3-Amino-1-(thio-phen-2-yl)-9,10-dihydro-phenanthrene-2,4-dicarbonitrile.

In the title compound, C(20)H(13)N(3)S, the partially saturated ring adopts a twisted half-boat conformation with the methyl-ene C atom closest to the amino-benzene ring lying 0.690 (6) Å out of the plane defined by the five remaining atoms. The dihydro-phenanthrene residue has a folded conformation [dihedral angle between the outer benzene rings = 26.27 (18)°]. The thio-phen-2-yl ring forms a dihedral angle of 63.76 (19)° with the benzene ring to which it is attached. In the crystal, inversion dimers linked by pairs of N-H⋯N hydrogen bonds generate R(2) (2)(12) loops. The dimers are linked into layers in the bc plane by weak C-H⋯π inter-actions. The thio-phen-2-yl ring is disordered over two essentially coplanar but opposite orientations in a 0.918 (4):0.082 (4) ratio.

Related literature

For background to the biological activity of related dicarbonitrile compounds, see: Aly et al. (1991 ▶); Rostom et al. (2011 ▶). For related structures, see: Asiri et al. (2011a ▶,b ▶).

Experimental

Crystal data

C20H13N3S

M = 327.39

Monoclinic,

a = 9.7882 (10) Å

b = 7.1199 (7) Å

c = 22.746 (3) Å

β = 93.171 (11)°

V = 1582.8 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.21 mm−1

T = 100 K

0.30 × 0.06 × 0.03 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T min = 0.940, T max = 0.994

5527 measured reflections

2805 independent reflections

1778 reflections with I > 2σ(I)

R int = 0.056

Refinement

R[F 2 > 2σ(F 2)] = 0.066

wR(F 2) = 0.164

S = 1.03

2805 reflections

236 parameters

56 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.67 e Å−3

Δρmin = −0.55 e Å−3

Data collection: CrysAlis PRO (Agilent, 2011 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812010033/hb6670sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812010033/hb6670Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812010033/hb6670Isup3.cml

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

C20H13N3S	F(000) = 680
Mr = 327.39	Dx = 1.374 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1132 reflections
a = 9.7882 (10) Å	θ = 2.7–25.0°
b = 7.1199 (7) Å	µ = 0.21 mm−1
c = 22.746 (3) Å	T = 100 K
β = 93.171 (11)°	Prism, orange
V = 1582.8 (3) Å3	0.30 × 0.06 × 0.03 mm
Z = 4

Agilent SuperNova Dual diffractometer with an Atlas detector	2805 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	1778 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.056
Detector resolution: 10.4041 pixels mm-1	θmax = 25.1°, θmin = 2.7°
ω scan	h = −9→11
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −8→6
Tmin = 0.940, Tmax = 0.994	l = −19→27
5527 measured 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)] = 0.066	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.164	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.0559P)2 + 1.2744P] where P = (Fo2 + 2Fc2)/3
2805 reflections	(Δ/σ)max = 0.001
236 parameters	Δρmax = 0.67 e Å−3
56 restraints	Δρmin = −0.55 e Å−3

	x	y	z	Uiso*/Ueq	Occ. (<1)
S1	0.98458 (11)	0.25812 (17)	0.64193 (6)	0.0331 (4)	0.918 (4)
S1'	0.976 (2)	0.275 (3)	0.5229 (7)	0.0358 (13)	0.082 (4)
N1	0.2456 (3)	0.6816 (5)	0.61810 (16)	0.0329 (9)
N2	0.3958 (3)	0.3401 (5)	0.54813 (14)	0.0213 (7)
H1	0.402 (4)	0.236 (3)	0.5276 (15)	0.026*
H2	0.3108 (16)	0.373 (5)	0.5535 (17)	0.026*
N3	0.6533 (3)	0.0358 (5)	0.51041 (15)	0.0255 (8)
C1	0.7477 (4)	0.6177 (5)	0.61652 (16)	0.0213 (9)
C2	0.8711 (4)	0.7249 (5)	0.64154 (18)	0.0262 (9)
H2A	0.8904	0.8322	0.6156	0.031*
H2B	0.9523	0.6418	0.6438	0.031*
C3	0.8422 (4)	0.7966 (6)	0.70321 (18)	0.0329 (11)
H3A	0.8278	0.6888	0.7297	0.039*
H3B	0.9215	0.8696	0.7196	0.039*
C4	0.7144 (4)	0.9209 (5)	0.69949 (19)	0.0295 (10)
C5	0.7052 (5)	1.0784 (6)	0.73318 (19)	0.0380 (11)
H5	0.7768	1.1082	0.7615	0.046*
C6	0.5919 (4)	1.1956 (6)	0.72634 (19)	0.0329 (11)
H6	0.5848	1.3024	0.7510	0.040*
C7	0.4905 (4)	1.1578 (5)	0.68423 (18)	0.0289 (10)
H7	0.4145	1.2402	0.6792	0.035*
C8	0.4980 (4)	0.9990 (5)	0.64865 (18)	0.0260 (10)
H8	0.4288	0.9752	0.6187	0.031*
C9	0.6089 (4)	0.8743 (5)	0.65742 (16)	0.0221 (9)
C10	0.6174 (4)	0.6957 (5)	0.62403 (16)	0.0201 (9)
C11	0.5006 (3)	0.5995 (5)	0.60216 (16)	0.0173 (8)
C12	0.5094 (4)	0.4290 (5)	0.57009 (16)	0.0184 (8)
C13	0.6410 (3)	0.3549 (5)	0.56377 (16)	0.0170 (8)
C14	0.7610 (3)	0.4495 (5)	0.58825 (16)	0.0202 (9)
C15	0.3602 (4)	0.6548 (5)	0.61278 (17)	0.0237 (9)
C16	0.6518 (3)	0.1773 (5)	0.53443 (16)	0.0193 (9)
C17	0.8889 (3)	0.3421 (4)	0.58171 (17)	0.0234 (9)
C18	0.9449 (5)	0.2974 (7)	0.5317 (2)	0.0358 (13)	0.918 (4)
H18	0.9073	0.3340	0.4940	0.043*	0.918 (4)
C18'	0.953 (2)	0.282 (3)	0.6333 (6)	0.0331 (4)	0.08
H18'	0.9194	0.3055	0.6710	0.040*	0.082 (4)
C19	1.0686 (4)	0.1878 (6)	0.5402 (2)	0.0325 (13)	0.918 (4)
H19	1.1203	0.1430	0.5089	0.039*	0.918 (4)
C19'	1.0749 (19)	0.179 (3)	0.6240 (13)	0.0361 (13)	0.082 (4)
H19'	1.1321	0.1274	0.6549	0.043*	0.082 (4)
C20	1.1022 (4)	0.1564 (6)	0.5979 (2)	0.0361 (13)	0.918 (4)
H20	1.1802	0.0875	0.6122	0.043*	0.918 (4)
C20'	1.1006 (14)	0.1645 (15)	0.5660 (15)	0.0325 (13)	0.08
H20'	1.1771	0.1011	0.5514	0.039*	0.082 (4)

	U11	U22	U33	U12	U13	U23
S1	0.0230 (7)	0.0336 (7)	0.0420 (8)	0.0037 (5)	−0.0030 (5)	0.0073 (6)
S1'	0.021 (3)	0.045 (3)	0.043 (3)	0.005 (2)	0.015 (2)	−0.020 (2)
N1	0.025 (2)	0.035 (2)	0.038 (2)	0.0062 (16)	0.0029 (17)	0.0003 (17)
N2	0.0165 (16)	0.0228 (17)	0.0244 (19)	−0.0001 (15)	−0.0003 (14)	−0.0056 (15)
N3	0.0169 (17)	0.0238 (19)	0.036 (2)	0.0003 (14)	0.0039 (15)	−0.0071 (17)
C1	0.022 (2)	0.021 (2)	0.021 (2)	−0.0035 (17)	0.0023 (16)	0.0002 (17)
C2	0.024 (2)	0.023 (2)	0.032 (2)	−0.0028 (18)	0.0044 (18)	−0.0083 (19)
C3	0.032 (2)	0.035 (2)	0.031 (3)	−0.005 (2)	−0.0030 (19)	−0.010 (2)
C4	0.034 (2)	0.021 (2)	0.032 (3)	−0.0097 (19)	−0.0055 (19)	0.0035 (19)
C5	0.047 (3)	0.041 (3)	0.026 (3)	−0.004 (2)	0.012 (2)	−0.006 (2)
C6	0.047 (3)	0.027 (2)	0.026 (2)	−0.002 (2)	0.018 (2)	−0.007 (2)
C7	0.040 (2)	0.020 (2)	0.029 (2)	0.0020 (19)	0.016 (2)	0.0036 (19)
C8	0.033 (2)	0.022 (2)	0.023 (2)	−0.0007 (19)	0.0085 (18)	−0.0005 (18)
C9	0.030 (2)	0.0173 (19)	0.020 (2)	−0.0026 (18)	0.0090 (17)	0.0006 (17)
C10	0.023 (2)	0.019 (2)	0.018 (2)	−0.0003 (17)	0.0038 (16)	0.0037 (16)
C11	0.0177 (19)	0.0141 (18)	0.021 (2)	0.0009 (16)	0.0038 (16)	0.0016 (16)
C12	0.021 (2)	0.0190 (19)	0.015 (2)	0.0010 (17)	0.0041 (16)	0.0029 (16)
C13	0.0161 (19)	0.0154 (18)	0.020 (2)	0.0000 (16)	0.0063 (15)	0.0004 (16)
C14	0.020 (2)	0.020 (2)	0.021 (2)	−0.0004 (16)	0.0051 (16)	0.0016 (17)
C15	0.032 (2)	0.018 (2)	0.020 (2)	−0.0007 (18)	−0.0020 (18)	−0.0004 (17)
C16	0.0144 (19)	0.022 (2)	0.021 (2)	−0.0030 (16)	0.0006 (16)	0.0018 (18)
C17	0.0176 (19)	0.023 (2)	0.030 (2)	−0.0044 (17)	0.0021 (17)	−0.0049 (18)
C18	0.021 (3)	0.045 (3)	0.043 (3)	0.005 (2)	0.015 (2)	−0.020 (2)
C18'	0.0230 (7)	0.0336 (7)	0.0420 (8)	0.0037 (5)	−0.0030 (5)	0.0073 (6)
C19	0.011 (2)	0.033 (2)	0.053 (3)	0.0018 (19)	0.000 (2)	−0.021 (2)
C19'	0.018 (2)	0.027 (2)	0.064 (4)	0.0064 (19)	0.004 (2)	−0.008 (3)
C20	0.018 (2)	0.027 (2)	0.064 (4)	0.0064 (19)	0.004 (2)	−0.008 (3)
C20'	0.011 (2)	0.033 (2)	0.053 (3)	0.0018 (19)	0.000 (2)	−0.021 (2)

S1—C17	1.723 (4)	C7—C8	1.395 (5)
S1—C20	1.727 (5)	C7—H7	0.9500
S1'—C17	1.695 (9)	C8—C9	1.408 (5)
S1'—C20'	1.713 (10)	C8—H8	0.9500
N1—C15	1.150 (5)	C9—C10	1.486 (5)
N2—C12	1.351 (5)	C10—C11	1.400 (5)
N2—H1	0.882 (10)	C11—C12	1.422 (5)
N2—H2	0.880 (10)	C11—C15	1.462 (5)
N3—C16	1.146 (5)	C12—C13	1.407 (5)
C1—C14	1.369 (5)	C13—C16	1.437 (5)
C1—C10	1.410 (5)	C13—C14	1.439 (5)
C1—C2	1.513 (5)	C14—C17	1.481 (5)
C2—C3	1.534 (5)	C17—C18	1.329 (6)
C2—H2A	0.9900	C17—C18'	1.367 (9)
C2—H2B	0.9900	C18—C19	1.445 (6)
C3—C4	1.531 (6)	C18—H18	0.9500
C3—H3A	0.9900	C18'—C19'	1.427 (9)
C3—H3B	0.9900	C18'—H18'	0.9500
C4—C5	1.364 (6)	C19—C20	1.354 (6)
C4—C9	1.408 (5)	C19—H19	0.9500
C5—C6	1.390 (6)	C19'—C20'	1.360 (9)
C5—H5	0.9500	C19'—H19'	0.9500
C6—C7	1.367 (6)	C20—H20	0.9500
C6—H6	0.9500	C20'—H20'	0.9500
C17—S1—C20	92.0 (2)	C1—C10—C9	118.4 (3)
C17—S1'—C20'	93.0 (5)	C10—C11—C12	121.9 (3)
C12—N2—H1	121 (2)	C10—C11—C15	124.5 (3)
C12—N2—H2	126 (3)	C12—C11—C15	113.5 (3)
H1—N2—H2	113 (4)	N2—C12—C13	121.8 (3)
C14—C1—C10	120.8 (3)	N2—C12—C11	121.2 (3)
C14—C1—C2	121.6 (3)	C13—C12—C11	117.0 (3)
C10—C1—C2	117.7 (3)	C12—C13—C16	117.9 (3)
C1—C2—C3	109.1 (3)	C12—C13—C14	121.2 (3)
C1—C2—H2A	109.9	C16—C13—C14	120.9 (3)
C3—C2—H2A	109.9	C1—C14—C13	119.6 (3)
C1—C2—H2B	109.9	C1—C14—C17	127.0 (3)
C3—C2—H2B	109.9	C13—C14—C17	113.3 (3)
H2A—C2—H2B	108.3	N1—C15—C11	172.9 (4)
C4—C3—C2	109.5 (3)	N3—C16—C13	176.6 (4)
C4—C3—H3A	109.8	C18—C17—C14	126.9 (4)
C2—C3—H3A	109.8	C18'—C17—C14	115.1 (11)
C4—C3—H3B	109.8	C18'—C17—S1'	111.3 (7)
C2—C3—H3B	109.8	C14—C17—S1'	133.6 (8)
H3A—C3—H3B	108.2	C18—C17—S1	111.5 (3)
C5—C4—C9	120.4 (4)	C14—C17—S1	121.6 (3)
C5—C4—C3	121.6 (4)	C17—C18—C19	113.4 (4)
C9—C4—C3	117.9 (4)	C17—C18—H18	123.3
C4—C5—C6	120.5 (4)	C19—C18—H18	123.3
C4—C5—H5	119.7	C17—C18'—C19'	112.4 (6)
C6—C5—H5	119.7	C17—C18'—H18'	123.8
C7—C6—C5	120.2 (4)	C19'—C18'—H18'	123.8
C7—C6—H6	119.9	C20—C19—C18	112.1 (4)
C5—C6—H6	119.9	C20—C19—H19	124.0
C6—C7—C8	120.5 (4)	C18—C19—H19	124.0
C6—C7—H7	119.8	C20'—C19'—C18'	112.7 (7)
C8—C7—H7	119.8	C20'—C19'—H19'	123.7
C7—C8—C9	119.6 (4)	C18'—C19'—H19'	123.7
C7—C8—H8	120.2	C19—C20—S1	111.1 (3)
C9—C8—H8	120.2	C19—C20—H20	124.5
C8—C9—C4	118.6 (4)	S1—C20—H20	124.5
C8—C9—C10	122.1 (3)	C19'—C20'—S1'	110.8 (8)
C4—C9—C10	119.3 (3)	C19'—C20'—H20'	124.6
C11—C10—C1	119.4 (3)	S1'—C20'—H20'	124.6
C11—C10—C9	122.2 (3)
C14—C1—C2—C3	−135.7 (4)	C2—C1—C14—C13	−178.3 (3)
C10—C1—C2—C3	43.4 (5)	C10—C1—C14—C17	−174.1 (3)
C1—C2—C3—C4	−58.1 (4)	C2—C1—C14—C17	5.0 (6)
C2—C3—C4—C5	−142.1 (4)	C12—C13—C14—C1	−2.2 (5)
C2—C3—C4—C9	34.1 (5)	C16—C13—C14—C1	−179.3 (3)
C9—C4—C5—C6	−0.3 (6)	C12—C13—C14—C17	174.9 (3)
C3—C4—C5—C6	175.8 (4)	C16—C13—C14—C17	−2.2 (5)
C4—C5—C6—C7	−2.3 (6)	C1—C14—C17—C18	−118.5 (4)
C5—C6—C7—C8	1.5 (6)	C13—C14—C17—C18	64.6 (3)
C6—C7—C8—C9	1.8 (6)	C1—C14—C17—C18'	62.6 (12)
C7—C8—C9—C4	−4.3 (5)	C13—C14—C17—C18'	−114.3 (11)
C7—C8—C9—C10	175.3 (3)	C1—C14—C17—S1'	−117.4 (11)
C5—C4—C9—C8	3.6 (6)	C13—C14—C17—S1'	65.7 (11)
C3—C4—C9—C8	−172.7 (4)	C1—C14—C17—S1	61.6 (4)
C5—C4—C9—C10	−176.1 (4)	C13—C14—C17—S1	−115.3 (3)
C3—C4—C9—C10	7.6 (5)	C20'—S1'—C17—C18	−173 (8)
C14—C1—C10—C11	−0.1 (5)	C20'—S1'—C17—C18'	0.1 (3)
C2—C1—C10—C11	−179.2 (3)	C20'—S1'—C17—C14	−179.92 (19)
C14—C1—C10—C9	177.3 (3)	C20'—S1'—C17—S1	1.0 (10)
C2—C1—C10—C9	−1.8 (5)	C20—S1—C17—C18	−0.9 (2)
C8—C9—C10—C11	−28.0 (6)	C20—S1—C17—C18'	171 (9)
C4—C9—C10—C11	151.7 (4)	C20—S1—C17—C14	178.99 (15)
C8—C9—C10—C1	154.7 (4)	C20—S1—C17—S1'	−1.8 (8)
C4—C9—C10—C1	−25.6 (5)	C18'—C17—C18—C19	0.2 (14)
C1—C10—C11—C12	−3.0 (5)	C14—C17—C18—C19	−178.7 (2)
C9—C10—C11—C12	179.8 (3)	S1'—C17—C18—C19	8 (7)
C1—C10—C11—C15	172.9 (3)	S1—C17—C18—C19	1.2 (3)
C9—C10—C11—C15	−4.3 (6)	C18—C17—C18'—C19'	1.0 (12)
C10—C11—C12—N2	−178.5 (3)	C14—C17—C18'—C19'	180.0 (3)
C15—C11—C12—N2	5.2 (5)	S1'—C17—C18'—C19'	0.0 (3)
C10—C11—C12—C13	3.3 (5)	S1—C17—C18'—C19'	−8 (9)
C15—C11—C12—C13	−173.0 (3)	C17—C18—C19—C20	−1.0 (4)
N2—C12—C13—C16	−1.7 (5)	C17—C18'—C19'—C20'	−0.1 (5)
C11—C12—C13—C16	176.5 (3)	C18—C19—C20—S1	0.2 (4)
N2—C12—C13—C14	−178.9 (3)	C17—S1—C20—C19	0.4 (3)
C11—C12—C13—C14	−0.7 (5)	C18'—C19'—C20'—S1'	0.1 (6)
C10—C1—C14—C13	2.6 (6)	C17—S1'—C20'—C19'	−0.1 (5)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1···N3i	0.88 (3)	2.18 (3)	3.016 (5)	160 (3)
C6—H6···Cg1ii	0.95	2.85	3.660 (5)	144

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C4–C9 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1⋯N3i	0.88 (3)	2.18 (3)	3.016 (5)	160 (3)
C6—H6⋯Cg1ii	0.95	2.85	3.660 (5)	144

Symmetry codes: (i) ; (ii) .