T = 293 K
V = 2910.6 (2) Å^3	Prismatic plate, colourless
Z = 8	0.66 × 0.43 × 0.11 mm

Data collection

Stoe IPDS II diffractometer	2852 independent reflections
Radiation source: fine-focus sealed tube	2153 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.078
Detector resolution: 6.67 pixels mm^-1	θmax = 26.0°, θmin = 2.0°
ω scans	h = −8→8
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −24→24
Tmin = 0.881, Tmax = 0.975	l = −24→24
32373 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.042	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.123	w = 1/[σ^2(Fo^2) + (0.0768P)^2 + 0.4236P] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max = 0.001
2852 reflections	Δρmax = 0.36 e Å^−3
206 parameters	Δρmin = −0.19 e Å^−3
40 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0127 (14)

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	Occ. (<1)
C1	0.5897 (3)	0.58195 (10)	0.72142 (10)	0.0474 (5)
C2	0.5409 (3)	0.64148 (11)	0.69131 (12)	0.0546 (5)
H2	0.5378	0.6456	0.6451	0.065*
C3	0.4962 (3)	0.69562 (12)	0.73275 (13)	0.0618 (6)
C4	0.5000 (4)	0.68683 (14)	0.80144 (14)	0.0700 (7)
H4	0.4682	0.7229	0.8285	0.084*
C5	0.5491 (3)	0.62663 (14)	0.83159 (13)	0.0666 (6)
H5	0.5509	0.6216	0.8777	0.080*
C6	0.5942 (3)	0.57553 (11)	0.78965 (11)	0.0527 (5)
C7	0.4474 (4)	0.76210 (13)	0.70312 (19)	0.0875 (9)
H7A	0.4061	0.7558	0.6581	0.105*
H7B	0.5534	0.7907	0.7033	0.105*
H7C	0.3514	0.7825	0.7289	0.105*
C8	0.6892 (3)	0.47767 (11)	0.74739 (11)	0.0550 (5)
C9	0.6716 (3)	0.50349 (11)	0.62625 (10)	0.0505 (5)
H9A	0.7428	0.4625	0.6227	0.061*
H9B	0.7398	0.5391	0.6045	0.061*
C10	0.4916 (3)	0.49418 (10)	0.59153 (9)	0.0449 (5)
C11	0.2362 (3)	0.44848 (11)	0.55338 (9)	0.0474 (5)
C12	0.4464 (3)	0.36922 (11)	0.61302 (12)	0.0563 (5)
H12A	0.3375	0.3457	0.6282	0.068*
H12B	0.5283	0.3744	0.6508	0.068*
C13	0.5381 (6)	0.32939 (16)	0.5608 (2)	0.1045 (12)
C14A	0.6727 (11)	0.2975 (3)	0.5582 (4)	0.143 (3)	0.747 (11)
H14A	0.6702	0.2546	0.5400	0.171*	0.747 (11)
H14B	0.7823	0.3151	0.5743	0.171*	0.747 (11)
C14B	0.508 (3)	0.2757 (7)	0.5359 (8)	0.116 (8)	0.253 (11)
H14C	0.6033	0.2449	0.5306	0.140*	0.253 (11)
H14D	0.3903	0.2648	0.5219	0.140*	0.253 (11)
N1	0.6470 (2)	0.52012 (8)	0.69605 (8)	0.0487 (4)
N2	0.3945 (2)	0.43549 (8)	0.58771 (8)	0.0454 (4)
N3	0.2479 (3)	0.51378 (9)	0.53926 (8)	0.0484 (4)
N4	0.4057 (2)	0.54327 (9)	0.56249 (8)	0.0484 (4)
O1	0.6534 (2)	0.51119 (8)	0.80607 (7)	0.0610 (4)
O2	0.7479 (3)	0.42155 (8)	0.74514 (9)	0.0727 (5)
S1	0.06870 (8)	0.39441 (3)	0.53337 (3)	0.0651 (2)
H3	0.164 (4)	0.5385 (13)	0.5201 (14)	0.074 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0413 (10)	0.0534 (11)	0.0476 (11)	−0.0027 (8)	−0.0055 (8)	−0.0018 (9)
C2	0.0520 (12)	0.0544 (12)	0.0574 (13)	−0.0014 (9)	−0.0062 (10)	0.0018 (10)
C3	0.0502 (12)	0.0550 (12)	0.0802 (17)	0.0001 (10)	−0.0047 (12)	−0.0064 (11)
C4	0.0606 (14)	0.0706 (15)	0.0787 (17)	−0.0002 (12)	0.0043 (13)	−0.0218 (13)
C5	0.0648 (15)	0.0831 (17)	0.0519 (13)	−0.0045 (13)	−0.0002 (11)	−0.0119 (12)
C6	0.0480 (11)	0.0622 (13)	0.0480 (11)	−0.0032 (9)	−0.0053 (9)	−0.0011 (10)
C7	0.0822 (19)	0.0572 (15)	0.123 (3)	0.0068 (13)	−0.0054 (18)	−0.0013 (16)
C8	0.0544 (12)	0.0580 (13)	0.0525 (12)	−0.0011 (10)	−0.0115 (9)	0.0045 (10)
C9	0.0484 (11)	0.0576 (11)	0.0455 (10)	−0.0002 (9)	−0.0018 (9)	−0.0024 (9)
C10	0.0488 (11)	0.0485 (10)	0.0373 (9)	−0.0006 (8)	0.0032 (8)	−0.0013 (8)
C11	0.0509 (11)	0.0525 (11)	0.0389 (9)	0.0006 (9)	−0.0003 (8)	−0.0009 (8)
C12	0.0599 (13)	0.0515 (11)	0.0576 (13)	−0.0005 (10)	−0.0057 (10)	0.0097 (10)
C13	0.135 (3)	0.0572 (17)	0.121 (3)	0.0325 (19)	0.045 (2)	0.0157 (18)
C14A	0.133 (6)	0.090 (4)	0.205 (7)	0.012 (4)	0.068 (6)	0.026 (4)
C14B	0.109 (14)	0.119 (13)	0.121 (12)	0.049 (10)	−0.011 (9)	−0.052 (9)
N1	0.0518 (10)	0.0512 (9)	0.0431 (9)	0.0012 (7)	−0.0073 (8)	0.0017 (7)
N2	0.0500 (9)	0.0463 (9)	0.0398 (8)	0.0002 (7)	−0.0007 (7)	0.0005 (7)
N3	0.0505 (10)	0.0516 (10)	0.0431 (9)	0.0011 (8)	−0.0050 (8)	0.0001 (7)
N4	0.0518 (10)	0.0517 (10)	0.0418 (9)	−0.0025 (8)	−0.0016 (7)	−0.0005 (7)
O1	0.0697 (10)	0.0679 (10)	0.0453 (8)	−0.0009 (8)	−0.0112 (7)	0.0047 (7)
O2	0.0839 (12)	0.0609 (10)	0.0731 (11)	0.0134 (9)	−0.0164 (9)	0.0076 (8)
S1	0.0596 (4)	0.0580 (4)	0.0776 (4)	−0.0082 (3)	−0.0178 (3)	0.0040 (3)

Geometric parameters (Å, º)

C1—C6	1.375 (3)	C9—H9A	0.9700
C1—C2	1.377 (3)	C9—H9B	0.9700
C1—N1	1.396 (3)	C10—N4	1.299 (3)
C2—C3	1.400 (3)	C10—N2	1.368 (2)
C2—H2	0.9300	C11—N3	1.334 (3)
C3—C4	1.390 (4)	C11—N2	1.368 (2)
C3—C7	1.494 (4)	C11—S1	1.676 (2)
C4—C5	1.390 (4)	C12—N2	1.464 (3)
C4—H4	0.9300	C12—C13	1.474 (4)
C5—C6	1.361 (3)	C12—H12A	0.9700
C5—H5	0.9300	C12—H12B	0.9700
C6—O1	1.391 (3)	C13—C14A	1.169 (7)
C7—H7A	0.9600	C13—C14B	1.200 (13)
C7—H7B	0.9600	C14A—H14A	0.9300
C7—H7C	0.9600	C14A—H14B	0.9300
C8—O2	1.198 (3)	C14B—H14C	0.9300
C8—N1	1.368 (3)	C14B—H14D	0.9300
C8—O1	1.378 (3)	N3—N4	1.373 (2)
C9—N1	1.450 (3)	N3—H3	0.87 (3)
C9—C10	1.496 (3)
C6—C1—C2	121.5 (2)	N4—C10—N2	111.65 (18)
C6—C1—N1	105.88 (18)	N4—C10—C9	122.53 (18)
C2—C1—N1	132.6 (2)	N2—C10—C9	125.80 (18)
C1—C2—C3	117.5 (2)	N3—C11—N2	103.75 (18)
C1—C2—H2	121.2	N3—C11—S1	128.44 (16)
C3—C2—H2	121.2	N2—C11—S1	127.80 (16)
C4—C3—C2	119.2 (2)	N2—C12—C13	110.8 (2)
C4—C3—C7	120.7 (2)	N2—C12—H12A	109.5
C2—C3—C7	120.1 (2)	C13—C12—H12A	109.5
C3—C4—C5	123.1 (2)	N2—C12—H12B	109.5
C3—C4—H4	118.5	C13—C12—H12B	109.5
C5—C4—H4	118.5	H12A—C12—H12B	108.1
C6—C5—C4	116.0 (2)	C14A—C13—C14B	69.5 (8)
C6—C5—H5	122.0	C14A—C13—C12	134.8 (6)
C4—C5—H5	122.0	C14B—C13—C12	133.9 (10)
C5—C6—C1	122.7 (2)	C13—C14A—H14A	120.0
C5—C6—O1	128.1 (2)	C13—C14A—H14B	120.0
C1—C6—O1	109.20 (19)	H14A—C14A—H14B	120.0
C3—C7—H7A	109.5	C13—C14B—H14C	120.0
C3—C7—H7B	109.5	C13—C14B—H14D	120.0
H7A—C7—H7B	109.5	H14C—C14B—H14D	120.0
C3—C7—H7C	109.5	C8—N1—C1	109.74 (17)
H7A—C7—H7C	109.5	C8—N1—C9	123.95 (18)
H7B—C7—H7C	109.5	C1—N1—C9	126.18 (17)
O2—C8—N1	129.0 (2)	C11—N2—C10	107.61 (16)
O2—C8—O1	123.5 (2)	C11—N2—C12	124.25 (17)
N1—C8—O1	107.55 (18)	C10—N2—C12	128.12 (17)
N1—C9—C10	111.70 (17)	C11—N3—N4	113.48 (17)
N1—C9—H9A	109.3	C11—N3—H3	126.7 (18)
C10—C9—H9A	109.3	N4—N3—H3	119.6 (18)
N1—C9—H9B	109.3	C10—N4—N3	103.51 (17)
C10—C9—H9B	109.3	C8—O1—C6	107.59 (16)
H9A—C9—H9B	107.9
C6—C1—C2—C3	0.1 (3)	C6—C1—N1—C9	−177.32 (18)
N1—C1—C2—C3	−177.5 (2)	C2—C1—N1—C9	0.6 (4)
C1—C2—C3—C4	−1.0 (3)	C10—C9—N1—C8	110.1 (2)
C1—C2—C3—C7	178.2 (2)	C10—C9—N1—C1	−74.4 (3)
C2—C3—C4—C5	1.0 (4)	N3—C11—N2—C10	−0.4 (2)
C7—C3—C4—C5	−178.3 (2)	S1—C11—N2—C10	179.11 (16)
C3—C4—C5—C6	0.0 (4)	N3—C11—N2—C12	−178.78 (18)
C4—C5—C6—C1	−0.9 (4)	S1—C11—N2—C12	0.7 (3)
C4—C5—C6—O1	177.8 (2)	N4—C10—N2—C11	0.4 (2)
C2—C1—C6—C5	0.9 (3)	C9—C10—N2—C11	178.45 (18)
N1—C1—C6—C5	179.1 (2)	N4—C10—N2—C12	178.69 (18)
C2—C1—C6—O1	−178.09 (19)	C9—C10—N2—C12	−3.2 (3)
N1—C1—C6—O1	0.1 (2)	C13—C12—N2—C11	84.5 (3)
N1—C9—C10—N4	90.2 (2)	C13—C12—N2—C10	−93.5 (3)
N1—C9—C10—N2	−87.7 (2)	N2—C11—N3—N4	0.3 (2)
N2—C12—C13—C14A	131.5 (6)	S1—C11—N3—N4	−179.20 (15)
N2—C12—C13—C14B	−122.9 (12)	N2—C10—N4—N3	−0.2 (2)
O2—C8—N1—C1	−177.5 (2)	C9—C10—N4—N3	−178.34 (17)
O1—C8—N1—C1	2.0 (2)	C11—N3—N4—C10	−0.1 (2)
O2—C8—N1—C9	−1.4 (4)	O2—C8—O1—C6	177.7 (2)
O1—C8—N1—C9	178.11 (18)	N1—C8—O1—C6	−1.9 (2)
C6—C1—N1—C8	−1.3 (2)	C5—C6—O1—C8	−177.8 (2)
C2—C1—N1—C8	176.6 (2)	C1—C6—O1—C8	1.1 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···S1^i	0.87 (3)	2.41 (3)	3.284 (2)	179 (3)
C14A—H14B···S1^ii	0.93	2.74	3.506 (7)	140

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