(+)-N-[2-(4-Chloro­phen­yl)propano­yl]bornane-10,2-sultam

Abstract

In the mol­ecular structure of the title compound, C₁₉H₂₄ClNO₃S, the six-membered ring of the bornane unit shows a boat form, while the five-membered ring of the sultam unit adopts a twist form. Intra­molecular C—H⋯N and C—H⋯O inter­actions are observed. In the crystal structure, mol­ecules are connected by inter­molecular C—H⋯O hydrogen bonds into a chain running along the b axis. The crystal was a partial inversion twin with a twin ratio of 0.73 (1):0.27 (1).

Related literature

For related literature, see: Boiadjiev & Lightner (2001 ▶); Oppolzer (1989 ▶, 1990 ▶).

Experimental

Crystal data

• C₁₉H₂₄ClNO₃S

• M _r = 381.90

• Monoclinic,

• a = 21.0863 (16) Å

• b = 7.7948 (6) Å

• c = 12.102 (1) Å

• β = 107.433 (1)°

• V = 1897.8 (3) ų

• Z = 4

• Mo Kα radiation

• μ = 0.33 mm⁻¹

• T = 295 (2) K

• 0.30 × 0.20 × 0.20 mm

Data collection

• Bruker SMART APEX CCD area-detector diffractometer

• Absorption correction: none

• 5780 measured reflections

• 3715 independent reflections

• 3146 reflections with I > 2σ(I)

• R _int = 0.032

Refinement

• R[F ² > 2σ(F ²)] = 0.052

• wR(F ²) = 0.180

• S = 1.10

• 3715 reflections

• 229 parameters

• 1 restraint

• H-atom parameters constrained

• Δρ_max = 0.34 e Å⁻³

• Δρ_min = −0.21 e Å⁻³

• Absolute structure: Flack (1983 ▶), 1503 Friedel pairs

• Flack parameter: 0.27 (1)

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT-Plus (Bruker, 2001 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: SHELXTL (Bruker, 2001 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8B⋯N1	0.96	2.54	3.129 (6)	120
C19—H19⋯O3	0.93	2.59	3.196 (6)	123
C12—H12⋯O1	0.98	2.49	3.268 (6)	137
C10—H10A⋯O3i	0.97	2.36	3.292 (5)	161

Symmetry code: (i) .

supplementary crystallographic information

Comment

Pioneering work of Oppolzer (1990) has resulted in the development of bornane[10,2]sultam serve as popular and widely used chiral auxiliaries in asymmetric synthesis. The resulting asymmetric induction using these auxiliaries are high in carbon-carbon bond formation such as alkylation (Oppolzer, 1989), and we have focused our attention on this field. In this paper, we present X-ray crystallographic analysis of the title compound, (I).

In (I), the six-membered ring of sultam shows a boat form (Fig. 1). The planes constructed by C3/C2/C1/C6and C3/C4/C5/C6 form a dihedral angle of 110.71°. The C7/C8/C9 plane makes dihedral angles of 93.92 and 90.93°, respectively, with C3/C2/C1/C6 and C3/C4/C5/C6 planes. Molecules are linked by the intermolecular C—H···O hydrogen bonds into a one-dimensional chain. No direction-specific interactions were observed between the adjacent chains along the b axis (Fig. 2).

Experimental

For the preparation of compound (I), 2.4 ml n-BuLi (hexane, 2.5 mol/L) was added over 30 min to the THF (25 ml) solution of (+)-N-[2-(4-chlorophenyl)-ethanoyl]bornane-10,2-sultam (1.84 g, 5 mmol) at 193 K. After stirring the mixture at 193 K for 1 h, iodomethane 1.6 ml in 4.5 ml HMPA was added and then stirred at 193 K for 3 h. The solution was slowly warming up to room temperature, quenched with water and extracted bt Et₂O to afford a crude product. Single crystals appropriate for data collection were obtained by slow evaporation of a dichloromethane solution at 293 K.

Refinement

All H atoms were constrained to an ideal geometry (C—H = 0.93 - 0.98 Å) and U_iso(H) = 1.2U_eq(C) or 1.5U_eq(methyl C). The ratio of the twin components (major to minor) in crystal selected for diffraction is 0.73 (1):0.27 (1). The absolute configuration of the sultam unit is consistent with the known absolute configuration of (+)-2,10-sultam (Boiadjiev & Lightner, 2001). The major component is (+)-N-[(2S)-(4-chlorophenyl)-propanoyl] bornane-10,2-sultam, and the minor is (+)-N-[(2R)-(4-chlorophenyl)-propanoyl] bornane-10,2-sultam. The result was confirmed by HPLC.

Figures

Fig. 1.

The molecular structure of (I), with atom labels and 50% probability displacement ellipsoids for non-H atoms.

Fig. 2.

Part of the crystal packing, showing the formation of the one-dimensional chain formed by a C10—H10A···O3 hydrogen bond.

Crystal data

C19H24ClNO3S	F000 = 808
Mr = 381.90	Dx = 1.337 Mg m−3
Monoclinic, C2	Mo Kα radiation λ = 0.71073 Å
Hall symbol: C 2y	Cell parameters from 2555 reflections
a = 21.0863 (16) Å	θ = 2.8–26.0º
b = 7.7948 (6) Å	µ = 0.33 mm−1
c = 12.102 (1) Å	T = 295 (2) K
β = 107.433 (1)º	Block, colorless
V = 1897.8 (3) Å3	0.30 × 0.20 × 0.20 mm
Z = 4

Data collection

Bruker SMART APEX CCD area-detector diffractometer	3146 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.032
Monochromator: graphite	θmax = 27.0º
T = 295(2) K	θmin = 1.8º
φ and ω scans	h = −25→26
Absorption correction: none	k = −9→9
5780 measured reflections	l = −14→15
3715 independent reflections

Refinement

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.052	w = 1/[σ2(Fo2) + (0.1128P)2 + 0.2113P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.180	(Δ/σ)max = 0.001
S = 1.10	Δρmax = 0.34 e Å−3
3715 reflections	Δρmin = −0.21 e Å−3
229 parameters	Extinction correction: none
1 restraint	Absolute structure: Flack (1983), 1503 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.27 (1)
Secondary atom site location: difference Fourier map

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.41765 (17)	0.1484 (5)	0.2515 (3)	0.0363 (8)
H1	0.4074	0.1971	0.3188	0.044*
C2	0.3700 (2)	0.2236 (6)	0.1388 (4)	0.0492 (10)
H2A	0.3436	0.3165	0.1552	0.059*
H2B	0.3942	0.2647	0.0873	0.059*
C3	0.32641 (19)	0.0678 (7)	0.0869 (4)	0.0501 (10)
H3	0.3002	0.0816	0.0056	0.060*
C4	0.28491 (19)	0.0218 (7)	0.1686 (4)	0.0568 (12)
H4A	0.2497	−0.0582	0.1318	0.068*
H4B	0.2655	0.1236	0.1913	0.068*
C5	0.33625 (18)	−0.0616 (6)	0.2743 (4)	0.0463 (10)
H5A	0.3387	−0.0004	0.3453	0.056*
H5B	0.3256	−0.1810	0.2829	0.056*
C6	0.40133 (17)	−0.0439 (5)	0.2421 (3)	0.0364 (8)
C7	0.37733 (19)	−0.0803 (6)	0.1092 (3)	0.0486 (10)
C8	0.4297 (2)	−0.0585 (7)	0.0450 (4)	0.0582 (13)
H8A	0.4640	−0.1429	0.0721	0.087*
H8B	0.4488	0.0542	0.0595	0.087*
H8C	0.4090	−0.0731	−0.0367	0.087*
C9	0.3474 (3)	−0.2582 (7)	0.0795 (5)	0.0661 (14)
H9A	0.3291	−0.2688	−0.0030	0.099*
H9B	0.3128	−0.2747	0.1150	0.099*
H9C	0.3813	−0.3433	0.1076	0.099*
C10	0.46138 (18)	−0.1414 (5)	0.3168 (4)	0.0421 (9)
H10A	0.4653	−0.2514	0.2819	0.051*
H10B	0.4570	−0.1614	0.3933	0.051*
C11	0.5168 (2)	0.3268 (5)	0.2714 (4)	0.0438 (9)
C12	0.59037 (19)	0.3421 (6)	0.2804 (4)	0.0511 (11)
H12	0.6053	0.2315	0.2587	0.061*
C13	0.5985 (3)	0.4787 (9)	0.1933 (5)	0.0770 (15)
H13A	0.5714	0.4486	0.1168	0.115*
H13B	0.6443	0.4837	0.1947	0.115*
H13C	0.5851	0.5886	0.2142	0.115*
C14	0.63302 (19)	0.3854 (6)	0.4024 (4)	0.0475 (10)
C15	0.7005 (2)	0.3585 (7)	0.4306 (5)	0.0612 (13)
H15	0.7185	0.3183	0.3741	0.073*
C16	0.7427 (2)	0.3902 (9)	0.5418 (5)	0.0722 (16)
H16	0.7879	0.3674	0.5602	0.087*
C17	0.7166 (2)	0.4547 (6)	0.6224 (4)	0.0513 (11)
C18	0.6501 (2)	0.4816 (7)	0.5981 (4)	0.0541 (10)
H18	0.6327	0.5210	0.6555	0.065*
C19	0.6085 (2)	0.4500 (6)	0.4877 (4)	0.0525 (11)
H19	0.5633	0.4726	0.4706	0.063*
Cl1	0.76886 (6)	0.4977 (2)	0.76187 (10)	0.0713 (4)
N1	0.48941 (14)	0.1662 (4)	0.2660 (3)	0.0379 (7)
O1	0.57014 (16)	−0.0733 (5)	0.2551 (4)	0.0704 (10)
O2	0.56815 (15)	0.0226 (5)	0.4436 (3)	0.0658 (9)
O3	0.48162 (16)	0.4517 (4)	0.2627 (3)	0.0652 (9)
S1	0.53270 (4)	−0.01249 (12)	0.32646 (8)	0.0425 (3)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.0282 (16)	0.043 (2)	0.0375 (19)	0.0012 (14)	0.0089 (15)	−0.0034 (15)
C2	0.036 (2)	0.055 (3)	0.054 (2)	0.0044 (18)	0.0085 (19)	0.0126 (19)
C3	0.035 (2)	0.070 (3)	0.040 (2)	0.0050 (19)	0.0048 (16)	0.0042 (19)
C4	0.0293 (17)	0.074 (3)	0.064 (3)	−0.0003 (19)	0.0094 (18)	−0.005 (2)
C5	0.0349 (19)	0.054 (3)	0.050 (2)	−0.0066 (16)	0.0133 (17)	−0.0024 (18)
C6	0.0295 (16)	0.042 (2)	0.0350 (17)	−0.0029 (14)	0.0053 (13)	−0.0059 (15)
C7	0.0311 (18)	0.068 (3)	0.040 (2)	−0.0032 (18)	0.0003 (16)	−0.0083 (19)
C8	0.050 (2)	0.086 (4)	0.039 (2)	−0.003 (2)	0.0138 (17)	−0.007 (2)
C9	0.050 (3)	0.078 (4)	0.062 (3)	−0.019 (2)	0.006 (2)	−0.027 (3)
C10	0.0339 (18)	0.042 (2)	0.046 (2)	−0.0011 (16)	0.0052 (16)	−0.0013 (17)
C11	0.040 (2)	0.040 (2)	0.050 (2)	−0.0063 (16)	0.0127 (17)	−0.0082 (17)
C12	0.0341 (19)	0.058 (3)	0.064 (3)	−0.0119 (18)	0.0193 (19)	−0.014 (2)
C13	0.065 (3)	0.094 (4)	0.074 (3)	−0.021 (3)	0.024 (3)	0.007 (4)
C14	0.040 (2)	0.039 (2)	0.069 (3)	−0.0104 (16)	0.023 (2)	−0.0057 (19)
C15	0.044 (2)	0.073 (3)	0.075 (3)	−0.001 (2)	0.029 (2)	−0.020 (3)
C16	0.032 (2)	0.099 (4)	0.082 (4)	0.000 (2)	0.011 (2)	−0.023 (3)
C17	0.045 (2)	0.053 (3)	0.056 (2)	−0.0047 (19)	0.0165 (19)	−0.002 (2)
C18	0.045 (2)	0.063 (3)	0.060 (2)	−0.009 (2)	0.0233 (18)	−0.009 (2)
C19	0.0355 (19)	0.049 (3)	0.075 (3)	−0.0019 (17)	0.0184 (19)	−0.009 (2)
Cl1	0.0574 (6)	0.0895 (9)	0.0600 (7)	−0.0096 (7)	0.0069 (5)	0.0001 (7)
N1	0.0274 (14)	0.0417 (17)	0.0414 (17)	−0.0041 (13)	0.0053 (13)	−0.0031 (13)
O1	0.0474 (17)	0.065 (2)	0.110 (3)	0.0134 (15)	0.0403 (19)	0.0048 (19)
O2	0.0575 (18)	0.068 (2)	0.0543 (17)	−0.0164 (16)	−0.0104 (14)	0.0087 (16)
O3	0.0473 (16)	0.0416 (19)	0.103 (3)	−0.0022 (13)	0.0172 (17)	−0.0090 (16)
S1	0.0290 (4)	0.0460 (5)	0.0476 (5)	0.0002 (4)	0.0041 (3)	0.0030 (5)

Geometric parameters (Å, °)

C1—N1	1.477 (4)	C10—S1	1.783 (4)
C1—C6	1.535 (6)	C10—H10A	0.9700
C1—C2	1.547 (5)	C10—H10B	0.9700
C1—H1	0.9800	C11—O3	1.209 (5)
C2—C3	1.539 (6)	C11—N1	1.371 (5)
C2—H2A	0.9700	C11—C12	1.528 (5)
C2—H2B	0.9700	C12—C14	1.518 (6)
C3—C7	1.544 (6)	C12—C13	1.544 (8)
C3—C4	1.545 (6)	C12—H12	0.9800
C3—H3	0.9800	C13—H13A	0.9600
C4—C5	1.549 (6)	C13—H13B	0.9600
C4—H4A	0.9700	C13—H13C	0.9600
C4—H4B	0.9700	C14—C15	1.377 (6)
C5—C6	1.541 (5)	C14—C19	1.380 (6)
C5—H5A	0.9700	C15—C16	1.395 (7)
C5—H5B	0.9700	C15—H15	0.9300
C6—C10	1.521 (5)	C16—C17	1.351 (7)
C6—C7	1.561 (5)	C16—H16	0.9300
C7—C9	1.522 (7)	C17—C18	1.360 (6)
C7—C8	1.538 (6)	C17—Cl1	1.749 (4)
C8—H8A	0.9600	C18—C19	1.384 (6)
C8—H8B	0.9600	C18—H18	0.9300
C8—H8C	0.9600	C19—H19	0.9300
C9—H9A	0.9600	N1—S1	1.706 (3)
C9—H9B	0.9600	O1—S1	1.415 (4)
C9—H9C	0.9600	O2—S1	1.417 (3)
N1—C1—C6	107.4 (3)	C7—C9—H9C	109.5
N1—C1—C2	116.2 (3)	H9A—C9—H9C	109.5
C6—C1—C2	103.4 (3)	H9B—C9—H9C	109.5
N1—C1—H1	109.8	C6—C10—S1	107.0 (3)
C6—C1—H1	109.8	C6—C10—H10A	110.3
C2—C1—H1	109.8	S1—C10—H10A	110.3
C3—C2—C1	102.2 (3)	C6—C10—H10B	110.3
C3—C2—H2A	111.3	S1—C10—H10B	110.3
C1—C2—H2A	111.3	H10A—C10—H10B	108.6
C3—C2—H2B	111.3	O3—C11—N1	119.5 (4)
C1—C2—H2B	111.3	O3—C11—C12	121.7 (4)
H2A—C2—H2B	109.2	N1—C11—C12	118.6 (4)
C2—C3—C7	102.7 (3)	C14—C12—C11	112.3 (3)
C2—C3—C4	107.8 (4)	C14—C12—C13	110.8 (4)
C7—C3—C4	102.3 (4)	C11—C12—C13	108.9 (4)
C2—C3—H3	114.3	C14—C12—H12	108.2
C7—C3—H3	114.3	C11—C12—H12	108.2
C4—C3—H3	114.3	C13—C12—H12	108.2
C3—C4—C5	103.6 (3)	C12—C13—H13A	109.5
C3—C4—H4A	111.0	C12—C13—H13B	109.5
C5—C4—H4A	111.0	H13A—C13—H13B	109.5
C3—C4—H4B	111.0	C12—C13—H13C	109.5
C5—C4—H4B	111.0	H13A—C13—H13C	109.5
H4A—C4—H4B	109.0	H13B—C13—H13C	109.5
C6—C5—C4	102.0 (3)	C15—C14—C19	117.4 (4)
C6—C5—H5A	111.4	C15—C14—C12	118.3 (4)
C4—C5—H5A	111.4	C19—C14—C12	124.2 (4)
C6—C5—H5B	111.4	C14—C15—C16	121.6 (4)
C4—C5—H5B	111.4	C14—C15—H15	119.2
H5A—C5—H5B	109.2	C16—C15—H15	119.2
C10—C6—C1	108.4 (3)	C17—C16—C15	118.9 (4)
C10—C6—C5	116.8 (3)	C17—C16—H16	120.5
C1—C6—C5	105.4 (3)	C15—C16—H16	120.5
C10—C6—C7	118.5 (3)	C16—C17—C18	121.1 (4)
C1—C6—C7	104.5 (3)	C16—C17—Cl1	119.6 (3)
C5—C6—C7	101.9 (3)	C18—C17—Cl1	119.3 (3)
C9—C7—C8	106.9 (4)	C17—C18—C19	119.7 (4)
C9—C7—C3	115.0 (4)	C17—C18—H18	120.1
C8—C7—C3	113.4 (4)	C19—C18—H18	120.1
C9—C7—C6	113.1 (4)	C14—C19—C18	121.1 (4)
C8—C7—C6	116.1 (3)	C14—C19—H19	119.4
C3—C7—C6	92.2 (3)	C18—C19—H19	119.4
C7—C8—H8A	109.5	C11—N1—C1	119.5 (3)
C7—C8—H8B	109.5	C11—N1—S1	124.2 (3)
H8A—C8—H8B	109.5	C1—N1—S1	111.8 (3)
C7—C8—H8C	109.5	O1—S1—O2	116.8 (2)
H8A—C8—H8C	109.5	O1—S1—N1	109.7 (2)
H8B—C8—H8C	109.5	O2—S1—N1	109.0 (2)
C7—C9—H9A	109.5	O1—S1—C10	112.6 (2)
C7—C9—H9B	109.5	O2—S1—C10	110.9 (2)
H9A—C9—H9B	109.5	N1—S1—C10	95.73 (16)
N1—C1—C2—C3	124.3 (3)	N1—C11—C12—C14	−103.2 (4)
C6—C1—C2—C3	6.9 (4)	O3—C11—C12—C13	−42.4 (6)
C1—C2—C3—C7	−41.2 (4)	N1—C11—C12—C13	133.6 (4)
C1—C2—C3—C4	66.3 (4)	C11—C12—C14—C15	163.0 (4)
C2—C3—C4—C5	−73.6 (4)	C13—C12—C14—C15	−75.0 (6)
C7—C3—C4—C5	34.3 (4)	C11—C12—C14—C19	−16.9 (6)
C3—C4—C5—C6	2.8 (5)	C13—C12—C14—C19	105.2 (5)
N1—C1—C6—C10	33.0 (4)	C19—C14—C15—C16	1.9 (8)
C2—C1—C6—C10	156.4 (3)	C12—C14—C15—C16	−178.0 (5)
N1—C1—C6—C5	158.8 (3)	C14—C15—C16—C17	−2.4 (9)
C2—C1—C6—C5	−77.8 (3)	C15—C16—C17—C18	3.0 (9)
N1—C1—C6—C7	−94.3 (3)	C15—C16—C17—Cl1	−179.2 (4)
C2—C1—C6—C7	29.1 (4)	C16—C17—C18—C19	−3.0 (8)
C4—C5—C6—C10	−169.3 (4)	Cl1—C17—C18—C19	179.2 (4)
C4—C5—C6—C1	70.3 (4)	C15—C14—C19—C18	−1.9 (7)
C4—C5—C6—C7	−38.6 (4)	C12—C14—C19—C18	178.0 (5)
C2—C3—C7—C9	173.1 (4)	C17—C18—C19—C14	2.4 (8)
C4—C3—C7—C9	61.4 (5)	O3—C11—N1—C1	−1.0 (6)
C2—C3—C7—C8	−63.5 (4)	C12—C11—N1—C1	−177.0 (3)
C4—C3—C7—C8	−175.2 (3)	O3—C11—N1—S1	−155.2 (4)
C2—C3—C7—C6	56.3 (4)	C12—C11—N1—S1	28.7 (5)
C4—C3—C7—C6	−55.5 (3)	C6—C1—N1—C11	177.1 (3)
C10—C6—C7—C9	69.0 (5)	C2—C1—N1—C11	61.9 (5)
C1—C6—C7—C9	−170.2 (4)	C6—C1—N1—S1	−25.7 (4)
C5—C6—C7—C9	−60.7 (4)	C2—C1—N1—S1	−140.9 (3)
C10—C6—C7—C8	−55.2 (5)	C11—N1—S1—O1	−78.3 (4)
C1—C6—C7—C8	65.6 (5)	C1—N1—S1—O1	125.7 (3)
C5—C6—C7—C8	175.1 (4)	C11—N1—S1—O2	50.7 (4)
C10—C6—C7—C3	−172.6 (3)	C1—N1—S1—O2	−105.2 (3)
C1—C6—C7—C3	−51.8 (3)	C11—N1—S1—C10	165.1 (3)
C5—C6—C7—C3	57.7 (4)	C1—N1—S1—C10	9.2 (3)
C1—C6—C10—S1	−26.2 (4)	C6—C10—S1—O1	−103.7 (3)
C5—C6—C10—S1	−145.0 (3)	C6—C10—S1—O2	123.2 (3)
C7—C6—C10—S1	92.5 (4)	C6—C10—S1—N1	10.3 (3)
O3—C11—C12—C14	80.8 (5)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8B···N1	0.96	2.54	3.129 (6)	120
C19—H19···O3	0.93	2.59	3.196 (6)	123
C12—H12···O1	0.98	2.49	3.268 (6)	137
C10—H10A···O3i	0.97	2.36	3.292 (5)	161

Symmetry codes: (i) x, y−1, z.