1,3-Diphenyl-3,4-dihydro-benzo[b][1,6]naphthyridine.

The title compound, C(24)H(18)N(2), is the first structural example containing the 3,4-dihydro-benzo[b][1,6]naphthyridine fragment. It was synthesized from 2,4,6,8-tetra-phenyl-3,7-diaza-bicyclo-[3.3.1]nonan-9-one and was crystallized from a methanol-ethanol solution over two years as a racemate. The C=N double bond [1.2868 (15) Å] is bent significantly out of the plane of the aromatic bicyclic ring system [N-C-C-C = -157.63 (12)°] and out of the plane of the phenyl ring bonded at the 1-position [N-C-C-C = 41.15 (16)°].

Related literature

For the synthesis of 1,3-diphenyl-1,2,3,4-tetra­hydro­benzo[b][1,6]naphthyridine, see: Sivakumar (2000 ▶). For the synthesis of 2,4,6,8-tetra­phenyl-3,7-diaza­bicyclo­[3.3.1]nonan-9-one, see Ravindran et al. (1991 ▶). For the crystal structures of other naphthyridine derivatives, see: Sivakumar et al. (2003 ▶); Laavanya et al. (2001 ▶).

Experimental

Crystal data

C24H18N2

M = 334.40

Monoclinic,

a = 10.2658 (4) Å

b = 10.8583 (5) Å

c = 16.1842 (7) Å

β = 107.909 (2)°

V = 1716.63 (13) Å3

Z = 4

Mo Kα radiation

μ = 0.08 mm−1

T = 100 K

0.32 × 0.28 × 0.16 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T min = 0.885, T max = 0.988

20360 measured reflections

3365 independent reflections

3060 reflections with I > 2σ(I)

R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.094

S = 1.02

3365 reflections

241 parameters

Only H-atom displacement parameters refined

Δρmax = 0.40 e Å−3

Δρmin = −0.28 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: modified ORTEP (Johnson, 1965 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810013619/bt5246sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810013619/bt5246Isup2.hkl

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

C24H18N2	F(000) = 704
Mr = 334.40	Dx = 1.294 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9913 reflections
a = 10.2658 (4) Å	θ = 2.7–26.0°
b = 10.8583 (5) Å	µ = 0.08 mm−1
c = 16.1842 (7) Å	T = 100 K
β = 107.909 (2)°	Block, yellow
V = 1716.63 (13) Å3	0.32 × 0.28 × 0.16 mm
Z = 4

Bruker APEXII CCD diffractometer	3365 independent reflections
Radiation source: sealed tube	3060 reflections with I > 2σ(I)
graphite	Rint = 0.029
φ and ω scans	θmax = 26.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −12→12
Tmin = 0.885, Tmax = 0.988	k = −13→13
20360 measured reflections	l = −19→19

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.094	Only H-atom displacement parameters refined
S = 1.02	w = 1/[σ2(Fo2) + (0.0446P)2 + 0.7644P] where P = (Fo2 + 2Fc2)/3
3365 reflections	(Δ/σ)max < 0.001
241 parameters	Δρmax = 0.40 e Å−3
0 restraints	Δρmin = −0.28 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > σ(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.The non-hydrogen atoms were refined with anisotropic displacement parameters without any constraints. The H atom of the tertiary C—H group was refined with an individual isotropic displacement parameter and all X—C—H angles equal at a C—H distance of 1.00 Å (AFIX 13 of SHELXL-97). The H atoms of the CH2 group were refined with common isotropic displacement parameters and idealized geometry with approximately tetrahedral angles and C—H distances of 0.99 Å (AFIX 23 of SHELXL-97). The H atoms of the phenyl rings as well as the atoma H6, H7, H8, and H9 were put at the external bisector of the C—C—C angle at a C—H distance of 0.95 Å and common isotropic displacement parameters were refined for the H atoms of the same ring (AFIX 43 of SHELXL-97). The H atom H10 was put at the external bisector of the C—C—C angle at a C—H distance of 0.95 Å but the individual isotropic displacement parameter was free to refine (AFIX 43 of SHELXL-97).

	x	y	z	Uiso*/Ueq
C1	0.60895 (12)	0.61918 (11)	0.71264 (8)	0.0221 (3)
N2	0.67352 (10)	0.72215 (9)	0.71977 (6)	0.0183 (2)
C3	0.61969 (11)	0.81335 (10)	0.64987 (7)	0.0162 (2)
H3	0.5364	0.8516	0.6588	0.016 (3)*
C4	0.57620 (11)	0.75231 (10)	0.55983 (7)	0.0167 (2)
H41	0.5341	0.8145	0.5148	0.022 (2)*
H42	0.6576	0.7180	0.5474	0.022 (2)*
C41	0.47489 (11)	0.65074 (10)	0.55714 (7)	0.0154 (2)
N5	0.37687 (9)	0.62770 (8)	0.48450 (6)	0.0160 (2)
C51	0.28123 (11)	0.53968 (10)	0.48615 (7)	0.0160 (2)
C6	0.17392 (11)	0.51425 (11)	0.40906 (7)	0.0186 (2)
H6	0.1692	0.5578	0.3573	0.0233 (17)*
C7	0.07669 (12)	0.42730 (11)	0.40843 (8)	0.0216 (3)
H7	0.0054	0.4109	0.3561	0.0233 (17)*
C8	0.08147 (12)	0.36181 (11)	0.48477 (8)	0.0220 (3)
H8	0.0143	0.3010	0.4833	0.0233 (17)*
C9	0.18252 (12)	0.38568 (11)	0.56076 (8)	0.0195 (2)
H9	0.1839	0.3429	0.6122	0.0233 (17)*
C91	0.28508 (11)	0.47405 (10)	0.56299 (7)	0.0168 (2)
C10	0.39474 (12)	0.49926 (10)	0.63871 (7)	0.0180 (2)
H10	0.4019	0.4564	0.6911	0.022 (3)*
C101	0.49068 (11)	0.58561 (10)	0.63637 (7)	0.0173 (2)
C11	0.66051 (11)	0.52633 (10)	0.78325 (7)	0.0173 (2)
C12	0.67192 (11)	0.40231 (11)	0.76360 (7)	0.0182 (2)
H12	0.6417	0.3754	0.7049	0.0262 (16)*
C13	0.72750 (11)	0.31812 (11)	0.82995 (8)	0.0217 (3)
H13	0.7371	0.2341	0.8164	0.0262 (16)*
C14	0.76892 (12)	0.35674 (12)	0.91590 (8)	0.0234 (3)
H14	0.8049	0.2988	0.9611	0.0262 (16)*
C15	0.75784 (12)	0.47979 (12)	0.93583 (8)	0.0236 (3)
H15	0.7867	0.5062	0.9946	0.0262 (16)*
C16	0.70445 (12)	0.56423 (11)	0.86972 (8)	0.0208 (3)
H16	0.6978	0.6486	0.8835	0.0262 (16)*
C21	0.72353 (11)	0.91467 (10)	0.65640 (7)	0.0154 (2)
C22	0.68122 (12)	1.03683 (11)	0.64243 (7)	0.0184 (2)
H22	0.5871	1.0563	0.6307	0.0257 (16)*
C23	0.77463 (13)	1.13070 (11)	0.64538 (7)	0.0210 (3)
H23	0.7441	1.2136	0.6357	0.0257 (16)*
C24	0.91240 (12)	1.10332 (11)	0.66241 (7)	0.0218 (3)
H24	0.9766	1.1672	0.6646	0.0257 (16)*
C25	0.95581 (12)	0.98180 (12)	0.67630 (8)	0.0220 (3)
H25	1.0500	0.9626	0.6876	0.0257 (16)*
C26	0.86247 (12)	0.88817 (11)	0.67380 (7)	0.0190 (2)
H26	0.8934	0.8055	0.6840	0.0257 (16)*

	U11	U22	U33	U12	U13	U23
C1	0.0239 (6)	0.0193 (6)	0.0199 (6)	−0.0017 (5)	0.0022 (5)	0.0022 (5)
N2	0.0227 (5)	0.0168 (5)	0.0146 (5)	−0.0015 (4)	0.0046 (4)	0.0017 (4)
C3	0.0175 (5)	0.0155 (5)	0.0157 (5)	0.0009 (4)	0.0051 (4)	0.0005 (4)
C4	0.0197 (5)	0.0160 (5)	0.0139 (5)	−0.0009 (4)	0.0043 (4)	0.0014 (4)
C41	0.0166 (5)	0.0135 (5)	0.0165 (5)	0.0029 (4)	0.0059 (4)	−0.0005 (4)
N5	0.0173 (5)	0.0144 (5)	0.0161 (5)	0.0017 (4)	0.0047 (4)	−0.0008 (4)
C51	0.0170 (5)	0.0133 (5)	0.0182 (5)	0.0029 (4)	0.0061 (4)	−0.0016 (4)
C6	0.0196 (6)	0.0181 (6)	0.0176 (6)	0.0033 (4)	0.0050 (4)	−0.0012 (4)
C7	0.0176 (6)	0.0225 (6)	0.0226 (6)	0.0008 (5)	0.0031 (5)	−0.0061 (5)
C8	0.0181 (6)	0.0198 (6)	0.0293 (6)	−0.0038 (4)	0.0091 (5)	−0.0038 (5)
C9	0.0205 (6)	0.0173 (6)	0.0227 (6)	0.0005 (4)	0.0098 (5)	−0.0007 (4)
C91	0.0178 (5)	0.0140 (5)	0.0194 (6)	0.0022 (4)	0.0071 (4)	−0.0017 (4)
C10	0.0218 (6)	0.0159 (5)	0.0169 (5)	0.0014 (4)	0.0067 (5)	0.0015 (4)
C101	0.0191 (6)	0.0150 (5)	0.0169 (6)	0.0014 (4)	0.0043 (4)	0.0003 (4)
C11	0.0151 (5)	0.0186 (6)	0.0177 (5)	−0.0011 (4)	0.0042 (4)	0.0029 (4)
C12	0.0164 (5)	0.0204 (6)	0.0192 (6)	−0.0019 (4)	0.0074 (4)	0.0001 (4)
C13	0.0171 (5)	0.0176 (6)	0.0328 (7)	0.0015 (4)	0.0112 (5)	0.0048 (5)
C14	0.0165 (6)	0.0288 (7)	0.0252 (6)	0.0029 (5)	0.0067 (5)	0.0138 (5)
C15	0.0206 (6)	0.0339 (7)	0.0158 (6)	−0.0013 (5)	0.0046 (5)	0.0035 (5)
C16	0.0204 (6)	0.0211 (6)	0.0197 (6)	−0.0004 (5)	0.0043 (5)	−0.0008 (5)
C21	0.0191 (5)	0.0164 (5)	0.0104 (5)	−0.0003 (4)	0.0040 (4)	−0.0005 (4)
C22	0.0199 (6)	0.0190 (6)	0.0172 (5)	0.0031 (4)	0.0068 (4)	0.0012 (4)
C23	0.0318 (6)	0.0141 (5)	0.0180 (6)	0.0006 (5)	0.0091 (5)	−0.0006 (4)
C24	0.0265 (6)	0.0221 (6)	0.0157 (5)	−0.0096 (5)	0.0051 (5)	−0.0034 (5)
C25	0.0169 (6)	0.0287 (6)	0.0183 (6)	−0.0010 (5)	0.0024 (4)	−0.0013 (5)
C26	0.0207 (6)	0.0168 (6)	0.0177 (5)	0.0031 (4)	0.0033 (4)	0.0004 (4)

C1—N2	1.2868 (15)	C10—C101	1.3688 (16)
C1—C101	1.4862 (16)	C10—H10	0.95
C1—C11	1.4936 (16)	C11—C16	1.3938 (16)
N2—C3	1.4769 (14)	C11—C12	1.3969 (16)
C3—C21	1.5128 (15)	C12—C13	1.3920 (16)
C3—C4	1.5369 (15)	C12—H12	0.95
C3—H3	1.00	C13—C14	1.3884 (18)
C4—C41	1.5073 (15)	C13—H13	0.95
C4—H41	0.99	C14—C15	1.3873 (19)
C4—H42	0.99	C14—H14	0.95
C41—N5	1.3152 (14)	C15—C16	1.3875 (17)
C41—C101	1.4293 (15)	C15—H15	0.95
N5—C51	1.3764 (14)	C16—H16	0.95
C51—C6	1.4146 (16)	C21—C22	1.3925 (16)
C51—C91	1.4233 (16)	C21—C26	1.3962 (16)
C6—C7	1.3717 (17)	C22—C23	1.3901 (17)
C6—H6	0.95	C22—H22	0.95
C7—C8	1.4132 (17)	C23—C24	1.3874 (17)
C7—H7	0.95	C23—H23	0.95
C8—C9	1.3679 (17)	C24—C25	1.3887 (18)
C8—H8	0.95	C24—H24	0.95
C9—C91	1.4168 (16)	C25—C26	1.3891 (17)
C9—H9	0.95	C25—H25	0.95
C91—C10	1.4126 (16)	C26—H26	0.95
N2—C1—C101	123.67 (11)	C91—C10—H10	120.1
N2—C1—C11	117.79 (10)	C10—C101—C41	118.67 (10)
C101—C1—C11	118.47 (10)	C10—C101—C1	123.78 (10)
C1—N2—C3	116.92 (9)	C41—C101—C1	117.52 (10)
N2—C3—C21	110.15 (9)	C16—C11—C12	119.29 (10)
N2—C3—C4	111.61 (9)	C16—C11—C1	119.87 (11)
C21—C3—C4	111.89 (9)	C12—C11—C1	120.75 (10)
N2—C3—H3	107.7	C13—C12—C11	120.04 (11)
C21—C3—H3	107.7	C13—C12—H12	120.0
C4—C3—H3	107.7	C11—C12—H12	120.0
C41—C4—C3	109.85 (9)	C14—C13—C12	120.07 (11)
C41—C4—H41	109.7	C14—C13—H13	120.0
C3—C4—H41	109.7	C12—C13—H13	120.0
C41—C4—H42	109.7	C15—C14—C13	120.13 (11)
C3—C4—H42	109.7	C15—C14—H14	119.9
H41—C4—H42	108.2	C13—C14—H14	119.9
N5—C41—C101	123.53 (10)	C14—C15—C16	119.89 (11)
N5—C41—C4	119.76 (10)	C14—C15—H15	120.1
C101—C41—C4	116.69 (9)	C16—C15—H15	120.1
C41—N5—C51	117.96 (9)	C15—C16—C11	120.55 (11)
N5—C51—C6	119.02 (10)	C15—C16—H16	119.7
N5—C51—C91	122.44 (10)	C11—C16—H16	119.7
C6—C51—C91	118.54 (10)	C22—C21—C26	118.52 (10)
C7—C6—C51	120.56 (11)	C22—C21—C3	120.23 (10)
C7—C6—H6	119.7	C26—C21—C3	121.23 (10)
C51—C6—H6	119.7	C23—C22—C21	121.02 (11)
C6—C7—C8	120.68 (11)	C23—C22—H22	119.5
C6—C7—H7	119.7	C21—C22—H22	119.5
C8—C7—H7	119.7	C24—C23—C22	120.00 (11)
C9—C8—C7	120.24 (11)	C24—C23—H23	120.0
C9—C8—H8	119.9	C22—C23—H23	120.0
C7—C8—H8	119.9	C23—C24—C25	119.51 (11)
C8—C9—C91	120.22 (11)	C23—C24—H24	120.2
C8—C9—H9	119.9	C25—C24—H24	120.2
C91—C9—H9	119.9	C24—C25—C26	120.43 (11)
C10—C91—C9	122.76 (11)	C24—C25—H25	119.8
C10—C91—C51	117.49 (10)	C26—C25—H25	119.8
C9—C91—C51	119.74 (10)	C25—C26—C21	120.52 (11)
C101—C10—C91	119.80 (10)	C25—C26—H26	119.7
C101—C10—H10	120.1	C21—C26—H26	119.7
C101—C1—N2—C3	3.86 (17)	C4—C41—C101—C1	−3.06 (15)
C11—C1—N2—C3	−179.16 (10)	N2—C1—C101—C10	−157.63 (12)
C1—N2—C3—C21	−166.72 (10)	C11—C1—C101—C10	25.41 (17)
C1—N2—C3—C4	−41.79 (14)	N2—C1—C101—C41	20.27 (17)
N2—C3—C4—C41	55.03 (12)	C11—C1—C101—C41	−156.69 (10)
C21—C3—C4—C41	178.98 (9)	N2—C1—C11—C16	41.15 (16)
C3—C4—C41—N5	146.44 (10)	C101—C1—C11—C16	−141.71 (11)
C3—C4—C41—C101	−32.39 (13)	N2—C1—C11—C12	−135.55 (12)
C101—C41—N5—C51	2.88 (16)	C101—C1—C11—C12	41.59 (16)
C4—C41—N5—C51	−175.87 (9)	C16—C11—C12—C13	−0.41 (16)
C41—N5—C51—C6	179.30 (10)	C1—C11—C12—C13	176.31 (10)
C41—N5—C51—C91	0.11 (15)	C11—C12—C13—C14	1.41 (17)
N5—C51—C6—C7	−179.86 (10)	C12—C13—C14—C15	−1.41 (17)
C91—C51—C6—C7	−0.64 (16)	C13—C14—C15—C16	0.39 (18)
C51—C6—C7—C8	0.24 (17)	C14—C15—C16—C11	0.61 (18)
C6—C7—C8—C9	0.89 (18)	C12—C11—C16—C15	−0.60 (17)
C7—C8—C9—C91	−1.58 (17)	C1—C11—C16—C15	−177.35 (11)
C8—C9—C91—C10	−177.57 (11)	N2—C3—C21—C22	−139.22 (10)
C8—C9—C91—C51	1.16 (17)	C4—C3—C21—C22	96.01 (12)
N5—C51—C91—C10	−2.06 (16)	N2—C3—C21—C26	42.74 (13)
C6—C51—C91—C10	178.75 (10)	C4—C3—C21—C26	−82.02 (12)
N5—C51—C91—C9	179.14 (10)	C26—C21—C22—C23	0.20 (16)
C6—C51—C91—C9	−0.05 (16)	C3—C21—C22—C23	−177.89 (10)
C9—C91—C10—C101	179.82 (10)	C21—C22—C23—C24	0.03 (17)
C51—C91—C10—C101	1.06 (16)	C22—C23—C24—C25	0.09 (17)
C91—C10—C101—C41	1.65 (16)	C23—C24—C25—C26	−0.43 (17)
C91—C10—C101—C1	179.53 (10)	C24—C25—C26—C21	0.66 (17)
N5—C41—C101—C10	−3.83 (17)	C22—C21—C26—C25	−0.54 (16)
C4—C41—C101—C10	174.95 (10)	C3—C21—C26—C25	177.53 (10)
N5—C41—C101—C1	178.16 (10)