2-Amino-4-(3,4-dimeth-oxy-phen-yl)-5,6-dihydro-benzo[h]quinoline-3-carbo-nitrile-3-amino-1-(3,4-dimeth-oxy-phen-yl)-9,10-dihydro-phenanthrene-2,4-dicarbonitrile (1/19).

The asymmetric unit of the 1:19 title co-crystal of 2-amino-4-(3,4-dimeth-oxy-phen-yl)-5,6-dihydro-benzo[h]quinoline-3-carbo-nitrile and 3-amino-1-(3,4-dimeth-oxy-phen-yl)-9,10-dihydro-phenanthrene-2,4-dicarbonitrile, 0.05C(22)H(19)N(3)O(2)·0.95C(24)H(19)N(3)O(2), has the atoms of the fused-ring system and those of the amino, cyano and dimeth-oxy-phenyl substitutents overlapped. The fused-ring system is buckled owing to the ethyl-ene linkage in the central ring with the two flanking aromatic rings being twisted by 31.9 (1)°. The ring of the dimeth-oxy-phenyl substituent is twisted by 72.4 (1)° relative to the amino- and cyano-bearing aromatic ring. In the crystal, mol-ecules are linked by duplex amine N-H⋯O(meth-oxy) hydrogen bonds in a cyclic association [graph-set R(2) (2)(7)], generating a helical chain structure extending along [201].

Related literature

For a similar co-crystal, see: Asiri et al. (2011 ▶). For graph-set analysis, see: Etter et al. (1990 ▶).

Experimental

Crystal data

0.05C22H19N3O2·0.95C24H19N3O2

M = 380.22

Monoclinic,

a = 8.9347 (3) Å

b = 14.4915 (5) Å

c = 14.7818 (6) Å

β = 103.446 (4)°

V = 1861.45 (12) Å3

Z = 4

Mo Kα radiation

μ = 0.09 mm−1

T = 100 K

0.30 × 0.25 × 0.20 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ▶) T min = 0.974, T max = 0.983

9240 measured reflections

4160 independent reflections

3146 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.049

wR(F 2) = 0.124

S = 1.04

4160 reflections

270 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.30 e Å−3

Δρmin = −0.24 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/S1600536811040517/zs2146sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811040517/zs2146Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811040517/zs2146Isup3.cml

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

0.05C22H19N3O2·0.95C24H19N3O2	F(000) = 797.6
Mr = 380.22	Dx = 1.357 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3220 reflections
a = 8.9347 (3) Å	θ = 2.3–29.2°
b = 14.4915 (5) Å	µ = 0.09 mm−1
c = 14.7818 (6) Å	T = 100 K
β = 103.446 (4)°	Block, orange
V = 1861.45 (12) Å3	0.30 × 0.25 × 0.20 mm
Z = 4

Agilent SuperNova Dual diffractometer with an Atlas detector	4160 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	3146 reflections with I > 2σ(I)
Mirror	Rint = 0.031
Detector resolution: 10.4041 pixels mm-1	θmax = 27.5°, θmin = 2.3°
ω scans	h = −11→8
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −18→17
Tmin = 0.974, Tmax = 0.983	l = −19→17
9240 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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.124	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0502P)2 + 0.6446P] where P = (Fo2 + 2Fc2)/3
4160 reflections	(Δ/σ)max = 0.001
270 parameters	Δρmax = 0.30 e Å−3
0 restraints	Δρmin = −0.24 e Å−3

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.30588 (13)	0.63995 (9)	0.10804 (8)	0.0271 (3)
O2	0.07648 (12)	0.69798 (8)	0.17421 (8)	0.0220 (3)
N1	0.94620 (18)	0.95400 (11)	0.33260 (11)	0.0197 (3)	0.05
C1'	0.94620 (18)	0.95400 (11)	0.33260 (11)	0.0197 (3)	0.95
N2	1.21403 (18)	1.02734 (11)	0.39566 (11)	0.0279 (4)	0.95
N3	1.00292 (18)	0.87635 (11)	0.48043 (11)	0.0271 (4)
H1	1.104 (3)	0.9012 (16)	0.4948 (16)	0.053 (7)*
H2	0.973 (2)	0.8423 (15)	0.5258 (15)	0.035 (6)*
N4	0.68515 (17)	0.74165 (11)	0.49326 (11)	0.0294 (4)
C1	0.84721 (19)	0.97189 (11)	0.24628 (11)	0.0209 (4)
C2	0.8945 (2)	1.02681 (12)	0.17292 (12)	0.0253 (4)
C3	1.0457 (2)	1.02878 (13)	0.16227 (13)	0.0315 (4)
H3	1.1232	0.9947	0.2038	0.038*
C4	1.0837 (3)	1.07998 (14)	0.09164 (14)	0.0374 (5)
H4	1.1867	1.0808	0.0847	0.045*
C5	0.9711 (3)	1.12980 (14)	0.03145 (14)	0.0425 (5)
H5	0.9976	1.1660	−0.0161	0.051*
C6	0.8200 (3)	1.12739 (13)	0.03999 (13)	0.0382 (5)
H6	0.7435	1.1618	−0.0019	0.046*
C7	0.7794 (2)	1.07502 (12)	0.10951 (12)	0.0295 (4)
C8	0.6159 (2)	1.06430 (13)	0.11720 (13)	0.0326 (4)
H8A	0.5449	1.0839	0.0585	0.039*
H8B	0.5970	1.1035	0.1682	0.039*
C9	0.5876 (2)	0.96303 (13)	0.13680 (12)	0.0292 (4)
H9A	0.4801	0.9547	0.1424	0.035*
H9B	0.6036	0.9242	0.0848	0.035*
C10	0.69749 (19)	0.93394 (12)	0.22619 (12)	0.0231 (4)
C11	0.65552 (18)	0.87253 (11)	0.28827 (11)	0.0213 (4)
C12	0.75689 (18)	0.85343 (11)	0.37374 (11)	0.0193 (3)
C13	0.90408 (18)	0.89474 (11)	0.39830 (11)	0.0196 (3)
C14	1.0941 (2)	0.99715 (12)	0.36327 (12)	0.0225 (4)	0.95
C15	0.71436 (18)	0.79079 (12)	0.43878 (12)	0.0224 (4)
C16	0.50312 (18)	0.82492 (12)	0.26343 (11)	0.0215 (4)
C17	0.47860 (19)	0.75520 (12)	0.19617 (12)	0.0224 (4)
H17	0.5599	0.7375	0.1683	0.027*
C18	0.33741 (18)	0.71173 (11)	0.16982 (11)	0.0203 (4)
C19	0.21512 (18)	0.74044 (11)	0.20790 (11)	0.0193 (3)
C20	0.2414 (2)	0.80721 (12)	0.27631 (12)	0.0249 (4)
H20	0.1605	0.8251	0.3044	0.030*
C21	0.3855 (2)	0.84870 (13)	0.30454 (12)	0.0262 (4)
H21	0.4026	0.8937	0.3526	0.031*
C22	0.4368 (2)	0.59651 (14)	0.08517 (15)	0.0368 (5)
H22A	0.4020	0.5462	0.0409	0.055*
H22B	0.5043	0.5716	0.1418	0.055*
H22C	0.4934	0.6420	0.0571	0.055*
C23	−0.05031 (19)	0.73108 (12)	0.20937 (13)	0.0260 (4)
H23A	−0.1430	0.6957	0.1814	0.039*
H23B	−0.0678	0.7965	0.1937	0.039*
H23C	−0.0268	0.7236	0.2771	0.039*

	U11	U22	U33	U12	U13	U23
O1	0.0180 (6)	0.0316 (7)	0.0312 (7)	0.0003 (5)	0.0050 (5)	−0.0126 (6)
O2	0.0152 (6)	0.0253 (6)	0.0258 (6)	−0.0021 (5)	0.0051 (5)	−0.0061 (5)
N1	0.0175 (8)	0.0197 (8)	0.0218 (8)	−0.0008 (7)	0.0042 (7)	−0.0027 (7)
C1'	0.0175 (8)	0.0197 (8)	0.0218 (8)	−0.0008 (7)	0.0042 (7)	−0.0027 (7)
N2	0.0214 (8)	0.0270 (8)	0.0354 (9)	−0.0022 (7)	0.0065 (7)	0.0011 (7)
N3	0.0209 (8)	0.0325 (9)	0.0240 (8)	−0.0045 (7)	−0.0028 (6)	0.0063 (7)
N4	0.0257 (8)	0.0309 (8)	0.0315 (8)	−0.0031 (7)	0.0065 (7)	0.0030 (7)
C1	0.0233 (8)	0.0196 (8)	0.0192 (8)	0.0004 (7)	0.0036 (7)	−0.0026 (7)
C2	0.0347 (10)	0.0209 (8)	0.0199 (8)	−0.0056 (8)	0.0056 (8)	−0.0035 (7)
C3	0.0391 (11)	0.0267 (10)	0.0308 (10)	−0.0063 (8)	0.0126 (9)	−0.0034 (8)
C4	0.0523 (13)	0.0317 (10)	0.0342 (11)	−0.0115 (10)	0.0219 (10)	−0.0042 (9)
C5	0.0717 (16)	0.0323 (11)	0.0272 (10)	−0.0162 (11)	0.0190 (11)	−0.0001 (9)
C6	0.0593 (14)	0.0284 (10)	0.0228 (9)	−0.0058 (10)	0.0013 (9)	0.0015 (8)
C7	0.0434 (11)	0.0237 (9)	0.0191 (9)	−0.0057 (8)	0.0026 (8)	−0.0020 (7)
C8	0.0400 (11)	0.0293 (10)	0.0217 (9)	0.0011 (9)	−0.0065 (8)	0.0023 (8)
C9	0.0298 (10)	0.0303 (10)	0.0225 (9)	−0.0031 (8)	−0.0041 (8)	0.0001 (8)
C10	0.0217 (8)	0.0244 (9)	0.0205 (8)	−0.0004 (7)	−0.0006 (7)	−0.0016 (7)
C11	0.0175 (8)	0.0229 (8)	0.0231 (8)	0.0010 (7)	0.0037 (7)	−0.0042 (7)
C12	0.0174 (8)	0.0204 (8)	0.0205 (8)	−0.0001 (7)	0.0051 (7)	−0.0015 (7)
C13	0.0180 (8)	0.0185 (8)	0.0216 (8)	0.0019 (7)	0.0031 (7)	−0.0025 (7)
C14	0.0246 (9)	0.0218 (9)	0.0218 (9)	0.0016 (8)	0.0068 (8)	0.0016 (7)
C15	0.0161 (8)	0.0247 (9)	0.0243 (9)	−0.0003 (7)	0.0007 (7)	−0.0036 (7)
C16	0.0159 (8)	0.0251 (8)	0.0210 (8)	0.0015 (7)	−0.0006 (7)	0.0023 (7)
C17	0.0164 (8)	0.0281 (9)	0.0225 (8)	0.0019 (7)	0.0041 (7)	−0.0008 (7)
C18	0.0198 (8)	0.0219 (8)	0.0184 (8)	0.0010 (7)	0.0026 (7)	−0.0027 (7)
C19	0.0151 (8)	0.0210 (8)	0.0203 (8)	−0.0001 (6)	0.0013 (7)	0.0029 (7)
C20	0.0195 (8)	0.0294 (9)	0.0266 (9)	−0.0019 (7)	0.0072 (7)	−0.0068 (7)
C21	0.0230 (9)	0.0300 (10)	0.0247 (9)	−0.0023 (8)	0.0035 (7)	−0.0072 (8)
C22	0.0242 (10)	0.0402 (12)	0.0475 (12)	0.0015 (9)	0.0115 (9)	−0.0201 (10)
C23	0.0168 (8)	0.0287 (9)	0.0334 (10)	−0.0011 (7)	0.0079 (7)	−0.0061 (8)

O1—C18	1.370 (2)	C8—H8A	0.9900
O1—C22	1.436 (2)	C8—H8B	0.9900
O2—C19	1.3690 (19)	C9—C10	1.512 (2)
O2—C23	1.434 (2)	C9—H9A	0.9900
N1—C1	1.397 (2)	C9—H9B	0.9900
N1—C13	1.411 (2)	C10—C11	1.391 (2)
N2—C14	1.153 (2)	C11—C12	1.400 (2)
N3—C13	1.351 (2)	C11—C16	1.494 (2)
N3—H1	0.95 (2)	C12—C13	1.413 (2)
N3—H2	0.92 (2)	C12—C15	1.436 (2)
N4—C15	1.150 (2)	C16—C21	1.374 (2)
C1—C10	1.413 (2)	C16—C17	1.399 (2)
C1—C2	1.484 (2)	C17—C18	1.383 (2)
C2—C3	1.396 (3)	C17—H17	0.9500
C2—C7	1.405 (3)	C18—C19	1.403 (2)
C3—C4	1.386 (3)	C19—C20	1.380 (2)
C3—H3	0.9500	C20—C21	1.394 (2)
C4—C5	1.381 (3)	C20—H20	0.9500
C4—H4	0.9500	C21—H21	0.9500
C5—C6	1.386 (3)	C22—H22A	0.9800
C5—H5	0.9500	C22—H22B	0.9800
C6—C7	1.392 (3)	C22—H22C	0.9800
C6—H6	0.9500	C23—H23A	0.9800
C7—C8	1.499 (3)	C23—H23B	0.9800
C8—C9	1.528 (3)	C23—H23C	0.9800
C18—O1—C22	115.94 (13)	C1—C10—C9	117.78 (15)
C19—O2—C23	116.23 (13)	C10—C11—C12	120.31 (15)
C1—N1—C13	121.85 (15)	C10—C11—C16	120.23 (15)
C13—N3—H1	121.0 (15)	C12—C11—C16	119.45 (15)
C13—N3—H2	121.2 (13)	C11—C12—C13	121.05 (15)
H1—N3—H2	117.7 (19)	C11—C12—C15	120.84 (14)
N1—C1—C10	119.15 (15)	C13—C12—C15	118.10 (14)
N1—C1—C2	122.66 (15)	N3—C13—N1	121.00 (15)
C10—C1—C2	118.16 (15)	N3—C13—C12	121.45 (16)
C3—C2—C7	119.44 (17)	N1—C13—C12	117.52 (14)
C3—C2—C1	122.73 (17)	N4—C15—C12	177.44 (18)
C7—C2—C1	117.76 (16)	C21—C16—C17	119.08 (15)
C4—C3—C2	120.60 (19)	C21—C16—C11	121.48 (15)
C4—C3—H3	119.7	C17—C16—C11	119.44 (15)
C2—C3—H3	119.7	C18—C17—C16	120.75 (15)
C5—C4—C3	119.7 (2)	C18—C17—H17	119.6
C5—C4—H4	120.1	C16—C17—H17	119.6
C3—C4—H4	120.1	O1—C18—C17	124.52 (15)
C4—C5—C6	120.47 (19)	O1—C18—C19	115.72 (14)
C4—C5—H5	119.8	C17—C18—C19	119.76 (15)
C6—C5—H5	119.8	O2—C19—C20	124.56 (15)
C5—C6—C7	120.5 (2)	O2—C19—C18	116.35 (14)
C5—C6—H6	119.7	C20—C19—C18	119.08 (15)
C7—C6—H6	119.7	C19—C20—C21	120.66 (16)
C6—C7—C2	119.19 (19)	C19—C20—H20	119.7
C6—C7—C8	122.56 (18)	C21—C20—H20	119.7
C2—C7—C8	118.19 (16)	C16—C21—C20	120.48 (16)
C7—C8—C9	108.73 (16)	C16—C21—H21	119.8
C7—C8—H8A	109.9	C20—C21—H21	119.8
C9—C8—H8A	109.9	O1—C22—H22A	109.5
C7—C8—H8B	109.9	O1—C22—H22B	109.5
C9—C8—H8B	109.9	H22A—C22—H22B	109.5
H8A—C8—H8B	108.3	O1—C22—H22C	109.5
C10—C9—C8	109.33 (14)	H22A—C22—H22C	109.5
C10—C9—H9A	109.8	H22B—C22—H22C	109.5
C8—C9—H9A	109.8	O2—C23—H23A	109.5
C10—C9—H9B	109.8	O2—C23—H23B	109.5
C8—C9—H9B	109.8	H23A—C23—H23B	109.5
H9A—C9—H9B	108.3	O2—C23—H23C	109.5
C11—C10—C1	119.86 (15)	H23A—C23—H23C	109.5
C11—C10—C9	122.36 (15)	H23B—C23—H23C	109.5

D—H···A	D—H	H···A	D···A	D—H···A
N3—H1···O1i	0.95 (2)	2.24 (2)	2.927 (2)	129 (2)
N3—H2···O2i	0.92 (2)	2.25 (2)	2.987 (2)	136 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H1⋯O1i	0.95 (2)	2.24 (2)	2.927 (2)	129 (2)
N3—H2⋯O2i	0.92 (2)	2.25 (2)	2.987 (2)	136 (2)

Symmetry code: (i) .