(E)-4-(Benzo[d]thiazol-2-yl)-N-(pyridin-3-ylmethylidene)aniline hemihydrate

Hong, L.; Xin, Z.

doi:10.1107/S2414314616016084

organic compounds

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ISSN: 2414-3146

Volume 1| Part 10| October 2016| x161608

https://doi.org/10.1107/S2414314616016084

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(E)-4-(Benzo[d]thiazol-2-yl)-N-(pyridin-3-ylmethylidene)aniline hemihydrate

Li Hong ^a,^b and Zhang Xin ^a,^b ^*

^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

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 6 September 2016; accepted 11 October 2016; online 28 October 2016)

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 O_water—H⋯N_pyridine 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 electron affinity and good planarity making them appropriate building blocks in the construction of optical materials (Liu et al., 2013 ). Herein, we report the synthesis and crystal structure 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.

Figure 1
The molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

In the crystal, molecules are linked by O_water—H⋯N_pyridine hydrogen bonds, forming dimers, which in turn are linked by C—H⋯O_water 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 + $[{3\over 2}]$ , −y + $[{1\over 2}]$ , −z].

Table 1
Hydrogen-bond geometry (Å, °)

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) $[x-{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ .

Figure 2
A view along the c axis of the crystal packing of the title compound. Hydrogen bonds are shown as dashed lines (see Table 1

) and for clarity, only H atoms H1 and H2 have been included.

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 refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₉H₁₃N₃S·0.5H₂O
M_r	324.39
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	34.026 (5), 10.447 (5), 8.967 (5)
β (°)	97.601 (5)
V (Å³)	3159 (2)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.21
Crystal size (mm)	0.23 × 0.22 × 0.21

Data collection
Diffractometer	Bruker SMART CCD area detector
Absorption correction	Multi-scan (SADABS; Bruker, 2002 )
T_min, T_max	0.953, 0.957
No. of measured, independent and observed [I > 2σ(I)] reflections	11032, 2794, 2444
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.131, 1.09
No. of reflections	2794
No. of parameters	217
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.23
Computer programs: SMART and SAINT (Bruker, 2002), SHELXS97, SHELXL97 and SHELXTL (Sheldrick, 2008 ) and Mercury (Macrae et al., 2008 ).

Structural data

CCDC reference: 1509237

Crystal structure: contains datablocks I, Global. DOI: https://doi.org/10.1107/S2414314616016084/su4071sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616016084/su4071Isup2.hkl

checkCIF report

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: 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).

(E)-4-(Benzo[d]thiazol-2-yl)-N-(pyridin-3-ylmethylidene)aniline hemihydrate top

Crystal data top

C₁₉H₁₃N₃S·0.5H₂O	F(000) = 1352
M_r = 324.39	D_x = 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

Data collection top

Bruker SMART CCD area detector diffractometer	2794 independent reflections
Radiation source: fine-focus sealed tube	2444 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
phi and ω scans	θ_max = 25.0°, θ_min = 1.2°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −37→40
T_min = 0.953, T_max = 0.957	k = −12→12
11032 measured reflections	l = −10→10

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)] = 0.034	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(F_o²) + (0.1P)²] where P = (F_o² + 2F_c²)/3
2794 reflections	(Δ/σ)_max = 0.001
217 parameters	Δρ_max = 0.19 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	0.640666 (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)*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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).

References

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

(E)-4-(Benzo[d]thiazol-2-yl)-N-(pyridin-3-ylmethyl­idene)aniline hemihydrate

Structure description

Synthesis and crystallization

Refinement

Structural data

Acknowledgements

References

organic compounds

(E)-4-(Benzo[d]thiazol-2-yl)-N-(pyridin-3-ylmethylidene)aniline hemihydrate