(2R,3R)-1-(4-Chloro-phen-yl)-2-[(S)-2-nitro-1-phenyl-eth-yl]-3-phenyl-pentan-1-one.

The title compound, C(25)H(24)ClNO(3), has three contiguous chiral centres. The absolute structure was determined by anomalous dispersion. The chloro-benzene ring is inclined to the two phenyl rings by 14.98 (9) and 59.05 (9)°. The two phenyl rings are inclined to one another by 49.51 (10)°. In the crystal, neighbouring mol-ecules are linked via C-H⋯O hydrogen bonds, forming chains propagating along [010]. There is also a C-H⋯π inter-action present that leads to the formation of a three-dimensional network.

Related literature

For the synthesis of the title compound, see: Xu et al. (2007 ▶). For the role of pyrrolidine motifs as organo-catalysts in asymmetric catalysis, see: Taylor & Jacobsen (2006 ▶) and for their role in bioactive mol­ecules, see: Kawasaki et al. (2005 ▶).

Experimental

Crystal data

C25H24ClNO3

M = 421.90

Orthorhombic,

a = 8.4700 (1) Å

b = 13.1515 (2) Å

c = 20.7060 (2) Å

V = 2306.51 (5) Å3

Z = 4

Cu Kα radiation

μ = 1.66 mm−1

T = 293 K

0.42 × 0.36 × 0.30 mm

Data collection

Gemini S Ultra Oxford Diffraction diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T min = 0.542, T max = 0.635

22729 measured reflections

4292 independent reflections

4173 reflections with I > 2σ(I)

R int = 0.019

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.099

S = 1.04

4292 reflections

272 parameters

H-atom parameters constrained

Δρmax = 0.14 e Å−3

Δρmin = −0.25 e Å−3

Absolute structure: Flack (1983 ▶), 1824 Friedel pairs

Flack parameter: −0.010 (13)

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▶); software used to prepare material for publication: OLEX2.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811050306/su2340sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811050306/su2340Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811050306/su2340Isup3.cml

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

C25H24ClNO3	F(000) = 888
Mr = 421.90	Dx = 1.215 Mg m−3
Orthorhombic, P212121	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: P 2ac 2ab	Cell parameters from 16354 reflections
a = 8.4700 (1) Å	θ = 3.4–69.8°
b = 13.1515 (2) Å	µ = 1.66 mm−1
c = 20.7060 (2) Å	T = 293 K
V = 2306.51 (5) Å3	Block, colourless
Z = 4	0.42 × 0.36 × 0.30 mm

Gemini S Ultra Oxford Diffraction diffractometer	4292 independent reflections
Radiation source: fine-focus sealed tube	4173 reflections with I > 2σ(I)
graphite	Rint = 0.019
Detector resolution: 15.9149 pixels mm-1	θmax = 69.9°, θmin = 4.0°
ω scans	h = −10→10
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −15→16
Tmin = 0.542, Tmax = 0.635	l = −21→25
22729 measured reflections

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)] = 0.035	H-atom parameters constrained
wR(F2) = 0.099	w = 1/[σ2(Fo2) + (0.0641P)2 + 0.1848P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max = 0.001
4292 reflections	Δρmax = 0.14 e Å−3
272 parameters	Δρmin = −0.25 e Å−3
0 restraints	Absolute structure: Flack (1983), 1824 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.010 (13)

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
Cl1	0.58917 (6)	0.37368 (4)	0.50249 (2)	0.08473 (17)
O1	0.50133 (14)	0.00173 (10)	0.28825 (7)	0.0700 (3)
O2	0.7782 (3)	−0.30696 (14)	0.25735 (12)	0.1277 (8)
O3	0.9069 (3)	−0.23945 (18)	0.18103 (18)	0.1769 (14)
N1	0.8118 (2)	−0.23648 (13)	0.22259 (12)	0.0826 (5)
C1	0.5978 (2)	0.28418 (13)	0.44074 (8)	0.0595 (4)
C2	0.46287 (19)	0.23354 (13)	0.42310 (7)	0.0565 (4)
H2	0.3673	0.2482	0.4431	0.068*
C3	0.47066 (18)	0.16045 (12)	0.37513 (7)	0.0509 (3)
H3	0.3801	0.1251	0.3634	0.061*
C4	0.61302 (18)	0.13951 (11)	0.34438 (7)	0.0495 (3)
C5	0.7473 (2)	0.19166 (15)	0.36286 (9)	0.0646 (4)
H5	0.8430	0.1778	0.3427	0.078*
C6	0.7404 (2)	0.26467 (16)	0.41126 (9)	0.0697 (5)
H6	0.8308	0.2999	0.4236	0.084*
C7	0.61293 (18)	0.05938 (12)	0.29275 (7)	0.0519 (3)
C8	0.74862 (17)	0.05223 (12)	0.24430 (7)	0.0499 (3)
H8	0.8271	0.1037	0.2561	0.060*
C9	0.68287 (19)	0.08030 (12)	0.17641 (8)	0.0544 (3)
H9	0.5912	0.0368	0.1681	0.065*
C10	0.80251 (19)	0.06096 (12)	0.12331 (7)	0.0528 (3)
C11	0.7672 (2)	−0.00341 (15)	0.07273 (8)	0.0664 (4)
H11	0.6694	−0.0355	0.0720	0.080*
C12	0.8725 (3)	−0.02151 (18)	0.02330 (10)	0.0846 (6)
H12	0.8454	−0.0651	−0.0103	0.102*
C13	1.0170 (3)	0.0248 (2)	0.02388 (11)	0.0923 (7)
H13	1.0893	0.0123	−0.0090	0.111*
C14	1.0545 (3)	0.0903 (2)	0.07361 (12)	0.0973 (7)
H14	1.1523	0.1224	0.0740	0.117*
C15	0.9477 (2)	0.10866 (18)	0.12305 (10)	0.0763 (5)
H15	0.9740	0.1533	0.1562	0.092*
C16	0.6259 (3)	0.19137 (16)	0.17528 (9)	0.0745 (5)
H16A	0.5516	0.2017	0.2104	0.089*
H16B	0.7154	0.2359	0.1826	0.089*
C17	0.5474 (3)	0.2207 (2)	0.11228 (12)	0.0983 (7)
H17A	0.4587	0.1769	0.1046	0.148*
H17B	0.6218	0.2139	0.0776	0.148*
H17C	0.5119	0.2899	0.1147	0.148*
C18	0.83087 (17)	−0.05335 (12)	0.24718 (7)	0.0512 (3)
H18	0.9132	−0.0522	0.2139	0.061*
C19	0.91484 (19)	−0.07057 (11)	0.31084 (7)	0.0529 (3)
C20	1.0760 (2)	−0.05423 (14)	0.31501 (9)	0.0652 (4)
H20	1.1310	−0.0316	0.2789	0.078*
C21	1.1568 (3)	−0.07107 (16)	0.37241 (12)	0.0809 (6)
H21	1.2651	−0.0595	0.3743	0.097*
C22	1.0794 (3)	−0.10408 (16)	0.42545 (10)	0.0813 (6)
H22	1.1345	−0.1166	0.4635	0.098*
C23	0.9185 (3)	−0.11912 (17)	0.42302 (9)	0.0825 (6)
H23	0.8646	−0.1406	0.4597	0.099*
C24	0.8368 (2)	−0.10225 (17)	0.36589 (9)	0.0702 (5)
H24	0.7282	−0.1124	0.3647	0.084*
C25	0.7198 (2)	−0.14079 (12)	0.22928 (9)	0.0595 (4)
H25A	0.6401	−0.1489	0.2626	0.071*
H25B	0.6667	−0.1255	0.1889	0.071*

	U11	U22	U33	U12	U13	U23
Cl1	0.0818 (3)	0.0920 (3)	0.0804 (3)	0.0158 (3)	−0.0070 (2)	−0.0388 (2)
O1	0.0573 (6)	0.0679 (7)	0.0848 (8)	−0.0145 (6)	0.0197 (6)	−0.0212 (6)
O2	0.173 (2)	0.0687 (10)	0.1411 (17)	0.0274 (12)	−0.0380 (16)	0.0015 (11)
O3	0.1117 (16)	0.1051 (15)	0.314 (4)	0.0056 (12)	0.093 (2)	−0.073 (2)
N1	0.0698 (10)	0.0618 (10)	0.1162 (14)	0.0089 (8)	−0.0152 (10)	−0.0261 (10)
C1	0.0637 (9)	0.0612 (9)	0.0537 (8)	0.0092 (8)	−0.0010 (7)	−0.0099 (7)
C2	0.0540 (8)	0.0620 (8)	0.0536 (8)	0.0105 (7)	0.0070 (6)	−0.0017 (7)
C3	0.0480 (7)	0.0555 (8)	0.0493 (7)	0.0025 (6)	0.0041 (6)	0.0031 (6)
C4	0.0502 (7)	0.0518 (7)	0.0465 (7)	0.0006 (6)	0.0057 (6)	−0.0005 (6)
C5	0.0518 (8)	0.0776 (11)	0.0645 (9)	−0.0060 (8)	0.0100 (7)	−0.0164 (8)
C6	0.0586 (9)	0.0806 (12)	0.0698 (10)	−0.0073 (9)	0.0011 (8)	−0.0215 (9)
C7	0.0490 (7)	0.0529 (7)	0.0539 (7)	−0.0023 (6)	0.0069 (6)	−0.0027 (6)
C8	0.0467 (7)	0.0538 (7)	0.0493 (7)	−0.0039 (6)	0.0071 (6)	−0.0063 (6)
C9	0.0505 (7)	0.0588 (8)	0.0540 (8)	0.0016 (6)	0.0059 (6)	−0.0044 (7)
C10	0.0554 (8)	0.0547 (8)	0.0481 (7)	0.0027 (7)	0.0048 (6)	−0.0021 (6)
C11	0.0731 (10)	0.0700 (10)	0.0561 (9)	−0.0023 (9)	−0.0004 (8)	−0.0106 (8)
C12	0.1079 (17)	0.0870 (13)	0.0590 (10)	0.0122 (12)	0.0094 (11)	−0.0191 (9)
C13	0.0968 (16)	0.1098 (17)	0.0703 (12)	0.0169 (13)	0.0332 (12)	−0.0050 (12)
C14	0.0749 (13)	0.129 (2)	0.0881 (14)	−0.0200 (13)	0.0292 (11)	−0.0019 (14)
C15	0.0699 (10)	0.0919 (14)	0.0670 (10)	−0.0222 (10)	0.0142 (9)	−0.0140 (10)
C16	0.0882 (13)	0.0710 (11)	0.0642 (10)	0.0241 (10)	0.0141 (9)	0.0008 (8)
C17	0.1010 (17)	0.1026 (17)	0.0914 (15)	0.0363 (14)	−0.0009 (13)	0.0153 (13)
C18	0.0470 (7)	0.0555 (8)	0.0511 (7)	−0.0004 (6)	0.0059 (6)	−0.0062 (6)
C19	0.0539 (8)	0.0496 (7)	0.0553 (8)	−0.0017 (6)	0.0004 (6)	−0.0061 (6)
C20	0.0575 (9)	0.0636 (9)	0.0745 (10)	−0.0104 (8)	−0.0033 (8)	0.0006 (8)
C21	0.0746 (12)	0.0727 (12)	0.0954 (15)	−0.0100 (10)	−0.0249 (11)	−0.0021 (11)
C22	0.1026 (15)	0.0691 (11)	0.0723 (11)	0.0028 (11)	−0.0278 (11)	−0.0100 (9)
C23	0.1092 (16)	0.0836 (13)	0.0548 (9)	0.0021 (13)	0.0032 (10)	0.0032 (9)
C24	0.0649 (10)	0.0858 (12)	0.0597 (9)	−0.0035 (9)	0.0063 (8)	0.0015 (9)
C25	0.0562 (8)	0.0541 (8)	0.0680 (9)	0.0028 (7)	−0.0036 (7)	−0.0117 (7)

Cl1—C1	1.7393 (15)	C12—H12	0.9300
O1—C7	1.2153 (19)	C13—C14	1.379 (4)
O2—N1	1.208 (3)	C13—H13	0.9300
O3—N1	1.180 (3)	C14—C15	1.387 (3)
N1—C25	1.487 (2)	C14—H14	0.9300
C1—C2	1.372 (3)	C15—H15	0.9300
C1—C6	1.378 (3)	C16—C17	1.514 (3)
C2—C3	1.384 (2)	C16—H16A	0.9700
C2—H2	0.9300	C16—H16B	0.9700
C3—C4	1.391 (2)	C17—H17A	0.9600
C3—H3	0.9300	C17—H17B	0.9600
C4—C5	1.382 (2)	C17—H17C	0.9600
C4—C7	1.501 (2)	C18—C19	1.515 (2)
C5—C6	1.389 (3)	C18—C25	1.531 (2)
C5—H5	0.9300	C18—H18	0.9800
C6—H6	0.9300	C19—C24	1.382 (2)
C7—C8	1.5285 (19)	C19—C20	1.385 (2)
C8—C18	1.555 (2)	C20—C21	1.389 (3)
C8—C9	1.556 (2)	C20—H20	0.9300
C8—H8	0.9800	C21—C22	1.351 (3)
C9—C10	1.517 (2)	C21—H21	0.9300
C9—C16	1.539 (2)	C22—C23	1.378 (4)
C9—H9	0.9800	C22—H22	0.9300
C10—C11	1.379 (2)	C23—C24	1.388 (3)
C10—C15	1.381 (2)	C23—H23	0.9300
C11—C12	1.378 (3)	C24—H24	0.9300
C11—H11	0.9300	C25—H25A	0.9700
C12—C13	1.367 (4)	C25—H25B	0.9700
O3—N1—O2	124.8 (2)	C13—C14—C15	120.6 (2)
O3—N1—C25	117.0 (2)	C13—C14—H14	119.7
O2—N1—C25	118.1 (2)	C15—C14—H14	119.7
C2—C1—C6	121.45 (14)	C10—C15—C14	120.29 (19)
C2—C1—Cl1	119.29 (12)	C10—C15—H15	119.9
C6—C1—Cl1	119.25 (14)	C14—C15—H15	119.9
C1—C2—C3	119.24 (14)	C17—C16—C9	113.12 (18)
C1—C2—H2	120.4	C17—C16—H16A	109.0
C3—C2—H2	120.4	C9—C16—H16A	109.0
C2—C3—C4	120.49 (14)	C17—C16—H16B	109.0
C2—C3—H3	119.8	C9—C16—H16B	109.0
C4—C3—H3	119.8	H16A—C16—H16B	107.8
C5—C4—C3	119.23 (13)	C16—C17—H17A	109.5
C5—C4—C7	123.09 (13)	C16—C17—H17B	109.5
C3—C4—C7	117.67 (13)	H17A—C17—H17B	109.5
C4—C5—C6	120.54 (16)	C16—C17—H17C	109.5
C4—C5—H5	119.7	H17A—C17—H17C	109.5
C6—C5—H5	119.7	H17B—C17—H17C	109.5
C1—C6—C5	119.03 (17)	C19—C18—C25	112.75 (14)
C1—C6—H6	120.5	C19—C18—C8	112.17 (12)
C5—C6—H6	120.5	C25—C18—C8	112.71 (13)
O1—C7—C4	119.54 (13)	C19—C18—H18	106.2
O1—C7—C8	119.74 (13)	C25—C18—H18	106.2
C4—C7—C8	120.68 (13)	C8—C18—H18	106.2
C7—C8—C18	111.51 (12)	C24—C19—C20	117.82 (16)
C7—C8—C9	108.01 (12)	C24—C19—C18	122.57 (15)
C18—C8—C9	114.01 (12)	C20—C19—C18	119.61 (15)
C7—C8—H8	107.7	C19—C20—C21	120.96 (19)
C18—C8—H8	107.7	C19—C20—H20	119.5
C9—C8—H8	107.7	C21—C20—H20	119.5
C10—C9—C16	110.97 (14)	C22—C21—C20	120.5 (2)
C10—C9—C8	112.08 (12)	C22—C21—H21	119.7
C16—C9—C8	110.56 (14)	C20—C21—H21	119.7
C10—C9—H9	107.7	C21—C22—C23	119.76 (19)
C16—C9—H9	107.7	C21—C22—H22	120.1
C8—C9—H9	107.7	C23—C22—H22	120.1
C11—C10—C15	117.99 (16)	C22—C23—C24	120.1 (2)
C11—C10—C9	120.55 (15)	C22—C23—H23	120.0
C15—C10—C9	121.44 (15)	C24—C23—H23	120.0
C12—C11—C10	121.95 (19)	C19—C24—C23	120.83 (19)
C12—C11—H11	119.0	C19—C24—H24	119.6
C10—C11—H11	119.0	C23—C24—H24	119.6
C13—C12—C11	119.7 (2)	N1—C25—C18	109.64 (14)
C13—C12—H12	120.1	N1—C25—H25A	109.7
C11—C12—H12	120.1	C18—C25—H25A	109.7
C12—C13—C14	119.41 (19)	N1—C25—H25B	109.7
C12—C13—H13	120.3	C18—C25—H25B	109.7
C14—C13—H13	120.3	H25A—C25—H25B	108.2
C6—C1—C2—C3	0.7 (3)	C10—C11—C12—C13	0.3 (4)
Cl1—C1—C2—C3	−178.32 (12)	C11—C12—C13—C14	−0.9 (4)
C1—C2—C3—C4	−1.0 (2)	C12—C13—C14—C15	0.5 (4)
C2—C3—C4—C5	0.8 (2)	C11—C10—C15—C14	−1.0 (3)
C2—C3—C4—C7	−179.95 (14)	C9—C10—C15—C14	−179.4 (2)
C3—C4—C5—C6	−0.4 (3)	C13—C14—C15—C10	0.4 (4)
C7—C4—C5—C6	−179.60 (17)	C10—C9—C16—C17	60.0 (2)
C2—C1—C6—C5	−0.3 (3)	C8—C9—C16—C17	−174.97 (18)
Cl1—C1—C6—C5	178.72 (16)	C7—C8—C18—C19	−66.22 (16)
C4—C5—C6—C1	0.2 (3)	C9—C8—C18—C19	171.13 (12)
C5—C4—C7—O1	164.28 (18)	C7—C8—C18—C25	62.33 (17)
C3—C4—C7—O1	−14.9 (2)	C9—C8—C18—C25	−60.31 (17)
C5—C4—C7—C8	−18.1 (2)	C25—C18—C19—C24	−47.1 (2)
C3—C4—C7—C8	162.74 (14)	C8—C18—C19—C24	81.41 (19)
O1—C7—C8—C18	−61.3 (2)	C25—C18—C19—C20	132.96 (16)
C4—C7—C8—C18	121.03 (15)	C8—C18—C19—C20	−98.51 (16)
O1—C7—C8—C9	64.69 (19)	C24—C19—C20—C21	1.2 (3)
C4—C7—C8—C9	−112.95 (15)	C18—C19—C20—C21	−178.86 (17)
C7—C8—C9—C10	−171.81 (13)	C19—C20—C21—C22	0.1 (3)
C18—C8—C9—C10	−47.28 (18)	C20—C21—C22—C23	−1.4 (3)
C7—C8—C9—C16	63.81 (17)	C21—C22—C23—C24	1.2 (3)
C18—C8—C9—C16	−171.65 (14)	C20—C19—C24—C23	−1.4 (3)
C16—C9—C10—C11	−113.53 (19)	C18—C19—C24—C23	178.72 (17)
C8—C9—C10—C11	122.32 (17)	C22—C23—C24—C19	0.2 (3)
C16—C9—C10—C15	64.8 (2)	O3—N1—C25—C18	−63.7 (3)
C8—C9—C10—C15	−59.3 (2)	O2—N1—C25—C18	120.2 (2)
C15—C10—C11—C12	0.7 (3)	C19—C18—C25—N1	−60.96 (19)
C9—C10—C11—C12	179.12 (18)	C8—C18—C25—N1	170.79 (16)

CgA is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O3i	0.93	2.43	3.198 (5)	140
C12—H12···CgAii	0.93	2.82	3.691 (4)	157

Table 1

Hydrogen-bond geometry (Å, °)

CgA is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯O3i	0.93	2.43	3.198 (5)	140
C12—H12⋯CgAii	0.93	2.82	3.691 (4)	157

Symmetry codes: (i) ; (ii) .