1-Bromo-acetyl-2,6-bis-(4-methoxy-phen-yl)-3,5-dimethyl-piperidin-4-one.

In the title compound, C(23)H(26)BrNO(4), the piperidinone ring adopts a boat conformation. The dihedral angle between the two benzene rings is 70.9 (1)°. The two meth-oxy groups are close to coplanar with the attached benzene rings [C-C-O-C torsion angles of 6.3 (5) and 16.4 (4)°]. A weak C-H⋯Br intra-molecular inter-action is observed. In the crystal structure, mol-ecules are linked into a chain along [101] by inter-molecular C-H⋯O hydrogen bonds. A short inter-molecular Br⋯O contact [3.063 (2) Å] is observed.

Related literature

For background on the piperidine ring system, see: O’Hagan (2000 ▶); Pinder (1992 ▶). For information on the aryl­piperidine scaffold, see: Horton et al. (2003 ▶). For piperidone derivatives, see: Baluja et al. (1964 ▶); Mutus et al. (1989 ▶). For the biological activities of compounds possessing an amide bond linkage, see: Priya et al. (2007 ▶); Bylov et al. (1999 ▶); Dollery (1999 ▶). For the activivities of chloro­acetyl and heterocyclicacetyl derivatives of variously functionalized 2,6-diaryl­piperidin-4-ones, see: Aridoss et al. (2007a ▶,b ▶; 2008a ▶). For a related structure, see: Aridoss et al. (2008b ▶). For ring conformational analysis, see: Cremer & Pople (1975 ▶); Nardelli (1983 ▶).

Experimental

Crystal data

C23H26BrNO4

M = 460.36

Monoclinic,

a = 12.9487 (9) Å

b = 25.2882 (18) Å

c = 8.9701 (6) Å

β = 132.930 (1)°

V = 2150.6 (3) Å3

Z = 4

Mo Kα radiation

μ = 1.94 mm−1

T = 293 (2) K

0.30 × 0.20 × 0.16 mm

Data collection

Bruker Kappa APEXII diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 1999 ▶) T min = 0.594, T max = 0.747

13660 measured reflections

5139 independent reflections

3748 reflections with I > 2σ(I)

R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.098

S = 1.02

5139 reflections

266 parameters

2 restraints

H-atom parameters constrained

Δρmax = 0.42 e Å−3

Δρmin = −0.22 e Å−3

Absolute structure: Flack (1983 ▶), 1651 Friedel pairs

Flack parameter: 0.004 (7)

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: PLATON (Spek, 2003 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808030213/ci2672sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808030213/ci2672Isup2.hkl

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

C23H26BrNO4	F(000) = 952
Mr = 460.36	Dx = 1.422 Mg m−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 5872 reflections
a = 12.9487 (9) Å	θ = 1.6–31.2°
b = 25.2882 (18) Å	µ = 1.94 mm−1
c = 8.9701 (6) Å	T = 293 K
β = 132.930 (1)°	Prism, colourless
V = 2150.6 (3) Å3	0.30 × 0.20 × 0.16 mm
Z = 4

Bruker Kappa APEXII CCD diffractometer	5139 independent reflections
Radiation source: fine-focus sealed tube	3748 reflections with I > 2σ(I)
graphite	Rint = 0.023
ω and φ scans	θmax = 31.2°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −11→18
Tmin = 0.594, Tmax = 0.747	k = −36→34
13660 measured reflections	l = −13→6

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)] = 0.033	H-atom parameters constrained
wR(F2) = 0.098	w = 1/[σ2(Fo2) + (0.0517P)2] where P = (Fo2 + 2Fc2)/3
S = 1.02	(Δ/σ)max = 0.001
5139 reflections	Δρmax = 0.42 e Å−3
266 parameters	Δρmin = −0.22 e Å−3
2 restraints	Absolute structure: Flack (1983), 1651 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.004 (7)

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.

	x	y	z	Uiso*/Ueq
Br1	0.66353 (4)	0.384464 (14)	1.04369 (5)	0.06848 (12)
O1	0.5273 (2)	0.48401 (7)	0.6690 (3)	0.0532 (5)
O2	0.6012 (3)	0.29025 (9)	0.3780 (5)	0.0771 (8)
O3	−0.0290 (3)	0.45775 (10)	−0.4164 (4)	0.0731 (7)
O4	−0.0766 (2)	0.31531 (9)	0.3554 (3)	0.0559 (5)
N1	0.4607 (2)	0.40235 (8)	0.5255 (3)	0.0345 (4)
C1	0.4291 (3)	0.34626 (9)	0.5282 (4)	0.0364 (5)
H1	0.5069	0.3326	0.6654	0.044*
C2	0.4229 (3)	0.31286 (10)	0.3780 (4)	0.0416 (5)
H2	0.3356	0.3223	0.2401	0.050*
C3	0.5436 (3)	0.32436 (11)	0.3917 (4)	0.0461 (6)
C4	0.5906 (4)	0.38105 (11)	0.4261 (6)	0.0446 (7)
H4	0.6004	0.3901	0.3300	0.054*
C5	0.4839 (3)	0.41869 (9)	0.3917 (4)	0.0381 (5)
H5	0.5306	0.4532	0.4424	0.046*
C6	0.3462 (3)	0.42782 (9)	0.1749 (4)	0.0393 (5)
C7	0.3089 (3)	0.40271 (11)	0.0059 (4)	0.0486 (6)
H7	0.3699	0.3780	0.0241	0.058*
C8	0.1835 (4)	0.41381 (12)	−0.1874 (5)	0.0561 (7)
H8	0.1600	0.3961	−0.2979	0.067*
C9	0.0921 (3)	0.45079 (11)	−0.2196 (4)	0.0513 (7)
C10	0.1278 (3)	0.47738 (12)	−0.0556 (5)	0.0516 (7)
H10	0.0682	0.5031	−0.0752	0.062*
C11	0.2541 (3)	0.46518 (10)	0.1394 (4)	0.0455 (6)
H11	0.2772	0.4828	0.2497	0.055*
C12	0.2944 (3)	0.33861 (9)	0.4838 (4)	0.0364 (5)
C13	0.1691 (3)	0.36284 (11)	0.3213 (4)	0.0432 (6)
H13	0.1668	0.3853	0.2371	0.052*
C14	0.0474 (3)	0.35416 (10)	0.2822 (4)	0.0447 (6)
H14	−0.0360	0.3709	0.1725	0.054*
C15	0.0489 (3)	0.32085 (10)	0.4052 (4)	0.0408 (5)
C16	0.1720 (4)	0.29517 (10)	0.5642 (5)	0.0492 (6)
H16	0.1732	0.2717	0.6453	0.059*
C17	0.2921 (3)	0.30430 (11)	0.6021 (5)	0.0488 (6)
H17	0.3747	0.2870	0.7105	0.059*
C18	0.4147 (5)	0.25375 (12)	0.4064 (7)	0.0680 (9)
H18A	0.4945	0.2439	0.5445	0.102*
H18B	0.4151	0.2337	0.3159	0.102*
H18C	0.3294	0.2466	0.3765	0.102*
C19	0.7355 (4)	0.38566 (13)	0.6430 (7)	0.0598 (10)
H19A	0.7995	0.3610	0.6607	0.090*
H19B	0.7269	0.3779	0.7389	0.090*
H19C	0.7708	0.4210	0.6653	0.090*
C20	−0.1223 (5)	0.49859 (18)	−0.4644 (7)	0.0873 (12)
H20A	−0.0771	0.5322	−0.4334	0.131*
H20B	−0.1470	0.4941	−0.3857	0.131*
H20C	−0.2060	0.4971	−0.6068	0.131*
C21	−0.0739 (4)	0.29285 (15)	0.5013 (6)	0.0656 (9)
H21A	−0.0047	0.3107	0.6291	0.098*
H21B	−0.0501	0.2560	0.5174	0.098*
H21C	−0.1650	0.2965	0.4571	0.098*
C22	0.4945 (3)	0.43860 (10)	0.6661 (4)	0.0384 (5)
C23	0.4904 (3)	0.42170 (11)	0.8232 (4)	0.0434 (6)
H23A	0.4100	0.3987	0.7608	0.052*
H23B	0.4802	0.4525	0.8766	0.052*

	U11	U22	U33	U12	U13	U23
Br1	0.05974 (18)	0.0974 (3)	0.04260 (14)	0.01855 (19)	0.03263 (13)	0.01594 (17)
O1	0.0652 (13)	0.0408 (10)	0.0590 (12)	−0.0060 (9)	0.0444 (11)	−0.0084 (9)
O2	0.0764 (17)	0.0581 (13)	0.123 (2)	−0.0063 (11)	0.0782 (18)	−0.0271 (13)
O3	0.0637 (15)	0.0801 (15)	0.0478 (12)	0.0042 (12)	0.0271 (12)	0.0110 (11)
O4	0.0489 (12)	0.0669 (13)	0.0613 (12)	−0.0003 (9)	0.0412 (11)	0.0063 (10)
N1	0.0395 (11)	0.0334 (9)	0.0376 (10)	−0.0026 (8)	0.0290 (9)	−0.0018 (8)
C1	0.0388 (12)	0.0350 (12)	0.0381 (12)	0.0030 (10)	0.0272 (11)	0.0031 (9)
C2	0.0473 (14)	0.0346 (12)	0.0520 (14)	−0.0020 (10)	0.0374 (13)	−0.0035 (11)
C3	0.0457 (15)	0.0475 (15)	0.0512 (14)	0.0007 (12)	0.0354 (13)	−0.0075 (12)
C4	0.0461 (19)	0.0498 (16)	0.0493 (19)	−0.0023 (11)	0.0370 (17)	−0.0005 (12)
C5	0.0482 (15)	0.0341 (12)	0.0449 (13)	−0.0028 (10)	0.0369 (13)	−0.0007 (10)
C6	0.0513 (15)	0.0337 (12)	0.0431 (12)	−0.0033 (10)	0.0362 (12)	0.0015 (9)
C7	0.0624 (18)	0.0442 (13)	0.0469 (15)	0.0056 (12)	0.0402 (15)	0.0020 (11)
C8	0.073 (2)	0.0501 (16)	0.0428 (14)	0.0030 (15)	0.0384 (16)	0.0000 (12)
C9	0.0532 (17)	0.0517 (16)	0.0436 (14)	−0.0031 (13)	0.0308 (14)	0.0089 (12)
C10	0.0560 (18)	0.0474 (15)	0.0543 (16)	0.0074 (13)	0.0387 (15)	0.0074 (12)
C11	0.0581 (17)	0.0417 (14)	0.0470 (14)	0.0004 (12)	0.0399 (14)	0.0006 (11)
C12	0.0423 (14)	0.0329 (11)	0.0405 (12)	−0.0008 (10)	0.0307 (11)	0.0005 (9)
C13	0.0485 (15)	0.0404 (13)	0.0439 (13)	−0.0005 (11)	0.0327 (13)	0.0079 (11)
C14	0.0392 (14)	0.0450 (16)	0.0425 (13)	0.0041 (11)	0.0250 (12)	0.0089 (11)
C15	0.0422 (14)	0.0377 (13)	0.0486 (14)	−0.0060 (11)	0.0333 (13)	−0.0068 (11)
C16	0.0549 (16)	0.0480 (14)	0.0563 (17)	0.0030 (14)	0.0424 (15)	0.0127 (13)
C17	0.0492 (16)	0.0482 (15)	0.0551 (16)	0.0106 (12)	0.0379 (15)	0.0188 (13)
C18	0.099 (3)	0.0367 (15)	0.105 (3)	−0.0042 (15)	0.084 (3)	−0.0081 (16)
C19	0.043 (2)	0.060 (2)	0.068 (3)	−0.0046 (13)	0.035 (2)	−0.0127 (15)
C20	0.076 (3)	0.091 (3)	0.078 (3)	0.021 (2)	0.046 (2)	0.030 (2)
C21	0.066 (2)	0.087 (2)	0.065 (2)	−0.0187 (17)	0.0529 (19)	−0.0098 (17)
C22	0.0332 (12)	0.0415 (13)	0.0373 (12)	0.0018 (10)	0.0227 (11)	−0.0022 (10)
C23	0.0412 (14)	0.0541 (16)	0.0376 (12)	0.0032 (11)	0.0278 (12)	−0.0022 (11)

Br1—C23	1.945 (3)	C10—C11	1.390 (4)
O1—C22	1.219 (3)	C10—H10	0.93
O2—C3	1.201 (3)	C11—H11	0.93
O3—C9	1.354 (4)	C12—C13	1.382 (4)
O3—C20	1.415 (5)	C12—C17	1.387 (4)
O4—C15	1.367 (3)	C13—C14	1.379 (4)
O4—C21	1.406 (4)	C13—H13	0.93
N1—C22	1.368 (3)	C14—C15	1.377 (4)
N1—C5	1.481 (3)	C14—H14	0.93
N1—C1	1.481 (3)	C15—C16	1.378 (4)
C1—C12	1.513 (3)	C16—C17	1.366 (5)
C1—C2	1.546 (3)	C16—H16	0.93
C1—H1	0.9800	C17—H17	0.93
C2—C3	1.509 (4)	C18—H18A	0.96
C2—C18	1.532 (4)	C18—H18B	0.96
C2—H2	0.98	C18—H18C	0.96
C3—C4	1.505 (4)	C19—H19A	0.96
C4—C5	1.526 (4)	C19—H19B	0.96
C4—C19	1.532 (4)	C19—H19C	0.96
C4—H4	0.98	C20—H20A	0.96
C5—C6	1.514 (4)	C20—H20B	0.96
C5—H5	0.98	C20—H20C	0.96
C6—C11	1.378 (4)	C21—H21A	0.96
C6—C7	1.392 (4)	C21—H21B	0.96
C7—C8	1.374 (4)	C21—H21C	0.96
C7—H7	0.93	C22—C23	1.507 (4)
C8—C9	1.375 (5)	C23—H23A	0.97
C8—H8	0.93	C23—H23B	0.97
C9—C10	1.380 (4)
C9—O3—C20	118.8 (3)	C13—C12—C1	122.4 (2)
C15—O4—C21	117.8 (2)	C17—C12—C1	120.0 (2)
C22—N1—C5	116.5 (2)	C14—C13—C12	121.0 (2)
C22—N1—C1	123.0 (2)	C14—C13—H13	119.5
C5—N1—C1	119.5 (2)	C12—C13—H13	119.5
N1—C1—C12	113.59 (19)	C15—C14—C13	120.2 (2)
N1—C1—C2	111.07 (19)	C15—C14—H14	119.9
C12—C1—C2	109.6 (2)	C13—C14—H14	119.9
N1—C1—H1	107.5	O4—C15—C14	115.8 (2)
C12—C1—H1	107.5	O4—C15—C16	124.7 (2)
C2—C1—H1	107.5	C14—C15—C16	119.5 (3)
C3—C2—C18	111.1 (2)	C17—C16—C15	119.7 (3)
C3—C2—C1	112.8 (2)	C17—C16—H16	120.1
C18—C2—C1	110.9 (2)	C15—C16—H16	120.1
C3—C2—H2	107.3	C16—C17—C12	122.0 (3)
C18—C2—H2	107.3	C16—C17—H17	119.0
C1—C2—H2	107.3	C12—C17—H17	119.0
O2—C3—C4	120.8 (3)	C2—C18—H18A	109.5
O2—C3—C2	122.3 (3)	C2—C18—H18B	109.5
C4—C3—C2	116.9 (2)	H18A—C18—H18B	109.5
C3—C4—C5	111.6 (3)	C2—C18—H18C	109.5
C3—C4—C19	107.9 (3)	H18A—C18—H18C	109.5
C5—C4—C19	111.5 (2)	H18B—C18—H18C	109.5
C3—C4—H4	108.6	C4—C19—H19A	109.5
C5—C4—H4	108.6	C4—C19—H19B	109.5
C19—C4—H4	108.6	H19A—C19—H19B	109.5
N1—C5—C6	111.9 (2)	C4—C19—H19C	109.5
N1—C5—C4	108.5 (2)	H19A—C19—H19C	109.5
C6—C5—C4	117.8 (2)	H19B—C19—H19C	109.5
N1—C5—H5	105.9	O3—C20—H20A	109.5
C6—C5—H5	105.9	O3—C20—H20B	109.5
C4—C5—H5	105.9	H20A—C20—H20B	109.5
C11—C6—C7	117.2 (3)	O3—C20—H20C	109.5
C11—C6—C5	118.5 (2)	H20A—C20—H20C	109.5
C7—C6—C5	124.2 (2)	H20B—C20—H20C	109.5
C8—C7—C6	121.1 (3)	O4—C21—H21A	109.5
C8—C7—H7	119.4	O4—C21—H21B	109.5
C6—C7—H7	119.4	H21A—C21—H21B	109.5
C7—C8—C9	120.8 (3)	O4—C21—H21C	109.5
C7—C8—H8	119.6	H21A—C21—H21C	109.5
C9—C8—H8	119.6	H21B—C21—H21C	109.5
O3—C9—C8	115.4 (3)	O1—C22—N1	122.6 (2)
O3—C9—C10	125.2 (3)	O1—C22—C23	118.8 (2)
C8—C9—C10	119.4 (3)	N1—C22—C23	118.6 (2)
C9—C10—C11	119.1 (3)	C22—C23—Br1	109.78 (17)
C9—C10—H10	120.5	C22—C23—H23A	109.7
C11—C10—H10	120.5	Br1—C23—H23A	109.7
C6—C11—C10	122.3 (3)	C22—C23—H23B	109.7
C6—C11—H11	118.9	Br1—C23—H23B	109.7
C10—C11—H11	118.9	H23A—C23—H23B	108.2
C13—C12—C17	117.5 (2)
C22—N1—C1—C12	66.9 (3)	C20—O3—C9—C8	−174.0 (3)
C5—N1—C1—C12	−125.1 (2)	C20—O3—C9—C10	6.3 (5)
C22—N1—C1—C2	−169.1 (2)	C7—C8—C9—O3	−179.1 (3)
C5—N1—C1—C2	−1.1 (3)	C7—C8—C9—C10	0.6 (4)
N1—C1—C2—C3	45.3 (3)	O3—C9—C10—C11	178.2 (3)
C12—C1—C2—C3	171.6 (2)	C8—C9—C10—C11	−1.6 (4)
N1—C1—C2—C18	170.6 (2)	C7—C6—C11—C10	0.8 (4)
C12—C1—C2—C18	−63.1 (3)	C5—C6—C11—C10	177.7 (3)
C18—C2—C3—O2	16.2 (4)	C9—C10—C11—C6	0.9 (4)
C1—C2—C3—O2	141.4 (3)	N1—C1—C12—C13	48.1 (3)
C18—C2—C3—C4	−163.2 (3)	C2—C1—C12—C13	−76.8 (3)
C1—C2—C3—C4	−38.0 (3)	N1—C1—C12—C17	−135.1 (2)
O2—C3—C4—C5	167.3 (3)	C2—C1—C12—C17	100.1 (3)
C2—C3—C4—C5	−13.3 (4)	C17—C12—C13—C14	1.7 (4)
O2—C3—C4—C19	−69.9 (4)	C1—C12—C13—C14	178.6 (2)
C2—C3—C4—C19	109.5 (3)	C12—C13—C14—C15	−0.2 (4)
C22—N1—C5—C6	−109.2 (2)	C21—O4—C15—C14	−164.6 (3)
C1—N1—C5—C6	82.0 (3)	C21—O4—C15—C16	16.4 (4)
C22—N1—C5—C4	119.1 (2)	C13—C14—C15—O4	179.3 (2)
C1—N1—C5—C4	−49.7 (3)	C13—C14—C15—C16	−1.7 (4)
C3—C4—C5—N1	55.9 (3)	O4—C15—C16—C17	−179.0 (3)
C19—C4—C5—N1	−64.8 (3)	C14—C15—C16—C17	2.1 (4)
C3—C4—C5—C6	−72.5 (3)	C15—C16—C17—C12	−0.6 (5)
C19—C4—C5—C6	166.8 (2)	C13—C12—C17—C16	−1.3 (4)
N1—C5—C6—C11	58.9 (3)	C1—C12—C17—C16	−178.3 (3)
C4—C5—C6—C11	−174.3 (2)	C5—N1—C22—O1	7.8 (4)
N1—C5—C6—C7	−124.5 (3)	C1—N1—C22—O1	176.2 (2)
C4—C5—C6—C7	2.3 (4)	C5—N1—C22—C23	−172.4 (2)
C11—C6—C7—C8	−1.8 (4)	C1—N1—C22—C23	−4.0 (4)
C5—C6—C7—C8	−178.4 (3)	O1—C22—C23—Br1	−98.9 (3)
C6—C7—C8—C9	1.1 (5)	N1—C22—C23—Br1	81.2 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···Br1	0.98	2.82	3.523 (3)	129
C20—H20C···O1i	0.96	2.60	3.357 (7)	136

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯Br1	0.98	2.82	3.523 (3)	129
C20—H20C⋯O1i	0.96	2.60	3.357 (7)	136

Symmetry code: (i) .