4-(4-Chloro­phen­yl)-6-meth­oxy-2,2′-bipyridine-5-carbonitrile

Ramesh, P.; Sundaresan, S.S.; Thirumurugan, P.; Perumal, P.T.; Ponnuswamy, M.N.

doi:10.1107/S1600536809012409

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 5| May 2009| Page o995

doi:10.1107/S1600536809012409

Open

access

4-(4-Chlorophenyl)-6-methoxy-2,2′-bipyridine-5-carbonitrile

P. Ramesh,^a S. S. Sundaresan,^b P. Thirumurugan,^c Paramasivan T. Perumal ^c and M. N. Ponnuswamy ^b ^*

^aDepartment of Physics, Presidency College (Autonomous), Chennai 600 005, India, ^bCentre of Advanced Study in Crystallography and Biophysics, University of Madras, Guindy Campus, Chennai 600 025, India, and ^cOrganic Chemistry Division, Central Leather Research Institute, Adyar, Chennai 600 020, India
^*Correspondence e-mail: mnpsy2004@yahoo.com

(Received 9 March 2009; accepted 2 April 2009; online 8 April 2009)

There are two independent molecules in the asymmetric unit of the title compound, C₁₈H₁₂ClN₃O. The two pyridine rings are almost coplanar [dihedral angles between the rings: 2.87 (15) and 5.36 (16)°] while the chlorophenyl rings are twisted out of the plane of the adjacent bipyridine ring by 44.1 (1) and 43.8 (1)° in the two molecules. The crystal packing is stabilized by C—H⋯N and C—H⋯Cl interactions.

Related literature

Pyridine derivatives possess phosphodiesterase-inhibiting (Heintzelman et al., 2003a ,b ), antifungal (Cook et al., 2004a ,b ), antifertility (Upton et al., 2000 ) and antiarrhythmic activities (Ellefson et al., 1978 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₈H₁₂ClN₃O
M_r = 321.76
Monoclinic, P 2₁
a = 9.5869 (5) Å
b = 13.8761 (7) Å
c = 12.2124 (6) Å
β = 106.896 (2)°
V = 1554.47 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 293 K
0.30 × 0.25 × 0.20 mm

Data collection

Bruker Kappa APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2001 ) T_min = 0.927, T_max = 0.951
17581 measured reflections
6950 independent reflections
4300 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.113
S = 1.00
6950 reflections
417 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.18 e Å⁻³
Absolute structure: Flack (1983 ), 3268 Friedel pairs
Flack parameter: 0.05 (6)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11⋯N9′ⁱ	0.93	2.58	3.321 (4)	137
C21—H21⋯Cl1ⁱⁱ	0.93	2.80	3.597 (3)	144
C11′—H11′⋯N9ⁱⁱⁱ	0.93	2.60	3.349 (4)	138
C21′—H21′⋯Cl1′ⁱⁱ	0.93	2.71	3.475 (3)	140
Symmetry codes: (i) $[-x, y+{\script{1\over 2}}, -z+2]$ ; (ii) x-1, y, z-1; (iii) $[-x, y-{\script{1\over 2}}, -z+2]$ .

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ); 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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809012409/bt2899sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809012409/bt2899Isup2.hkl

checkCIF report

Comment top

Pyridine derivatives possess phosphodiesterase inhibiting (Heintzelman et al., 2003a,b), antifungal (Cook et al., 2004a,b), antifertility (Upton et al.,2000) and antiarrhythmic activities (Ellefson et al., 1978). The crystallographic study was useful to ascertain the molecular conformation.

The ORTEP plot of the molecule is shown in Fig.1. There are two crystallographically independent molecules in the asymmetric unit. The two pyridine rings lie in the same plane which is evidenced from the dihedral angles of 2.87 (15)° and 5.36 (16)° for the molecules 1 & 2 respectively. The planar chlorophenyl rings are twisted away from the bipyridine ring by 44.1 (1)° for (molecule 1) and 43.8 (1)° for (molecule 2), respectively. The bond angles of C3—C8—N9 (177.9 (4))° and C3'-C8'-N9' (178.3 (3))° show linearity of the cyano group, a feature observed in carbonitrile compounds.

The crystal packing is controlled by C—H···N and C—H···Cl intermolecular interactions in addition to van der Waals forces. Atoms C11 and C11' at (x, y, z) donate one proton each to N9' (-x,+y + 1/2,-z + 2) and N9 (-x,+y - 1/2,-z + 2) which connect the molecules to form a dimer with a graph-set-motiff R²₂(14) (Bernstein et al., 1995). These dimers are linked through intermolecular C21—H21···Cl1 hydrogen bond chain running along c axis which is shown in Fig. 2.

Related literature top

Pyridine derivatives possess phosphodiesterase-inhibiting (Heintzelman et al., 2003a,b), antifungal (Cook et al., 2004a,b), antifertility (Upton et al., 2000) and antiarrhythmic activities (Ellefson et al., 1978). For hydrogen-bond motifs, see: Bernstein et al. (1995).

Experimental top

A mixture of p-chlorobenzaldehyde (1 eq), 2-acetyl pyridine and sodium hydroxide (1.2 eq) in methanol was refluxed for 30 min. After that malanonitrile (1 eq) was added and the reaction was continued to 3 h. With the completion of the reaction (as monitored by TLC), it was poured into water and extracted with ethyl acetate. The organic layer was dried over sodium sulfate and concentrated under vacuo. The crude product was chromatographed and isolated in 76% yield (90:10, petroleum ether: ethyl acetate). The compound was recrystallized in ethanol.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. Perspective view of the molecule showing the displacement ellipsoids at 50% probability level. The H atoms are shown as small circles of arbitrary radii.
	Fig. 2. The crystal packing of the molecules viewed down b axis. H atoms not involved in hydrogen bonding have been omitted for clarity.

4-(4-Chlorophenyl)-6-methoxy-2,2'-bipyridine-5-carbonitrile top

Crystal data top

C₁₈H₁₂ClN₃O	F(000) = 664
M_r = 321.76	D_x = 1.375 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 3721 reflections
a = 9.5869 (5) Å	θ = 1.7–27.5°
b = 13.8761 (7) Å	µ = 0.25 mm⁻¹
c = 12.2124 (6) Å	T = 293 K
β = 106.896 (2)°	Block, colorless
V = 1554.47 (14) Å³	0.30 × 0.25 × 0.20 mm
Z = 4

Data collection top

Bruker Kappa APEXII area-detector diffractometer	6950 independent reflections
Radiation source: fine-focus sealed tube	4300 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
ω and ϕ scans	θ_max = 27.5°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −12→12
T_min = 0.927, T_max = 0.951	k = −17→17
17581 measured reflections	l = −15→15

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.043	H-atom parameters constrained
wR(F²) = 0.113	w = 1/[σ²(F_o²) + (0.0461P)² + 0.1394P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max = 0.002
6950 reflections	Δρ_max = 0.24 e Å⁻³
417 parameters	Δρ_min = −0.18 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 3268 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.05 (6)

Crystal data top

C₁₈H₁₂ClN₃O	V = 1554.47 (14) Å³
M_r = 321.76	Z = 4
Monoclinic, P2₁	Mo Kα radiation
a = 9.5869 (5) Å	µ = 0.25 mm⁻¹
b = 13.8761 (7) Å	T = 293 K
c = 12.2124 (6) Å	0.30 × 0.25 × 0.20 mm
β = 106.896 (2)°

Data collection top

Bruker Kappa APEXII area-detector diffractometer	6950 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	4300 reflections with I > 2σ(I)
T_min = 0.927, T_max = 0.951	R_int = 0.035
17581 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	H-atom parameters constrained
wR(F²) = 0.113	Δρ_max = 0.24 e Å⁻³
S = 1.00	Δρ_min = −0.18 e Å⁻³
6950 reflections	Absolute structure: Flack (1983), 3268 Friedel pairs
417 parameters	Absolute structure parameter: 0.05 (6)
1 restraint

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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.

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

	x	y	z	U_iso*/U_eq
C2'	−0.0524 (3)	0.2747 (2)	0.5616 (2)	0.0453 (7)
C2	−0.1641 (3)	0.5282 (2)	0.7627 (2)	0.0485 (7)
C3'	0.0529 (3)	0.2755 (2)	0.66886 (19)	0.0438 (6)
C3	−0.0610 (3)	0.5309 (2)	0.86978 (19)	0.0448 (6)
C4'	0.1994 (3)	0.2704 (2)	0.67256 (19)	0.0450 (6)
C4	0.0852 (3)	0.53628 (19)	0.87589 (19)	0.0427 (6)
C5	0.1208 (3)	0.5349 (2)	0.77260 (19)	0.0452 (6)
H5	0.2177	0.5373	0.7726	0.054*
C5'	0.2306 (3)	0.2696 (2)	0.56900 (19)	0.0467 (6)
H5'	0.3271	0.2672	0.5679	0.056*
C6	0.0109 (3)	0.5301 (2)	0.6710 (2)	0.0439 (6)
C6'	0.1199 (3)	0.2723 (2)	0.4671 (2)	0.0430 (6)
C7'	−0.3014 (3)	0.2777 (3)	0.4542 (2)	0.0730 (9)
H7D	−0.2843	0.3307	0.4092	0.110*
H7F	−0.3957	0.2845	0.4658	0.110*
H7E	−0.2977	0.2183	0.4147	0.110*
C7	−0.4109 (3)	0.5274 (3)	0.6510 (2)	0.0769 (10)
H7A	−0.3862	0.5766	0.6046	0.115*
H7B	−0.5054	0.5407	0.6598	0.115*
H7C	−0.4125	0.4659	0.6147	0.115*
C8'	0.0057 (3)	0.2856 (2)	0.7694 (2)	0.0506 (7)
C8	−0.1112 (3)	0.5223 (2)	0.9698 (2)	0.0509 (7)
C10	0.2010 (3)	0.5420 (2)	0.9863 (2)	0.0452 (7)
C10'	0.3164 (3)	0.2671 (2)	0.78201 (19)	0.0451 (6)
C11	0.1893 (3)	0.6056 (2)	1.0710 (2)	0.0488 (7)
H11	0.1081	0.6455	1.0575	0.059*
C11'	0.3071 (3)	0.2046 (2)	0.8686 (2)	0.0540 (7)
H11'	0.2262	0.1646	0.8573	0.065*
C12'	0.4158 (3)	0.2011 (2)	0.9709 (2)	0.0601 (8)
H12'	0.4089	0.1587	1.0281	0.072*
C12	0.2950 (3)	0.6106 (2)	1.1738 (2)	0.0540 (7)
H12	0.2867	0.6538	1.2298	0.065*
C13'	0.5332 (3)	0.2601 (3)	0.9877 (2)	0.0609 (9)
C13	0.4138 (3)	0.5507 (3)	1.1932 (2)	0.0565 (8)
C14	0.4309 (3)	0.4900 (3)	1.1102 (2)	0.0646 (9)
H14	0.5141	0.4520	1.1233	0.078*
C14'	0.5486 (3)	0.3210 (3)	0.9047 (3)	0.0661 (9)
H14'	0.6307	0.3600	0.9172	0.079*
C15'	0.4401 (3)	0.3240 (2)	0.8012 (2)	0.0567 (8)
H15'	0.4504	0.3648	0.7436	0.068*
C15	0.3241 (3)	0.4854 (2)	1.0067 (2)	0.0572 (8)
H15	0.3351	0.4438	0.9501	0.069*
C16	0.0424 (3)	0.5259 (2)	0.5593 (2)	0.0454 (7)
C16'	0.1494 (3)	0.2756 (2)	0.3547 (2)	0.0464 (6)
C18'	0.3136 (4)	0.2815 (3)	0.2542 (3)	0.0821 (11)
H18'	0.4099	0.2807	0.2524	0.098*
C18	0.2082 (4)	0.5207 (3)	0.4595 (3)	0.0717 (10)
H18	0.3052	0.5202	0.4594	0.086*
C19	0.1032 (4)	0.5161 (2)	0.3559 (3)	0.0662 (10)
H19	0.1284	0.5128	0.2880	0.079*
C19'	0.2062 (4)	0.2900 (3)	0.1528 (2)	0.0715 (10)
H19'	0.2299	0.2950	0.0844	0.086*
C20'	0.0658 (4)	0.2910 (3)	0.1527 (2)	0.0643 (9)
H20'	−0.0091	0.2968	0.0848	0.077*
C20	−0.0384 (4)	0.5166 (3)	0.3552 (2)	0.0629 (9)
H20	−0.1127	0.5133	0.2866	0.075*
C21	−0.0705 (3)	0.5222 (2)	0.4585 (2)	0.0554 (7)
H21	−0.1668	0.5236	0.4601	0.067*
C21'	0.0364 (3)	0.2832 (2)	0.2554 (2)	0.0550 (8)
H21'	−0.0596	0.2831	0.2581	0.066*
N1	−0.1311 (2)	0.52769 (17)	0.66537 (16)	0.0476 (6)
N1'	−0.0218 (2)	0.27322 (17)	0.46358 (16)	0.0477 (5)
N9'	−0.0333 (3)	0.2959 (2)	0.8486 (2)	0.0696 (8)
N9	−0.1527 (3)	0.5130 (2)	1.0466 (2)	0.0711 (8)
N17'	0.2879 (3)	0.2742 (2)	0.35573 (18)	0.0655 (7)
N17	0.1810 (3)	0.5257 (2)	0.56052 (18)	0.0594 (7)
O1	−0.3049 (2)	0.52612 (18)	0.76094 (15)	0.0623 (6)
O1'	−0.1919 (2)	0.27689 (18)	0.56248 (16)	0.0617 (6)
Cl1'	0.66572 (10)	0.25841 (9)	1.11925 (7)	0.0970 (4)
Cl1	0.54493 (9)	0.55353 (8)	1.32596 (6)	0.0888 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C2'	0.0455 (16)	0.0402 (16)	0.0507 (15)	−0.0023 (15)	0.0149 (12)	0.0032 (13)
C2	0.0441 (15)	0.0460 (17)	0.0545 (15)	−0.0014 (14)	0.0130 (12)	0.0042 (14)
C3'	0.0524 (16)	0.0416 (16)	0.0372 (13)	−0.0055 (15)	0.0126 (11)	0.0029 (14)
C3	0.0522 (16)	0.0423 (15)	0.0408 (13)	0.0036 (14)	0.0149 (11)	0.0003 (13)
C4'	0.0522 (15)	0.0395 (15)	0.0422 (13)	−0.0043 (15)	0.0121 (11)	0.0023 (14)
C4	0.0472 (15)	0.0382 (15)	0.0422 (13)	0.0042 (13)	0.0120 (11)	−0.0021 (13)
C5	0.0436 (14)	0.0473 (16)	0.0448 (13)	0.0024 (13)	0.0130 (10)	−0.0011 (13)
C5'	0.0505 (15)	0.0454 (16)	0.0433 (13)	0.0005 (14)	0.0122 (11)	0.0043 (13)
C6	0.0504 (16)	0.0392 (15)	0.0416 (13)	−0.0009 (13)	0.0128 (11)	−0.0008 (13)
C6'	0.0496 (16)	0.0355 (14)	0.0427 (13)	0.0009 (14)	0.0113 (11)	0.0023 (13)
C7'	0.0506 (17)	0.090 (3)	0.0700 (19)	0.002 (2)	0.0034 (14)	0.000 (2)
C7	0.0470 (17)	0.102 (3)	0.074 (2)	−0.010 (2)	0.0058 (14)	0.011 (2)
C8'	0.0565 (18)	0.0444 (19)	0.0512 (16)	−0.0023 (16)	0.0161 (14)	0.0052 (14)
C8	0.0524 (16)	0.0514 (18)	0.0482 (15)	0.0058 (15)	0.0137 (12)	−0.0002 (15)
C10	0.0432 (15)	0.0486 (17)	0.0427 (13)	−0.0014 (14)	0.0108 (11)	0.0027 (14)
C10'	0.0512 (15)	0.0468 (15)	0.0377 (12)	−0.0019 (14)	0.0135 (10)	−0.0030 (13)
C11	0.0535 (17)	0.0529 (17)	0.0414 (14)	0.0028 (14)	0.0159 (12)	−0.0007 (13)
C11'	0.0587 (18)	0.0557 (18)	0.0451 (15)	−0.0016 (14)	0.0110 (12)	0.0012 (14)
C12'	0.068 (2)	0.066 (2)	0.0444 (15)	0.0144 (17)	0.0133 (14)	0.0025 (15)
C12	0.0605 (18)	0.0609 (19)	0.0416 (14)	−0.0107 (16)	0.0167 (13)	−0.0050 (13)
C13'	0.0528 (18)	0.076 (2)	0.0464 (15)	0.0167 (18)	0.0034 (13)	−0.0115 (17)
C13	0.0516 (17)	0.069 (2)	0.0411 (14)	−0.0138 (17)	0.0015 (12)	0.0058 (16)
C14	0.0552 (19)	0.068 (2)	0.0638 (19)	0.0076 (17)	0.0063 (16)	0.0046 (18)
C14'	0.0426 (17)	0.078 (2)	0.074 (2)	−0.0076 (16)	0.0120 (16)	−0.0202 (19)
C15'	0.0550 (18)	0.060 (2)	0.0569 (17)	−0.0061 (15)	0.0200 (14)	−0.0035 (15)
C15	0.0569 (18)	0.057 (2)	0.0541 (16)	0.0098 (15)	0.0107 (14)	−0.0035 (15)
C16	0.0549 (17)	0.0386 (16)	0.0418 (14)	−0.0049 (15)	0.0124 (12)	−0.0012 (13)
C16'	0.0569 (16)	0.0394 (15)	0.0427 (13)	−0.0013 (15)	0.0143 (11)	−0.0003 (13)
C18'	0.076 (2)	0.122 (3)	0.0567 (18)	0.010 (2)	0.0321 (16)	0.009 (2)
C18	0.077 (2)	0.083 (3)	0.065 (2)	−0.008 (2)	0.0367 (18)	−0.004 (2)
C19	0.097 (3)	0.059 (2)	0.0525 (18)	−0.012 (2)	0.0378 (18)	−0.0001 (16)
C19'	0.094 (3)	0.081 (3)	0.0451 (16)	0.003 (2)	0.0294 (17)	0.0030 (18)
C20'	0.083 (2)	0.065 (2)	0.0393 (15)	−0.0019 (19)	0.0100 (15)	−0.0059 (16)
C20	0.085 (2)	0.058 (2)	0.0422 (16)	−0.0044 (19)	0.0135 (16)	0.0041 (15)
C21	0.0601 (18)	0.0571 (19)	0.0465 (15)	0.0019 (16)	0.0113 (12)	0.0031 (14)
C21'	0.0580 (17)	0.062 (2)	0.0438 (15)	−0.0013 (16)	0.0121 (12)	−0.0027 (15)
N1	0.0496 (13)	0.0515 (15)	0.0400 (11)	−0.0026 (12)	0.0102 (9)	0.0012 (11)
N1'	0.0509 (13)	0.0470 (13)	0.0436 (12)	−0.0002 (13)	0.0113 (10)	0.0018 (11)
N9'	0.093 (2)	0.0659 (19)	0.0600 (16)	−0.0049 (15)	0.0382 (15)	0.0010 (14)
N9	0.0778 (18)	0.084 (2)	0.0598 (15)	0.0023 (16)	0.0336 (13)	−0.0006 (15)
N17'	0.0601 (16)	0.089 (2)	0.0499 (13)	0.0088 (17)	0.0201 (11)	0.0099 (15)
N17	0.0592 (15)	0.0710 (18)	0.0500 (13)	−0.0052 (15)	0.0190 (11)	−0.0064 (14)
O1	0.0460 (11)	0.0844 (17)	0.0555 (11)	−0.0024 (12)	0.0132 (9)	0.0104 (12)
O1'	0.0462 (11)	0.0785 (16)	0.0605 (12)	0.0000 (12)	0.0160 (9)	−0.0005 (12)
Cl1'	0.0709 (5)	0.1312 (9)	0.0664 (5)	0.0322 (6)	−0.0157 (4)	−0.0216 (6)
Cl1	0.0726 (5)	0.1207 (8)	0.0551 (4)	−0.0156 (5)	−0.0101 (3)	0.0127 (5)

Geometric parameters (Å, º) top

C2'—N1'	1.313 (3)	C11—H11	0.9300
C2'—O1'	1.341 (3)	C11'—C12'	1.375 (3)
C2'—C3'	1.403 (3)	C11'—H11'	0.9300
C2—N1	1.316 (3)	C12'—C13'	1.358 (5)
C2—O1	1.344 (3)	C12'—H12'	0.9300
C2—C3	1.391 (3)	C12—C13	1.374 (4)
C3'—C4'	1.394 (3)	C12—H12	0.9300
C3'—C8'	1.433 (4)	C13'—C14'	1.361 (5)
C3—C4	1.384 (3)	C13'—Cl1'	1.735 (3)
C3—C8	1.442 (4)	C13—C14	1.364 (4)
C4'—C5'	1.382 (3)	C13—Cl1	1.739 (3)
C4'—C10'	1.475 (3)	C14—C15	1.378 (4)
C4—C5	1.399 (3)	C14—H14	0.9300
C4—C10	1.478 (3)	C14'—C15'	1.384 (4)
C5—C6	1.376 (3)	C14'—H14'	0.9300
C5—H5	0.9300	C15'—H15'	0.9300
C5'—C6'	1.382 (3)	C15—H15	0.9300
C5'—H5'	0.9300	C16—N17	1.324 (3)
C6—N1	1.343 (3)	C16—C21	1.384 (3)
C6—C16	1.481 (3)	C16'—N17'	1.325 (3)
C6'—N1'	1.346 (3)	C16'—C21'	1.376 (3)
C6'—C16'	1.481 (3)	C18'—N17'	1.337 (4)
C7'—O1'	1.430 (3)	C18'—C19'	1.366 (4)
C7'—H7D	0.9600	C18'—H18'	0.9300
C7'—H7F	0.9600	C18—N17	1.335 (3)
C7'—H7E	0.9600	C18—C19	1.370 (4)
C7—O1	1.430 (3)	C18—H18	0.9300
C7—H7A	0.9600	C19—C20	1.355 (4)
C7—H7B	0.9600	C19—H19	0.9300
C7—H7C	0.9600	C19'—C20'	1.346 (4)
C8'—N9'	1.143 (4)	C19'—H19'	0.9300
C8—N9	1.127 (3)	C20'—C21'	1.367 (4)
C10—C15	1.379 (4)	C20'—H20'	0.9300
C10—C11	1.388 (4)	C20—C21	1.384 (4)
C10'—C15'	1.387 (4)	C20—H20	0.9300
C10'—C11'	1.391 (4)	C21—H21	0.9300
C11—C12	1.368 (4)	C21'—H21'	0.9300

N1'—C2'—O1'	119.7 (2)	C11'—C12'—H12'	120.3
N1'—C2'—C3'	124.1 (2)	C11—C12—C13	118.9 (3)
O1'—C2'—C3'	116.2 (2)	C11—C12—H12	120.5
N1—C2—O1	119.3 (2)	C13—C12—H12	120.5
N1—C2—C3	123.9 (2)	C12'—C13'—C14'	121.7 (3)
O1—C2—C3	116.8 (2)	C12'—C13'—Cl1'	118.9 (3)
C4'—C3'—C2'	118.4 (2)	C14'—C13'—Cl1'	119.3 (3)
C4'—C3'—C8'	122.9 (2)	C14—C13—C12	121.2 (2)
C2'—C3'—C8'	118.7 (2)	C14—C13—Cl1	119.8 (3)
C4—C3—C2	118.9 (2)	C12—C13—Cl1	119.0 (2)
C4—C3—C8	122.8 (2)	C13—C14—C15	119.5 (3)
C2—C3—C8	118.2 (2)	C13—C14—H14	120.2
C5'—C4'—C3'	117.0 (2)	C15—C14—H14	120.2
C5'—C4'—C10'	121.3 (2)	C13'—C14'—C15'	118.9 (3)
C3'—C4'—C10'	121.6 (2)	C13'—C14'—H14'	120.5
C3—C4—C5	117.3 (2)	C15'—C14'—H14'	120.5
C3—C4—C10	122.1 (2)	C14'—C15'—C10'	121.0 (3)
C5—C4—C10	120.5 (2)	C14'—C15'—H15'	119.5
C6—C5—C4	119.4 (2)	C10'—C15'—H15'	119.5
C6—C5—H5	120.3	C14—C15—C10	120.6 (3)
C4—C5—H5	120.3	C14—C15—H15	119.7
C4'—C5'—C6'	120.7 (2)	C10—C15—H15	119.7
C4'—C5'—H5'	119.7	N17—C16—C21	122.2 (2)
C6'—C5'—H5'	119.7	N17—C16—C6	117.5 (2)
N1—C6—C5	123.1 (2)	C21—C16—C6	120.3 (2)
N1—C6—C16	115.3 (2)	N17'—C16'—C21'	122.7 (2)
C5—C6—C16	121.6 (2)	N17'—C16'—C6'	116.9 (2)
N1'—C6'—C5'	122.2 (2)	C21'—C16'—C6'	120.4 (3)
N1'—C6'—C16'	115.6 (2)	N17'—C18'—C19'	123.6 (3)
C5'—C6'—C16'	122.1 (2)	N17'—C18'—H18'	118.2
O1'—C7'—H7D	109.5	C19'—C18'—H18'	118.2
O1'—C7'—H7F	109.5	N17—C18—C19	124.5 (3)
H7D—C7'—H7F	109.5	N17—C18—H18	117.7
O1'—C7'—H7E	109.5	C19—C18—H18	117.7
H7D—C7'—H7E	109.5	C20—C19—C18	118.1 (3)
H7F—C7'—H7E	109.5	C20—C19—H19	120.9
O1—C7—H7A	109.5	C18—C19—H19	120.9
O1—C7—H7B	109.5	C20'—C19'—C18'	119.5 (3)
H7A—C7—H7B	109.5	C20'—C19'—H19'	120.3
O1—C7—H7C	109.5	C18'—C19'—H19'	120.3
H7A—C7—H7C	109.5	C19'—C20'—C21'	118.1 (3)
H7B—C7—H7C	109.5	C19'—C20'—H20'	120.9
N9'—C8'—C3'	178.3 (4)	C21'—C20'—H20'	120.9
N9—C8—C3	177.9 (3)	C19—C20—C21	118.8 (3)
C15—C10—C11	118.5 (2)	C19—C20—H20	120.6
C15—C10—C4	120.7 (2)	C21—C20—H20	120.6
C11—C10—C4	120.8 (2)	C16—C21—C20	119.3 (3)
C15'—C10'—C11'	117.9 (2)	C16—C21—H21	120.4
C15'—C10'—C4'	121.6 (2)	C20—C21—H21	120.4
C11'—C10'—C4'	120.6 (2)	C20'—C21'—C16'	119.7 (3)
C12—C11—C10	121.2 (3)	C20'—C21'—H21'	120.2
C12—C11—H11	119.4	C16'—C21'—H21'	120.2
C10—C11—H11	119.4	C2—N1—C6	117.4 (2)
C12'—C11'—C10'	120.9 (3)	C2'—N1'—C6'	117.50 (19)
C12'—C11'—H11'	119.6	C16'—N17'—C18'	116.4 (3)
C10'—C11'—H11'	119.6	C16—N17—C18	117.1 (2)
C13'—C12'—C11'	119.5 (3)	C2—O1—C7	116.9 (2)
C13'—C12'—H12'	120.3	C2'—O1'—C7'	117.3 (2)

N1'—C2'—C3'—C4'	−2.8 (5)	C12—C13—C14—C15	−3.0 (5)
O1'—C2'—C3'—C4'	178.1 (3)	Cl1—C13—C14—C15	177.6 (2)
N1'—C2'—C3'—C8'	174.6 (3)	C12'—C13'—C14'—C15'	1.2 (5)
O1'—C2'—C3'—C8'	−4.5 (4)	Cl1'—C13'—C14'—C15'	−178.0 (2)
N1—C2—C3—C4	2.0 (4)	C13'—C14'—C15'—C10'	0.8 (5)
O1—C2—C3—C4	−178.0 (3)	C11'—C10'—C15'—C14'	−2.1 (4)
N1—C2—C3—C8	−174.4 (3)	C4'—C10'—C15'—C14'	179.4 (3)
O1—C2—C3—C8	5.6 (4)	C13—C14—C15—C10	0.5 (5)
C2'—C3'—C4'—C5'	3.1 (4)	C11—C10—C15—C14	1.8 (4)
C8'—C3'—C4'—C5'	−174.2 (3)	C4—C10—C15—C14	−179.2 (3)
C2'—C3'—C4'—C10'	−177.7 (3)	N1—C6—C16—N17	−178.4 (3)
C8'—C3'—C4'—C10'	5.1 (5)	C5—C6—C16—N17	0.8 (4)
C2—C3—C4—C5	−2.4 (4)	N1—C6—C16—C21	1.6 (4)
C8—C3—C4—C5	173.8 (3)	C5—C6—C16—C21	−179.2 (3)
C2—C3—C4—C10	178.3 (3)	N1'—C6'—C16'—N17'	−179.6 (3)
C8—C3—C4—C10	−5.4 (4)	C5'—C6'—C16'—N17'	1.2 (4)
C3—C4—C5—C6	1.1 (4)	N1'—C6'—C16'—C21'	2.5 (4)
C10—C4—C5—C6	−179.6 (3)	C5'—C6'—C16'—C21'	−176.7 (3)
C3'—C4'—C5'—C6'	−1.0 (4)	N17—C18—C19—C20	−0.1 (6)
C10'—C4'—C5'—C6'	179.7 (3)	N17'—C18'—C19'—C20'	−0.2 (7)
C4—C5—C6—N1	0.8 (4)	C18'—C19'—C20'—C21'	−0.1 (6)
C4—C5—C6—C16	−178.3 (3)	C18—C19—C20—C21	0.3 (5)
C4'—C5'—C6'—N1'	−1.8 (4)	N17—C16—C21—C20	1.1 (5)
C4'—C5'—C6'—C16'	177.4 (3)	C6—C16—C21—C20	−178.9 (3)
C4'—C3'—C8'—N9'	116 (12)	C19—C20—C21—C16	−0.8 (5)
C2'—C3'—C8'—N9'	−62 (12)	C19'—C20'—C21'—C16'	0.6 (5)
C4—C3—C8—N9	−124 (9)	N17'—C16'—C21'—C20'	−0.9 (5)
C2—C3—C8—N9	52 (9)	C6'—C16'—C21'—C20'	176.8 (3)
C3—C4—C10—C15	134.3 (3)	O1—C2—N1—C6	179.8 (3)
C5—C4—C10—C15	−45.0 (4)	C3—C2—N1—C6	−0.2 (4)
C3—C4—C10—C11	−46.8 (4)	C5—C6—N1—C2	−1.2 (4)
C5—C4—C10—C11	134.0 (3)	C16—C6—N1—C2	177.9 (2)
C5'—C4'—C10'—C15'	45.0 (4)	O1'—C2'—N1'—C6'	179.2 (3)
C3'—C4'—C10'—C15'	−134.2 (3)	C3'—C2'—N1'—C6'	0.1 (5)
C5'—C4'—C10'—C11'	−133.5 (3)	C5'—C6'—N1'—C2'	2.2 (4)
C3'—C4'—C10'—C11'	47.3 (4)	C16'—C6'—N1'—C2'	−177.0 (2)
C15—C10—C11—C12	−1.8 (4)	C21'—C16'—N17'—C18'	0.6 (5)
C4—C10—C11—C12	179.2 (3)	C6'—C16'—N17'—C18'	−177.2 (3)
C15'—C10'—C11'—C12'	1.4 (4)	C19'—C18'—N17'—C16'	0.0 (6)
C4'—C10'—C11'—C12'	179.9 (3)	C21—C16—N17—C18	−0.8 (5)
C10'—C11'—C12'—C13'	0.5 (4)	C6—C16—N17—C18	179.2 (3)
C10—C11—C12—C13	−0.6 (4)	C19—C18—N17—C16	0.3 (6)
C11'—C12'—C13'—C14'	−1.9 (5)	N1—C2—O1—C7	−2.6 (4)
C11'—C12'—C13'—Cl1'	177.3 (2)	C3—C2—O1—C7	177.5 (3)
C11—C12—C13—C14	3.0 (5)	N1'—C2'—O1'—C7'	−0.1 (4)
C11—C12—C13—Cl1	−177.5 (2)	C3'—C2'—O1'—C7'	179.1 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···N9′ⁱ	0.93	2.58	3.321 (4)	137
C21—H21···Cl1ⁱⁱ	0.93	2.80	3.597 (3)	144
C11′—H11′···N9ⁱⁱⁱ	0.93	2.60	3.349 (4)	138
C21′—H21′···Cl1′ⁱⁱ	0.93	2.71	3.475 (3)	140

Symmetry codes: (i) −x, y+1/2, −z+2; (ii) x−1, y, z−1; (iii) −x, y−1/2, −z+2.

Experimental details

Crystal data
Chemical formula	C₁₈H₁₂ClN₃O
M_r	321.76
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	293
a, b, c (Å)	9.5869 (5), 13.8761 (7), 12.2124 (6)
β (°)	106.896 (2)
V (Å³)	1554.47 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.25
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2001)
T_min, T_max	0.927, 0.951
No. of measured, independent and observed [I > 2σ(I)] reflections	17581, 6950, 4300
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.113, 1.00
No. of reflections	6950
No. of parameters	417
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.18
Absolute structure	Flack (1983), 3268 Friedel pairs
Absolute structure parameter	0.05 (6)

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SIR92 (Altomare et al., 1993), ORTEP-3 (Farrugia, 1997), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···N9'ⁱ	0.93	2.58	3.321 (4)	136.8
C21—H21···Cl1ⁱⁱ	0.93	2.80	3.597 (3)	143.8
C11'—H11'···N9ⁱⁱⁱ	0.93	2.60	3.349 (4)	137.5
C21'—H21'···Cl1'ⁱⁱ	0.93	2.71	3.475 (3)	140.4

Symmetry codes: (i) −x, y+1/2, −z+2; (ii) x−1, y, z−1; (iii) −x, y−1/2, −z+2.

Acknowledgements

PR thanks Dr Babu Varghese, SAIF, IIT-Madras, India, for his help with the data collection.

References

Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343–350. CrossRef Web of Science IUCr Journals Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N. L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cook, C. E., Sloan, C. D., Thomas, B. F., Navarro, H. A. (2004a). Chem. Abstr. 141, 157039, 861. Google Scholar
Cook, C. E., Sloan, C. D., Thomas, B. F., Navarro, H. A. (2004b). US Patent 2004147539. Google Scholar
Ellefson, C. R., Woo, C. M. & Cusic, J. W. (1978). J. Med. Chem., 21, 340–343. CrossRef CAS PubMed Web of Science Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Heintzelman, G. R., Averill, K. M., Dodd, J. H., Demarest, K. T., Tang, Y., Jackson, P. F. (2003a). Chem. Abstr. 139, 350637, 730. Google Scholar
Heintzelman, G. R., Averill, K. M., Dodd, J. H., Demarest, K. T., Tang, Y., Jackson, P. F. (2003b). World Patent WO 2003088963. Google Scholar
Sheldrick, G. M. (2001). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Upton, C., Osborne, R. H. & Jaffar, M. (2000). Bioorg. Med. Chem. Lett., 10, 1277–1279. Web of Science CrossRef PubMed CAS Google Scholar