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

In the title compound, C21H14N2O2S, a donor-acceptor type of benzo[b]pheno-thia-zine (bpz) derivative, the thia-zine 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 thia-zine ring is 32.76 (5)°. In the crystal, carb-oxy-lic-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 inter-actions also occur.

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 = 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

Δρmax = 0.29 e Å−3

Δρmin = −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 ▶).

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

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

Click here for additional data file.

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

Click here for additional data file.

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.

. 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.

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

C21H14N2O2S	F(000) = 372
Mr = 358.40	Dx = 1.402 Mg m−3
Triclinic, P1	Melting point: 351 K
a = 6.7915 (17) Å	Mo Kα radiation, λ = 0.71075 Å
b = 9.196 (3) Å	Cell parameters from 14164 reflections
c = 13.941 (3) Å	θ = 3.0–27.5°
α = 95.831 (13)°	µ = 0.21 mm−1
β = 101.214 (10)°	T = 123 K
γ = 90.850 (15)°	Block, dark red
V = 849.1 (4) Å3	0.40 × 0.40 × 0.15 mm
Z = 2

Rigaku R-AXIS RAPID CCD diffractometer	Rint = 0.020
ω/2θ scans	θmax = 27.5°, θmin = 3.0°
14164 measured reflections	h = −8→8
3877 independent reflections	k = −11→11
3663 reflections with I > 2σ(I)	l = −18→16

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.036	H-atom parameters constrained
wR(F2) = 0.100	w = 1/[σ2(Fo2) + (0.0609P)2 + 0.2744P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max < 0.001
3877 reflections	Δρmax = 0.29 e Å−3
290 parameters	Δρmin = −0.40 e Å−3

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.

	x	y	z	Uiso*/Ueq
H2	0.953 (3)	−0.333 (2)	0.4654 (13)	0.041 (5)*
H3	0.968 (3)	−0.526 (2)	0.3462 (15)	0.056 (6)*
C1	0.71497 (19)	−0.23569 (15)	0.38906 (10)	0.0297 (3)
H10	0.213 (2)	−0.0357 (18)	0.3396 (12)	0.029 (4)*
C2	0.8586 (2)	−0.34194 (17)	0.40418 (12)	0.0371 (3)
C3	0.8644 (2)	−0.45592 (16)	0.33152 (13)	0.0402 (3)
C4	0.7256 (2)	−0.46500 (15)	0.24404 (12)	0.0353 (3)
C5	0.12589 (17)	0.17296 (15)	−0.11405 (9)	0.0274 (3)
H5	0.290 (2)	−0.2245 (18)	−0.0436 (12)	0.033 (4)*
H6	0.163 (2)	−0.0447 (18)	−0.1546 (12)	0.031 (4)*
H9	0.238 (2)	0.3227 (18)	0.1163 (12)	0.031 (4)*
C6	0.22142 (17)	0.24648 (13)	0.06076 (9)	0.0223 (2)
C7	0.34176 (15)	0.06021 (12)	0.17662 (8)	0.0173 (2)
S1	0.39308 (5)	−0.37579 (3)	0.12102 (2)	0.02878 (11)
O1	0.65112 (12)	0.36226 (9)	0.47776 (6)	0.02296 (18)
H7	0.075 (3)	0.1979 (19)	−0.1817 (13)	0.038 (4)*
H1	0.714 (2)	−0.1535 (19)	0.4397 (12)	0.029 (4)*
H8	0.124 (3)	0.386 (2)	−0.0451 (13)	0.040 (4)*
C8	0.24793 (16)	−0.00669 (13)	−0.00306 (8)	0.0202 (2)
H4	0.725 (3)	−0.541 (2)	0.1909 (13)	0.041 (5)*
C9	0.26789 (15)	0.10113 (12)	0.07897 (8)	0.0181 (2)
O2	0.35247 (13)	0.41863 (10)	0.39083 (6)	0.0275 (2)
H14	0.353 (3)	0.507 (2)	0.4467 (13)	0.041*
N1	0.42827 (14)	−0.13630 (10)	0.28349 (7)	0.0208 (2)
C10	0.38246 (15)	−0.08478 (12)	0.19057 (8)	0.0177 (2)
H13	0.246 (2)	0.2398 (16)	0.2575 (11)	0.023 (3)*
C11	0.35977 (16)	0.17829 (12)	0.25662 (8)	0.0186 (2)
C12	0.50856 (16)	0.34153 (12)	0.40510 (8)	0.0185 (2)
N2	0.86564 (16)	0.10083 (13)	0.34623 (9)	0.0336 (3)
H11	0.312 (2)	−0.1618 (18)	0.3995 (12)	0.031 (4)*
H12	0.420 (3)	−0.003 (2)	0.4129 (13)	0.041 (5)*
C13	0.30285 (16)	−0.15078 (13)	0.01314 (8)	0.0219 (2)
C14	0.36473 (16)	−0.18954 (12)	0.10592 (8)	0.0201 (2)
C15	0.17442 (17)	0.03230 (15)	−0.09906 (8)	0.0250 (2)
C16	0.15205 (18)	0.28132 (14)	−0.03332 (9)	0.0266 (3)
C17	0.57900 (18)	−0.36047 (13)	0.22895 (10)	0.0262 (2)
C18	0.57427 (17)	−0.24412 (12)	0.30077 (9)	0.0231 (2)
C19	0.33548 (19)	−0.08052 (14)	0.36491 (9)	0.0248 (2)
C20	0.51890 (16)	0.21732 (12)	0.32950 (8)	0.0186 (2)
C21	0.70959 (17)	0.14883 (13)	0.33855 (8)	0.0222 (2)

	U11	U22	U33	U12	U13	U23
C1	0.0244 (6)	0.0300 (6)	0.0354 (7)	0.0032 (5)	0.0037 (5)	0.0107 (5)
C2	0.0239 (6)	0.0388 (7)	0.0513 (8)	0.0065 (5)	0.0052 (6)	0.0218 (6)
C3	0.0290 (6)	0.0339 (7)	0.0655 (10)	0.0136 (5)	0.0183 (6)	0.0231 (7)
C4	0.0344 (7)	0.0229 (6)	0.0559 (9)	0.0083 (5)	0.0227 (6)	0.0106 (6)
C5	0.0187 (5)	0.0433 (7)	0.0200 (5)	−0.0067 (5)	0.0017 (4)	0.0078 (5)
C6	0.0189 (5)	0.0240 (6)	0.0231 (5)	−0.0022 (4)	0.0023 (4)	0.0017 (4)
C7	0.0140 (4)	0.0198 (5)	0.0168 (5)	−0.0007 (4)	0.0021 (4)	−0.0026 (4)
S1	0.03269 (18)	0.01645 (16)	0.03660 (19)	−0.00299 (11)	0.00977 (13)	−0.00517 (11)
O1	0.0245 (4)	0.0230 (4)	0.0180 (4)	0.0017 (3)	−0.0007 (3)	−0.0045 (3)
C8	0.0143 (4)	0.0278 (6)	0.0176 (5)	−0.0054 (4)	0.0043 (4)	−0.0026 (4)
C9	0.0130 (4)	0.0223 (5)	0.0177 (5)	−0.0028 (4)	0.0019 (4)	−0.0009 (4)
O2	0.0262 (4)	0.0258 (4)	0.0262 (4)	0.0094 (3)	−0.0004 (3)	−0.0080 (3)
N1	0.0208 (4)	0.0211 (5)	0.0207 (4)	0.0053 (4)	0.0046 (4)	0.0015 (3)
C10	0.0137 (4)	0.0198 (5)	0.0186 (5)	−0.0008 (4)	0.0034 (4)	−0.0020 (4)
C11	0.0195 (5)	0.0178 (5)	0.0179 (5)	0.0024 (4)	0.0034 (4)	−0.0003 (4)
C12	0.0197 (5)	0.0177 (5)	0.0170 (5)	0.0013 (4)	0.0028 (4)	−0.0012 (4)
N2	0.0236 (5)	0.0391 (6)	0.0338 (6)	0.0074 (4)	0.0017 (4)	−0.0098 (5)
C13	0.0183 (5)	0.0251 (6)	0.0210 (5)	−0.0056 (4)	0.0065 (4)	−0.0083 (4)
C14	0.0174 (5)	0.0178 (5)	0.0247 (5)	−0.0024 (4)	0.0065 (4)	−0.0042 (4)
C15	0.0176 (5)	0.0392 (7)	0.0171 (5)	−0.0080 (4)	0.0042 (4)	−0.0018 (5)
C16	0.0204 (5)	0.0320 (6)	0.0276 (6)	−0.0026 (4)	0.0024 (4)	0.0089 (5)
C17	0.0241 (5)	0.0197 (5)	0.0381 (6)	0.0017 (4)	0.0131 (5)	0.0055 (5)
C18	0.0191 (5)	0.0209 (5)	0.0312 (6)	0.0027 (4)	0.0077 (4)	0.0066 (4)
C19	0.0270 (6)	0.0275 (6)	0.0218 (5)	0.0055 (5)	0.0086 (4)	0.0035 (4)
C20	0.0197 (5)	0.0177 (5)	0.0176 (5)	0.0020 (4)	0.0034 (4)	−0.0026 (4)
C21	0.0218 (5)	0.0226 (5)	0.0195 (5)	0.0005 (4)	0.0018 (4)	−0.0064 (4)

C1—C2	1.3933 (18)	C8—C15	1.4185 (16)
C1—C18	1.3982 (18)	C8—C9	1.4192 (15)
C1—H1	0.982 (17)	O2—C12	1.2786 (14)
C2—C3	1.388 (2)	O2—H14	1.063 (18)
C2—H2	0.959 (18)	N1—C10	1.4042 (14)
C3—C4	1.383 (2)	N1—C18	1.4174 (14)
C3—H3	0.97 (2)	N1—C19	1.4553 (14)
C4—C17	1.3956 (17)	C10—C14	1.4301 (15)
C4—H4	0.963 (19)	C11—C20	1.3478 (15)
C5—C15	1.366 (2)	C11—H13	0.964 (15)
C5—C16	1.4072 (19)	C12—C20	1.4855 (15)
C5—H7	0.990 (17)	N2—C21	1.1440 (16)
C6—C16	1.3764 (17)	C13—C14	1.3650 (17)
C6—C9	1.4145 (16)	C13—H5	0.978 (17)
C6—H9	0.978 (17)	C15—H6	0.985 (17)
C7—C10	1.3908 (16)	C16—H8	1.006 (18)
C7—C9	1.4458 (15)	C17—C18	1.3942 (18)
C7—C11	1.4611 (15)	C19—H10	0.958 (16)
S1—C14	1.7556 (13)	C19—H11	0.957 (17)
S1—C17	1.7581 (14)	C19—H12	1.013 (19)
O1—C12	1.2544 (14)	C20—C21	1.4376 (15)
C8—C13	1.4101 (17)
C2—C1—C18	120.09 (13)	C20—C11—C7	128.50 (10)
C2—C1—H1	120.2 (9)	C20—C11—H13	114.1 (9)
C18—C1—H1	119.7 (9)	C7—C11—H13	117.3 (9)
C3—C2—C1	120.34 (14)	O1—C12—O2	125.12 (10)
C3—C2—H2	121.5 (11)	O1—C12—C20	118.13 (10)
C1—C2—H2	118.2 (11)	O2—C12—C20	116.75 (9)
C4—C3—C2	119.87 (12)	C14—C13—C8	121.34 (10)
C4—C3—H3	123.7 (12)	C14—C13—H5	120.0 (10)
C2—C3—H3	116.5 (12)	C8—C13—H5	118.6 (10)
C3—C4—C17	120.17 (14)	C13—C14—C10	121.42 (10)
C3—C4—H4	123.1 (11)	C13—C14—S1	118.47 (8)
C17—C4—H4	116.8 (11)	C10—C14—S1	119.66 (9)
C15—C5—C16	119.59 (11)	C5—C15—C8	120.96 (11)
C15—C5—H7	119.6 (10)	C5—C15—H6	121.2 (9)
C16—C5—H7	120.8 (10)	C8—C15—H6	117.8 (9)
C16—C6—C9	121.02 (11)	C6—C16—C5	120.73 (12)
C16—C6—H9	119.9 (9)	C6—C16—H8	119.9 (10)
C9—C6—H9	119.1 (9)	C5—C16—H8	119.4 (10)
C10—C7—C9	120.36 (9)	C18—C17—C4	120.36 (13)
C10—C7—C11	123.92 (10)	C18—C17—S1	118.84 (9)
C9—C7—C11	115.66 (10)	C4—C17—S1	120.77 (11)
C14—S1—C17	99.34 (6)	C17—C18—C1	119.14 (11)
C13—C8—C15	121.48 (10)	C17—C18—N1	119.89 (11)
C13—C8—C9	118.85 (10)	C1—C18—N1	120.97 (11)
C15—C8—C9	119.67 (11)	N1—C19—H10	109.2 (9)
C6—C9—C8	117.97 (10)	N1—C19—H11	107.3 (10)
C6—C9—C7	122.69 (10)	H10—C19—H11	111.2 (14)
C8—C9—C7	119.29 (10)	N1—C19—H12	114.0 (10)
C12—O2—H14	113.7 (10)	H10—C19—H12	106.4 (14)
C10—N1—C18	119.48 (9)	H11—C19—H12	108.7 (14)
C10—N1—C19	122.62 (9)	C11—C20—C21	123.98 (10)
C18—N1—C19	117.88 (9)	C11—C20—C12	120.73 (10)
C7—C10—N1	123.61 (9)	C21—C20—C12	115.25 (9)
C7—C10—C14	118.54 (10)	N2—C21—C20	176.72 (13)
N1—C10—C14	117.73 (10)
C18—C1—C2—C3	0.6 (2)	C7—C10—C14—S1	−174.34 (8)
C1—C2—C3—C4	−0.7 (2)	N1—C10—C14—S1	1.83 (13)
C2—C3—C4—C17	−0.4 (2)	C17—S1—C14—C13	152.24 (9)
C16—C6—C9—C8	2.30 (16)	C17—S1—C14—C10	−35.38 (10)
C16—C6—C9—C7	179.77 (10)	C16—C5—C15—C8	0.99 (17)
C13—C8—C9—C6	176.94 (9)	C13—C8—C15—C5	−178.54 (10)
C15—C8—C9—C6	−2.82 (15)	C9—C8—C15—C5	1.22 (16)
C13—C8—C9—C7	−0.62 (15)	C9—C6—C16—C5	−0.12 (18)
C15—C8—C9—C7	179.61 (9)	C15—C5—C16—C6	−1.56 (18)
C10—C7—C9—C6	179.09 (9)	C3—C4—C17—C18	1.62 (19)
C11—C7—C9—C6	1.88 (15)	C3—C4—C17—S1	−176.53 (10)
C10—C7—C9—C8	−3.47 (15)	C14—S1—C17—C18	36.16 (10)
C11—C7—C9—C8	179.32 (9)	C14—S1—C17—C4	−145.67 (10)
C9—C7—C10—N1	−171.10 (9)	C4—C17—C18—C1	−1.66 (17)
C11—C7—C10—N1	5.86 (16)	S1—C17—C18—C1	176.53 (9)
C9—C7—C10—C14	4.83 (15)	C4—C17—C18—N1	178.19 (11)
C11—C7—C10—C14	−178.20 (9)	S1—C17—C18—N1	−3.63 (15)
C18—N1—C10—C7	−142.33 (11)	C2—C1—C18—C17	0.53 (18)
C19—N1—C10—C7	35.94 (16)	C2—C1—C18—N1	−179.31 (11)
C18—N1—C10—C14	41.71 (14)	C10—N1—C18—C17	−41.32 (15)
C19—N1—C10—C14	−140.02 (11)	C19—N1—C18—C17	140.33 (11)
C10—C7—C11—C20	53.51 (17)	C10—N1—C18—C1	138.52 (11)
C9—C7—C11—C20	−129.39 (12)	C19—N1—C18—C1	−39.83 (16)
C15—C8—C13—C14	−176.93 (10)	C7—C11—C20—C21	2.65 (19)
C9—C8—C13—C14	3.31 (16)	C7—C11—C20—C12	−179.85 (10)
C8—C13—C14—C10	−1.94 (16)	O1—C12—C20—C11	171.53 (10)
C8—C13—C14—S1	170.30 (8)	O2—C12—C20—C11	−7.97 (16)
C7—C10—C14—C13	−2.19 (15)	O1—C12—C20—C21	−10.77 (15)
N1—C10—C14—C13	173.98 (10)	O2—C12—C20—C21	169.73 (10)

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)

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)

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