Methyl 3-(4-bromo-phen-yl)-1-methyl-1,2,3,3a,4,9b-hexa-hydro-benzo[f]chromeno[4,3-b]pyrrole-3a-carboxyl-ate.

In the title compound, C(24)H(22)BrNO(3), the dihydro-pyran ring adopts a half-chair conformation, whereas the pyrrolidine ring is in an envelope conformation. The bromo-phenyl group is oriented at an angle of 66.44 (4)° with respect to the naphthalene ring system. In the crystal structure, mol-ecules are linked into centrosymmetric dimers by C-H⋯π inter-actions and the dimers are connected via C-H⋯Br hydrogen bonds. The crystal structure is further stabilized by π-π inter-actions [centroid-centroid distance = 3.453 (1) Å].

Related literature

For the biological activity of pyrrole derivatives, see: Biava et al. (2005 ▶); Borthwick et al. (2000 ▶); Caine (1993 ▶); Carlson (1993 ▶); Fernandes et al. (2004 ▶); Jiang et al. (2004 ▶); Sokoloff et al. (1990 ▶); Tidey (1992 ▶); Wilner (1985 ▶). For a related structure, see: Nirmala et al. (2009 ▶). For ring-puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C24H22BrNO3

M = 452.34

Monoclinic,

a = 12.7856 (4) Å

b = 19.9348 (6) Å

c = 8.0189 (3) Å

β = 106.163 (2)°

V = 1963.06 (11) Å3

Z = 4

Mo Kα radiation

μ = 2.12 mm−1

T = 293 K

0.25 × 0.20 × 0.15 mm

Data collection

Bruker Kappa APEXII area-detector diffractometer

Absorption correction: multi-scan (Blessing, 1995 ▶) T min = 0.619, T max = 0.742

49847 measured reflections

6162 independent reflections

4068 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.102

S = 1.02

6162 reflections

262 parameters

H-atom parameters constrained

Δρmax = 0.58 e Å−3

Δρmin = −0.51 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809029389/ci2858sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809029389/ci2858Isup2.hkl

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

C24H22BrNO3	F(000) = 928
Mr = 452.34	Dx = 1.531 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 14860 reflections
a = 12.7856 (4) Å	θ = 2.6–25.2°
b = 19.9348 (6) Å	µ = 2.12 mm−1
c = 8.0189 (3) Å	T = 293 K
β = 106.163 (2)°	Prism, colourless
V = 1963.06 (11) Å3	0.25 × 0.20 × 0.15 mm
Z = 4

Bruker Kappa APEXII area-detector diffractometer	6162 independent reflections
Radiation source: fine-focus sealed tube	4068 reflections with I > 2σ(I)
graphite	Rint = 0.031
ω and φ scans	θmax = 30.9°, θmin = 2.0°
Absorption correction: multi-scan (Blessing, 1995)	h = −18→18
Tmin = 0.619, Tmax = 0.742	k = −16→28
49847 measured reflections	l = −11→11

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.102	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.0439P)2 + 0.7192P] where P = (Fo2 + 2Fc2)/3
6162 reflections	(Δ/σ)max = 0.001
262 parameters	Δρmax = 0.58 e Å−3
0 restraints	Δρmin = −0.51 e Å−3

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
C1	0.68758 (13)	0.58289 (8)	0.6893 (2)	0.0281 (3)
H1	0.7433	0.6171	0.6940	0.034*
C2	0.73957 (13)	0.52048 (8)	0.7836 (2)	0.0287 (3)
C3	0.84557 (13)	0.49812 (8)	0.7827 (2)	0.0306 (3)
C4	0.91361 (15)	0.53431 (10)	0.7029 (2)	0.0381 (4)
H4	0.8889	0.5745	0.6470	0.046*
C5	1.01452 (16)	0.51164 (11)	0.7061 (2)	0.0455 (5)
H5	1.0576	0.5367	0.6530	0.055*
C6	1.05416 (17)	0.45149 (12)	0.7878 (3)	0.0510 (5)
H6	1.1226	0.4360	0.7869	0.061*
C7	0.99246 (17)	0.41579 (11)	0.8685 (3)	0.0474 (5)
H7	1.0195	0.3759	0.9241	0.057*
C8	0.88813 (15)	0.43783 (9)	0.8699 (2)	0.0357 (4)
C9	0.82649 (16)	0.40202 (9)	0.9600 (3)	0.0425 (4)
H9	0.8535	0.3620	1.0149	0.051*
C10	0.72848 (16)	0.42484 (9)	0.9681 (2)	0.0417 (4)
H10	0.6893	0.4013	1.0309	0.050*
C11	0.68588 (14)	0.48451 (8)	0.8811 (2)	0.0329 (3)
C12	0.52824 (14)	0.55294 (8)	0.7923 (2)	0.0338 (4)
H12A	0.4714	0.5700	0.8396	0.041*
H12B	0.4935	0.5324	0.6810	0.041*
C13	0.59903 (13)	0.61089 (8)	0.7656 (2)	0.0289 (3)
C14	0.53395 (14)	0.65915 (8)	0.6186 (2)	0.0333 (4)
H14	0.5695	0.7031	0.6403	0.040*
C15	0.55720 (16)	0.63062 (10)	0.4547 (2)	0.0424 (4)
H15A	0.4896	0.6189	0.3692	0.051*
H15B	0.5952	0.6635	0.4040	0.051*
C16	0.41597 (13)	0.66967 (8)	0.6127 (2)	0.0308 (3)
C17	0.38794 (16)	0.72456 (9)	0.6967 (3)	0.0449 (5)
H17	0.4420	0.7544	0.7536	0.054*
C18	0.28173 (17)	0.73619 (10)	0.6981 (3)	0.0491 (5)
H18	0.2645	0.7732	0.7558	0.059*
C19	0.20242 (15)	0.69243 (9)	0.6136 (2)	0.0379 (4)
C20	0.22678 (14)	0.63726 (9)	0.5282 (2)	0.0362 (4)
H20	0.1721	0.6077	0.4715	0.043*
C21	0.33319 (14)	0.62635 (8)	0.5280 (2)	0.0337 (4)
H21	0.3499	0.5892	0.4699	0.040*
C22	0.68903 (16)	0.55698 (9)	0.3883 (2)	0.0385 (4)
H22A	0.7326	0.5177	0.4259	0.058*
H22B	0.7357	0.5945	0.3858	0.058*
H22C	0.6413	0.5496	0.2740	0.058*
C23	0.63964 (14)	0.65052 (8)	0.9323 (2)	0.0338 (4)
C24	0.7836 (2)	0.71536 (12)	1.1053 (3)	0.0631 (7)
H24A	0.8555	0.7299	1.1072	0.095*
H24B	0.7869	0.6896	1.2078	0.095*
H24C	0.7378	0.7538	1.1018	0.095*
N1	0.62481 (12)	0.57086 (7)	0.50776 (18)	0.0322 (3)
O1	0.58933 (10)	0.50339 (6)	0.90663 (17)	0.0412 (3)
O2	0.73947 (11)	0.67466 (8)	0.9542 (2)	0.0529 (4)
O3	0.58771 (13)	0.66160 (9)	1.03113 (19)	0.0594 (4)
Br1	0.056104 (18)	0.708461 (13)	0.61041 (4)	0.06427 (10)

	U11	U22	U33	U12	U13	U23
C1	0.0292 (8)	0.0257 (7)	0.0314 (8)	−0.0020 (6)	0.0121 (6)	0.0029 (6)
C2	0.0324 (8)	0.0275 (7)	0.0275 (8)	0.0002 (6)	0.0103 (7)	0.0006 (6)
C3	0.0332 (8)	0.0333 (8)	0.0255 (8)	0.0009 (6)	0.0085 (6)	−0.0059 (6)
C4	0.0382 (9)	0.0452 (10)	0.0322 (9)	0.0007 (7)	0.0118 (7)	−0.0013 (7)
C5	0.0370 (10)	0.0638 (13)	0.0382 (10)	−0.0007 (9)	0.0144 (8)	−0.0083 (9)
C6	0.0379 (10)	0.0685 (14)	0.0469 (12)	0.0140 (10)	0.0121 (9)	−0.0119 (10)
C7	0.0477 (11)	0.0486 (11)	0.0429 (11)	0.0169 (9)	0.0076 (9)	−0.0056 (9)
C8	0.0382 (9)	0.0375 (9)	0.0297 (9)	0.0063 (7)	0.0064 (7)	−0.0052 (7)
C9	0.0523 (11)	0.0324 (9)	0.0405 (10)	0.0103 (8)	0.0092 (9)	0.0053 (8)
C10	0.0512 (11)	0.0344 (9)	0.0426 (10)	0.0008 (8)	0.0181 (9)	0.0105 (8)
C11	0.0362 (9)	0.0315 (8)	0.0326 (9)	0.0004 (7)	0.0124 (7)	0.0030 (7)
C12	0.0304 (8)	0.0343 (8)	0.0397 (9)	0.0005 (6)	0.0146 (7)	0.0089 (7)
C13	0.0278 (8)	0.0288 (7)	0.0324 (8)	0.0006 (6)	0.0122 (6)	0.0043 (6)
C14	0.0322 (8)	0.0302 (8)	0.0375 (9)	0.0009 (6)	0.0100 (7)	0.0072 (7)
C15	0.0399 (10)	0.0523 (11)	0.0375 (10)	0.0099 (8)	0.0150 (8)	0.0143 (8)
C16	0.0321 (8)	0.0260 (7)	0.0334 (9)	0.0029 (6)	0.0077 (7)	0.0028 (6)
C17	0.0396 (10)	0.0328 (9)	0.0559 (12)	0.0008 (7)	0.0024 (9)	−0.0141 (8)
C18	0.0480 (11)	0.0385 (10)	0.0585 (13)	0.0110 (8)	0.0106 (10)	−0.0155 (9)
C19	0.0348 (9)	0.0392 (9)	0.0401 (10)	0.0095 (7)	0.0110 (8)	0.0041 (7)
C20	0.0348 (9)	0.0346 (9)	0.0373 (9)	−0.0027 (7)	0.0068 (7)	−0.0015 (7)
C21	0.0377 (9)	0.0293 (8)	0.0346 (9)	0.0016 (7)	0.0110 (7)	−0.0045 (7)
C22	0.0453 (10)	0.0421 (10)	0.0315 (9)	−0.0002 (8)	0.0164 (8)	0.0016 (7)
C23	0.0333 (9)	0.0317 (8)	0.0367 (9)	0.0059 (7)	0.0103 (7)	0.0042 (7)
C24	0.0480 (13)	0.0636 (14)	0.0739 (16)	−0.0068 (10)	0.0107 (11)	−0.0321 (12)
N1	0.0346 (7)	0.0358 (7)	0.0280 (7)	−0.0006 (6)	0.0118 (6)	0.0051 (6)
O1	0.0393 (7)	0.0416 (7)	0.0498 (8)	0.0059 (5)	0.0238 (6)	0.0190 (6)
O2	0.0394 (7)	0.0582 (9)	0.0646 (9)	−0.0116 (6)	0.0203 (7)	−0.0283 (7)
O3	0.0555 (9)	0.0822 (11)	0.0476 (8)	−0.0085 (8)	0.0263 (7)	−0.0169 (8)
Br1	0.04256 (13)	0.07000 (17)	0.0859 (2)	0.01747 (10)	0.02724 (12)	0.00945 (12)

C1—N1	1.473 (2)	C14—C16	1.511 (2)
C1—C2	1.510 (2)	C14—C15	1.536 (3)
C1—C13	1.534 (2)	C14—H14	0.98
C1—H1	0.98	C15—N1	1.464 (2)
C2—C11	1.377 (2)	C15—H15A	0.97
C2—C3	1.429 (2)	C15—H15B	0.97
C3—C4	1.413 (2)	C16—C17	1.383 (2)
C3—C8	1.421 (2)	C16—C21	1.388 (2)
C4—C5	1.361 (3)	C17—C18	1.381 (3)
C4—H4	0.93	C17—H17	0.93
C5—C6	1.392 (3)	C18—C19	1.366 (3)
C5—H5	0.93	C18—H18	0.93
C6—C7	1.353 (3)	C19—C20	1.376 (3)
C6—H6	0.93	C19—Br1	1.8910 (18)
C7—C8	1.408 (3)	C20—C21	1.378 (2)
C7—H7	0.93	C20—H20	0.93
C8—C9	1.403 (3)	C21—H21	0.93
C9—C10	1.352 (3)	C22—N1	1.452 (2)
C9—H9	0.93	C22—H22A	0.96
C10—C11	1.410 (2)	C22—H22B	0.96
C10—H10	0.93	C22—H22C	0.96
C11—O1	1.360 (2)	C23—O3	1.188 (2)
C12—O1	1.424 (2)	C23—O2	1.329 (2)
C12—C13	1.519 (2)	C24—O2	1.437 (3)
C12—H12A	0.97	C24—H24A	0.96
C12—H12B	0.97	C24—H24B	0.96
C13—C23	1.514 (2)	C24—H24C	0.96
C13—C14	1.569 (2)
N1—C1—C2	113.78 (13)	C16—C14—C13	115.15 (13)
N1—C1—C13	101.17 (13)	C15—C14—C13	103.15 (13)
C2—C1—C13	111.80 (13)	C16—C14—H14	107.0
N1—C1—H1	109.9	C15—C14—H14	107.0
C2—C1—H1	109.9	C13—C14—H14	107.0
C13—C1—H1	109.9	N1—C15—C14	106.96 (14)
C11—C2—C3	117.65 (15)	N1—C15—H15A	110.3
C11—C2—C1	119.57 (14)	C14—C15—H15A	110.3
C3—C2—C1	122.72 (14)	N1—C15—H15B	110.3
C4—C3—C8	117.08 (16)	C14—C15—H15B	110.3
C4—C3—C2	123.20 (15)	H15A—C15—H15B	108.6
C8—C3—C2	119.69 (15)	C17—C16—C21	117.69 (16)
C5—C4—C3	121.46 (18)	C17—C16—C14	119.11 (15)
C5—C4—H4	119.3	C21—C16—C14	123.20 (15)
C3—C4—H4	119.3	C18—C17—C16	121.72 (17)
C4—C5—C6	120.93 (19)	C18—C17—H17	119.1
C4—C5—H5	119.5	C16—C17—H17	119.1
C6—C5—H5	119.5	C19—C18—C17	118.97 (17)
C7—C6—C5	119.57 (18)	C19—C18—H18	120.5
C7—C6—H6	120.2	C17—C18—H18	120.5
C5—C6—H6	120.2	C18—C19—C20	121.18 (17)
C6—C7—C8	121.30 (19)	C18—C19—Br1	119.58 (14)
C6—C7—H7	119.4	C20—C19—Br1	119.23 (14)
C8—C7—H7	119.4	C19—C20—C21	119.14 (16)
C9—C8—C7	120.97 (17)	C19—C20—H20	120.4
C9—C8—C3	119.39 (16)	C21—C20—H20	120.4
C7—C8—C3	119.61 (18)	C20—C21—C16	121.29 (15)
C10—C9—C8	120.98 (17)	C20—C21—H21	119.4
C10—C9—H9	119.5	C16—C21—H21	119.4
C8—C9—H9	119.5	N1—C22—H22A	109.5
C9—C10—C11	119.71 (17)	N1—C22—H22B	109.5
C9—C10—H10	120.1	H22A—C22—H22B	109.5
C11—C10—H10	120.1	N1—C22—H22C	109.5
O1—C11—C2	123.97 (15)	H22A—C22—H22C	109.5
O1—C11—C10	113.62 (15)	H22B—C22—H22C	109.5
C2—C11—C10	122.39 (16)	O3—C23—O2	122.60 (17)
O1—C12—C13	112.14 (14)	O3—C23—C13	124.61 (16)
O1—C12—H12A	109.2	O2—C23—C13	112.73 (14)
C13—C12—H12A	109.2	O2—C24—H24A	109.5
O1—C12—H12B	109.2	O2—C24—H24B	109.5
C13—C12—H12B	109.2	H24A—C24—H24B	109.5
H12A—C12—H12B	107.9	O2—C24—H24C	109.5
C23—C13—C12	110.09 (14)	H24A—C24—H24C	109.5
C23—C13—C1	115.59 (13)	H24B—C24—H24C	109.5
C12—C13—C1	108.33 (13)	C22—N1—C15	111.10 (13)
C23—C13—C14	108.83 (13)	C22—N1—C1	115.52 (14)
C12—C13—C14	111.11 (13)	C15—N1—C1	105.67 (13)
C1—C13—C14	102.70 (13)	C11—O1—C12	116.96 (12)
C16—C14—C15	117.01 (15)	C23—O2—C24	116.95 (16)
N1—C1—C2—C11	−94.11 (18)	C12—C13—C14—C16	37.3 (2)
C13—C1—C2—C11	19.7 (2)	C1—C13—C14—C16	152.89 (14)
N1—C1—C2—C3	88.72 (18)	C23—C13—C14—C15	147.21 (14)
C13—C1—C2—C3	−157.44 (15)	C12—C13—C14—C15	−91.41 (16)
C11—C2—C3—C4	−173.26 (16)	C1—C13—C14—C15	24.21 (16)
C1—C2—C3—C4	4.0 (2)	C16—C14—C15—N1	−125.38 (15)
C11—C2—C3—C8	4.7 (2)	C13—C14—C15—N1	2.14 (18)
C1—C2—C3—C8	−178.13 (15)	C15—C14—C16—C17	−143.63 (18)
C8—C3—C4—C5	1.5 (3)	C13—C14—C16—C17	94.9 (2)
C2—C3—C4—C5	179.42 (16)	C15—C14—C16—C21	37.0 (2)
C3—C4—C5—C6	0.3 (3)	C13—C14—C16—C21	−84.4 (2)
C4—C5—C6—C7	−1.5 (3)	C21—C16—C17—C18	0.5 (3)
C5—C6—C7—C8	0.7 (3)	C14—C16—C17—C18	−178.94 (19)
C6—C7—C8—C9	−177.30 (18)	C16—C17—C18—C19	−0.3 (3)
C6—C7—C8—C3	1.1 (3)	C17—C18—C19—C20	0.2 (3)
C4—C3—C8—C9	176.27 (16)	C17—C18—C19—Br1	−178.80 (16)
C2—C3—C8—C9	−1.8 (2)	C18—C19—C20—C21	−0.2 (3)
C4—C3—C8—C7	−2.1 (2)	Br1—C19—C20—C21	178.80 (13)
C2—C3—C8—C7	179.83 (16)	C19—C20—C21—C16	0.3 (3)
C7—C8—C9—C10	176.89 (18)	C17—C16—C21—C20	−0.5 (3)
C3—C8—C9—C10	−1.5 (3)	C14—C16—C21—C20	178.91 (16)
C8—C9—C10—C11	1.8 (3)	C12—C13—C23—O3	−37.5 (2)
C3—C2—C11—O1	173.77 (15)	C1—C13—C23—O3	−160.58 (17)
C1—C2—C11—O1	−3.5 (3)	C14—C13—C23—O3	84.5 (2)
C3—C2—C11—C10	−4.5 (3)	C12—C13—C23—O2	145.27 (15)
C1—C2—C11—C10	178.16 (16)	C1—C13—C23—O2	22.1 (2)
C9—C10—C11—O1	−177.08 (17)	C14—C13—C23—O2	−92.74 (17)
C9—C10—C11—C2	1.4 (3)	C14—C15—N1—C22	−155.30 (15)
O1—C12—C13—C23	−67.90 (18)	C14—C15—N1—C1	−29.30 (18)
O1—C12—C13—C1	59.38 (18)	C2—C1—N1—C22	−72.26 (17)
O1—C12—C13—C14	171.46 (13)	C13—C1—N1—C22	167.70 (13)
N1—C1—C13—C23	−160.07 (13)	C2—C1—N1—C15	164.50 (13)
C2—C1—C13—C23	78.49 (17)	C13—C1—N1—C15	44.46 (15)
N1—C1—C13—C12	75.89 (15)	C2—C11—O1—C12	16.4 (2)
C2—C1—C13—C12	−45.55 (18)	C10—C11—O1—C12	−165.22 (16)
N1—C1—C13—C14	−41.73 (14)	C13—C12—O1—C11	−45.0 (2)
C2—C1—C13—C14	−163.17 (13)	O3—C23—O2—C24	0.2 (3)
C23—C13—C14—C16	−84.11 (17)	C13—C23—O2—C24	177.54 (17)

D—H···A	D—H	H···A	D···A	D—H···A
C24—H24A···Br1i	0.96	2.84	3.789 (3)	172
C20—H20···Cg1ii	0.93	2.77	3.653 (2)	160

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C24—H24A⋯Br1i	0.96	2.84	3.789 (3)	172
C20—H20⋯Cg1ii	0.93	2.77	3.653 (2)	160

Symmetry codes: (i) ; (ii) . Cg1 is the centroid of the C3–C8 ring.