Absolute configuration of (+)-(S)-2-(5-fluoro-2-methoxy-1,4-benzodioxan-2-yl)­imidazolinium bromide

The title compound, C₁₂H₁₄FN₂O₃⁺·Br⁻, crystallizes in the non-centrosymmetric P2₁2₁2₁ space group. The absolute configuration of the pharmacologically active mol­ecule could be resolved in the hydro­bromide salt, the structure of which is reported. The mol­ecule of the title compound has the S configuration. The molecular packing in the crystal is stabilized by weak N—H...Br [N...Br = 3.240 (4) and 3.302 (4) Å] hydrogen bonding.

Computing details

Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: local program; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP (Farrugia, 1997).

(f14413)

Crystal data

C12H14FN2O3^+·Br^−	Dx = 1.607 Mg m^−3
Mr = 333.16	Mo Kα radiation, λ = 0.71069 Å
Orthorhombic, P212121	Cell parameters from 25 reflections
a = 8.220 (3) Å	θ = 6.1–17.6°
b = 9.365 (3) Å	µ = 3.00 mm^−1
c = 17.890 (3) Å	T = 293 K
V = 1377.2 (7) Å^3	Needle, colourless
Z = 4	0.7 × 0.15 × 0.15 mm
F(000) = 672

Data collection

Nonius CAD 4 diffractometer	Rint = 0.024
Radiation source: fine-focus sealed tube	θmax = 26.0°, θmin = 2.3°
Graphite monochromator	h = −10→10
ω–θ scans	k = −11→11
3134 measured reflections	l = −22→22
2689 independent reflections	3 standard reflections every 100 reflections
1869 reflections with I > 2σ(I)	intensity decay: <1%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.096	Calculated w = 1/[σ^2(Fo^2) + (0.0477P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.97	(Δ/σ)max < 0.001
2689 reflections	Δρmax = 0.64 e Å^−3
178 parameters	Δρmin = −0.58 e Å^−3
0 restraints	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.007 (15)

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
Br	1.22657 (5)	0.81042 (6)	−0.15534 (3)	0.05013 (17)
N1	0.5947 (4)	0.6879 (5)	−0.1645 (3)	0.0509 (11)
N2	0.8545 (4)	0.6788 (5)	−0.1456 (3)	0.0509 (11)
C9	0.7186 (6)	0.7471 (5)	−0.1327 (2)	0.0379 (10)
O1	0.5874 (5)	0.9866 (4)	0.02402 (19)	0.0527 (10)
C7	0.5868 (6)	0.8658 (5)	−0.0232 (3)	0.0442 (13)
H7A	0.4785	0.8526	−0.0436	0.053*
H7B	0.6138	0.7816	0.0058	0.053*
C6	0.7353 (7)	1.0451 (5)	0.0358 (2)	0.0488 (13)
C10	0.6416 (6)	0.5599 (6)	−0.2064 (3)	0.0515 (15)
H10A	0.6120	0.5679	−0.2588	0.062*
H10B	0.5922	0.4748	−0.1856	0.062*
O2	0.8661 (4)	0.9007 (3)	−0.05711 (19)	0.0448 (9)
O3	0.6586 (4)	0.9970 (4)	−0.12964 (17)	0.0450 (8)
F	0.6196 (6)	1.1926 (5)	0.1267 (2)	0.0975 (13)
C8	0.7072 (5)	0.8814 (5)	−0.0866 (2)	0.0360 (10)
C1	0.7539 (9)	1.1549 (6)	0.0880 (3)	0.0716 (18)
C12	0.7661 (8)	1.0357 (6)	−0.1898 (3)	0.0714 (18)
H12A	0.8769	1.0219	−0.1743	0.107*
H12B	0.7494	1.1341	−0.2026	0.107*
H12C	0.7438	0.9769	−0.2325	0.107*
C5	0.8745 (7)	1.0061 (6)	−0.0034 (3)	0.0439 (13)
C4	1.0218 (8)	1.0721 (6)	0.0076 (3)	0.0618 (16)
H4	1.1131	1.0442	−0.0194	0.074*
C3	1.0316 (9)	1.1799 (8)	0.0593 (4)	0.081 (2)
H3	1.1312	1.2243	0.0678	0.098*
C11	0.8275 (6)	0.5590 (7)	−0.1961 (4)	0.070 (2)
H11A	0.8642	0.4700	−0.1741	0.084*
H11B	0.8831	0.5734	−0.2434	0.084*
C2	0.8975 (11)	1.2235 (7)	0.0987 (4)	0.085 (2)
H2	0.9048	1.2989	0.1324	0.102*
HN1	0.505 (6)	0.712 (5)	−0.159 (3)	0.050*
HN2	0.950 (6)	0.710 (5)	−0.126 (3)	0.050*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br	0.0248 (2)	0.0728 (3)	0.0528 (3)	0.0026 (2)	0.0020 (2)	0.0062 (3)
N1	0.0221 (18)	0.059 (3)	0.071 (3)	0.003 (2)	−0.004 (2)	−0.020 (3)
N2	0.029 (2)	0.054 (3)	0.070 (3)	0.003 (2)	−0.004 (2)	−0.020 (3)
C9	0.027 (2)	0.045 (2)	0.042 (2)	0.004 (2)	0.000 (2)	0.002 (2)
O1	0.054 (2)	0.055 (2)	0.049 (2)	−0.0012 (19)	0.0146 (17)	−0.0092 (19)
C7	0.039 (3)	0.051 (3)	0.043 (3)	0.000 (2)	0.007 (2)	0.002 (2)
C6	0.067 (4)	0.042 (3)	0.038 (2)	−0.004 (3)	0.001 (3)	0.000 (2)
C10	0.036 (3)	0.060 (4)	0.059 (4)	−0.004 (3)	−0.003 (2)	−0.009 (3)
O2	0.0317 (18)	0.047 (2)	0.056 (2)	−0.0008 (15)	−0.0046 (15)	−0.0077 (19)
O3	0.0368 (17)	0.051 (2)	0.0471 (19)	0.0068 (16)	0.0068 (15)	0.0095 (16)
F	0.132 (3)	0.091 (3)	0.070 (2)	−0.001 (3)	0.033 (2)	−0.029 (3)
C8	0.026 (2)	0.043 (3)	0.040 (2)	0.006 (2)	−0.002 (2)	0.004 (2)
C1	0.114 (6)	0.059 (4)	0.042 (3)	−0.009 (4)	0.008 (4)	−0.006 (2)
C12	0.072 (4)	0.089 (4)	0.054 (3)	0.004 (4)	0.019 (3)	0.027 (3)
C5	0.052 (3)	0.037 (3)	0.043 (3)	−0.009 (2)	−0.003 (2)	0.004 (2)
C4	0.065 (4)	0.062 (4)	0.058 (4)	−0.028 (3)	−0.013 (3)	0.006 (3)
C3	0.107 (6)	0.073 (5)	0.064 (4)	−0.045 (5)	−0.018 (4)	−0.002 (4)
C11	0.041 (3)	0.080 (5)	0.088 (4)	0.015 (3)	−0.006 (3)	−0.045 (4)
C2	0.132 (7)	0.070 (5)	0.053 (4)	−0.034 (5)	−0.002 (4)	−0.016 (3)

Geometric parameters (Å, º)

Br—HN1^i	2.47 (5)	C10—H10A	0.9700
Br—HN2	2.52 (5)	C10—H10B	0.9700
Br—N1^i	3.240 (4)	O2—C5	1.379 (6)
Br—N2	3.302 (4)	O2—C8	1.420 (5)
N1—C9	1.292 (6)	O3—C8	1.387 (5)
N1—C10	1.465 (7)	O3—C12	1.438 (6)
N1—HN1	0.78 (5)	F—C1	1.350 (7)
N2—C9	1.308 (6)	C1—C2	1.358 (9)
N2—C11	1.458 (7)	C12—H12A	0.9600
N2—HN2	0.91 (5)	C12—H12B	0.9600
C9—C8	1.506 (6)	C12—H12C	0.9600
O1—C6	1.350 (7)	C5—C4	1.373 (8)
O1—C7	1.412 (6)	C4—C3	1.371 (8)
C7—C8	1.513 (6)	C4—H4	0.9300
C7—H7A	0.9700	C3—C2	1.371 (10)
C7—H7B	0.9700	C3—H3	0.9300
C6—C5	1.391 (8)	C11—H11A	0.9700
C6—C1	1.397 (7)	C11—H11B	0.9700
C10—C11	1.539 (7)	C2—H2	0.9300
HN1^i—Br—HN2	134.8 (16)	C8—O3—C12	115.8 (4)
HN1^i—Br—N1^i	1.9 (12)	O3—C8—O2	111.8 (4)
HN2—Br—N1^i	136.2 (11)	O3—C8—C9	111.4 (3)
HN1^i—Br—N2	136.2 (12)	O2—C8—C9	104.6 (4)
HN2—Br—N2	9.1 (11)	O3—C8—C7	107.7 (4)
N1^i—Br—N2	137.33 (11)	O2—C8—C7	109.6 (4)
C9—N1—C10	111.7 (4)	C9—C8—C7	111.7 (4)
C9—N1—HN1	124 (4)	F—C1—C2	121.0 (5)
C10—N1—HN1	124 (4)	F—C1—C6	116.5 (6)
C9—N2—C11	110.9 (4)	C2—C1—C6	122.5 (6)
C9—N2—Br	128.1 (3)	O3—C12—H12A	109.5
C11—N2—Br	113.3 (3)	O3—C12—H12B	109.5
C9—N2—HN2	121 (3)	H12A—C12—H12B	109.5
C11—N2—HN2	128 (3)	O3—C12—H12C	109.5
Br—N2—HN2	26 (3)	H12A—C12—H12C	109.5
N1—C9—N2	112.6 (4)	H12B—C12—H12C	109.5
N1—C9—C8	123.4 (4)	C4—C5—O2	117.8 (5)
N2—C9—C8	123.9 (4)	C4—C5—C6	122.3 (5)
C6—O1—C7	114.9 (4)	O2—C5—C6	119.8 (5)
O1—C7—C8	111.6 (4)	C3—C4—C5	118.7 (6)
O1—C7—H7A	109.3	C3—C4—H4	120.6
C8—C7—H7A	109.3	C5—C4—H4	120.6
O1—C7—H7B	109.3	C2—C3—C4	121.2 (6)
C8—C7—H7B	109.3	C2—C3—H3	119.4
H7A—C7—H7B	108.0	C4—C3—H3	119.4
O1—C6—C5	123.8 (4)	N2—C11—C10	102.7 (4)
O1—C6—C1	120.1 (5)	N2—C11—H11A	111.2
C5—C6—C1	116.1 (6)	C10—C11—H11A	111.2
N1—C10—C11	101.8 (4)	N2—C11—H11B	111.2
N1—C10—H10A	111.4	C10—C11—H11B	111.2
C11—C10—H10A	111.4	H11A—C11—H11B	109.1
N1—C10—H10B	111.4	C1—C2—C3	119.1 (6)
C11—C10—H10B	111.4	C1—C2—H2	120.5
H10A—C10—H10B	109.3	C3—C2—H2	120.5
C5—O2—C8	113.3 (4)

Symmetry code: (i) x+1, y, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—HN1···Br^ii	0.77 (5)	2.47 (5)	3.240 (4)	172 (5)
N2—HN2···Br	0.91 (5)	2.52 (5)	3.302 (4)	145 (4)

Symmetry code: (ii) x−1, y, z.