1-(1,3-Benzothia­zol-2-yl)-3-phenyl-2-pyrazoline

Li, D.-F.; Zhu, X.-F.; Guan, S.; Hou, R.-B.

doi:10.1107/S1600536812013219

organic compounds

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ISSN: 2056-9890

Volume 68| Part 4| April 2012| Page o1248

doi:10.1107/S1600536812013219

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1-(1,3-Benzothiazol-2-yl)-3-phenyl-2-pyrazoline

Dong-Feng Li,^a Xiao-Fei Zhu,^a Shuang Guan ^a and Rui-Bin Hou ^a ^*

^aSchool of Chemistry and Life Science, Changchun University of Technology, Changchun 130012, People's Republic of China
^*Correspondence e-mail: hrb1018@163.com

(Received 6 March 2012; accepted 26 March 2012; online 31 March 2012)

In the title compound, C₁₆H₁₃N₃S, the pyrazoline ring forms dihedral angles of 6.89 (14) and 4.96 (11)° with the benzene ring and the benzothiazole group, respectively. In the crystal, weak C—H⋯N interactions link the molecules into chains extending along the b-axis direction.

Related literature

For background to the title compound, see: Sano et al. (1995 ); Xian et al. (2008 ). For details of the synthesis, see: Xian et al. (2008).

Experimental

Crystal data

C₁₆H₁₃N₃S
M_r = 279.35
Monoclinic, P 2₁ /c
a = 16.946 (8) Å
b = 5.449 (3) Å
c = 17.306 (11) Å
β = 119.96 (2)°
V = 1384.4 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 288 K
0.54 × 0.30 × 0.28 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.887, T_max = 0.938
11972 measured reflections
3141 independent reflections
2227 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.116
S = 1.14
3141 reflections
181 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯N3ⁱ	0.93	2.61	3.340 (3)	135
Symmetry code: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (MSC & Rigaku, 2002 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812013219/gk2466sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812013219/gk2466Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812013219/gk2466Isup3.cml

checkCIF report

Comment top

Pyrazoline derivatives have been investigated in many repects due to their blue light emission with high quantum yield, accessibility. They are used as carrier transporting as well as emitting materials (Sano et al., 1995). Recently, Xian reported the synthesis and optical properties of novel pyrazoline derivatives as blue light fluorescence compounds (Xian et al., 2008). In this paper, we describe the crystal structure of the title compound with blue light fluorescence.

The molecular structure of title compound, C₁₆H₁₃N₃S, is shown in Fig. 1, all bond lengths and angles are in the normal ranges. The pyrazoline ring and benzothiazole ring are nearly coplanar and make dihedral angle of 4.96 (11)°. The molecules are linked by intermolecular C—H···N hydrogen bonds (Table 1), generating chains along the b direction.

Related literature top

For background to the title compound, see: Sano et al. (1995); Xian et al. (2008). For details of the synthesis, see: Xian et al. (2008).

Experimental top

The title compound was prepared according to the literature (Xian et al., 2008). Single crystals suitable for X-ray diffraction were prepared by slow evaporation method from a solution in dichloromethane/petroleum (60–90 °C) at room temperature.

Structure description top

For background to the title compound, see: Sano et al. (1995); Xian et al. (2008). For details of the synthesis, see: Xian et al. (2008).

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (MSC & Rigaku, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. Molecular structure of the title compound with displacement ellipsoids drawn at the 30% probalility level.

1-(1,3-Benzothiazol-2-yl)-3-phenyl-2-pyrazoline top

Crystal data top

C₁₆H₁₃N₃S	F(000) = 584
M_r = 279.35	D_x = 1.340 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8759 reflections
a = 16.946 (8) Å	θ = 3.6–27.6°
b = 5.449 (3) Å	µ = 0.23 mm⁻¹
c = 17.306 (11) Å	T = 288 K
β = 119.96 (2)°	Block, colorless
V = 1384.4 (14) Å³	0.54 × 0.30 × 0.28 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID diffractometer	3141 independent reflections
Radiation source: fine-focus sealed tube	2227 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ω scans	θ_max = 27.5°, θ_min = 3.6°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −21→21
T_min = 0.887, T_max = 0.938	k = −7→6
11972 measured reflections	l = −22→22

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.116	H-atom parameters constrained
S = 1.14	w = 1/[σ²(F_o²) + (0.0607P)² + 0.0076P] where P = (F_o² + 2F_c²)/3
3141 reflections	(Δ/σ)_max < 0.001
181 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₁₆H₁₃N₃S	V = 1384.4 (14) Å³
M_r = 279.35	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 16.946 (8) Å	µ = 0.23 mm⁻¹
b = 5.449 (3) Å	T = 288 K
c = 17.306 (11) Å	0.54 × 0.30 × 0.28 mm
β = 119.96 (2)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	3141 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	2227 reflections with I > 2σ(I)
T_min = 0.887, T_max = 0.938	R_int = 0.028
11972 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.116	H-atom parameters constrained
S = 1.14	Δρ_max = 0.20 e Å⁻³
3141 reflections	Δρ_min = −0.20 e Å⁻³
181 parameters

Special details top

Experimental. (See detailed section in the paper)

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	0.50225 (3)	−0.17993 (8)	0.32651 (3)	0.05497 (16)
N1	0.43537 (9)	0.1902 (2)	0.37317 (10)	0.0552 (4)
N2	0.59086 (9)	0.1280 (3)	0.46547 (10)	0.0569 (4)
N3	0.66870 (9)	0.0055 (2)	0.48121 (9)	0.0541 (3)
C1	0.38592 (10)	−0.1199 (3)	0.26333 (11)	0.0502 (4)
C2	0.32007 (12)	−0.2465 (4)	0.18951 (13)	0.0617 (5)
H2	0.3354	−0.3833	0.1677	0.074*
C3	0.23125 (12)	−0.1641 (4)	0.14930 (13)	0.0678 (5)
H3	0.1862	−0.2452	0.0994	0.081*
C4	0.20868 (12)	0.0380 (4)	0.18261 (13)	0.0690 (5)
H4	0.1485	0.0913	0.1544	0.083*
C5	0.27335 (12)	0.1621 (3)	0.25656 (13)	0.0629 (5)
H5	0.2570	0.2966	0.2786	0.075*
C6	0.36345 (10)	0.0836 (3)	0.29788 (11)	0.0509 (4)
C7	0.50936 (10)	0.0702 (3)	0.39398 (11)	0.0499 (4)
C8	0.60831 (11)	0.3438 (3)	0.52172 (12)	0.0554 (4)
H8A	0.5770	0.3329	0.5557	0.066*
H8B	0.5901	0.4934	0.4867	0.066*
C9	0.71109 (11)	0.3312 (3)	0.58214 (12)	0.0568 (4)
H9A	0.7402	0.4805	0.5784	0.068*
H9B	0.7274	0.3038	0.6437	0.068*
C10	0.73713 (11)	0.1147 (3)	0.54526 (11)	0.0493 (4)
C11	0.83120 (11)	0.0387 (3)	0.57541 (12)	0.0546 (4)
C12	0.85070 (13)	−0.1548 (4)	0.53559 (14)	0.0704 (5)
H12	0.8037	−0.2453	0.4906	0.085*
C13	0.94034 (15)	−0.2128 (5)	0.56296 (17)	0.0892 (7)
H13	0.9533	−0.3426	0.5362	0.107*
C14	1.01079 (15)	−0.0798 (5)	0.62958 (18)	0.0935 (7)
H14	1.0709	−0.1183	0.6471	0.112*
C15	0.99182 (13)	0.1075 (5)	0.66937 (17)	0.0882 (7)
H15	1.0392	0.1961	0.7147	0.106*
C16	0.90289 (12)	0.1677 (4)	0.64329 (14)	0.0725 (5)
H16	0.8909	0.2958	0.6714	0.087*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0594 (3)	0.0536 (3)	0.0590 (3)	0.00083 (18)	0.0349 (2)	−0.00678 (19)
N1	0.0564 (8)	0.0489 (8)	0.0602 (9)	−0.0009 (6)	0.0290 (7)	−0.0076 (6)
N2	0.0519 (7)	0.0566 (8)	0.0600 (9)	0.0041 (6)	0.0262 (7)	−0.0112 (7)
N3	0.0600 (8)	0.0525 (8)	0.0543 (8)	0.0057 (6)	0.0318 (7)	−0.0010 (6)
C1	0.0578 (9)	0.0483 (9)	0.0526 (9)	−0.0047 (7)	0.0336 (8)	−0.0014 (7)
C2	0.0682 (11)	0.0625 (10)	0.0650 (12)	−0.0099 (8)	0.0413 (9)	−0.0154 (9)
C3	0.0627 (10)	0.0779 (13)	0.0625 (12)	−0.0164 (9)	0.0311 (9)	−0.0172 (9)
C4	0.0552 (10)	0.0773 (13)	0.0703 (13)	−0.0026 (9)	0.0281 (9)	−0.0058 (10)
C5	0.0601 (9)	0.0554 (11)	0.0721 (12)	0.0015 (8)	0.0322 (9)	−0.0074 (9)
C6	0.0569 (9)	0.0448 (9)	0.0544 (10)	−0.0052 (7)	0.0304 (8)	−0.0018 (7)
C7	0.0570 (9)	0.0450 (9)	0.0533 (10)	−0.0026 (7)	0.0317 (8)	−0.0020 (7)
C8	0.0613 (9)	0.0485 (9)	0.0548 (10)	0.0041 (7)	0.0279 (8)	−0.0052 (7)
C9	0.0593 (9)	0.0516 (10)	0.0588 (11)	0.0004 (7)	0.0291 (8)	−0.0049 (8)
C10	0.0564 (9)	0.0482 (9)	0.0478 (9)	0.0045 (7)	0.0294 (7)	0.0060 (7)
C11	0.0592 (9)	0.0552 (10)	0.0550 (10)	0.0082 (8)	0.0327 (8)	0.0117 (8)
C12	0.0716 (11)	0.0737 (13)	0.0710 (13)	0.0159 (9)	0.0393 (10)	0.0026 (10)
C13	0.0864 (15)	0.0968 (17)	0.0963 (18)	0.0324 (13)	0.0546 (14)	0.0062 (14)
C14	0.0644 (12)	0.118 (2)	0.1009 (19)	0.0243 (13)	0.0430 (13)	0.0210 (16)
C15	0.0573 (11)	0.0989 (16)	0.0930 (17)	0.0079 (11)	0.0259 (11)	0.0044 (14)
C16	0.0586 (10)	0.0765 (13)	0.0736 (14)	0.0073 (9)	0.0264 (10)	0.0004 (10)

Geometric parameters (Å, º) top

S1—C1	1.7424 (18)	C8—C9	1.521 (2)
S1—C7	1.7591 (18)	C8—H8A	0.9700
N1—C7	1.296 (2)	C8—H8B	0.9700
N1—C6	1.391 (2)	C9—C10	1.508 (2)
N2—C7	1.353 (2)	C9—H9A	0.9700
N2—N3	1.3788 (18)	C9—H9B	0.9700
N2—C8	1.459 (2)	C10—C11	1.468 (2)
N3—C10	1.282 (2)	C11—C12	1.387 (3)
C1—C2	1.389 (2)	C11—C16	1.387 (3)
C1—C6	1.400 (2)	C12—C13	1.383 (3)
C2—C3	1.380 (3)	C12—H12	0.9300
C2—H2	0.9300	C13—C14	1.380 (3)
C3—C4	1.382 (3)	C13—H13	0.9300
C3—H3	0.9300	C14—C15	1.356 (4)
C4—C5	1.377 (2)	C14—H14	0.9300
C4—H4	0.9300	C15—C16	1.379 (3)
C5—C6	1.391 (2)	C15—H15	0.9300
C5—H5	0.9300	C16—H16	0.9300

C1—S1—C7	87.26 (8)	N2—C8—H8B	111.4
C7—N1—C6	108.86 (14)	C9—C8—H8B	111.4
C7—N2—N3	120.46 (14)	H8A—C8—H8B	109.3
C7—N2—C8	124.87 (14)	C10—C9—C8	102.76 (13)
N3—N2—C8	113.78 (13)	C10—C9—H9A	111.2
C10—N3—N2	108.00 (14)	C8—C9—H9A	111.2
C2—C1—C6	121.40 (15)	C10—C9—H9B	111.2
C2—C1—S1	128.44 (14)	C8—C9—H9B	111.2
C6—C1—S1	110.15 (12)	H9A—C9—H9B	109.1
C3—C2—C1	118.38 (17)	N3—C10—C11	121.95 (15)
C3—C2—H2	120.8	N3—C10—C9	113.54 (13)
C1—C2—H2	120.8	C11—C10—C9	124.44 (15)
C2—C3—C4	120.52 (17)	C12—C11—C16	118.72 (16)
C2—C3—H3	119.7	C12—C11—C10	121.59 (17)
C4—C3—H3	119.7	C16—C11—C10	119.65 (16)
C5—C4—C3	121.41 (17)	C13—C12—C11	119.8 (2)
C5—C4—H4	119.3	C13—C12—H12	120.1
C3—C4—H4	119.3	C11—C12—H12	120.1
C4—C5—C6	119.12 (16)	C14—C13—C12	120.7 (2)
C4—C5—H5	120.4	C14—C13—H13	119.7
C6—C5—H5	120.4	C12—C13—H13	119.7
N1—C6—C5	125.20 (15)	C15—C14—C13	119.6 (2)
N1—C6—C1	115.65 (14)	C15—C14—H14	120.2
C5—C6—C1	119.14 (15)	C13—C14—H14	120.2
N1—C7—N2	122.74 (15)	C14—C15—C16	120.7 (2)
N1—C7—S1	118.07 (12)	C14—C15—H15	119.7
N2—C7—S1	119.18 (12)	C16—C15—H15	119.7
N2—C8—C9	101.73 (12)	C15—C16—C11	120.6 (2)
N2—C8—H8A	111.4	C15—C16—H16	119.7
C9—C8—H8A	111.4	C11—C16—H16	119.7

C7—N2—N3—C10	171.82 (15)	C8—N2—C7—S1	173.69 (13)
C8—N2—N3—C10	2.14 (19)	C1—S1—C7—N1	−0.77 (13)
C7—S1—C1—C2	−178.47 (17)	C1—S1—C7—N2	178.58 (14)
C7—S1—C1—C6	0.79 (12)	C7—N2—C8—C9	−173.15 (16)
C6—C1—C2—C3	1.2 (3)	N3—N2—C8—C9	−4.01 (18)
S1—C1—C2—C3	−179.59 (14)	N2—C8—C9—C10	3.99 (16)
C1—C2—C3—C4	−0.7 (3)	N2—N3—C10—C11	−176.45 (14)
C2—C3—C4—C5	−0.3 (3)	N2—N3—C10—C9	0.87 (19)
C3—C4—C5—C6	0.7 (3)	C8—C9—C10—N3	−3.27 (19)
C7—N1—C6—C5	179.52 (15)	C8—C9—C10—C11	173.97 (15)
C7—N1—C6—C1	0.2 (2)	N3—C10—C11—C12	0.4 (3)
C4—C5—C6—N1	−179.49 (17)	C9—C10—C11—C12	−176.66 (16)
C4—C5—C6—C1	−0.2 (3)	N3—C10—C11—C16	178.12 (17)
C2—C1—C6—N1	178.56 (15)	C9—C10—C11—C16	1.1 (2)
S1—C1—C6—N1	−0.76 (18)	C16—C11—C12—C13	−1.0 (3)
C2—C1—C6—C5	−0.8 (3)	C10—C11—C12—C13	176.74 (18)
S1—C1—C6—C5	179.88 (13)	C11—C12—C13—C14	0.0 (3)
C6—N1—C7—N2	−178.85 (15)	C12—C13—C14—C15	0.9 (4)
C6—N1—C7—S1	0.47 (18)	C13—C14—C15—C16	−0.6 (4)
N3—N2—C7—N1	−175.46 (14)	C14—C15—C16—C11	−0.4 (4)
C8—N2—C7—N1	−7.0 (3)	C12—C11—C16—C15	1.3 (3)
N3—N2—C7—S1	5.2 (2)	C10—C11—C16—C15	−176.54 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···N3ⁱ	0.93	2.61	3.340 (3)	135

Symmetry code: (i) −x+1, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₃N₃S
M_r	279.35
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	288
a, b, c (Å)	16.946 (8), 5.449 (3), 17.306 (11)
β (°)	119.96 (2)
V (Å³)	1384.4 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.23
Crystal size (mm)	0.54 × 0.30 × 0.28

Data collection
Diffractometer	Rigaku R-AXIS RAPID
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.887, 0.938
No. of measured, independent and observed [I > 2σ(I)] reflections	11972, 3141, 2227
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.116, 1.14
No. of reflections	3141
No. of parameters	181
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.20

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (MSC & Rigaku, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···N3ⁱ	0.93	2.61	3.340 (3)	135

Symmetry code: (i) −x+1, y−1/2, −z+1/2.

Acknowledgements

The authors acknowledge financial support from the National Natural Science Foundation of Jilin Province (grant No. 20101548).

References

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