2-Methyl-3-(10H-pheno-thia-zin-10-yl)buta-1,3-diene-1,1,4,4-tetra-carbo-nitrile.

In the title compound, C21H11N5S, the pheno-thia-zine unit has a butterfly structure, and the central six-membered ring adopts a boat conformation. The dihedral angle between the benzene rings is 127.64 (6)°, which is smaller than those reported for similar compounds because of the steric repulsion between the pheno-thia-zine and its tetra-cyano-1,3-butadiene substituent. The di-cyano-vinyl groups are almost orthogonal to one another, making a dihedral angle of 80.58 (6)°. In the crystal, the mol-ecules are aligned along the b axis. Four kinds of weak C-H⋯N inter-actions are recognized, one of which connects the mol-ecules into a one-dimensional array and the remaining three link these arrays.

Related literature

For applications of tetra­cyano-1,3-butadienes in photonics and non-linear optics, see: Faupel et al. (2007 ▶). For the preparation and structure of 10-(prop-1-yn-1-yl)-10H-pheno­thia­zine, see: Zaugg et al. (1958 ▶); Umezono & Okuno (2012 ▶). For the structures of other related N-substituted pheno­thia­zines, see: Chu & Van der Helm (1974 ▶, 1975 ▶); Tokunaga & Okuno (2012 ▶).

Experimental

Crystal data

C21H11N5S

M = 365.41

Monoclinic,

a = 10.217 (3) Å

b = 7.848 (3) Å

c = 11.369 (3) Å

β = 97.316 (4)°

V = 904.2 (5) Å3

Z = 2

Mo Kα radiation

μ = 0.19 mm−1

T = 93 K

0.10 × 0.10 × 0.05 mm

Data collection

Rigaku Saturn724+ diffractometer

7524 measured reflections

3753 independent reflections

3494 reflections with F 2 > 2σ(F 2)

R int = 0.022

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.078

S = 1.04

3753 reflections

244 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.21 e Å−3

Δρmin = −0.25 e Å−3

Absolute structure: Flack (1983 ▶), 1526 Friedel pairs

Flack parameter: 0.01 (6)

Data collection: CrystalClear (Rigaku, 2008 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: CrystalStructure (Rigaku, 2010 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813008799/sj5308sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813008799/sj5308Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813008799/sj5308Isup3.cml

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

C21H11N5S	F(000) = 376.00
Mr = 365.41	Dx = 1.342 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: P 2yb	Cell parameters from 3683 reflections
a = 10.217 (3) Å	θ = 1.8–30.7°
b = 7.848 (3) Å	µ = 0.19 mm−1
c = 11.369 (3) Å	T = 93 K
β = 97.316 (4)°	Block, pale blue
V = 904.2 (5) Å3	0.10 × 0.10 × 0.05 mm
Z = 2

Rigaku Saturn724+ diffractometer	Rint = 0.022
Detector resolution: 28.445 pixels mm-1	θmax = 27.5°
ω scans	h = −12→13
7524 measured reflections	k = −9→10
3753 independent reflections	l = −14→14
3494 reflections with F2 > 2σ(F2)

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.032	H-atom parameters constrained
wR(F2) = 0.078	w = 1/[σ2(Fo2) + (0.045P)2 + 0.1327P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max < 0.001
3753 reflections	Δρmax = 0.21 e Å−3
244 parameters	Δρmin = −0.25 e Å−3
1 restraint	Absolute structure: Flack (1983), 1526 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.01 (6)
Secondary atom site location: difference Fourier map

Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt).

	x	y	z	Uiso*/Ueq
S1	0.46875 (4)	0.28150 (5)	0.24265 (4)	0.02108 (10)
N1	0.27521 (13)	0.00720 (18)	0.24818 (12)	0.0165 (3)
N2	0.25743 (15)	−0.0784 (3)	−0.09700 (14)	0.0250 (4)
N3	−0.12618 (16)	0.0506 (3)	−0.02155 (14)	0.0300 (4)
N4	−0.03764 (19)	−0.3121 (3)	0.2637 (2)	0.0404 (5)
N5	−0.20384 (18)	0.1361 (3)	0.42695 (17)	0.0368 (5)
C1	0.30948 (16)	0.0842 (3)	0.36326 (14)	0.0173 (4)
C2	0.26062 (16)	0.0219 (3)	0.46368 (14)	0.0192 (4)
C3	0.29033 (17)	0.1081 (3)	0.57034 (15)	0.0239 (4)
C4	0.36780 (17)	0.2539 (3)	0.57534 (15)	0.0253 (4)
C5	0.42255 (17)	0.3100 (3)	0.47617 (16)	0.0235 (4)
C6	0.39519 (16)	0.2229 (3)	0.36953 (14)	0.0181 (4)
C7	0.48704 (16)	0.0732 (3)	0.18623 (13)	0.0167 (4)
C8	0.59958 (17)	0.0265 (3)	0.13638 (14)	0.0199 (4)
C9	0.61205 (17)	−0.1403 (3)	0.09858 (15)	0.0209 (4)
C10	0.51615 (17)	−0.2620 (3)	0.11218 (15)	0.0210 (4)
C11	0.40235 (15)	−0.2157 (3)	0.16050 (13)	0.0190 (3)
C12	0.38819 (16)	−0.0473 (3)	0.19417 (14)	0.0165 (4)
C13	0.15512 (16)	0.0349 (2)	0.18619 (14)	0.0162 (4)
C14	0.05534 (16)	0.1133 (3)	0.25659 (14)	0.0180 (4)
C15	0.05982 (17)	0.3019 (3)	0.27492 (15)	0.0218 (4)
C16	0.11722 (16)	0.0065 (3)	0.06727 (15)	0.0169 (4)
C17	0.19996 (17)	−0.0424 (3)	−0.01964 (15)	0.0190 (4)
C18	−0.01790 (17)	0.0327 (3)	0.01951 (14)	0.0208 (4)
C19	−0.03508 (17)	0.0124 (3)	0.29768 (15)	0.0202 (4)
C20	−0.03738 (18)	−0.1681 (3)	0.27904 (18)	0.0253 (4)
C21	−0.13076 (18)	0.0814 (3)	0.36816 (17)	0.0260 (4)
H2	0.2078	−0.0780	0.4593	0.0231*
H3	0.2577	0.0674	0.6398	0.0287*
H4	0.3837	0.3162	0.6474	0.0303*
H5	0.4783	0.4073	0.4814	0.0282*
H8	0.6668	0.1077	0.1284	0.0239*
H9	0.6875	−0.1719	0.0627	0.0250*
H10	0.5281	−0.3765	0.0886	0.0252*
H11	0.3361	−0.2976	0.1702	0.0228*
H15A	0.0728	0.3268	0.3601	0.0261*
H15B	−0.0234	0.3525	0.2389	0.0261*
H15C	0.1330	0.3500	0.2378	0.0261*

	U11	U22	U33	U12	U13	U23
S1	0.0262 (2)	0.0173 (2)	0.0209 (2)	−0.00254 (18)	0.00752 (15)	0.00042 (16)
N1	0.0147 (7)	0.0192 (8)	0.0154 (7)	−0.0000 (6)	0.0014 (5)	−0.0034 (6)
N2	0.0252 (8)	0.0294 (9)	0.0208 (8)	0.0023 (7)	0.0040 (6)	−0.0002 (7)
N3	0.0214 (8)	0.0444 (11)	0.0240 (8)	0.0023 (8)	0.0017 (7)	−0.0006 (7)
N4	0.0411 (11)	0.0224 (10)	0.0632 (14)	−0.0058 (8)	0.0282 (10)	−0.0079 (9)
N5	0.0355 (10)	0.0319 (11)	0.0470 (11)	−0.0014 (8)	0.0204 (9)	−0.0128 (8)
C1	0.0180 (8)	0.0184 (9)	0.0151 (8)	0.0022 (7)	0.0008 (6)	−0.0008 (7)
C2	0.0175 (8)	0.0192 (9)	0.0215 (8)	0.0015 (7)	0.0040 (7)	0.0028 (7)
C3	0.0217 (9)	0.0338 (11)	0.0168 (8)	0.0078 (8)	0.0047 (7)	0.0035 (7)
C4	0.0232 (9)	0.0339 (12)	0.0180 (8)	0.0067 (8)	−0.0003 (7)	−0.0069 (8)
C5	0.0203 (8)	0.0246 (11)	0.0251 (9)	−0.0011 (8)	0.0009 (7)	−0.0074 (7)
C6	0.0180 (8)	0.0194 (8)	0.0171 (8)	0.0018 (7)	0.0030 (7)	0.0009 (6)
C7	0.0187 (8)	0.0174 (8)	0.0136 (7)	0.0018 (7)	0.0002 (6)	0.0012 (6)
C8	0.0175 (8)	0.0266 (9)	0.0154 (8)	0.0004 (8)	0.0018 (6)	0.0037 (7)
C9	0.0183 (8)	0.0294 (10)	0.0152 (8)	0.0064 (8)	0.0034 (6)	0.0018 (7)
C10	0.0221 (9)	0.0224 (10)	0.0172 (8)	0.0048 (7)	−0.0020 (7)	−0.0039 (6)
C11	0.0177 (8)	0.0210 (8)	0.0175 (7)	0.0000 (8)	−0.0009 (6)	−0.0019 (7)
C12	0.0156 (8)	0.0210 (8)	0.0126 (7)	0.0030 (7)	0.0002 (6)	−0.0011 (6)
C13	0.0180 (8)	0.0109 (8)	0.0199 (8)	−0.0016 (7)	0.0033 (6)	−0.0001 (6)
C14	0.0188 (9)	0.0173 (9)	0.0173 (8)	0.0015 (7)	−0.0001 (6)	−0.0016 (6)
C15	0.0243 (9)	0.0173 (10)	0.0244 (8)	0.0010 (8)	0.0057 (7)	−0.0003 (7)
C16	0.0159 (8)	0.0155 (8)	0.0195 (8)	−0.0017 (7)	0.0033 (6)	0.0002 (7)
C17	0.0184 (8)	0.0193 (9)	0.0186 (8)	−0.0000 (7)	0.0003 (7)	0.0007 (6)
C18	0.0230 (10)	0.0238 (9)	0.0159 (8)	0.0027 (8)	0.0037 (7)	−0.0016 (7)
C19	0.0197 (8)	0.0179 (9)	0.0234 (8)	0.0010 (7)	0.0045 (7)	−0.0050 (7)
C20	0.0208 (9)	0.0246 (10)	0.0331 (10)	−0.0042 (7)	0.0139 (8)	−0.0049 (8)
C21	0.0234 (10)	0.0231 (10)	0.0329 (10)	−0.0047 (8)	0.0090 (8)	−0.0066 (8)

S1—C6	1.7701 (18)	C11—C12	1.389 (3)
S1—C7	1.7745 (19)	C13—C14	1.505 (3)
N1—C1	1.443 (2)	C13—C16	1.376 (3)
N1—C12	1.440 (3)	C14—C15	1.495 (3)
N1—C13	1.352 (2)	C14—C19	1.345 (3)
N2—C17	1.153 (3)	C16—C17	1.432 (3)
N3—C18	1.153 (3)	C16—C18	1.432 (3)
N4—C20	1.143 (3)	C19—C20	1.432 (3)
N5—C21	1.147 (3)	C19—C21	1.446 (3)
C1—C2	1.392 (3)	C2—H2	0.950
C1—C6	1.393 (3)	C3—H3	0.950
C2—C3	1.388 (3)	C4—H4	0.950
C3—C4	1.388 (3)	C5—H5	0.950
C4—C5	1.392 (3)	C8—H8	0.950
C5—C6	1.389 (3)	C9—H9	0.950
C7—C8	1.394 (3)	C10—H10	0.950
C7—C12	1.395 (3)	C11—H11	0.950
C8—C9	1.389 (3)	C15—H15A	0.980
C9—C10	1.391 (3)	C15—H15B	0.980
C10—C11	1.396 (3)	C15—H15C	0.980
C6—S1—C7	97.49 (9)	C13—C16—C18	119.09 (16)
C1—N1—C12	113.32 (13)	C17—C16—C18	113.70 (15)
C1—N1—C13	120.28 (14)	N2—C17—C16	174.02 (18)
C12—N1—C13	123.30 (14)	N3—C18—C16	178.0 (2)
N1—C1—C2	121.70 (15)	C14—C19—C20	122.01 (18)
N1—C1—C6	116.87 (15)	C14—C19—C21	120.99 (18)
C2—C1—C6	121.43 (15)	C20—C19—C21	116.93 (17)
C1—C2—C3	118.95 (17)	N4—C20—C19	179.1 (3)
C2—C3—C4	119.83 (17)	N5—C21—C19	178.0 (2)
C3—C4—C5	120.88 (17)	C1—C2—H2	120.520
C4—C5—C6	119.61 (17)	C3—C2—H2	120.526
S1—C6—C1	119.39 (13)	C2—C3—H3	120.088
S1—C6—C5	121.62 (14)	C4—C3—H3	120.079
C1—C6—C5	118.99 (16)	C3—C4—H4	119.564
S1—C7—C8	121.29 (14)	C5—C4—H4	119.554
S1—C7—C12	119.38 (13)	C4—C5—H5	120.189
C8—C7—C12	119.32 (16)	C6—C5—H5	120.199
C7—C8—C9	119.11 (17)	C7—C8—H8	120.448
C8—C9—C10	121.28 (17)	C9—C8—H8	120.446
C9—C10—C11	119.94 (18)	C8—C9—H9	119.360
C10—C11—C12	118.51 (17)	C10—C9—H9	119.363
N1—C12—C7	116.93 (15)	C9—C10—H10	120.029
N1—C12—C11	121.16 (15)	C11—C10—H10	120.035
C7—C12—C11	121.71 (16)	C10—C11—H11	120.744
N1—C13—C14	114.81 (14)	C12—C11—H11	120.746
N1—C13—C16	127.51 (16)	C14—C15—H15A	109.470
C14—C13—C16	117.63 (14)	C14—C15—H15B	109.468
C13—C14—C15	117.89 (15)	C14—C15—H15C	109.466
C13—C14—C19	119.08 (16)	H15A—C15—H15B	109.474
C15—C14—C19	123.01 (17)	H15A—C15—H15C	109.475
C13—C16—C17	127.17 (15)	H15B—C15—H15C	109.474

D—H···A	D—H	H···A	D···A	D—H···A
C15—H15B···N4i	0.98	2.65	3.186 (3)	114
C2—H2···N5ii	0.95	2.59	3.352 (3)	137
C10—H10···N2iii	0.95	2.70	3.413 (3)	133
C8—H8···N2iv	0.95	2.62	3.480 (3)	151

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C15—H15B⋯N4i	0.98	2.65	3.186 (3)	114
C2—H2⋯N5ii	0.95	2.59	3.352 (3)	137
C10—H10⋯N2iii	0.95	2.70	3.413 (3)	133
C8—H8⋯N2iv	0.95	2.62	3.480 (3)	151

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