(R,R)-Disynephrine ether bis-(hydrogen sulfate).

THE ASYMMETRIC UNIT OF THE TITLE COMPOUND [SYSTEMATIC NAME: (R,R)-2,4-bis-(4-hydroxy-phen-yl)-N,N'-dimethyl-3-oxapentane-1,5-diammonium bis-(hydrogen sulfate)], C(18)H(26)N(2)O(3) (2+)·2HSO(4) (-), contains one half-cation and one hydrogen sulfate anion. The cation has crystallographically imposed twofold symmetry with the rotation axis passing through the central ether O atom. Hydrogen bonds between the hydr-oxy group and amine H atoms of the cation to two hydrogen sulfate anions link the three ions in a ring motif. A three-dimensional network is accomplished by additional O-H⋯O hydrogen bonds between the anions and by N-H⋯O hydrogen bonds between the cations. Disorder with equally occupied sites affects the H-atom position in the anion.

Related literature

For the preparation and structure of the equivalent bromide salt, see: Mukhopadhyay & Dattagupta (1984 ▶, 1988 ▶). For recent examples of synephrine use, see: Blanck et al. (2007 ▶): Haller et al. (2008 ▶). For general background, see: Bruice (2007 ▶); Jacques et al. (1981 ▶).

Experimental

Crystal data

C18H26N2O3 2+·2HSO4 −

M = 512.54

Monoclinic,

a = 13.7204 (9) Å

b = 11.5853 (5) Å

c = 7.6579 (5) Å

β = 116.413 (8)°

V = 1090.19 (13) Å3

Z = 2

Mo Kα radiation

μ = 0.31 mm−1

T = 123 K

0.23 × 0.15 × 0.11 mm

Data collection

Oxford Diffraction Gemini S CCD diffractometer

Absorption correction: multi-scan (ABSPACK; Oxford Diffraction, 2007 ▶) T min = 0.974, T max = 1.000 (expected range = 0.942–0.967)

5888 measured reflections

2401 independent reflections

2034 reflections with I > 2σ(I)

R int = 0.027

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.111

S = 1.03

2401 reflections

161 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.57 e Å−3

Δρmin = −0.43 e Å−3

Absolute structure: Flack (1983 ▶), 1032 Friedel pairs

Flack parameter: 0.08 (11)

Data collection: CrysAlis CCD (Oxford Diffraction, 2007 ▶); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2007 ▶); 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: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809025288/wm2243sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809025288/wm2243Isup2.hkl

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

C18H26N2O32+·2HSO4−	F(000) = 540
Mr = 512.54	Dx = 1.561 Mg m−3
Monoclinic, C2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2y	Cell parameters from 3122 reflections
a = 13.7204 (9) Å	θ = 2.4–29.1°
b = 11.5853 (5) Å	µ = 0.31 mm−1
c = 7.6579 (5) Å	T = 123 K
β = 116.413 (8)°	Prism, colourless
V = 1090.19 (13) Å3	0.23 × 0.15 × 0.11 mm
Z = 2

Oxford Diffraction Gemini S CCD diffractometer	2401 independent reflections
Radiation source: fine-focus sealed tube	2034 reflections with I > 2σ(I)
graphite	Rint = 0.027
ω scans	θmax = 28.0°, θmin = 2.4°
Absorption correction: multi-scan (ABSPACK; Oxford Diffraction, 2007)	h = −17→16
Tmin = 0.974, Tmax = 1.000	k = −14→14
5888 measured reflections	l = −10→10

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)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.111	w = 1/[σ2(Fo2) + (0.071P)2] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max < 0.001
2401 reflections	Δρmax = 0.57 e Å−3
161 parameters	Δρmin = −0.43 e Å−3
1 restraint	Absolute structure: Flack (1983), 1032 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.08 (11)

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	Occ. (<1)
S1	0.08291 (6)	0.20896 (7)	0.33257 (10)	0.0289 (2)
O1	0.17446 (14)	0.40319 (17)	−0.2357 (3)	0.0181 (4)
H1	0.1185	0.3616	−0.2796	0.027*
O2	0.5000	0.1062 (2)	0.5000	0.0128 (5)
O3	0.02688 (19)	0.31541 (19)	0.3192 (4)	0.0304 (6)
O4	0.19286 (16)	0.2108 (3)	0.4864 (3)	0.0395 (6)
O5	0.0193 (2)	0.1104 (2)	0.3550 (4)	0.0456 (7)
H1S	0.0204	0.1255	0.4724	0.068*	0.50
O6	0.0896 (2)	0.1834 (3)	0.1477 (4)	0.0519 (8)
H2S	0.0295	0.2160	0.0149	0.078*	0.50
N1	0.6712 (2)	0.0279 (2)	0.4186 (4)	0.0191 (5)
C1	0.4315 (2)	0.2368 (2)	0.2158 (3)	0.0135 (6)
C2	0.3329 (2)	0.1795 (2)	0.1126 (4)	0.0156 (6)
H2	0.3247	0.1025	0.1470	0.019*
C3	0.2473 (2)	0.2329 (2)	−0.0382 (4)	0.0166 (6)
H3	0.1807	0.1927	−0.1078	0.020*
C4	0.2581 (2)	0.3458 (2)	−0.0891 (4)	0.0139 (5)
C5	0.3554 (2)	0.4041 (3)	0.0124 (4)	0.0182 (6)
H5	0.3633	0.4812	−0.0217	0.022*
C6	0.4414 (2)	0.3491 (2)	0.1646 (4)	0.0173 (6)
H6	0.5079	0.3893	0.2346	0.021*
C7	0.5277 (2)	0.1742 (2)	0.3714 (4)	0.0136 (5)
H7	0.5851	0.2315	0.4495	0.016*
C8	0.5734 (2)	0.0900 (3)	0.2748 (4)	0.0172 (6)
H8A	0.5165	0.0329	0.1989	0.021*
H8B	0.5928	0.1326	0.1827	0.021*
C9	0.7267 (3)	−0.0381 (3)	0.3240 (5)	0.0302 (7)
H9A	0.7837	−0.0864	0.4212	0.045*
H9B	0.7595	0.0155	0.2662	0.045*
H9C	0.6738	−0.0873	0.2216	0.045*
H1N	0.711 (2)	0.082 (3)	0.482 (4)	0.013 (8)*
H2N	0.648 (3)	−0.011 (3)	0.480 (4)	0.012 (8)*

	U11	U22	U33	U12	U13	U23
S1	0.0228 (4)	0.0289 (4)	0.0312 (4)	0.0004 (4)	0.0086 (3)	−0.0031 (4)
O1	0.0142 (9)	0.0149 (9)	0.0191 (10)	0.0002 (8)	0.0019 (8)	0.0039 (8)
O2	0.0139 (12)	0.0143 (13)	0.0101 (11)	0.000	0.0053 (10)	0.000
O3	0.0196 (11)	0.0272 (12)	0.0420 (13)	0.0024 (9)	0.0117 (10)	−0.0016 (10)
O4	0.0275 (11)	0.0363 (12)	0.0388 (12)	0.0082 (14)	0.0005 (9)	0.0003 (14)
O5	0.0485 (16)	0.0330 (14)	0.0552 (17)	−0.0104 (13)	0.0231 (14)	−0.0060 (13)
O6	0.0427 (15)	0.072 (2)	0.0398 (14)	0.0081 (15)	0.0172 (13)	−0.0090 (13)
N1	0.0160 (12)	0.0187 (13)	0.0244 (12)	0.0036 (10)	0.0106 (11)	0.0065 (11)
C1	0.0139 (13)	0.0157 (15)	0.0108 (11)	0.0032 (9)	0.0054 (10)	0.0027 (9)
C2	0.0190 (13)	0.0106 (13)	0.0178 (12)	−0.0004 (10)	0.0088 (11)	0.0009 (9)
C3	0.0134 (13)	0.0172 (16)	0.0178 (12)	−0.0026 (10)	0.0057 (10)	−0.0019 (10)
C4	0.0164 (13)	0.0118 (12)	0.0125 (12)	0.0040 (10)	0.0055 (11)	0.0010 (10)
C5	0.0184 (14)	0.0138 (12)	0.0217 (14)	0.0003 (12)	0.0082 (12)	0.0044 (11)
C6	0.0135 (13)	0.0140 (13)	0.0224 (13)	−0.0030 (11)	0.0063 (11)	−0.0010 (11)
C7	0.0143 (12)	0.0120 (12)	0.0133 (12)	−0.0016 (9)	0.0053 (10)	0.0011 (9)
C8	0.0145 (13)	0.0239 (15)	0.0148 (12)	0.0049 (11)	0.0079 (10)	0.0031 (11)
C9	0.0292 (18)	0.0236 (17)	0.047 (2)	0.0087 (13)	0.0251 (16)	0.0051 (14)

S1—O3	1.433 (2)	C1—C7	1.513 (3)
S1—O4	1.443 (2)	C2—C3	1.375 (4)
S1—O6	1.488 (3)	C2—H2	0.9500
S1—O5	1.492 (3)	C3—C4	1.392 (4)
O1—C4	1.368 (3)	C3—H3	0.9500
O1—H1	0.8400	C4—C5	1.386 (4)
O2—C7	1.438 (3)	C5—C6	1.390 (4)
O2—C7i	1.438 (3)	C5—H5	0.9500
O5—H1S	0.9095	C6—H6	0.9500
O6—H2S	1.0540	C7—C8	1.517 (4)
N1—C9	1.477 (4)	C7—H7	1.0000
N1—C8	1.489 (3)	C8—H8A	0.9900
N1—H1N	0.83 (3)	C8—H8B	0.9900
N1—H2N	0.82 (3)	C9—H9A	0.9800
C1—C6	1.383 (4)	C9—H9B	0.9800
C1—C2	1.395 (4)	C9—H9C	0.9800
O3—S1—O4	112.25 (15)	O1—C4—C3	122.1 (2)
O3—S1—O6	111.20 (16)	C5—C4—C3	119.8 (2)
O4—S1—O6	107.16 (15)	C4—C5—C6	119.6 (3)
O3—S1—O5	110.11 (14)	C4—C5—H5	120.2
O4—S1—O5	111.70 (16)	C6—C5—H5	120.2
O6—S1—O5	104.10 (17)	C1—C6—C5	121.0 (2)
C4—O1—H1	109.5	C1—C6—H6	119.5
C7—O2—C7i	113.6 (3)	C5—C6—H6	119.5
S1—O5—H1S	102.3	O2—C7—C1	113.45 (19)
S1—O6—H2S	119.6	O2—C7—C8	105.9 (2)
C9—N1—C8	112.3 (2)	C1—C7—C8	109.2 (2)
C9—N1—H1N	109 (2)	O2—C7—H7	109.4
C8—N1—H1N	102 (2)	C1—C7—H7	109.4
C9—N1—H2N	114 (2)	C8—C7—H7	109.4
C8—N1—H2N	104 (2)	N1—C8—C7	112.5 (2)
H1N—N1—H2N	114 (3)	N1—C8—H8A	109.1
C6—C1—C2	118.7 (2)	C7—C8—H8A	109.1
C6—C1—C7	120.9 (2)	N1—C8—H8B	109.1
C2—C1—C7	120.3 (2)	C7—C8—H8B	109.1
C3—C2—C1	120.8 (2)	H8A—C8—H8B	107.8
C3—C2—H2	119.6	N1—C9—H9A	109.5
C1—C2—H2	119.6	N1—C9—H9B	109.5
C2—C3—C4	120.1 (2)	H9A—C9—H9B	109.5
C2—C3—H3	120.0	N1—C9—H9C	109.5
C4—C3—H3	120.0	H9A—C9—H9C	109.5
O1—C4—C5	118.1 (2)	H9B—C9—H9C	109.5
C6—C1—C2—C3	0.6 (4)	C7i—O2—C7—C1	−70.07 (17)
C7—C1—C2—C3	−175.4 (2)	C7i—O2—C7—C8	170.1 (2)
C1—C2—C3—C4	−0.4 (4)	C6—C1—C7—O2	139.0 (2)
C2—C3—C4—O1	−178.7 (2)	C2—C1—C7—O2	−45.1 (3)
C2—C3—C4—C5	0.2 (4)	C6—C1—C7—C8	−103.1 (3)
O1—C4—C5—C6	178.8 (2)	C2—C1—C7—C8	72.8 (3)
C3—C4—C5—C6	−0.1 (4)	C9—N1—C8—C7	−169.9 (2)
C2—C1—C6—C5	−0.5 (4)	O2—C7—C8—N1	−59.6 (3)
C7—C1—C6—C5	175.4 (2)	C1—C7—C8—N1	177.9 (2)
C4—C5—C6—C1	0.3 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3ii	0.84	1.95	2.739 (3)	155
N1—H1N···O4i	0.83 (3)	1.93 (3)	2.700 (4)	153 (3)
N1—H2N···O1iii	0.82 (3)	2.27 (3)	2.999 (3)	149 (3)
O5—H1S···O5iv	0.91	1.65	2.502 (6)	155
O6—H2S···O6ii	1.05	1.60	2.493 (5)	139

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O3i	0.84	1.95	2.739 (3)	155
N1—H1N⋯O4ii	0.83 (3)	1.93 (3)	2.700 (4)	153 (3)
N1—H2N⋯O1iii	0.82 (3)	2.27 (3)	2.999 (3)	149 (3)
O5—H1S⋯O5iv	0.91	1.65	2.502 (6)	155
O6—H2S⋯O6i	1.05	1.60	2.493 (5)	139

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