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

Abstract

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,

• a = 6.4980 (1) Å

• b = 11.8740 (1) Å

• c = 20.5897 (2) Å

• V = 1588.64 (3) ų

• 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[F ² > 2σ(F ²)] = 0.034

• wR(F ²) = 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

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.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536811015534/cv5073Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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⋯O5iv	0.946 (18)	1.857 (19)	2.7876 (14)	167.2 (15)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

The formic acid and N-bound H atoms located in a difference Fourier map and isotropically refined. All others H atoms were geometrically positioned [C—H 0.97 Å; O—H 0.82 Å] and refined as riding with U_iso(H) = 1.2-1.5 U_eqof the parent atom.

Figures

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.

Crystal data

C4H12NO3+·CHO2−	F(000) = 720
Mr = 167.16	Dx = 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

Bruker APEXII diffractometer	1368 independent reflections
Radiation source: fine-focus sealed tube	1304 reflections with I > 2σ(I)
graphite	Rint = 0.016
Detector resolution: 0 pixels mm-1	θmax = 67.3°, θmin = 7.5°
φ and ω scans	h = −7→7
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −13→13
Tmin = 0.789, Tmax = 0.899	l = −22→24
4402 measured reflections

Refinement

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(Fo2) + (0.055P)2 + 0.4117P] where P = (Fo2 + 2Fc2)/3
S = 1.09	(Δ/σ)max < 0.001
1368 reflections	Δρmax = 0.28 e Å−3
117 parameters	Δρmin = −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)

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
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 (Ų)

	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, °)

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, °)

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···O5iv	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.