10-(Prop-2-yn-1-yl)-2,7-diaza-phenothia-zine.

In the title mol-ecule [systematic name: 10-(prop-2-yn-1-yl)dipyrido[3,4-b:3',4'-e][1,4]thia-zine], C(13)H(9)N(3)S, the dihedral angle between the two pyridine rings is 146.33 (7)° and the angle between two halves of the thia-zine ring is 138.84 (8)°, resulting in a butterfly shape for the tricyclic system. The central thia-zine ring adopts a boat conformation, with the 2-propynyl substituent at the thia-zine N atom located in a pseudo-equatorial position and oriented to the concave side of the diaza-phenothia-zine system. In the crystal, mol-ecules are arranged via π-π inter-actions between the pyridine rings [centroid-centroid distances = 3.838 (1) and 3.845 (1) Å] into stacks extending along [001]. There are C-H⋯C and C-H⋯N inter-actions between mol-ecules of neighbouring stacks.

Related literature

For recent literature on the biological activity of phenothia­zines, see: Aaron et al. (2009 ▶); Pluta et al. (2011 ▶). For the structure of 10-(2-propyn­yl)phenothia­zine and its transformations into anti­cancer derivatives, see: Bisi et al. (2008 ▶). For the synthesis and the anti­cancer and immunosuppressive activity of 2,7-diaza­phenothia­zines, see: Morak-Młodawska & Pluta (2009 ▶); Zimecki et al. (2009 ▶); Pluta et al. (2010 ▶). For planar and folded structures of the 2,7-diaza­phenothia­zine system, see: Morak et al. (2002 ▶); Morak-Młodawska et al. (2010 ▶). For alkyl­ation of aza­phenothia­zines, see: Pluta et al. (2009 ▶).

Experimental

Crystal data

C13H9N3S

M = 239.29

Monoclinic,

a = 14.1150 (9) Å

b = 10.1909 (6) Å

c = 7.6749 (5) Å

β = 104.212 (3)°

V = 1070.20 (12) Å3

Z = 4

Mo Kα radiation

μ = 0.28 mm−1

T = 100 K

0.60 × 0.50 × 0.35 mm

Data collection

Nonius KappaCCD diffractometer upgraded with APEXII detector

7015 measured reflections

2407 independent reflections

2011 reflections with I > 2σ(I)

R int = 0.041

Refinement

R[F 2 > 2σ(F 2)] = 0.049

wR(F 2) = 0.114

S = 1.11

2407 reflections

154 parameters

H-atom parameters constrained

Δρmax = 0.45 e Å−3

Δρmin = −0.35 e Å−3

Data collection: COLLECT (Nonius, 1998 ▶); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812018879/gk2475sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812018879/gk2475Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812018879/gk2475Isup3.cml

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

C13H9N3S	F(000) = 496
Mr = 239.29	Dx = 1.485 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2229 reflections
a = 14.1150 (9) Å	θ = 2.5–27.5°
b = 10.1909 (6) Å	µ = 0.28 mm−1
c = 7.6749 (5) Å	T = 100 K
β = 104.212 (3)°	Block, yellow
V = 1070.20 (12) Å3	0.60 × 0.50 × 0.35 mm
Z = 4

Nonius KappaCCD diffractometer upgraded with APEXII detector	2011 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.041
Graphite monochromator	θmax = 27.5°, θmin = 3.4°
Detector resolution: 8.3 pixels mm-1	h = −18→18
ω scan	k = −12→13
7015 measured reflections	l = −9→9
2407 independent reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.114	H-atom parameters constrained
S = 1.11	w = 1/[σ2(Fo2) + (0.0285P)2 + 1.4885P] where P = (Fo2 + 2Fc2)/3
2407 reflections	(Δ/σ)max = 0.001
154 parameters	Δρmax = 0.45 e Å−3
0 restraints	Δρmin = −0.35 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.

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 > 2σ(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.

	x	y	z	Uiso*/Ueq
C1	0.92188 (15)	0.1074 (2)	0.5605 (3)	0.0172 (4)
H1	0.9145	0.0148	0.5522	0.021*
C3	1.01573 (17)	0.2865 (2)	0.6685 (3)	0.0218 (5)
H3	1.0762	0.3225	0.7335	0.026*
C4	0.94013 (16)	0.3721 (2)	0.5945 (3)	0.0195 (5)
H4	0.9479	0.4640	0.6135	0.023*
C4a	0.85325 (16)	0.3212 (2)	0.4927 (3)	0.0159 (4)
C5a	0.65940 (16)	0.3263 (2)	0.3914 (3)	0.0164 (4)
C6	0.57174 (16)	0.3834 (2)	0.4013 (3)	0.0197 (5)
H6	0.5703	0.4759	0.4161	0.024*
C8	0.49541 (17)	0.1852 (2)	0.3756 (3)	0.0226 (5)
H8	0.4377	0.1351	0.3665	0.027*
C9	0.58017 (16)	0.1180 (2)	0.3718 (3)	0.0192 (5)
H9	0.5801	0.0249	0.3640	0.023*
C9a	0.66564 (15)	0.1889 (2)	0.3797 (3)	0.0154 (4)
C10a	0.84271 (15)	0.1850 (2)	0.4757 (3)	0.0147 (4)
C11	0.75374 (17)	−0.0072 (2)	0.3179 (3)	0.0182 (5)
H11a	0.8152	−0.0251	0.2819	0.022*
H11b	0.6992	−0.0198	0.2102	0.022*
C12	0.74397 (16)	−0.1054 (2)	0.4530 (3)	0.0194 (5)
C13	0.73370 (18)	−0.1884 (3)	0.5542 (4)	0.0284 (6)
H13	0.7254	−0.2552	0.6356	0.034*
S5	0.75938 (4)	0.42507 (5)	0.37659 (8)	0.01880 (16)
N2	1.00796 (13)	0.15579 (19)	0.6532 (3)	0.0204 (4)
N7	0.48877 (14)	0.3163 (2)	0.3912 (3)	0.0226 (4)
N10	0.75434 (13)	0.12936 (18)	0.3721 (2)	0.0158 (4)

	U11	U22	U33	U12	U13	U23
C1	0.0160 (10)	0.0151 (10)	0.0217 (11)	0.0027 (8)	0.0071 (9)	0.0011 (8)
C3	0.0170 (11)	0.0228 (12)	0.0250 (12)	−0.0042 (10)	0.0041 (9)	−0.0051 (10)
C4	0.0194 (11)	0.0165 (10)	0.0244 (12)	−0.0023 (9)	0.0085 (9)	−0.0050 (9)
C4a	0.0165 (10)	0.0147 (10)	0.0178 (11)	0.0005 (8)	0.0070 (8)	0.0003 (8)
C5a	0.0176 (10)	0.0166 (10)	0.0142 (10)	0.0009 (8)	0.0025 (8)	0.0013 (8)
C6	0.0195 (11)	0.0186 (10)	0.0197 (11)	0.0028 (9)	0.0023 (9)	−0.0007 (9)
C8	0.0168 (11)	0.0245 (12)	0.0250 (12)	−0.0011 (9)	0.0024 (9)	−0.0024 (10)
C9	0.0175 (10)	0.0170 (10)	0.0217 (11)	−0.0004 (9)	0.0022 (9)	−0.0013 (9)
C9a	0.0155 (10)	0.0156 (10)	0.0143 (10)	0.0027 (8)	0.0022 (8)	−0.0005 (8)
C10a	0.0141 (10)	0.0144 (10)	0.0169 (11)	−0.0017 (8)	0.0064 (8)	0.0000 (8)
C11	0.0199 (11)	0.0136 (10)	0.0218 (11)	0.0011 (9)	0.0064 (9)	−0.0028 (9)
C12	0.0149 (10)	0.0177 (10)	0.0250 (12)	0.0000 (9)	0.0037 (9)	−0.0034 (9)
C13	0.0256 (13)	0.0242 (12)	0.0360 (15)	0.0034 (10)	0.0086 (11)	0.0067 (11)
S5	0.0187 (3)	0.0143 (3)	0.0241 (3)	0.0015 (2)	0.0066 (2)	0.0035 (2)
N2	0.0131 (9)	0.0226 (10)	0.0248 (10)	0.0021 (8)	0.0033 (7)	−0.0002 (8)
N7	0.0164 (9)	0.0244 (10)	0.0254 (11)	0.0039 (8)	0.0020 (8)	−0.0014 (8)
N10	0.0119 (8)	0.0185 (9)	0.0167 (9)	0.0014 (7)	0.0030 (7)	−0.0005 (7)

C1—N2	1.342 (3)	C6—H6	0.9500
C1—C10a	1.393 (3)	C8—N7	1.347 (3)
C1—H1	0.9500	C8—C9	1.385 (3)
C3—N2	1.339 (3)	C8—H8	0.9500
C3—C4	1.387 (3)	C9—C9a	1.395 (3)
C3—H3	0.9500	C9—H9	0.9500
C4—C4a	1.383 (3)	C9a—N10	1.405 (3)
C4—H4	0.9500	C10a—N10	1.422 (3)
C4a—C10a	1.398 (3)	C11—N10	1.452 (3)
C4a—S5	1.758 (2)	C11—C12	1.471 (3)
C5a—C6	1.386 (3)	C11—H11a	0.9900
C5a—C9a	1.407 (3)	C11—H11b	0.9900
C5a—S5	1.760 (2)	C12—C13	1.181 (3)
C6—N7	1.342 (3)	C13—H13	0.9500
N2—C1—C10a	123.9 (2)	C8—C9—H9	120.5
N2—C1—H1	118.1	C9a—C9—H9	120.5
C10a—C1—H1	118.1	C9—C9a—N10	122.98 (19)
N2—C3—C4	123.5 (2)	C9—C9a—C5a	116.82 (19)
N2—C3—H3	118.3	N10—C9a—C5a	120.18 (19)
C4—C3—H3	118.3	C1—C10a—C4a	117.7 (2)
C4a—C4—C3	118.8 (2)	C1—C10a—N10	121.87 (19)
C4a—C4—H4	120.6	C4a—C10a—N10	120.42 (19)
C3—C4—H4	120.6	N10—C11—C12	116.42 (19)
C4—C4a—C10a	119.0 (2)	N10—C11—H11a	108.2
C4—C4a—S5	120.91 (17)	C12—C11—H11a	108.2
C10a—C4a—S5	120.04 (17)	N10—C11—H11b	108.2
C6—C5a—C9a	119.5 (2)	C12—C11—H11b	108.2
C6—C5a—S5	120.26 (17)	H11a—C11—H11b	107.3
C9a—C5a—S5	120.09 (16)	C13—C12—C11	176.5 (3)
N7—C6—C5a	124.1 (2)	C12—C13—H13	180.0
N7—C6—H6	117.9	C4a—S5—C5a	98.00 (10)
C5a—C6—H6	117.9	C3—N2—C1	117.1 (2)
N7—C8—C9	124.9 (2)	C6—N7—C8	115.6 (2)
N7—C8—H8	117.6	C9a—N10—C10a	118.21 (18)
C9—C8—H8	117.6	C9a—N10—C11	118.89 (18)
C8—C9—C9a	119.0 (2)	C10a—N10—C11	119.00 (18)
N2—C3—C4—C4a	−2.9 (4)	C4—C4a—S5—C5a	−148.01 (19)
C3—C4—C4a—C10a	3.3 (3)	C10a—C4a—S5—C5a	35.26 (19)
C3—C4—C4a—S5	−173.43 (17)	C6—C5a—S5—C4a	148.16 (19)
C9a—C5a—C6—N7	−3.6 (4)	C9a—C5a—S5—C4a	−36.6 (2)
S5—C5a—C6—N7	171.68 (18)	C4—C3—N2—C1	0.1 (3)
N7—C8—C9—C9a	−1.8 (4)	C10a—C1—N2—C3	2.2 (3)
C8—C9—C9a—N10	−178.4 (2)	C5a—C6—N7—C8	1.9 (3)
C8—C9—C9a—C5a	0.1 (3)	C9—C8—N7—C6	0.8 (4)
C6—C5a—C9a—C9	2.4 (3)	C9—C9a—N10—C10a	−144.8 (2)
S5—C5a—C9a—C9	−172.88 (17)	C5a—C9a—N10—C10a	36.8 (3)
C6—C5a—C9a—N10	−179.1 (2)	C9—C9a—N10—C11	12.8 (3)
S5—C5a—C9a—N10	5.6 (3)	C5a—C9a—N10—C11	−165.6 (2)
N2—C1—C10a—C4a	−1.7 (3)	C1—C10a—N10—C9a	142.9 (2)
N2—C1—C10a—N10	177.10 (19)	C4a—C10a—N10—C9a	−38.3 (3)
C4—C4a—C10a—C1	−1.2 (3)	C1—C10a—N10—C11	−14.6 (3)
S5—C4a—C10a—C1	175.63 (16)	C4a—C10a—N10—C11	164.16 (19)
C4—C4a—C10a—N10	179.98 (19)	C12—C11—N10—C9a	−76.0 (3)
S5—C4a—C10a—N10	−3.2 (3)	C12—C11—N10—C10a	81.3 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···N2i	0.95	2.62	3.457 (3)	147
C13—H13···C11ii	0.95	2.78	3.677 (3)	159
C13—H13···C12ii	0.95	2.78	3.686 (3)	161
C3—H3···C13i	0.95	2.78	3.662 (3)	155
C8—H8···C13iii	0.95	2.69	3.407 (3)	133

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯N2i	0.95	2.62	3.457 (3)	147
C13—H13⋯C11ii	0.95	2.78	3.677 (3)	159
C13—H13⋯C12ii	0.95	2.78	3.686 (3)	161
C3—H3⋯C13i	0.95	2.78	3.662 (3)	155
C8—H8⋯C13iii	0.95	2.69	3.407 (3)	133

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