Crystal structure of (E)-2-cyano-3-(12-methyl-12H-benzo[b]pheno­thia­zin-11-yl)acrylic acid

Motonori Watanabe; Tatsumi Ishihara

doi:10.1107/S1600536814018388

. 2014 Aug 20;70(Pt 9):o1026–o1027. doi: 10.1107/S1600536814018388

Crystal structure of (E)-2-cyano-3-(12-methyl-12H-benzo[b]phenothiazin-11-yl)acrylic acid

Motonori Watanabe ^a,^*, Tatsumi Ishihara ^a,^b

PMCID: PMC4186111 PMID: 25309206

Abstract

In the title compound, C₂₁H₁₄N₂O₂S, a donor–acceptor type of benzo[b]phenothiazine (bpz) derivative, the thiazine ring adopts a boat conformation and the bond-angle sum at the N atom is 360.0°. The dihedral angle between the benzene ring and the naphthelene ring system fused to the thiazine ring is 32.76 (5)°. In the crystal, carboxylic-acid inversion dimers linked by pairs of O—H⋯O hydrogen bonds generate R ₂ ²(8) loops. Aromatic π–π stacking [shortest centroid–centroid separaton = 3.5242 (13)Å] consolidates the structure and very weak C—H⋯O and C—H⋯N interactions also occur.

Keywords: crystal structure, benzo[b]phenothiazine derivative, inversion dimers, hydrogen bonding, π–π stacking

Related literature

For related structures, see: Bell et al. (1968 ▶), van de Waal & Feil (1977 ▶), Sun et al. (2004 ▶); Harrison et al. (2007 ▶). For applications of the title compound in dye-sensitized solar cells, see: Watanabe et al. (2014 ▶).

Experimental

Crystal data

C₂₁H₁₄N₂O₂S
M _r = 358.40
Triclinic,
a = 6.7915 (17) Å
b = 9.196 (3) Å
c = 13.941 (3) Å
α = 95.831 (13)°
β = 101.214 (10)°
γ = 90.850 (15)°
V = 849.1 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 123 K
0.40 × 0.40 × 0.15 mm

Data collection

Rigaku R-AXIS RAPID CCD diffractometer
14164 measured reflections
3877 independent reflections
3663 reflections with I > 2σ(I)
R _int = 0.020

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.100
S = 1.06
3877 reflections
290 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Data collection: RAPID-AUTO (Rigaku, 1998 ▶); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: Yadokari-XG 2009 (Wakita, 2001 ▶; Kabuto et al., 2009 ▶) and POV-RAY (Persistence of Vision Team, 2004 ▶).

Supplementary Material

Crystal structure: contains datablock(s) General, I. DOI: 10.1107/S1600536814018388/hb7264sup1.cif

e-70-o1026-sup1.cif^{(427.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814018388/hb7264Isup2.hkl

e-70-o1026-Isup2.hkl^{(212.7KB, hkl)}

Click here for additional data file.^{(6.6KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814018388/hb7264Isup3.cml

Click here for additional data file.^{(1.7MB, tif)}

21 14 2 2 . DOI: 10.1107/S1600536814018388/hb7264fig1.tif

The molecular structure of C₂₁H₁₄N₂O₂S with displacement ellipsoids drawn at the 50% probability level.

Click here for additional data file.^{(1.2MB, tif)}

. DOI: 10.1107/S1600536814018388/hb7264fig2.tif

Intermolecular hydrogen bonding O1—H14—O2′ (1.520 Å) in the two molecule structure of carboxylic acid moiety.

Click here for additional data file.^{(2.8MB, tif)}

21 14 2 2 . DOI: 10.1107/S1600536814018388/hb7264fig3.tif

Packing diagram of C₂₁H₁₄N₂O₂S.

CCDC reference: 1018980

Additional supporting information: crystallographic information; 3D view; checkCIF report

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H14⋯O1ⁱ	1.063 (18)	1.524 (18)	2.5856 (13)	176.8 (16)
C19—H10⋯N2ⁱⁱ	0.958 (16)	2.699 (16)	3.5991 (18)	156.8 (13)
C19—H11⋯O1ⁱⁱⁱ	0.957 (17)	2.623 (17)	3.5518 (17)	163.7 (13)

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

This work was supported by a Grant-in-Aid for Science Research (YB 26810107) from the Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan, and was performed under the Cooperative Research Program of "Network Joint Research Center for Materials and Devices (IMCE, Kyushu University)". MW thanks the World Premier International Research Center Initiative (WPI), Ministry of Education, Culture, Sports, Science and Technology of Japan (MEXT), Japan.

supplementary crystallographic information

S1. Structural commentary

Phenothiazine, C₁₂H₉NS showed stable redox properties. This crystal struture have been reported for the neutral state (Bell et al., 1968, and van de Wall & Feli, 1977), and for the C₁₂H₉NS+ radical cation state (Sun et al., 2004), and phenothiazine-picric acid (1/1) (Harrison et al., 2007).

As part of our studies for understanding the donor-acceptor interaction type dye molecule for dye-sensitized solar cell (Watanabe et al., 2014), we now report the title compound. In the title compound, C₂₁H₁₄N₂O₂S, consists a 12-methyl-12H-benzo[b]phenothiazine as a donor moiety, which has a (E)-2-cyanobut-2-enoic acid moiety as acceptor at C-11 position of 12-methyl-12H-benzo[b]phenothiazine.

Dark-red crystals were obtained from 0.013 g of title compound in tetrahydrofuran (10 ml) solution by slow diffusion.

The C₂₁H₁₄N₂O₂S of 12-methyl-12H-benzo[b]phenothiazine moiety takes pyramidal structure, in which benzene and naphthalene had 147.2°, while the olefin bond at the cyanoacrylic moiety existed 123.8° from the naphthalene plane (Figure 1). The title compounds showed an intermolecular hydrogen bonding at O1—H14 - O2' (1.520 Å) in the two molecule structure of carboxylic acid moiety (Figure 2). Furthermore, title compound have π-π stacking orientation along with a axis, where the two-naphthalene moieties oriented the parallel structures, which has a transannular distance at 3.273 Å (Figure 3).

S2. Crystallization

The chloroform solution (10 ml) of title compound (0.013 g) was standing under ambient condition until the desired single crystal was produced.

S3. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. All the hydrogen atoms of the compound are fixed geometrically (C—H = 0.95 - 1.01 Å) and allowed to ride on their parent atoms. Structure was refined with unique reflections and with a cut-off sigma = 2.00.