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

Ren, G.-B.; Qi, M.-H.; Chen, J.-Y.; Meng, K.-Y.; Zhong, J.-L.

doi:10.1107/S1600536811015534

organic compounds

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ISSN: 2056-9890

Volume 67| Part 5| May 2011| Page o1264

doi:10.1107/S1600536811015534

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

Guo-Bin Ren,^a ^* Ming-Hui Qi,^a Jin-Yao Chen,^a Kun-Yan Meng ^a and Jia-Liang Zhong ^a

^aPharmaceutical Crystal Engineering Research Group, Shanghai Institute of Pharmaceutical Industry, 1320 Beijing Road (W), Shanghai 200040, People's Republic of China
^*Correspondence e-mail: renguobin2557@yahoo.com.cn

(Received 7 April 2011; accepted 25 April 2011; online 29 April 2011)

The title compound, C₄H₁₂NO₃⁺·CHO₂⁻, was obtained from 1,3-dihydroxy-2-(hydroxymethyl)propan-2-aminium acetate and ethyl formate. In the crystal, the cations and anions are held together by intermolecular N—H⋯O and O—H⋯O hydrogen bonds.

Related literature

For background to the use of tris(hydroxymethyl)aminomethane in biochemistry and molecular biology, see: Gomori (1955 ). For related structrues, see: Stepniak et al. (2003 ); Yu & Qian (2009 ).

Experimental

Crystal data

C₄H₁₂NO₃⁺·CHO₂⁻
M_r = 167.16
Orthorhombic, P b c a
a = 6.4980 (1) Å
b = 11.8740 (1) Å
c = 20.5897 (2) Å
V = 1588.64 (3) Å³
Z = 8
Cu Kα radiation
μ = 1.08 mm⁻¹
T = 296 K
0.23 × 0.18 × 0.10 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.789, T_max = 0.899
4402 measured reflections
1368 independent reflections
1304 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.095
S = 1.09
1368 reflections
117 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O4	0.82	1.92	2.7378 (14)	175
O2—H2A⋯O3ⁱ	0.82	1.87	2.6845 (12)	173
O3—H3A⋯O5ⁱⁱ	0.82	1.85	2.6659 (14)	180
N1—H1B⋯O2ⁱⁱⁱ	0.918 (18)	1.933 (19)	2.8233 (14)	163.0 (15)
N1—H1C⋯O4ⁱⁱ	0.960 (18)	1.861 (18)	2.8171 (15)	173.4 (15)
N1—H1D⋯O5^iv	0.946 (18)	1.857 (19)	2.7876 (14)	167.2 (15)
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (ii) $[x-{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ ; (iii) -x, -y+1, -z; (iv) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811015534/cv5073sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811015534/cv5073Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811015534/cv5073Isup3.cml

checkCIF report

Comment top

Tris(hydroxymethyl)aminomethane (Tris) is extensively used in biochemistry and molecular biology (Gomori, 1955). In biochemistry, Tris is widely used as a component of buffer solutions. In this paper, we report the crystal structure of its formate salt - the title compound (I).

The structure of (I) is built up from cations and anions (Fig. 1) connected through strong intermolecular hydrogen bonds (Table 1, Fig. 2). The bond lengths and angles in the molecule are normal and comparable with those observed in the related compounds (Stepniak et al., 2003; Yu et al., 2009).

Related literature top

For general background to the use of tris(hydroxymethyl)aminomethane in biochemistry and molecular biology, see: Gomori (1955). For related structrues, see: Stepniak et al. (2003); Yu et al. (2009).

Experimental top

Suitable X-ray crystals of the title compound was obtained by dissolving 1,3-dihydroxy-2-(hydroxymethyl)propan-2-aminium asiatate in ethyl formate, and standing overnight at room temperature.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The content of asymmetric unit of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The packing of the title compound, viewed down the a axis. The dashed lines indicate the hydrogen bonds.

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

Crystal data top

C₄H₁₂NO₃⁺·CHO₂⁻	F(000) = 720
M_r = 167.16	D_x = 1.398 Mg m⁻³
Orthorhombic, Pbca	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 3109 reflections
a = 6.4980 (1) Å	θ = 7.5–66.8°
b = 11.8740 (1) Å	µ = 1.08 mm⁻¹
c = 20.5897 (2) Å	T = 296 K
V = 1588.64 (3) Å³	Block, colourless
Z = 8	0.23 × 0.18 × 0.10 mm

Data collection top

Bruker APEXII diffractometer	1368 independent reflections
Radiation source: fine-focus sealed tube	1304 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
Detector resolution: 0 pixels mm^-1	θ_max = 67.3°, θ_min = 7.5°
ϕ and ω scans	h = −7→7
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −13→13
T_min = 0.789, T_max = 0.899	l = −22→24
4402 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)] = 0.034	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.095	w = 1/[σ²(F_o²) + (0.055P)² + 0.4117P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max < 0.001
1368 reflections	Δρ_max = 0.28 e Å⁻³
117 parameters	Δρ_min = −0.20 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0049 (6)

Crystal data top

C₄H₁₂NO₃⁺·CHO₂⁻	V = 1588.64 (3) Å³
M_r = 167.16	Z = 8
Orthorhombic, Pbca	Cu Kα radiation
a = 6.4980 (1) Å	µ = 1.08 mm⁻¹
b = 11.8740 (1) Å	T = 296 K
c = 20.5897 (2) Å	0.23 × 0.18 × 0.10 mm

Data collection top

Bruker APEXII diffractometer	1368 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1304 reflections with I > 2σ(I)
T_min = 0.789, T_max = 0.899	R_int = 0.016
4402 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.095	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	Δρ_max = 0.28 e Å⁻³
1368 reflections	Δρ_min = −0.20 e Å⁻³
117 parameters

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 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
O1	0.12876 (16)	0.52355 (9)	0.22191 (4)	0.0392 (3)
H1A	0.1666	0.5765	0.2445	0.059*
O2	0.20496 (15)	0.43932 (8)	0.02376 (4)	0.0340 (3)
H2A	0.2808	0.3926	0.0407	0.051*
O3	0.06605 (15)	0.77248 (7)	0.07395 (5)	0.0349 (3)
H3A	−0.0395	0.7945	0.0917	0.052*
N1	−0.06449 (16)	0.55746 (9)	0.10599 (5)	0.0254 (3)
C1	0.16134 (18)	0.58258 (10)	0.10896 (6)	0.0251 (3)
C2	0.2530 (2)	0.51726 (11)	0.16588 (6)	0.0322 (3)
H2B	0.2694	0.4389	0.1535	0.039*
H2C	0.3883	0.5472	0.1758	0.039*
C3	0.2620 (2)	0.54863 (11)	0.04459 (6)	0.0308 (3)
H3B	0.2234	0.6026	0.0114	0.037*
H3C	0.4103	0.5516	0.0495	0.037*
C4	0.1855 (2)	0.70956 (11)	0.11900 (7)	0.0318 (3)
H4A	0.1435	0.7288	0.1628	0.038*
H4B	0.3293	0.7298	0.1142	0.038*
O4	0.23553 (18)	0.69672 (9)	0.30298 (5)	0.0481 (3)
O5	0.22296 (18)	0.84393 (9)	0.36823 (5)	0.0454 (3)
C5	0.1807 (2)	0.79327 (12)	0.31701 (7)	0.0360 (4)
H5A	0.098 (3)	0.8304 (16)	0.2871 (8)	0.051 (5)*
H1B	−0.120 (3)	0.5727 (13)	0.0659 (9)	0.040 (4)*
H1C	−0.142 (2)	0.6018 (15)	0.1363 (8)	0.041 (4)*
H1D	−0.098 (3)	0.4814 (16)	0.1148 (8)	0.044 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0514 (6)	0.0413 (6)	0.0248 (5)	−0.0045 (5)	−0.0007 (4)	−0.0006 (4)
O2	0.0468 (6)	0.0275 (5)	0.0277 (5)	0.0099 (4)	−0.0082 (4)	−0.0036 (3)
O3	0.0403 (6)	0.0239 (5)	0.0406 (6)	0.0002 (4)	0.0064 (4)	0.0060 (4)
N1	0.0302 (6)	0.0215 (5)	0.0244 (6)	−0.0025 (4)	−0.0019 (4)	0.0015 (4)
C1	0.0274 (6)	0.0227 (6)	0.0253 (6)	−0.0020 (5)	−0.0008 (5)	−0.0011 (5)
C2	0.0378 (7)	0.0317 (7)	0.0272 (7)	0.0042 (5)	−0.0046 (5)	−0.0019 (5)
C3	0.0352 (7)	0.0297 (7)	0.0276 (7)	0.0003 (5)	0.0027 (5)	−0.0001 (5)
C4	0.0354 (7)	0.0239 (7)	0.0360 (7)	−0.0044 (5)	−0.0009 (5)	−0.0019 (5)
O4	0.0633 (7)	0.0367 (6)	0.0444 (6)	0.0148 (5)	−0.0142 (5)	−0.0112 (4)
O5	0.0551 (7)	0.0359 (6)	0.0451 (6)	0.0153 (5)	−0.0088 (5)	−0.0116 (4)
C5	0.0388 (8)	0.0327 (7)	0.0366 (8)	0.0069 (6)	−0.0024 (6)	−0.0001 (6)

Geometric parameters (Å, º) top

O1—C2	1.4100 (16)	C1—C4	1.5299 (16)
O1—H1A	0.8200	C1—C3	1.5317 (17)
O2—C3	1.4163 (16)	C2—H2B	0.9700
O2—H2A	0.8200	C2—H2C	0.9700
O3—C4	1.4217 (16)	C3—H3B	0.9700
O3—H3A	0.8200	C3—H3C	0.9700
N1—C1	1.4987 (15)	C4—H4A	0.9700
N1—H1B	0.918 (18)	C4—H4B	0.9700
N1—H1C	0.960 (18)	O4—C5	1.2348 (18)
N1—H1D	0.946 (18)	O5—C5	1.2449 (18)
C1—C2	1.5265 (17)	C5—H5A	0.928 (19)

C2—O1—H1A	109.5	O1—C2—H2C	109.2
C3—O2—H2A	109.5	C1—C2—H2C	109.2
C4—O3—H3A	109.5	H2B—C2—H2C	107.9
C1—N1—H1B	112.4 (11)	O2—C3—C1	113.05 (10)
C1—N1—H1C	112.2 (10)	O2—C3—H3B	109.0
H1B—N1—H1C	105.7 (14)	C1—C3—H3B	109.0
C1—N1—H1D	113.9 (10)	O2—C3—H3C	109.0
H1B—N1—H1D	105.7 (14)	C1—C3—H3C	109.0
H1C—N1—H1D	106.2 (14)	H3B—C3—H3C	107.8
N1—C1—C2	108.19 (10)	O3—C4—C1	111.94 (10)
N1—C1—C4	107.59 (10)	O3—C4—H4A	109.2
C2—C1—C4	110.91 (10)	C1—C4—H4A	109.2
N1—C1—C3	109.28 (10)	O3—C4—H4B	109.2
C2—C1—C3	111.35 (10)	C1—C4—H4B	109.2
C4—C1—C3	109.43 (10)	H4A—C4—H4B	107.9
O1—C2—C1	112.20 (10)	O4—C5—O5	125.67 (14)
O1—C2—H2B	109.2	O4—C5—H5A	116.9 (12)
C1—C2—H2B	109.2	O5—C5—H5A	117.4 (11)

N1—C1—C2—O1	−43.81 (13)	C4—C1—C3—O2	−165.66 (10)
C4—C1—C2—O1	73.96 (13)	N1—C1—C4—O3	−49.91 (13)
C3—C1—C2—O1	−163.92 (11)	C2—C1—C4—O3	−168.05 (10)
N1—C1—C3—O2	−48.09 (14)	C3—C1—C4—O3	68.72 (13)
C2—C1—C3—O2	71.38 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O4	0.82	1.92	2.7378 (14)	175
O2—H2A···O3ⁱ	0.82	1.87	2.6845 (12)	173
O3—H3A···O5ⁱⁱ	0.82	1.85	2.6659 (14)	180
N1—H1B···O2ⁱⁱⁱ	0.918 (18)	1.933 (19)	2.8233 (14)	163.0 (15)
N1—H1C···O4ⁱⁱ	0.960 (18)	1.861 (18)	2.8171 (15)	173.4 (15)
N1—H1D···O5^iv	0.946 (18)	1.857 (19)	2.7876 (14)	167.2 (15)

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

Experimental details

Crystal data
Chemical formula	C₄H₁₂NO₃⁺·CHO₂⁻
M_r	167.16
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	296
a, b, c (Å)	6.4980 (1), 11.8740 (1), 20.5897 (2)
V (Å³)	1588.64 (3)
Z	8
Radiation type	Cu Kα
µ (mm⁻¹)	1.08
Crystal size (mm)	0.23 × 0.18 × 0.10

Data collection
Diffractometer	Bruker APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.789, 0.899
No. of measured, independent and observed [I > 2σ(I)] reflections	4402, 1368, 1304
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.095, 1.09
No. of reflections	1368
No. of parameters	117
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.20

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O4	0.82	1.92	2.7378 (14)	175
O2—H2A···O3ⁱ	0.82	1.87	2.6845 (12)	173
O3—H3A···O5ⁱⁱ	0.82	1.85	2.6659 (14)	180
N1—H1B···O2ⁱⁱⁱ	0.918 (18)	1.933 (19)	2.8233 (14)	163.0 (15)
N1—H1C···O4ⁱⁱ	0.960 (18)	1.861 (18)	2.8171 (15)	173.4 (15)
N1—H1D···O5^iv	0.946 (18)	1.857 (19)	2.7876 (14)	167.2 (15)

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

Acknowledgements

This work was supported by "New Drug Innovation 2009ZX09301–007" by the Ministry of Science and Technology of China.

References

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Stepniak, K., Lis, T. & Koziol, A. E. (2003). Z. Kristallogr. New Cryst. Struct. 218, 37–38. CAS Google Scholar
Yu, Y.-H. & Qian, K. (2009). Acta Cryst. E65, o1278. Web of Science CSD CrossRef IUCr Journals Google Scholar