A second monoclinic polymorph for 3-amino-1-(4-meth­oxy­phen­yl)-9,10-dihydro­phenanthrene-2,4-dicarbonitrile

Asiri, A.M.; Faidallah, H.M.; Alamry, K.A.; Ng, S.W.; Tiekink, E.R.T.

doi:10.1107/S1600536812011798

organic compounds

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ISSN: 2056-9890

Volume 68| Part 4| April 2012| Pages o1157-o1158

doi:10.1107/S1600536812011798

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A second monoclinic polymorph for 3-amino-1-(4-methoxyphenyl)-9,10-dihydrophenanthrene-2,4-dicarbonitrile

Abdullah M. Asiri,^a,^b ‡ Hassan M. Faidallah,^a Khalid A. Alamry,^a Seik Weng Ng ^c,^a and Edward R. T. Tiekink ^c ^*

^aChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203, Jeddah, Saudi Arabia, ^bThe Center of Excellence for Advanced Materials Research, King Abdulaziz University, Jeddah, PO Box 80203, Saudi Arabia, and ^cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: edward.tiekink@gmail.com

(Received 18 March 2012; accepted 19 March 2012; online 24 March 2012)

The title compound, C₂₃H₁₇N₃O, has been previously described in a monoclinic P2₁/c polymorph with Z = 4 [Asiri, Al-Youbi, Faidallah, Ng & Tiekink (2011). Acta Cryst. E67, o2449]. In the new monoclinic P2₁/n form, with Z = 8, there are two independent molecules, A and B, in the asymmetric unit. In both molecules, the cyclohexa-1,3-diene ring has a screw-boat conformation, whereas it is a distorted half-chair in the original polymorph. There is a fold in each molecule, as indicated by the dihedral angle between the benzene rings of the 1,2-dihydronaphthalene and aniline residues of 33.19 (10)° (molecule A) and 30.6 (10)° (molecule B). The methoxybenzene ring is twisted out of the plane of the aniline residue to which it is connected [dihedral angles = 49.22 (10) and 73.27 (10)°, in A and B respectively]. In the crystal, the two independent molecules self-associate via N—H⋯N hydrogen bonds, generating a 12-membered {⋯HNC₃N}₂ synthon. These are connected into a supramolecular tape in the (-101) plane by N—H⋯O(methoxy) interactions. In the P2₁/c polymorph, supramolecular layers are formed by N—H⋯N and N—H⋯O interactions.

Related literature

For background to the biological activity of related phenanthrene compounds, see: Wang et al. (2010 ); Rostom et al. (2011 ). For related structures, see: Asiri et al. (2011a ,b ); Al-Youbi et al. (2012 ). For ring puckering parameters, see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₂₃H₁₇N₃O
M_r = 351.40
Monoclinic, P 2₁ /n
a = 11.5197 (6) Å
b = 25.1585 (12) Å
c = 11.9564 (6) Å
β = 90.719 (5)°
V = 3464.9 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 100 K
0.35 × 0.35 × 0.10 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ) T_min = 0.971, T_max = 0.992
20450 measured reflections
7990 independent reflections
5348 reflections with I > 2σ(I)
R_int = 0.055

Refinement

R[F² > 2σ(F²)] = 0.060
wR(F²) = 0.156
S = 1.04
7990 reflections
503 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯N6	0.89 (1)	2.25 (2)	3.081 (3)	157 (3)
N5—H3⋯N1	0.88 (1)	2.36 (1)	3.213 (3)	162 (2)
N2—H1⋯O1ⁱ	0.88 (2)	2.56 (2)	3.271 (3)	139 (2)
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812011798/bt5850sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812011798/bt5850Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812011798/bt5850Isup3.cml

checkCIF report

Comment top

In connection with structural studies on phenanthrene compounds (Asiri et al., 2011a; Asiri et al., 2011b; Al-Youbi et al., 2012), of interest owing to biological activity (Wang et al. 2010; Rostom et al., 2011), a new monoclinic polymorph of the title compound 3-amino-1-(4-methoxyphenyl)-9,10-dihydrophenanthrene-2,4-dicarbonitrile (I) was found. Previously (I) was isolated in the monoclinic space group P2₁/c with Z = 4 (Asiri et al., 2011b). The new form crystallizes in the monoclinic space group P2₁/n with two independent molecules in the asymmetric unit, Fig. 1.

The conformations of the two independent molecules in (I) differ in two regions of the molecule. In the N1-containing molecule, the cyclohexa-1,3-diene ring has a screw-boat conformation as defined by the following geometric parameters (Cremer & Pople, 1975): puckering parameters q₂ = 0.527 (2) Å and q₃ = 0.156 (2) Å, and amplitudes: Q = 0.549 (2) Å, θ = 73.5 (2)° and φ₂ = 93.2 (3)°. By contrast, in the N4-containing molecule, the conformation is based on a distorted half-chair with puckering parameters: q₂ = 0.530 (2) Å, q₃ = -0.178 (2) Å, Q = 0.558 (2) Å, θ = 108.5 (2)° and φ₂ = 265.8 (3) °. In the P2₁/c polymorph of (I), the conformation matches more closely a distorted half-chair.

For the first independent molecule, the benzene rings of the 1,2-dihydronaphthalene and methoxybenzene residues form dihedral angles of 33.19 (10) and 49.22 (10)°, respectively, with the amino-benzene ring, indicating non-planarity in the fused ring system and a twist of the methoxybenzene out of the plane of the benzene ring to which it is connected. The comparable angles for the second independent molecule are 30.6 (10) and 73.27 (10)°, respectively. Figure 2 shows an overlay diagram for the three independent molecules of (I) characterized in the two polymorphs.

In the crystal structure of (I) the two independent molecules self-associate via N—H···N hydrogen bonds to generate 12-membered {···HNC₃N}₂ synthons, Fig. 3 and Table 1. One of the amino-H atoms forms a hydrogen bond to a methoxy-O atom leading to the formation of a supramolecular tape along [1 0 1], Fig. 3 and Table 1. The fourth independent amino-H atom does not participate in a significant intermolecular interaction. In the previously described P2₁/c form of (I), supramolecular arrays with a zigzag topology were formed through N—H···N hydrogen bonds, leading to {···HNC₃N}₂ synthons, as well N—H···O(methoxy) hydrogen bonding.

Related literature top

For background to the biological activity of related phenanthrene compounds, see: Wang et al. (2010); Rostom et al. (2011). For related structures, see: Asiri et al. (2011a,b); Al-Youbi et al. (2012). For ring puckering parameters, see: Cremer & Pople (1975).

Experimental top

A mixture of 4-methoxybenzaldehyde (1.38 g, 0.01 mmol), 1-tetralone (1.46 g, 0.01 mmol), malononitrile (0.66 g, 0.01 mmol) and ammonium acetate (6.2 g, 0.08 mmol) in absolute ethanol (50 ml) was refluxed for 6 h. The reaction mixture was allowed to cool, and the formed precipitate was filtered, washed with water, dried and recrystallized from ethanol. Yield: 69%. M.pt: 533–535 K.

Structure description top

For background to the biological activity of related phenanthrene compounds, see: Wang et al. (2010); Rostom et al. (2011). For related structures, see: Asiri et al. (2011a,b); Al-Youbi et al. (2012). For ring puckering parameters, see: Cremer & Pople (1975).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); 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).

Figures top

	Fig. 1. The molecular structure of (I) showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level.
	Fig. 2. Overlay diagram of the two independent molecules of (I) and the polymorph of (I). The molecules have been aligned so that nitrile-N atom closest to the partially saturated ring, amino-N and the C atom diagonally opposite to the amino-N atom have been superimposed. Colour code: red = N1-molecule of (I), green = N4-molecule (inverted) of (I) and blue = polymorph of (I).
	Fig. 3. A view of the supramolecular tape along [1 0 1] in (I). The N—H···N and N—H···O hydrogen bonds are shown as blue and orange dashed lines, respectively.

3-amino-1-(4-methoxyphenyl)-9,10-dihydrophenanthrene-2,4-dicarbonitrile top

Crystal data top

C₂₃H₁₇N₃O	F(000) = 1472
M_r = 351.40	D_x = 1.347 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4701 reflections
a = 11.5197 (6) Å	θ = 2.4–27.5°
b = 25.1585 (12) Å	µ = 0.09 mm⁻¹
c = 11.9564 (6) Å	T = 100 K
β = 90.719 (5)°	Prism, orange
V = 3464.9 (3) Å³	0.35 × 0.35 × 0.10 mm
Z = 8

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	7990 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	5348 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.055
Detector resolution: 10.4041 pixels mm^-1	θ_max = 27.6°, θ_min = 2.4°
ω scan	h = −14→14
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −24→32
T_min = 0.971, T_max = 0.992	l = −15→12
20450 measured reflections

Refinement top

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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.156	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.057P)² + 0.839P] where P = (F_o² + 2F_c²)/3
7990 reflections	(Δ/σ)_max = 0.001
503 parameters	Δρ_max = 0.33 e Å⁻³
4 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₂₃H₁₇N₃O	V = 3464.9 (3) Å³
M_r = 351.40	Z = 8
Monoclinic, P2₁/n	Mo Kα radiation
a = 11.5197 (6) Å	µ = 0.09 mm⁻¹
b = 25.1585 (12) Å	T = 100 K
c = 11.9564 (6) Å	0.35 × 0.35 × 0.10 mm
β = 90.719 (5)°

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	7990 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	5348 reflections with I > 2σ(I)
T_min = 0.971, T_max = 0.992	R_int = 0.055
20450 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.060	4 restraints
wR(F²) = 0.156	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.33 e Å⁻³
7990 reflections	Δρ_min = −0.25 e Å⁻³
503 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.10070 (14)	0.15244 (6)	0.28185 (14)	0.0303 (4)
O2	0.84581 (15)	0.39154 (6)	1.09183 (14)	0.0328 (4)
N1	0.35813 (17)	0.54827 (8)	0.59073 (16)	0.0301 (5)
N2	0.44427 (18)	0.41933 (8)	0.60868 (17)	0.0286 (4)
N3	0.45795 (18)	0.28657 (8)	0.52814 (17)	0.0341 (5)
N4	0.48229 (19)	0.77085 (8)	0.78737 (19)	0.0377 (5)
N5	0.49102 (17)	0.64209 (8)	0.72209 (16)	0.0268 (4)
N6	0.56385 (16)	0.51011 (7)	0.73917 (15)	0.0249 (4)
C1	0.15965 (18)	0.40545 (8)	0.38717 (18)	0.0220 (5)
C2	0.04533 (18)	0.40182 (9)	0.32242 (19)	0.0242 (5)
H2A	0.0596	0.4063	0.2415	0.029*
H2B	0.0102	0.3664	0.3338	0.029*
C3	−0.03757 (19)	0.44473 (8)	0.36222 (19)	0.0256 (5)
H3A	−0.1106	0.4432	0.3178	0.031*
H3B	−0.0566	0.4386	0.4417	0.031*
C4	0.01701 (19)	0.49843 (9)	0.34957 (18)	0.0235 (5)
C5	−0.0443 (2)	0.54234 (9)	0.31252 (19)	0.0275 (5)
H5	−0.1252	0.5393	0.2974	0.033*
C6	0.0111 (2)	0.59115 (9)	0.29700 (19)	0.0292 (5)
H6	−0.0323	0.6216	0.2748	0.035*
C7	0.1298 (2)	0.59477 (9)	0.31422 (18)	0.0268 (5)
H7	0.1686	0.6273	0.2992	0.032*
C8	0.1925 (2)	0.55150 (9)	0.35315 (18)	0.0249 (5)
H8	0.2738	0.5546	0.3653	0.030*
C9	0.13701 (19)	0.50318 (8)	0.37478 (17)	0.0222 (5)
C10	0.19815 (18)	0.45619 (8)	0.41975 (18)	0.0220 (5)
C11	0.29307 (18)	0.46056 (8)	0.49625 (18)	0.0218 (5)
C12	0.35534 (19)	0.41555 (8)	0.53271 (18)	0.0225 (5)
C13	0.32176 (19)	0.36595 (8)	0.48802 (18)	0.0225 (5)
C14	0.22155 (19)	0.36049 (8)	0.41905 (18)	0.0211 (5)
C15	0.32687 (18)	0.51051 (9)	0.54559 (18)	0.0221 (5)
C16	0.3947 (2)	0.32124 (9)	0.51117 (18)	0.0256 (5)
C17	0.18686 (18)	0.30606 (8)	0.38398 (18)	0.0228 (5)
C18	0.1762 (2)	0.26602 (9)	0.46277 (19)	0.0268 (5)
H18	0.1886	0.2742	0.5396	0.032*
C19	0.1478 (2)	0.21416 (9)	0.4326 (2)	0.0278 (5)
H19	0.1418	0.1872	0.4879	0.033*
C20	0.12838 (18)	0.20240 (9)	0.3206 (2)	0.0248 (5)
C21	0.13611 (18)	0.24202 (9)	0.24038 (19)	0.0248 (5)
H21	0.1213	0.2339	0.1639	0.030*
C22	0.16527 (18)	0.29310 (9)	0.27145 (18)	0.0242 (5)
H22	0.1708	0.3199	0.2159	0.029*
C23	0.1006 (2)	0.11064 (9)	0.3630 (2)	0.0355 (6)
H23A	0.0808	0.0770	0.3263	0.053*
H23B	0.0430	0.1185	0.4204	0.053*
H23C	0.1777	0.1078	0.3980	0.053*
C24	0.69808 (19)	0.63961 (8)	1.01349 (18)	0.0218 (5)
C25	0.7659 (2)	0.64074 (9)	1.12243 (18)	0.0259 (5)
H25A	0.8455	0.6540	1.1092	0.031*
H25B	0.7717	0.6043	1.1535	0.031*
C26	0.7052 (2)	0.67681 (9)	1.20495 (18)	0.0262 (5)
H26A	0.6265	0.6630	1.2203	0.031*
H26B	0.7496	0.6780	1.2763	0.031*
C27	0.69672 (18)	0.73163 (9)	1.15568 (18)	0.0233 (5)
C28	0.71185 (19)	0.77700 (9)	1.22026 (19)	0.0269 (5)
H28	0.7195	0.7738	1.2992	0.032*
C29	0.71595 (19)	0.82680 (9)	1.1717 (2)	0.0290 (5)
H29	0.7253	0.8575	1.2172	0.035*
C30	0.7064 (2)	0.83184 (9)	1.0572 (2)	0.0279 (5)
H30	0.7140	0.8658	1.0233	0.033*
C31	0.68564 (19)	0.78737 (9)	0.99132 (19)	0.0252 (5)
H31	0.6764	0.7912	0.9127	0.030*
C32	0.67824 (18)	0.73687 (8)	1.03971 (19)	0.0229 (5)
C33	0.65311 (18)	0.68813 (8)	0.97334 (18)	0.0219 (5)
C34	0.58428 (18)	0.68879 (8)	0.87531 (18)	0.0213 (5)
C35	0.56000 (18)	0.64163 (8)	0.81431 (18)	0.0210 (5)
C36	0.61077 (18)	0.59420 (8)	0.85423 (18)	0.0213 (5)
C37	0.67812 (19)	0.59281 (8)	0.95346 (18)	0.0215 (5)
C38	0.5298 (2)	0.73604 (9)	0.8308 (2)	0.0275 (5)
C39	0.58701 (18)	0.54667 (9)	0.79306 (18)	0.0215 (5)
C40	0.72664 (19)	0.54034 (8)	0.99069 (17)	0.0209 (5)
C41	0.6805 (2)	0.51357 (9)	1.08273 (19)	0.0266 (5)
H41	0.6193	0.5293	1.1237	0.032*
C42	0.7230 (2)	0.46448 (9)	1.11451 (19)	0.0282 (5)
H42	0.6908	0.4467	1.1769	0.034*
C43	0.81266 (19)	0.44099 (9)	1.05564 (18)	0.0244 (5)
C44	0.8609 (2)	0.46710 (9)	0.96590 (19)	0.0253 (5)
H44	0.9237	0.4517	0.9266	0.030*
C45	0.81622 (19)	0.51622 (8)	0.93386 (18)	0.0240 (5)
H45	0.8482	0.5337	0.8710	0.029*
C46	0.9325 (2)	0.36427 (10)	1.0298 (2)	0.0368 (6)
H46A	0.9475	0.3295	1.0640	0.055*
H46B	1.0041	0.3852	1.0303	0.055*
H46C	0.9052	0.3593	0.9525	0.055*
H1	0.4837 (17)	0.3901 (6)	0.6221 (18)	0.020 (6)*
H2	0.466 (2)	0.4511 (6)	0.633 (2)	0.044 (8)*
H3	0.469 (2)	0.6121 (6)	0.690 (2)	0.037 (7)*
H4	0.460 (2)	0.6715 (6)	0.695 (2)	0.034 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0352 (9)	0.0210 (8)	0.0348 (9)	−0.0020 (7)	−0.0035 (8)	−0.0052 (7)
O2	0.0406 (10)	0.0253 (9)	0.0326 (9)	0.0105 (7)	0.0036 (8)	0.0064 (7)
N1	0.0324 (11)	0.0285 (11)	0.0292 (11)	0.0001 (9)	−0.0087 (9)	−0.0013 (9)
N2	0.0327 (11)	0.0217 (11)	0.0312 (11)	−0.0024 (9)	−0.0098 (9)	−0.0009 (9)
N3	0.0395 (12)	0.0264 (11)	0.0360 (12)	0.0011 (10)	−0.0081 (10)	0.0000 (9)
N4	0.0426 (12)	0.0272 (11)	0.0431 (13)	0.0031 (10)	−0.0126 (11)	0.0005 (10)
N5	0.0344 (11)	0.0204 (11)	0.0254 (10)	0.0015 (9)	−0.0075 (9)	0.0019 (9)
N6	0.0275 (10)	0.0229 (10)	0.0240 (10)	0.0010 (8)	−0.0055 (8)	0.0010 (8)
C1	0.0230 (11)	0.0243 (11)	0.0187 (10)	−0.0033 (9)	0.0022 (9)	−0.0005 (9)
C2	0.0256 (11)	0.0244 (11)	0.0226 (11)	−0.0036 (9)	−0.0024 (10)	−0.0009 (9)
C3	0.0243 (11)	0.0280 (12)	0.0246 (11)	−0.0025 (9)	−0.0003 (10)	−0.0016 (10)
C4	0.0249 (11)	0.0267 (12)	0.0190 (11)	0.0006 (9)	0.0006 (9)	−0.0039 (9)
C5	0.0280 (12)	0.0300 (13)	0.0245 (12)	−0.0007 (10)	−0.0009 (10)	−0.0031 (10)
C6	0.0370 (13)	0.0264 (12)	0.0243 (12)	0.0070 (10)	−0.0035 (11)	−0.0011 (10)
C7	0.0352 (13)	0.0240 (12)	0.0213 (11)	−0.0032 (10)	−0.0014 (10)	−0.0053 (9)
C8	0.0301 (12)	0.0242 (12)	0.0204 (11)	−0.0010 (9)	−0.0024 (10)	−0.0037 (9)
C9	0.0270 (11)	0.0222 (11)	0.0174 (10)	0.0000 (9)	0.0013 (9)	−0.0037 (9)
C10	0.0220 (11)	0.0244 (11)	0.0199 (11)	−0.0014 (9)	0.0044 (9)	−0.0006 (9)
C11	0.0222 (11)	0.0205 (11)	0.0228 (11)	−0.0030 (9)	0.0025 (9)	−0.0018 (9)
C12	0.0233 (11)	0.0238 (11)	0.0205 (11)	−0.0027 (9)	0.0033 (9)	0.0002 (9)
C13	0.0269 (11)	0.0213 (11)	0.0194 (11)	−0.0003 (9)	0.0017 (9)	0.0018 (9)
C14	0.0255 (11)	0.0200 (11)	0.0180 (10)	−0.0019 (9)	0.0035 (9)	−0.0004 (9)
C15	0.0218 (11)	0.0222 (11)	0.0221 (11)	0.0009 (9)	−0.0009 (9)	−0.0005 (9)
C16	0.0327 (12)	0.0219 (12)	0.0220 (11)	−0.0069 (10)	−0.0011 (10)	−0.0020 (9)
C17	0.0223 (11)	0.0224 (11)	0.0238 (11)	−0.0005 (9)	0.0010 (10)	−0.0008 (9)
C18	0.0326 (12)	0.0253 (12)	0.0225 (11)	−0.0028 (10)	−0.0016 (10)	−0.0028 (10)
C19	0.0330 (12)	0.0224 (12)	0.0279 (12)	−0.0025 (10)	0.0010 (11)	0.0024 (10)
C20	0.0212 (11)	0.0221 (11)	0.0311 (12)	−0.0010 (9)	0.0008 (10)	−0.0064 (10)
C21	0.0227 (11)	0.0276 (12)	0.0239 (11)	−0.0003 (9)	−0.0008 (10)	−0.0044 (10)
C22	0.0241 (11)	0.0273 (12)	0.0212 (11)	0.0005 (9)	0.0033 (10)	0.0007 (9)
C23	0.0446 (15)	0.0202 (12)	0.0415 (15)	−0.0017 (11)	−0.0057 (13)	−0.0033 (11)
C24	0.0239 (11)	0.0224 (11)	0.0191 (11)	−0.0022 (9)	0.0000 (9)	0.0012 (9)
C25	0.0321 (12)	0.0221 (11)	0.0232 (12)	−0.0008 (9)	−0.0065 (10)	−0.0004 (9)
C26	0.0326 (12)	0.0269 (12)	0.0190 (11)	−0.0045 (10)	−0.0032 (10)	0.0012 (9)
C27	0.0222 (11)	0.0253 (12)	0.0223 (11)	−0.0014 (9)	0.0005 (10)	−0.0021 (9)
C28	0.0280 (12)	0.0277 (12)	0.0250 (12)	0.0024 (10)	−0.0025 (10)	−0.0041 (10)
C29	0.0259 (12)	0.0286 (12)	0.0323 (13)	0.0041 (10)	−0.0031 (11)	−0.0106 (10)
C30	0.0296 (12)	0.0191 (11)	0.0349 (13)	0.0007 (9)	−0.0021 (11)	−0.0006 (10)
C31	0.0272 (11)	0.0239 (12)	0.0246 (12)	0.0012 (9)	−0.0014 (10)	−0.0003 (10)
C32	0.0210 (11)	0.0214 (11)	0.0266 (12)	−0.0008 (9)	0.0033 (10)	−0.0022 (9)
C33	0.0227 (11)	0.0238 (11)	0.0195 (11)	−0.0012 (9)	0.0031 (9)	0.0002 (9)
C34	0.0242 (11)	0.0191 (11)	0.0206 (11)	−0.0007 (9)	0.0009 (9)	0.0009 (9)
C35	0.0222 (11)	0.0222 (11)	0.0187 (11)	−0.0015 (9)	0.0016 (9)	−0.0004 (9)
C36	0.0250 (11)	0.0187 (11)	0.0201 (11)	−0.0016 (9)	0.0016 (9)	−0.0011 (9)
C37	0.0263 (11)	0.0199 (11)	0.0183 (10)	−0.0016 (9)	0.0019 (9)	0.0028 (9)
C38	0.0295 (12)	0.0256 (12)	0.0274 (12)	0.0002 (10)	−0.0029 (10)	−0.0034 (10)
C39	0.0212 (11)	0.0242 (11)	0.0193 (10)	0.0030 (9)	0.0003 (9)	0.0037 (9)
C40	0.0256 (11)	0.0199 (11)	0.0170 (10)	−0.0032 (9)	−0.0042 (9)	−0.0005 (9)
C41	0.0278 (12)	0.0273 (12)	0.0248 (11)	0.0025 (10)	0.0029 (10)	0.0012 (10)
C42	0.0332 (13)	0.0277 (12)	0.0240 (12)	−0.0001 (10)	0.0045 (11)	0.0057 (10)
C43	0.0285 (12)	0.0224 (11)	0.0223 (11)	0.0008 (9)	−0.0043 (10)	0.0018 (9)
C44	0.0263 (11)	0.0261 (12)	0.0236 (11)	0.0002 (9)	0.0022 (10)	−0.0038 (10)
C45	0.0301 (12)	0.0226 (11)	0.0191 (11)	−0.0052 (9)	0.0007 (10)	0.0010 (9)
C46	0.0420 (14)	0.0291 (13)	0.0392 (15)	0.0112 (11)	0.0017 (13)	0.0003 (11)

Geometric parameters (Å, º) top

O1—C20	1.376 (3)	C20—C21	1.387 (3)
O1—C23	1.431 (3)	C21—C22	1.378 (3)
O2—C43	1.370 (3)	C21—H21	0.9500
O2—C46	1.427 (3)	C22—H22	0.9500
N1—C15	1.148 (3)	C23—H23A	0.9800
N2—C12	1.364 (3)	C23—H23B	0.9800
N2—H1	0.879 (9)	C23—H23C	0.9800
N2—H2	0.887 (10)	C24—C37	1.396 (3)
N3—C16	1.153 (3)	C24—C33	1.408 (3)
N4—C38	1.153 (3)	C24—C25	1.511 (3)
N5—C35	1.351 (3)	C25—C26	1.518 (3)
N5—H3	0.884 (10)	C25—H25A	0.9900
N5—H4	0.881 (10)	C25—H25B	0.9900
N6—C39	1.152 (3)	C26—C27	1.503 (3)
C1—C14	1.388 (3)	C26—H26A	0.9900
C1—C10	1.405 (3)	C26—H26B	0.9900
C1—C2	1.522 (3)	C27—C28	1.388 (3)
C2—C3	1.521 (3)	C27—C32	1.406 (3)
C2—H2A	0.9900	C28—C29	1.382 (3)
C2—H2B	0.9900	C28—H28	0.9500
C3—C4	1.499 (3)	C29—C30	1.378 (3)
C3—H3A	0.9900	C29—H29	0.9500
C3—H3B	0.9900	C30—C31	1.387 (3)
C4—C5	1.381 (3)	C30—H30	0.9500
C4—C9	1.416 (3)	C31—C32	1.399 (3)
C5—C6	1.398 (3)	C31—H31	0.9500
C5—H5	0.9500	C32—C33	1.487 (3)
C6—C7	1.383 (3)	C33—C34	1.407 (3)
C6—H6	0.9500	C34—C35	1.419 (3)
C7—C8	1.384 (3)	C34—C38	1.443 (3)
C7—H7	0.9500	C35—C36	1.410 (3)
C8—C9	1.399 (3)	C36—C37	1.410 (3)
C8—H8	0.9500	C36—C39	1.426 (3)
C9—C10	1.474 (3)	C37—C40	1.499 (3)
C10—C11	1.421 (3)	C40—C45	1.383 (3)
C11—C12	1.407 (3)	C40—C41	1.401 (3)
C11—C15	1.440 (3)	C41—C42	1.380 (3)
C12—C13	1.410 (3)	C41—H41	0.9500
C13—C14	1.417 (3)	C42—C43	1.389 (3)
C13—C16	1.429 (3)	C42—H42	0.9500
C14—C17	1.486 (3)	C43—C44	1.381 (3)
C17—C18	1.386 (3)	C44—C45	1.391 (3)
C17—C22	1.404 (3)	C44—H44	0.9500
C18—C19	1.391 (3)	C45—H45	0.9500
C18—H18	0.9500	C46—H46A	0.9800
C19—C20	1.387 (3)	C46—H46B	0.9800
C19—H19	0.9500	C46—H46C	0.9800

C20—O1—C23	116.44 (18)	H23A—C23—H23B	109.5
C43—O2—C46	117.81 (17)	O1—C23—H23C	109.5
C12—N2—H1	116.5 (15)	H23A—C23—H23C	109.5
C12—N2—H2	119.4 (18)	H23B—C23—H23C	109.5
H1—N2—H2	123 (2)	C37—C24—C33	119.9 (2)
C35—N5—H3	121.0 (18)	C37—C24—C25	122.62 (19)
C35—N5—H4	122.4 (17)	C33—C24—C25	117.50 (19)
H3—N5—H4	116 (2)	C24—C25—C26	109.51 (19)
C14—C1—C10	120.3 (2)	C24—C25—H25A	109.8
C14—C1—C2	121.95 (19)	C26—C25—H25A	109.8
C10—C1—C2	117.62 (19)	C24—C25—H25B	109.8
C3—C2—C1	109.93 (18)	C26—C25—H25B	109.8
C3—C2—H2A	109.7	H25A—C25—H25B	108.2
C1—C2—H2A	109.7	C27—C26—C25	108.80 (17)
C3—C2—H2B	109.7	C27—C26—H26A	109.9
C1—C2—H2B	109.7	C25—C26—H26A	109.9
H2A—C2—H2B	108.2	C27—C26—H26B	109.9
C4—C3—C2	110.02 (18)	C25—C26—H26B	109.9
C4—C3—H3A	109.7	H26A—C26—H26B	108.3
C2—C3—H3A	109.7	C28—C27—C32	119.2 (2)
C4—C3—H3B	109.7	C28—C27—C26	122.0 (2)
C2—C3—H3B	109.7	C32—C27—C26	118.74 (19)
H3A—C3—H3B	108.2	C29—C28—C27	121.1 (2)
C5—C4—C9	119.7 (2)	C29—C28—H28	119.5
C5—C4—C3	122.7 (2)	C27—C28—H28	119.5
C9—C4—C3	117.7 (2)	C30—C29—C28	119.9 (2)
C4—C5—C6	120.8 (2)	C30—C29—H29	120.1
C4—C5—H5	119.6	C28—C29—H29	120.1
C6—C5—H5	119.6	C29—C30—C31	120.1 (2)
C7—C6—C5	119.4 (2)	C29—C30—H30	120.0
C7—C6—H6	120.3	C31—C30—H30	120.0
C5—C6—H6	120.3	C30—C31—C32	120.6 (2)
C6—C7—C8	120.6 (2)	C30—C31—H31	119.7
C6—C7—H7	119.7	C32—C31—H31	119.7
C8—C7—H7	119.7	C31—C32—C27	118.9 (2)
C7—C8—C9	120.5 (2)	C31—C32—C33	122.7 (2)
C7—C8—H8	119.7	C27—C32—C33	118.35 (19)
C9—C8—H8	119.7	C24—C33—C34	119.70 (19)
C8—C9—C4	118.7 (2)	C24—C33—C32	117.69 (19)
C8—C9—C10	123.2 (2)	C34—C33—C32	122.59 (19)
C4—C9—C10	118.07 (19)	C33—C34—C35	121.59 (19)
C1—C10—C11	119.1 (2)	C33—C34—C38	123.69 (19)
C1—C10—C9	118.7 (2)	C35—C34—C38	114.69 (19)
C11—C10—C9	122.21 (19)	N5—C35—C36	121.38 (19)
C12—C11—C10	121.5 (2)	N5—C35—C34	121.51 (19)
C12—C11—C15	116.2 (2)	C36—C35—C34	117.11 (19)
C10—C11—C15	122.23 (19)	C35—C36—C37	121.83 (19)
N2—C12—C13	121.0 (2)	C35—C36—C39	117.39 (19)
N2—C12—C11	121.7 (2)	C37—C36—C39	120.71 (19)
C13—C12—C11	117.3 (2)	C24—C37—C36	119.81 (19)
C12—C13—C14	121.6 (2)	C24—C37—C40	122.10 (19)
C12—C13—C16	117.7 (2)	C36—C37—C40	118.09 (18)
C14—C13—C16	120.6 (2)	N4—C38—C34	173.6 (2)
C1—C14—C13	119.5 (2)	N6—C39—C36	175.8 (2)
C1—C14—C17	122.6 (2)	C45—C40—C41	117.9 (2)
C13—C14—C17	117.90 (19)	C45—C40—C37	121.21 (18)
N1—C15—C11	175.0 (2)	C41—C40—C37	120.86 (19)
N3—C16—C13	176.7 (2)	C42—C41—C40	120.6 (2)
C18—C17—C22	117.8 (2)	C42—C41—H41	119.7
C18—C17—C14	120.3 (2)	C40—C41—H41	119.7
C22—C17—C14	121.90 (19)	C41—C42—C43	120.3 (2)
C17—C18—C19	121.9 (2)	C41—C42—H42	119.8
C17—C18—H18	119.1	C43—C42—H42	119.8
C19—C18—H18	119.1	O2—C43—C44	124.35 (19)
C20—C19—C18	119.0 (2)	O2—C43—C42	115.62 (19)
C20—C19—H19	120.5	C44—C43—C42	120.0 (2)
C18—C19—H19	120.5	C43—C44—C45	119.1 (2)
O1—C20—C19	123.6 (2)	C43—C44—H44	120.5
O1—C20—C21	116.1 (2)	C45—C44—H44	120.5
C19—C20—C21	120.2 (2)	C40—C45—C44	122.0 (2)
C22—C21—C20	120.1 (2)	C40—C45—H45	119.0
C22—C21—H21	119.9	C44—C45—H45	119.0
C20—C21—H21	119.9	O2—C46—H46A	109.5
C21—C22—C17	121.0 (2)	O2—C46—H46B	109.5
C21—C22—H22	119.5	H46A—C46—H46B	109.5
C17—C22—H22	119.5	O2—C46—H46C	109.5
O1—C23—H23A	109.5	H46A—C46—H46C	109.5
O1—C23—H23B	109.5	H46B—C46—H46C	109.5

C14—C1—C2—C3	142.7 (2)	C37—C24—C25—C26	−137.3 (2)
C10—C1—C2—C3	−33.8 (3)	C33—C24—C25—C26	42.0 (3)
C1—C2—C3—C4	57.0 (2)	C24—C25—C26—C27	−59.1 (2)
C2—C3—C4—C5	139.7 (2)	C25—C26—C27—C28	−141.3 (2)
C2—C3—C4—C9	−38.9 (3)	C25—C26—C27—C32	35.7 (3)
C9—C4—C5—C6	1.5 (3)	C32—C27—C28—C29	−3.9 (3)
C3—C4—C5—C6	−177.0 (2)	C26—C27—C28—C29	173.1 (2)
C4—C5—C6—C7	2.9 (3)	C27—C28—C29—C30	−0.8 (3)
C5—C6—C7—C8	−4.0 (3)	C28—C29—C30—C31	3.9 (3)
C6—C7—C8—C9	0.6 (3)	C29—C30—C31—C32	−2.2 (3)
C7—C8—C9—C4	3.9 (3)	C30—C31—C32—C27	−2.5 (3)
C7—C8—C9—C10	−177.96 (19)	C30—C31—C32—C33	178.4 (2)
C5—C4—C9—C8	−4.9 (3)	C28—C27—C32—C31	5.5 (3)
C3—C4—C9—C8	173.76 (19)	C26—C27—C32—C31	−171.6 (2)
C5—C4—C9—C10	176.82 (19)	C28—C27—C32—C33	−175.32 (19)
C3—C4—C9—C10	−4.5 (3)	C26—C27—C32—C33	7.6 (3)
C14—C1—C10—C11	−7.3 (3)	C37—C24—C33—C34	2.6 (3)
C2—C1—C10—C11	169.22 (19)	C25—C24—C33—C34	−176.74 (18)
C14—C1—C10—C9	173.81 (19)	C37—C24—C33—C32	−179.21 (18)
C2—C1—C10—C9	−9.7 (3)	C25—C24—C33—C32	1.5 (3)
C8—C9—C10—C1	−147.5 (2)	C31—C32—C33—C24	151.2 (2)
C4—C9—C10—C1	30.7 (3)	C27—C32—C33—C24	−27.9 (3)
C8—C9—C10—C11	33.7 (3)	C31—C32—C33—C34	−30.6 (3)
C4—C9—C10—C11	−148.1 (2)	C27—C32—C33—C34	150.2 (2)
C1—C10—C11—C12	5.4 (3)	C24—C33—C34—C35	−0.9 (3)
C9—C10—C11—C12	−175.76 (19)	C32—C33—C34—C35	−179.01 (19)
C1—C10—C11—C15	−171.03 (18)	C24—C33—C34—C38	176.9 (2)
C9—C10—C11—C15	7.8 (3)	C32—C33—C34—C38	−1.2 (3)
C10—C11—C12—N2	−178.0 (2)	C33—C34—C35—N5	177.97 (19)
C15—C11—C12—N2	−1.4 (3)	C38—C34—C35—N5	0.0 (3)
C10—C11—C12—C13	1.6 (3)	C33—C34—C35—C36	−1.9 (3)
C15—C11—C12—C13	178.25 (18)	C38—C34—C35—C36	−179.84 (19)
N2—C12—C13—C14	172.7 (2)	N5—C35—C36—C37	−176.77 (19)
C11—C12—C13—C14	−6.9 (3)	C34—C35—C36—C37	3.1 (3)
N2—C12—C13—C16	−9.5 (3)	N5—C35—C36—C39	0.3 (3)
C11—C12—C13—C16	170.85 (19)	C34—C35—C36—C39	−179.80 (18)
C10—C1—C14—C13	2.2 (3)	C33—C24—C37—C36	−1.4 (3)
C2—C1—C14—C13	−174.18 (19)	C25—C24—C37—C36	177.87 (19)
C10—C1—C14—C17	−178.03 (18)	C33—C24—C37—C40	178.31 (18)
C2—C1—C14—C17	5.6 (3)	C25—C24—C37—C40	−2.4 (3)
C12—C13—C14—C1	5.1 (3)	C35—C36—C37—C24	−1.5 (3)
C16—C13—C14—C1	−172.57 (19)	C39—C36—C37—C24	−178.50 (19)
C12—C13—C14—C17	−174.65 (18)	C35—C36—C37—C40	178.76 (18)
C16—C13—C14—C17	7.6 (3)	C39—C36—C37—C40	1.7 (3)
C1—C14—C17—C18	−129.0 (2)	C24—C37—C40—C45	−108.3 (2)
C13—C14—C17—C18	50.8 (3)	C36—C37—C40—C45	71.4 (3)
C1—C14—C17—C22	51.8 (3)	C24—C37—C40—C41	73.3 (3)
C13—C14—C17—C22	−128.4 (2)	C36—C37—C40—C41	−107.0 (2)
C22—C17—C18—C19	1.5 (3)	C45—C40—C41—C42	−0.5 (3)
C14—C17—C18—C19	−177.7 (2)	C37—C40—C41—C42	177.9 (2)
C17—C18—C19—C20	−0.7 (3)	C40—C41—C42—C43	0.2 (4)
C23—O1—C20—C19	−4.4 (3)	C46—O2—C43—C44	−2.8 (3)
C23—O1—C20—C21	175.8 (2)	C46—O2—C43—C42	176.1 (2)
C18—C19—C20—O1	179.52 (19)	C41—C42—C43—O2	−177.9 (2)
C18—C19—C20—C21	−0.7 (3)	C41—C42—C43—C44	1.0 (4)
O1—C20—C21—C22	−178.95 (18)	O2—C43—C44—C45	177.0 (2)
C19—C20—C21—C22	1.2 (3)	C42—C43—C44—C45	−1.8 (3)
C20—C21—C22—C17	−0.4 (3)	C41—C40—C45—C44	−0.3 (3)
C18—C17—C22—C21	−1.0 (3)	C37—C40—C45—C44	−178.8 (2)
C14—C17—C22—C21	178.30 (19)	C43—C44—C45—C40	1.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N6	0.89 (1)	2.25 (2)	3.081 (3)	157 (3)
N5—H3···N1	0.88 (1)	2.36 (1)	3.213 (3)	162 (2)
N2—H1···O1ⁱ	0.88 (2)	2.56 (2)	3.271 (3)	139 (2)

Symmetry code: (i) x+1/2, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₂₃H₁₇N₃O
M_r	351.40
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	11.5197 (6), 25.1585 (12), 11.9564 (6)
β (°)	90.719 (5)
V (Å³)	3464.9 (3)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.35 × 0.35 × 0.10

Data collection
Diffractometer	Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2011)
T_min, T_max	0.971, 0.992
No. of measured, independent and observed [I > 2σ(I)] reflections	20450, 7990, 5348
R_int	0.055

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.060, 0.156, 1.04
No. of reflections	7990
No. of parameters	503
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.25

Computer programs: CrysAlis PRO (Agilent, 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N6	0.89 (1)	2.25 (2)	3.081 (3)	157 (3)
N5—H3···N1	0.88 (1)	2.36 (1)	3.213 (3)	162 (2)
N2—H1···O1ⁱ	0.878 (17)	2.56 (2)	3.271 (3)	138.9 (17)

Symmetry code: (i) x+1/2, −y+1/2, z+1/2.

Footnotes

‡Additional correspondence author, e-mail: aasiri2@kau.edu.sa.

Acknowledgements

The authors are thankful to the Center of Excellence for Advanced Materials Research and the Chemistry Department at King Abdulaziz University for providing the research facilities. We also thank the Ministry of Higher Education (Malaysia) for funding structural studies through the High-Impact Research scheme (UM.C/HIR/MOHE/SC/12).

References

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Volume 68| Part 4| April 2012| Pages o1157-o1158

doi:10.1107/S1600536812011798

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

A second monoclinic polymorph for 3-amino-1-(4-meth­­oxy­phen­yl)-9,10-di­hydro­phenanthrene-2,4-dicarbo­nitrile

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Footnotes

Acknowledgements

References

organic compounds

A second monoclinic polymorph for 3-amino-1-(4-methoxyphenyl)-9,10-dihydrophenanthrene-2,4-dicarbonitrile