4-(Benzo[d]thia­zol-2-yl)-N,N-di­methyl­aniline

Tang, Y.-W.; Wang, J.-H.; Xie, Q.-Y.; Wang, Q.; Wu, J.-Y.

doi:10.1107/S2414314616018472

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 11| November 2016| x161847

https://doi.org/10.1107/S2414314616018472

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4-(Benzo[d]thiazol-2-yl)-N,N-dimethylaniline

Yi-Wen Tang,^a Jing-Hang Wang,^a Qing-Yuan Xie,^a Quan Wang ^a and Jie-Ying Wu ^a ^*

^aDeparment of Chemistry, Anhui University, Hefei 230039, Peoples Republic of China, Key Laboratory of Functional Inorganic Materials, Chemistry, Hefei 230039, People's Republic of China
^*Correspondence e-mail: jywu1957@163.com

Edited by J. Simpson, University of Otago, New Zealand (Received 1 October 2016; accepted 18 November 2016; online 29 November 2016)

The whole molecule of the title compound, C₁₅H₁₄N₂S, is approximately planar, with an r.m.s. deviation of 0.0382 Å from the best-fit mean plane through all 18 non-H atoms. In the crystal, dimers form through π–π stacking interactions between the benzene rings of adjacent benzothiazole ring systems, with a centroid–centroid separation of 3.6834 (16) Å.

Keywords: crystal structure; benzothiazole; π–π stacking.

CCDC reference: 1502512

Structure description

Benzothiazole is an important bicyclic ring system that is present in a variety of materials with biological applications (Prajapati et al., 2014 ). Water solubility and biocompatibility can be tuned in such systems by introducing different substituent groups on the benzothiazole ring system (Li et al., 2015 ). Also, because of their unique photophysical properties, solid-state emitters based on benzothiazole have been attracting considerable interest over the past few years in the field of optoelectronic devices (Padalkar et al., 2016 ). A series of benzothiazole derivatives have also been used recently recently both as fluorescent probes for anions and as bioactive molecules in living cells (Li et al., 2015; Zhang et al., 2015 ; Qian et al., 2016 ). In order to better understand the structure-property relationships of benzothiazole derivatives, we have synthesized the title compound and its structure is reported here.

As shown in Fig. 1, the whole molecule is approximately planar, with an r.m.s. deviation of 0.0382 Å from the best-fit mean plane through all 18 non-H atoms. The benzothiazole ring system is inclined to the benzene ring by 4.59 (4)°. This planarity is reinforced by a weak intramolecular C13—H13⋯S1 contact (Table 1) that encloses an S(5) ring. The bond lengths in the structure are similar to those found in a closely related compound (Lynn et al., 2012 ). In the crystal, dimers are formed through an offset π–π stacking interaction between two adjacent C1–C6 rings (Fig. 2) [Cg2⋯Cg2ⁱ = 3.6834 (16) Å; symmetry code: (i) −x + 2, −y, −z + 1]. No other significant contacts are found between the dimers.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13⋯S1	0.93	2.71	3.127 (3)	108

Figure 1
The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level.

Figure 2
Stacking interactions between adjacent C1–C6 rings forming dimeric molecular pairs. Centroids are shown as red spheres linked by green dotted lines.

Synthesis and crystallization

4-(Dimethylamino)benzaldehyde (2.98 g, 20 mmol) and 4-aminothiophenol (2.50 g, 20 mmol) were dissolved in 50 ml of ethyl alcohol and heated to reflux for 6 h. The reaction mixture was cooled to room temperature and filtered to obtain 4.69 g of yellow crystals (yield = 92.3%). ¹H NMR (400 MHz, DMSO-d₆): δ 8.04 (d, J = 7.8 Hz, 1H), 7.93 (d, J = 8.1 Hz, 1H), 7.89 (d, J = 8.9 Hz, 2H), 7.47 (t, J = 7.6 Hz, 1H), 7.36 (t, J = 7.6 Hz, 1H), 6.82 (d, J = 8.9 Hz, 2H), 3.02 (s, 6H).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₅H₁₄N₂S
M_r	254.34
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	296
a, b, c (Å)	11.0177 (15), 7.8508 (11), 29.691 (4)
V (Å³)	2568.2 (6)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.23
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Bruker SMART2 CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2000 )
T_min, T_max	0.933, 0.955
No. of measured, independent and observed [I > 2σ(I)] reflections	16833, 2256, 1606
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.154, 1.05
No. of reflections	2256
No. of parameters	165
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.23
Computer programs: SMART2 and SAINT (Bruker, 2000), SHELXS97, SHELXL97 and SHELXTL (Sheldrick, 2008 ).

Structural data

CCDC reference: 1502512

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314616018472/sj4063sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616018472/sj4063Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314616018472/sj4063Isup3.cml

checkCIF report

Computing details top

Data collection: SMART2 (Bruker, 2000); cell refinement: SMART2 (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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: SHELXTL (Sheldrick, 2008).

4-(Benzo[d]thiazol-2-yl)-N,N-dimethylaniline top

Crystal data top

C₁₅H₁₄N₂S	F(000) = 1072
M_r = 254.34	D_x = 1.316 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 3029 reflections
a = 11.0177 (15) Å	θ = 2.3–23.8°
b = 7.8508 (11) Å	µ = 0.23 mm⁻¹
c = 29.691 (4) Å	T = 296 K
V = 2568.2 (6) Å³	Rod-like, colourless
Z = 8	0.30 × 0.20 × 0.20 mm

Data collection top

Bruker SMART2 CCD area-detector diffractometer	2256 independent reflections
Radiation source: fine-focus sealed tube	1606 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
phi and ω scans	θ_max = 25.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −13→13
T_min = 0.933, T_max = 0.955	k = −9→9
16833 measured reflections	l = −34→35

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.154	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.1P)²] where P = (F_o² + 2F_c²)/3
2256 reflections	(Δ/σ)_max < 0.001
165 parameters	Δρ_max = 0.14 e Å⁻³
0 restraints	Δρ_min = −0.23 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.

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
S1	0.77770 (6)	0.01253 (8)	0.60466 (2)	0.0696 (3)
N1	0.96074 (15)	0.2173 (2)	0.61401 (7)	0.0612 (5)
C9	0.96654 (17)	0.2058 (3)	0.71182 (9)	0.0568 (6)
H9	1.0276	0.2661	0.6972	0.068*
C6	0.93875 (18)	0.2027 (3)	0.56823 (8)	0.0593 (6)
C8	0.87971 (17)	0.1203 (2)	0.68596 (7)	0.0529 (5)
C11	0.87395 (17)	0.1146 (2)	0.78151 (8)	0.0562 (6)
C10	0.96477 (17)	0.2037 (3)	0.75759 (8)	0.0585 (6)
H10	1.0245	0.2620	0.7735	0.070*
C1	0.8422 (2)	0.0953 (3)	0.55647 (8)	0.0632 (6)
C7	0.88269 (17)	0.1277 (2)	0.63709 (8)	0.0551 (6)
C13	0.78936 (17)	0.0326 (3)	0.70975 (9)	0.0598 (6)
H13	0.7297	−0.0254	0.6937	0.072*
N2	0.87142 (17)	0.1140 (3)	0.82771 (7)	0.0711 (6)
C12	0.78625 (18)	0.0298 (3)	0.75562 (9)	0.0607 (6)
H12	0.7246	−0.0297	0.7701	0.073*
C5	1.0048 (2)	0.2827 (3)	0.53448 (10)	0.0757 (7)
H5	1.0690	0.3546	0.5418	0.091*
C2	0.8123 (2)	0.0686 (3)	0.51142 (10)	0.0779 (7)
H2	0.7482	−0.0025	0.5036	0.093*
C15	0.7785 (2)	0.0236 (4)	0.85263 (10)	0.0843 (8)
H15A	0.7000	0.0662	0.8443	0.126*
H15B	0.7909	0.0404	0.8843	0.126*
H15C	0.7832	−0.0958	0.8458	0.126*
C4	0.9750 (3)	0.2551 (3)	0.49059 (10)	0.0834 (8)
H4	1.0195	0.3084	0.4680	0.100*
C3	0.8790 (3)	0.1487 (4)	0.47891 (9)	0.0867 (8)
H3	0.8601	0.1319	0.4487	0.104*
C14	0.9704 (2)	0.1817 (4)	0.85393 (9)	0.0875 (8)
H14A	1.0460	0.1539	0.8396	0.131*
H14B	0.9686	0.1331	0.8836	0.131*
H14C	0.9626	0.3032	0.8560	0.131*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0590 (4)	0.0574 (4)	0.0923 (6)	−0.0116 (3)	−0.0100 (3)	−0.0052 (3)
N1	0.0511 (10)	0.0507 (11)	0.0818 (14)	−0.0054 (9)	−0.0010 (9)	−0.0012 (9)
C9	0.0404 (10)	0.0462 (11)	0.0840 (17)	−0.0056 (9)	0.0036 (10)	0.0009 (10)
C6	0.0549 (11)	0.0485 (12)	0.0745 (16)	0.0051 (10)	−0.0017 (11)	−0.0053 (10)
C8	0.0413 (10)	0.0371 (10)	0.0802 (15)	0.0027 (8)	−0.0037 (9)	−0.0019 (10)
C11	0.0469 (11)	0.0385 (11)	0.0833 (16)	0.0057 (9)	0.0043 (10)	0.0030 (10)
C10	0.0428 (11)	0.0533 (12)	0.0795 (17)	−0.0059 (9)	−0.0013 (10)	−0.0042 (11)
C1	0.0592 (12)	0.0496 (13)	0.0807 (16)	0.0071 (10)	−0.0074 (11)	−0.0070 (11)
C7	0.0429 (11)	0.0384 (11)	0.0838 (16)	0.0047 (9)	−0.0070 (10)	−0.0029 (10)
C13	0.0458 (12)	0.0431 (12)	0.0906 (19)	−0.0058 (9)	−0.0089 (11)	0.0002 (11)
N2	0.0649 (13)	0.0693 (13)	0.0791 (14)	−0.0098 (10)	0.0046 (10)	0.0022 (10)
C12	0.0458 (12)	0.0472 (13)	0.0890 (18)	−0.0075 (9)	0.0031 (10)	0.0068 (11)
C5	0.0708 (15)	0.0705 (16)	0.086 (2)	−0.0048 (13)	0.0014 (13)	−0.0022 (13)
C2	0.0772 (16)	0.0642 (16)	0.092 (2)	0.0036 (13)	−0.0166 (15)	−0.0115 (15)
C15	0.0753 (17)	0.0795 (19)	0.098 (2)	−0.0083 (14)	0.0139 (14)	0.0124 (15)
C4	0.0898 (18)	0.0784 (19)	0.082 (2)	0.0054 (15)	0.0059 (15)	0.0010 (14)
C3	0.099 (2)	0.0790 (18)	0.0820 (18)	0.0163 (16)	−0.0088 (16)	−0.0074 (16)
C14	0.0789 (17)	0.102 (2)	0.0818 (19)	−0.0037 (16)	−0.0025 (14)	−0.0044 (15)

Geometric parameters (Å, º) top

S1—C1	1.725 (2)	C13—H13	0.9300
S1—C7	1.756 (2)	N2—C14	1.442 (3)
N1—C7	1.305 (3)	N2—C15	1.449 (3)
N1—C6	1.385 (3)	C12—H12	0.9300
C9—C10	1.359 (3)	C5—C4	1.361 (4)
C9—C8	1.398 (3)	C5—H5	0.9300
C9—H9	0.9300	C2—C3	1.366 (4)
C6—C5	1.389 (3)	C2—H2	0.9300
C6—C1	1.402 (3)	C15—H15A	0.9600
C8—C13	1.401 (3)	C15—H15B	0.9600
C8—C7	1.452 (3)	C15—H15C	0.9600
C11—N2	1.372 (3)	C4—C3	1.392 (4)
C11—C12	1.403 (3)	C4—H4	0.9300
C11—C10	1.413 (3)	C3—H3	0.9300
C10—H10	0.9300	C14—H14A	0.9600
C1—C2	1.393 (3)	C14—H14B	0.9600
C13—C12	1.363 (4)	C14—H14C	0.9600

C1—S1—C7	89.41 (11)	C14—N2—C15	116.0 (2)
C7—N1—C6	110.82 (18)	C13—C12—C11	121.5 (2)
C10—C9—C8	122.2 (2)	C13—C12—H12	119.2
C10—C9—H9	118.9	C11—C12—H12	119.2
C8—C9—H9	118.9	C4—C5—C6	119.5 (2)
N1—C6—C5	125.4 (2)	C4—C5—H5	120.3
N1—C6—C1	115.3 (2)	C6—C5—H5	120.3
C5—C6—C1	119.4 (2)	C3—C2—C1	118.8 (3)
C9—C8—C13	116.4 (2)	C3—C2—H2	120.6
C9—C8—C7	120.94 (19)	C1—C2—H2	120.6
C13—C8—C7	122.62 (19)	N2—C15—H15A	109.5
N2—C11—C12	122.2 (2)	N2—C15—H15B	109.5
N2—C11—C10	121.2 (2)	H15A—C15—H15B	109.5
C12—C11—C10	116.6 (2)	N2—C15—H15C	109.5
C9—C10—C11	121.3 (2)	H15A—C15—H15C	109.5
C9—C10—H10	119.4	H15B—C15—H15C	109.5
C11—C10—H10	119.4	C5—C4—C3	121.2 (3)
C2—C1—C6	120.6 (2)	C5—C4—H4	119.4
C2—C1—S1	130.0 (2)	C3—C4—H4	119.4
C6—C1—S1	109.43 (17)	C2—C3—C4	120.6 (3)
N1—C7—C8	124.11 (18)	C2—C3—H3	119.7
N1—C7—S1	115.06 (17)	C4—C3—H3	119.7
C8—C7—S1	120.83 (15)	N2—C14—H14A	109.5
C12—C13—C8	122.0 (2)	N2—C14—H14B	109.5
C12—C13—H13	119.0	H14A—C14—H14B	109.5
C8—C13—H13	119.0	N2—C14—H14C	109.5
C11—N2—C14	121.6 (2)	H14A—C14—H14C	109.5
C11—N2—C15	121.8 (2)	H14B—C14—H14C	109.5

C7—N1—C6—C5	179.6 (2)	C1—S1—C7—N1	−1.29 (16)
C7—N1—C6—C1	−1.3 (3)	C1—S1—C7—C8	178.67 (17)
C10—C9—C8—C13	0.5 (3)	C9—C8—C13—C12	−0.3 (3)
C10—C9—C8—C7	178.81 (19)	C7—C8—C13—C12	−178.59 (19)
C8—C9—C10—C11	−0.2 (3)	C12—C11—N2—C14	171.5 (2)
N2—C11—C10—C9	−179.3 (2)	C10—C11—N2—C14	−9.5 (3)
C12—C11—C10—C9	−0.3 (3)	C12—C11—N2—C15	0.8 (3)
N1—C6—C1—C2	−179.1 (2)	C10—C11—N2—C15	179.80 (19)
C5—C6—C1—C2	0.0 (3)	C8—C13—C12—C11	−0.2 (3)
N1—C6—C1—S1	0.4 (2)	N2—C11—C12—C13	179.4 (2)
C5—C6—C1—S1	179.49 (17)	C10—C11—C12—C13	0.4 (3)
C7—S1—C1—C2	179.9 (2)	N1—C6—C5—C4	178.8 (2)
C7—S1—C1—C6	0.47 (16)	C1—C6—C5—C4	−0.2 (3)
C6—N1—C7—C8	−178.27 (18)	C6—C1—C2—C3	0.1 (4)
C6—N1—C7—S1	1.7 (2)	S1—C1—C2—C3	−179.2 (2)
C9—C8—C7—N1	−2.9 (3)	C6—C5—C4—C3	0.3 (4)
C13—C8—C7—N1	175.30 (18)	C1—C2—C3—C4	−0.1 (4)
C9—C8—C7—S1	177.11 (14)	C5—C4—C3—C2	−0.2 (4)
C13—C8—C7—S1	−4.7 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···S1	0.93	2.71	3.127 (3)	108

Acknowledgements

This work was supported by grants from the National Natural Science Foundation of China (grant Nos. 51372003 and 5167220).

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