organic compounds
4-(Benzo[d]thiazol-2-yl)-N,N-dimethylaniline
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
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.
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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 .
details are summarized in Table 2Structural data
CCDC reference: 1502512
https://doi.org/10.1107/S2414314616018472/sj4063sup1.cif
contains datablock I. DOI: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
Data collection: SMART2 (Bruker, 2000); cell
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).C15H14N2S | F(000) = 1072 |
Mr = 254.34 | Dx = 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 |
Bruker SMART2 CCD area-detector diffractometer | 2256 independent reflections |
Radiation source: fine-focus sealed tube | 1606 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.043 |
phi and ω scans | θmax = 25.0°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −13→13 |
Tmin = 0.933, Tmax = 0.955 | k = −9→9 |
16833 measured reflections | l = −34→35 |
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(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3 |
2256 reflections | (Δ/σ)max < 0.001 |
165 parameters | Δρmax = 0.14 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | ||
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* |
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) |
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) |
Acknowledgements
This work was supported by grants from the National Natural Science Foundation of China (grant Nos. 51372003 and 5167220).
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