2-Amino-4-phenyl-5,6-dihydro-benzo[h]quinoline-3-carbonitrile-3-amino-1-phenyl-9,10-dihydro-phenanthrene-2,4-dicarbonitrile (5/3).

The asymmetric unit of the 5:3 title co-crystal of 2-amino-4-phenyl-5,6-dihydro-benzo[h]quinoline-3-carbonitrile and 3-amino-1-phenyl-9,10-dihydro-phenanthrene-2,4-dicarbonitrile, 0.625C(20)H(15)N(3).0.375C(22)H(15)N(3), has the atoms of the fused-ring system and those of the amino, cyano and phenyl substitutents overlapped. The fused-ring system is buckled owing to the ethyl-ene linkage in the central ring, the two flanking aromatic rings being twisted by 20.1 (1)°. This ethyl-ene portion is disordered over two positions in a 1:1 ratio. The phenyl ring is twisted by 69.5 (1)° relative to the amino- and cyano-bearing aromatic ring. In the crystal, two mol-ecules are linked by an N-H⋯N hydrogen bond, generating a a helical chain along [010].

Related literature

For the synthesis, see: Aly et al. (1991 ▶); Paul et al. (1998 ▶). For related structures, see: Asiri et al. (2011a ▶,b ▶).

Experimental

Crystal data

0.625C20H15N3·0.375C22H15N3

M = 306.36

Orthorhombic,

a = 6.9611 (2) Å

b = 12.6093 (2) Å

c = 17.4933 (3) Å

V = 1535.47 (6) Å3

Z = 4

Cu Kα radiation

μ = 0.62 mm−1

T = 100 K

0.30 × 0.20 × 0.02 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ▶) T min = 0.835, T max = 0.988

6293 measured reflections

1794 independent reflections

1707 reflections with I > 2σ(I)

R int = 0.018

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.119

S = 1.05

1794 reflections

240 parameters

24 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.19 e Å−3

Δρmin = −0.23 e Å−3

Data collection: CrysAlis PRO (Agilent, 2010 ▶); 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: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811040505/zs2145sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811040505/zs2145Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811040505/zs2145Isup3.cml

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

0.625C20H15N3·0.375C22H15N3	F(000) = 642
Mr = 306.36	Dx = 1.325 Mg m−3
Orthorhombic, P212121	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: P 2ac 2ab	Cell parameters from 3717 reflections
a = 6.9611 (2) Å	θ = 3.5–74.3°
b = 12.6093 (2) Å	µ = 0.62 mm−1
c = 17.4933 (3) Å	T = 100 K
V = 1535.47 (6) Å3	Plate, brown-orange
Z = 4	0.30 × 0.20 × 0.02 mm

Agilent SuperNova Dual diffractometer with an Atlas detector	1794 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	1707 reflections with I > 2σ(I)
Mirror	Rint = 0.018
Detector resolution: 10.4041 pixels mm-1	θmax = 74.5°, θmin = 4.3°
ω scans	h = −8→7
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −13→15
Tmin = 0.835, Tmax = 0.988	l = −21→20
6293 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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.119	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0796P)2 + 0.2871P] where P = (Fo2 + 2Fc2)/3
1794 reflections	(Δ/σ)max = 0.001
240 parameters	Δρmax = 0.19 e Å−3
24 restraints	Δρmin = −0.23 e Å−3

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	0.9898 (3)	0.26050 (14)	1.05516 (10)	0.0294 (4)	0.625
C1'	0.9898 (3)	0.26050 (14)	1.05516 (10)	0.0294 (4)	0.375
N2	1.0082 (3)	0.28041 (13)	1.18789 (10)	0.0339 (4)
H1	1.035 (5)	0.3483 (10)	1.1827 (17)	0.052 (8)*
H2	1.031 (4)	0.254 (2)	1.2335 (9)	0.045 (8)*
N3	0.9475 (4)	0.02407 (14)	1.26992 (10)	0.0396 (5)
C1	0.9186 (4)	−0.07603 (16)	1.08021 (11)	0.0369 (5)
C2	1.0684 (4)	−0.13801 (17)	1.10772 (12)	0.0414 (6)
H2A	1.1883	−0.1063	1.1200	0.050*
C3	1.0422 (5)	−0.24706 (17)	1.11721 (12)	0.0463 (7)
H3	1.1450	−0.2896	1.1355	0.056*
C4	0.8687 (5)	−0.29307 (17)	1.10017 (12)	0.0500 (8)
H4	0.8513	−0.3671	1.1075	0.060*
C5	0.7187 (5)	−0.23191 (18)	1.07229 (14)	0.0521 (7)
H5	0.5990	−0.2641	1.0603	0.063*
C6	0.7439 (5)	−0.12301 (18)	1.06183 (13)	0.0478 (6)
H6	0.6418	−0.0811	1.0422	0.057*
C7	0.9453 (4)	0.04111 (15)	1.06991 (11)	0.0336 (5)
C8	0.9536 (4)	0.08663 (16)	0.99730 (11)	0.0391 (6)
C9	0.9790 (10)	0.0170 (5)	0.9251 (4)	0.0390 (15)	0.50
H9A	1.0343	−0.0525	0.9396	0.047*	0.50
H9B	0.8524	0.0043	0.9010	0.047*	0.50
C10	1.1119 (9)	0.0727 (5)	0.8684 (3)	0.0440 (15)	0.50
H10A	1.1216	0.0310	0.8206	0.053*	0.50
H10B	1.2422	0.0801	0.8905	0.053*	0.50
C9'	0.9024 (9)	0.0270 (5)	0.9245 (4)	0.0390 (15)	0.50
H9'C	0.9220	−0.0500	0.9322	0.047*	0.50
H9'D	0.7656	0.0390	0.9117	0.047*	0.50
C10'	1.0290 (10)	0.0659 (5)	0.8592 (3)	0.0440 (15)	0.50
H10C	1.1628	0.0426	0.8683	0.053*	0.50
H10D	0.9847	0.0335	0.8108	0.053*	0.50
C11	1.0247 (5)	0.18419 (19)	0.85163 (13)	0.0485 (7)
C12	1.0305 (5)	0.2290 (2)	0.77912 (15)	0.0561 (7)
H12	1.0608	0.1859	0.7362	0.067*
C13	0.9929 (5)	0.3351 (3)	0.76887 (17)	0.0606 (8)
H13	0.9963	0.3651	0.7191	0.073*
C14	0.9497 (5)	0.3981 (3)	0.8318 (2)	0.0699 (10)
H14	0.9246	0.4716	0.8250	0.084*
C15	0.9431 (5)	0.3542 (2)	0.90409 (18)	0.0593 (9)
H15	0.9134	0.3976	0.9469	0.071*
C16	0.9798 (4)	0.24669 (16)	0.91469 (12)	0.0355 (5)
C17	0.9738 (3)	0.19760 (15)	0.99194 (12)	0.0331 (5)
C18	0.9871 (3)	0.21628 (14)	1.12653 (11)	0.0281 (4)
C19	0.9622 (3)	0.10550 (15)	1.13457 (11)	0.0291 (4)
C20	0.9531 (4)	0.05995 (15)	1.20987 (11)	0.0308 (5)
N4	1.0072 (11)	0.4629 (4)	1.0526 (3)	0.0471 (15)	0.375
C21	0.9965 (10)	0.3721 (4)	1.0492 (3)	0.0337 (12)	0.375

	U11	U22	U33	U12	U13	U23
N1	0.0427 (10)	0.0207 (8)	0.0249 (8)	0.0010 (8)	0.0045 (8)	0.0015 (7)
C1'	0.0427 (10)	0.0207 (8)	0.0249 (8)	0.0010 (8)	0.0045 (8)	0.0015 (7)
N2	0.0607 (12)	0.0210 (7)	0.0200 (7)	−0.0002 (9)	−0.0011 (8)	−0.0010 (6)
N3	0.0672 (14)	0.0253 (8)	0.0263 (8)	0.0000 (9)	−0.0015 (9)	0.0044 (7)
C1	0.0703 (16)	0.0214 (9)	0.0189 (8)	−0.0041 (10)	−0.0016 (10)	0.0008 (7)
C2	0.0705 (16)	0.0260 (10)	0.0277 (9)	0.0011 (11)	−0.0012 (11)	−0.0002 (8)
C3	0.087 (2)	0.0257 (10)	0.0259 (10)	0.0058 (12)	0.0027 (12)	0.0009 (8)
C4	0.106 (2)	0.0201 (9)	0.0239 (10)	−0.0060 (13)	0.0035 (12)	0.0016 (8)
C5	0.089 (2)	0.0300 (10)	0.0370 (12)	−0.0174 (13)	−0.0096 (13)	0.0029 (10)
C6	0.0785 (18)	0.0283 (10)	0.0365 (11)	−0.0092 (12)	−0.0159 (13)	0.0053 (9)
C7	0.0539 (13)	0.0211 (9)	0.0258 (9)	−0.0025 (9)	−0.0007 (10)	0.0002 (8)
C8	0.0704 (16)	0.0228 (9)	0.0241 (9)	−0.0043 (11)	−0.0002 (11)	0.0017 (8)
C9	0.069 (4)	0.0245 (14)	0.0237 (10)	0.001 (3)	−0.002 (3)	0.0004 (10)
C10	0.082 (5)	0.0283 (13)	0.0211 (15)	−0.013 (3)	−0.001 (2)	−0.0071 (11)
C9'	0.069 (4)	0.0245 (14)	0.0237 (10)	0.001 (3)	−0.002 (3)	0.0004 (10)
C10'	0.082 (5)	0.0283 (13)	0.0211 (15)	−0.013 (3)	−0.001 (2)	−0.0071 (11)
C11	0.0804 (19)	0.0357 (11)	0.0293 (11)	−0.0080 (14)	0.0008 (12)	0.0083 (9)
C12	0.080 (2)	0.0562 (15)	0.0321 (12)	−0.0134 (16)	0.0003 (13)	0.0126 (11)
C13	0.0538 (14)	0.0720 (19)	0.0559 (16)	0.0019 (16)	0.0020 (14)	0.0404 (15)
C14	0.0675 (19)	0.0549 (16)	0.087 (2)	0.0299 (16)	0.0384 (18)	0.0452 (16)
C15	0.0674 (18)	0.0408 (13)	0.0698 (18)	0.0201 (14)	0.0372 (16)	0.0274 (13)
C16	0.0429 (11)	0.0291 (10)	0.0347 (11)	0.0004 (10)	0.0053 (9)	0.0096 (9)
C17	0.0456 (11)	0.0240 (9)	0.0297 (10)	0.0003 (10)	0.0041 (10)	0.0026 (8)
C18	0.0405 (11)	0.0215 (8)	0.0224 (9)	0.0005 (9)	0.0001 (8)	−0.0002 (7)
C19	0.0432 (11)	0.0224 (9)	0.0218 (9)	−0.0005 (9)	0.0001 (9)	0.0028 (7)
C20	0.0480 (12)	0.0195 (8)	0.0249 (9)	−0.0013 (9)	−0.0017 (9)	−0.0011 (7)
N4	0.094 (5)	0.021 (2)	0.026 (2)	−0.002 (3)	0.001 (3)	−0.0014 (18)
C21	0.055 (3)	0.027 (3)	0.018 (2)	0.003 (3)	0.005 (2)	−0.0001 (19)

N1—C17	1.366 (3)	C9—H9B	0.9900
N1—C18	1.367 (2)	C10—C11	1.560 (7)
N2—C18	1.352 (2)	C10—H10A	0.9900
N2—H1	0.88 (1)	C10—H10B	0.9900
N2—H2	0.88 (1)	C9'—C10'	1.523 (7)
N3—C20	1.144 (3)	C9'—H9'C	0.9900
C1—C6	1.391 (4)	C9'—H9'D	0.9900
C1—C2	1.389 (4)	C10'—C11	1.498 (7)
C1—C7	1.499 (3)	C10'—H10C	0.9900
C2—C3	1.397 (3)	C10'—H10D	0.9900
C2—H2A	0.9500	C11—C12	1.389 (3)
C3—C4	1.373 (4)	C11—C16	1.391 (3)
C3—H3	0.9500	C12—C13	1.375 (4)
C4—C5	1.387 (4)	C12—H12	0.9500
C4—H4	0.9500	C13—C14	1.390 (5)
C5—C6	1.396 (3)	C13—H13	0.9500
C5—H5	0.9500	C14—C15	1.382 (4)
C6—H6	0.9500	C14—H14	0.9500
C7—C19	1.397 (3)	C15—C16	1.392 (3)
C7—C8	1.395 (3)	C15—H15	0.9500
C8—C17	1.410 (3)	C16—C17	1.487 (3)
C8—C9'	1.521 (7)	C18—C19	1.415 (2)
C8—C9	1.548 (7)	C19—C20	1.438 (3)
C9—C10	1.527 (7)	N4—C21	1.149 (7)
C9—H9A	0.9900
C17—N1—C18	120.11 (16)	C10'—C9'—C8	109.5 (4)
C18—N2—H1	122 (2)	C10'—C9'—H9'C	109.8
C18—N2—H2	120.8 (19)	C8—C9'—H9'C	109.8
H1—N2—H2	115 (3)	C10'—C9'—H9'D	109.8
C6—C1—C2	119.8 (2)	C8—C9'—H9'D	109.8
C6—C1—C7	120.0 (2)	H9'C—C9'—H9'D	108.2
C2—C1—C7	120.2 (2)	C11—C10'—C9'	112.1 (5)
C1—C2—C3	119.8 (3)	C11—C10'—H10C	109.2
C1—C2—H2A	120.1	C9'—C10'—H10C	109.2
C3—C2—H2A	120.1	C11—C10'—H10D	109.2
C4—C3—C2	120.3 (3)	C9'—C10'—H10D	109.2
C4—C3—H3	119.8	H10C—C10'—H10D	107.9
C2—C3—H3	119.8	C12—C11—C16	120.0 (2)
C3—C4—C5	120.2 (2)	C12—C11—C10'	119.0 (3)
C3—C4—H4	119.9	C16—C11—C10'	119.9 (3)
C5—C4—H4	119.9	C12—C11—C10	121.8 (3)
C4—C5—C6	119.9 (3)	C16—C11—C10	116.7 (3)
C4—C5—H5	120.0	C13—C12—C11	120.6 (3)
C6—C5—H5	120.0	C13—C12—H12	119.7
C1—C6—C5	119.9 (3)	C11—C12—H12	119.7
C1—C6—H6	120.1	C12—C13—C14	119.6 (2)
C5—C6—H6	120.1	C12—C13—H13	120.2
C19—C7—C8	119.64 (17)	C14—C13—H13	120.2
C19—C7—C1	119.05 (17)	C15—C14—C13	120.1 (3)
C8—C7—C1	121.31 (17)	C15—C14—H14	119.9
C7—C8—C17	118.24 (18)	C13—C14—H14	119.9
C7—C8—C9'	123.3 (3)	C14—C15—C16	120.4 (3)
C17—C8—C9'	117.3 (3)	C14—C15—H15	119.8
C7—C8—C9	120.9 (3)	C16—C15—H15	119.8
C17—C8—C9	119.8 (3)	C15—C16—C11	119.2 (2)
C10—C9—C8	109.7 (5)	C15—C16—C17	121.4 (2)
C10—C9—H9A	109.7	C11—C16—C17	119.40 (18)
C8—C9—H9A	109.7	N1—C17—C8	122.06 (18)
C10—C9—H9B	109.7	N1—C17—C16	119.48 (18)
C8—C9—H9B	109.7	C8—C17—C16	118.46 (18)
H9A—C9—H9B	108.2	N2—C18—N1	118.65 (16)
C9—C10—C11	107.5 (5)	N2—C18—C19	121.67 (16)
C9—C10—H10A	110.2	N1—C18—C19	119.68 (17)
C11—C10—H10A	110.2	C7—C19—C18	120.24 (17)
C9—C10—H10B	110.2	C7—C19—C20	120.37 (17)
C11—C10—H10B	110.2	C18—C19—C20	119.39 (17)
H10A—C10—H10B	108.5	N3—C20—C19	179.3 (3)
C6—C1—C2—C3	−0.4 (3)	C10—C11—C12—C13	−165.4 (4)
C7—C1—C2—C3	179.9 (2)	C11—C12—C13—C14	0.4 (5)
C1—C2—C3—C4	−0.6 (3)	C12—C13—C14—C15	−0.5 (5)
C2—C3—C4—C5	1.0 (4)	C13—C14—C15—C16	0.1 (5)
C3—C4—C5—C6	−0.3 (4)	C14—C15—C16—C11	0.5 (5)
C2—C1—C6—C5	1.1 (4)	C14—C15—C16—C17	179.9 (3)
C7—C1—C6—C5	−179.3 (2)	C12—C11—C16—C15	−0.7 (5)
C4—C5—C6—C1	−0.7 (4)	C10'—C11—C16—C15	−168.7 (4)
C6—C1—C7—C19	110.6 (3)	C10—C11—C16—C15	165.6 (3)
C2—C1—C7—C19	−69.8 (3)	C12—C11—C16—C17	179.9 (3)
C6—C1—C7—C8	−69.5 (3)	C10'—C11—C16—C17	11.8 (5)
C2—C1—C7—C8	110.1 (3)	C10—C11—C16—C17	−13.8 (4)
C19—C7—C8—C17	−1.7 (4)	C18—N1—C17—C8	0.2 (4)
C1—C7—C8—C17	178.4 (2)	C18—N1—C17—C16	−179.2 (2)
C19—C7—C8—C9'	−169.0 (4)	C7—C8—C17—N1	1.5 (4)
C1—C7—C8—C9'	11.0 (5)	C9'—C8—C17—N1	169.6 (3)
C19—C7—C8—C9	166.8 (4)	C9—C8—C17—N1	−167.1 (4)
C1—C7—C8—C9	−13.1 (5)	C7—C8—C17—C16	−179.1 (2)
C7—C8—C9—C10	−141.5 (4)	C9'—C8—C17—C16	−11.0 (4)
C17—C8—C9—C10	26.9 (6)	C9—C8—C17—C16	12.3 (5)
C9'—C8—C9—C10	115.4 (13)	C15—C16—C17—N1	−19.7 (4)
C8—C9—C10—C11	−55.9 (6)	C11—C16—C17—N1	159.7 (2)
C7—C8—C9'—C10'	−146.4 (4)	C15—C16—C17—C8	160.9 (3)
C17—C8—C9'—C10'	46.2 (6)	C11—C16—C17—C8	−19.7 (4)
C9—C8—C9'—C10'	−56.5 (11)	C17—N1—C18—N2	178.3 (2)
C8—C9'—C10'—C11	−52.0 (6)	C17—N1—C18—C19	−1.8 (3)
C9'—C10'—C11—C12	−143.3 (4)	C8—C7—C19—C18	0.2 (4)
C9'—C10'—C11—C16	24.9 (6)	C1—C7—C19—C18	−179.9 (2)
C9'—C10'—C11—C10	113.0 (11)	C8—C7—C19—C20	179.7 (2)
C9—C10—C11—C12	−142.0 (4)	C1—C7—C19—C20	−0.4 (3)
C9—C10—C11—C16	51.9 (5)	N2—C18—C19—C7	−178.5 (2)
C9—C10—C11—C10'	−52.2 (9)	N1—C18—C19—C7	1.6 (3)
C16—C11—C12—C13	0.2 (5)	N2—C18—C19—C20	2.0 (4)
C10'—C11—C12—C13	168.4 (4)	N1—C18—C19—C20	−177.9 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1···N3i	0.88 (1)	2.37 (2)	3.175 (2)	152 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1⋯N3i	0.88 (1)	2.37 (2)	3.175 (2)	152 (3)

Symmetry code: (i) .