(2S,NS)-N-Allyl-N-benzyl-1-hydr-oxy-3-(4-hydroxy-phen-yl)-N-methyl-propan-2-aminium bromide.

The title compound, C(20)H(26)NO(2) (+)·Br(-), is an N-chiral quaternary ammonium salt synthesized from (2S*)-N-benzyl-N-methyl-tyrosine methyl ester. The dihedral angle between the phenyl ring and the benzene ring is 11.61 (19)°. In the crystal structure, the allyl group is disordered over two positions with site occupancy factors of ca 0.8 and 0.2. The bromide anion links to the quaternary ammonium cations via O-H⋯Br hydrogen bonding. An intramolecular O-H⋯Br hydrogen bond is also observed.

Related literature

For general background, see: Maruoka & Ooi (2003 ▶); Ooi & Maruoka (2007 ▶). For a related structure, see: Tayama & Tanaka (2007 ▶). For synthesis, see: White & Konopelski (2005 ▶).

Experimental

Crystal data

C20H26NO2 +·Br−

M = 392.33

Orthorhombic,

a = 10.3716 (10) Å

b = 12.1566 (10) Å

c = 15.6790 (16) Å

V = 1976.9 (3) Å3

Z = 4

Mo Kα radiation

μ = 2.09 mm−1

T = 293 (2) K

0.45 × 0.43 × 0.40 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.406, T max = 0.433

18872 measured reflections

4524 independent reflections

2606 reflections with I > 2σ(I)

R int = 0.057

Refinement

R[F 2 > 2σ(F 2)] = 0.054

wR(F 2) = 0.211

S = 1.00

4524 reflections

225 parameters

2 restraints

H-atom parameters constrained

Δρmax = 0.89 e Å−3

Δρmin = −0.69 e Å−3

Absolute structure: Flack (1983 ▶), with 1949 Friedel pairs

Flack parameter: 0.009 (19)

Data collection: RAPID-AUTO (Rigaku, 2004 ▶); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808023210/xu2435sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808023210/xu2435Isup2.hkl

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

C20H26NO2+·Br–	Dx = 1.318 Mg m−3
Mr = 392.33	Melting point: 449(5) K
Orthorhombic, P212121	Mo Kα radiation λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 10762 reflections
a = 10.3716 (10) Å	θ = 3.1–27.4º
b = 12.1566 (10) Å	µ = 2.09 mm−1
c = 15.6790 (16) Å	T = 293 (2) K
V = 1976.9 (3) Å3	Block, colourless
Z = 4	0.45 × 0.43 × 0.40 mm
F000 = 816

Rigaku R-AXIS RAPID IP diffractometer	4524 independent reflections
Radiation source: Rotating anode	2606 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.057
T = 293(2) K	θmax = 27.5º
ω scans	θmin = 3.1º
Absorption correction: multi-scan(ABSCOR; Higashi, 1995)	h = −13→13
Tmin = 0.406, Tmax = 0.434	k = −15→15
18872 measured reflections	l = −20→20

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.054	w = 1/[σ2(Fo2) + (0.128P)2 + 0.338P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.211	(Δ/σ)max = 0.001
S = 1.00	Δρmax = 0.89 e Å−3
4524 reflections	Δρmin = −0.69 e Å−3
225 parameters	Extinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
2 restraints	Extinction coefficient: 0.058 (6)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), with 1949 Friedel pairs
Secondary atom site location: difference Fourier map	Flack parameter: 0.009 (19)

Experimental. IR (KBr): 3297, 3034, 1612, 1515, 1464, 1264, 1058, 850 (cm-1); 13CNMR (150 MHz, DMSO-d6, δ, p.p.m.): 156.8, 133.7, 130.8, 129.4, 128.5, 127.4, 126.9, 126.8, 116.0, 73.9, 63.7, 62.9, 56.6, 47.0, 29.6.

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)
Br1	0.63828 (7)	0.06624 (5)	0.31732 (5)	0.0766 (3)
O1	0.6728 (4)	0.3120 (4)	0.3923 (3)	0.0748 (12)
H1O	0.6764	0.2479	0.3762	0.090*
O2	0.7918 (4)	0.8588 (4)	0.3897 (4)	0.0863 (14)
H2O	0.7452	0.9091	0.3736	0.104*
N1	0.3651 (4)	0.3213 (4)	0.4017 (3)	0.0552 (10)
C1	0.7120 (6)	0.5784 (6)	0.4504 (5)	0.0739 (17)
H1	0.7557	0.5151	0.4668	0.089*
C2	0.7823 (6)	0.6731 (5)	0.4309 (5)	0.0739 (18)
H2	0.8718	0.6726	0.4334	0.089*
C3	0.7171 (6)	0.7673 (5)	0.4080 (4)	0.0680 (16)
C4	0.5853 (6)	0.7668 (5)	0.4011 (4)	0.0696 (16)
H4	0.5420	0.8296	0.3830	0.083*
C5	0.5173 (6)	0.6733 (5)	0.4210 (5)	0.0667 (16)
H5	0.4278	0.6747	0.4178	0.080*
C6	0.5784 (5)	0.5767 (5)	0.4459 (4)	0.0595 (13)
C7	0.5053 (7)	0.4747 (5)	0.4658 (4)	0.0666 (15)
H7A	0.4282	0.4936	0.4976	0.080*
H7B	0.5578	0.4271	0.5013	0.080*
C8	0.4670 (5)	0.4131 (4)	0.3849 (4)	0.0538 (12)
H8	0.4261	0.4670	0.3471	0.065*
C9	0.5867 (5)	0.3719 (5)	0.3389 (4)	0.0576 (13)
H9A	0.5603	0.3251	0.2919	0.069*
H9B	0.6322	0.4345	0.3149	0.069*
C10	0.4099 (6)	0.2377 (5)	0.4638 (4)	0.0606 (13)
H10A	0.3393	0.1905	0.4790	0.073*
H10B	0.4419	0.2738	0.5140	0.073*
H10C	0.4775	0.1947	0.4386	0.073*
C11	0.2426 (6)	0.3716 (6)	0.4391 (4)	0.0707 (16)
H11A	0.1774	0.3147	0.4435	0.085*
H11B	0.2611	0.3974	0.4964	0.085*
C12	0.1902 (7)	0.4635 (6)	0.3892 (5)	0.092 (2)	0.778 (18)
H12	0.1973	0.4594	0.3302	0.111*	0.778 (18)
C13	0.1339 (16)	0.5511 (10)	0.4216 (8)	0.132 (6)	0.778 (18)
H13A	0.1250	0.5581	0.4804	0.158*	0.778 (18)
H13B	0.1030	0.6060	0.3857	0.158*	0.778 (18)
C12'	0.1902 (7)	0.4635 (6)	0.3892 (5)	0.092 (2)	0.222 (18)
H12'	0.2394	0.5064	0.3525	0.111*	0.222 (18)
C13'	0.0657 (12)	0.479 (5)	0.402 (3)	0.132 (6)	0.222 (18)
H13C	0.0212	0.4331	0.4396	0.158*	0.222 (18)
H13D	0.0225	0.5346	0.3736	0.158*	0.222 (18)
C14	0.3330 (5)	0.2665 (5)	0.3165 (4)	0.0644 (14)
H14A	0.3090	0.3235	0.2762	0.077*
H14B	0.4106	0.2317	0.2950	0.077*
C15	0.2279 (6)	0.1823 (6)	0.3179 (5)	0.0728 (17)
C16	0.2603 (7)	0.0727 (7)	0.3287 (5)	0.086 (2)
H16	0.3459	0.0529	0.3372	0.103*
C17	0.1623 (10)	−0.0099 (9)	0.3266 (6)	0.111 (3)
H17	0.1820	−0.0839	0.3346	0.133*
C18	0.0386 (10)	0.0242 (12)	0.3125 (7)	0.121 (4)
H18	−0.0263	−0.0285	0.3114	0.145*
C19	0.0055 (9)	0.1317 (14)	0.3001 (7)	0.119 (4)
H19	−0.0799	0.1514	0.2902	0.143*
C20	0.1000 (6)	0.2092 (8)	0.3026 (5)	0.093 (2)
H20	0.0781	0.2826	0.2938	0.112*

	U11	U22	U33	U12	U13	U23
Br1	0.0760 (4)	0.0657 (4)	0.0881 (5)	0.0026 (3)	−0.0014 (4)	−0.0123 (3)
O1	0.066 (2)	0.060 (2)	0.098 (3)	0.004 (2)	−0.012 (2)	−0.007 (2)
O2	0.069 (3)	0.062 (2)	0.127 (4)	−0.015 (2)	0.000 (3)	0.015 (3)
N1	0.048 (2)	0.066 (3)	0.051 (2)	−0.006 (2)	0.003 (2)	0.0028 (19)
C1	0.068 (4)	0.060 (4)	0.093 (5)	0.006 (3)	−0.008 (3)	0.002 (4)
C2	0.061 (3)	0.055 (3)	0.105 (5)	0.001 (3)	−0.007 (3)	0.008 (3)
C3	0.066 (3)	0.057 (3)	0.081 (4)	−0.014 (3)	0.001 (3)	−0.001 (3)
C4	0.068 (3)	0.057 (3)	0.083 (4)	−0.001 (3)	−0.008 (3)	0.000 (3)
C5	0.061 (3)	0.059 (3)	0.081 (4)	−0.007 (3)	0.002 (3)	−0.004 (3)
C6	0.065 (3)	0.048 (3)	0.065 (3)	−0.005 (3)	0.002 (3)	−0.004 (3)
C7	0.076 (4)	0.059 (3)	0.065 (4)	−0.007 (3)	0.002 (3)	−0.002 (3)
C8	0.055 (3)	0.053 (3)	0.054 (3)	−0.009 (2)	0.001 (2)	0.007 (2)
C9	0.055 (3)	0.054 (3)	0.064 (3)	−0.002 (2)	0.003 (2)	0.001 (2)
C10	0.067 (3)	0.055 (3)	0.060 (3)	−0.012 (3)	−0.001 (3)	0.012 (2)
C11	0.060 (3)	0.087 (4)	0.065 (4)	0.011 (3)	0.009 (3)	−0.003 (3)
C12	0.063 (4)	0.115 (7)	0.099 (5)	0.019 (4)	0.010 (4)	0.011 (5)
C13	0.178 (14)	0.128 (11)	0.089 (7)	0.077 (12)	−0.012 (8)	−0.028 (7)
C12'	0.063 (4)	0.115 (7)	0.099 (5)	0.019 (4)	0.010 (4)	0.011 (5)
C13'	0.178 (14)	0.128 (11)	0.089 (7)	0.077 (12)	−0.012 (8)	−0.028 (7)
C14	0.057 (3)	0.086 (4)	0.050 (3)	−0.013 (3)	0.000 (3)	−0.004 (3)
C15	0.059 (3)	0.097 (5)	0.062 (3)	−0.020 (3)	0.007 (3)	−0.014 (4)
C16	0.071 (4)	0.100 (5)	0.086 (5)	−0.031 (4)	0.010 (3)	−0.024 (5)
C17	0.122 (8)	0.113 (7)	0.097 (6)	−0.055 (6)	0.026 (5)	−0.032 (5)
C18	0.093 (6)	0.193 (12)	0.076 (5)	−0.070 (7)	0.017 (5)	−0.032 (7)
C19	0.066 (5)	0.203 (11)	0.089 (7)	−0.037 (6)	−0.002 (4)	−0.040 (8)
C20	0.059 (3)	0.139 (7)	0.080 (5)	−0.018 (4)	−0.012 (3)	−0.003 (5)

O1—C9	1.425 (7)	C10—H10A	0.9600
O1—H1O	0.8200	C10—H10B	0.9600
O2—C3	1.385 (7)	C10—H10C	0.9600
O2—H2O	0.8200	C11—C12	1.468 (10)
N1—C10	1.482 (7)	C11—H11A	0.9700
N1—C11	1.527 (7)	C11—H11B	0.9700
N1—C14	1.531 (7)	C12—C13	1.317 (3)
N1—C8	1.560 (6)	C12—H12	0.9300
C1—C6	1.387 (9)	C13—H13A	0.9300
C1—C2	1.396 (10)	C13—H13B	0.9300
C1—H1	0.9300	C13'—H13C	0.9300
C2—C3	1.377 (9)	C13'—H13D	0.9300
C2—H2	0.9300	C14—C15	1.495 (8)
C3—C4	1.372 (9)	C14—H14A	0.9700
C4—C5	1.373 (9)	C14—H14B	0.9700
C4—H4	0.9300	C15—C16	1.384 (11)
C5—C6	1.391 (9)	C15—C20	1.388 (10)
C5—H5	0.9300	C16—C17	1.429 (10)
C6—C7	1.487 (8)	C16—H16	0.9300
C7—C8	1.525 (8)	C17—C18	1.367 (17)
C7—H7A	0.9700	C17—H17	0.9300
C7—H7B	0.9700	C18—C19	1.365 (17)
C8—C9	1.520 (8)	C18—H18	0.9300
C8—H8	0.9800	C19—C20	1.361 (13)
C9—H9A	0.9700	C19—H19	0.9300
C9—H9B	0.9700	C20—H20	0.9300
C9—O1—H1O	109.5	N1—C10—H10A	109.5
C3—O2—H2O	109.5	N1—C10—H10B	109.5
C10—N1—C11	106.5 (4)	H10A—C10—H10B	109.5
C10—N1—C14	110.1 (5)	N1—C10—H10C	109.5
C11—N1—C14	109.2 (4)	H10A—C10—H10C	109.5
C10—N1—C8	112.9 (4)	H10B—C10—H10C	109.5
C11—N1—C8	110.0 (4)	C12—C11—N1	114.1 (5)
C14—N1—C8	108.1 (4)	C12—C11—H11A	108.7
C6—C1—C2	121.5 (7)	N1—C11—H11A	108.7
C6—C1—H1	119.2	C12—C11—H11B	108.7
C2—C1—H1	119.2	N1—C11—H11B	108.7
C3—C2—C1	119.1 (6)	H11A—C11—H11B	107.6
C3—C2—H2	120.5	C13—C12—C11	125.0 (9)
C1—C2—H2	120.5	C13—C12—H12	117.5
C4—C3—C2	120.4 (6)	C11—C12—H12	117.5
C4—C3—O2	123.0 (6)	C12—C13—H13A	120.0
C2—C3—O2	116.5 (6)	C12—C13—H13B	120.0
C3—C4—C5	119.8 (6)	H13A—C13—H13B	120.0
C3—C4—H4	120.1	H13C—C13'—H13D	120.0
C5—C4—H4	120.1	C15—C14—N1	116.3 (5)
C4—C5—C6	121.9 (6)	C15—C14—H14A	108.2
C4—C5—H5	119.0	N1—C14—H14A	108.2
C6—C5—H5	119.0	C15—C14—H14B	108.2
C1—C6—C5	117.1 (6)	N1—C14—H14B	108.2
C1—C6—C7	120.8 (6)	H14A—C14—H14B	107.4
C5—C6—C7	122.1 (5)	C16—C15—C20	118.7 (7)
C6—C7—C8	111.6 (5)	C16—C15—C14	118.9 (6)
C6—C7—H7A	109.3	C20—C15—C14	122.2 (7)
C8—C7—H7A	109.3	C15—C16—C17	120.1 (8)
C6—C7—H7B	109.3	C15—C16—H16	120.0
C8—C7—H7B	109.3	C17—C16—H16	120.0
H7A—C7—H7B	108.0	C18—C17—C16	117.2 (10)
C9—C8—C7	110.1 (5)	C18—C17—H17	121.4
C9—C8—N1	113.5 (4)	C16—C17—H17	121.4
C7—C8—N1	112.8 (4)	C19—C18—C17	123.4 (9)
C9—C8—H8	106.7	C19—C18—H18	118.3
C7—C8—H8	106.7	C17—C18—H18	118.3
N1—C8—H8	106.7	C20—C19—C18	118.5 (10)
O1—C9—C8	113.6 (5)	C20—C19—H19	120.7
O1—C9—H9A	108.8	C18—C19—H19	120.7
C8—C9—H9A	108.8	C19—C20—C15	122.0 (10)
O1—C9—H9B	108.8	C19—C20—H20	119.0
C8—C9—H9B	108.8	C15—C20—H20	119.0
H9A—C9—H9B	107.7
C6—C1—C2—C3	1.0 (12)	C7—C8—C9—O1	51.2 (6)
C1—C2—C3—C4	−2.6 (12)	N1—C8—C9—O1	−76.3 (6)
C1—C2—C3—O2	179.8 (7)	C10—N1—C11—C12	175.1 (6)
C2—C3—C4—C5	3.1 (12)	C14—N1—C11—C12	−66.1 (7)
O2—C3—C4—C5	−179.5 (6)	C8—N1—C11—C12	52.5 (7)
C3—C4—C5—C6	−2.0 (11)	N1—C11—C12—C13	−144.3 (12)
C2—C1—C6—C5	0.1 (11)	C10—N1—C14—C15	61.4 (6)
C2—C1—C6—C7	179.2 (6)	C11—N1—C14—C15	−55.1 (7)
C4—C5—C6—C1	0.4 (10)	C8—N1—C14—C15	−174.8 (5)
C4—C5—C6—C7	−178.7 (6)	N1—C14—C15—C16	−93.4 (8)
C1—C6—C7—C8	−98.8 (8)	N1—C14—C15—C20	91.5 (9)
C5—C6—C7—C8	80.4 (8)	C20—C15—C16—C17	−2.0 (12)
C6—C7—C8—C9	65.0 (6)	C14—C15—C16—C17	−177.3 (7)
C6—C7—C8—N1	−167.1 (5)	C15—C16—C17—C18	1.0 (13)
C10—N1—C8—C9	67.4 (6)	C16—C17—C18—C19	0.4 (17)
C11—N1—C8—C9	−173.9 (4)	C17—C18—C19—C20	−0.6 (18)
C14—N1—C8—C9	−54.6 (6)	C18—C19—C20—C15	−0.5 (16)
C10—N1—C8—C7	−58.7 (6)	C16—C15—C20—C19	1.7 (14)
C11—N1—C8—C7	60.0 (6)	C14—C15—C20—C19	176.9 (8)
C14—N1—C8—C7	179.3 (5)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···Br1	0.82	2.43	3.231 (4)	167
O2—H2O···Br1i	0.82	2.38	3.192 (5)	171

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯Br1	0.82	2.43	3.231 (4)	167
O2—H2O⋯Br1i	0.82	2.38	3.192 (5)	171

Symmetry code: (i) .