1,4-Bis(benzothia­zol-2-yl)benzene

The title compound, C₂₀H₁₂N₂S₂, was prepared by the reaction of amino­thio­phenol with 1,4-dicarboxy­aldehyde. The mol­ecule is centrosymmetric. The crystal structure is stabilized by an intra­molecular C—H...S hydrogen-bonding inter­action.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.031
• wR factor = 0.084
• Data-to-parameter ratio = 12.6

checkCIF/PLATON results

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Alert level C
PLAT322_ALERT_2_C Check Hybridisation of  S1     in Main Residue .          ?
PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) .       1.14 Ratio

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

In this work we communicate the synthesis and the structural characterization of the C₂₀H₁₂N₂S₂, molecule (I). Organic molecules with pairs of free electrons can be useful as ligand precursors in the synthesis of coordination complexes. The other very interesting aspect for this study are the intermolecular interactions driven by C—H··· π, directional forces, a feature with known influence to the development of supramolecular architectures. Even as weak interactions, is now clear that they play an important role in the tuning and prediction of important supramolecular precursors.

Compound (I) was synthesized considering the above statements, and his structural analysis showed a central phenyl ring environment hardwired with two phenylthiazole terminations, scheme 1. Figure 1 shows an ORTEP plot corresponding to 70% probability ellipsoids. Distance parameters of C—C, C—S and C—N bonds shown in table 1 are in good agreement with literature values (Allen et al., 1987).

The crystal structure is stabilized by a single intramolecular C—H···S hydrogen bond (Jeffrey et al., 1985) producing a five-membered ring. The corresponding geometric parameters are listed in table 2.

The C1/C2/S1/C7/N1 ring derives from the plane of C8/C9/C10/C10ⁱⁱ/C9ⁱⁱ/C8ⁱⁱ [Symmetry code: (ii) = -x, 1 - y, -z)] ring from 18,3(1)°.

Related literature

For related literature, see: Allen et al. (1987); Jeffrey et al. (1985).

S2. Experimental

1,4-dicarboxyaldehyde (0.1 mol, 0,134 g) was heated in ethanol to 313 K and the mixture stirred for 15 min. 2-aminothiophenol (0.2 mol, 0,250 g) was added dropwise over 10 min. The temperature was maintained at this temperature for 2 h with efficient stirring before cooling to room temperature. The resulting yellow powder was filtered and dried overnight. The solid was recrystallized with methanol to yield 1,4-bis(benzothiazol-2-yl)benzene as yellow crystals. (yield: 0.28 g, 82%; m.p. 436 K).

S3. Refinement

H10 and H8 atoms where located in a difference map and refined with distances of C10—H10 = 0.91 (2) Å and C8—H8 = 0.95 (2) and withU_iso(H) = 1.2U_eq(C). The others H atoms bonded to phenyl carbon atoms were obtained geometrically, the C—H distances fixed (0.93 Å for C_sp2 H atoms),and the atoms refined as riding on their respective C atoms, with anisotropic displacement parameter 1.2 times the U_eq value for the attached C_sp2 atom.

Computing details

Data collection: COLLECT (Nonius, 1998); cell refinement: PhiChi (Duisenberg et al., 2000); data reduction: DIRAX (Duisenberg, 1992); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

Fig. 1. - ORTEP of (I) with thermal parameters in a level of 70% probability.

1,4-Bis(benzothiazol-2-yl)benzene

Crystal data

C20H12N2S2	F(000) = 712
Mr = 344.44	Dx = 1.432 Mg m^−3
Monoclinic, C2/c	Melting point: 436 K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 22.702 (5) Å	θ = 1–27.5°
b = 6.4839 (13) Å	µ = 0.34 mm^−1
c = 11.626 (2) Å	T = 295 K
β = 110.96 (3)°	Block, yellow
V = 1598.1 (6) Å^3	0.4 × 0.04 × 0.04 mm
Z = 4

Data collection

Nonius KappaCCD diffractometer	1230 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.046
Graphite monochromator	θmax = 25.5°, θmin = 3.3°
φ scans, and ω scans with κ	h = −26→27
8151 measured reflections	k = −7→7
1475 independent reflections	l = −12→14

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.084	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0408P)^2 + 1.278P] where P = (Fo^2 + 2Fc^2)/3
1475 reflections	(Δ/σ)max < 0.001
117 parameters	Δρmax = 0.19 e Å^−3
0 restraints	Δρmin = −0.24 e Å^−3

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.

Distance BIND

3.1392 (0.0019) C10 - S1 2.7569 (0.0222) S1 - H10 3.4624 (0.0036) C10 - C10_$2 2.8586 (0.0226) H10 - C10_$2

Angle ANG

106.71 (1.61) C10 - H10 - S1 125.40 (1.70) C10 - H10 - C10_$2

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

17.7363 (0.0131) x + 3.6740 (0.0046) y - 0.4059 (0.0069) z = 1.9060 (0.0018)

* -0.0041 (0.0011) C1 * 0.0057 (0.0009) C2 * -0.0050 (0.0007) S1 * 0.0042 (0.0009) C7 * -0.0009 (0.0010) N1

Rms deviation of fitted atoms = 0.0043

19.8212 (0.0150) x + 3.1548 (0.0058) y - 3.9670 (0.0119) z = 1.5774 (0.0029)

Angle to previous plane (with approximate e.s.d.) = 18.25 (0.10)

* -0.0001 (0.0010) C8 * 0.0001 (0.0010) C9 * -0.0001 (0.0010) C10 * 0.0001 (0.0010) C10_$1 * -0.0001 (0.0010) C9_$1 * 0.0001 (0.0010) C8_$1

Rms deviation of fitted atoms = 0.0001

17.8471 (0.0109) x + 3.6414 (0.0027) y - 0.4678 (0.0063) z = 1.9056 (0.0016)

Angle to previous plane (with approximate e.s.d.) = 17.89 (0.09)

* 0.0065 (0.0015) C1 * -0.0071 (0.0015) C6 * -0.0082 (0.0015) C5 * 0.0023 (0.0016) C4 * 0.0064 (0.0014) C3 * 0.0082 (0.0015) C2 * -0.0150 (0.0009) S1 * 0.0008 (0.0012) C7 * 0.0061 (0.0012) N1

Rms deviation of fitted atoms = 0.0077

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
C7	0.07816 (8)	0.1561 (3)	0.12153 (15)	0.0281 (4)
C8	0.01168 (9)	0.3397 (3)	−0.06910 (16)	0.0325 (4)
C9	0.03848 (8)	0.3333 (2)	0.05965 (14)	0.0267 (4)
C10	0.02618 (9)	0.4955 (3)	0.12723 (16)	0.0332 (4)
N1	0.10344 (7)	0.0265 (2)	0.06667 (13)	0.0312 (3)
C1	0.13679 (8)	−0.1263 (3)	0.14851 (15)	0.0299 (4)
C2	0.13663 (8)	−0.1094 (3)	0.26963 (15)	0.0304 (4)
C3	0.16811 (9)	−0.2525 (3)	0.36115 (17)	0.0390 (4)
H3	0.1678	−0.2405	0.4407	0.047*
C4	0.19969 (9)	−0.4124 (3)	0.32934 (19)	0.0434 (5)
H4	0.2212	−0.5090	0.3887	0.052*
C5	0.19989 (9)	−0.4317 (3)	0.20961 (19)	0.0430 (5)
H5	0.2213	−0.5413	0.1908	0.052*
C6	0.16897 (9)	−0.2915 (3)	0.11902 (18)	0.0383 (4)
H6	0.1694	−0.3059	0.0397	0.046*
S1	0.09188 (2)	0.10461 (7)	0.27816 (4)	0.03404 (17)
H8	0.0184 (9)	0.231 (3)	−0.1181 (18)	0.042 (5)*
H10	0.0433 (11)	0.494 (3)	0.211 (2)	0.055 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C7	0.0315 (9)	0.0276 (8)	0.0257 (8)	−0.0022 (7)	0.0109 (7)	0.0015 (7)
C8	0.0410 (10)	0.0297 (9)	0.0278 (9)	0.0033 (7)	0.0135 (8)	−0.0033 (7)
C9	0.0289 (9)	0.0258 (8)	0.0269 (8)	−0.0011 (7)	0.0119 (7)	0.0014 (7)
C10	0.0412 (10)	0.0352 (10)	0.0216 (9)	0.0034 (8)	0.0094 (8)	0.0008 (7)
N1	0.0364 (8)	0.0303 (8)	0.0285 (7)	0.0025 (6)	0.0134 (6)	0.0019 (6)
C1	0.0305 (9)	0.0291 (9)	0.0304 (8)	−0.0007 (7)	0.0113 (7)	0.0018 (7)
C2	0.0306 (9)	0.0294 (9)	0.0319 (9)	−0.0004 (7)	0.0119 (7)	0.0013 (7)
C3	0.0415 (11)	0.0413 (10)	0.0334 (9)	0.0049 (8)	0.0125 (8)	0.0087 (8)
C4	0.0409 (11)	0.0386 (10)	0.0478 (11)	0.0096 (9)	0.0123 (9)	0.0132 (9)
C5	0.0388 (11)	0.0360 (10)	0.0542 (12)	0.0087 (8)	0.0165 (9)	−0.0002 (9)
C6	0.0417 (11)	0.0374 (10)	0.0383 (10)	0.0044 (8)	0.0174 (8)	−0.0021 (8)
S1	0.0443 (3)	0.0340 (3)	0.0256 (2)	0.00824 (19)	0.01467 (19)	0.00382 (17)

Geometric parameters (Å, º)

C7—N1	1.305 (2)	C1—C2	1.414 (2)
C7—C9	1.478 (2)	C2—C3	1.400 (2)
C7—S1	1.7659 (17)	C2—S1	1.7435 (17)
C8—C10^i	1.386 (3)	C3—C4	1.384 (3)
C8—C9	1.400 (2)	C3—H3	0.9300
C8—H8	0.95 (2)	C4—C5	1.399 (3)
C9—C10	1.399 (2)	C4—H4	0.9300
C10—C8^i	1.386 (3)	C5—C6	1.378 (3)
C10—S1	3.1392 (19)	C5—H5	0.9300
C10—H10	0.91 (2)	C6—H6	0.9300
N1—C1	1.394 (2)	S1—H10	2.76 (2)
C1—C6	1.406 (2)
N1—C7—C9	124.08 (15)	C6—C1—C2	119.22 (16)
N1—C7—S1	115.85 (13)	C3—C2—C1	121.56 (16)
C9—C7—S1	120.04 (12)	C3—C2—S1	129.33 (14)
C10^i—C8—C9	120.04 (16)	C1—C2—S1	109.09 (12)
C10^i—C8—H8	118.8 (12)	C4—C3—C2	117.77 (17)
C9—C8—H8	121.1 (12)	C4—C3—H3	121.1
C10—C9—C8	118.70 (15)	C2—C3—H3	121.1
C10—C9—C7	121.34 (15)	C3—C4—C5	121.28 (17)
C8—C9—C7	119.95 (15)	C3—C4—H4	119.4
C8^i—C10—C9	121.26 (16)	C5—C4—H4	119.4
C8^i—C10—S1	169.30 (13)	C6—C5—C4	121.27 (17)
C9—C10—S1	63.69 (9)	C6—C5—H5	119.4
C8^i—C10—C10^ii	93.80 (11)	C4—C5—H5	119.4
C9—C10—C10^ii	131.24 (10)	C5—C6—C1	118.90 (17)
S1—C10—C10^ii	76.92 (5)	C5—C6—H6	120.5
C8^i—C10—H10	118.8 (14)	C1—C6—H6	120.5
C9—C10—H10	119.9 (14)	C2—S1—C7	89.04 (8)
S1—C10—H10	57.3 (14)	C2—S1—H10	153.5 (5)
C7—N1—C1	110.49 (14)	C7—S1—H10	68.1 (5)
N1—C1—C6	125.26 (16)	C2—S1—C10	141.34 (7)
N1—C1—C2	115.51 (15)	C7—S1—C10	52.97 (6)
C10^i—C8—C9—C10	0.0 (3)	C4—C5—C6—C1	0.1 (3)
C10^i—C8—C9—C7	179.20 (16)	N1—C1—C6—C5	−179.84 (17)
N1—C7—C9—C10	−163.27 (17)	C2—C1—C6—C5	−0.5 (3)
S1—C7—C9—C10	18.7 (2)	C3—C2—S1—C7	−179.78 (18)
N1—C7—C9—C8	17.6 (3)	C1—C2—S1—C7	−0.84 (13)
S1—C7—C9—C8	−160.46 (13)	C3—C2—S1—H10	150.6 (11)
C8—C9—C10—C8^i	0.0 (3)	C1—C2—S1—H10	−30.4 (11)
C7—C9—C10—C8^i	−179.19 (16)	C3—C2—S1—C10	170.32 (14)
C8—C9—C10—S1	169.13 (17)	C1—C2—S1—C10	−10.74 (19)
C7—C9—C10—S1	−10.02 (12)	N1—C7—S1—C2	0.74 (14)
C8—C9—C10—C10^ii	129.40 (17)	C9—C7—S1—C2	178.94 (14)
C7—C9—C10—C10^ii	−49.8 (3)	N1—C7—S1—H10	167.0 (5)
C9—C7—N1—C1	−178.50 (15)	C9—C7—S1—H10	−14.8 (5)
S1—C7—N1—C1	−0.38 (18)	N1—C7—S1—C10	173.01 (17)
C7—N1—C1—C6	179.07 (17)	C9—C7—S1—C10	−8.79 (11)
C7—N1—C1—C2	−0.3 (2)	C8^i—C10—S1—C2	141.5 (7)
N1—C1—C2—C3	179.88 (16)	C9—C10—S1—C2	21.41 (16)
C6—C1—C2—C3	0.5 (3)	C10^ii—C10—S1—C2	171.84 (10)
N1—C1—C2—S1	0.85 (19)	C8^i—C10—S1—C7	129.1 (7)
C6—C1—C2—S1	−178.58 (14)	C9—C10—S1—C7	8.97 (11)
C1—C2—C3—C4	0.0 (3)	C10^ii—C10—S1—C7	159.40 (10)
S1—C2—C3—C4	178.80 (15)	C8^i—C10—S1—H10	−71.5 (18)
C2—C3—C4—C5	−0.4 (3)	C9—C10—S1—H10	168.5 (17)
C3—C4—C5—C6	0.4 (3)	C10^ii—C10—S1—H10	−41.1 (17)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···S1	0.91 (2)	2.75 (2)	3.139 (2)	106.7 (14)