6-(4-Chloro­phenyl)-4-[4-(di­methyl­amino)­phenyl]-2-(pyrrolidin-1-yl)­nicotino­nitrile

Thinagar, S.; Velmurugan, D.; Shanmuga Sundara Raj, S.; Fun, H.-K.; Raghukumar, V.

doi:10.1107/S1600536802019931

6-(4-Chlorophenyl)-4-[4-(dimethylamino)phenyl]-2-(pyrrolidin-1-yl)nicotinonitrile

S. Thinagar, D. Velmurugan, S. Shanmuga Sundara Raj, H.-K. Fun and V. Raghukumar

The title compound, C₂₄H₂₃ClN₄, crystallizes in space group P $\overline 1$ , with two crystallographically independent molecules in the asymmetric unit. In both molecules, the pyrrolidine ring adopts a half-chair conformation. The molecular packing in the crystal is stabilized by intermolecular C—H

N hydrogen bonds, through the formation of hydrogen-bonded molecular chains.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802019931/ci6179sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536802019931/ci6179Isup2.hkl Contains datablock I

CCDC reference: 202362

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.003 Å
R factor = 0.054
wR factor = 0.160
Data-to-parameter ratio = 18.2

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           28.31
         From the CIF: _reflns_number_total               9579
         TEST2: Reflns within _diffrn_reflns_theta_max
         Count of symmetry unique reflns        10436
         Completeness (_total/calc)             91.79%
          Alert C: < 95% complete

PLAT_360  Alert C Short  C(sp3)-C(sp3) Bond  C(8B)  -   C(9B)  =       1.42 Ang.

PLAT_371  Alert C Long   C(sp2)-C(sp1) Bond  C(3A)  -   C(11A) =       1.43 Ang.

PLAT_371  Alert C Long   C(sp2)-C(sp1) Bond  C(3B)  -   C(11B) =       1.44 Ang.


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 4 Alert Level C = Please check

Comment top

Nicotine-containing compounds show interesting biological properties. The nicotinic acid derivative N,N-diethylnicotinamide, which is commonly known as DENA, has the respiratory stimulating property (Hokelek & Necefouglu, 1996). Niacin is a vitamin that contains nicotinamide, deficiency of which makes the body to lose copper thereby creating the pellagra disease (Hokelek & Necefouglu, 1999). The redox pair NAD⁺ (nicotinamide adenine dinucleotide) molecule, which is the oxidized form of the coenzyme NADH, plays a key role in energy-producing processes (Stryer, 1988) and in the redox processes catalysed by various protein families, the dehydrogenases being the largest group (Guillot et al., 2000). The X-ray investigation of the title compound, (I), was taken up as a part of our study on the structures of a nicotine derivatives,

The asymmetric unit of the title compound, (I), contains two molecules; the corresponding bond lengths and angles of these two molecules agree with each other, except for some deviations in Csp³—Csp³ distances of the pyrrolidine ring. A molecular fit for these two molecules shows a weighted r.m.s. deviation of 0.52 Å. The geometry of the two molecules slightly differ in the orientation of the dimethylaminophenyl ring and the nitrile group with respect to the pyridine ring. The N2—C2—C3 angles [124.2 (2) and 124.6 (2)°] are wider than the N1—C2—N2 angles [114.8 (1) and 114.7 (2)°], as a result of the repulsive force exerted by the nitrile group on the pyrrolidine ring. Also, as a result of the steric repulsion between atoms H5 and H19 (H5···H19 = 2.18 Å each), the exocyclic angles C5—C6—C18 [122.9 (2) and 122.4 (2)°] are wider compared with N1—C6—C18 [115.0 (1) and 115.0 (1)°]. Similar distortions in the bond angles have been reported previously for a related structure (Thinagar et al., 2002). The pyrrolidine rings of both the molecules adopt half-chair conformations, with ΔC²(N2) values of 0.012 (1) and 0.002 (1) (Nardelli, 1983), and mean planes through them form dihedral angles of 18.4 (1) and 13.1 (1)° with the pyridine rings. The twisting of the chlorophenyl ring from the pyridine ring is less [12.83 (9) and 14.36 (9)°] compared to that of the other phenyl ring [43.14 (9) and 49.36 (9)°].

In the asymmetric unit, the two crystallographically independent molecules are linked by C19B—H19B···N3A hydrogen bonds. In the crystal, these pairs translated a unit along the b axis are linked by C19A—H19A···N3B hydrogen bonds to form an infinite one-dimensional molecular chain (Table 2). The molecules of these chains are interlinked to those in the adjacent inversion-related chain by C24B—H24F···N3A(1 − x, 1 − y, 1 − z) hydrogen bonds to form double-chain structures.

Experimental top

To a refluxing solution of 4-dimethylamino-4'-(chlorobenzoyl)acetophenone (1.8 mmol) in 10 ml of ethanol, malononitrile (1.8 mmol) and pyrrolidine (1.8 mmol) were added and the resulting solution refluxed for 9 h. The solvent was distilled off under reduced pressure and the resulting residue was purified by column chromatography on silica-gel (100–200 mesh). Single crystals were obtained by slow evaporation method using petroleum ether and ethyl acetate (1:3) solvent system.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ZORTEP (Zsolnai, 1997); software used to prepare material for publication: SHELXL97 and PARST (Nardelli, 1983, 1995).

Figures top

Fig. 1. View of the two independent molecules of the title compound, showing 30% probability displacement ellipsoids and the atom-numbering scheme for the non-H atoms.

6-(4-Chlorophenyl)-4-[4-(dimethylamino)phenyl]-2-(pyrrolidin-1- yl)nicotinonitrile top

Crystal data top

C₂₄H₂₃ClN₄	Z = 4
M_r = 402.91	F(000) = 848
Triclinic, P1	D_x = 1.276 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 11.1490 (1) Å	Cell parameters from 7711 reflections
b = 13.7330 (1) Å	θ = 1.4–28.3°
c = 14.6666 (1) Å	µ = 0.20 mm⁻¹
α = 100.487 (1)°	T = 293 K
β = 93.240 (1)°	Block, yellow
γ = 107.014 (1)°	0.48 × 0.44 × 0.26 mm
V = 2096.93 (2) Å³

Data collection top

Siemens SMART CCD area-detector diffractometer	6307 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.048
Graphite monochromator	θ_max = 28.3°, θ_min = 1.4°
ω scans	h = −13→14
14581 measured reflections	k = −17→14
9579 independent reflections	l = −12→19

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.160	H-atom parameters constrained
S = 0.97	w = 1/[σ²(F_o²) + (0.0793P)²] where P = (F_o² + 2F_c²)/3
9579 reflections	(Δ/σ)_max < 0.001
527 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

C₂₄H₂₃ClN₄	γ = 107.014 (1)°
M_r = 402.91	V = 2096.93 (2) Å³
Triclinic, P1	Z = 4
a = 11.1490 (1) Å	Mo Kα radiation
b = 13.7330 (1) Å	µ = 0.20 mm⁻¹
c = 14.6666 (1) Å	T = 293 K
α = 100.487 (1)°	0.48 × 0.44 × 0.26 mm
β = 93.240 (1)°

Data collection top

Siemens SMART CCD area-detector diffractometer	6307 reflections with I > 2σ(I)
14581 measured reflections	R_int = 0.048
9579 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.160	H-atom parameters constrained
S = 0.97	Δρ_max = 0.35 e Å⁻³
9579 reflections	Δρ_min = −0.32 e Å⁻³
527 parameters

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
Cl1A	−0.02596 (6)	−0.38678 (5)	0.59338 (5)	0.0866 (2)
N1A	0.21081 (13)	0.08918 (11)	0.51050 (9)	0.0431 (3)
N2A	0.28907 (15)	0.26496 (11)	0.55895 (10)	0.0481 (4)
N3A	0.39956 (18)	0.35530 (13)	0.34391 (12)	0.0628 (4)
N4A	0.15588 (17)	0.09242 (14)	−0.06908 (11)	0.0640 (5)
C2A	0.25494 (16)	0.18186 (13)	0.48645 (11)	0.0407 (4)
C3A	0.26408 (16)	0.18899 (13)	0.39066 (11)	0.0407 (4)
C4A	0.21067 (16)	0.09795 (13)	0.32108 (11)	0.0404 (4)
C5A	0.16151 (17)	0.00392 (13)	0.34922 (11)	0.0437 (4)
H5A	0.1256	−0.0573	0.3049	0.052*
C6A	0.16631 (15)	0.00203 (13)	0.44416 (11)	0.0397 (4)
C7A	0.2726 (2)	0.24839 (15)	0.65427 (12)	0.0577 (5)
H7A	0.3256	0.2089	0.6727	0.069*
H7B	0.1853	0.2116	0.6591	0.069*
C8A	0.3119 (3)	0.35634 (18)	0.71363 (16)	0.0777 (7)
H8A	0.3994	0.3765	0.7404	0.093*
H8B	0.2595	0.3601	0.7639	0.093*
C9A	0.2948 (2)	0.42604 (16)	0.64905 (15)	0.0685 (6)
H9A	0.3542	0.4954	0.6696	0.082*
H9B	0.2096	0.4309	0.6464	0.082*
C10A	0.3198 (2)	0.37435 (14)	0.55470 (13)	0.0545 (5)
H10A	0.2665	0.3840	0.5047	0.065*
H10B	0.4075	0.4024	0.5450	0.065*
C11A	0.33675 (18)	0.28231 (15)	0.36491 (12)	0.0470 (4)
C12A	0.20264 (16)	0.10013 (13)	0.22023 (11)	0.0425 (4)
C13A	0.16198 (17)	0.17451 (14)	0.18509 (12)	0.0459 (4)
H13A	0.1461	0.2278	0.2266	0.055*
C14A	0.14480 (17)	0.17124 (15)	0.09087 (13)	0.0495 (4)
H14A	0.1159	0.2214	0.0703	0.059*
C15A	0.16985 (16)	0.09399 (15)	0.02500 (12)	0.0472 (4)
C16A	0.21283 (19)	0.02003 (15)	0.06020 (12)	0.0517 (4)
H16A	0.2322	−0.0317	0.0190	0.062*
C17A	0.22686 (18)	0.02288 (14)	0.15493 (12)	0.0500 (4)
H17A	0.2533	−0.0284	0.1758	0.060*
C18A	0.11896 (15)	−0.09523 (13)	0.47940 (11)	0.0400 (4)
C19A	0.09205 (18)	−0.19282 (14)	0.42202 (13)	0.0488 (4)
H19A	0.1034	−0.1980	0.3592	0.059*
C20A	0.04842 (19)	−0.28293 (15)	0.45645 (14)	0.0559 (5)
H20A	0.0314	−0.3480	0.4173	0.067*
C21A	0.03079 (18)	−0.27462 (15)	0.54923 (14)	0.0538 (5)
C22A	0.05682 (19)	−0.17883 (16)	0.60837 (14)	0.0566 (5)
H22A	0.0450	−0.1742	0.6711	0.068*
C23A	0.10068 (18)	−0.08987 (15)	0.57333 (12)	0.0493 (4)
H23A	0.1184	−0.0251	0.6130	0.059*
C24A	0.1804 (3)	0.0111 (2)	−0.13572 (15)	0.0832 (7)
H24A	0.2623	0.0063	−0.1181	0.125*
H24B	0.1777	0.0272	−0.1967	0.125*
H24C	0.1174	−0.0540	−0.1366	0.125*
C25A	0.0992 (2)	0.1623 (2)	−0.10475 (16)	0.0761 (7)
H25A	0.1477	0.2330	−0.0777	0.114*
H25B	0.0144	0.1495	−0.0888	0.114*
H25C	0.0978	0.1507	−0.1714	0.114*
Cl1B	0.56120 (7)	0.11966 (5)	−0.06469 (5)	0.0903 (2)
N1B	0.27692 (14)	0.48400 (11)	0.01936 (10)	0.0450 (3)
N2B	0.16274 (16)	0.58056 (13)	−0.03099 (10)	0.0546 (4)
N3B	0.1058 (2)	0.73715 (19)	0.19077 (13)	0.0944 (8)
N4B	0.40411 (19)	0.80256 (14)	0.58715 (12)	0.0674 (5)
C2B	0.22383 (17)	0.55999 (14)	0.04215 (12)	0.0448 (4)
C3B	0.23303 (17)	0.61224 (14)	0.13737 (12)	0.0464 (4)
C4B	0.30233 (16)	0.58518 (13)	0.20667 (11)	0.0427 (4)
C5B	0.35384 (16)	0.50485 (13)	0.18000 (12)	0.0442 (4)
H5B	0.3966	0.4830	0.2246	0.053*
C6B	0.34082 (15)	0.45748 (13)	0.08610 (11)	0.0407 (4)
C7B	0.1653 (2)	0.52465 (18)	−0.12654 (13)	0.0652 (6)
H7C	0.1231	0.4506	−0.1342	0.078*
H7D	0.2513	0.5354	−0.1413	0.078*
C8B	0.0948 (3)	0.5730 (2)	−0.18689 (17)	0.0961 (9)
H8C	0.1318	0.5785	−0.2448	0.115*
H8D	0.0068	0.5311	−0.2017	0.115*
C9B	0.1053 (4)	0.6731 (3)	−0.13448 (19)	0.1218 (14)
H9C	0.0323	0.6935	−0.1517	0.146*
H9D	0.1805	0.7240	−0.1465	0.146*
C10B	0.1131 (2)	0.66733 (18)	−0.03218 (15)	0.0681 (6)
H10C	0.1697	0.7313	0.0061	0.082*
H10D	0.0305	0.6537	−0.0103	0.082*
C11B	0.1642 (2)	0.68392 (17)	0.16594 (13)	0.0622 (5)
C12B	0.32554 (17)	0.64203 (13)	0.30520 (12)	0.0435 (4)
C13B	0.37128 (18)	0.74982 (14)	0.32965 (13)	0.0506 (4)
H13B	0.3836	0.7877	0.2826	0.061*
C14B	0.39903 (19)	0.80240 (14)	0.42143 (13)	0.0523 (4)
H14B	0.4316	0.8746	0.4348	0.063*
C15B	0.37941 (17)	0.74988 (14)	0.49475 (12)	0.0471 (4)
C16B	0.33469 (19)	0.64076 (14)	0.47045 (12)	0.0521 (4)
H16B	0.3219	0.6028	0.5174	0.063*
C17B	0.30930 (18)	0.58880 (14)	0.37856 (12)	0.0480 (4)
H17B	0.2806	0.5164	0.3649	0.058*
C18B	0.40065 (15)	0.37612 (13)	0.05188 (11)	0.0401 (4)
C19B	0.44773 (18)	0.32400 (15)	0.11074 (13)	0.0526 (4)
H19B	0.4461	0.3422	0.1748	0.063*
C20B	0.4970 (2)	0.24541 (17)	0.07529 (15)	0.0608 (5)
H20B	0.5267	0.2099	0.1151	0.073*
C21B	0.50179 (18)	0.22026 (15)	−0.01918 (15)	0.0556 (5)
C22B	0.45904 (19)	0.27182 (15)	−0.07922 (14)	0.0555 (5)
H22B	0.4636	0.2547	−0.1430	0.067*
C23B	0.40904 (18)	0.34975 (14)	−0.04320 (12)	0.0485 (4)
H23B	0.3804	0.3853	−0.0835	0.058*
C24B	0.3554 (2)	0.75155 (19)	0.66077 (15)	0.0736 (6)
H24D	0.2678	0.7128	0.6430	0.110*
H24E	0.3641	0.8028	0.7169	0.110*
H24F	0.4017	0.7050	0.6715	0.110*
C25B	0.4560 (3)	0.91400 (17)	0.60971 (17)	0.0794 (7)
H25D	0.5295	0.9351	0.5783	0.119*
H25E	0.4789	0.9371	0.6759	0.119*
H25F	0.3941	0.9443	0.5900	0.119*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1A	0.0898 (5)	0.0735 (4)	0.0984 (5)	0.0092 (3)	0.0033 (3)	0.0514 (3)
N1A	0.0528 (8)	0.0457 (8)	0.0340 (7)	0.0189 (6)	0.0069 (6)	0.0098 (6)
N2A	0.0651 (9)	0.0467 (8)	0.0331 (7)	0.0195 (7)	0.0039 (6)	0.0067 (6)
N3A	0.0851 (12)	0.0563 (10)	0.0516 (10)	0.0212 (9)	0.0165 (9)	0.0213 (8)
N4A	0.0773 (12)	0.0837 (12)	0.0337 (8)	0.0254 (10)	0.0039 (8)	0.0183 (8)
C2A	0.0459 (9)	0.0463 (9)	0.0344 (8)	0.0197 (7)	0.0065 (7)	0.0102 (7)
C3A	0.0470 (9)	0.0460 (9)	0.0357 (8)	0.0208 (7)	0.0091 (7)	0.0129 (7)
C4A	0.0470 (9)	0.0488 (10)	0.0327 (8)	0.0233 (7)	0.0079 (7)	0.0120 (7)
C5A	0.0541 (10)	0.0457 (9)	0.0336 (8)	0.0187 (8)	0.0067 (7)	0.0083 (7)
C6A	0.0431 (9)	0.0471 (9)	0.0347 (8)	0.0212 (7)	0.0078 (7)	0.0098 (7)
C7A	0.0784 (14)	0.0613 (12)	0.0342 (9)	0.0244 (10)	0.0027 (9)	0.0087 (8)
C8A	0.1068 (19)	0.0696 (15)	0.0454 (12)	0.0187 (13)	0.0015 (12)	0.0000 (10)
C9A	0.0876 (16)	0.0564 (12)	0.0553 (13)	0.0227 (11)	0.0051 (11)	−0.0037 (10)
C10A	0.0661 (12)	0.0478 (10)	0.0473 (11)	0.0165 (9)	0.0033 (9)	0.0070 (8)
C11A	0.0594 (11)	0.0505 (11)	0.0369 (9)	0.0235 (9)	0.0089 (8)	0.0123 (8)
C12A	0.0495 (9)	0.0511 (10)	0.0332 (8)	0.0223 (8)	0.0074 (7)	0.0125 (7)
C13A	0.0551 (10)	0.0524 (10)	0.0387 (9)	0.0269 (8)	0.0093 (7)	0.0127 (7)
C14A	0.0521 (10)	0.0617 (11)	0.0439 (10)	0.0255 (9)	0.0056 (8)	0.0209 (8)
C15A	0.0463 (9)	0.0604 (11)	0.0348 (9)	0.0128 (8)	0.0048 (7)	0.0156 (8)
C16A	0.0670 (12)	0.0566 (11)	0.0365 (9)	0.0276 (9)	0.0089 (8)	0.0071 (8)
C17A	0.0678 (12)	0.0525 (11)	0.0395 (9)	0.0307 (9)	0.0093 (8)	0.0132 (8)
C18A	0.0405 (8)	0.0478 (9)	0.0372 (8)	0.0188 (7)	0.0087 (6)	0.0130 (7)
C19A	0.0589 (11)	0.0514 (10)	0.0406 (9)	0.0216 (8)	0.0104 (8)	0.0122 (8)
C20A	0.0615 (12)	0.0474 (11)	0.0588 (12)	0.0169 (9)	0.0015 (9)	0.0125 (9)
C21A	0.0473 (10)	0.0568 (11)	0.0631 (12)	0.0154 (8)	0.0053 (8)	0.0287 (9)
C22A	0.0615 (12)	0.0668 (13)	0.0479 (11)	0.0204 (10)	0.0159 (9)	0.0241 (9)
C23A	0.0591 (11)	0.0542 (11)	0.0390 (9)	0.0209 (9)	0.0129 (8)	0.0127 (8)
C24A	0.107 (2)	0.0993 (19)	0.0368 (11)	0.0250 (15)	0.0107 (11)	0.0079 (11)
C25A	0.0753 (15)	0.1039 (18)	0.0522 (12)	0.0211 (13)	−0.0041 (10)	0.0379 (12)
Cl1B	0.1053 (5)	0.0866 (4)	0.1052 (5)	0.0675 (4)	0.0291 (4)	0.0182 (4)
N1B	0.0523 (8)	0.0503 (8)	0.0377 (8)	0.0228 (7)	0.0050 (6)	0.0110 (6)
N2B	0.0718 (11)	0.0664 (10)	0.0370 (8)	0.0402 (8)	0.0014 (7)	0.0093 (7)
N3B	0.143 (2)	0.1261 (18)	0.0459 (11)	0.1012 (16)	−0.0007 (11)	0.0010 (11)
N4B	0.0941 (14)	0.0619 (11)	0.0394 (9)	0.0204 (9)	−0.0015 (8)	0.0024 (8)
C2B	0.0495 (10)	0.0521 (10)	0.0382 (9)	0.0221 (8)	0.0057 (7)	0.0120 (7)
C3B	0.0550 (10)	0.0518 (10)	0.0384 (9)	0.0247 (8)	0.0066 (7)	0.0104 (7)
C4B	0.0491 (9)	0.0439 (9)	0.0361 (9)	0.0141 (7)	0.0070 (7)	0.0106 (7)
C5B	0.0495 (10)	0.0476 (10)	0.0389 (9)	0.0172 (8)	0.0032 (7)	0.0143 (7)
C6B	0.0439 (9)	0.0432 (9)	0.0373 (8)	0.0141 (7)	0.0074 (7)	0.0125 (7)
C7B	0.0894 (16)	0.0775 (14)	0.0392 (10)	0.0460 (12)	−0.0002 (10)	0.0078 (9)
C8B	0.141 (3)	0.126 (2)	0.0493 (14)	0.085 (2)	−0.0014 (14)	0.0223 (14)
C9B	0.220 (4)	0.150 (3)	0.0569 (16)	0.141 (3)	0.0197 (19)	0.0344 (17)
C10B	0.0957 (16)	0.0833 (15)	0.0473 (11)	0.0586 (13)	0.0085 (11)	0.0176 (10)
C11B	0.0863 (15)	0.0743 (14)	0.0378 (10)	0.0470 (12)	0.0013 (9)	0.0065 (9)
C12B	0.0500 (9)	0.0447 (9)	0.0377 (9)	0.0163 (7)	0.0062 (7)	0.0105 (7)
C13B	0.0646 (11)	0.0480 (10)	0.0424 (10)	0.0172 (9)	0.0101 (8)	0.0166 (8)
C14B	0.0625 (12)	0.0432 (10)	0.0489 (11)	0.0132 (8)	0.0051 (8)	0.0098 (8)
C15B	0.0531 (10)	0.0502 (10)	0.0384 (9)	0.0186 (8)	0.0019 (7)	0.0073 (7)
C16B	0.0706 (12)	0.0524 (11)	0.0378 (9)	0.0213 (9)	0.0080 (8)	0.0165 (8)
C17B	0.0623 (11)	0.0414 (9)	0.0419 (10)	0.0159 (8)	0.0070 (8)	0.0119 (7)
C18B	0.0397 (8)	0.0428 (9)	0.0405 (9)	0.0129 (7)	0.0071 (7)	0.0142 (7)
C19B	0.0611 (11)	0.0651 (12)	0.0427 (10)	0.0294 (9)	0.0107 (8)	0.0211 (8)
C20B	0.0656 (13)	0.0754 (14)	0.0619 (13)	0.0426 (11)	0.0125 (10)	0.0298 (10)
C21B	0.0558 (11)	0.0543 (11)	0.0672 (13)	0.0291 (9)	0.0181 (9)	0.0157 (9)
C22B	0.0667 (12)	0.0579 (12)	0.0493 (11)	0.0274 (10)	0.0166 (9)	0.0131 (9)
C23B	0.0604 (11)	0.0508 (10)	0.0412 (9)	0.0238 (8)	0.0089 (8)	0.0151 (8)
C24B	0.0931 (17)	0.0963 (18)	0.0416 (11)	0.0446 (14)	0.0099 (11)	0.0139 (11)
C25B	0.0989 (18)	0.0630 (14)	0.0626 (15)	0.0223 (13)	−0.0107 (13)	−0.0108 (11)

Geometric parameters (Å, º) top

Cl1A—C21A	1.741 (2)	Cl1B—C21B	1.7444 (19)
N1A—C6A	1.341 (2)	N1B—C6B	1.342 (2)
N1A—C2A	1.343 (2)	N1B—C2B	1.345 (2)
N2A—C2A	1.355 (2)	N2B—C2B	1.354 (2)
N2A—C10A	1.454 (2)	N2B—C10B	1.455 (2)
N2A—C7A	1.470 (2)	N2B—C7B	1.476 (2)
N3A—C11A	1.147 (2)	N3B—C11B	1.140 (3)
N4A—C15A	1.375 (2)	N4B—C15B	1.386 (2)
N4A—C24A	1.445 (3)	N4B—C25B	1.436 (3)
N4A—C25A	1.447 (3)	N4B—C24B	1.439 (3)
C2A—C3A	1.433 (2)	C2B—C3B	1.432 (2)
C3A—C4A	1.411 (2)	C3B—C4B	1.409 (2)
C3A—C11A	1.430 (2)	C3B—C11B	1.436 (3)
C4A—C5A	1.394 (2)	C4B—C5B	1.392 (2)
C4A—C12A	1.483 (2)	C4B—C12B	1.481 (2)
C5A—C6A	1.396 (2)	C5B—C6B	1.392 (2)
C5A—H5A	0.93	C5B—H5B	0.93
C6A—C18A	1.483 (2)	C6B—C18B	1.488 (2)
C7A—C8A	1.502 (3)	C7B—C8B	1.511 (3)
C7A—H7A	0.97	C7B—H7C	0.97
C7A—H7B	0.97	C7B—H7D	0.97
C8A—C9A	1.505 (3)	C8B—C9B	1.416 (4)
C8A—H8A	0.97	C8B—H8C	0.97
C8A—H8B	0.97	C8B—H8D	0.97
C9A—C10A	1.516 (3)	C9B—C10B	1.516 (3)
C9A—H9A	0.97	C9B—H9C	0.97
C9A—H9B	0.97	C9B—H9D	0.97
C10A—H10A	0.97	C10B—H10C	0.97
C10A—H10B	0.97	C10B—H10D	0.97
C12A—C17A	1.394 (2)	C12B—C13B	1.387 (2)
C12A—C13A	1.397 (2)	C12B—C17B	1.398 (2)
C13A—C14A	1.375 (2)	C13B—C14B	1.377 (3)
C13A—H13A	0.93	C13B—H13B	0.93
C14A—C15A	1.403 (3)	C14B—C15B	1.393 (3)
C14A—H14A	0.93	C14B—H14B	0.93
C15A—C16A	1.406 (3)	C15B—C16B	1.403 (3)
C16A—C17A	1.381 (2)	C16B—C17B	1.376 (2)
C16A—H16A	0.93	C16B—H16B	0.93
C17A—H17A	0.93	C17B—H17B	0.93
C18A—C19A	1.386 (2)	C18B—C19B	1.388 (2)
C18A—C23A	1.396 (2)	C18B—C23B	1.391 (2)
C19A—C20A	1.388 (3)	C19B—C20B	1.383 (3)
C19A—H19A	0.93	C19B—H19B	0.93
C20A—C21A	1.375 (3)	C20B—C21B	1.374 (3)
C20A—H20A	0.93	C20B—H20B	0.93
C21A—C22A	1.378 (3)	C21B—C22B	1.371 (3)
C22A—C23A	1.380 (3)	C22B—C23B	1.383 (2)
C22A—H22A	0.93	C22B—H22B	0.93
C23A—H23A	0.93	C23B—H23B	0.93
C24A—H24A	0.96	C24B—H24D	0.96
C24A—H24B	0.96	C24B—H24E	0.96
C24A—H24C	0.96	C24B—H24F	0.96
C25A—H25A	0.96	C25B—H25D	0.96
C25A—H25B	0.96	C25B—H25E	0.96
C25A—H25C	0.96	C25B—H25F	0.96

C6A—N1A—C2A	120.03 (14)	C6B—N1B—C2B	119.91 (14)
C2A—N2A—C10A	127.52 (15)	C2B—N2B—C10B	128.03 (16)
C2A—N2A—C7A	119.42 (15)	C2B—N2B—C7B	119.39 (15)
C10A—N2A—C7A	112.01 (14)	C10B—N2B—C7B	111.36 (15)
C15A—N4A—C24A	120.53 (19)	C15B—N4B—C25B	120.12 (18)
C15A—N4A—C25A	120.97 (18)	C15B—N4B—C24B	121.23 (18)
C24A—N4A—C25A	117.89 (18)	C25B—N4B—C24B	117.40 (19)
N1A—C2A—N2A	114.81 (14)	N1B—C2B—N2B	114.66 (15)
N1A—C2A—C3A	121.00 (14)	N1B—C2B—C3B	120.71 (15)
N2A—C2A—C3A	124.19 (16)	N2B—C2B—C3B	124.62 (16)
C4A—C3A—C11A	119.50 (14)	C4B—C3B—C2B	118.92 (15)
C4A—C3A—C2A	118.41 (15)	C4B—C3B—C11B	118.55 (16)
C11A—C3A—C2A	121.74 (15)	C2B—C3B—C11B	122.26 (16)
C5A—C4A—C3A	118.23 (14)	C5B—C4B—C3B	118.28 (15)
C5A—C4A—C12A	119.65 (15)	C5B—C4B—C12B	119.68 (15)
C3A—C4A—C12A	122.10 (15)	C3B—C4B—C12B	121.99 (15)
C4A—C5A—C6A	119.77 (15)	C6B—C5B—C4B	119.50 (16)
C4A—C5A—H5A	120.1	C6B—C5B—H5B	120.3
C6A—C5A—H5A	120.1	C4B—C5B—H5B	120.3
N1A—C6A—C5A	122.09 (16)	N1B—C6B—C5B	122.60 (15)
N1A—C6A—C18A	114.99 (14)	N1B—C6B—C18B	115.00 (14)
C5A—C6A—C18A	122.89 (15)	C5B—C6B—C18B	122.37 (15)
N2A—C7A—C8A	104.21 (17)	N2B—C7B—C8B	103.24 (17)
N2A—C7A—H7A	110.9	N2B—C7B—H7C	111.1
C8A—C7A—H7A	110.9	C8B—C7B—H7C	111.1
N2A—C7A—H7B	110.9	N2B—C7B—H7D	111.1
C8A—C7A—H7B	110.9	C8B—C7B—H7D	111.1
H7A—C7A—H7B	108.9	H7C—C7B—H7D	109.1
C7A—C8A—C9A	105.59 (18)	C9B—C8B—C7B	106.3 (2)
C7A—C8A—H8A	110.6	C9B—C8B—H8C	110.5
C9A—C8A—H8A	110.6	C7B—C8B—H8C	110.5
C7A—C8A—H8B	110.6	C9B—C8B—H8D	110.5
C9A—C8A—H8B	110.6	C7B—C8B—H8D	110.5
H8A—C8A—H8B	108.8	H8C—C8B—H8D	108.7
C8A—C9A—C10A	104.69 (17)	C8B—C9B—C10B	107.5 (2)
C8A—C9A—H9A	110.8	C8B—C9B—H9C	110.2
C10A—C9A—H9A	110.8	C10B—C9B—H9C	110.2
C8A—C9A—H9B	110.8	C8B—C9B—H9D	110.2
C10A—C9A—H9B	110.8	C10B—C9B—H9D	110.2
H9A—C9A—H9B	108.9	H9C—C9B—H9D	108.5
N2A—C10A—C9A	104.13 (16)	N2B—C10B—C9B	102.85 (17)
N2A—C10A—H10A	110.9	N2B—C10B—H10C	111.2
C9A—C10A—H10A	110.9	C9B—C10B—H10C	111.2
N2A—C10A—H10B	110.9	N2B—C10B—H10D	111.2
C9A—C10A—H10B	110.9	C9B—C10B—H10D	111.2
H10A—C10A—H10B	108.9	H10C—C10B—H10D	109.1
N3A—C11A—C3A	176.9 (2)	N3B—C11B—C3B	176.5 (3)
C17A—C12A—C13A	116.61 (15)	C13B—C12B—C17B	116.67 (16)
C17A—C12A—C4A	121.11 (15)	C13B—C12B—C4B	122.05 (15)
C13A—C12A—C4A	122.12 (15)	C17B—C12B—C4B	121.18 (15)
C14A—C13A—C12A	121.95 (16)	C14B—C13B—C12B	122.01 (17)
C14A—C13A—H13A	119.0	C14B—C13B—H13B	119.0
C12A—C13A—H13A	119.0	C12B—C13B—H13B	119.0
C13A—C14A—C15A	121.57 (17)	C13B—C14B—C15B	121.53 (17)
C13A—C14A—H14A	119.2	C13B—C14B—H14B	119.2
C15A—C14A—H14A	119.2	C15B—C14B—H14B	119.2
N4A—C15A—C14A	121.53 (18)	N4B—C15B—C14B	121.75 (17)
N4A—C15A—C16A	121.83 (17)	N4B—C15B—C16B	121.56 (17)
C14A—C15A—C16A	116.62 (16)	C14B—C15B—C16B	116.69 (16)
C17A—C16A—C15A	121.15 (16)	C17B—C16B—C15B	121.35 (17)
C17A—C16A—H16A	119.4	C17B—C16B—H16B	119.3
C15A—C16A—H16A	119.4	C15B—C16B—H16B	119.3
C16A—C17A—C12A	122.06 (17)	C16B—C17B—C12B	121.71 (17)
C16A—C17A—H17A	119.0	C16B—C17B—H17B	119.1
C12A—C17A—H17A	119.0	C12B—C17B—H17B	119.1
C19A—C18A—C23A	118.05 (16)	C19B—C18B—C23B	118.05 (16)
C19A—C18A—C6A	122.17 (15)	C19B—C18B—C6B	122.85 (15)
C23A—C18A—C6A	119.77 (15)	C23B—C18B—C6B	119.10 (15)
C18A—C19A—C20A	121.30 (17)	C20B—C19B—C18B	120.82 (18)
C18A—C19A—H19A	119.3	C20B—C19B—H19B	119.6
C20A—C19A—H19A	119.3	C18B—C19B—H19B	119.6
C21A—C20A—C19A	119.02 (18)	C21B—C20B—C19B	119.47 (18)
C21A—C20A—H20A	120.5	C21B—C20B—H20B	120.3
C19A—C20A—H20A	120.5	C19B—C20B—H20B	120.3
C20A—C21A—C22A	121.25 (18)	C22B—C21B—C20B	121.33 (17)
C20A—C21A—Cl1A	119.70 (16)	C22B—C21B—Cl1B	118.91 (16)
C22A—C21A—Cl1A	119.05 (16)	C20B—C21B—Cl1B	119.75 (16)
C21A—C22A—C23A	119.14 (18)	C21B—C22B—C23B	118.78 (18)
C21A—C22A—H22A	120.4	C21B—C22B—H22B	120.6
C23A—C22A—H22A	120.4	C23B—C22B—H22B	120.6
C22A—C23A—C18A	121.24 (17)	C22B—C23B—C18B	121.50 (17)
C22A—C23A—H23A	119.4	C22B—C23B—H23B	119.2
C18A—C23A—H23A	119.4	C18B—C23B—H23B	119.2
N4A—C24A—H24A	109.5	N4B—C24B—H24D	109.5
N4A—C24A—H24B	109.5	N4B—C24B—H24E	109.5
H24A—C24A—H24B	109.5	H24D—C24B—H24E	109.5
N4A—C24A—H24C	109.5	N4B—C24B—H24F	109.5
H24A—C24A—H24C	109.5	H24D—C24B—H24F	109.5
H24B—C24A—H24C	109.5	H24E—C24B—H24F	109.5
N4A—C25A—H25A	109.5	N4B—C25B—H25D	109.5
N4A—C25A—H25B	109.5	N4B—C25B—H25E	109.5
H25A—C25A—H25B	109.5	H25D—C25B—H25E	109.5
N4A—C25A—H25C	109.5	N4B—C25B—H25F	109.5
H25A—C25A—H25C	109.5	H25D—C25B—H25F	109.5
H25B—C25A—H25C	109.5	H25E—C25B—H25F	109.5

C6A—N1A—C2A—N2A	175.55 (15)	C6B—N1B—C2B—N2B	179.49 (16)
C6A—N1A—C2A—C3A	−4.6 (2)	C6B—N1B—C2B—C3B	−0.9 (3)
C10A—N2A—C2A—N1A	−168.95 (17)	C10B—N2B—C2B—N1B	−169.62 (19)
C7A—N2A—C2A—N1A	−1.7 (2)	C7B—N2B—C2B—N1B	−3.4 (3)
C10A—N2A—C2A—C3A	11.2 (3)	C10B—N2B—C2B—C3B	10.8 (3)
C7A—N2A—C2A—C3A	178.52 (16)	C7B—N2B—C2B—C3B	177.07 (18)
N1A—C2A—C3A—C4A	8.1 (2)	N1B—C2B—C3B—C4B	2.1 (3)
N2A—C2A—C3A—C4A	−172.10 (16)	N2B—C2B—C3B—C4B	−178.35 (18)
N1A—C2A—C3A—C11A	−165.16 (15)	N1B—C2B—C3B—C11B	−171.72 (19)
N2A—C2A—C3A—C11A	14.7 (3)	N2B—C2B—C3B—C11B	7.8 (3)
C11A—C3A—C4A—C5A	167.86 (16)	C2B—C3B—C4B—C5B	−3.1 (3)
C2A—C3A—C4A—C5A	−5.5 (2)	C11B—C3B—C4B—C5B	170.93 (18)
C11A—C3A—C4A—C12A	−13.7 (2)	C2B—C3B—C4B—C12B	174.50 (15)
C2A—C3A—C4A—C12A	172.88 (15)	C11B—C3B—C4B—C12B	−11.4 (3)
C3A—C4A—C5A—C6A	−0.1 (2)	C3B—C4B—C5B—C6B	3.1 (3)
C12A—C4A—C5A—C6A	−178.52 (15)	C12B—C4B—C5B—C6B	−174.62 (15)
C2A—N1A—C6A—C5A	−1.3 (2)	C2B—N1B—C6B—C5B	0.9 (3)
C2A—N1A—C6A—C18A	−179.35 (14)	C2B—N1B—C6B—C18B	−177.10 (15)
C4A—C5A—C6A—N1A	3.7 (2)	C4B—C5B—C6B—N1B	−2.0 (3)
C4A—C5A—C6A—C18A	−178.42 (15)	C4B—C5B—C6B—C18B	175.85 (15)
C2A—N2A—C7A—C8A	−176.48 (18)	C2B—N2B—C7B—C8B	−176.8 (2)
C10A—N2A—C7A—C8A	−7.3 (2)	C10B—N2B—C7B—C8B	−8.4 (3)
N2A—C7A—C8A—C9A	23.7 (2)	N2B—C7B—C8B—C9B	24.0 (3)
C7A—C8A—C9A—C10A	−31.2 (3)	C7B—C8B—C9B—C10B	−30.8 (4)
C2A—N2A—C10A—C9A	156.24 (18)	C2B—N2B—C10B—C9B	158.1 (2)
C7A—N2A—C10A—C9A	−11.8 (2)	C7B—N2B—C10B—C9B	−9.1 (3)
C8A—C9A—C10A—N2A	26.2 (2)	C8B—C9B—C10B—N2B	24.7 (4)
C5A—C4A—C12A—C17A	−42.0 (2)	C5B—C4B—C12B—C13B	128.23 (19)
C3A—C4A—C12A—C17A	139.55 (18)	C3B—C4B—C12B—C13B	−49.4 (3)
C5A—C4A—C12A—C13A	133.25 (18)	C5B—C4B—C12B—C17B	−47.9 (2)
C3A—C4A—C12A—C13A	−45.2 (2)	C3B—C4B—C12B—C17B	134.50 (19)
C17A—C12A—C13A—C14A	0.9 (3)	C17B—C12B—C13B—C14B	−0.3 (3)
C4A—C12A—C13A—C14A	−174.58 (16)	C4B—C12B—C13B—C14B	−176.56 (17)
C12A—C13A—C14A—C15A	−1.4 (3)	C12B—C13B—C14B—C15B	−1.7 (3)
C24A—N4A—C15A—C14A	−179.0 (2)	C25B—N4B—C15B—C14B	−2.5 (3)
C25A—N4A—C15A—C14A	−8.1 (3)	C24B—N4B—C15B—C14B	164.4 (2)
C24A—N4A—C15A—C16A	2.6 (3)	C25B—N4B—C15B—C16B	176.8 (2)
C25A—N4A—C15A—C16A	173.49 (19)	C24B—N4B—C15B—C16B	−16.4 (3)
C13A—C14A—C15A—N4A	−178.23 (17)	C13B—C14B—C15B—N4B	−178.31 (19)
C13A—C14A—C15A—C16A	0.3 (3)	C13B—C14B—C15B—C16B	2.4 (3)
N4A—C15A—C16A—C17A	179.74 (17)	N4B—C15B—C16B—C17B	179.46 (19)
C14A—C15A—C16A—C17A	1.3 (3)	C14B—C15B—C16B—C17B	−1.2 (3)
C15A—C16A—C17A—C12A	−1.7 (3)	C15B—C16B—C17B—C12B	−0.7 (3)
C13A—C12A—C17A—C16A	0.6 (3)	C13B—C12B—C17B—C16B	1.4 (3)
C4A—C12A—C17A—C16A	176.17 (17)	C4B—C12B—C17B—C16B	177.76 (17)
N1A—C6A—C18A—C19A	−167.70 (15)	N1B—C6B—C18B—C19B	−166.42 (17)
C5A—C6A—C18A—C19A	14.3 (2)	C5B—C6B—C18B—C19B	15.6 (3)
N1A—C6A—C18A—C23A	12.1 (2)	N1B—C6B—C18B—C23B	12.9 (2)
C5A—C6A—C18A—C23A	−165.89 (16)	C5B—C6B—C18B—C23B	−165.10 (16)
C23A—C18A—C19A—C20A	−0.1 (3)	C23B—C18B—C19B—C20B	−2.5 (3)
C6A—C18A—C19A—C20A	179.66 (16)	C6B—C18B—C19B—C20B	176.84 (17)
C18A—C19A—C20A—C21A	0.5 (3)	C18B—C19B—C20B—C21B	1.4 (3)
C19A—C20A—C21A—C22A	−0.7 (3)	C19B—C20B—C21B—C22B	0.2 (3)
C19A—C20A—C21A—Cl1A	179.11 (15)	C19B—C20B—C21B—Cl1B	−178.85 (17)
C20A—C21A—C22A—C23A	0.4 (3)	C20B—C21B—C22B—C23B	−0.7 (3)
Cl1A—C21A—C22A—C23A	−179.40 (15)	Cl1B—C21B—C22B—C23B	178.37 (15)
C21A—C22A—C23A—C18A	0.0 (3)	C21B—C22B—C23B—C18B	−0.4 (3)
C19A—C18A—C23A—C22A	−0.2 (3)	C19B—C18B—C23B—C22B	2.0 (3)
C6A—C18A—C23A—C22A	−179.97 (16)	C6B—C18B—C23B—C22B	−177.35 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C19B—H19B···N3A	0.93	2.55	3.461 (3)	167
C19A—H19A···N3Bⁱ	0.93	2.47	3.378 (3)	164
C24B—H24F···N3Aⁱⁱ	0.96	2.59	3.457 (3)	150
C23A—H23A···N1A	0.93	2.42	2.755 (2)	101
C23B—H23B···N1B	0.93	2.41	2.745 (3)	101

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

Experimental details

Crystal data
Chemical formula	C₂₄H₂₃ClN₄
M_r	402.91
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	11.1490 (1), 13.7330 (1), 14.6666 (1)
α, β, γ (°)	100.487 (1), 93.240 (1), 107.014 (1)
V (Å³)	2096.93 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.20
Crystal size (mm)	0.48 × 0.44 × 0.26

Data collection
Diffractometer	Siemens SMART CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	14581, 9579, 6307
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.160, 0.97
No. of reflections	9579
No. of parameters	527
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.32

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ZORTEP (Zsolnai, 1997), SHELXL97 and PARST (Nardelli, 1983, 1995).

Selected geometric parameters (Å, º) top

N2A—C2A	1.355 (2)	N2B—C7B	1.476 (2)
N2A—C10A	1.454 (2)	N4B—C15B	1.386 (2)
N2A—C7A	1.470 (2)	N4B—C25B	1.436 (3)
N4A—C15A	1.375 (2)	N4B—C24B	1.439 (3)
N4A—C24A	1.445 (3)	C7B—C8B	1.511 (3)
N4A—C25A	1.447 (3)	C8B—C9B	1.416 (4)
N2B—C2B	1.354 (2)	C9B—C10B	1.516 (3)
N2B—C10B	1.455 (2)

N1A—C2A—N2A	114.81 (14)	N1B—C2B—N2B	114.66 (15)
N2A—C2A—C3A	124.19 (16)	N2B—C2B—C3B	124.62 (16)
N1A—C6A—C18A	114.99 (14)	N1B—C6B—C18B	115.00 (14)
C5A—C6A—C18A	122.89 (15)	C5B—C6B—C18B	122.37 (15)