organic compounds
(E)-4-(Benzo[d]thiazol-2-yl)-N-(pyridin-3-ylmethylidene)aniline hemihydrate
aDepartment of Chemistry, Anhui University, Hefei 230039, People's Republic of China, and bKey Laboratory of Functional Inorganic Materials, Chemistry, Hefei 230039, People's Republic of China
*Correspondence e-mail: 1532484496@qq.com
The title compound, C19H13N3S·0.5H2O, is a benzothiazole derivative that crystallized as a hemihydrate, the water O atom being situated on a twofold rotation axis. The dihedral angles between the central benzene ring and the benzothiazole (r.m.s. deviation = 0.012 Å) and pyridine rings are 3.57 (6) and 10.12 (8)°, respectively, indicating that the molecule is nearly planar. The conformation about the N=C bond is E. In the crystal, molecules are linked by Owater—H⋯Npyridine hydrogen bonds, forming dimers, which in turn are linked by C—H⋯O hydrogen bonds into layers parallel to the ab plane. The layers are linked by offset π–π interactions, forming a three-dimensional network [shortest intercentroid distance = 3.721 (2) Å].
Keywords: crystal structure; benzothiazole; pyridine; aniline; hydrogen bonding.
CCDC reference: 1509237
Structure description
Benzothiazole derivatives are considered to be important because of their wide range of biological activities (Bakthadoss & Selvakumar, 2016), and also because of their high and good planarity making them appropriate building blocks in the construction of optical materials (Liu et al., 2013). Herein, we report the synthesis and of the title benzothiazole derivative.
The molecular structure is illustrated in Fig. 1. The molecule is relatively planar with dihedral angles between the central benzene ring (C8–C13) and the benzothiazole (r.m.s. deviation = 0.012 Å) and pyridine rings being 3.57 (6) and 10.12 (8)°, respectively.
In the crystal, molecules are linked by Owater—H⋯Npyridine hydrogen bonds, forming dimers, which in turn are linked by C—H⋯Owater hydrogen bonds into layers parallel to the ab plane (Table 1 and Fig. 2). The layers are linked by offset π–π interactions forming a three-dimensional network [shortest intercentroid distance Cg2⋯Cg3i = 3.721 (2) Å; Cg2 and Cg3 are the centroids of rings C1–C6 and N3/C15–C19, respectively; symmetry code: (i) −x + , −y + , −z].
Synthesis and crystallization
3-Pyridinecarboxaldehyde (0.29 g, 2.7 mmol) was dissolved in 20 ml of ethanol and added dropwise into 20 ml of an ethanol solution of 4-(benzothiazol-2-yl)aniline (0.61 g, 2.7 mmol). The mixture was stirred at room temperature, and a yellow solid precipitate gradually appeared after 30 min. On completion of the reaction, monitored by TLC, the solid was filtered and recrystallized from ethanol solution to produce block-like yellow crystals (yield 78.04%, 0.66 g).
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 1509237
https://doi.org/10.1107/S2414314616016084/su4071sup1.cif
contains datablocks I, Global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616016084/su4071Isup2.hkl
Data collection: SMART (Bruker, 2002); cell
SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).C19H13N3S·0.5H2O | F(000) = 1352 |
Mr = 324.39 | Dx = 1.364 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: -C 2yc | Cell parameters from 5584 reflections |
a = 34.026 (5) Å | θ = 2.4–26.7° |
b = 10.447 (5) Å | µ = 0.21 mm−1 |
c = 8.967 (5) Å | T = 296 K |
β = 97.601 (5)° | Block, yellow |
V = 3159 (2) Å3 | 0.23 × 0.22 × 0.21 mm |
Z = 8 |
Bruker SMART CCD area detector diffractometer | 2794 independent reflections |
Radiation source: fine-focus sealed tube | 2444 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.019 |
phi and ω scans | θmax = 25.0°, θmin = 1.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −37→40 |
Tmin = 0.953, Tmax = 0.957 | k = −12→12 |
11032 measured reflections | l = −10→10 |
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)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.131 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.09 | w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3 |
2794 reflections | (Δ/σ)max = 0.001 |
217 parameters | Δρmax = 0.19 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 | 0.640666 (11) | 0.04206 (4) | 0.17319 (4) | 0.0537 (2) | |
N1 | 0.66886 (3) | 0.21158 (11) | 0.37023 (13) | 0.0455 (3) | |
O1 | 1.0000 | 0.35524 (18) | 0.2500 | 0.0718 (5) | |
C6 | 0.63000 (4) | 0.18945 (13) | 0.39216 (15) | 0.0449 (3) | |
N2 | 0.83432 (4) | 0.14991 (12) | 0.10104 (14) | 0.0518 (3) | |
C1 | 0.60952 (4) | 0.09943 (13) | 0.29545 (16) | 0.0477 (4) | |
C7 | 0.67836 (4) | 0.14078 (12) | 0.26047 (15) | 0.0424 (3) | |
C11 | 0.79462 (4) | 0.14324 (13) | 0.13047 (16) | 0.0459 (4) | |
C16 | 0.89930 (5) | 0.06086 (14) | −0.16991 (18) | 0.0546 (4) | |
H16 | 0.8817 | 0.0151 | −0.2382 | 0.066* | |
C15 | 0.88592 (4) | 0.12279 (13) | −0.05054 (15) | 0.0455 (4) | |
C14 | 0.84443 (4) | 0.11634 (14) | −0.02344 (16) | 0.0475 (4) | |
H14 | 0.8253 | 0.0870 | −0.0993 | 0.057* | |
C8 | 0.71788 (4) | 0.14141 (12) | 0.21252 (15) | 0.0420 (3) | |
C5 | 0.61062 (5) | 0.24786 (15) | 0.50285 (18) | 0.0539 (4) | |
H5 | 0.6237 | 0.3079 | 0.5680 | 0.065* | |
C12 | 0.76579 (5) | 0.06122 (15) | 0.0601 (2) | 0.0570 (4) | |
H12 | 0.7720 | 0.0063 | −0.0150 | 0.068* | |
C13 | 0.72815 (5) | 0.06029 (15) | 0.10019 (18) | 0.0546 (4) | |
H13 | 0.7092 | 0.0048 | 0.0517 | 0.066* | |
C10 | 0.78445 (5) | 0.22285 (16) | 0.24345 (18) | 0.0564 (4) | |
H10 | 0.8035 | 0.2773 | 0.2932 | 0.068* | |
N3 | 0.95197 (4) | 0.19941 (15) | 0.02959 (16) | 0.0677 (4) | |
C4 | 0.57205 (5) | 0.21506 (17) | 0.51363 (19) | 0.0616 (4) | |
H4 | 0.5589 | 0.2539 | 0.5862 | 0.074* | |
C2 | 0.57032 (5) | 0.06641 (16) | 0.3070 (2) | 0.0598 (4) | |
H2 | 0.5568 | 0.0070 | 0.2420 | 0.072* | |
C9 | 0.74685 (4) | 0.22258 (15) | 0.28291 (18) | 0.0542 (4) | |
H9 | 0.7407 | 0.2776 | 0.3580 | 0.065* | |
C19 | 0.91367 (5) | 0.19251 (15) | 0.04519 (18) | 0.0562 (4) | |
H19 | 0.9049 | 0.2368 | 0.1245 | 0.067* | |
C17 | 0.93888 (5) | 0.06715 (17) | −0.1874 (2) | 0.0655 (5) | |
H17 | 0.9484 | 0.0255 | −0.2670 | 0.079* | |
C3 | 0.55236 (5) | 0.12481 (17) | 0.4178 (2) | 0.0653 (5) | |
H3 | 0.5264 | 0.1032 | 0.4288 | 0.078* | |
C18 | 0.96381 (5) | 0.13569 (17) | −0.0857 (2) | 0.0670 (5) | |
H18 | 0.9906 | 0.1382 | −0.0972 | 0.080* | |
H1 | 0.9871 (7) | 0.300 (2) | 0.188 (3) | 0.107 (8)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0521 (3) | 0.0531 (3) | 0.0567 (3) | −0.00853 (15) | 0.0102 (2) | −0.01417 (16) |
N1 | 0.0479 (7) | 0.0446 (6) | 0.0440 (7) | −0.0002 (5) | 0.0058 (5) | −0.0019 (5) |
O1 | 0.0611 (11) | 0.0734 (12) | 0.0771 (13) | 0.000 | −0.0049 (9) | 0.000 |
C6 | 0.0478 (8) | 0.0437 (7) | 0.0428 (8) | 0.0019 (6) | 0.0043 (6) | 0.0062 (6) |
N2 | 0.0454 (7) | 0.0584 (8) | 0.0514 (8) | 0.0014 (5) | 0.0060 (6) | −0.0009 (6) |
C1 | 0.0515 (9) | 0.0448 (7) | 0.0472 (8) | −0.0021 (6) | 0.0078 (6) | 0.0016 (6) |
C7 | 0.0482 (8) | 0.0392 (7) | 0.0396 (7) | 0.0012 (5) | 0.0045 (6) | 0.0029 (6) |
C11 | 0.0445 (8) | 0.0477 (8) | 0.0446 (8) | 0.0017 (6) | 0.0029 (6) | 0.0037 (6) |
C16 | 0.0568 (10) | 0.0552 (8) | 0.0528 (9) | −0.0105 (7) | 0.0105 (7) | −0.0033 (7) |
C15 | 0.0474 (8) | 0.0446 (7) | 0.0438 (8) | −0.0009 (6) | 0.0037 (6) | 0.0086 (6) |
C14 | 0.0451 (8) | 0.0510 (8) | 0.0450 (8) | −0.0007 (6) | 0.0005 (6) | 0.0045 (6) |
C8 | 0.0459 (8) | 0.0408 (7) | 0.0385 (7) | 0.0007 (5) | 0.0027 (6) | 0.0037 (5) |
C5 | 0.0565 (9) | 0.0563 (9) | 0.0496 (9) | 0.0048 (7) | 0.0096 (7) | −0.0026 (7) |
C12 | 0.0573 (10) | 0.0568 (8) | 0.0595 (9) | −0.0051 (7) | 0.0170 (7) | −0.0154 (7) |
C13 | 0.0513 (9) | 0.0559 (8) | 0.0576 (9) | −0.0098 (6) | 0.0108 (7) | −0.0135 (7) |
C10 | 0.0497 (9) | 0.0625 (9) | 0.0564 (9) | −0.0081 (7) | 0.0043 (7) | −0.0131 (7) |
N3 | 0.0520 (8) | 0.0852 (10) | 0.0645 (9) | −0.0153 (7) | 0.0024 (7) | −0.0035 (8) |
C4 | 0.0596 (10) | 0.0702 (10) | 0.0577 (10) | 0.0102 (8) | 0.0175 (8) | 0.0050 (8) |
C2 | 0.0514 (9) | 0.0627 (9) | 0.0658 (10) | −0.0098 (7) | 0.0101 (8) | −0.0023 (8) |
C9 | 0.0539 (9) | 0.0579 (9) | 0.0511 (9) | −0.0044 (7) | 0.0084 (7) | −0.0143 (7) |
C19 | 0.0537 (9) | 0.0663 (9) | 0.0481 (9) | −0.0056 (7) | 0.0046 (7) | −0.0020 (7) |
C17 | 0.0654 (11) | 0.0642 (10) | 0.0715 (12) | −0.0072 (8) | 0.0259 (9) | −0.0082 (8) |
C3 | 0.0517 (9) | 0.0744 (11) | 0.0721 (11) | −0.0022 (8) | 0.0164 (8) | 0.0085 (9) |
C18 | 0.0498 (9) | 0.0773 (11) | 0.0761 (12) | −0.0068 (8) | 0.0163 (9) | 0.0017 (9) |
S1—C1 | 1.7297 (16) | C8—C13 | 1.396 (2) |
S1—C7 | 1.7482 (14) | C5—C4 | 1.372 (2) |
N1—C7 | 1.3056 (18) | C5—H5 | 0.9300 |
N1—C6 | 1.3818 (19) | C12—C13 | 1.375 (2) |
O1—H1 | 0.87 (2) | C12—H12 | 0.9300 |
C6—C1 | 1.401 (2) | C13—H13 | 0.9300 |
C6—C5 | 1.402 (2) | C10—C9 | 1.372 (2) |
N2—C14 | 1.261 (2) | C10—H10 | 0.9300 |
N2—C11 | 1.4118 (18) | N3—C19 | 1.331 (2) |
C1—C2 | 1.394 (2) | N3—C18 | 1.336 (2) |
C7—C8 | 1.465 (2) | C4—C3 | 1.387 (3) |
C11—C10 | 1.389 (2) | C4—H4 | 0.9300 |
C11—C12 | 1.389 (2) | C2—C3 | 1.377 (2) |
C16—C17 | 1.378 (2) | C2—H2 | 0.9300 |
C16—C15 | 1.378 (2) | C9—H9 | 0.9300 |
C16—H16 | 0.9300 | C19—H19 | 0.9300 |
C15—C19 | 1.394 (2) | C17—C18 | 1.364 (2) |
C15—C14 | 1.465 (2) | C17—H17 | 0.9300 |
C14—H14 | 0.9300 | C3—H3 | 0.9300 |
C8—C9 | 1.387 (2) | C18—H18 | 0.9300 |
C1—S1—C7 | 89.23 (7) | C13—C12—H12 | 119.6 |
C7—N1—C6 | 110.47 (12) | C11—C12—H12 | 119.6 |
N1—C6—C1 | 115.55 (12) | C12—C13—C8 | 120.99 (14) |
N1—C6—C5 | 125.20 (13) | C12—C13—H13 | 119.5 |
C1—C6—C5 | 119.25 (13) | C8—C13—H13 | 119.5 |
C14—N2—C11 | 122.13 (12) | C9—C10—C11 | 121.16 (14) |
C2—C1—C6 | 121.50 (14) | C9—C10—H10 | 119.4 |
C2—C1—S1 | 129.30 (13) | C11—C10—H10 | 119.4 |
C6—C1—S1 | 109.19 (11) | C19—N3—C18 | 117.01 (15) |
N1—C7—C8 | 123.18 (12) | C5—C4—C3 | 120.96 (15) |
N1—C7—S1 | 115.56 (11) | C5—C4—H4 | 119.5 |
C8—C7—S1 | 121.26 (10) | C3—C4—H4 | 119.5 |
C10—C11—C12 | 118.12 (14) | C3—C2—C1 | 117.67 (16) |
C10—C11—N2 | 116.32 (13) | C3—C2—H2 | 121.2 |
C12—C11—N2 | 125.52 (13) | C1—C2—H2 | 121.2 |
C17—C16—C15 | 119.62 (15) | C10—C9—C8 | 120.97 (14) |
C17—C16—H16 | 120.2 | C10—C9—H9 | 119.5 |
C15—C16—H16 | 120.2 | C8—C9—H9 | 119.5 |
C16—C15—C19 | 117.20 (14) | N3—C19—C15 | 123.79 (15) |
C16—C15—C14 | 122.10 (13) | N3—C19—H19 | 118.1 |
C19—C15—C14 | 120.70 (13) | C15—C19—H19 | 118.1 |
N2—C14—C15 | 121.06 (13) | C18—C17—C16 | 118.65 (16) |
N2—C14—H14 | 119.5 | C18—C17—H17 | 120.7 |
C15—C14—H14 | 119.5 | C16—C17—H17 | 120.7 |
C9—C8—C13 | 117.97 (14) | C2—C3—C4 | 121.61 (15) |
C9—C8—C7 | 119.58 (13) | C2—C3—H3 | 119.2 |
C13—C8—C7 | 122.42 (12) | C4—C3—H3 | 119.2 |
C4—C5—C6 | 119.01 (15) | N3—C18—C17 | 123.70 (16) |
C4—C5—H5 | 120.5 | N3—C18—H18 | 118.2 |
C6—C5—H5 | 120.5 | C17—C18—H18 | 118.2 |
C13—C12—C11 | 120.77 (14) | ||
C7—N1—C6—C1 | −0.22 (17) | N1—C6—C5—C4 | −178.82 (13) |
C7—N1—C6—C5 | 178.72 (13) | C1—C6—C5—C4 | 0.1 (2) |
N1—C6—C1—C2 | 178.88 (13) | C10—C11—C12—C13 | 0.8 (2) |
C5—C6—C1—C2 | −0.1 (2) | N2—C11—C12—C13 | 178.31 (14) |
N1—C6—C1—S1 | −0.18 (16) | C11—C12—C13—C8 | −0.1 (3) |
C5—C6—C1—S1 | −179.19 (11) | C9—C8—C13—C12 | −0.3 (2) |
C7—S1—C1—C2 | −178.59 (16) | C7—C8—C13—C12 | −178.52 (14) |
C7—S1—C1—C6 | 0.39 (11) | C12—C11—C10—C9 | −1.2 (2) |
C6—N1—C7—C8 | −178.89 (11) | N2—C11—C10—C9 | −178.94 (13) |
C6—N1—C7—S1 | 0.54 (15) | C6—C5—C4—C3 | 0.5 (2) |
C1—S1—C7—N1 | −0.56 (11) | C6—C1—C2—C3 | −0.5 (2) |
C1—S1—C7—C8 | 178.88 (11) | S1—C1—C2—C3 | 178.41 (12) |
C14—N2—C11—C10 | −157.22 (14) | C11—C10—C9—C8 | 0.9 (2) |
C14—N2—C11—C12 | 25.2 (2) | C13—C8—C9—C10 | −0.1 (2) |
C17—C16—C15—C19 | 1.7 (2) | C7—C8—C9—C10 | 178.17 (14) |
C17—C16—C15—C14 | −178.10 (14) | C18—N3—C19—C15 | 0.4 (3) |
C11—N2—C14—C15 | −179.28 (12) | C16—C15—C19—N3 | −1.8 (2) |
C16—C15—C14—N2 | 164.97 (15) | C14—C15—C19—N3 | 178.03 (14) |
C19—C15—C14—N2 | −14.8 (2) | C15—C16—C17—C18 | −0.4 (3) |
N1—C7—C8—C9 | −1.6 (2) | C1—C2—C3—C4 | 1.1 (3) |
S1—C7—C8—C9 | 178.97 (11) | C5—C4—C3—C2 | −1.2 (3) |
N1—C7—C8—C13 | 176.59 (13) | C19—N3—C18—C17 | 1.1 (3) |
S1—C7—C8—C13 | −2.81 (19) | C16—C17—C18—N3 | −1.2 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N3 | 0.88 (2) | 2.03 (2) | 2.894 (2) | 170 (2) |
C2—H2···O1i | 0.93 | 2.51 | 3.245 (3) | 136 |
Symmetry code: (i) x−1/2, y−1/2, z. |
Acknowledgements
This work was supported by the Graduate Students Innovative Program of Anhui University (J18515024, J18515019, 201310357155).
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