2,4-Bis(4-chloro-phen-yl)-1-methyl-3-aza-bicyclo-[3.3.1]nonan-9-one.

The title compound, C(21)H(21)Cl(2)NO, exists in a twin-chair conformation with an equatorial orientation of the 4-chloro-phenyl groups on both sides of the secondary amino group; the dihedral angle between the 4-chloro-phenyl rings is 36.58 (2)°. The crystal packing is stabilized by an inter-molecular N-H⋯O hydrogen bond and a weak Cl⋯Cl [3.4331 (9) Å] inter-action.

Related literature

For the synthesis and biological activity of 3-aza­bicyclo­[3.3.1] nonan-9-ones, see: Parthiban et al. (2009 ▶); Hardick et al. (1996 ▶); Jeyaraman & Avila (1981 ▶). For the structure of the non-methyl­ated analog of the title compound, see: Parthiban et al. (2009a ▶). For related structures with similar conformations, see: Parthiban et al. (2009b ▶, 2010 ▶). For a related structure with chair–boat conformation, see: Smith-Verdier et al. (1983 ▶). For a related structure with boat–boat conformation, see: Padegimas & Kovacic (1972 ▶). For ring puckering and asymmetry parameters, see: Cremer & Pople (1975 ▶); Nardelli (1983 ▶). Scheme: resolution poor

Experimental

Crystal data

C21H21Cl2NO

M = 374.29

Monoclinic,

a = 28.4515 (14) Å

b = 7.0380 (3) Å

c = 21.2771 (12) Å

β = 117.148 (4)°

V = 3791.2 (3) Å3

Z = 8

Mo Kα radiation

μ = 0.35 mm−1

T = 298 K

0.58 × 0.42 × 0.18 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 1999 ▶) T min = 0.822, T max = 0.940

24985 measured reflections

4661 independent reflections

3149 reflections with I > 2σ(I)

R int = 0.033

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.125

S = 1.02

4661 reflections

231 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.36 e Å−3

Δρmin = −0.43 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT-Plus (Bruker, 2004 ▶); data reduction: SAINT-Plus and XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810004095/hb5322sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810004095/hb5322Isup2.hkl

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

C21H21Cl2NO	F(000) = 1568
Mr = 374.29	Dx = 1.312 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 7359 reflections
a = 28.4515 (14) Å	θ = 2.5–27.3°
b = 7.0380 (3) Å	µ = 0.35 mm−1
c = 21.2771 (12) Å	T = 298 K
β = 117.148 (4)°	Rectangular block, colourless
V = 3791.2 (3) Å3	0.58 × 0.42 × 0.18 mm
Z = 8

Bruker APEXII CCD diffractometer	4661 independent reflections
Radiation source: fine-focus sealed tube	3149 reflections with I > 2σ(I)
graphite	Rint = 0.033
phi and ω scans	θmax = 28.2°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −36→37
Tmin = 0.822, Tmax = 0.940	k = −8→9
24985 measured reflections	l = −28→27

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.125	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ2(Fo2) + (0.0487P)2 + 3.2087P] where P = (Fo2 + 2Fc2)/3
4661 reflections	(Δ/σ)max = 0.001
231 parameters	Δρmax = 0.36 e Å−3
0 restraints	Δρmin = −0.43 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)are estimated using the full covariance matrix. The cell esds are takeninto account individually in the estimation of esds in distances, anglesand torsion angles; correlations between esds in cell parameters are onlyused when they are defined by crystal symmetry. An approximate (isotropic)treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR andgoodness of fit S are based on F2, conventional R-factors R are basedon F, with F set to zero for negative F2. The threshold expression ofF2 > σ(F2) is used only for calculating R-factors(gt) etc. and isnot relevant to the choice of reflections for refinement. R-factors basedon F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
C1	0.17656 (7)	0.4818 (2)	0.98420 (9)	0.0357 (4)
H1	0.2131	0.4889	0.9916	0.043*
C2	0.15724 (7)	0.6894 (2)	0.98539 (10)	0.0393 (4)
C3	0.09894 (8)	0.7068 (3)	0.97191 (11)	0.0501 (5)
H3A	0.0949	0.6354	1.0082	0.060*
H3B	0.0919	0.8391	0.9772	0.060*
C4	0.05740 (8)	0.6377 (3)	0.90001 (12)	0.0556 (5)
H4A	0.0228	0.6790	0.8929	0.067*
H4B	0.0575	0.4999	0.8993	0.067*
C5	0.06735 (8)	0.7126 (3)	0.83970 (11)	0.0559 (5)
H5A	0.0564	0.8446	0.8311	0.067*
H5B	0.0456	0.6416	0.7972	0.067*
C6	0.12516 (8)	0.6988 (3)	0.85398 (10)	0.0450 (4)
H6	0.1292	0.7694	0.8171	0.054*
C7	0.14595 (7)	0.4935 (2)	0.85650 (9)	0.0395 (4)
H7	0.1826	0.5010	0.8644	0.047*
C8	0.15846 (7)	0.7924 (2)	0.92360 (10)	0.0413 (4)
C9	0.17610 (7)	0.3620 (2)	1.04297 (9)	0.0376 (4)
C10	0.22206 (8)	0.3354 (3)	1.10561 (10)	0.0478 (5)
H10	0.2537	0.3846	1.1099	0.057*
C11	0.22168 (9)	0.2369 (3)	1.16196 (10)	0.0537 (5)
H11	0.2528	0.2196	1.2035	0.064*
C12	0.17493 (9)	0.1654 (3)	1.15562 (10)	0.0487 (5)
C13	0.12899 (8)	0.1845 (3)	1.09386 (11)	0.0504 (5)
H13	0.0976	0.1325	1.0897	0.061*
C14	0.12984 (7)	0.2817 (3)	1.03794 (10)	0.0443 (4)
H14	0.0988	0.2938	0.9960	0.053*
C15	0.19367 (9)	0.7841 (3)	1.05543 (11)	0.0562 (5)
H15A	0.2298	0.7607	1.0662	0.084*
H15B	0.1869	0.7328	1.0923	0.084*
H15C	0.1872	0.9186	1.0519	0.084*
C16	0.11369 (7)	0.3942 (3)	0.78664 (10)	0.0426 (4)
C17	0.11848 (10)	0.4523 (3)	0.72767 (12)	0.0616 (6)
H17	0.1433	0.5445	0.7324	0.074*
C18	0.08692 (11)	0.3752 (4)	0.66173 (12)	0.0692 (7)
H18	0.0898	0.4179	0.6222	0.083*
C19	0.05165 (8)	0.2361 (3)	0.65530 (10)	0.0542 (5)
C20	0.04760 (9)	0.1701 (4)	0.71289 (12)	0.0633 (6)
H20	0.0243	0.0719	0.7082	0.076*
C21	0.07852 (9)	0.2507 (3)	0.77862 (11)	0.0571 (5)
H21	0.0754	0.2070	0.8178	0.068*
Cl1	0.17372 (3)	0.04670 (9)	1.22681 (3)	0.0770 (2)
Cl2	0.01186 (2)	0.13710 (11)	0.57245 (3)	0.0829 (2)
N1	0.14499 (6)	0.3905 (2)	0.91547 (8)	0.0379 (3)
O1	0.18212 (6)	0.94051 (19)	0.92903 (8)	0.0570 (4)
H1A	0.1580 (8)	0.278 (3)	0.9181 (11)	0.050 (6)*

	U11	U22	U33	U12	U13	U23
C1	0.0365 (9)	0.0322 (8)	0.0378 (9)	−0.0037 (7)	0.0163 (7)	−0.0053 (7)
C2	0.0433 (10)	0.0310 (8)	0.0429 (10)	−0.0022 (7)	0.0190 (8)	−0.0065 (7)
C3	0.0534 (11)	0.0426 (10)	0.0625 (13)	0.0049 (9)	0.0335 (10)	−0.0002 (9)
C4	0.0380 (10)	0.0519 (12)	0.0729 (15)	0.0024 (9)	0.0218 (10)	0.0035 (10)
C5	0.0498 (11)	0.0484 (11)	0.0540 (12)	0.0071 (9)	0.0103 (10)	0.0044 (10)
C6	0.0557 (11)	0.0341 (9)	0.0436 (10)	−0.0041 (8)	0.0212 (9)	0.0039 (8)
C7	0.0442 (10)	0.0363 (9)	0.0395 (9)	−0.0073 (7)	0.0204 (8)	−0.0038 (7)
C8	0.0413 (9)	0.0289 (8)	0.0556 (11)	0.0005 (7)	0.0239 (9)	−0.0021 (8)
C9	0.0425 (9)	0.0316 (8)	0.0358 (9)	−0.0020 (7)	0.0153 (8)	−0.0045 (7)
C10	0.0442 (10)	0.0454 (10)	0.0447 (11)	−0.0050 (8)	0.0123 (9)	−0.0015 (8)
C11	0.0578 (12)	0.0486 (11)	0.0391 (10)	−0.0002 (9)	0.0086 (9)	0.0007 (9)
C12	0.0700 (13)	0.0355 (9)	0.0435 (11)	0.0047 (9)	0.0286 (10)	0.0030 (8)
C13	0.0528 (11)	0.0438 (10)	0.0589 (12)	−0.0018 (9)	0.0292 (10)	0.0052 (9)
C14	0.0428 (10)	0.0417 (10)	0.0425 (10)	−0.0033 (8)	0.0143 (8)	0.0022 (8)
C15	0.0680 (13)	0.0418 (10)	0.0543 (12)	−0.0053 (10)	0.0240 (11)	−0.0157 (9)
C16	0.0498 (10)	0.0395 (9)	0.0400 (10)	−0.0036 (8)	0.0219 (8)	−0.0034 (8)
C17	0.0870 (16)	0.0565 (13)	0.0506 (12)	−0.0205 (12)	0.0395 (12)	−0.0065 (10)
C18	0.1041 (19)	0.0679 (15)	0.0417 (12)	−0.0056 (14)	0.0385 (13)	−0.0044 (11)
C19	0.0510 (11)	0.0640 (13)	0.0403 (11)	0.0042 (10)	0.0146 (9)	−0.0157 (10)
C20	0.0584 (13)	0.0781 (16)	0.0545 (13)	−0.0249 (12)	0.0268 (11)	−0.0228 (12)
C21	0.0655 (13)	0.0656 (13)	0.0428 (11)	−0.0235 (11)	0.0270 (10)	−0.0106 (10)
Cl1	0.1104 (5)	0.0655 (4)	0.0658 (4)	0.0146 (3)	0.0494 (4)	0.0240 (3)
Cl2	0.0677 (4)	0.1129 (6)	0.0483 (3)	0.0084 (4)	0.0094 (3)	−0.0332 (3)
N1	0.0474 (9)	0.0284 (7)	0.0358 (8)	−0.0031 (6)	0.0170 (7)	−0.0040 (6)
O1	0.0632 (9)	0.0357 (7)	0.0738 (10)	−0.0121 (6)	0.0328 (8)	−0.0032 (7)

C1—N1	1.469 (2)	C10—C11	1.389 (3)
C1—C9	1.513 (2)	C10—H10	0.9300
C1—C2	1.565 (2)	C11—C12	1.370 (3)
C1—H1	0.9800	C11—H11	0.9300
C2—C8	1.516 (3)	C12—C13	1.373 (3)
C2—C15	1.527 (3)	C12—Cl1	1.744 (2)
C2—C3	1.554 (3)	C13—C14	1.382 (3)
C3—C4	1.524 (3)	C13—H13	0.9300
C3—H3A	0.9700	C14—H14	0.9300
C3—H3B	0.9700	C15—H15A	0.9600
C4—C5	1.529 (3)	C15—H15B	0.9600
C4—H4A	0.9700	C15—H15C	0.9600
C4—H4B	0.9700	C16—C21	1.377 (3)
C5—C6	1.533 (3)	C16—C17	1.384 (3)
C5—H5A	0.9700	C17—C18	1.386 (3)
C5—H5B	0.9700	C17—H17	0.9300
C6—C8	1.498 (3)	C18—C19	1.363 (3)
C6—C7	1.553 (3)	C18—H18	0.9300
C6—H6	0.9800	C19—C20	1.364 (3)
C7—N1	1.460 (2)	C19—Cl2	1.747 (2)
C7—C16	1.515 (2)	C20—C21	1.389 (3)
C7—H7	0.9800	C20—H20	0.9300
C8—O1	1.217 (2)	C21—H21	0.9300
C9—C10	1.389 (3)	N1—H1A	0.87 (2)
C9—C14	1.391 (3)
N1—C1—C9	110.30 (13)	C10—C9—C14	117.55 (17)
N1—C1—C2	111.38 (14)	C10—C9—C1	120.56 (16)
C9—C1—C2	111.78 (14)	C14—C9—C1	121.83 (16)
N1—C1—H1	107.7	C11—C10—C9	121.37 (18)
C9—C1—H1	107.7	C11—C10—H10	119.3
C2—C1—H1	107.7	C9—C10—H10	119.3
C8—C2—C15	111.32 (15)	C12—C11—C10	119.18 (18)
C8—C2—C3	104.31 (15)	C12—C11—H11	120.4
C15—C2—C3	109.74 (16)	C10—C11—H11	120.4
C8—C2—C1	106.57 (14)	C11—C12—C13	121.07 (18)
C15—C2—C1	109.68 (15)	C11—C12—Cl1	119.56 (16)
C3—C2—C1	115.08 (14)	C13—C12—Cl1	119.36 (16)
C4—C3—C2	115.70 (16)	C12—C13—C14	119.27 (19)
C4—C3—H3A	108.4	C12—C13—H13	120.4
C2—C3—H3A	108.4	C14—C13—H13	120.4
C4—C3—H3B	108.4	C13—C14—C9	121.50 (18)
C2—C3—H3B	108.4	C13—C14—H14	119.3
H3A—C3—H3B	107.4	C9—C14—H14	119.3
C3—C4—C5	112.12 (17)	C2—C15—H15A	109.5
C3—C4—H4A	109.2	C2—C15—H15B	109.5
C5—C4—H4A	109.2	H15A—C15—H15B	109.5
C3—C4—H4B	109.2	C2—C15—H15C	109.5
C5—C4—H4B	109.2	H15A—C15—H15C	109.5
H4A—C4—H4B	107.9	H15B—C15—H15C	109.5
C4—C5—C6	113.87 (16)	C21—C16—C17	118.09 (18)
C4—C5—H5A	108.8	C21—C16—C7	122.73 (17)
C6—C5—H5A	108.8	C17—C16—C7	119.16 (17)
C4—C5—H5B	108.8	C16—C17—C18	121.1 (2)
C6—C5—H5B	108.8	C16—C17—H17	119.5
H5A—C5—H5B	107.7	C18—C17—H17	119.5
C8—C6—C5	107.78 (16)	C19—C18—C17	119.4 (2)
C8—C6—C7	108.41 (15)	C19—C18—H18	120.3
C5—C6—C7	115.04 (15)	C17—C18—H18	120.3
C8—C6—H6	108.5	C18—C19—C20	120.96 (19)
C5—C6—H6	108.5	C18—C19—Cl2	119.73 (18)
C7—C6—H6	108.5	C20—C19—Cl2	119.29 (18)
N1—C7—C16	111.94 (14)	C19—C20—C21	119.4 (2)
N1—C7—C6	109.61 (15)	C19—C20—H20	120.3
C16—C7—C6	110.16 (15)	C21—C20—H20	120.3
N1—C7—H7	108.3	C16—C21—C20	121.0 (2)
C16—C7—H7	108.3	C16—C21—H21	119.5
C6—C7—H7	108.3	C20—C21—H21	119.5
O1—C8—C6	122.90 (18)	C7—N1—C1	113.28 (13)
O1—C8—C2	123.91 (18)	C7—N1—H1A	109.6 (13)
C6—C8—C2	113.12 (14)	C1—N1—H1A	106.6 (14)
N1—C1—C2—C8	−54.97 (18)	C2—C1—C9—C14	79.6 (2)
C9—C1—C2—C8	−178.85 (14)	C14—C9—C10—C11	−1.7 (3)
N1—C1—C2—C15	−175.58 (15)	C1—C9—C10—C11	175.53 (17)
C9—C1—C2—C15	60.54 (19)	C9—C10—C11—C12	−0.3 (3)
N1—C1—C2—C3	60.1 (2)	C10—C11—C12—C13	2.1 (3)
C9—C1—C2—C3	−63.8 (2)	C10—C11—C12—Cl1	−178.40 (15)
C8—C2—C3—C4	54.2 (2)	C11—C12—C13—C14	−1.7 (3)
C15—C2—C3—C4	173.54 (17)	Cl1—C12—C13—C14	178.79 (15)
C1—C2—C3—C4	−62.2 (2)	C12—C13—C14—C9	−0.5 (3)
C2—C3—C4—C5	−46.7 (2)	C10—C9—C14—C13	2.1 (3)
C3—C4—C5—C6	44.8 (2)	C1—C9—C14—C13	−175.09 (17)
C4—C5—C6—C8	−52.9 (2)	N1—C7—C16—C21	13.9 (3)
C4—C5—C6—C7	68.2 (2)	C6—C7—C16—C21	−108.3 (2)
C8—C6—C7—N1	57.08 (19)	N1—C7—C16—C17	−167.77 (18)
C5—C6—C7—N1	−63.6 (2)	C6—C7—C16—C17	70.0 (2)
C8—C6—C7—C16	−179.33 (15)	C21—C16—C17—C18	3.2 (4)
C5—C6—C7—C16	60.0 (2)	C7—C16—C17—C18	−175.2 (2)
C5—C6—C8—O1	−111.7 (2)	C16—C17—C18—C19	−1.9 (4)
C7—C6—C8—O1	123.23 (19)	C17—C18—C19—C20	−1.0 (4)
C5—C6—C8—C2	65.39 (19)	C17—C18—C19—Cl2	−179.72 (19)
C7—C6—C8—C2	−59.72 (19)	C18—C19—C20—C21	2.4 (4)
C15—C2—C8—O1	−5.7 (3)	Cl2—C19—C20—C21	−178.89 (18)
C3—C2—C8—O1	112.63 (19)	C17—C16—C21—C20	−1.8 (3)
C1—C2—C8—O1	−125.20 (18)	C7—C16—C21—C20	176.5 (2)
C15—C2—C8—C6	177.33 (16)	C19—C20—C21—C16	−0.9 (4)
C3—C2—C8—C6	−64.39 (18)	C16—C7—N1—C1	179.17 (14)
C1—C2—C8—C6	57.77 (19)	C6—C7—N1—C1	−58.29 (19)
N1—C1—C9—C10	137.96 (17)	C9—C1—N1—C7	−176.97 (14)
C2—C1—C9—C10	−97.55 (19)	C2—C1—N1—C7	58.32 (19)
N1—C1—C9—C14	−44.9 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1i	0.87 (2)	2.45 (2)	3.309 (2)	170.2 (18)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1i	0.87 (2)	2.45 (2)	3.309 (2)	170.2 (18)

Symmetry code: (i) .