1,3-Dihydr­oxy-2-(hydroxy­meth­yl)propan-2-aminium 2,2-dichloro­acetate

Yu, Y.-H.; Qian, K.

doi:10.1107/S1600536809016626

organic compounds

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Volume 65| Part 6| June 2009| Page o1278

doi:10.1107/S1600536809016626

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1,3-Dihydroxy-2-(hydroxymethyl)propan-2-aminium 2,2-dichloroacetate

Yan-Hong Yu ^a ^* and Kun Qian ^b

^aJiangxi Key Laboratory of Organic Chemistry, Jiangxi Science and Technology Normal University, Nanchang 330013, People's Republic of China, and ^bAcademic Administration of JiangXi University of Traditional Chinese Medicine, Nanchang 330047, People's Republic of China
^*Correspondence e-mail: yuyanhong001@yahoo.com.cn

(Received 1 April 2009; accepted 4 May 2009; online 14 May 2009)

The title compound, C₄H₁₂NO₃⁺·C₂HCl₂O₂⁻, was obtained from dichloroacetic acid and 2-amino-2-(hydroxymethyl)propane-1,3-diol. In the crystal structure, the cations and anions are connected by intermolecular N—H⋯O and O—H⋯O hydrogen bonding, forming a two-dimensional array parallel to (001). The crystal used for analysis was a merohedral twin, as indicated by the Flack parameter of 0.67 (6).

Related literature

For the engineering of organic crystals for quadratic non-linear optics, see: Etter & Frankenbach (1989 ); Yaghi et al. (1997 ). For hydrogen-bond networks, see: Etter (1990 ).

Experimental

Crystal data

C₄H₁₂NO₃⁺·C₂HCl₂O₂⁻
M_r = 250.07
Monoclinic, P 2₁
a = 8.6231 (17) Å
b = 6.1376 (12) Å
c = 9.898 (2) Å
β = 97.03 (3)°
V = 519.92 (18) Å³
Z = 2
Mo Kα radiation
μ = 0.62 mm⁻¹
T = 293 K
0.22 × 0.18 × 0.12 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.875, T_max = 0.929
4914 measured reflections
2044 independent reflections
1951 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.069
S = 1.10
2044 reflections
130 parameters
3 restraints
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.25 e Å⁻³
Absolute structure: Flack (1983 ), 920 Friedel pairs
Flack parameter: 0.67 (6)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O3ⁱ	0.89	2.00	2.881 (2)	169
N1—H1B⋯O2ⁱⁱ	0.89	1.97	2.858 (2)	172
N1—H1C⋯O5ⁱⁱⁱ	0.89	2.03	2.909 (2)	169
O3—H3⋯O4^iv	0.81	1.85	2.654 (2)	169
O4—H4⋯O1	0.82	1.84	2.655 (2)	173
O5—H5⋯O2^v	0.82	1.88	2.691 (2)	168
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+1]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z+1]$ ; (iii) $[-x, y+{\script{1\over 2}}, -z+1]$ ; (iv) x, y-1, z; (v) x-1, y, z.

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ), ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809016626/dn2442sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809016626/dn2442Isup2.hkl

checkCIF report

Comment top

During the past 15 years, organic crystals for quadratic nonlinear optics have been intensely engineered (Etter & Frankenbach, 1989; Yaghi et al., 1997). Arising from the complexation of organic and inorganic molecules based on acid–base interactions, highly polarisable cations, responsible for NLO properties, are linked to inorganic anions through hydrogen bond networks which generate a noncentrosymmetric structural organization (Etter, 1990). In this paper, a novel nonlinear hybrid molecular crystal, NH₂C(CH₂OH)₃, has been prepared by complexation between dichloroacetic and tris(hydroxymethyl)amino methane.

The structure is built up from cations and anions (Fig. 1) connected through strong intermolecular hydrogen bonds (Table 1, Fig. 2) to form a two-dimensional layer developing parallel to the (001) plane. As suggested by the value of the Flack parameter (Flack, 1983), 0.67 (6), based on 920 Friedel's pairs, the particular crystal is twinned by inversion.

Related literature top

For the engineering of organic crystals for quadratic non-linear optics, see: Etter & Frankenbach (1989); Yaghi et al. (1997). For hydrogen-bond networks, see: Etter (1990).

Experimental top

The crystals were grown by slow evaporation at ambient temperature of the solution prepared by adding dichloroacetic acid to the aqueous solution of tris(hydroxymethyl)aminomethane in a stoichiometric ratio. For the X-ray diffraction analysis, suitable single crystals of compound (I) were obtained after one night by slow evaporation from an filtration water solution.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with the atom labeling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii. H bond is drawn as dashed line.
	Fig. 2. Partial packing view showing the intricated hydrogen bond framework. H atoms not involved in hydrogen bondings were omitted. [Symmetry code: (i) -x + 1, y + 1/2, -z + 1.]

1,3-Dihydroxy-2-(hydroxymethyl)propan-2-aminium 2,2-dichloroacetate top

Crystal data top

C₄H₁₂NO₃⁺·C₂HCl₂O₂⁻	F(000) = 260
M_r = 250.07	D_x = 1.597 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 735 reflections
a = 8.6231 (17) Å	θ = 2.8–27.5°
b = 6.1376 (12) Å	µ = 0.62 mm⁻¹
c = 9.898 (2) Å	T = 293 K
β = 97.03 (3)°	Prism, colourless
V = 519.92 (18) Å³	0.22 × 0.18 × 0.12 mm
Z = 2

Data collection top

Rigaku SCXmini diffractometer	2044 independent reflections
Radiation source: fine-focus sealed tube	1951 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
Detector resolution: 13.6612 pixels mm^-1	θ_max = 26.0°, θ_min = 3.3°
ω scans	h = −10→10
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −7→7
T_min = 0.875, T_max = 0.929	l = −12→12
4914 measured reflections

Refinement top

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)] = 0.031	H-atom parameters constrained
wR(F²) = 0.069	w = 1/[σ²(F_o²) + (0.0218P)² + 0.166P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max < 0.001
2044 reflections	Δρ_max = 0.23 e Å⁻³
130 parameters	Δρ_min = −0.25 e Å⁻³
3 restraints	Absolute structure: Flack (1983), 920 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.67 (6)

Crystal data top

C₄H₁₂NO₃⁺·C₂HCl₂O₂⁻	V = 519.92 (18) Å³
M_r = 250.07	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 8.6231 (17) Å	µ = 0.62 mm⁻¹
b = 6.1376 (12) Å	T = 293 K
c = 9.898 (2) Å	0.22 × 0.18 × 0.12 mm
β = 97.03 (3)°

Data collection top

Rigaku SCXmini diffractometer	2044 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1951 reflections with I > 2σ(I)
T_min = 0.875, T_max = 0.929	R_int = 0.025
4914 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	H-atom parameters constrained
wR(F²) = 0.069	Δρ_max = 0.23 e Å⁻³
S = 1.10	Δρ_min = −0.25 e Å⁻³
2044 reflections	Absolute structure: Flack (1983), 920 Friedel pairs
130 parameters	Absolute structure parameter: 0.67 (6)
3 restraints

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.86491 (9)	0.39154 (15)	0.00483 (7)	0.0630 (2)
Cl2	0.70850 (10)	0.03942 (11)	0.13016 (8)	0.0598 (2)
C1	0.6938 (3)	0.3135 (4)	0.0737 (2)	0.0342 (5)
H1	0.6046	0.3263	0.0026	0.041*
C2	0.6675 (2)	0.4656 (4)	0.1919 (2)	0.0282 (5)
C3	0.2265 (2)	0.2569 (3)	0.3756 (2)	0.0215 (4)
C4	0.3748 (2)	0.1471 (3)	0.3394 (2)	0.0248 (4)
H4A	0.3540	0.0827	0.2496	0.030*
H4B	0.4558	0.2562	0.3365	0.030*
C5	0.0883 (2)	0.0986 (3)	0.3577 (2)	0.0249 (4)
H5A	0.0543	0.0801	0.2613	0.030*
H5B	0.1226	−0.0423	0.3944	0.030*
C6	0.1911 (2)	0.4607 (3)	0.2892 (2)	0.0270 (4)
H6A	0.1841	0.4215	0.1937	0.032*
H6B	0.0905	0.5188	0.3058	0.032*
N1	0.25465 (19)	0.3243 (3)	0.52217 (16)	0.0221 (3)
H1A	0.3470	0.3903	0.5382	0.033*
H1B	0.2540	0.2070	0.5750	0.033*
H1C	0.1797	0.4156	0.5403	0.033*
O1	0.54454 (19)	0.5709 (3)	0.17435 (18)	0.0444 (4)
O2	0.76863 (19)	0.4708 (3)	0.29336 (16)	0.0403 (4)
O3	0.42905 (16)	−0.0160 (2)	0.43407 (15)	0.0306 (4)
H3	0.3857	−0.1281	0.4071	0.046*
O4	0.30642 (17)	0.6233 (2)	0.31776 (17)	0.0336 (4)
H4	0.3805	0.5959	0.2759	0.050*
O5	−0.04042 (15)	0.1704 (3)	0.42311 (15)	0.0274 (3)
H5	−0.0931	0.2564	0.3735	0.041*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0535 (4)	0.0984 (7)	0.0405 (4)	−0.0075 (4)	0.0196 (3)	−0.0042 (4)
Cl2	0.0872 (5)	0.0321 (3)	0.0549 (4)	−0.0001 (4)	−0.0123 (4)	−0.0081 (3)
C1	0.0339 (12)	0.0377 (13)	0.0292 (11)	0.0008 (10)	−0.0040 (9)	−0.0007 (10)
C2	0.0274 (11)	0.0271 (10)	0.0304 (11)	−0.0002 (10)	0.0048 (9)	0.0064 (9)
C3	0.0185 (9)	0.0225 (10)	0.0233 (10)	−0.0014 (8)	0.0018 (8)	0.0011 (8)
C4	0.0213 (10)	0.0248 (11)	0.0288 (11)	0.0005 (9)	0.0052 (9)	0.0000 (9)
C5	0.0191 (9)	0.0233 (11)	0.0324 (11)	−0.0007 (8)	0.0029 (8)	−0.0030 (9)
C6	0.0247 (10)	0.0227 (10)	0.0332 (11)	0.0007 (9)	0.0017 (9)	0.0044 (9)
N1	0.0180 (7)	0.0224 (8)	0.0259 (9)	0.0000 (7)	0.0031 (7)	−0.0006 (7)
O1	0.0347 (9)	0.0503 (11)	0.0494 (10)	0.0142 (8)	0.0097 (8)	0.0129 (9)
O2	0.0424 (9)	0.0425 (10)	0.0337 (9)	0.0120 (8)	−0.0048 (7)	−0.0105 (7)
O3	0.0238 (7)	0.0236 (8)	0.0433 (9)	0.0036 (6)	−0.0002 (7)	0.0001 (7)
O4	0.0293 (8)	0.0219 (7)	0.0510 (10)	−0.0038 (6)	0.0105 (7)	0.0024 (7)
O5	0.0179 (7)	0.0308 (8)	0.0337 (8)	−0.0002 (6)	0.0043 (6)	0.0027 (6)

Geometric parameters (Å, º) top

Cl1—C1	1.765 (2)	C5—O5	1.421 (2)
Cl2—C1	1.773 (3)	C5—H5A	0.9700
C1—C2	1.536 (3)	C5—H5B	0.9700
C1—H1	0.9800	C6—O4	1.413 (3)
C2—O1	1.236 (3)	C6—H6A	0.9700
C2—O2	1.247 (3)	C6—H6B	0.9700
C3—N1	1.499 (3)	N1—H1A	0.8900
C3—C6	1.525 (3)	N1—H1B	0.8900
C3—C4	1.527 (3)	N1—H1C	0.8900
C3—C5	1.531 (3)	O3—H3	0.8119
C4—O3	1.411 (2)	O4—H4	0.8205
C4—H4A	0.9700	O5—H5	0.8200
C4—H4B	0.9700

C2—C1—Cl1	109.75 (16)	O5—C5—C3	112.99 (16)
C2—C1—Cl2	110.36 (16)	O5—C5—H5A	109.0
Cl1—C1—Cl2	110.39 (14)	C3—C5—H5A	109.0
C2—C1—H1	108.8	O5—C5—H5B	109.0
Cl1—C1—H1	108.8	C3—C5—H5B	109.0
Cl2—C1—H1	108.8	H5A—C5—H5B	107.8
O1—C2—O2	127.1 (2)	O4—C6—C3	112.27 (17)
O1—C2—C1	114.5 (2)	O4—C6—H6A	109.2
O2—C2—C1	118.38 (19)	C3—C6—H6A	109.2
N1—C3—C6	108.33 (17)	O4—C6—H6B	109.2
N1—C3—C4	107.93 (16)	C3—C6—H6B	109.2
C6—C3—C4	110.28 (16)	H6A—C6—H6B	107.9
N1—C3—C5	108.57 (16)	C3—N1—H1A	109.5
C6—C3—C5	110.83 (16)	C3—N1—H1B	109.5
C4—C3—C5	110.81 (17)	H1A—N1—H1B	109.5
O3—C4—C3	112.12 (16)	C3—N1—H1C	109.5
O3—C4—H4A	109.2	H1A—N1—H1C	109.5
C3—C4—H4A	109.2	H1B—N1—H1C	109.5
O3—C4—H4B	109.2	C4—O3—H3	106.3
C3—C4—H4B	109.2	C6—O4—H4	109.1
H4A—C4—H4B	107.9	C5—O5—H5	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3ⁱ	0.89	2.00	2.881 (2)	169
N1—H1B···O2ⁱⁱ	0.89	1.97	2.858 (2)	172
N1—H1C···O5ⁱⁱⁱ	0.89	2.03	2.909 (2)	169
O3—H3···O4^iv	0.81	1.85	2.654 (2)	169
O4—H4···O1	0.82	1.84	2.655 (2)	173
O5—H5···O2^v	0.82	1.88	2.691 (2)	168

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

Experimental details

Crystal data
Chemical formula	C₄H₁₂NO₃⁺·C₂HCl₂O₂⁻
M_r	250.07
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	293
a, b, c (Å)	8.6231 (17), 6.1376 (12), 9.898 (2)
β (°)	97.03 (3)
V (Å³)	519.92 (18)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.62
Crystal size (mm)	0.22 × 0.18 × 0.12

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.875, 0.929
No. of measured, independent and observed [I > 2σ(I)] reflections	4914, 2044, 1951
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.069, 1.10
No. of reflections	2044
No. of parameters	130
No. of restraints	3
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.25
Absolute structure	Flack (1983), 920 Friedel pairs
Absolute structure parameter	0.67 (6)

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3ⁱ	0.89	2.00	2.881 (2)	169.2
N1—H1B···O2ⁱⁱ	0.89	1.97	2.858 (2)	171.7
N1—H1C···O5ⁱⁱⁱ	0.89	2.03	2.909 (2)	168.6
O3—H3···O4^iv	0.81	1.85	2.654 (2)	169.3
O4—H4···O1	0.82	1.84	2.655 (2)	172.6
O5—H5···O2^v	0.82	1.88	2.691 (2)	167.9

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

References

Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
Etter, M. C. (1990). Acc. Chem. Res. 23, 120–126. CrossRef CAS Web of Science Google Scholar
Etter, M. C. & Frankenbach, G. M. (1989). Chem. Mater. 1, 10–12. CSD CrossRef CAS Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yaghi, O. M., Davis, C. E., Li, G.-M. & Li, H.-L. (1997). J. Am. Chem. Soc. 119, 2861–2868. CSD CrossRef CAS Web of Science Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page o1278

doi:10.1107/S1600536809016626

Open

access