Bis(benzothia­zol-2-ylmeth­yl)amine

Abstract

In the title compound, C₁₆H₁₃N₃S₂, the dihedral angle between the two benzothia­zole ring systems is 20.41 (2)°. In the crystal structure, inter­molecular N—H⋯N hydrogen bonds link mol­ecules into a chain along the b axis. The packing is further stabilized by C—H⋯π stacking inter­actions involving the two benzothia­zole ring systems.

Related literature

For applications of benzothiazole devivatives, see: Pinheiro et al. (1990 ▶); Emad et al. (2009 ▶). For their use as ligands, see: Oughtred et al. (1982 ▶); Akther et al. (2008 ▶). For related structures, see: Laurence et al. (1980 ▶.

Experimental

Crystal data

• C₁₆H₁₃N₃S₂

• M _r = 311.41

• Monoclinic,

• a = 7.8478 (5) Å

• b = 5.8042 (3) Å

• c = 16.1548 (9) Å

• β = 97.910 (1)°

• V = 728.85 (7) ų

• Z = 2

• Mo Kα radiation

• μ = 0.36 mm⁻¹

• T = 298 K

• 0.23 × 0.12 × 0.10 mm

Data collection

• Bruker SMART APEX CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.889, T _max = 0.965

• 9009 measured reflections

• 3603 independent reflections

• 3473 reflections with I > 2σ(I)

• R _int = 0.032

Refinement

• R[F ² > 2σ(F ²)] = 0.029

• wR(F ²) = 0.079

• S = 1.07

• 3603 reflections

• 193 parameters

• 1 restraint

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.19 e Å⁻³

• Δρ_min = −0.22 e Å⁻³

• Absolute structure: Flack (1983 ▶), 1623 Friedel pairs

• Flack parameter: −0.07 (4)

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT-Plus (Bruker, 2001 ▶; data reduction: SAINT-Plus program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N2i	0.821 (19)	2.489 (19)	3.3054 (18)	173.5 (17)
C1—H1⋯Cg1ii	0.97	2.78	3.737 (16)	168
C9—H9⋯Cg2ii	0.97	2.73	3.689 (17)	170
C14—H14⋯Cg3iii	0.93	2.89	3.598 (2)	134

Symmetry codes: (i) ; (ii) ; (iii) . Cg1, Cg2, Cg3 are the centroids of the S1,C2,N2,C3,C8, C3–C8 and C11–C16 rings, respectively.

supplementary crystallographic information

Comment

Benzothiazole devivatives have been used as photostablizers and metal chelating agents (Pinheiro et al., 1990; Emad et al., 2009). Many chelating heterocyclic ligands bearing benzothiazole group have been reported in recent years (Oughtred et al., 1982; Akther et al., 2008). The wide range of application of the benzothiazole chelators and their metal complexes aroused our interest to prepare a new series of metal complexes. With this mind, the title compound was prepared and we report the crystal stucture herein.

In the molecular structure (Fig. 1), the dihedral angle between the two benzothiazole ring systems is 20.41 (2)°. The C—N bond distances range from 1.2906 (18) to 1.4567 (18) Å, and the C—N(amino) bonds are longer than the C—N (benzothiazolyl) bonds. In the crystal structure (Fig. 2), intermolecular N—H···N hydrogen bond links molecules into a chain along the b axis. The packing is further stabilized by C—H···π stacking interactions involving two benzothiazole ring systems.

Experimental

The title compound was synthesized according to a literature procedure (Laurence et al., 1980). Single crystals suitable for X-ray diffraction were obtained by slow evaporation of a dichloromethane solution at room temperature.

Refinement

H atoms bonded to carbon atoms were placed in idealized positions [C—H(methylene)=0.97 Å and C—H(aromatic) =0.93 Å] and included in therefinement in the riding-model approximation, with U_iso(methyl and aromatic H) = 1.2Ueq(C). H atoms bonded to N atom was found from the difference map and refined with the restraint of N—H=0.86 (1)Å and U_iso(H)=1.2U_eq(N).

Figures

Fig. 1.

The molecular structure with displacement ellipsoids drawn at the 50% probability level.

Fig. 2.

Part of the crystal structure showing hydrogen bonds as dashed lines.

Crystal data

C16H13N3S2	F(000) = 324
Mr = 311.41	Dx = 1.419 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 6428 reflections
a = 7.8478 (5) Å	θ = 2.6–28.2°
b = 5.8042 (3) Å	µ = 0.36 mm−1
c = 16.1548 (9) Å	T = 298 K
β = 97.910 (1)°	Block, colourless
V = 728.85 (7) Å3	0.23 × 0.12 × 0.10 mm
Z = 2

Data collection

Bruker SMART APEX CCD area-detector diffractometer	3603 independent reflections
Radiation source: fine focus sealed Siemens Mo tube	3473 reflections with I > 2σ(I)
graphite	Rint = 0.032
0.3° wide ω exposures scans	θmax = 28.3°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −10→10
Tmin = 0.889, Tmax = 0.965	k = −7→7
9009 measured reflections	l = −21→21

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.029	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.079	w = 1/[σ2(Fo2) + (0.0549P)2 + 0.0014P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max = 0.002
3603 reflections	Δρmax = 0.19 e Å−3
193 parameters	Δρmin = −0.22 e Å−3
1 restraint	Absolute structure: Flack (1983), 1621 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.07 (4)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.32522 (18)	−0.2480 (3)	0.92805 (8)	0.0469 (3)
H1A	0.4335	−0.3306	0.9380	0.056*
H1B	0.2355	−0.3573	0.9078	0.056*
C2	0.28685 (17)	−0.1421 (3)	1.00759 (9)	0.0421 (3)
C3	0.27501 (17)	−0.0905 (3)	1.14199 (9)	0.0419 (3)
C4	0.30208 (19)	−0.1344 (3)	1.22742 (9)	0.0508 (3)
H4	0.3569	−0.2685	1.2483	0.061*
C5	0.2453 (2)	0.0270 (3)	1.28049 (10)	0.0563 (4)
H5	0.2626	0.0001	1.3378	0.068*
C6	0.1634 (2)	0.2274 (4)	1.25053 (10)	0.0552 (4)
H6	0.1279	0.3328	1.2880	0.066*
C7	0.13337 (18)	0.2734 (3)	1.16584 (9)	0.0512 (3)
H7	0.0775	0.4074	1.1456	0.061*
C8	0.18981 (17)	0.1116 (3)	1.11172 (8)	0.0430 (3)
C9	0.3518 (2)	−0.1629 (3)	0.78314 (9)	0.0520 (4)
H9A	0.2734	−0.2916	0.7712	0.062*
H9B	0.4680	−0.2194	0.7827	0.062*
C10	0.31251 (18)	0.0167 (3)	0.71708 (9)	0.0440 (3)
C11	0.30569 (18)	0.1982 (3)	0.59715 (9)	0.0463 (3)
C12	0.3417 (2)	0.2449 (4)	0.51678 (10)	0.0589 (4)
H12	0.4135	0.1486	0.4912	0.071*
C13	0.2688 (2)	0.4370 (4)	0.47583 (10)	0.0628 (5)
H13	0.2930	0.4705	0.4224	0.075*
C14	0.1602 (2)	0.5812 (4)	0.51276 (11)	0.0617 (4)
H14	0.1131	0.7100	0.4840	0.074*
C15	0.1213 (2)	0.5352 (3)	0.59197 (11)	0.0571 (4)
H15	0.0482	0.6313	0.6168	0.069*
C16	0.19401 (18)	0.3417 (3)	0.63367 (9)	0.0449 (3)
N1	0.33530 (16)	−0.0701 (2)	0.86544 (8)	0.0462 (3)
H1	0.413 (2)	0.023 (3)	0.8796 (11)	0.055*
N2	0.32946 (14)	−0.2309 (2)	1.08061 (7)	0.0448 (3)
N3	0.37321 (16)	0.0144 (3)	0.64678 (8)	0.0499 (3)
S1	0.17864 (5)	0.12218 (6)	1.00381 (2)	0.04752 (10)
S2	0.17133 (5)	0.23922 (7)	0.73265 (2)	0.05010 (11)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.0526 (7)	0.0424 (7)	0.0455 (7)	0.0054 (7)	0.0062 (6)	0.0017 (6)
C2	0.0395 (6)	0.0388 (7)	0.0475 (7)	0.0010 (5)	0.0043 (5)	0.0032 (6)
C3	0.0399 (6)	0.0417 (7)	0.0443 (7)	−0.0007 (5)	0.0062 (5)	0.0049 (5)
C4	0.0519 (8)	0.0532 (8)	0.0471 (8)	0.0010 (7)	0.0059 (6)	0.0091 (7)
C5	0.0587 (9)	0.0677 (10)	0.0437 (8)	−0.0003 (8)	0.0109 (7)	0.0042 (7)
C6	0.0572 (8)	0.0576 (9)	0.0528 (8)	0.0004 (8)	0.0145 (6)	−0.0076 (8)
C7	0.0522 (8)	0.0476 (8)	0.0536 (8)	0.0050 (7)	0.0065 (6)	0.0001 (7)
C8	0.0416 (6)	0.0446 (7)	0.0425 (6)	−0.0012 (6)	0.0044 (5)	0.0024 (6)
C9	0.0669 (9)	0.0443 (8)	0.0453 (8)	0.0058 (7)	0.0093 (7)	−0.0039 (6)
C10	0.0469 (6)	0.0413 (7)	0.0435 (7)	0.0005 (6)	0.0046 (5)	−0.0077 (6)
C11	0.0440 (7)	0.0546 (9)	0.0392 (6)	−0.0016 (6)	0.0022 (5)	−0.0045 (6)
C12	0.0568 (8)	0.0778 (12)	0.0426 (7)	0.0046 (9)	0.0082 (6)	−0.0028 (9)
C13	0.0641 (9)	0.0788 (13)	0.0439 (8)	−0.0109 (9)	0.0011 (7)	0.0083 (8)
C14	0.0631 (9)	0.0596 (11)	0.0592 (9)	−0.0012 (8)	−0.0036 (7)	0.0124 (8)
C15	0.0592 (8)	0.0528 (9)	0.0589 (9)	0.0037 (8)	0.0059 (7)	0.0034 (8)
C16	0.0432 (7)	0.0445 (7)	0.0469 (7)	−0.0045 (6)	0.0055 (5)	−0.0024 (6)
N1	0.0540 (7)	0.0441 (7)	0.0405 (6)	−0.0066 (6)	0.0063 (5)	−0.0029 (5)
N2	0.0470 (6)	0.0423 (6)	0.0454 (6)	0.0026 (5)	0.0079 (5)	0.0056 (5)
N3	0.0542 (6)	0.0545 (7)	0.0411 (6)	0.0064 (6)	0.0066 (5)	−0.0048 (6)
S1	0.0553 (2)	0.04359 (19)	0.04214 (17)	0.00959 (16)	0.00134 (13)	0.00366 (15)
S2	0.0592 (2)	0.04371 (19)	0.05053 (19)	0.00410 (16)	0.01872 (15)	−0.00142 (15)

Geometric parameters (Å, °)

C1—N1	1.4554 (19)	C9—C10	1.493 (2)
C1—C2	1.4922 (19)	C9—H9A	0.9700
C1—H1A	0.9700	C9—H9B	0.9700
C1—H1B	0.9700	C10—N3	1.2906 (18)
C2—N2	1.2884 (18)	C10—S2	1.7424 (15)
C2—S1	1.7503 (15)	C11—C12	1.393 (2)
C3—C4	1.391 (2)	C11—N3	1.394 (2)
C3—N2	1.3951 (18)	C11—C16	1.397 (2)
C3—C8	1.404 (2)	C12—C13	1.380 (3)
C4—C5	1.384 (2)	C12—H12	0.9300
C4—H4	0.9300	C13—C14	1.387 (3)
C5—C6	1.383 (3)	C13—H13	0.9300
C5—H5	0.9300	C14—C15	1.382 (2)
C6—C7	1.382 (2)	C14—H14	0.9300
C6—H6	0.9300	C15—C16	1.391 (2)
C7—C8	1.396 (2)	C15—H15	0.9300
C7—H7	0.9300	C16—S2	1.7382 (15)
C8—S1	1.7344 (13)	N1—H1	0.821 (19)
C9—N1	1.4567 (18)
N1—C1—C2	110.05 (13)	C10—C9—H9B	109.4
N1—C1—H1A	109.7	H9A—C9—H9B	108.0
C2—C1—H1A	109.7	N3—C10—C9	123.85 (14)
N1—C1—H1B	109.7	N3—C10—S2	116.97 (13)
C2—C1—H1B	109.7	C9—C10—S2	119.14 (11)
H1A—C1—H1B	108.2	C12—C11—N3	125.12 (15)
N2—C2—C1	124.47 (14)	C12—C11—C16	119.78 (16)
N2—C2—S1	116.49 (12)	N3—C11—C16	115.10 (12)
C1—C2—S1	119.04 (11)	C13—C12—C11	118.72 (17)
C4—C3—N2	125.36 (14)	C13—C12—H12	120.6
C4—C3—C8	119.93 (14)	C11—C12—H12	120.6
N2—C3—C8	114.70 (12)	C12—C13—C14	121.34 (16)
C5—C4—C3	118.20 (15)	C12—C13—H13	119.3
C5—C4—H4	120.9	C14—C13—H13	119.3
C3—C4—H4	120.9	C15—C14—C13	120.60 (17)
C6—C5—C4	121.73 (15)	C15—C14—H14	119.7
C6—C5—H5	119.1	C13—C14—H14	119.7
C4—C5—H5	119.1	C14—C15—C16	118.44 (16)
C7—C6—C5	121.09 (17)	C14—C15—H15	120.8
C7—C6—H6	119.5	C16—C15—H15	120.8
C5—C6—H6	119.5	C15—C16—C11	121.09 (14)
C6—C7—C8	117.68 (16)	C15—C16—S2	129.40 (13)
C6—C7—H7	121.2	C11—C16—S2	109.50 (11)
C8—C7—H7	121.2	C1—N1—C9	113.07 (13)
C7—C8—C3	121.37 (13)	C1—N1—H1	112.4 (13)
C7—C8—S1	128.98 (12)	C9—N1—H1	110.0 (12)
C3—C8—S1	109.60 (11)	C2—N2—C3	110.55 (13)
N1—C9—C10	111.02 (13)	C10—N3—C11	109.95 (13)
N1—C9—H9A	109.4	C8—S1—C2	88.66 (7)
C10—C9—H9A	109.4	C16—S2—C10	88.47 (7)
N1—C9—H9B	109.4
N1—C1—C2—N2	−153.63 (14)	C12—C11—C16—C15	−1.8 (2)
N1—C1—C2—S1	25.69 (16)	N3—C11—C16—C15	178.18 (14)
N2—C3—C4—C5	177.62 (14)	C12—C11—C16—S2	179.13 (13)
C8—C3—C4—C5	−0.9 (2)	N3—C11—C16—S2	−0.91 (16)
C3—C4—C5—C6	0.1 (2)	C2—C1—N1—C9	−173.01 (13)
C4—C5—C6—C7	0.6 (3)	C10—C9—N1—C1	164.09 (13)
C5—C6—C7—C8	−0.5 (2)	C1—C2—N2—C3	−179.90 (13)
C6—C7—C8—C3	−0.4 (2)	S1—C2—N2—C3	0.76 (16)
C6—C7—C8—S1	−177.64 (12)	C4—C3—N2—C2	−179.17 (14)
C4—C3—C8—C7	1.1 (2)	C8—C3—N2—C2	−0.58 (18)
N2—C3—C8—C7	−177.61 (13)	C9—C10—N3—C11	176.92 (14)
C4—C3—C8—S1	178.83 (11)	S2—C10—N3—C11	−0.93 (17)
N2—C3—C8—S1	0.15 (15)	C12—C11—N3—C10	−178.86 (15)
N1—C9—C10—N3	154.02 (15)	C16—C11—N3—C10	1.18 (18)
N1—C9—C10—S2	−28.18 (18)	C7—C8—S1—C2	177.75 (14)
N3—C11—C12—C13	−178.31 (16)	C3—C8—S1—C2	0.21 (10)
C16—C11—C12—C13	1.7 (2)	N2—C2—S1—C8	−0.59 (11)
C11—C12—C13—C14	−0.6 (3)	C1—C2—S1—C8	−179.96 (12)
C12—C13—C14—C15	−0.3 (3)	C15—C16—S2—C10	−178.68 (16)
C13—C14—C15—C16	0.2 (3)	C11—C16—S2—C10	0.31 (11)
C14—C15—C16—C11	0.8 (2)	N3—C10—S2—C16	0.37 (13)
C14—C15—C16—S2	179.72 (13)	C9—C10—S2—C16	−177.58 (13)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N2i	0.821 (19)	2.489 (19)	3.3054 (18)	173.5 (17)
C1—H1···Cg1ii	0.97	2.78	3.737 (16)	168
C9—H9···Cg2ii	0.97	2.73	3.689 (17)	170
C14—H14···Cg3iii	0.93	2.89	3.598 (2)	134

Symmetry codes: (i) −x+1, y+1/2, −z+2; (ii) −x+1, y−1/2, −z+2; (iii) −x, y+1/2, −z+1.