N-[2-(2-Chloro­phen­yl)-2-hydroxy­ethyl]propan-2-aminium hemioxalate

Tang, Z.; Xu, M.; Zhang, H.-C.; Feng, H.

doi:10.1107/S1600536809022740

organic compounds

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ISSN: 2056-9890

Volume 65| Part 7| July 2009| Page o1670

doi:10.1107/S1600536809022740

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N-[2-(2-Chlorophenyl)-2-hydroxyethyl]propan-2-aminium hemioxalate

Zhan Tang,^a Min Xu,^a Hui-Cheng Zhang ^b and Hai Feng ^a ^*

^aCollege of Pharmaceutical Sciences, Zhejiang University of Technology, Hangzhou 310014, People's Republic of China, and ^bOphthalmology department, Hangzhou First People's Hospital, Hangzhou 310014, People's Republic of China
^*Correspondence e-mail: fenghai289289@163.com

(Received 27 May 2009; accepted 13 June 2009; online 24 June 2009)

The asymmetric unit of the title compound, C₁₁H₁₇ClNO⁺·0.5C₂O₄²⁻, consists of one N-[2-(2-chlorophenyl)-2-hydroxyethyl]propan-2-ammonium cation and one-half of a centrosymmetric oxalate anion. In the cation, the C/C/N plane of the ethylammonium group is almost perpendicular to the benzene ring, with a dihedral angle of 88.72 (17)°. In the crystal structure, the two components are connected by O—H⋯O and N—H⋯O hydrogen bonds, forming a supramolecular tape along the a axis. Between the tapes, a C—H⋯O interaction is observed.

Related literature

For related structures, see: Czugler et al. (2007 ); Marsau et al. (1979 ); Martin & Pinkerton (1998 ); Tang et al. (2009 ).

Experimental

Crystal data

C₁₁H₁₇ClNO⁺·0.5C₂O₄²⁻
M_r = 258.72
Monoclinic, P 2₁ /n
a = 6.9951 (3) Å
b = 17.8821 (8) Å
c = 11.2236 (6) Å
β = 110.8377 (13)°
V = 1312.10 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 296 K
0.53 × 0.24 × 0.22 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.836, T_max = 0.939
12562 measured reflections
2978 independent reflections
1974 reflections with F² > 2σ(F²)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.089
S = 1.00
2978 reflections
156 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H201⋯O3ⁱ	0.82	1.89	2.707 (2)	175
N1—H301⋯O2ⁱ	0.86	1.96	2.816 (2)	179
N1—H302⋯O3	0.86	2.34	3.070 (2)	143
N1—H302⋯O2ⁱⁱ	0.86	2.09	2.807 (2)	141
C6—H6⋯O1ⁱⁱⁱ	0.93	2.56	3.433 (3)	156
Symmetry codes: (i) x-1, y, z; (ii) -x+1, -y+1, -z+1; (iii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: PROCESS-AUTO (Rigaku/MSC, 2004 ); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2004).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809022740/is2425sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809022740/is2425Isup2.hkl

checkCIF report

Comment top

Many crystalline compounds of oxalic acid has been studied previously (Marsau et al., 1979; Martin & Pinkerton, 1998; Czugler et al., 2007). To test the capability of oxalic acid we have synthesized the title compound, (I), containing oxalic acid and clorprenaline (Tang et al., 2009) which is one of a series of structurally related β-adrenoceptorblocking drugs.

Association of one clorprenaline and half of oxalic acid acid molecule leads to the title compound (Fig. 1). Compared with previous studies, in (I), there are no unusual bond distances or angles. In the molecule of clorprenaline the Cl atom and the phenyl plane is almost planar with the deviation of 0.0115 Å.The dihedral angle between the plane formed by C1/C2/C8 and the benzene plane is 88.4°, which shows that the two planes are almost perpendicular.

O—H···O and N—H···O hydrogen bonds are found in the cystal structure and are essential forces in crystal formation.

Related literature top

For related structures, see: Czugler et al. (2007); Marsau et al. (1979); Martin & Pinkerton (1998); Tang et al. (2009).

Experimental top

Racemic clorprenaline was prepared by clorprenaline hydrochloride purchased from ShangHai Shengxin Medicine & Chemical Co., Ltd. ShangHai, China. Clorprenaline hydrochloride and NaOH in a molar ratio of 1:1 were mixed and dissolved in a methanol-water solution (1:1 v/v). The precipitate formed was filtered off, washed with water and dried. It was used without further purification. Racemic Clorprenaline (0.5 g, 0.0023 mol) was dissolved in ethanol (20 ml) and oxalic acid (0.21, 0.0023 mol) was dissolved in water (10 ml). The mixture was dissovled by heating to 353 K where a clear solution resulted. The resulting solution was concentrated and colorless block-shaped crystals of (I) were obtained within two weeks at room temperature.

Computing details top

Data collection: PROCESS-AUTO (Rigaku/MSC, 2004); cell refinement: PROCESS-AUTO (Rigaku/MSC, 2004); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2004).

Figures top

Fig. 1. The molecular structure of the title compound with atom labels, showing 40% probability displacement ellipsoids. The dashed line shows an N—H···O hydrogen bond.

Bis{N-[2-(2-chlorophenyl)-2-hydroxyethyl]propan-2-aminium} oxalate top

Crystal data top

C₁₁H₁₇ClNO⁺·0.5C₂O₄²⁻	F(000) = 548.00
M_r = 258.72	D_x = 1.310 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: -P 2yn	Cell parameters from 8056 reflections
a = 6.9951 (3) Å	θ = 3.0–27.4°
b = 17.8821 (8) Å	µ = 0.29 mm⁻¹
c = 11.2236 (6) Å	T = 296 K
β = 110.8377 (13)°	Chunk, colorless
V = 1312.10 (11) Å³	0.53 × 0.24 × 0.22 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID diffractometer	1974 reflections with F² > 2σ(F²)
Detector resolution: 10.00 pixels mm^-1	R_int = 0.032
ω scans	θ_max = 27.4°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −8→9
T_min = 0.836, T_max = 0.939	k = −23→23
12562 measured reflections	l = −14→14
2978 independent reflections

Refinement top

Refinement on F²	w = 1/[σ²(F_o²) + (0.01P)² + P] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.036	(Δ/σ)_max < 0.001
wR(F²) = 0.089	Δρ_max = 0.26 e Å⁻³
S = 1.00	Δρ_min = −0.28 e Å⁻³
2978 reflections	Extinction correction: SHELXL97 (Sheldrick, 2008)
156 parameters	Extinction coefficient: 0.0233 (11)
H-atom parameters constrained

Crystal data top

C₁₁H₁₇ClNO⁺·0.5C₂O₄²⁻	V = 1312.10 (11) Å³
M_r = 258.72	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.9951 (3) Å	µ = 0.29 mm⁻¹
b = 17.8821 (8) Å	T = 296 K
c = 11.2236 (6) Å	0.53 × 0.24 × 0.22 mm
β = 110.8377 (13)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	2978 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1974 reflections with F² > 2σ(F²)
T_min = 0.836, T_max = 0.939	R_int = 0.032
12562 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	156 parameters
wR(F²) = 0.089	H-atom parameters constrained
S = 1.00	Δρ_max = 0.26 e Å⁻³
2978 reflections	Δρ_min = −0.28 e Å⁻³

Special details top

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 using reflections with F² > 2.0 σ(F²). The weighted R-factor(wR), goodness of fit (S) and R-factor (gt) are based on F, with F set to zero for negative F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.23746 (9)	0.45230 (3)	0.93857 (6)	0.0615 (2)
O1	−0.11289 (19)	0.65111 (8)	0.75048 (13)	0.0482 (3)
O2	0.7592 (2)	0.51348 (8)	0.52819 (14)	0.0533 (4)
O3	0.5489 (2)	0.57840 (8)	0.59837 (14)	0.0545 (4)
N1	0.1107 (2)	0.60395 (9)	0.59068 (14)	0.0407 (3)
C1	0.0439 (2)	0.59654 (11)	0.79473 (18)	0.0388 (4)
C2	0.1458 (2)	0.60032 (11)	0.93762 (18)	0.0396 (4)
C3	0.2344 (2)	0.53840 (12)	1.0113 (2)	0.0444 (4)
C4	0.3216 (3)	0.54182 (14)	1.1422 (2)	0.0586 (6)
C5	0.3270 (3)	0.60876 (17)	1.2028 (2)	0.0660 (6)
C6	0.2451 (3)	0.67209 (14)	1.1332 (2)	0.0625 (6)
C7	0.1541 (3)	0.66749 (12)	1.0015 (2)	0.0508 (5)
C8	0.2025 (2)	0.60998 (12)	0.73238 (19)	0.0449 (4)
C9	0.0455 (3)	0.67572 (12)	0.5169 (2)	0.0551 (5)
C10	0.2283 (4)	0.72303 (14)	0.5249 (2)	0.0847 (8)
C11	−0.0786 (4)	0.65560 (18)	0.3802 (2)	0.0861 (9)
C12	0.5890 (2)	0.52673 (10)	0.53649 (18)	0.0392 (4)
H1	−0.0160	0.5468	0.7708	0.047*
H4	0.3763	0.4991	1.1890	0.070*
H5	0.3860	0.6115	1.2912	0.079*
H6	0.2509	0.7177	1.1743	0.075*
H7	0.0975	0.7102	0.9551	0.061*
H9	−0.0414	0.7039	0.5528	0.066*
H81	0.3105	0.5731	0.7640	0.054*
H82	0.2596	0.6597	0.7548	0.054*
H101	0.3196	0.6945	0.4959	0.102*
H102	0.2982	0.7382	0.6116	0.102*
H103	0.1835	0.7665	0.4721	0.102*
H111	0.0052	0.6279	0.3442	0.103*
H112	−0.1938	0.6257	0.3779	0.103*
H113	−0.1261	0.7005	0.3318	0.103*
H201	−0.2198	0.6315	0.7042	0.056*
H301	0.0045	0.5758	0.5726	0.049*
H302	0.1996	0.5829	0.5649	0.049*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0558 (3)	0.0521 (3)	0.0871 (4)	0.0098 (2)	0.0383 (3)	0.0072 (2)
O1	0.0378 (7)	0.0493 (8)	0.0556 (9)	0.0046 (6)	0.0144 (6)	−0.0037 (6)
O2	0.0357 (7)	0.0627 (9)	0.0671 (10)	−0.0080 (6)	0.0252 (6)	−0.0189 (7)
O3	0.0411 (7)	0.0567 (8)	0.0662 (10)	0.0009 (6)	0.0198 (7)	−0.0194 (7)
N1	0.0394 (8)	0.0443 (8)	0.0430 (9)	0.0000 (7)	0.0206 (7)	−0.0041 (7)
C1	0.0341 (9)	0.0391 (9)	0.0451 (11)	−0.0016 (8)	0.0164 (8)	−0.0018 (8)
C2	0.0328 (9)	0.0469 (10)	0.0428 (11)	−0.0061 (8)	0.0182 (8)	−0.0007 (8)
C3	0.0328 (9)	0.0549 (12)	0.0512 (12)	0.0008 (8)	0.0221 (8)	0.0040 (9)
C4	0.0411 (11)	0.0856 (17)	0.0540 (14)	0.0099 (11)	0.0230 (10)	0.0188 (12)
C5	0.0499 (12)	0.101 (2)	0.0460 (13)	−0.0074 (13)	0.0160 (10)	0.0018 (14)
C6	0.0678 (14)	0.0711 (16)	0.0518 (14)	−0.0222 (13)	0.0254 (11)	−0.0182 (12)
C7	0.0561 (12)	0.0492 (11)	0.0501 (13)	−0.0104 (10)	0.0225 (10)	−0.0045 (9)
C8	0.0356 (9)	0.0569 (12)	0.0440 (11)	−0.0018 (9)	0.0163 (8)	−0.0020 (9)
C9	0.0627 (13)	0.0510 (12)	0.0593 (14)	0.0133 (10)	0.0313 (11)	0.0094 (10)
C10	0.111 (2)	0.0592 (15)	0.087 (2)	−0.0184 (15)	0.0387 (18)	0.0117 (14)
C11	0.0840 (19)	0.106 (2)	0.0580 (17)	−0.0009 (17)	0.0130 (14)	0.0242 (15)
C12	0.0346 (9)	0.0427 (10)	0.0420 (10)	0.0026 (8)	0.0158 (8)	0.0021 (8)

Geometric parameters (Å, º) top

Cl1—C3	1.746 (2)	O1—H201	0.822
O1—C1	1.419 (2)	N1—H301	0.860
O2—C12	1.249 (2)	N1—H302	0.860
O3—C12	1.246 (2)	C1—H1	0.980
N1—C8	1.492 (2)	C4—H4	0.930
N1—C9	1.507 (2)	C5—H5	0.930
C1—C2	1.507 (2)	C6—H6	0.930
C1—C8	1.527 (3)	C7—H7	0.930
C2—C3	1.389 (2)	C8—H81	0.970
C2—C7	1.389 (2)	C8—H82	0.970
C3—C4	1.377 (3)	C9—H9	0.980
C4—C5	1.371 (3)	C10—H101	0.960
C5—C6	1.379 (3)	C10—H102	0.960
C6—C7	1.388 (3)	C10—H103	0.960
C9—C10	1.509 (4)	C11—H111	0.960
C9—C11	1.513 (3)	C11—H112	0.960
C12—C12ⁱ	1.552 (2)	C11—H113	0.960

C8—N1—C9	117.09 (15)	C8—C1—H1	109.1
O1—C1—C2	110.83 (16)	C3—C4—H4	120.3
O1—C1—C8	109.18 (16)	C5—C4—H4	120.3
C2—C1—C8	109.57 (14)	C4—C5—H5	119.9
C1—C2—C3	122.66 (18)	C6—C5—H5	119.9
C1—C2—C7	120.33 (17)	C5—C6—H6	120.2
C3—C2—C7	117.01 (17)	C7—C6—H6	120.2
Cl1—C3—C2	120.12 (15)	C2—C7—H7	119.3
Cl1—C3—C4	117.61 (17)	C6—C7—H7	119.3
C2—C3—C4	122.3 (2)	N1—C8—H81	108.9
C3—C4—C5	119.5 (2)	N1—C8—H82	108.9
C4—C5—C6	120.2 (2)	C1—C8—H81	108.9
C5—C6—C7	119.7 (2)	C1—C8—H82	108.9
C2—C7—C6	121.31 (19)	H81—C8—H82	109.5
N1—C8—C1	111.70 (14)	N1—C9—H9	108.9
N1—C9—C10	111.11 (17)	C10—C9—H9	108.9
N1—C9—C11	107.88 (18)	C11—C9—H9	108.9
C10—C9—C11	111.2 (2)	C9—C10—H101	109.5
O2—C12—O3	126.27 (16)	C9—C10—H102	109.5
O2—C12—C12ⁱ	116.79 (17)	C9—C10—H103	109.5
O3—C12—C12ⁱ	116.94 (17)	H101—C10—H102	109.5
C1—O1—H201	110.2	H101—C10—H103	109.5
C8—N1—H301	107.5	H102—C10—H103	109.5
C8—N1—H302	107.5	C9—C11—H111	109.5
C9—N1—H301	107.5	C9—C11—H112	109.5
C9—N1—H302	107.5	C9—C11—H113	109.5
H301—N1—H302	109.5	H111—C11—H112	109.5
O1—C1—H1	109.1	H111—C11—H113	109.5
C2—C1—H1	109.1	H112—C11—H113	109.5

C8—N1—C9—C10	68.7 (2)	C1—C2—C7—C6	179.3 (2)
C8—N1—C9—C11	−169.2 (2)	C3—C2—C7—C6	−0.7 (3)
C9—N1—C8—C1	96.3 (2)	C7—C2—C3—Cl1	−178.20 (17)
O1—C1—C2—C3	151.32 (19)	C7—C2—C3—C4	2.0 (3)
O1—C1—C2—C7	−28.6 (2)	Cl1—C3—C4—C5	178.38 (19)
O1—C1—C8—N1	−60.6 (2)	C2—C3—C4—C5	−1.8 (3)
C2—C1—C8—N1	177.85 (15)	C3—C4—C5—C6	0.2 (3)
C8—C1—C2—C3	−88.1 (2)	C4—C5—C6—C7	1.1 (4)
C8—C1—C2—C7	91.9 (2)	C5—C6—C7—C2	−0.9 (3)
C1—C2—C3—Cl1	1.9 (2)	O2—C12—C12ⁱ—O3ⁱ	−0.5 (2)
C1—C2—C3—C4	−177.9 (2)	O3—C12—C12ⁱ—O2ⁱ	0.5 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H201···O3ⁱⁱ	0.82	1.89	2.707 (2)	175
N1—H301···O2ⁱⁱ	0.86	1.96	2.816 (2)	179
N1—H302···O3	0.86	2.34	3.070 (2)	143
N1—H302···O2ⁱ	0.86	2.09	2.807 (2)	141
C6—H6···O1ⁱⁱⁱ	0.93	2.56	3.433 (3)	156

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x−1, y, z; (iii) x+1/2, −y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₇ClNO⁺·0.5C₂O₄²⁻
M_r	258.72
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	6.9951 (3), 17.8821 (8), 11.2236 (6)
β (°)	110.8377 (13)
V (Å³)	1312.10 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.29
Crystal size (mm)	0.53 × 0.24 × 0.22

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.836, 0.939
No. of measured, independent and observed [F² > 2σ(F²)] reflections	12562, 2978, 1974
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.089, 1.00
No. of reflections	2978
No. of parameters	156
No. of restraints	?
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.28

Computer programs: PROCESS-AUTO (Rigaku/MSC, 2004), CrystalStructure (Rigaku/MSC, 2004), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H201···O3ⁱ	0.82	1.89	2.707 (2)	175
N1—H301···O2ⁱ	0.86	1.96	2.816 (2)	179
N1—H302···O3	0.86	2.34	3.070 (2)	143
N1—H302···O2ⁱⁱ	0.86	2.09	2.807 (2)	141
C6—H6···O1ⁱⁱⁱ	0.93	2.56	3.433 (3)	156

Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+1, −z+1; (iii) x+1/2, −y+3/2, z+1/2.

References

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ISSN: 2056-9890

Volume 65| Part 7| July 2009| Page o1670

doi:10.1107/S1600536809022740

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