2-Propyl 3,3-dibromo-2-hydroxy-pyrrolidine-1-carboxyl-ate.

The title compound, C(8)H(13)Br(2)NO(3), crystallizes as a non-merohedral twin with twin law -0.6 0 0.4/0 - 1 0 /1.6 0 0.6, and the structure has a refined twin domain ratio of 0.546 (5). The structure shows a compact conformation, with the ester unit roughly coplanar with a mean plane fitted through the non-H atoms of the pyrrolidine ring [dihedral angle = 8.23 (9)°]. In the crystal, inversion dimers linked by pairs of O-H⋯O hydrogen bonds generate an R(2) (2)(12) motif.

Related literature

For details of the synthesis, see: Magnus et al. (1994 ▶); Salamant & Hulme (2006 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶). For hydrogen-bonding motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C8H13Br2NO3

M = 331.01

Monoclinic,

a = 10.1061 (5) Å

b = 5.9914 (3) Å

c = 18.5496 (9) Å

β = 95.880 (2)°

V = 1117.26 (10) Å3

Z = 4

Mo Kα radiation

μ = 7.24 mm−1

T = 100 K

0.44 × 0.16 × 0.11 mm

Data collection

Bruker Kappa APEXII DUO CCD diffractometer

Absorption correction: multi-scan (TWINABS; Sheldrick, 1996 ▶) T min = 0.144, T max = 0.514

34994 measured reflections

9572 independent reflections

7956 reflections with I > 2σ(I)

R int = 0.042

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.082

S = 1.03

9572 reflections

138 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.41 e Å−3

Δρmin = −0.77 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT and CELL_NOW (Sheldrick, 2004 ▶); program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXTL and local programs.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810005106/fj2278sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810005106/fj2278Isup2.hkl

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

C8H13Br2NO3	F(000) = 648
Mr = 331.01	Dx = 1.968 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4995 reflections
a = 10.1061 (5) Å	θ = 2.2–36.3°
b = 5.9914 (3) Å	µ = 7.24 mm−1
c = 18.5496 (9) Å	T = 100 K
β = 95.880 (2)°	Rod, colourless
V = 1117.26 (10) Å3	0.44 × 0.16 × 0.11 mm
Z = 4

Bruker Kappa APEXII DUO CCD diffractometer	9572 independent reflections
Radiation source: fine-focus sealed tube with Miracol optics	7956 reflections with I > 2σ(I)
graphite	Rint = 0.042
φ and ω scans	θmax = 36.4°, θmin = 2.2°
Absorption correction: multi-scan (TWINABS; Sheldrick, 1996)	h = −16→16
Tmin = 0.144, Tmax = 0.514	k = 0→9
34994 measured reflections	l = 0→30

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)] = 0.032	Hydrogen site location: difference Fourier map
wR(F2) = 0.082	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.041P)2 + 0.6397P] where P = (Fo2 + 2Fc2)/3
9572 reflections	(Δ/σ)max < 0.001
138 parameters	Δρmax = 1.41 e Å−3
0 restraints	Δρmin = −0.77 e Å−3

Experimental. 1H- NMR (300 MHz, CDCl3) δ ppm 1.26 (d, J = 6.0 Hz, 6H), 2.78 (m, 1H), 3.00 (m, 1H), 3.55 (m, 2H), 4.65 (s, 1H), 5.00 (m, 1H), 5.66 (d, J = 18.6 Hz, 1H)13 C-NMR (75 MHz, CDCl3) δ ppm 22.6, 43.4, 44.6, 64.9, 70.2, 77.9, 155.3

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 taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used 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 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	0.276925 (16)	0.10387 (3)	0.190848 (8)	0.01807 (4)
Br2	0.113078 (15)	0.17803 (3)	0.039208 (9)	0.01933 (4)
O1	0.39288 (12)	0.2381 (2)	−0.01016 (6)	0.01668 (19)
H1O	0.371 (3)	0.120 (5)	−0.0310 (15)	0.029 (7)*
O2	0.68184 (12)	0.16332 (19)	0.07343 (7)	0.0190 (2)
O3	0.69480 (10)	0.47225 (18)	0.14461 (6)	0.01432 (18)
N	0.49624 (12)	0.3442 (2)	0.10291 (7)	0.0134 (2)
C1	0.27415 (14)	0.2599 (2)	0.09769 (7)	0.0137 (2)
C2	0.40238 (14)	0.1940 (2)	0.06403 (7)	0.0125 (2)
H2	0.4265	0.0345	0.0745	0.015*
C3	0.43486 (14)	0.5339 (2)	0.13709 (8)	0.0153 (2)
H3A	0.4716	0.6776	0.1219	0.018*
H3B	0.4479	0.5230	0.1906	0.018*
C4	0.28818 (15)	0.5100 (2)	0.10886 (8)	0.0156 (2)
H4A	0.2297	0.5644	0.1448	0.019*
H4B	0.2673	0.5919	0.0628	0.019*
C5	0.62874 (14)	0.3155 (2)	0.10427 (8)	0.0137 (2)
C6	0.84008 (14)	0.4710 (2)	0.14715 (8)	0.0146 (2)
H6	0.862 (2)	0.423 (4)	0.1000 (12)	0.014 (5)*
C7	0.88361 (16)	0.7097 (2)	0.16218 (9)	0.0185 (3)
H7A	0.8399	0.8076	0.1247	0.028*
H7B	0.9803	0.7206	0.1619	0.028*
H7C	0.8588	0.7553	0.2097	0.028*
C8	0.89639 (17)	0.3118 (3)	0.20548 (10)	0.0223 (3)
H8A	0.9936	0.3090	0.2069	0.033*
H8B	0.8610	0.1617	0.1949	0.033*
H8C	0.8711	0.3613	0.2525	0.033*

	U11	U22	U33	U12	U13	U23
Br1	0.02072 (7)	0.02068 (7)	0.01338 (6)	−0.00119 (5)	0.00450 (5)	0.00190 (5)
Br2	0.01232 (6)	0.02662 (8)	0.01853 (7)	−0.00274 (5)	−0.00098 (5)	−0.00543 (5)
O1	0.0195 (5)	0.0195 (5)	0.0112 (4)	−0.0029 (4)	0.0021 (4)	−0.0022 (4)
O2	0.0149 (5)	0.0183 (5)	0.0239 (5)	0.0008 (4)	0.0017 (4)	−0.0089 (4)
O3	0.0113 (4)	0.0153 (4)	0.0160 (4)	−0.0003 (3)	−0.0004 (3)	−0.0044 (4)
N	0.0116 (5)	0.0136 (5)	0.0150 (5)	−0.0012 (4)	0.0007 (4)	−0.0046 (4)
C1	0.0126 (5)	0.0162 (5)	0.0119 (5)	−0.0013 (4)	−0.0003 (4)	−0.0009 (4)
C2	0.0120 (5)	0.0142 (5)	0.0113 (5)	−0.0017 (4)	0.0016 (4)	−0.0021 (4)
C3	0.0142 (6)	0.0137 (5)	0.0179 (6)	0.0002 (4)	0.0018 (5)	−0.0047 (5)
C4	0.0148 (6)	0.0145 (6)	0.0173 (6)	0.0018 (4)	0.0010 (5)	−0.0021 (5)
C5	0.0127 (5)	0.0149 (5)	0.0132 (5)	0.0000 (4)	0.0004 (4)	−0.0014 (4)
C6	0.0106 (5)	0.0160 (5)	0.0170 (6)	−0.0002 (4)	0.0009 (4)	−0.0011 (5)
C7	0.0160 (6)	0.0165 (6)	0.0226 (7)	−0.0032 (5)	−0.0006 (5)	0.0003 (5)
C8	0.0187 (7)	0.0180 (6)	0.0286 (8)	0.0002 (5)	−0.0052 (6)	0.0022 (6)

Br1—C1	1.9624 (14)	C3—H3B	0.990
Br2—C1	1.9250 (14)	C3—C4	1.527 (2)
O1—H1O	0.83 (3)	C4—H4A	0.990
O1—C2	1.3949 (17)	C4—H4B	0.990
O2—C5	1.2286 (18)	C6—H6	0.97 (2)
O3—C5	1.3360 (17)	C6—C7	1.513 (2)
O3—C6	1.4641 (18)	C6—C8	1.510 (2)
N—C2	1.4457 (18)	C7—H7A	0.980
N—C3	1.4695 (19)	C7—H7B	0.980
N—C5	1.3478 (19)	C7—H7C	0.980
C1—C2	1.546 (2)	C8—H8A	0.980
C1—C4	1.517 (2)	C8—H8B	0.980
C2—H2	1.000	C8—H8C	0.980
C3—H3A	0.990
H1O—O1—C2	106.6 (19)	C1—C4—H4B	111.3
C5—O3—C6	117.15 (11)	C3—C4—H4A	111.3
C2—N—C3	114.36 (12)	C3—C4—H4B	111.3
C2—N—C5	121.99 (12)	H4A—C4—H4B	109.2
C3—N—C5	123.58 (12)	O2—C5—O3	124.43 (13)
Br1—C1—Br2	108.05 (7)	O2—C5—N	124.50 (13)
Br1—C1—C2	107.27 (9)	O3—C5—N	111.06 (12)
Br1—C1—C4	110.95 (9)	O3—C6—H6	107.0 (13)
Br2—C1—C2	113.74 (9)	O3—C6—C7	105.83 (12)
Br2—C1—C4	112.98 (10)	O3—C6—C8	109.23 (12)
C2—C1—C4	103.71 (12)	H6—C6—C7	111.1 (13)
O1—C2—N	110.45 (12)	H6—C6—C8	110.8 (13)
O1—C2—C1	111.97 (11)	C7—C6—C8	112.58 (13)
O1—C2—H2	111.3	C6—C7—H7A	109.5
N—C2—C1	99.99 (11)	C6—C7—H7B	109.5
N—C2—H2	111.3	C6—C7—H7C	109.5
C1—C2—H2	111.3	H7A—C7—H7B	109.5
N—C3—H3A	111.3	H7A—C7—H7C	109.5
N—C3—H3B	111.3	H7B—C7—H7C	109.5
N—C3—C4	102.54 (11)	C6—C8—H8A	109.5
H3A—C3—H3B	109.2	C6—C8—H8B	109.5
H3A—C3—C4	111.3	C6—C8—H8C	109.5
H3B—C3—C4	111.3	H8A—C8—H8B	109.5
C1—C4—C3	102.32 (11)	H8A—C8—H8C	109.5
C1—C4—H4A	111.3	H8B—C8—H8C	109.5
C3—N—C2—O1	99.81 (14)	Br1—C1—C4—C3	73.49 (12)
C3—N—C2—C1	−18.30 (15)	Br2—C1—C4—C3	−165.00 (10)
C5—N—C2—O1	−77.31 (17)	C2—C1—C4—C3	−41.39 (13)
C5—N—C2—C1	164.59 (13)	N—C3—C4—C1	29.33 (14)
Br1—C1—C2—O1	161.81 (9)	C6—O3—C5—O2	5.0 (2)
Br1—C1—C2—N	−81.21 (11)	C6—O3—C5—N	−176.05 (12)
Br2—C1—C2—O1	42.39 (14)	C2—N—C5—O2	0.1 (2)
Br2—C1—C2—N	159.37 (9)	C2—N—C5—O3	−178.85 (12)
C4—C1—C2—O1	−80.72 (13)	C3—N—C5—O2	−176.76 (14)
C4—C1—C2—N	36.26 (13)	C3—N—C5—O3	4.3 (2)
C2—N—C3—C4	−6.68 (16)	C5—O3—C6—C7	152.87 (13)
C5—N—C3—C4	170.38 (13)	C5—O3—C6—C8	−85.69 (15)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···O2i	0.83 (3)	1.92 (3)	2.7479 (16)	176 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯O2i	0.83 (3)	1.92 (3)	2.7479 (16)	176 (3)

Symmetry code: (i) .