C—Halogen...π interactions in 4-chloro-2-(9-ethyl­carbazol-3-yl)-1,2-dihydroquinoline-1-carb­aldehyde

The title compound, C₂₄H₁₉ClN₂O, consists of a carbazole skeleton with ethyl and 4-chloroquinoline-N-aldehyde substit­uents. The di­hydro­pyridine ring adopts a half-chair conform­ation. The molecular packing is stabilized by C—Cl...π interactions.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.049
• wR factor = 0.141
• Data-to-parameter ratio = 15.0

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT029_ALERT_3_A _diffrn_measured_fraction_theta_full Low .......       0.90

Alert level B
REFLT03_ALERT_3_B  Reflection count < 90% complete (theta max?)
           From the CIF: _diffrn_reflns_theta_max           28.01
           From the CIF: _diffrn_reflns_theta_full           0.00
           From the CIF: _reflns_number_total               4119
           TEST2: Reflns within _diffrn_reflns_theta_max
           Count of symmetry unique reflns         4583
           Completeness (_total/calc)             89.88%

Alert level C
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.57 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.21 Ratio
PLAT242_ALERT_2_C Check Low    U(eq) as Compared to Neighbors ....        C9B
PLAT301_ALERT_3_C Main Residue  Disorder .........................       7.00 Perc.

   1 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion

---

Computing details

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) and PLATON (Spek, 1990); software used to prepare material for publication: SHELXL97 and PARST (Nardelli, 1995).

C-halogen···π interaction: 4-Chloro-2-(9-ethylcarbazol-3-yl)quinoline-1(2H)- carbaldehyde.

Crystal data

C24H19ClN2O	Z = 2
Mr = 386.86	F(000) = 404
Triclinic, P1	Dx = 1.356 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.4147 (8) Å	Cell parameters from 2301 reflections
b = 9.6714 (8) Å	θ = 2.3–27.3°
c = 11.1245 (9) Å	µ = 0.22 mm^−1
α = 85.336 (1)°	T = 293 K
β = 70.235 (1)°	Needle, colourless
γ = 84.351 (2)°	0.24 × 0.18 × 0.12 mm
V = 947.37 (14) Å^3

Data collection

Siemens SMART CCD area detector diffractometer	3187 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.017
Graphite monochromator	θmax = 28.0°, θmin = 2.0°
ω scans	h = −11→11
5918 measured reflections	k = −12→12
4119 independent reflections	l = −14→9

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.141	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0818P)^2 + 0.0963P] where P = (Fo^2 + 2Fc^2)/3
4119 reflections	(Δ/σ)max = 0.001
274 parameters	Δρmax = 0.28 e Å^−3
0 restraints	Δρmin = −0.16 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cl1	0.09873 (7)	1.12653 (5)	0.15707 (5)	0.0698 (2)
O1	0.43464 (15)	0.58798 (15)	−0.15635 (13)	0.0670 (4)
N1	−0.11123 (19)	0.34051 (19)	0.40043 (18)	0.0683 (5)
C1	−0.1116 (2)	0.5125 (2)	0.2187 (2)	0.0587 (5)
H1	−0.2102	0.5016	0.2228	0.070*
C1A	−0.0486 (2)	0.43800 (18)	0.30247 (18)	0.0520 (4)
C2	−0.0232 (2)	0.60329 (19)	0.12899 (18)	0.0517 (4)
H2	−0.0629	0.6530	0.0709	0.062*
C3	0.12533 (18)	0.62301 (16)	0.12273 (15)	0.0416 (4)
C4	0.18811 (18)	0.54624 (15)	0.20539 (15)	0.0401 (3)
H4	0.2867	0.5577	0.2011	0.048*
C4A	0.10195 (18)	0.45140 (16)	0.29532 (15)	0.0419 (4)
C5	0.2583 (2)	0.31688 (19)	0.42779 (17)	0.0543 (4)
H5	0.3487	0.3579	0.3865	0.065*
C5A	0.13211 (19)	0.35540 (17)	0.39217 (15)	0.0453 (4)
C6	0.2482 (3)	0.2166 (2)	0.52573 (19)	0.0676 (6)
H6	0.3324	0.1899	0.5504	0.081*
C7	0.1124 (3)	0.1549 (2)	0.5879 (2)	0.0734 (6)
H7	0.1075	0.0883	0.6542	0.088*
C8	−0.0125 (3)	0.1898 (2)	0.5540 (2)	0.0703 (6)
H8	−0.1021	0.1476	0.5957	0.084*
C8A	−0.0034 (2)	0.2901 (2)	0.45538 (18)	0.0561 (5)
C9A	−0.2762 (7)	0.3251 (7)	0.4616 (7)	0.0659 (19)	0.484 (8)
H9A	−0.3345	0.4083	0.4449	0.079*	0.484 (8)
H9B	−0.3018	0.3084	0.5534	0.079*	0.484 (8)
C10A	−0.3076 (6)	0.2029 (6)	0.4029 (5)	0.0791 (19)	0.484 (8)
H10A	−0.2853	0.2227	0.3127	0.119*	0.484 (8)
H10B	−0.4123	0.1850	0.4416	0.119*	0.484 (8)
H10C	−0.2453	0.1227	0.4168	0.119*	0.484 (8)
C9B	−0.2572 (8)	0.2771 (7)	0.4206 (7)	0.0691 (17)	0.516 (8)
H9C	−0.2822	0.2850	0.3424	0.083*	0.516 (8)
H9D	−0.2506	0.1796	0.4481	0.083*	0.516 (8)
C10B	−0.3732 (7)	0.3585 (7)	0.5226 (7)	0.103 (2)	0.516 (8)
H10D	−0.3599	0.3331	0.6036	0.154*	0.516 (8)
H10E	−0.4726	0.3386	0.5266	0.154*	0.516 (8)
H10F	−0.3614	0.4561	0.5030	0.154*	0.516 (8)
C11	0.20888 (18)	0.73320 (16)	0.02609 (15)	0.0430 (4)
H11	0.2010	0.7157	−0.0569	0.052*
C12	0.1339 (2)	0.87624 (17)	0.06181 (17)	0.0494 (4)
H12	0.0432	0.9035	0.0474	0.059*
C13	0.1939 (2)	0.96398 (16)	0.11316 (16)	0.0480 (4)
C14	0.3342 (2)	0.93001 (16)	0.13989 (15)	0.0460 (4)
C15	0.3859 (2)	1.0075 (2)	0.21574 (18)	0.0600 (5)
H15	0.3293	1.0876	0.2512	0.072*
C16	0.5189 (3)	0.9670 (2)	0.2385 (2)	0.0706 (6)
H16	0.5524	1.0206	0.2878	0.085*
C17	0.6030 (3)	0.8471 (2)	0.1887 (2)	0.0671 (5)
H17	0.6935	0.8209	0.2037	0.081*
C18	0.5531 (2)	0.7658 (2)	0.11633 (18)	0.0539 (4)
H18	0.6077	0.6830	0.0860	0.065*
C19	0.42161 (19)	0.80795 (17)	0.08919 (15)	0.0435 (4)
N20	0.37072 (15)	0.73058 (13)	0.00993 (12)	0.0422 (3)
C21	0.4711 (2)	0.65973 (18)	−0.08888 (17)	0.0507 (4)
H21	0.5738	0.6670	−0.1055	0.061*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0821 (4)	0.0428 (3)	0.0766 (4)	0.0104 (2)	−0.0184 (3)	−0.0106 (2)
O1	0.0611 (8)	0.0675 (9)	0.0684 (9)	−0.0077 (7)	−0.0100 (7)	−0.0277 (7)
N1	0.0474 (9)	0.0711 (11)	0.0782 (11)	−0.0233 (8)	−0.0099 (8)	0.0174 (9)
C1	0.0393 (9)	0.0595 (11)	0.0771 (13)	−0.0107 (8)	−0.0183 (9)	0.0010 (9)
C1A	0.0447 (9)	0.0476 (9)	0.0584 (10)	−0.0107 (7)	−0.0086 (8)	−0.0005 (8)
C2	0.0457 (10)	0.0513 (10)	0.0606 (11)	−0.0019 (7)	−0.0213 (8)	−0.0024 (8)
C3	0.0426 (9)	0.0368 (8)	0.0432 (8)	−0.0038 (6)	−0.0102 (7)	−0.0059 (6)
C4	0.0386 (8)	0.0377 (8)	0.0427 (8)	−0.0055 (6)	−0.0104 (6)	−0.0061 (6)
C4A	0.0425 (9)	0.0367 (8)	0.0432 (8)	−0.0070 (6)	−0.0078 (7)	−0.0069 (6)
C5	0.0615 (11)	0.0567 (11)	0.0442 (9)	−0.0127 (8)	−0.0156 (8)	0.0014 (8)
C5A	0.0519 (10)	0.0408 (8)	0.0388 (8)	−0.0105 (7)	−0.0069 (7)	−0.0048 (6)
C6	0.0797 (15)	0.0723 (14)	0.0509 (11)	−0.0089 (11)	−0.0237 (10)	0.0090 (10)
C7	0.0952 (17)	0.0652 (13)	0.0514 (11)	−0.0148 (12)	−0.0151 (11)	0.0147 (9)
C8	0.0750 (14)	0.0645 (13)	0.0594 (12)	−0.0230 (11)	−0.0052 (10)	0.0111 (10)
C8A	0.0576 (11)	0.0510 (10)	0.0519 (10)	−0.0127 (8)	−0.0062 (8)	0.0004 (8)
C9A	0.047 (4)	0.056 (4)	0.078 (5)	−0.012 (3)	0.005 (4)	−0.007 (3)
C10A	0.058 (3)	0.078 (4)	0.100 (4)	−0.024 (3)	−0.019 (3)	−0.010 (3)
C9B	0.065 (4)	0.066 (4)	0.073 (4)	−0.032 (4)	−0.010 (3)	−0.005 (3)
C10B	0.056 (4)	0.123 (5)	0.110 (4)	−0.025 (3)	0.008 (3)	−0.024 (4)
C11	0.0460 (9)	0.0399 (8)	0.0421 (8)	−0.0033 (6)	−0.0136 (7)	−0.0013 (6)
C12	0.0507 (10)	0.0419 (9)	0.0521 (10)	0.0002 (7)	−0.0151 (8)	0.0042 (7)
C13	0.0571 (10)	0.0351 (8)	0.0439 (9)	−0.0011 (7)	−0.0076 (7)	0.0008 (7)
C14	0.0551 (10)	0.0392 (8)	0.0388 (8)	−0.0101 (7)	−0.0085 (7)	0.0023 (6)
C15	0.0774 (14)	0.0483 (10)	0.0530 (11)	−0.0133 (9)	−0.0169 (9)	−0.0063 (8)
C16	0.0865 (16)	0.0694 (14)	0.0677 (13)	−0.0213 (12)	−0.0356 (12)	−0.0097 (10)
C17	0.0667 (13)	0.0736 (14)	0.0700 (13)	−0.0153 (10)	−0.0326 (10)	0.0003 (11)
C18	0.0531 (10)	0.0510 (10)	0.0558 (10)	−0.0075 (8)	−0.0155 (8)	0.0007 (8)
C19	0.0461 (9)	0.0414 (8)	0.0397 (8)	−0.0122 (7)	−0.0088 (7)	0.0028 (6)
N20	0.0441 (7)	0.0374 (7)	0.0411 (7)	−0.0066 (5)	−0.0084 (6)	−0.0010 (5)
C21	0.0474 (10)	0.0461 (9)	0.0527 (10)	−0.0069 (7)	−0.0070 (8)	−0.0069 (8)

Geometric parameters (Å, º)

Cl1—C13	1.751 (2)	C9A—H9B	0.9700
O1—C21	1.212 (2)	C10A—H10A	0.9600
N1—C8A	1.384 (3)	C10A—H10B	0.9600
N1—C1A	1.390 (2)	C10A—H10C	0.9600
N1—C9A	1.487 (7)	C9B—C10B	1.495 (8)
N1—C9B	1.500 (7)	C9B—H9C	0.9700
C1—C2	1.378 (3)	C9B—H9D	0.9700
C1—C1A	1.386 (3)	C10B—H10D	0.9601
C1—H1	0.9300	C10B—H10E	0.9601
C1A—C4A	1.410 (2)	C10B—H10F	0.9601
C2—C3	1.408 (2)	C11—N20	1.471 (2)
C2—H2	0.9300	C11—C12	1.509 (2)
C3—C4	1.384 (2)	C11—H11	0.9800
C3—C11	1.522 (2)	C12—C13	1.326 (3)
C4—C4A	1.396 (2)	C12—H12	0.9300
C4—H4	0.9300	C13—C14	1.450 (3)
C4A—C5A	1.448 (2)	C14—C15	1.401 (3)
C5—C5A	1.384 (3)	C14—C19	1.412 (2)
C5—C6	1.383 (3)	C15—C16	1.374 (3)
C5—H5	0.9300	C15—H15	0.9300
C5A—C8A	1.414 (2)	C16—C17	1.380 (3)
C6—C7	1.398 (3)	C16—H16	0.9300
C6—H6	0.9300	C17—C18	1.385 (3)
C7—C8	1.357 (3)	C17—H17	0.9300
C7—H7	0.9300	C18—C19	1.387 (3)
C8—C8A	1.390 (3)	C18—H18	0.9300
C8—H8	0.9300	C19—N20	1.425 (2)
C9A—C10A	1.494 (8)	N20—C21	1.365 (2)
C9A—H9A	0.9700	C21—H21	0.9300
C8A—N1—C1A	108.9 (2)	C10B—C9B—H9C	110.8
C8A—N1—C9A	123.9 (3)	N1—C9B—H9C	110.8
C1A—N1—C9A	124.8 (3)	C10B—C9B—H9D	110.8
C8A—N1—C9B	125.4 (3)	N1—C9B—H9D	110.8
C2—C1—C1A	117.8 (2)	H9C—C9B—H9D	108.8
C2—C1—H1	121.1	C9B—C10B—H10D	109.5
C1A—C1—H1	121.1	C9B—C10B—H10E	109.5
C1—C1A—N1	129.7 (2)	H10D—C10B—H10E	109.5
C1—C1A—C4A	121.6 (2)	C9B—C10B—H10F	109.5
N1—C1A—C4A	108.7 (2)	H10D—C10B—H10F	109.5
C1—C2—C3	121.9 (2)	H10E—C10B—H10F	109.5
C1—C2—H2	119.0	N20—C11—C12	109.7 (1)
C3—C2—H2	119.0	N20—C11—C3	113.9 (1)
C4—C3—C2	119.8 (2)	C12—C11—C3	110.4 (1)
C4—C3—C11	122.6 (2)	N20—C11—H11	107.5
C2—C3—C11	117.5 (2)	C12—C11—H11	107.5
C3—C4—C4A	119.3 (2)	C3—C11—H11	107.5
C3—C4—H4	120.3	C13—C12—C11	121.7 (2)
C4A—C4—H4	120.3	C13—C12—H12	119.2
C4—C4A—C1A	119.5 (2)	C11—C12—H12	119.2
C4—C4A—C5A	133.6 (2)	C12—C13—C14	123.0 (2)
C1A—C4A—C5A	107.0 (1)	C12—C13—Cl1	119.6 (2)
C5A—C5—C6	119.1 (2)	C14—C13—Cl1	117.4 (1)
C5A—C5—H5	120.5	C15—C14—C19	118.0 (2)
C6—C5—H5	120.5	C15—C14—C13	124.5 (2)
C5—C5A—C8A	119.3 (2)	C19—C14—C13	117.5 (2)
C5—C5A—C4A	134.3 (2)	C16—C15—C14	121.0 (2)
C8A—C5A—C4A	106.3 (2)	C16—C15—H15	119.5
C5—C6—C7	120.5 (2)	C14—C15—H15	119.5
C5—C6—H6	119.7	C15—C16—C17	120.4 (2)
C7—C6—H6	119.7	C15—C16—H16	119.8
C8—C7—C6	121.6 (2)	C17—C16—H16	119.8
C8—C7—H7	119.2	C16—C17—C18	120.2 (2)
C6—C7—H7	119.2	C16—C17—H17	119.9
C7—C8—C8A	118.4 (2)	C18—C17—H17	119.9
C7—C8—H8	120.8	C17—C18—C19	119.9 (2)
C8A—C8—H8	120.8	C17—C18—H18	120.0
N1—C8A—C8	129.8 (2)	C19—C18—H18	120.0
N1—C8A—C5A	109.1 (2)	C18—C19—C14	120.4 (2)
C8—C8A—C5A	121.1 (2)	C18—C19—N20	121.5 (2)
N1—C9A—C10A	105.6 (4)	C14—C19—N20	118.1 (2)
N1—C9A—H9A	110.6	C21—N20—C19	121.1 (2)
C10A—C9A—H9A	110.6	C21—N20—C11	117.9 (2)
N1—C9A—H9B	110.6	C19—N20—C11	120.9 (2)
C10A—C9A—H9B	110.6	O1—C21—N20	124.1 (2)
H9A—C9A—H9B	108.8	O1—C21—H21	118.0
C10B—C9B—N1	105.0 (5)	N20—C21—H21	118.0
C2—C1—C1A—N1	−179.7 (2)	C8A—N1—C9A—C10A	−98.2 (6)
C2—C1—C1A—C4A	−1.4 (3)	C1A—N1—C9A—C10A	101.3 (5)
C8A—N1—C1A—C1	177.9 (2)	C9B—N1—C9A—C10A	3.6 (9)
C9A—N1—C1A—C1	−19.2 (5)	C8A—N1—C9B—C10B	97.1 (6)
C9B—N1—C1A—C1	11.2 (4)	C1A—N1—C9B—C10B	−98.5 (5)
C8A—N1—C1A—C4A	−0.6 (2)	C9A—N1—C9B—C10B	1.3 (9)
C9A—N1—C1A—C4A	162.3 (4)	C4—C3—C11—N20	12.0 (2)
C9B—N1—C1A—C4A	−167.2 (3)	C2—C3—C11—N20	−169.9 (1)
C1A—C1—C2—C3	−1.1 (3)	C4—C3—C11—C12	−111.9 (2)
C1—C2—C3—C4	2.3 (3)	C2—C3—C11—C12	66.2 (2)
C1—C2—C3—C11	−175.8 (2)	N20—C11—C12—C13	−21.5 (2)
C2—C3—C4—C4A	−0.9 (2)	C3—C11—C12—C13	104.8 (2)
C11—C3—C4—C4A	177.1 (1)	C11—C12—C13—C14	−0.5 (3)
C3—C4—C4A—C1A	−1.6 (2)	C11—C12—C13—Cl1	−178.1 (1)
C3—C4—C4A—C5A	178.9 (2)	C12—C13—C14—C15	−167.0 (1)
C1—C1A—C4A—C4	2.8 (3)	Cl1—C13—C14—C15	10.6 (2)
N1—C1A—C4A—C4	−178.6 (2)	C12—C13—C14—C19	10.9 (2)
C1—C1A—C4A—C5A	−177.5 (2)	Cl1—C13—C14—C19	−171.5 (1)
N1—C1A—C4A—C5A	1.1 (2)	C19—C14—C15—C16	0.9 (3)
C6—C5—C5A—C8A	−0.9 (3)	C13—C14—C15—C16	178.8 (2)
C6—C5—C5A—C4A	−178.5 (2)	C14—C15—C16—C17	−1.2 (3)
C4—C4A—C5A—C5	−3.7 (3)	C15—C16—C17—C18	−0.7 (3)
C1A—C4A—C5A—C5	176.7 (2)	C16—C17—C18—C19	2.8 (3)
C4—C4A—C5A—C8A	178.5 (2)	C17—C18—C19—C14	−3.0 (3)
C1A—C4A—C5A—C8A	−1.1 (2)	C17—C18—C19—N20	176.9 (2)
C5A—C5—C6—C7	0.0 (3)	C15—C14—C19—C18	1.2 (2)
C5—C6—C7—C8	0.7 (3)	C13—C14—C19—C18	−176.8 (2)
C6—C7—C8—C8A	−0.4 (3)	C15—C14—C19—N20	−178.8 (1)
C1A—N1—C8A—C8	−178.5 (2)	C13—C14—C19—N20	3.2 (2)
C9A—N1—C8A—C8	18.4 (4)	C18—C19—N20—C21	−32.7 (2)
C9B—N1—C8A—C8	−12.1 (5)	C14—C19—N20—C21	147.2 (2)
C1A—N1—C8A—C5A	−0.1 (2)	C18—C19—N20—C11	151.9 (2)
C9A—N1—C8A—C5A	−163.2 (3)	C14—C19—N20—C11	−28.2 (2)
C9B—N1—C8A—C5A	166.3 (3)	C12—C11—N20—C21	−139.7 (2)
C7—C8—C8A—N1	177.8 (2)	C3—C11—N20—C21	96.0 (2)
C7—C8—C8A—C5A	−0.5 (3)	C12—C11—N20—C19	35.8 (2)
C5—C5A—C8A—N1	−177.4 (2)	C3—C11—N20—C19	−88.5 (2)
C4A—C5A—C8A—N1	0.8 (2)	C19—N20—C21—O1	177.1 (2)
C5—C5A—C8A—C8	1.1 (3)	C11—N20—C21—O1	−7.4 (3)
C4A—C5A—C8A—C8	179.4 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···N20	0.93	2.55	2.882 (2)	102
C11—H11···O1	0.98	2.37	2.751 (2)	102
C15—H15···Cl1	0.93	2.69	3.085 (2)	106