Ammonium [(1S)-(endo,anti)]-(-)-3-bromo-camphor-8-sulfonate.

In the title mol-ecular salt, NH(4) (+)·C(10)H(14)BrO(4)S(-), the norbornane skeleton of the anion is composed of two five-membered rings in envelope conformations and a six-membered ring with one Br atom, one carbonyl O atom and a methyl group held in a boat conformation by a bridging methyl-ene group. Short intra-molecular C-H⋯O and C-H⋯Br inter-actions occur. In the crystal, the component ions are linked by inter-molecular N-H⋯O and C-H⋯O hydrogen bonds.

Related literature

For further synthetic details, see: Smith et al. (2008 ▶). For other structures with the norbornane skeleton, see: Jauch et al. (1992 ▶); Ustabaş et al. (2006 ▶); Ersanlı et al. (2005 ▶). For the use of 3-bromo­camphor-8-sulfonic acid and its ammonium salts as chiral auxillaries for the optical resolution of enanti­omeric amines through diasteriomeric salt formation, see: Bálint et al. (1999 ▶); Pellati et al. (2010 ▶); Roy et al. (2009 ▶); Zhao et al. (2002 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

NH4 +·C10H14BrO4S−

M = 328.22

Monoclinic,

a = 7.2449 (2) Å

b = 7.0049 (1) Å

c = 13.2428 (3) Å

β = 104.704 (1)°

V = 650.06 (3) Å3

Z = 2

Mo Kα radiation

μ = 3.33 mm−1

T = 296 K

0.42 × 0.14 × 0.11 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: refined from ΔF (XABS2; Parkin et al., 1995 ▶) T min = 0.336, T max = 0.711

2775 measured reflections

2775 independent reflections

2586 reflections with I > 2σ(I)

Refinement

R[F 2 > 2σ(F 2)] = 0.027

wR(F 2) = 0.065

S = 1.03

2775 reflections

168 parameters

5 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.35 e Å−3

Δρmin = −0.47 e Å−3

Absolute structure: Flack (1983 ▶), 1155 Freidel pairs

Flack parameter: −0.021 (7)

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); 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: WinGX (Farrugia, 1999 ▶), PARST (Nardelli, 1983 ▶) and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810022804/hb5484sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810022804/hb5484Isup2.hkl

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

NH4+·C10H14BrO4S−	F(000) = 336
Mr = 328.22	Dx = 1.677 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 3356 reflections
a = 7.2449 (2) Å	θ = 2.9–28.3°
b = 7.0049 (1) Å	µ = 3.33 mm−1
c = 13.2428 (3) Å	T = 296 K
β = 104.704 (1)°	Prism, colourless
V = 650.06 (3) Å3	0.42 × 0.14 × 0.11 mm
Z = 2

Bruker Kappa APEXII CCD diffractometer	2775 independent reflections
Radiation source: sealed tube	2586 reflections with I > 2σ(I)
graphite	Rint = 0.0000
φ and ω scans	θmax = 27.5°, θmin = 3.3°
Absorption correction: part of the refinement model (ΔF) (XABS2; Parkin et al., 1995; quadratic fit to sin(θ)/λ - 18 parameters)	h = −9→9
Tmin = 0.336, Tmax = 0.711	k = −8→9
2775 measured reflections	l = 0→17

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)] = 0.027	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.065	w = 1/[σ2(Fo2) + (0.033P)2 + 0.1814P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max < 0.001
2775 reflections	Δρmax = 0.35 e Å−3
168 parameters	Δρmin = −0.47 e Å−3
5 restraints	Absolute structure: Flack (1983), 1155 Freidel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.021 (7)

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. 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-obs 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	0.09450 (4)	0.00017 (4)	0.27520 (3)	0.0440 (1)
S1	0.65799 (9)	0.68509 (9)	0.36429 (5)	0.0242 (2)
O1	0.7216 (3)	0.8793 (3)	0.3541 (2)	0.0434 (8)
O2	0.8199 (3)	0.5560 (3)	0.39714 (16)	0.0332 (6)
O3	0.5283 (3)	0.6697 (4)	0.42972 (17)	0.0448 (8)
O4	0.2268 (4)	0.0517 (4)	0.0568 (2)	0.0596 (10)
C1	0.5311 (4)	0.6201 (4)	0.2339 (2)	0.0277 (8)
C2	0.4754 (4)	0.4086 (4)	0.2154 (2)	0.0213 (7)
C3	0.3597 (3)	0.3263 (4)	0.2899 (2)	0.0223 (7)
C4	0.1802 (4)	0.4500 (4)	0.2647 (2)	0.0272 (8)
C5	0.1351 (4)	0.4758 (5)	0.1462 (2)	0.0352 (9)
C6	0.3067 (4)	0.3804 (4)	0.1148 (2)	0.0310 (9)
C7	0.3318 (6)	0.4411 (6)	0.0112 (2)	0.0519 (13)
C8	0.6514 (4)	0.2949 (4)	0.2067 (2)	0.0316 (9)
C9	0.2719 (4)	0.1690 (5)	0.1248 (2)	0.0342 (9)
C10	0.3097 (4)	0.1283 (4)	0.2418 (2)	0.0298 (8)
N1	0.8032 (3)	0.1906 (4)	0.4952 (2)	0.0311 (7)
H1A	0.41550	0.69600	0.21450	0.0330*
H1B	0.60920	0.65480	0.18710	0.0330*
H3	0.42880	0.32500	0.36380	0.0270*
H4A	0.20390	0.57210	0.30010	0.0330*
H4B	0.07600	0.38650	0.28480	0.0330*
H5A	0.12590	0.61000	0.12770	0.0420*
H5B	0.01620	0.41320	0.11210	0.0420*
H7A	0.22080	0.40620	−0.04250	0.0780*
H7B	0.44200	0.37920	−0.00150	0.0780*
H7C	0.34880	0.57700	0.01080	0.0780*
H8A	0.74270	0.29220	0.27340	0.0470*
H8B	0.70750	0.35440	0.15630	0.0470*
H8C	0.61420	0.16680	0.18500	0.0470*
H10	0.42240	0.04610	0.26290	0.0360*
H1N	0.775 (5)	0.096 (4)	0.445 (2)	0.0470*
H2N	0.914 (4)	0.170 (6)	0.543 (2)	0.0470*
H3N	0.806 (5)	0.305 (4)	0.461 (3)	0.0470*
H4N	0.706 (4)	0.195 (6)	0.528 (3)	0.0470*

	U11	U22	U33	U12	U13	U23
Br1	0.0329 (2)	0.0300 (2)	0.0673 (2)	−0.0085 (1)	0.0093 (1)	0.0087 (2)
S1	0.0199 (3)	0.0209 (3)	0.0303 (3)	−0.0028 (2)	0.0036 (2)	−0.0024 (3)
O1	0.0492 (13)	0.0217 (11)	0.0526 (15)	−0.0096 (9)	0.0007 (11)	−0.0030 (9)
O2	0.0246 (9)	0.0298 (11)	0.0393 (12)	0.0024 (7)	−0.0029 (8)	−0.0036 (8)
O3	0.0304 (10)	0.0674 (17)	0.0391 (13)	−0.0101 (11)	0.0133 (9)	−0.0175 (12)
O4	0.0552 (15)	0.060 (2)	0.0580 (16)	−0.0138 (12)	0.0042 (12)	−0.0336 (13)
C1	0.0241 (13)	0.0248 (14)	0.0298 (15)	−0.0018 (11)	−0.0010 (11)	0.0010 (11)
C2	0.0168 (12)	0.0239 (13)	0.0226 (13)	−0.0016 (10)	0.0041 (10)	−0.0026 (10)
C3	0.0170 (11)	0.0207 (12)	0.0274 (14)	−0.0020 (9)	0.0022 (10)	−0.0004 (10)
C4	0.0184 (11)	0.0235 (15)	0.0403 (16)	0.0017 (9)	0.0084 (10)	−0.0020 (11)
C5	0.0222 (12)	0.0368 (19)	0.0406 (16)	0.0024 (13)	−0.0030 (11)	0.0017 (14)
C6	0.0239 (13)	0.0409 (17)	0.0248 (15)	−0.0040 (12)	−0.0002 (11)	−0.0024 (12)
C7	0.056 (2)	0.070 (3)	0.0247 (17)	−0.0134 (18)	0.0011 (15)	0.0033 (15)
C8	0.0206 (13)	0.0359 (16)	0.0382 (17)	−0.0007 (12)	0.0074 (11)	−0.0104 (13)
C9	0.0198 (12)	0.0392 (17)	0.0405 (16)	−0.0051 (12)	0.0018 (11)	−0.0130 (14)
C10	0.0213 (12)	0.0212 (13)	0.0444 (17)	−0.0006 (10)	0.0039 (11)	−0.0016 (11)
N1	0.0266 (12)	0.0334 (13)	0.0329 (13)	0.0019 (11)	0.0066 (10)	0.0030 (11)

Br1—C10	1.945 (3)	C6—C7	1.491 (4)
S1—O1	1.454 (2)	C6—C9	1.514 (4)
S1—O2	1.457 (2)	C9—C10	1.530 (4)
S1—O3	1.435 (2)	C1—H1B	0.9700
S1—C1	1.797 (3)	C1—H1A	0.9700
O4—C9	1.201 (4)	C3—H3	0.9800
N1—H1N	0.92 (3)	C4—H4B	0.9700
N1—H2N	0.90 (3)	C4—H4A	0.9700
N1—H3N	0.92 (3)	C5—H5A	0.9700
N1—H4N	0.92 (3)	C5—H5B	0.9700
C1—C2	1.539 (4)	C7—H7A	0.9600
C2—C3	1.558 (4)	C7—H7B	0.9600
C2—C6	1.575 (4)	C7—H7C	0.9600
C2—C8	1.532 (4)	C8—H8B	0.9600
C3—C4	1.527 (4)	C8—H8C	0.9600
C3—C10	1.531 (4)	C8—H8A	0.9600
C4—C5	1.530 (4)	C10—H10	0.9800
C5—C6	1.558 (4)
O1—S1—O2	111.00 (13)	C3—C10—C9	102.4 (2)
O1—S1—O3	113.46 (15)	S1—C1—H1B	108.00
O1—S1—C1	104.17 (14)	S1—C1—H1A	108.00
O2—S1—O3	111.96 (14)	C2—C1—H1A	108.00
O2—S1—C1	107.84 (13)	C2—C1—H1B	108.00
O3—S1—C1	107.92 (14)	H1A—C1—H1B	107.00
H3N—N1—H4N	109 (3)	C10—C3—H3	114.00
H2N—N1—H4N	109 (3)	C4—C3—H3	114.00
H1N—N1—H3N	107 (3)	C2—C3—H3	115.00
H1N—N1—H4N	108 (3)	C5—C4—H4A	111.00
H1N—N1—H2N	113 (3)	C3—C4—H4B	111.00
H2N—N1—H3N	111 (3)	C3—C4—H4A	111.00
S1—C1—C2	116.52 (19)	C5—C4—H4B	111.00
C1—C2—C8	108.8 (2)	H4A—C4—H4B	109.00
C1—C2—C6	111.8 (2)	H5A—C5—H5B	109.00
C1—C2—C3	114.6 (2)	C4—C5—H5A	111.00
C6—C2—C8	110.7 (2)	C4—C5—H5B	111.00
C3—C2—C6	93.6 (2)	C6—C5—H5A	111.00
C3—C2—C8	116.6 (2)	C6—C5—H5B	111.00
C4—C3—C10	108.9 (2)	H7B—C7—H7C	109.00
C2—C3—C4	102.5 (2)	C6—C7—H7C	109.00
C2—C3—C10	100.4 (2)	C6—C7—H7A	110.00
C3—C4—C5	103.9 (2)	C6—C7—H7B	109.00
C4—C5—C6	104.2 (2)	H7A—C7—H7B	109.00
C7—C6—C9	114.9 (3)	H7A—C7—H7C	109.00
C2—C6—C7	119.5 (3)	C2—C8—H8B	109.00
C2—C6—C5	102.8 (2)	C2—C8—H8A	109.00
C5—C6—C9	103.6 (2)	H8A—C8—H8C	109.00
C2—C6—C9	99.2 (2)	C2—C8—H8C	109.00
C5—C6—C7	114.5 (3)	H8A—C8—H8B	109.00
O4—C9—C6	128.6 (3)	H8B—C8—H8C	110.00
O4—C9—C10	125.2 (3)	C9—C10—H10	109.00
C6—C9—C10	106.3 (2)	Br1—C10—H10	109.00
Br1—C10—C3	116.24 (18)	C3—C10—H10	109.00
Br1—C10—C9	111.62 (19)
O1—S1—C1—C2	169.7 (2)	C2—C3—C4—C5	39.1 (3)
O2—S1—C1—C2	51.7 (2)	C10—C3—C4—C5	−66.7 (3)
O3—S1—C1—C2	−69.4 (3)	C2—C3—C10—Br1	−159.47 (17)
S1—C1—C2—C3	54.3 (3)	C2—C3—C10—C9	−37.5 (3)
S1—C1—C2—C6	159.2 (2)	C4—C3—C10—Br1	−52.3 (3)
S1—C1—C2—C8	−78.2 (3)	C4—C3—C10—C9	69.7 (3)
C1—C2—C3—C4	61.2 (3)	C3—C4—C5—C6	−5.6 (3)
C1—C2—C3—C10	173.5 (2)	C4—C5—C6—C2	−29.3 (3)
C6—C2—C3—C4	−54.8 (2)	C4—C5—C6—C7	−160.5 (3)
C6—C2—C3—C10	57.5 (2)	C4—C5—C6—C9	73.6 (3)
C8—C2—C3—C4	−170.0 (2)	C2—C6—C9—O4	−144.1 (3)
C8—C2—C3—C10	−57.8 (3)	C2—C6—C9—C10	34.8 (3)
C1—C2—C6—C5	−67.8 (3)	C5—C6—C9—O4	110.3 (4)
C1—C2—C6—C7	60.4 (4)	C5—C6—C9—C10	−70.9 (3)
C1—C2—C6—C9	−174.0 (2)	C7—C6—C9—O4	−15.4 (5)
C3—C2—C6—C5	50.6 (2)	C7—C6—C9—C10	163.5 (3)
C3—C2—C6—C7	178.7 (3)	O4—C9—C10—Br1	−54.7 (4)
C3—C2—C6—C9	−55.7 (2)	O4—C9—C10—C3	−179.8 (3)
C8—C2—C6—C5	170.7 (2)	C6—C9—C10—Br1	126.4 (2)
C8—C2—C6—C7	−61.1 (4)	C6—C9—C10—C3	1.3 (3)
C8—C2—C6—C9	64.5 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1i	0.92 (3)	1.92 (3)	2.835 (4)	173 (3)
N1—H2N···O2ii	0.90 (3)	2.05 (3)	2.899 (3)	157 (3)
N1—H3N···O2	0.92 (3)	1.97 (3)	2.887 (3)	176 (3)
N1—H4N···O3iii	0.92 (3)	1.93 (3)	2.827 (3)	167 (4)
C4—H4B···Br1	0.97	2.71	3.221 (3)	113
C8—H8A···O2	0.96	2.44	3.104 (3)	126
C10—H10···O1i	0.98	2.49	3.451 (4)	167

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1i	0.92 (3)	1.92 (3)	2.835 (4)	173 (3)
N1—H2N⋯O2ii	0.90 (3)	2.05 (3)	2.899 (3)	157 (3)
N1—H3N⋯O2	0.92 (3)	1.97 (3)	2.887 (3)	176 (3)
N1—H4N⋯O3iii	0.92 (3)	1.93 (3)	2.827 (3)	167 (4)
C4—H4B⋯Br1	0.97	2.71	3.221 (3)	113
C8—H8A⋯O2	0.96	2.44	3.104 (3)	126
C10—H10⋯O1i	0.98	2.49	3.451 (4)	167

Symmetry codes: (i) ; (ii) ; (iii) .