2-(2,4-Dichloro-5-fluoro­phen­yl)-4-(2-hydroxy­ethyl)morpholin-4-ium chloride

The title compound, C₁₂H₁₅Cl₂FNO₂⁺·Cl⁻, has been synthesized from 2-(2,4-dichloro-5-fluoro­phen­yl)-4-(2-hydroxy­ethyl)morpholin-2-ol via reduction by formic acid and acidification by hydrogen chloride. The morpholine unit adopts an almost ideal chair conformation. The crystal structure is consolidated by N—H...Cl and O—H...Cl inter­molecular hydrogen bonding.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C)= 0.003 Å
• R factor = 0.035
• wR factor = 0.091
• Data-to-parameter ratio = 17.7

checkCIF/PLATON results

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Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2003); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

2-(2,4-dichloro-5-fluorophenyl)-4-(2-hydroxyethyl)morpholin-4-ium chloride

Crystal data

C12H15Cl2FNO2^+·Cl^−	F(000) = 680
Mr = 330.60	Dx = 1.557 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4650 reflections
a = 14.1063 (8) Å	θ = 2.9–26.9°
b = 7.2927 (4) Å	µ = 0.66 mm^−1
c = 13.8748 (8) Å	T = 294 K
β = 98.834 (1)°	Block, colorless
V = 1410.41 (14) Å^3	0.48 × 0.45 × 0.40 mm
Z = 4

Data collection

Bruker SMART 1000 CCD diffractometer	3064 independent reflections
Radiation source: fine-focus sealed tube	2288 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
ω scans	θmax = 27.1°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −16→17
Tmin = 0.735, Tmax = 0.771	k = −9→9
11388 measured reflections	l = −17→17

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.091	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0365P)^2 + 0.6923P] where P = (Fo^2 + 2Fc^2)/3
3064 reflections	(Δ/σ)max = 0.001
173 parameters	Δρmax = 0.30 e Å^−3
0 restraints	Δρmin = −0.35 e Å^−3

Special details

Experimental. Spectroscopic analysis: ¹H-NMR (CD₃SOCD₃, 400 MHz) (p.p.m.): 3.17–3.26 (m, 4H, morpholine ring 5-H, NCH₂), 3.42–3.64 (m, 2H, morpholine ring 3-H), 3.79–4.01 (m, 4H, CH₂O, morpholine ring 6-H), 5.35 (dd, J= 9.8 Hz, J= 3.8 Hz, 1H, morpholine ring 2-H), 6.73(s, 1H, OH), 7.59 (d, J= 10 Hz, 1H, benzene ring 6-H), 7.89 (d, J= 6.8 Hz, 1H, benzene ring 3-H), 10.64(br s, 1H, N⁺H). M.p. 462–464 K. The crystals suitable for X-ray structure determination were obtained by slow evaporation of an ethanol solution at room temperature.

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
C1	0.80231 (13)	0.8701 (3)	0.58018 (14)	0.0351 (4)
H1	0.7747	0.9207	0.5166	0.042*
C2	0.74569 (14)	0.7015 (3)	0.60124 (14)	0.0345 (4)
H2A	0.7472	0.6117	0.5499	0.041*
H2B	0.7751	0.6469	0.6623	0.041*
C3	0.64082 (14)	0.9030 (3)	0.67910 (13)	0.0363 (4)
H3A	0.6646	0.8594	0.7444	0.044*
H3B	0.5752	0.9437	0.6776	0.044*
C4	0.70137 (14)	1.0603 (3)	0.65452 (15)	0.0413 (5)
H4A	0.6748	1.1087	0.5910	0.050*
H4B	0.7000	1.1572	0.7021	0.050*
C5	0.58902 (14)	0.5839 (3)	0.63134 (14)	0.0383 (5)
H5A	0.6202	0.5328	0.6927	0.046*
H5B	0.5913	0.4921	0.5811	0.046*
C6	0.48533 (15)	0.6240 (3)	0.63917 (15)	0.0428 (5)
H6A	0.4530	0.5104	0.6506	0.051*
H6B	0.4826	0.7041	0.6945	0.051*
C7	0.90687 (14)	0.8267 (3)	0.57974 (14)	0.0362 (4)
C8	0.94133 (14)	0.7640 (3)	0.49689 (15)	0.0380 (5)
C9	1.03812 (15)	0.7322 (3)	0.49693 (16)	0.0430 (5)
H9	1.0596	0.6915	0.4406	0.052*
C10	1.10220 (14)	0.7610 (3)	0.58061 (17)	0.0424 (5)
C11	1.06879 (15)	0.8221 (3)	0.66266 (15)	0.0430 (5)
C12	0.97307 (15)	0.8548 (3)	0.66340 (15)	0.0425 (5)
H12	0.9525	0.8960	0.7201	0.051*
Cl1	0.86278 (4)	0.72887 (9)	0.38958 (4)	0.05085 (17)
Cl2	1.22350 (4)	0.72822 (9)	0.58072 (5)	0.05733 (18)
Cl3	0.59218 (4)	0.88210 (8)	0.39437 (3)	0.04703 (16)
F1	1.13133 (9)	0.8565 (2)	0.74429 (10)	0.0613 (4)
N1	0.64350 (11)	0.7502 (2)	0.60754 (10)	0.0300 (3)
H1A	0.6159	0.7915	0.5479	0.036*
O1	0.79812 (10)	1.0050 (2)	0.65362 (10)	0.0424 (4)
O2	0.43736 (11)	0.7079 (2)	0.55396 (11)	0.0493 (4)
H2	0.4319	0.8180	0.5636	0.074*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0325 (10)	0.0405 (11)	0.0323 (9)	0.0035 (9)	0.0050 (8)	−0.0002 (8)
C2	0.0334 (10)	0.0388 (11)	0.0318 (9)	0.0060 (8)	0.0062 (8)	−0.0004 (8)
C3	0.0332 (10)	0.0449 (12)	0.0308 (9)	0.0038 (9)	0.0046 (8)	−0.0088 (8)
C4	0.0371 (11)	0.0402 (12)	0.0457 (11)	0.0044 (9)	0.0031 (9)	−0.0095 (9)
C5	0.0418 (11)	0.0376 (11)	0.0350 (10)	−0.0039 (9)	0.0045 (8)	0.0022 (9)
C6	0.0408 (12)	0.0485 (13)	0.0398 (11)	−0.0100 (10)	0.0091 (9)	0.0006 (9)
C7	0.0335 (11)	0.0387 (11)	0.0367 (10)	0.0011 (8)	0.0063 (8)	0.0057 (8)
C8	0.0355 (11)	0.0398 (12)	0.0390 (10)	−0.0019 (9)	0.0067 (8)	0.0024 (9)
C9	0.0400 (12)	0.0432 (12)	0.0490 (12)	0.0007 (10)	0.0171 (10)	0.0015 (10)
C10	0.0298 (10)	0.0399 (12)	0.0580 (13)	0.0011 (9)	0.0085 (9)	0.0137 (10)
C11	0.0355 (11)	0.0475 (13)	0.0436 (11)	−0.0003 (9)	−0.0014 (9)	0.0114 (10)
C12	0.0390 (12)	0.0528 (14)	0.0357 (10)	0.0036 (10)	0.0058 (9)	0.0060 (9)
Cl1	0.0464 (3)	0.0653 (4)	0.0403 (3)	−0.0030 (3)	0.0049 (2)	−0.0074 (3)
Cl2	0.0309 (3)	0.0645 (4)	0.0780 (4)	0.0021 (3)	0.0128 (3)	0.0158 (3)
Cl3	0.0558 (3)	0.0527 (3)	0.0302 (2)	0.0041 (3)	−0.0011 (2)	0.0015 (2)
F1	0.0425 (7)	0.0822 (10)	0.0538 (8)	0.0026 (7)	−0.0095 (6)	0.0088 (7)
N1	0.0294 (8)	0.0358 (9)	0.0243 (7)	0.0025 (7)	0.0028 (6)	−0.0004 (6)
O1	0.0318 (7)	0.0442 (9)	0.0506 (8)	−0.0007 (6)	0.0041 (6)	−0.0107 (7)
O2	0.0447 (9)	0.0566 (10)	0.0437 (8)	0.0010 (8)	−0.0023 (7)	−0.0045 (7)

Geometric parameters (Å, º)

C1—O1	1.424 (2)	C5—H5B	0.9700
C1—C7	1.509 (3)	C6—O2	1.409 (2)
C1—C2	1.519 (3)	C6—H6A	0.9700
C1—H1	0.9800	C6—H6B	0.9700
C2—N1	1.500 (2)	C7—C12	1.389 (3)
C2—H2A	0.9700	C7—C8	1.392 (3)
C2—H2B	0.9700	C8—C9	1.385 (3)
C3—N1	1.496 (2)	C8—Cl1	1.733 (2)
C3—C4	1.501 (3)	C9—C10	1.374 (3)
C3—H3A	0.9700	C9—H9	0.9300
C3—H3B	0.9700	C10—C11	1.372 (3)
C4—O1	1.425 (2)	C10—Cl2	1.728 (2)
C4—H4A	0.9700	C11—F1	1.348 (2)
C4—H4B	0.9700	C11—C12	1.373 (3)
C5—N1	1.500 (2)	C12—H12	0.9300
C5—C6	1.512 (3)	N1—H1A	0.9100
C5—H5A	0.9700	O2—H2	0.8200
O1—C1—C7	107.19 (15)	O2—C6—H6A	109.3
O1—C1—C2	109.92 (15)	C5—C6—H6A	109.3
C7—C1—C2	111.97 (16)	O2—C6—H6B	109.3
O1—C1—H1	109.2	C5—C6—H6B	109.3
C7—C1—H1	109.2	H6A—C6—H6B	107.9
C2—C1—H1	109.2	C12—C7—C8	117.61 (18)
N1—C2—C1	110.95 (16)	C12—C7—C1	119.86 (18)
N1—C2—H2A	109.4	C8—C7—C1	122.51 (17)
C1—C2—H2A	109.4	C9—C8—C7	121.59 (19)
N1—C2—H2B	109.4	C9—C8—Cl1	118.42 (16)
C1—C2—H2B	109.4	C7—C8—Cl1	119.98 (15)
H2A—C2—H2B	108.0	C10—C9—C8	119.70 (19)
N1—C3—C4	110.19 (15)	C10—C9—H9	120.2
N1—C3—H3A	109.6	C8—C9—H9	120.2
C4—C3—H3A	109.6	C11—C10—C9	119.07 (19)
N1—C3—H3B	109.6	C11—C10—Cl2	120.72 (17)
C4—C3—H3B	109.6	C9—C10—Cl2	120.17 (17)
H3A—C3—H3B	108.1	F1—C11—C10	119.59 (19)
O1—C4—C3	111.41 (17)	F1—C11—C12	118.6 (2)
O1—C4—H4A	109.3	C10—C11—C12	121.76 (19)
C3—C4—H4A	109.3	C11—C12—C7	120.3 (2)
O1—C4—H4B	109.3	C11—C12—H12	119.9
C3—C4—H4B	109.3	C7—C12—H12	119.9
H4A—C4—H4B	108.0	C3—N1—C5	112.96 (14)
N1—C5—C6	113.15 (17)	C3—N1—C2	109.72 (14)
N1—C5—H5A	108.9	C5—N1—C2	110.51 (15)
C6—C5—H5A	108.9	C3—N1—H1A	107.8
N1—C5—H5B	108.9	C5—N1—H1A	107.8
C6—C5—H5B	108.9	C2—N1—H1A	107.8
H5A—C5—H5B	107.8	C1—O1—C4	110.30 (14)
O2—C6—C5	111.66 (16)	C6—O2—H2	109.5
O1—C1—C2—N1	57.40 (19)	Cl2—C10—C11—F1	−0.1 (3)
C7—C1—C2—N1	176.42 (15)	C9—C10—C11—C12	0.1 (3)
N1—C3—C4—O1	−57.9 (2)	Cl2—C10—C11—C12	177.86 (18)
N1—C5—C6—O2	55.4 (2)	F1—C11—C12—C7	177.92 (19)
O1—C1—C7—C12	25.0 (3)	C10—C11—C12—C7	−0.1 (3)
C2—C1—C7—C12	−95.6 (2)	C8—C7—C12—C11	0.4 (3)
O1—C1—C7—C8	−152.87 (19)	C1—C7—C12—C11	−177.64 (19)
C2—C1—C7—C8	86.5 (2)	C4—C3—N1—C5	176.60 (15)
C12—C7—C8—C9	−0.7 (3)	C4—C3—N1—C2	52.8 (2)
C1—C7—C8—C9	177.28 (19)	C6—C5—N1—C3	56.4 (2)
C12—C7—C8—Cl1	−179.16 (16)	C6—C5—N1—C2	179.75 (15)
C1—C7—C8—Cl1	−1.2 (3)	C1—C2—N1—C3	−53.09 (19)
C7—C8—C9—C10	0.7 (3)	C1—C2—N1—C5	−178.29 (15)
Cl1—C8—C9—C10	179.21 (16)	C7—C1—O1—C4	176.77 (16)
C8—C9—C10—C11	−0.4 (3)	C2—C1—O1—C4	−61.3 (2)
C8—C9—C10—Cl2	−178.16 (17)	C3—C4—O1—C1	62.4 (2)
C9—C10—C11—F1	−177.89 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl3	0.91	2.21	3.0886 (15)	163
O2—H2···Cl3^i	0.82	2.30	3.1178 (18)	173

Symmetry code: (i) −x+1, −y+2, −z+1.