3-(4-Chloro­benzoyl)-7-(N,N-di­methyl­amino)-1-phenyl­indolizine and 3-(2,4-di­chloro­benzoyl)-7-(N,N-di­methyl­amino)-1-phenyl­indolizine

In both of the title compounds, C₂₃H₁₉ClN₂O, (I), and C₂₃H₁₈Cl₂N₂O, (II), the molecular packing is influenced by weak intermolecular C-H...O and C-H...[pi] interactions, but despite the chemical similarity of the compounds, the packing in (II) is entirely different from that observed in (I).

S1. Comment

The indolizines constitute the core structure of many naturally occurring alkaloids, viz. (-)-slaframine (Pourashraf et al., 2000; Cossy et al., 2002), (-)-dendroprimine (Diederich & Nubbemeyer, 1999), indalozin 167B (Chalard et al., 1999) and coniceine (Park et al., 2001). Heterocyclic compounds, such as indolizines, are important bioactive compounds that have wide applications in biology, pharmacology and agrochemistry (Wu & Chen, 2003, and references therein). The synthesis of biologically active indolizines (Gubin et al., 1992) continues to attract the attention of organic chemists (Bora et al., 2003, and references therein), because they are important as potential central nervous depressants, calcium entry blockers, cardiovascular agents, spectral sensitizers and novel dyes (Katritzky et al., 1999, and references therein). They are also used for the treatment of angina pectoris (Rosseels et al., 1982) and as testosterone 5α-reductase inhibitors (Okada et al., 1993). In view of these important attributes, we report here the crystal structures of the title compounds, (I) and (II). Full details of the syntheses of these compounds and their biological activities will be published elsewhere (Sarkunam & Nallu, 2003).

Perspective views of molecules of (I) and (II), with the atomic numbering schemes, are shown in Figs. 1 and 2, respectively. The corresponding bond lengths and bond angles in (I) and (II) are essentially equivalent and are comparable with those in related structures (Pritchard, 1988; Usman et al., 2002). The indolizine rings of (I) and (II) can be superimposed on one another, with only a small r.m.s. deviation of the constituent atoms [0.011 Å]. The carbonyl (C16═O16) bond lengths [1.243 (2) and 1.247 (2) Å for (I) and (II), respectively] are significantly longer than typical carbonyl bonds. This fact may be due to the involvement of atom O16 in intermolecular C—H···O interactions in both (I) and (II) (Tables 1 and 2). The dihedral angles between the plane of the indolizine ring and the planes of the phenyl and chlorobenzyol moieties are 31.58 (4) and 60.93 (5)°, respectively, for (I), and 33.42 (4) and 72.47 (4)°, respectively, for (II). The angles between the planes of the phenyl and chlorobenzyol rings are 70.94 (6) and 67.73 (4)° for (I) and (II), respectively.

In (I), atom C6 is involved in a weak intermolecular C—H···O interaction with atom O16 of a centrosymmetrically related molecule, thus forming an R₂²(14) motif (Bernstein et al., 1995). Atom C18 (via atom H18) acts as a donor for a weak intermolecular C—H···π interaction with the centroid (Cg1) of the six-membered ring of the indolizine moiety in an adjacent molecule at (x, 1/2 − y, −1/2 + z). Atom C13 (via atom H13) is involved in a weak intermolecular C—H···π interaction with the centroid (Cg2) of the chlorobenzyol ring in the molecule at (-x, −y, −z) (Table 1).

Despite the similar chemical composition of the title compounds, the packing of the molecules in the crystal structures of (I) and (II) is entirely different. In (II), atom C13 acts as a donor in a weak intermolecular C—H···O interaction with carbonyl atom O16 of an adjacent molecule. This interaction links the molecules into chains that run parallel to the b axis and have a graph-set motif of C(10). Atom C22 also acts as a donor for a weak intermolecular C—H···O interaction with atom O16 of a different adjacent molecule. This interaction produces a continuous chain that runs parallel to the c axis and has a graph-set motif of C(5) (Bernstein et al., 1995). In addition, atom C19 (via atom H19) acts as a donor for a weak intermolecular C—H···π interaction with the centroid (Cg3) of the phenyl ring in the molecule at (−1 + x, y, z). Atom C24 (via atom H241) has a weak intermolecular C—H···π interaction with the centroid (Cg4) of the six-membered ring of the indolizine moiety in the molecule at (x, 1/2 − y, 1/2 + z) (Table 2). It is of interest to note that the shortest intermolecular Cl1···Cl1 contact is 3.1818 (6) Å, which is smaller than the sum of the van der Waals radii of the corresponding atoms.

S2. Experimental

A mixture of 4-dimethylaminopyridinium-1-(4-chloro)phenacylide (1.4 mmol), phenyl acetylene (1.6 mmol) and potassium carbonate (1.6 mmol) in dimethyl formamide (30 ml) was kept at room temperature overnight. The insoluble materials were removed by filtration, and the filtrate was extracted with a brine–dilute HCl mixture. The organic layer was evaporated and chromatographed to give crystals of (I) suitable for X-ray diffraction, which were recrystallized from ethyl acetate (yield 0.29 g, 55%; m.p. 474–476 K). Compound (II) was prepared in an identical fashion but with 4-dimethylaminopyridinium-1-(2,4-dichloro)phenacylide as a starting material (yield 0.31 g, 63%; m.p. 516–518 K). Crystals suitable for X-ray diffraction were grown from ethyl acetate.

S3. Refinement

For both compounds, methyl H atoms were constrained to an ideal geometry (C—H = 0.98 Å), with U_iso values of 1.5U_eq(C), but were allowed to rotate freely about the C—C bond. All remaining H atoms were placed in idealized positions (C—H = 0.95 Å) and constrained to ride on their parent atoms, with U_iso(H) values of 1.2U_eq(C). For compound (II), reflections −1 3 1, −2 2 1 and 0 2 1 were partially obscured by the beam stop and were omitted.

Computing details

For both compounds, data collection: COLLECT (Nonius, 2000); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003).

Figures

	Fig. 1. A view of the molecule of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented by circles of arbitrary radii.
	Fig. 2. A view of the molecule of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented by circles of arbitrary radii.

(I) 3-(4-Chlorobenzoyl)-7-(N,N-dimethylamino)-1-phenylindolizine

Crystal data

C23H19ClN2O	F(000) = 784
Mr = 374.85	Dx = 1.353 Mg m^−3
Monoclinic, P21/c	Melting point: 474 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 10.4641 (2) Å	Cell parameters from 67543 reflections
b = 16.3479 (3) Å	θ = 2.0–27.5°
c = 11.0110 (2) Å	µ = 0.22 mm^−1
β = 102.4144 (11)°	T = 160 K
V = 1839.57 (6) Å^3	Prism, yellow
Z = 4	0.25 × 0.13 × 0.13 mm

Data collection

Nonius KappaCCD diffractometer	4225 independent reflections
Radiation source: Nonius FR591 sealed tube generator	3353 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromator	Rint = 0.072
Detector resolution: 9 pixels mm^-1	θmax = 27.5°, θmin = 2.3°
ϕ and ω scans with κ offsets	h = −13→13
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	k = −21→21
Tmin = 0.842, Tmax = 0.977	l = −14→14
41157 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.047	H-atom parameters constrained
wR(F^2) = 0.131	w = 1/[σ^2(Fo^2) + (0.0706P)^2 + 0.614P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max < 0.001
4225 reflections	Δρmax = 0.32 e Å^−3
247 parameters	Δρmin = −0.35 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.010 (3)

Special details

Experimental. Solvent used: ethyl acetate Cooling Device: Oxford Cryosystems Cryostream 700 Crystal mount: glued on a glass fibre Mosaicity (°.): 0.707 (1) Frames collected: 639 Seconds exposure per frame: 100 Degrees rotation per frame: 1.0 Crystal-Detector distance (mm): 40.0

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
Cl1	−0.49345 (5)	0.11765 (3)	−0.54943 (5)	0.04739 (18)
O16	−0.11659 (12)	0.39519 (7)	−0.19807 (12)	0.0351 (3)
N4	0.09373 (13)	0.31888 (8)	−0.02034 (12)	0.0260 (3)
N23	0.36468 (15)	0.39986 (9)	0.28933 (14)	0.0359 (4)
C1	0.11992 (15)	0.18242 (10)	0.01436 (15)	0.0269 (3)
C2	0.02542 (15)	0.19495 (10)	−0.09374 (15)	0.0274 (3)
H2	−0.0197	0.1526	−0.1447	0.033*
C3	0.00594 (15)	0.27869 (10)	−0.11708 (14)	0.0268 (3)
C5	0.11420 (16)	0.40083 (10)	0.00041 (15)	0.0292 (4)
H5	0.0662	0.4392	−0.0564	0.035*
C6	0.20226 (16)	0.42777 (11)	0.10111 (15)	0.0314 (4)
H6	0.2151	0.4849	0.1141	0.038*
C7	0.27654 (16)	0.37117 (10)	0.18864 (15)	0.0288 (4)
C8	0.25373 (15)	0.28823 (10)	0.16619 (15)	0.0271 (3)
H8	0.3007	0.2493	0.2227	0.033*
C9	0.16255 (15)	0.26114 (10)	0.06150 (14)	0.0254 (3)
C10	0.16490 (15)	0.10186 (10)	0.06672 (15)	0.0273 (3)
C11	0.20536 (17)	0.08822 (11)	0.19505 (16)	0.0314 (4)
H11	0.2043	0.1321	0.2514	0.038*
C12	0.24679 (17)	0.01144 (11)	0.24042 (16)	0.0342 (4)
H12	0.2748	0.0034	0.3275	0.041*
C13	0.24789 (17)	−0.05347 (11)	0.16073 (17)	0.0346 (4)
H13	0.2776	−0.1057	0.1925	0.042*
C14	0.20521 (17)	−0.04180 (11)	0.03362 (17)	0.0346 (4)
H14	0.2034	−0.0865	−0.0218	0.042*
C15	0.16532 (16)	0.03490 (11)	−0.01250 (16)	0.0319 (4)
H15	0.1376	0.0423	−0.0998	0.038*
C16	−0.09633 (15)	0.32034 (10)	−0.20090 (14)	0.0276 (3)
C17	−0.19093 (15)	0.26863 (10)	−0.29089 (14)	0.0271 (3)
C18	−0.15198 (16)	0.20955 (11)	−0.36654 (15)	0.0307 (4)
H18	−0.0614	0.2007	−0.3624	0.037*
C19	−0.24424 (18)	0.16335 (11)	−0.44813 (15)	0.0336 (4)
H19	−0.2176	0.1236	−0.5006	0.040*
C20	−0.37563 (17)	0.17639 (11)	−0.45134 (15)	0.0321 (4)
C21	−0.41665 (17)	0.23497 (11)	−0.37745 (15)	0.0316 (4)
H21	−0.5072	0.2429	−0.3806	0.038*
C22	−0.32409 (16)	0.28177 (11)	−0.29899 (15)	0.0293 (4)
H22	−0.3516	0.3234	−0.2500	0.035*
C24	0.40051 (18)	0.48597 (11)	0.30131 (17)	0.0370 (4)
H241	0.4323	0.5034	0.2280	0.055*
H242	0.4696	0.4939	0.3760	0.055*
H243	0.3237	0.5186	0.3080	0.055*
C25	0.42867 (18)	0.34406 (11)	0.38532 (16)	0.0361 (4)
H251	0.3628	0.3101	0.4123	0.054*
H252	0.4774	0.3753	0.4563	0.054*
H253	0.4892	0.3090	0.3524	0.054*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0496 (3)	0.0497 (3)	0.0402 (3)	−0.0159 (2)	0.0039 (2)	−0.0106 (2)
O16	0.0377 (7)	0.0274 (7)	0.0367 (7)	0.0029 (5)	0.0001 (5)	−0.0002 (5)
N4	0.0263 (7)	0.0254 (7)	0.0260 (7)	0.0007 (5)	0.0053 (5)	0.0010 (5)
N23	0.0428 (9)	0.0282 (8)	0.0314 (8)	−0.0008 (6)	−0.0041 (6)	0.0007 (6)
C1	0.0271 (8)	0.0262 (8)	0.0282 (8)	0.0014 (6)	0.0076 (6)	0.0015 (6)
C2	0.0272 (8)	0.0281 (8)	0.0276 (8)	−0.0010 (6)	0.0073 (6)	−0.0009 (6)
C3	0.0270 (8)	0.0277 (8)	0.0257 (8)	−0.0013 (6)	0.0054 (6)	−0.0011 (6)
C5	0.0324 (8)	0.0252 (8)	0.0298 (8)	0.0020 (6)	0.0058 (6)	0.0033 (6)
C6	0.0360 (9)	0.0247 (8)	0.0323 (9)	0.0001 (7)	0.0043 (7)	0.0017 (6)
C7	0.0282 (8)	0.0301 (9)	0.0281 (8)	0.0010 (6)	0.0060 (6)	0.0013 (6)
C8	0.0272 (8)	0.0273 (8)	0.0265 (8)	0.0024 (6)	0.0053 (6)	0.0022 (6)
C9	0.0236 (7)	0.0270 (8)	0.0266 (8)	0.0021 (6)	0.0073 (6)	0.0033 (6)
C10	0.0237 (7)	0.0267 (8)	0.0320 (8)	0.0003 (6)	0.0071 (6)	0.0021 (6)
C11	0.0365 (9)	0.0279 (9)	0.0302 (8)	−0.0015 (7)	0.0079 (7)	−0.0001 (7)
C12	0.0367 (9)	0.0334 (9)	0.0316 (9)	−0.0007 (7)	0.0052 (7)	0.0050 (7)
C13	0.0344 (9)	0.0271 (9)	0.0427 (10)	0.0017 (7)	0.0093 (7)	0.0070 (7)
C14	0.0385 (9)	0.0267 (9)	0.0397 (10)	0.0014 (7)	0.0105 (7)	−0.0025 (7)
C15	0.0344 (9)	0.0300 (9)	0.0311 (8)	−0.0005 (7)	0.0067 (7)	−0.0010 (7)
C16	0.0277 (8)	0.0302 (9)	0.0258 (8)	0.0008 (6)	0.0076 (6)	0.0013 (6)
C17	0.0305 (8)	0.0276 (8)	0.0230 (7)	0.0008 (6)	0.0051 (6)	0.0047 (6)
C18	0.0301 (8)	0.0365 (9)	0.0271 (8)	0.0013 (7)	0.0099 (6)	0.0020 (7)
C19	0.0430 (10)	0.0322 (9)	0.0266 (8)	−0.0001 (7)	0.0100 (7)	−0.0014 (7)
C20	0.0387 (9)	0.0327 (9)	0.0235 (8)	−0.0060 (7)	0.0037 (6)	0.0003 (6)
C21	0.0285 (8)	0.0360 (9)	0.0290 (8)	0.0003 (7)	0.0033 (6)	0.0039 (7)
C22	0.0328 (9)	0.0301 (9)	0.0255 (8)	0.0037 (7)	0.0073 (6)	0.0012 (6)
C24	0.0384 (10)	0.0291 (9)	0.0394 (10)	−0.0037 (7)	−0.0006 (7)	0.0005 (7)
C25	0.0402 (10)	0.0341 (10)	0.0297 (9)	0.0023 (8)	−0.0022 (7)	0.0025 (7)

Geometric parameters (Å, º)

Cl1—C20	1.7425 (17)	C12—C13	1.379 (3)
O16—C16	1.243 (2)	C12—H12	0.9500
N4—C5	1.368 (2)	C13—C14	1.388 (3)
N4—C9	1.394 (2)	C13—H13	0.9500
N4—C3	1.411 (2)	C14—C15	1.383 (2)
N23—C7	1.364 (2)	C14—H14	0.9500
N23—C25	1.447 (2)	C15—H15	0.9500
N23—C24	1.456 (2)	C16—C17	1.502 (2)
C1—C2	1.389 (2)	C17—C18	1.392 (2)
C1—C9	1.423 (2)	C17—C22	1.394 (2)
C1—C10	1.474 (2)	C18—C19	1.392 (2)
C2—C3	1.400 (2)	C18—H18	0.9500
C2—H2	0.9500	C19—C20	1.384 (3)
C3—C16	1.427 (2)	C19—H19	0.9500
C5—C6	1.354 (2)	C20—C21	1.383 (2)
C5—H5	0.9500	C21—C22	1.382 (2)
C6—C7	1.438 (2)	C21—H21	0.9500
C6—H6	0.9500	C22—H22	0.9500
C7—C8	1.390 (2)	C24—H241	0.9800
C8—C9	1.401 (2)	C24—H242	0.9800
C8—H8	0.9500	C24—H243	0.9800
C10—C15	1.400 (2)	C25—H251	0.9800
C10—C11	1.403 (2)	C25—H252	0.9800
C11—C12	1.386 (2)	C25—H253	0.9800
C11—H11	0.9500
C5—N4—C9	120.97 (14)	C14—C13—H13	120.3
C5—N4—C3	129.46 (14)	C15—C14—C13	120.08 (16)
C9—N4—C3	109.56 (13)	C15—C14—H14	120.0
C7—N23—C25	120.19 (15)	C13—C14—H14	120.0
C7—N23—C24	121.49 (15)	C14—C15—C10	121.41 (16)
C25—N23—C24	118.28 (14)	C14—C15—H15	119.3
C2—C1—C9	106.79 (14)	C10—C15—H15	119.3
C2—C1—C10	125.13 (15)	O16—C16—C3	124.17 (15)
C9—C1—C10	128.08 (14)	O16—C16—C17	118.61 (14)
C1—C2—C3	110.50 (15)	C3—C16—C17	117.03 (14)
C1—C2—H2	124.8	C18—C17—C22	119.07 (15)
C3—C2—H2	124.8	C18—C17—C16	123.30 (14)
C2—C3—N4	105.75 (13)	C22—C17—C16	117.62 (14)
C2—C3—C16	130.16 (15)	C19—C18—C17	120.73 (15)
N4—C3—C16	122.84 (14)	C19—C18—H18	119.6
C6—C5—N4	120.66 (15)	C17—C18—H18	119.6
C6—C5—H5	119.7	C20—C19—C18	118.70 (16)
N4—C5—H5	119.7	C20—C19—H19	120.6
C5—C6—C7	120.95 (16)	C18—C19—H19	120.6
C5—C6—H6	119.5	C21—C20—C19	121.59 (16)
C7—C6—H6	119.5	C21—C20—Cl1	118.58 (14)
N23—C7—C8	122.71 (15)	C19—C20—Cl1	119.83 (13)
N23—C7—C6	119.82 (15)	C22—C21—C20	119.11 (16)
C8—C7—C6	117.46 (15)	C22—C21—H21	120.4
C7—C8—C9	121.02 (15)	C20—C21—H21	120.4
C7—C8—H8	119.5	C21—C22—C17	120.76 (16)
C9—C8—H8	119.5	C21—C22—H22	119.6
N4—C9—C8	118.93 (14)	C17—C22—H22	119.6
N4—C9—C1	107.38 (13)	N23—C24—H241	109.5
C8—C9—C1	133.69 (15)	N23—C24—H242	109.5
C15—C10—C11	117.54 (15)	H241—C24—H242	109.5
C15—C10—C1	119.90 (15)	N23—C24—H243	109.5
C11—C10—C1	122.54 (15)	H241—C24—H243	109.5
C12—C11—C10	120.69 (16)	H242—C24—H243	109.5
C12—C11—H11	119.7	N23—C25—H251	109.5
C10—C11—H11	119.7	N23—C25—H252	109.5
C13—C12—C11	120.84 (16)	H251—C25—H252	109.5
C13—C12—H12	119.6	N23—C25—H253	109.5
C11—C12—H12	119.6	H251—C25—H253	109.5
C12—C13—C14	119.41 (16)	H252—C25—H253	109.5
C12—C13—H13	120.3
C9—C1—C2—C3	−0.17 (18)	C9—C1—C10—C15	−148.86 (17)
C10—C1—C2—C3	−179.98 (15)	C2—C1—C10—C11	−147.54 (16)
C1—C2—C3—N4	0.99 (18)	C9—C1—C10—C11	32.7 (2)
C1—C2—C3—C16	−166.23 (16)	C15—C10—C11—C12	1.4 (2)
C5—N4—C3—C2	179.85 (15)	C1—C10—C11—C12	179.90 (15)
C9—N4—C3—C2	−1.44 (17)	C10—C11—C12—C13	−0.7 (3)
C5—N4—C3—C16	−11.8 (2)	C11—C12—C13—C14	−0.9 (3)
C9—N4—C3—C16	166.94 (14)	C12—C13—C14—C15	1.7 (3)
C9—N4—C5—C6	0.1 (2)	C13—C14—C15—C10	−1.0 (3)
C3—N4—C5—C6	178.71 (15)	C11—C10—C15—C14	−0.6 (2)
N4—C5—C6—C7	0.1 (3)	C1—C10—C15—C14	−179.10 (16)
C25—N23—C7—C8	−6.8 (3)	C2—C3—C16—O16	166.39 (16)
C24—N23—C7—C8	170.96 (16)	N4—C3—C16—O16	1.1 (2)
C25—N23—C7—C6	172.80 (16)	C2—C3—C16—C17	−8.5 (2)
C24—N23—C7—C6	−9.4 (3)	N4—C3—C16—C17	−173.84 (14)
C5—C6—C7—N23	179.98 (16)	O16—C16—C17—C18	133.83 (17)
C5—C6—C7—C8	−0.4 (2)	C3—C16—C17—C18	−51.0 (2)
N23—C7—C8—C9	−179.85 (15)	O16—C16—C17—C22	−45.5 (2)
C6—C7—C8—C9	0.6 (2)	C3—C16—C17—C22	129.75 (16)
C5—N4—C9—C8	0.0 (2)	C22—C17—C18—C19	−0.8 (2)
C3—N4—C9—C8	−178.82 (13)	C16—C17—C18—C19	179.91 (15)
C5—N4—C9—C1	−179.81 (14)	C17—C18—C19—C20	−1.0 (2)
C3—N4—C9—C1	1.36 (17)	C18—C19—C20—C21	1.2 (3)
C7—C8—C9—N4	−0.4 (2)	C18—C19—C20—Cl1	−178.28 (13)
C7—C8—C9—C1	179.39 (17)	C19—C20—C21—C22	0.3 (3)
C2—C1—C9—N4	−0.72 (17)	Cl1—C20—C21—C22	179.80 (13)
C10—C1—C9—N4	179.07 (15)	C20—C21—C22—C17	−2.1 (2)
C2—C1—C9—C8	179.49 (16)	C18—C17—C22—C21	2.4 (2)
C10—C1—C9—C8	−0.7 (3)	C16—C17—C22—C21	−178.31 (15)
C2—C1—C10—C15	30.9 (2)	C16—C17—C18—H18	−0.1

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O16^i	0.95	2.48	3.276 (2)	141
C13—H13···Cg2^ii	0.95	2.74	3.580 (2)	148
C18—H18···Cg1^iii	0.95	2.86	3.781 (2)	164

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

(II) 3-(2,4-Dichlorobenzoyl)-7-(N,N-dimethylamino)-1-phenylindolizine

Crystal data

C23H18Cl2N2O	F(000) = 848
Mr = 409.29	Dx = 1.395 Mg m^−3
Monoclinic, P21/c	Melting point: 516 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 9.5888 (2) Å	Cell parameters from 34641 reflections
b = 19.0878 (4) Å	θ = 2.0–27.5°
c = 10.6508 (2) Å	µ = 0.35 mm^−1
β = 90.7580 (13)°	T = 160 K
V = 1949.24 (7) Å^3	Prism, yellow
Z = 4	0.25 × 0.23 × 0.20 mm

Data collection

Nonius KappaCCD diffractometer	4465 independent reflections
Radiation source: Nonius FR591 sealed tube generator	3434 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromator	Rint = 0.071
Detector resolution: 9 pixels mm^-1	θmax = 27.5°, θmin = 2.1°
ϕ and ω scans with κ offsets	h = −12→12
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	k = −24→23
Tmin = 0.842, Tmax = 0.936	l = −13→13
45923 measured reflections

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.117	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0623P)^2 + 0.7326P] where P = (Fo^2 + 2Fc^2)/3
4465 reflections	(Δ/σ)max < 0.001
255 parameters	Δρmax = 0.25 e Å^−3
0 restraints	Δρmin = −0.37 e Å^−3

Special details

Experimental. Solvent used: ethyl acetate Cooling Device: Oxford Cryosystems Cryostream 700 Crystal mount: glued on a glass fibre Mosaicity (°.): 0.558 (1) Frames collected: 381 Seconds exposure per frame: 32 Degrees rotation per frame: 1.8 Crystal-Detector distance (mm): 30.0

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
Cl1	0.03651 (5)	0.46401 (2)	0.36978 (4)	0.03622 (14)
Cl2	−0.22330 (6)	0.43130 (3)	−0.07726 (5)	0.04995 (17)
O16	0.14559 (12)	0.27657 (6)	0.36970 (12)	0.0323 (3)
N4	0.42783 (14)	0.33413 (7)	0.40907 (13)	0.0248 (3)
N23	0.77134 (15)	0.29188 (8)	0.63802 (14)	0.0312 (3)
C1	0.50803 (17)	0.43405 (8)	0.31911 (16)	0.0247 (3)
C2	0.37829 (17)	0.41813 (9)	0.26813 (16)	0.0263 (3)
H2	0.3318	0.4449	0.2051	0.032*
C3	0.32510 (17)	0.35699 (9)	0.32244 (16)	0.0257 (3)
C5	0.42754 (18)	0.27708 (9)	0.48632 (17)	0.0286 (4)
H5	0.3495	0.2464	0.4858	0.034*
C6	0.53780 (18)	0.26382 (9)	0.56383 (17)	0.0311 (4)
H6	0.5349	0.2246	0.6187	0.037*
C7	0.65860 (17)	0.30806 (9)	0.56430 (15)	0.0267 (4)
C8	0.65662 (16)	0.36610 (9)	0.48472 (15)	0.0255 (3)
H8	0.7352	0.3964	0.4824	0.031*
C9	0.54036 (16)	0.38021 (8)	0.40831 (15)	0.0241 (3)
C10	0.58970 (16)	0.49703 (8)	0.29029 (16)	0.0249 (3)
C11	0.67224 (17)	0.53156 (9)	0.37963 (16)	0.0275 (4)
H11	0.6799	0.5132	0.4624	0.033*
C12	0.74333 (18)	0.59242 (9)	0.34894 (17)	0.0313 (4)
H12	0.8000	0.6150	0.4106	0.038*
C13	0.73244 (19)	0.62070 (10)	0.22912 (19)	0.0350 (4)
H13	0.7807	0.6626	0.2087	0.042*
C14	0.6505 (2)	0.58711 (10)	0.13989 (18)	0.0355 (4)
H14	0.6421	0.6061	0.0577	0.043*
C15	0.58045 (18)	0.52588 (9)	0.16994 (17)	0.0301 (4)
H15	0.5252	0.5031	0.1075	0.036*
C16	0.19096 (17)	0.32723 (8)	0.30866 (16)	0.0249 (3)
C17	0.09647 (16)	0.35855 (8)	0.20927 (15)	0.0240 (3)
C18	0.01709 (17)	0.41852 (9)	0.22929 (16)	0.0257 (3)
C19	−0.08009 (18)	0.44279 (9)	0.14192 (17)	0.0305 (4)
H19	−0.1333	0.4838	0.1573	0.037*
C20	−0.09686 (18)	0.40523 (10)	0.03173 (17)	0.0320 (4)
C21	−0.01867 (19)	0.34574 (10)	0.00696 (17)	0.0324 (4)
H21	−0.0307	0.3210	−0.0698	0.039*
C22	0.07729 (17)	0.32325 (9)	0.09657 (16)	0.0289 (4)
H22	0.1313	0.2826	0.0804	0.035*
C24	0.7604 (2)	0.23997 (10)	0.73725 (18)	0.0365 (4)
H241	0.6895	0.2548	0.7971	0.055*
H242	0.8506	0.2354	0.7808	0.055*
H243	0.7338	0.1947	0.7007	0.055*
C25	0.89512 (19)	0.33557 (10)	0.63370 (18)	0.0345 (4)
H251	0.9287	0.3378	0.5473	0.052*
H252	0.9679	0.3155	0.6882	0.052*
H253	0.8723	0.3829	0.6627	0.052*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0407 (3)	0.0352 (3)	0.0325 (2)	0.00855 (18)	−0.00822 (18)	−0.01185 (18)
Cl2	0.0493 (3)	0.0624 (4)	0.0376 (3)	0.0172 (2)	−0.0194 (2)	−0.0030 (2)
O16	0.0300 (6)	0.0284 (6)	0.0384 (7)	−0.0042 (5)	−0.0040 (5)	0.0075 (5)
N4	0.0230 (7)	0.0242 (7)	0.0271 (7)	0.0004 (5)	−0.0020 (5)	0.0033 (5)
N23	0.0282 (7)	0.0341 (8)	0.0311 (8)	0.0000 (6)	−0.0073 (6)	0.0097 (6)
C1	0.0251 (8)	0.0247 (8)	0.0242 (8)	−0.0006 (6)	−0.0026 (6)	0.0023 (6)
C2	0.0263 (8)	0.0265 (8)	0.0261 (8)	0.0020 (7)	−0.0031 (6)	0.0027 (7)
C3	0.0236 (8)	0.0261 (8)	0.0273 (8)	0.0023 (6)	−0.0041 (6)	0.0016 (7)
C5	0.0271 (8)	0.0244 (8)	0.0342 (9)	−0.0015 (7)	−0.0006 (7)	0.0068 (7)
C6	0.0299 (9)	0.0296 (9)	0.0337 (9)	0.0019 (7)	−0.0038 (7)	0.0096 (7)
C7	0.0266 (8)	0.0280 (9)	0.0254 (8)	0.0039 (7)	−0.0016 (6)	0.0008 (7)
C8	0.0239 (8)	0.0263 (8)	0.0263 (8)	−0.0012 (6)	−0.0026 (6)	0.0021 (7)
C9	0.0233 (8)	0.0243 (8)	0.0248 (8)	0.0001 (6)	−0.0001 (6)	0.0005 (6)
C10	0.0223 (8)	0.0249 (8)	0.0275 (8)	0.0026 (6)	−0.0011 (6)	0.0027 (7)
C11	0.0282 (8)	0.0275 (8)	0.0267 (8)	0.0016 (7)	−0.0019 (7)	0.0000 (7)
C12	0.0291 (9)	0.0282 (9)	0.0366 (10)	−0.0010 (7)	−0.0038 (7)	−0.0037 (7)
C13	0.0330 (9)	0.0263 (9)	0.0457 (11)	−0.0030 (7)	0.0007 (8)	0.0067 (8)
C14	0.0385 (10)	0.0340 (10)	0.0340 (10)	−0.0020 (8)	−0.0036 (8)	0.0125 (8)
C15	0.0300 (9)	0.0323 (9)	0.0278 (9)	−0.0013 (7)	−0.0055 (7)	0.0039 (7)
C16	0.0239 (8)	0.0232 (8)	0.0276 (8)	0.0015 (6)	−0.0014 (6)	−0.0029 (6)
C17	0.0211 (7)	0.0239 (8)	0.0271 (8)	−0.0018 (6)	−0.0013 (6)	−0.0006 (6)
C18	0.0267 (8)	0.0252 (8)	0.0252 (8)	−0.0017 (6)	−0.0023 (6)	−0.0028 (6)
C19	0.0296 (9)	0.0290 (9)	0.0330 (10)	0.0057 (7)	−0.0029 (7)	0.0000 (7)
C20	0.0294 (9)	0.0388 (10)	0.0277 (9)	0.0031 (7)	−0.0051 (7)	0.0023 (8)
C21	0.0325 (9)	0.0376 (10)	0.0270 (9)	0.0014 (7)	−0.0031 (7)	−0.0073 (7)
C22	0.0274 (8)	0.0281 (9)	0.0312 (9)	0.0029 (7)	−0.0009 (7)	−0.0039 (7)
C24	0.0369 (10)	0.0385 (10)	0.0339 (10)	0.0023 (8)	−0.0073 (8)	0.0097 (8)
C25	0.0295 (9)	0.0389 (10)	0.0349 (10)	−0.0026 (7)	−0.0078 (7)	0.0059 (8)

Geometric parameters (Å, º)

Cl1—C18	1.7379 (17)	C11—H11	0.9500
Cl2—C20	1.7401 (18)	C12—C13	1.388 (3)
O16—C16	1.247 (2)	C12—H12	0.9500
N4—C5	1.365 (2)	C13—C14	1.383 (3)
N4—C9	1.392 (2)	C13—H13	0.9500
N4—C3	1.410 (2)	C14—C15	1.388 (3)
N23—C7	1.363 (2)	C14—H14	0.9500
N23—C25	1.452 (2)	C15—H15	0.9500
N23—C24	1.454 (2)	C16—C17	1.508 (2)
C1—C2	1.385 (2)	C17—C22	1.387 (2)
C1—C9	1.431 (2)	C17—C18	1.393 (2)
C1—C10	1.469 (2)	C18—C19	1.388 (2)
C2—C3	1.401 (2)	C19—C20	1.383 (3)
C2—H2	0.9500	C19—H19	0.9500
C3—C16	1.412 (2)	C20—C21	1.388 (3)
C5—C6	1.357 (2)	C21—C22	1.385 (2)
C5—H5	0.9500	C21—H21	0.9500
C6—C7	1.434 (2)	C22—H22	0.9500
C6—H6	0.9500	C24—H241	0.9800
C7—C8	1.395 (2)	C24—H242	0.9800
C8—C9	1.398 (2)	C24—H243	0.9800
C8—H8	0.9500	C25—H251	0.9800
C10—C11	1.395 (2)	C25—H252	0.9800
C10—C15	1.397 (2)	C25—H253	0.9800
C11—C12	1.388 (2)
C5—N4—C9	121.02 (14)	C12—C13—H13	120.4
C5—N4—C3	129.38 (14)	C13—C14—C15	120.29 (17)
C9—N4—C3	109.60 (13)	C13—C14—H14	119.9
C7—N23—C25	119.60 (14)	C15—C14—H14	119.9
C7—N23—C24	120.61 (15)	C14—C15—C10	121.24 (17)
C25—N23—C24	118.78 (14)	C14—C15—H15	119.4
C2—C1—C9	106.76 (14)	C10—C15—H15	119.4
C2—C1—C10	125.19 (15)	O16—C16—C3	125.56 (16)
C9—C1—C10	127.95 (15)	O16—C16—C17	117.58 (14)
C1—C2—C3	110.55 (15)	C3—C16—C17	116.84 (14)
C1—C2—H2	124.7	C22—C17—C18	117.74 (15)
C3—C2—H2	124.7	C22—C17—C16	119.12 (14)
C2—C3—N4	105.84 (14)	C18—C17—C16	122.89 (14)
C2—C3—C16	128.91 (15)	C19—C18—C17	122.35 (15)
N4—C3—C16	124.82 (15)	C19—C18—Cl1	118.29 (13)
C6—C5—N4	120.53 (16)	C17—C18—Cl1	119.34 (13)
C6—C5—H5	119.7	C20—C19—C18	117.75 (16)
N4—C5—H5	119.7	C20—C19—H19	121.1
C5—C6—C7	121.02 (16)	C18—C19—H19	121.1
C5—C6—H6	119.5	C19—C20—C21	121.90 (16)
C7—C6—H6	119.5	C19—C20—Cl2	119.34 (14)
N23—C7—C8	122.30 (15)	C21—C20—Cl2	118.72 (14)
N23—C7—C6	120.21 (15)	C22—C21—C20	118.56 (16)
C8—C7—C6	117.47 (15)	C22—C21—H21	120.7
C7—C8—C9	120.74 (15)	C20—C21—H21	120.7
C7—C8—H8	119.6	C21—C22—C17	121.68 (16)
C9—C8—H8	119.6	C21—C22—H22	119.2
N4—C9—C8	119.16 (14)	C17—C22—H22	119.2
N4—C9—C1	107.25 (14)	N23—C24—H241	109.5
C8—C9—C1	133.56 (15)	N23—C24—H242	109.5
C11—C10—C15	117.92 (15)	H241—C24—H242	109.5
C11—C10—C1	122.90 (15)	N23—C24—H243	109.5
C15—C10—C1	119.12 (15)	H241—C24—H243	109.5
C12—C11—C10	120.71 (16)	H242—C24—H243	109.5
C12—C11—H11	119.6	N23—C25—H251	109.5
C10—C11—H11	119.6	N23—C25—H252	109.5
C11—C12—C13	120.70 (17)	H251—C25—H252	109.5
C11—C12—H12	119.7	N23—C25—H253	109.5
C13—C12—H12	119.7	H251—C25—H253	109.5
C14—C13—C12	119.13 (17)	H252—C25—H253	109.5
C14—C13—H13	120.4
C9—C1—C2—C3	0.99 (19)	C2—C1—C10—C15	−32.9 (2)
C10—C1—C2—C3	−175.63 (15)	C9—C1—C10—C15	151.23 (17)
C1—C2—C3—N4	−0.83 (19)	C15—C10—C11—C12	−0.4 (2)
C1—C2—C3—C16	171.81 (17)	C1—C10—C11—C12	−177.54 (15)
C5—N4—C3—C2	−179.96 (16)	C10—C11—C12—C13	0.8 (3)
C9—N4—C3—C2	0.34 (18)	C11—C12—C13—C14	−0.5 (3)
C5—N4—C3—C16	7.0 (3)	C12—C13—C14—C15	−0.2 (3)
C9—N4—C3—C16	−172.69 (15)	C13—C14—C15—C10	0.5 (3)
C9—N4—C5—C6	−0.4 (3)	C11—C10—C15—C14	−0.3 (3)
C3—N4—C5—C6	179.94 (17)	C1—C10—C15—C14	176.99 (16)
N4—C5—C6—C7	−1.7 (3)	C2—C3—C16—O16	−172.16 (17)
C25—N23—C7—C8	−0.7 (3)	N4—C3—C16—O16	−0.8 (3)
C24—N23—C7—C8	167.66 (16)	C2—C3—C16—C17	9.4 (3)
C25—N23—C7—C6	177.49 (16)	N4—C3—C16—C17	−179.20 (14)
C24—N23—C7—C6	−14.2 (3)	O16—C16—C17—C22	−75.5 (2)
C5—C6—C7—N23	−176.57 (17)	C3—C16—C17—C22	103.05 (18)
C5—C6—C7—C8	1.7 (3)	O16—C16—C17—C18	98.58 (19)
N23—C7—C8—C9	178.54 (15)	C3—C16—C17—C18	−82.9 (2)
C6—C7—C8—C9	0.3 (2)	C22—C17—C18—C19	0.9 (2)
C5—N4—C9—C8	2.4 (2)	C16—C17—C18—C19	−173.24 (16)
C3—N4—C9—C8	−177.90 (14)	C22—C17—C18—Cl1	179.42 (12)
C5—N4—C9—C1	−179.49 (15)	C16—C17—C18—Cl1	5.3 (2)
C3—N4—C9—C1	0.25 (18)	C17—C18—C19—C20	0.0 (3)
C7—C8—C9—N4	−2.3 (2)	Cl1—C18—C19—C20	−178.54 (14)
C7—C8—C9—C1	−179.84 (17)	C18—C19—C20—C21	−0.9 (3)
C2—C1—C9—N4	−0.75 (18)	C18—C19—C20—Cl2	176.97 (14)
C10—C1—C9—N4	175.75 (15)	C19—C20—C21—C22	0.9 (3)
C2—C1—C9—C8	177.02 (18)	Cl2—C20—C21—C22	−176.99 (14)
C10—C1—C9—C8	−6.5 (3)	C20—C21—C22—C17	0.1 (3)
C2—C1—C10—C11	144.24 (18)	C18—C17—C22—C21	−0.9 (3)
C9—C1—C10—C11	−31.7 (3)	C16—C17—C22—C21	173.45 (16)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···O16^i	0.95	2.44	3.370 (2)	167
C22—H22···O16^ii	0.95	2.52	3.153 (2)	124
C19—H19···Cg3^iii	0.95	2.68	3.568 (2)	156
C24—H241···Cg4^iv	0.98	2.86	3.600 (2)	132

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