organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890
Volume 67| Part 5| May 2011| Page o1264

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

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[Gomori, G. (1955). Methods in Enzymology, Vol. 1, edited by S. P. Colowick & N. O. Kaplan, pp. 138-146. New York: Academic Press.]). For related structrues, see: Stepniak et al. (2003[Stepniak, K., Lis, T. & Koziol, A. E. (2003). Z. Kristallogr. New Cryst. Struct. 218, 37-38.]); Yu & Qian (2009[Yu, Y.-H. & Qian, K. (2009). Acta Cryst. E65, o1278.]).

[Scheme 1]

Experimental

Crystal data
  • C4H12NO3+·CHO2

  • Mr = 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[Bruker (2005). SADABS, APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.789, Tmax = 0.899

  • 4402 measured reflections

  • 1368 independent reflections

  • 1304 reflections with I > 2σ(I)

  • Rint = 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

  • Δρmax = 0.28 e Å−3

  • Δρmin = −0.20 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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+{\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[Bruker (2005). SADABS, APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2005[Bruker (2005). SADABS, APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXL97.

Supporting information


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.

Refinement top

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 Uiso(H) = 1.2-1.5 Ueqof the parent atom.

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
[Figure 1] Fig. 1. The content of asymmetric unit of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] 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+·CHO2F(000) = 720
Mr = 167.16Dx = 1.398 Mg m3
Orthorhombic, PbcaCu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ac 2abCell parameters from 3109 reflections
a = 6.4980 (1) Åθ = 7.5–66.8°
b = 11.8740 (1) ŵ = 1.08 mm1
c = 20.5897 (2) ÅT = 296 K
V = 1588.64 (3) Å3Block, colourless
Z = 80.23 × 0.18 × 0.10 mm
Data collection top
Bruker APEXII
diffractometer
1368 independent reflections
Radiation source: fine-focus sealed tube1304 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.016
Detector resolution: 0 pixels mm-1θmax = 67.3°, θmin = 7.5°
ϕ and ω scansh = 77
Absorption correction: multi-scan
(SADABS; Bruker, 2005)
k = 1313
Tmin = 0.789, Tmax = 0.899l = 2224
4402 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.034H 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 reflectionsΔρmax = 0.28 e Å3
117 parametersΔρmin = 0.20 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0049 (6)
Crystal data top
C4H12NO3+·CHO2V = 1588.64 (3) Å3
Mr = 167.16Z = 8
Orthorhombic, PbcaCu Kα radiation
a = 6.4980 (1) ŵ = 1.08 mm1
b = 11.8740 (1) ÅT = 296 K
c = 20.5897 (2) Å0.23 × 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)
Tmin = 0.789, Tmax = 0.899Rint = 0.016
4402 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0340 restraints
wR(F2) = 0.095H atoms treated by a mixture of independent and constrained refinement
S = 1.09Δρmax = 0.28 e Å3
1368 reflectionsΔρmin = 0.20 e Å3
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
xyzUiso*/Ueq
O10.12876 (16)0.52355 (9)0.22191 (4)0.0392 (3)
H1A0.16660.57650.24450.059*
O20.20496 (15)0.43932 (8)0.02376 (4)0.0340 (3)
H2A0.28080.39260.04070.051*
O30.06605 (15)0.77248 (7)0.07395 (5)0.0349 (3)
H3A0.03950.79450.09170.052*
N10.06449 (16)0.55746 (9)0.10599 (5)0.0254 (3)
C10.16134 (18)0.58258 (10)0.10896 (6)0.0251 (3)
C20.2530 (2)0.51726 (11)0.16588 (6)0.0322 (3)
H2B0.26940.43890.15350.039*
H2C0.38830.54720.17580.039*
C30.2620 (2)0.54863 (11)0.04459 (6)0.0308 (3)
H3B0.22340.60260.01140.037*
H3C0.41030.55160.04950.037*
C40.1855 (2)0.70956 (11)0.11900 (7)0.0318 (3)
H4A0.14350.72880.16280.038*
H4B0.32930.72980.11420.038*
O40.23553 (18)0.69672 (9)0.30298 (5)0.0481 (3)
O50.22296 (18)0.84393 (9)0.36823 (5)0.0454 (3)
C50.1807 (2)0.79327 (12)0.31701 (7)0.0360 (4)
H5A0.098 (3)0.8304 (16)0.2871 (8)0.051 (5)*
H1B0.120 (3)0.5727 (13)0.0659 (9)0.040 (4)*
H1C0.142 (2)0.6018 (15)0.1363 (8)0.041 (4)*
H1D0.098 (3)0.4814 (16)0.1148 (8)0.044 (4)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0514 (6)0.0413 (6)0.0248 (5)0.0045 (5)0.0007 (4)0.0006 (4)
O20.0468 (6)0.0275 (5)0.0277 (5)0.0099 (4)0.0082 (4)0.0036 (3)
O30.0403 (6)0.0239 (5)0.0406 (6)0.0002 (4)0.0064 (4)0.0060 (4)
N10.0302 (6)0.0215 (5)0.0244 (6)0.0025 (4)0.0019 (4)0.0015 (4)
C10.0274 (6)0.0227 (6)0.0253 (6)0.0020 (5)0.0008 (5)0.0011 (5)
C20.0378 (7)0.0317 (7)0.0272 (7)0.0042 (5)0.0046 (5)0.0019 (5)
C30.0352 (7)0.0297 (7)0.0276 (7)0.0003 (5)0.0027 (5)0.0001 (5)
C40.0354 (7)0.0239 (7)0.0360 (7)0.0044 (5)0.0009 (5)0.0019 (5)
O40.0633 (7)0.0367 (6)0.0444 (6)0.0148 (5)0.0142 (5)0.0112 (4)
O50.0551 (7)0.0359 (6)0.0451 (6)0.0153 (5)0.0088 (5)0.0116 (4)
C50.0388 (8)0.0327 (7)0.0366 (8)0.0069 (6)0.0024 (6)0.0001 (6)
Geometric parameters (Å, º) top
O1—C21.4100 (16)C1—C41.5299 (16)
O1—H1A0.8200C1—C31.5317 (17)
O2—C31.4163 (16)C2—H2B0.9700
O2—H2A0.8200C2—H2C0.9700
O3—C41.4217 (16)C3—H3B0.9700
O3—H3A0.8200C3—H3C0.9700
N1—C11.4987 (15)C4—H4A0.9700
N1—H1B0.918 (18)C4—H4B0.9700
N1—H1C0.960 (18)O4—C51.2348 (18)
N1—H1D0.946 (18)O5—C51.2449 (18)
C1—C21.5265 (17)C5—H5A0.928 (19)
C2—O1—H1A109.5O1—C2—H2C109.2
C3—O2—H2A109.5C1—C2—H2C109.2
C4—O3—H3A109.5H2B—C2—H2C107.9
C1—N1—H1B112.4 (11)O2—C3—C1113.05 (10)
C1—N1—H1C112.2 (10)O2—C3—H3B109.0
H1B—N1—H1C105.7 (14)C1—C3—H3B109.0
C1—N1—H1D113.9 (10)O2—C3—H3C109.0
H1B—N1—H1D105.7 (14)C1—C3—H3C109.0
H1C—N1—H1D106.2 (14)H3B—C3—H3C107.8
N1—C1—C2108.19 (10)O3—C4—C1111.94 (10)
N1—C1—C4107.59 (10)O3—C4—H4A109.2
C2—C1—C4110.91 (10)C1—C4—H4A109.2
N1—C1—C3109.28 (10)O3—C4—H4B109.2
C2—C1—C3111.35 (10)C1—C4—H4B109.2
C4—C1—C3109.43 (10)H4A—C4—H4B107.9
O1—C2—C1112.20 (10)O4—C5—O5125.67 (14)
O1—C2—H2B109.2O4—C5—H5A116.9 (12)
C1—C2—H2B109.2O5—C5—H5A117.4 (11)
N1—C1—C2—O143.81 (13)C4—C1—C3—O2165.66 (10)
C4—C1—C2—O173.96 (13)N1—C1—C4—O349.91 (13)
C3—C1—C2—O1163.92 (11)C2—C1—C4—O3168.05 (10)
N1—C1—C3—O248.09 (14)C3—C1—C4—O368.72 (13)
C2—C1—C3—O271.38 (14)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···O40.821.922.7378 (14)175
O2—H2A···O3i0.821.872.6845 (12)173
O3—H3A···O5ii0.821.852.6659 (14)180
N1—H1B···O2iii0.918 (18)1.933 (19)2.8233 (14)163.0 (15)
N1—H1C···O4ii0.960 (18)1.861 (18)2.8171 (15)173.4 (15)
N1—H1D···O5iv0.946 (18)1.857 (19)2.7876 (14)167.2 (15)
Symmetry codes: (i) x+1/2, y1/2, z; (ii) x1/2, y, z+1/2; (iii) x, y+1, z; (iv) x, y1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC4H12NO3+·CHO2
Mr167.16
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)296
a, b, c (Å)6.4980 (1), 11.8740 (1), 20.5897 (2)
V3)1588.64 (3)
Z8
Radiation typeCu Kα
µ (mm1)1.08
Crystal size (mm)0.23 × 0.18 × 0.10
Data collection
DiffractometerBruker APEXII
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2005)
Tmin, Tmax0.789, 0.899
No. of measured, independent and
observed [I > 2σ(I)] reflections
4402, 1368, 1304
Rint0.016
(sin θ/λ)max1)0.599
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.034, 0.095, 1.09
No. of reflections1368
No. of parameters117
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
O1—H1A···O40.821.922.7378 (14)175
O2—H2A···O3i0.821.872.6845 (12)173
O3—H3A···O5ii0.821.852.6659 (14)180
N1—H1B···O2iii0.918 (18)1.933 (19)2.8233 (14)163.0 (15)
N1—H1C···O4ii0.960 (18)1.861 (18)2.8171 (15)173.4 (15)
N1—H1D···O5iv0.946 (18)1.857 (19)2.7876 (14)167.2 (15)
Symmetry codes: (i) x+1/2, y1/2, z; (ii) x1/2, y, z+1/2; (iii) x, y+1, z; (iv) x, y1/2, z+1/2.
 

Acknowledgements

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

References

First citationBruker (2005). SADABS, APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
First citationGomori, G. (1955). Methods in Enzymology, Vol. 1, edited by S. P. Colowick & N. O. Kaplan, pp. 138–146. New York: Academic Press.
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationStepniak, K., Lis, T. & Koziol, A. E. (2003). Z. Kristallogr. New Cryst. Struct. 218, 37–38.  CAS
First citationYu, Y.-H. & Qian, K. (2009). Acta Cryst. E65, o1278.  Web of Science CSD CrossRef IUCr Journals

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Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 67| Part 5| May 2011| Page o1264
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