7-(2-Chloro-phen-yl)-2,6,9-trimethyl-dibenzo[b,h][1,6]naphthyridine.

In the title compound, C(25)H(19)ClN(2), the dibenzo[b,h][1,6]naphthyridine system is planar to within 0.16 (2) Å, and the chloro-phenyl ring is inclined to it by 82.53 (7)°. In the crystal, mol-ecules are linked by C-H⋯N hydrogen bonds, forming chains propagating in [100]. There are also a number of weak π-π stacking inter-actions present [centroid-centroid distances = 3.8531 (1) and 3.7631 (1) Å].

Related literature

For the biological properties of [1,6]naphthyridine derivatives, see: Zhuang et al. (2003 ▶); Bedard et al. (2003 ▶); Hinschberger et al. (2003 ▶); Naik et al. (2006 ▶). For the synthesis of the precursor of the title compound, see: Nandha Kumar et al. (2007 ▶). For the crystal structures of other naphthrydine derivatives, see: Sivakumar et al. (2003 ▶); Fun et al. (2009 ▶); Vennila et al. (2010 ▶). For standard bond lengths, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C25H19ClN2

M = 382.87

Triclinic,

a = 6.5575 (4) Å

b = 10.6538 (7) Å

c = 14.3522 (9) Å

α = 93.755 (3)°

β = 103.099 (3)°

γ = 102.074 (3)°

V = 948.25 (10) Å3

Z = 2

Mo Kα radiation

μ = 0.21 mm−1

T = 293 K

0.27 × 0.25 × 0.23 mm

Data collection

Bruker SMART APEXII area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.944, T max = 0.952

17317 measured reflections

4771 independent reflections

3514 reflections with I > 2σ(I)

R int = 0.025

Refinement

R[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 0.143

S = 1.00

4771 reflections

255 parameters

H-atom parameters constrained

Δρmax = 0.32 e Å−3

Δρmin = −0.51 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810030576/su2198sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810030576/su2198Isup2.hkl

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

C25H19ClN2	Z = 2
Mr = 382.87	F(000) = 400
Triclinic, P1	Dx = 1.341 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.5575 (4) Å	Cell parameters from 4797 reflections
b = 10.6538 (7) Å	θ = 1.5–28.5°
c = 14.3522 (9) Å	µ = 0.21 mm−1
α = 93.755 (3)°	T = 293 K
β = 103.099 (3)°	Block, yellow
γ = 102.074 (3)°	0.27 × 0.25 × 0.23 mm
V = 948.25 (10) Å3

Bruker SMART APEXII area-detector diffractometer	4771 independent reflections
Radiation source: fine-focus sealed tube	3514 reflections with I > 2σ(I)
graphite	Rint = 0.025
ω and φ scans	θmax = 28.5°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −8→8
Tmin = 0.944, Tmax = 0.952	k = −14→14
17317 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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.143	H-atom parameters constrained
S = 1.00	w = 1/[σ2(Fo2) + (0.0694P)2 + 0.2763P] where P = (Fo2 + 2Fc2)/3
4771 reflections	(Δ/σ)max = 0.001
255 parameters	Δρmax = 0.32 e Å−3
0 restraints	Δρmin = −0.51 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 > 2sigma(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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cl1	0.22259 (9)	0.49217 (5)	0.41457 (4)	0.0809 (2)
C9	0.1060 (2)	0.63949 (13)	0.20011 (10)	0.0345 (3)
C14	−0.0361 (2)	0.61889 (13)	0.25997 (11)	0.0354 (3)
N11	0.1756 (2)	0.87266 (11)	0.24184 (9)	0.0396 (3)
C10	0.2149 (2)	0.77063 (13)	0.19709 (10)	0.0353 (3)
C13	−0.0816 (2)	0.72702 (14)	0.30668 (11)	0.0371 (3)
C6	0.3810 (2)	0.79371 (14)	0.14465 (10)	0.0367 (3)
C1	0.4188 (2)	0.68758 (14)	0.09475 (11)	0.0382 (3)
C12	0.0265 (2)	0.85236 (14)	0.29330 (11)	0.0379 (3)
N7	0.2977 (2)	0.56271 (12)	0.09035 (9)	0.0405 (3)
C5	0.5087 (3)	0.91727 (15)	0.14455 (12)	0.0427 (3)
H5	0.4829	0.9885	0.1770	0.051*
C21	−0.1424 (2)	0.48827 (13)	0.28004 (11)	0.0383 (3)
C15	−0.2299 (3)	0.71701 (15)	0.36619 (12)	0.0426 (3)
H15	−0.2983	0.6356	0.3770	0.051*
C2	0.5826 (3)	0.70513 (17)	0.04574 (13)	0.0478 (4)
H2	0.6075	0.6347	0.0119	0.057*
C18	−0.0219 (3)	0.96186 (15)	0.33756 (12)	0.0459 (4)
H18	0.0465	1.0444	0.3289	0.055*
C8	0.1537 (2)	0.53873 (14)	0.13957 (11)	0.0376 (3)
C16	−0.2740 (3)	0.82394 (16)	0.40769 (12)	0.0435 (4)
C4	0.6710 (3)	0.93469 (16)	0.09730 (12)	0.0463 (4)
C26	−0.0401 (3)	0.42446 (15)	0.35054 (12)	0.0450 (4)
C17	−0.1666 (3)	0.94743 (16)	0.39226 (12)	0.0471 (4)
H17	−0.1960	1.0206	0.4204	0.057*
C22	−0.3525 (3)	0.42820 (16)	0.23021 (15)	0.0529 (4)
H22	−0.4273	0.4693	0.1833	0.063*
C3	0.7064 (3)	0.82702 (17)	0.04798 (13)	0.0512 (4)
H3	0.8162	0.8381	0.0160	0.061*
C23	−0.4512 (3)	0.30820 (18)	0.24972 (17)	0.0622 (5)
H23	−0.5900	0.2684	0.2146	0.075*
C19	0.0335 (3)	0.39954 (15)	0.12548 (14)	0.0502 (4)
H19A	0.0790	0.3520	0.0779	0.075*
H19B	−0.1181	0.3942	0.1043	0.075*
H19C	0.0630	0.3635	0.1853	0.075*
C25	−0.1401 (3)	0.30526 (16)	0.37131 (14)	0.0563 (5)
H25	−0.0683	0.2646	0.4195	0.068*
C24	−0.3463 (3)	0.24775 (17)	0.32009 (15)	0.0583 (5)
H24	−0.4144	0.1676	0.3334	0.070*
C20	0.8124 (3)	1.06674 (18)	0.10020 (15)	0.0613 (5)
H20A	0.9161	1.0606	0.0635	0.092*	0.50
H20B	0.8857	1.0999	0.1658	0.092*	0.50
H20C	0.7254	1.1239	0.0732	0.092*	0.50
H20D	0.7687	1.1290	0.1382	0.092*	0.50
H20E	0.7992	1.0897	0.0359	0.092*	0.50
H20F	0.9594	1.0657	0.1284	0.092*	0.50
C27	−0.4337 (3)	0.81378 (19)	0.46916 (15)	0.0603 (5)
H27A	−0.5716	0.8179	0.4303	0.090*
H27B	−0.3858	0.8839	0.5203	0.090*
H27C	−0.4454	0.7331	0.4960	0.090*

	U11	U22	U33	U12	U13	U23
Cl1	0.0751 (4)	0.0620 (3)	0.0805 (4)	−0.0032 (2)	−0.0189 (3)	0.0237 (3)
C9	0.0369 (7)	0.0290 (6)	0.0383 (7)	0.0081 (5)	0.0095 (6)	0.0067 (5)
C14	0.0374 (7)	0.0284 (7)	0.0415 (8)	0.0080 (5)	0.0105 (6)	0.0080 (6)
N11	0.0477 (7)	0.0294 (6)	0.0430 (7)	0.0072 (5)	0.0149 (6)	0.0055 (5)
C10	0.0388 (7)	0.0309 (7)	0.0359 (7)	0.0069 (6)	0.0089 (6)	0.0071 (5)
C13	0.0415 (8)	0.0318 (7)	0.0391 (8)	0.0092 (6)	0.0111 (6)	0.0063 (6)
C6	0.0393 (7)	0.0333 (7)	0.0366 (7)	0.0048 (6)	0.0098 (6)	0.0074 (6)
C1	0.0400 (8)	0.0353 (7)	0.0388 (8)	0.0057 (6)	0.0110 (6)	0.0062 (6)
C12	0.0451 (8)	0.0318 (7)	0.0372 (7)	0.0093 (6)	0.0103 (6)	0.0051 (6)
N7	0.0450 (7)	0.0326 (6)	0.0461 (7)	0.0072 (5)	0.0171 (6)	0.0044 (5)
C5	0.0490 (9)	0.0339 (7)	0.0428 (8)	0.0014 (6)	0.0137 (7)	0.0050 (6)
C21	0.0423 (8)	0.0293 (7)	0.0478 (8)	0.0088 (6)	0.0194 (6)	0.0061 (6)
C15	0.0464 (8)	0.0366 (8)	0.0481 (9)	0.0089 (6)	0.0180 (7)	0.0078 (6)
C2	0.0514 (9)	0.0449 (9)	0.0506 (9)	0.0080 (7)	0.0230 (7)	0.0033 (7)
C18	0.0616 (10)	0.0308 (7)	0.0475 (9)	0.0104 (7)	0.0181 (8)	0.0046 (6)
C8	0.0411 (8)	0.0308 (7)	0.0416 (8)	0.0083 (6)	0.0114 (6)	0.0057 (6)
C16	0.0455 (8)	0.0433 (8)	0.0435 (8)	0.0122 (7)	0.0131 (7)	0.0031 (7)
C4	0.0469 (9)	0.0426 (8)	0.0446 (9)	−0.0026 (7)	0.0128 (7)	0.0081 (7)
C26	0.0552 (9)	0.0343 (7)	0.0445 (9)	0.0064 (7)	0.0134 (7)	0.0069 (6)
C17	0.0599 (10)	0.0380 (8)	0.0470 (9)	0.0170 (7)	0.0165 (8)	0.0001 (7)
C22	0.0446 (9)	0.0416 (9)	0.0728 (12)	0.0090 (7)	0.0142 (8)	0.0142 (8)
C3	0.0487 (9)	0.0539 (10)	0.0520 (10)	0.0013 (7)	0.0239 (8)	0.0071 (8)
C23	0.0433 (9)	0.0473 (10)	0.0937 (15)	−0.0002 (8)	0.0221 (10)	0.0087 (10)
C19	0.0589 (10)	0.0321 (7)	0.0617 (11)	0.0036 (7)	0.0268 (8)	−0.0009 (7)
C25	0.0803 (13)	0.0368 (8)	0.0536 (10)	0.0088 (8)	0.0216 (9)	0.0145 (7)
C24	0.0701 (12)	0.0359 (8)	0.0749 (13)	0.0029 (8)	0.0367 (10)	0.0121 (8)
C20	0.0643 (12)	0.0476 (10)	0.0667 (12)	−0.0099 (8)	0.0265 (10)	0.0076 (9)
C27	0.0630 (11)	0.0554 (11)	0.0694 (12)	0.0128 (9)	0.0334 (10)	−0.0011 (9)

Cl1—C26	1.7342 (18)	C8—C19	1.504 (2)
C9—C14	1.399 (2)	C16—C17	1.413 (2)
C9—C10	1.4381 (19)	C16—C27	1.507 (2)
C9—C8	1.465 (2)	C4—C3	1.397 (2)
C14—C13	1.414 (2)	C4—C20	1.507 (2)
C14—C21	1.4978 (19)	C26—C25	1.386 (2)
N11—C10	1.3272 (18)	C17—H17	0.9300
N11—C12	1.3449 (19)	C22—C23	1.384 (2)
C10—C6	1.448 (2)	C22—H22	0.9300
C13—C12	1.422 (2)	C3—H3	0.9300
C13—C15	1.425 (2)	C23—C24	1.365 (3)
C6—C1	1.395 (2)	C23—H23	0.9300
C6—C5	1.405 (2)	C19—H19A	0.9600
C1—N7	1.3888 (19)	C19—H19B	0.9600
C1—C2	1.399 (2)	C19—H19C	0.9600
C12—C18	1.419 (2)	C25—C24	1.374 (3)
N7—C8	1.2966 (19)	C25—H25	0.9300
C5—C4	1.374 (2)	C24—H24	0.9300
C5—H5	0.9300	C20—H20A	0.9600
C21—C26	1.382 (2)	C20—H20B	0.9600
C21—C22	1.394 (2)	C20—H20C	0.9600
C15—C16	1.365 (2)	C20—H20D	0.9600
C15—H15	0.9300	C20—H20E	0.9600
C2—C3	1.374 (2)	C20—H20F	0.9600
C2—H2	0.9300	C27—H27A	0.9600
C18—C17	1.353 (2)	C27—H27B	0.9600
C18—H18	0.9300	C27—H27C	0.9600
C14—C9—C10	117.59 (12)	C18—C17—H17	119.2
C14—C9—C8	125.62 (13)	C16—C17—H17	119.2
C10—C9—C8	116.79 (13)	C23—C22—C21	120.83 (17)
C9—C14—C13	118.93 (13)	C23—C22—H22	119.6
C9—C14—C21	124.24 (12)	C21—C22—H22	119.6
C13—C14—C21	116.82 (13)	C2—C3—C4	121.42 (15)
C10—N11—C12	118.23 (12)	C2—C3—H3	119.3
N11—C10—C9	123.65 (13)	C4—C3—H3	119.3
N11—C10—C6	117.60 (13)	C24—C23—C22	120.50 (18)
C9—C10—C6	118.73 (12)	C24—C23—H23	119.8
C14—C13—C12	118.07 (13)	C22—C23—H23	119.8
C14—C13—C15	123.54 (13)	C8—C19—H19A	109.5
C12—C13—C15	118.39 (13)	C8—C19—H19B	109.5
C1—C6—C5	119.07 (14)	H19A—C19—H19B	109.5
C1—C6—C10	118.10 (13)	C8—C19—H19C	109.5
C5—C6—C10	122.80 (14)	H19A—C19—H19C	109.5
N7—C1—C6	122.51 (13)	H19B—C19—H19C	109.5
N7—C1—C2	117.55 (13)	C24—C25—C26	119.42 (17)
C6—C1—C2	119.94 (14)	C24—C25—H25	120.3
N11—C12—C18	118.06 (13)	C26—C25—H25	120.3
N11—C12—C13	123.19 (13)	C23—C24—C25	120.02 (16)
C18—C12—C13	118.73 (14)	C23—C24—H24	120.0
C8—N7—C1	120.50 (13)	C25—C24—H24	120.0
C4—C5—C6	121.15 (15)	C4—C20—H20A	109.5
C4—C5—H5	119.4	C4—C20—H20B	109.5
C6—C5—H5	119.4	H20A—C20—H20B	109.5
C26—C21—C22	117.31 (14)	C4—C20—H20C	109.5
C26—C21—C14	121.67 (14)	H20A—C20—H20C	109.5
C22—C21—C14	120.98 (14)	H20B—C20—H20C	109.5
C16—C15—C13	121.68 (15)	C4—C20—H20D	109.5
C16—C15—H15	119.2	H20A—C20—H20D	141.1
C13—C15—H15	119.2	H20B—C20—H20D	56.3
C3—C2—C1	119.59 (15)	H20C—C20—H20D	56.3
C3—C2—H2	120.2	C4—C20—H20E	109.5
C1—C2—H2	120.2	H20A—C20—H20E	56.3
C17—C18—C12	120.70 (15)	H20B—C20—H20E	141.1
C17—C18—H18	119.6	H20C—C20—H20E	56.3
C12—C18—H18	119.6	H20D—C20—H20E	109.5
N7—C8—C9	122.88 (13)	C4—C20—H20F	109.5
N7—C8—C19	114.02 (13)	H20A—C20—H20F	56.3
C9—C8—C19	123.05 (13)	H20B—C20—H20F	56.3
C15—C16—C17	118.83 (15)	H20C—C20—H20F	141.1
C15—C16—C27	121.87 (15)	H20D—C20—H20F	109.5
C17—C16—C27	119.31 (14)	H20E—C20—H20F	109.5
C5—C4—C3	118.82 (15)	C16—C27—H27A	109.5
C5—C4—C20	120.96 (16)	C16—C27—H27B	109.5
C3—C4—C20	120.20 (15)	H27A—C27—H27B	109.5
C21—C26—C25	121.90 (16)	C16—C27—H27C	109.5
C21—C26—Cl1	119.98 (12)	H27A—C27—H27C	109.5
C25—C26—Cl1	118.11 (14)	H27B—C27—H27C	109.5
C18—C17—C16	121.65 (14)
C10—C9—C14—C13	6.1 (2)	C13—C14—C21—C22	82.85 (19)
C8—C9—C14—C13	−173.70 (13)	C14—C13—C15—C16	−178.02 (15)
C10—C9—C14—C21	−172.70 (13)	C12—C13—C15—C16	1.9 (2)
C8—C9—C14—C21	7.5 (2)	N7—C1—C2—C3	179.93 (16)
C12—N11—C10—C9	0.4 (2)	C6—C1—C2—C3	0.6 (3)
C12—N11—C10—C6	−177.97 (13)	N11—C12—C18—C17	−178.30 (15)
C14—C9—C10—N11	−5.4 (2)	C13—C12—C18—C17	0.6 (2)
C8—C9—C10—N11	174.47 (13)	C1—N7—C8—C9	1.4 (2)
C14—C9—C10—C6	172.95 (13)	C1—N7—C8—C19	178.83 (14)
C8—C9—C10—C6	−7.2 (2)	C14—C9—C8—N7	−175.27 (14)
C9—C14—C13—C12	−2.4 (2)	C10—C9—C8—N7	4.9 (2)
C21—C14—C13—C12	176.51 (13)	C14—C9—C8—C19	7.5 (2)
C9—C14—C13—C15	177.54 (14)	C10—C9—C8—C19	−172.28 (14)
C21—C14—C13—C15	−3.6 (2)	C13—C15—C16—C17	−1.1 (2)
N11—C10—C6—C1	−177.95 (13)	C13—C15—C16—C27	178.85 (16)
C9—C10—C6—C1	3.6 (2)	C6—C5—C4—C3	0.6 (3)
N11—C10—C6—C5	4.1 (2)	C6—C5—C4—C20	−177.91 (16)
C9—C10—C6—C5	−174.35 (14)	C22—C21—C26—C25	0.3 (2)
C5—C6—C1—N7	−179.11 (14)	C14—C21—C26—C25	178.09 (15)
C10—C6—C1—N7	2.8 (2)	C22—C21—C26—Cl1	179.19 (13)
C5—C6—C1—C2	0.1 (2)	C14—C21—C26—Cl1	−3.0 (2)
C10—C6—C1—C2	−177.91 (14)	C12—C18—C17—C16	0.2 (3)
C10—N11—C12—C18	−177.28 (14)	C15—C16—C17—C18	0.0 (3)
C10—N11—C12—C13	3.8 (2)	C27—C16—C17—C18	−179.91 (17)
C14—C13—C12—N11	−2.8 (2)	C26—C21—C22—C23	−1.4 (3)
C15—C13—C12—N11	177.25 (14)	C14—C21—C22—C23	−179.24 (16)
C14—C13—C12—C18	178.29 (14)	C1—C2—C3—C4	−0.8 (3)
C15—C13—C12—C18	−1.6 (2)	C5—C4—C3—C2	0.2 (3)
C6—C1—N7—C8	−5.5 (2)	C20—C4—C3—C2	178.72 (18)
C2—C1—N7—C8	175.23 (15)	C21—C22—C23—C24	1.7 (3)
C1—C6—C5—C4	−0.8 (2)	C21—C26—C25—C24	0.6 (3)
C10—C6—C5—C4	177.17 (14)	Cl1—C26—C25—C24	−178.38 (14)
C9—C14—C21—C26	83.9 (2)	C22—C23—C24—C25	−0.9 (3)
C13—C14—C21—C26	−94.89 (17)	C26—C25—C24—C23	−0.3 (3)
C9—C14—C21—C22	−98.31 (19)

D—H···A	D—H	H···A	D···A	D—H···A
C22—H22···N7i	0.93	2.42	3.318 (2)	162

Cg(I)	Cg(J)	Centroid-to-Centroid
Cg(2)	Cg(3i)	3.8531 (1)
Cg(3)	Cg(2ii)	3.8531 (1)
Cg(3)	Cg(4ii)	3.7631 (1)
Cg(4)	Cg(3i)	3.7631 (1)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C22—H22⋯N7i	0.93	2.42	3.318 (2)	162

Symmetry code: (i) .