3[alpha]-Tosyl­oxy­methyl­tropane(N⁸-B)borane

The title compound [alternative name: 8-methyl-8-aza­bi­cyclo­[3.2.1]­octan-3-yl­methyl p-toluene­sulfonate(N⁸-B)-bor­ane], C₁₆H₂₆BNO₃S, has the tosyl­oxy­methyl substituent in an endo position. The BH₃ group is equatorial and the (N-bonded) methyl group is axial, relative to the six-membered heterocycle. The N-B bond of 1.649 (8) Å is one of the longest known.

Computing details

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1991); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1989); program(s) used to solve structure: SHELXTL (Bruker, 1997); program(s) used to refine structure: SHELXTL; software used to prepare material for publication: SHELXTL.

3α-Tosyloxymethyltropane(N⁸—B)–borane

Crystal data

C16H26BNO3S	Dx = 1.230 Mg m^−3
Mr = 323.25	Melting point: 113.8–116.5 ° C K
Orthorhombic, Pna21	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2c -2n	Cell parameters from 25 reflections
a = 21.443 (2) Å	θ = 20.5–25.2°
b = 7.959 (1) Å	µ = 1.73 mm^−1
c = 10.224 (2) Å	T = 293 K
V = 1744.9 (4) Å^3	Prism, colourless
Z = 4	0.28 × 0.22 × 0.11 mm
F(000) = 696

Data collection

Rigaku AFC-6S four-circle diffractometer	1613 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.020
Graphite monochromator	θmax = 75°, θmin = 4.1°
2θ/ω scans	h = −16→26
Absorption correction: analytical (de Meulenaer & Tompa, 1965)	k = −6→9
Tmin = 0.726, Tmax = 0.837	l = −8→12
2243 measured reflections	3 standard reflections every 147 reflections
2157 independent reflections	intensity decay: 0.8%

Refinement

Refinement on F^2	Hydrogen site location: difference Fourier map
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.043	w = 1/[σ^2(Fo^2) + (0.0473P)^2 + 0.4507P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.103	(Δ/σ)max = −0.001
S = 1.05	Δρmax = 0.21 e Å^−3
2157 reflections	Δρmin = −0.17 e Å^−3
208 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.00081 (14)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983)
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.35 (3)

Special details

Experimental. The crystal was a racemic twin with the component contributions of 0.65 (3) and 0.35 (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 on F² for ALL reflections. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating _R_factor_gt etc. and is not relevant to the choice of reflections for refinement.

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

	x	y	z	Uiso*/Ueq
S	0.62305 (5)	0.40959 (14)	0.49106 (13)	0.0519 (3)
O1	0.55683 (14)	0.4624 (4)	0.4392 (3)	0.0549 (9)
O2	0.6527 (2)	0.3351 (4)	0.3808 (4)	0.0656 (10)
O3	0.6162 (2)	0.3152 (5)	0.6094 (4)	0.0647 (10)
N	0.3988 (2)	0.9398 (4)	0.5051 (4)	0.0487 (10)
C1	0.3977 (2)	0.8095 (6)	0.6114 (5)	0.0490 (12)
H1	0.3598 (2)	0.8212 (6)	0.6641 (5)	0.059*
C2	0.4024 (2)	0.6322 (6)	0.5566 (6)	0.0543 (13)
H21	0.3641 (2)	0.6071 (6)	0.5100 (6)	0.071*
H22	0.4055 (2)	0.5540 (6)	0.6290 (6)	0.071*
C3	0.4580 (2)	0.6017 (6)	0.4633 (5)	0.0500 (13)
H3	0.4436 (2)	0.5223 (6)	0.3966 (5)	0.060*
C4	0.4783 (2)	0.7622 (6)	0.3904 (5)	0.0555 (13)
H41	0.5225 (2)	0.7541 (6)	0.3716 (5)	0.072*
H42	0.4564 (2)	0.7666 (6)	0.3074 (5)	0.072*
C5	0.4665 (2)	0.9258 (6)	0.4631 (5)	0.0546 (14)
H5	0.4780 (2)	1.0218 (6)	0.4082 (5)	0.066*
C6	0.5006 (2)	0.9343 (7)	0.5936 (5)	0.0615 (15)
H61	0.5103 (2)	1.0496 (7)	0.6165 (5)	0.080*
H62	0.5390 (2)	0.8701 (7)	0.5906 (5)	0.080*
C7	0.4546 (3)	0.8577 (7)	0.6921 (5)	0.0597 (14)
H71	0.4726 (3)	0.7594 (7)	0.7338 (5)	0.078*
H72	0.4436 (3)	0.9387 (7)	0.7591 (5)	0.078*
C8	0.3543 (3)	0.9034 (7)	0.3959 (6)	0.076 (2)
H81	0.3609 (12)	0.982 (3)	0.3263 (17)	0.114 (14)*
H82	0.3122 (3)	0.913 (5)	0.4271 (11)	0.114 (14)*
H83	0.3612 (12)	0.7914 (19)	0.364 (3)	0.114 (14)*
C9	0.5105 (2)	0.5163 (6)	0.5362 (5)	0.0560 (14)
H91	0.5293 (2)	0.5937 (6)	0.5980 (5)	0.073*
H92	0.4948 (2)	0.4200 (6)	0.5841 (5)	0.073*
C10	0.7495 (3)	1.0692 (7)	0.6108 (7)	0.082 (2)
H101	0.7187 (4)	1.1483 (19)	0.640 (4)	0.137 (16)*
H102	0.7693 (18)	1.111 (3)	0.5332 (13)	0.137 (16)*
H103	0.7802 (15)	1.0534 (14)	0.678 (3)	0.137 (16)*
C11	0.6586 (2)	0.6013 (6)	0.5268 (5)	0.0476 (12)
C12	0.6851 (2)	0.6273 (7)	0.6478 (5)	0.0589 (14)
H12	0.6829 (2)	0.5447 (7)	0.7120 (5)	0.071*
C13	0.7151 (3)	0.7806 (7)	0.6730 (6)	0.064 (2)
H13	0.7333 (3)	0.7988 (7)	0.7543 (6)	0.077*
C14	0.7180 (2)	0.9020 (8)	0.5810 (6)	0.0612 (15)
C15	0.6919 (2)	0.8745 (7)	0.4600 (6)	0.061 (2)
H15	0.6940 (2)	0.9585 (7)	0.3969 (6)	0.074*
C16	0.6628 (2)	0.7257 (7)	0.4310 (5)	0.0581 (14)
H16	0.6458 (2)	0.7079 (7)	0.3484 (5)	0.070*
B	0.3812 (3)	1.1297 (9)	0.5579 (8)	0.075 (2)
H1B	0.4151 (12)	1.1668 (19)	0.646 (3)	0.077 (9)*
H2B	0.3286 (12)	1.1315 (13)	0.595 (3)	0.077 (9)*
H3B	0.3871 (12)	1.228 (3)	0.471 (2)	0.077 (9)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S	0.0494 (6)	0.0530 (6)	0.0534 (7)	0.0071 (6)	−0.0019 (7)	−0.0057 (8)
O1	0.047 (2)	0.063 (2)	0.054 (2)	0.004 (2)	−0.003 (2)	−0.013 (2)
O2	0.062 (2)	0.071 (2)	0.063 (2)	0.007 (2)	0.004 (2)	−0.022 (2)
O3	0.067 (2)	0.055 (2)	0.072 (3)	0.006 (2)	0.001 (2)	0.014 (2)
N	0.050 (2)	0.050 (2)	0.047 (3)	0.003 (2)	−0.001 (2)	0.002 (2)
C1	0.048 (3)	0.058 (3)	0.041 (3)	−0.005 (2)	0.002 (2)	0.005 (3)
C2	0.043 (2)	0.053 (3)	0.067 (3)	−0.007 (2)	−0.002 (3)	0.003 (3)
C3	0.046 (2)	0.056 (3)	0.048 (4)	−0.003 (2)	−0.002 (2)	−0.004 (3)
C4	0.056 (3)	0.069 (3)	0.041 (3)	0.003 (3)	0.010 (3)	0.000 (3)
C5	0.062 (3)	0.052 (3)	0.050 (4)	−0.006 (2)	0.011 (3)	0.007 (3)
C6	0.054 (3)	0.058 (3)	0.073 (4)	−0.007 (3)	−0.004 (3)	−0.012 (3)
C7	0.061 (3)	0.078 (4)	0.040 (3)	−0.001 (3)	−0.001 (3)	−0.001 (3)
C8	0.064 (3)	0.095 (5)	0.068 (4)	0.020 (3)	−0.015 (3)	−0.001 (4)
C9	0.049 (3)	0.058 (3)	0.061 (4)	0.007 (2)	0.008 (3)	0.005 (3)
C10	0.055 (3)	0.057 (4)	0.136 (6)	−0.003 (3)	0.004 (4)	−0.023 (4)
C11	0.043 (2)	0.051 (3)	0.048 (4)	0.004 (2)	−0.004 (2)	−0.004 (3)
C12	0.059 (3)	0.067 (4)	0.050 (3)	0.006 (3)	0.001 (3)	−0.007 (3)
C13	0.068 (4)	0.064 (4)	0.060 (4)	0.008 (3)	−0.017 (3)	−0.016 (3)
C14	0.036 (3)	0.064 (4)	0.084 (4)	0.003 (3)	0.000 (3)	−0.016 (4)
C15	0.060 (3)	0.060 (3)	0.064 (4)	−0.003 (3)	0.005 (3)	0.008 (3)
C16	0.057 (3)	0.068 (4)	0.049 (3)	0.000 (3)	−0.002 (3)	−0.002 (3)
B	0.084 (4)	0.059 (4)	0.083 (5)	0.019 (4)	0.009 (5)	0.000 (4)

Geometric parameters (Å, º)

S—O2	1.424 (4)	C3—C9	1.513 (6)
S—O3	1.432 (4)	C3—C4	1.541 (6)
S—O1	1.573 (3)	C4—C5	1.520 (6)
S—C11	1.745 (5)	C5—C6	1.523 (7)
O1—C9	1.467 (5)	C6—C7	1.536 (7)
N—C8	1.497 (7)	C10—C14	1.523 (7)
N—C1	1.502 (6)	C11—C12	1.376 (7)
N—C5	1.518 (6)	C11—C16	1.396 (7)
N—B	1.649 (8)	C12—C13	1.403 (7)
C1—C2	1.522 (6)	C13—C14	1.350 (8)
C1—C7	1.523 (7)	C14—C15	1.375 (7)
C2—C3	1.545 (6)	C15—C16	1.372 (7)
O2—S—O3	119.8 (2)	C4—C3—C2	112.7 (4)
O2—S—O1	104.4 (2)	C5—C4—C3	115.3 (4)
O3—S—O1	109.4 (2)	N—C5—C4	111.1 (4)
O2—S—C11	109.6 (2)	N—C5—C6	102.0 (4)
O3—S—C11	109.0 (2)	C4—C5—C6	112.7 (4)
O1—S—C11	103.4 (2)	C5—C6—C7	104.4 (4)
C9—O1—S	117.5 (3)	C1—C7—C6	105.0 (4)
C8—N—C1	113.3 (4)	O1—C9—C3	107.7 (4)
C8—N—C5	112.6 (4)	C12—C11—C16	119.9 (5)
C1—N—C5	99.7 (3)	C12—C11—S	120.0 (4)
C8—N—B	106.0 (4)	C16—C11—S	120.1 (4)
C1—N—B	113.1 (4)	C11—C12—C13	119.0 (5)
C5—N—B	112.3 (4)	C14—C13—C12	121.0 (5)
N—C1—C2	111.9 (4)	C13—C14—C15	119.6 (5)
N—C1—C7	101.9 (4)	C13—C14—C10	120.4 (6)
C2—C1—C7	112.3 (4)	C15—C14—C10	120.0 (6)
C1—C2—C3	115.0 (4)	C16—C15—C14	121.2 (5)
C9—C3—C4	113.6 (4)	C15—C16—C11	119.3 (5)
C9—C3—C2	110.0 (4)