Tris(hy­droxy­meth­yl)methanaminium trifluoro­acetate

Liu, M.-L.

doi:10.1107/S1600536811052226

organic compounds

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Volume 68| Part 1| January 2012| Page o60

doi:10.1107/S1600536811052226

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Tris(hydroxymethyl)methanaminium trifluoroacetate

Ming-Liang Liu ^a ^*

^aOrdered Matter Science Research Center, Southeast University, Nanjing 211189, People's Republic of China
^*Correspondence e-mail: jgsdxlml@163.com

(Received 24 November 2011; accepted 3 December 2011; online 10 December 2011)

In the crystal structure of the title salt, C₄H₁₂NO₃⁺·C₂F₃O₂⁻, N—H⋯O and O—H⋯O hydrogen bonds link the ions, forming a complex three-dimensional network.

Related literature

For background to ferroelectric complexes, see: Fu et al. (2011 ); Zhang et al. (2010 ). For a related structure, see: Rudman et al. (1983 ).

Experimental

Crystal data

C₄H₁₂NO₃⁺·C₂F₃O₂⁻
M_r = 235.17
Monoclinic, P 2₁ /c
a = 8.5137 (17) Å
b = 6.1210 (12) Å
c = 18.283 (4) Å
β = 99.34 (3)°
V = 940.1 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.18 mm⁻¹
T = 293 K
0.36 × 0.32 × 0.28 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.963, T_max = 0.971
9320 measured reflections
2148 independent reflections
1755 reflections with I > 2σ(I)
R_int = 0.041
3 standard reflections every 180 reflections intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.061
wR(F²) = 0.155
S = 1.02
2148 reflections
137 parameters
H-atom parameters constrained
Δρ_max = 0.62 e Å⁻³
Δρ_min = −0.57 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2ⁱ	0.82	1.86	2.644 (2)	159
O2—H2⋯O5	0.82	1.86	2.673 (3)	170
O3—H3⋯O4ⁱⁱ	0.82	1.87	2.677 (3)	170
N1—H1A⋯O4ⁱⁱⁱ	0.89	1.91	2.795 (3)	171
N1—H1B⋯O1^iv	0.89	1.98	2.854 (2)	168
N1—H1C⋯O3^v	0.89	2.02	2.899 (2)	169
Symmetry codes: (i) x, y-1, z; (ii) x-1, y, z; (iii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (v) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811052226/go2038sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811052226/go2038Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811052226/go2038Isup3.cml

checkCIF report

Comment top

Recently much attention has been devoted to crystals containing organic ions and inorganic ions due to the possibility of tuning their special structural features and their potential ferroelectrics properties (Fu et al., 2011; Zhang et al., 2010.).

The compound (C₄H₁₂O₃N)⁺(C₂F₃O₂)^- has an asymmetric unit that consists of one tris(hydroxymethyl)methanaminium cation and one trifluoroacetate anion (Fig 1). N-H···O and O-H···O hydrogen bonds form a complex three-dimensional network, (Fig 2). The trifluoromethyl group is quite mobile, but examination of a difference map in the plane of the fluorine atoms does show that the fluorine atoms exist as three distinct atoms.

For structure of the related tris(hydroxymethyl)methanaminium hydrogenhalides seen (Rudman et al., 1983).

Related literature top

For background to ferroelectric complexes, see: Fu et al. (2011); Zhang et al. ( 2010). For a related structure, see: Rudman et al. (1983).

Experimental top

1.21 g (0.01 mol) of tris(hydroxymethyl)methanaminium was firstly dissolved in 30 ml of ethanol, to which 1.14 g (0.01 mol) of trifluoroacetic acid was added at the ambient temperature. Single crystals suitable for X-ray structure analysis were obtained by the slow evaporation of the above solution after 3 days in air.

The dielectric constant of the compound as a function of temperature indicates that the permittivity is basically temperature-independent (ε = C/(T–T₀)), suggesting that this compound is not ferroelectric or that there may be no distinct phase transition occurring within the measured temperatur (below the melting point).

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, showing the atomic numbering scheme with 30% probability displacement ellipsoids.
	Fig. 2. Crystal structure of the title compound with view along the b axis. Intermolecular interactions are shown as dashed lines.

Tris(hydroxymethyl)methanaminium trifluoroacetate top

Crystal data top

C₄H₁₂NO₃⁺·C₂F₃O₂⁻	F(000) = 488
M_r = 235.17	D_x = 1.661 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1755 reflections
a = 8.5137 (17) Å	θ = 3.4°
b = 6.1210 (12) Å	µ = 0.18 mm⁻¹
c = 18.283 (4) Å	T = 293 K
β = 99.34 (3)°	Block, colourless
V = 940.1 (3) Å³	0.36 × 0.32 × 0.28 mm
Z = 4

Data collection top

Rigaku Mercury2 diffractometer	1755 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.041
Graphite monochromator	θ_max = 27.5°, θ_min = 3.5°
CCD_Profile_fitting scans	h = −11→11
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −7→7
T_min = 0.963, T_max = 0.971	l = −23→23
9320 measured reflections	3 standard reflections every 180 reflections
2148 independent reflections	intensity decay: none

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)] = 0.061	H-atom parameters constrained
wR(F²) = 0.155	w = 1/[σ²(F_o²) + (0.0616P)² + 1.3289P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
2148 reflections	Δρ_max = 0.62 e Å⁻³
137 parameters	Δρ_min = −0.57 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: 0.052 (5)

Crystal data top

C₄H₁₂NO₃⁺·C₂F₃O₂⁻	V = 940.1 (3) Å³
M_r = 235.17	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.5137 (17) Å	µ = 0.18 mm⁻¹
b = 6.1210 (12) Å	T = 293 K
c = 18.283 (4) Å	0.36 × 0.32 × 0.28 mm
β = 99.34 (3)°

Data collection top

Rigaku Mercury2 diffractometer	1755 reflections with I > 2σ(I)
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	R_int = 0.041
T_min = 0.963, T_max = 0.971	3 standard reflections every 180 reflections
9320 measured reflections	intensity decay: none
2148 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.061	0 restraints
wR(F²) = 0.155	H-atom parameters constrained
S = 1.02	Δρ_max = 0.62 e Å⁻³
2148 reflections	Δρ_min = −0.57 e Å⁻³
137 parameters

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 > 2sigma(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	0.44769 (19)	0.4524 (3)	0.28724 (10)	0.0314 (4)
H1	0.4052	0.3397	0.2984	0.047*
O2	0.3706 (2)	1.0901 (3)	0.35171 (10)	0.0335 (4)
H2	0.4552	1.0724	0.3797	0.050*
O3	−0.01510 (17)	0.6467 (3)	0.28917 (9)	0.0278 (4)
H3	−0.0496	0.7427	0.3136	0.042*
N1	0.2497 (2)	0.8010 (3)	0.23954 (10)	0.0228 (4)
H1A	0.2320	0.6848	0.2101	0.027*
H1B	0.3386	0.8674	0.2318	0.027*
H1C	0.1682	0.8931	0.2297	0.027*
C1	0.2672 (2)	0.7304 (3)	0.31806 (12)	0.0222 (5)
C2	0.1335 (3)	0.5753 (4)	0.32623 (13)	0.0262 (5)
H2A	0.1569	0.4334	0.3069	0.031*
H2B	0.1280	0.5578	0.3785	0.031*
C3	0.2617 (3)	0.9309 (4)	0.36617 (13)	0.0283 (5)
H3A	0.1551	0.9919	0.3572	0.034*
H3B	0.2854	0.8888	0.4179	0.034*
C4	0.4261 (3)	0.6174 (4)	0.33775 (13)	0.0274 (5)
H4A	0.5105	0.7245	0.3390	0.033*
H4B	0.4340	0.5544	0.3869	0.033*
F1	0.9653 (4)	0.7549 (5)	0.4913 (2)	0.1536 (18)
F2	0.8144 (3)	0.5578 (3)	0.42180 (12)	0.0720 (7)
F3	0.7347 (5)	0.7020 (5)	0.50960 (16)	0.1421 (17)
O4	0.8379 (2)	0.9534 (3)	0.35771 (10)	0.0412 (5)
O5	0.6631 (2)	1.0433 (4)	0.42917 (12)	0.0490 (6)
C5	0.8217 (4)	0.7380 (5)	0.45986 (15)	0.0476 (8)
C6	0.7677 (3)	0.9331 (4)	0.41107 (13)	0.0305 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0273 (8)	0.0234 (8)	0.0455 (10)	0.0040 (7)	0.0114 (7)	−0.0019 (7)
O2	0.0306 (9)	0.0218 (8)	0.0464 (10)	−0.0048 (7)	0.0010 (7)	−0.0019 (7)
O3	0.0198 (8)	0.0282 (8)	0.0354 (9)	−0.0011 (6)	0.0050 (6)	−0.0026 (7)
N1	0.0198 (9)	0.0204 (9)	0.0285 (10)	−0.0003 (7)	0.0049 (7)	−0.0001 (7)
C1	0.0205 (10)	0.0197 (10)	0.0265 (11)	0.0002 (8)	0.0039 (8)	−0.0004 (8)
C2	0.0219 (10)	0.0230 (11)	0.0342 (12)	−0.0021 (9)	0.0055 (9)	0.0031 (9)
C3	0.0304 (11)	0.0226 (11)	0.0324 (12)	−0.0016 (9)	0.0063 (9)	−0.0033 (9)
C4	0.0225 (10)	0.0233 (11)	0.0353 (12)	0.0018 (9)	0.0011 (9)	0.0000 (9)
F1	0.140 (3)	0.0813 (19)	0.190 (3)	−0.0144 (18)	−0.122 (3)	0.057 (2)
F2	0.1160 (18)	0.0335 (10)	0.0696 (13)	0.0116 (11)	0.0240 (12)	0.0072 (9)
F3	0.260 (5)	0.099 (2)	0.099 (2)	0.064 (3)	0.124 (3)	0.0499 (17)
O4	0.0514 (11)	0.0379 (10)	0.0361 (10)	0.0140 (9)	0.0126 (8)	0.0091 (8)
O5	0.0337 (10)	0.0566 (13)	0.0558 (13)	0.0119 (9)	0.0047 (9)	−0.0129 (10)
C5	0.072 (2)	0.0389 (16)	0.0323 (14)	0.0066 (15)	0.0093 (14)	0.0041 (12)
C6	0.0277 (11)	0.0311 (13)	0.0311 (12)	0.0014 (10)	−0.0006 (9)	−0.0031 (10)

Geometric parameters (Å, º) top

O1—C4	1.400 (3)	C2—H2A	0.9700
O1—H1	0.8197	C2—H2B	0.9700
O2—C3	1.400 (3)	C3—H3A	0.9700
O2—H2	0.8202	C3—H3B	0.9700
O3—C2	1.405 (3)	C4—H4A	0.9700
O3—H3	0.8207	C4—H4B	0.9700
N1—C1	1.483 (3)	F1—C5	1.268 (4)
N1—H1A	0.8904	F2—C5	1.300 (4)
N1—H1B	0.8906	F3—C5	1.282 (4)
N1—H1C	0.8895	O4—C6	1.230 (3)
C1—C2	1.508 (3)	O5—C6	1.206 (3)
C1—C4	1.510 (3)	C5—C6	1.517 (4)
C1—C3	1.515 (3)

C4—O1—H1	109.4	O2—C3—C1	111.74 (19)
C3—O2—H2	109.4	O2—C3—H3A	109.3
C2—O3—H3	109.5	C1—C3—H3A	109.3
C1—N1—H1A	109.5	O2—C3—H3B	109.3
C1—N1—H1B	109.4	C1—C3—H3B	109.3
H1A—N1—H1B	109.4	H3A—C3—H3B	107.9
C1—N1—H1C	109.5	O1—C4—C1	112.42 (18)
H1A—N1—H1C	109.5	O1—C4—H4A	109.1
H1B—N1—H1C	109.5	C1—C4—H4A	109.1
N1—C1—C2	108.68 (18)	O1—C4—H4B	109.1
N1—C1—C4	108.04 (18)	C1—C4—H4B	109.1
C2—C1—C4	110.46 (18)	H4A—C4—H4B	107.9
N1—C1—C3	108.54 (18)	F1—C5—F3	108.6 (4)
C2—C1—C3	110.94 (18)	F1—C5—F2	105.7 (3)
C4—C1—C3	110.10 (18)	F3—C5—F2	104.5 (3)
O3—C2—C1	113.05 (18)	F1—C5—C6	112.3 (3)
O3—C2—H2A	109.0	F3—C5—C6	113.4 (3)
C1—C2—H2A	109.0	F2—C5—C6	111.7 (2)
O3—C2—H2B	109.0	O5—C6—O4	129.6 (3)
C1—C2—H2B	109.0	O5—C6—C5	116.5 (2)
H2A—C2—H2B	107.8	O4—C6—C5	113.9 (2)

N1—C1—C2—O3	−44.3 (2)	C3—C1—C4—O1	−170.24 (18)
C4—C1—C2—O3	−162.62 (19)	F1—C5—C6—O5	−115.9 (4)
C3—C1—C2—O3	75.0 (2)	F3—C5—C6—O5	7.7 (4)
N1—C1—C3—O2	−52.4 (2)	F2—C5—C6—O5	125.5 (3)
C2—C1—C3—O2	−171.71 (19)	F1—C5—C6—O4	64.8 (4)
C4—C1—C3—O2	65.7 (2)	F3—C5—C6—O4	−171.6 (3)
N1—C1—C4—O1	−51.9 (2)	F2—C5—C6—O4	−53.8 (4)
C2—C1—C4—O1	66.9 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.82	1.86	2.644 (2)	159
O2—H2···O5	0.82	1.86	2.673 (3)	170
O3—H3···O4ⁱⁱ	0.82	1.87	2.677 (3)	170
N1—H1A···O4ⁱⁱⁱ	0.89	1.91	2.795 (3)	171
N1—H1B···O1^iv	0.89	1.98	2.854 (2)	168
N1—H1C···O3^v	0.89	2.02	2.899 (2)	169

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

Experimental details

Crystal data
Chemical formula	C₄H₁₂NO₃⁺·C₂F₃O₂⁻
M_r	235.17
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	8.5137 (17), 6.1210 (12), 18.283 (4)
β (°)	99.34 (3)
V (Å³)	940.1 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.18
Crystal size (mm)	0.36 × 0.32 × 0.28

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.963, 0.971
No. of measured, independent and observed [I > 2σ(I)] reflections	9320, 2148, 1755
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.061, 0.155, 1.02
No. of reflections	2148
No. of parameters	137
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.62, −0.57

Computer programs: CrystalClear (Rigaku, 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—H1···O2ⁱ	0.82	1.86	2.644 (2)	159.1
O2—H2···O5	0.82	1.86	2.673 (3)	170.2
O3—H3···O4ⁱⁱ	0.82	1.87	2.677 (3)	169.8
N1—H1A···O4ⁱⁱⁱ	0.89	1.91	2.795 (3)	171.2
N1—H1B···O1^iv	0.89	1.98	2.854 (2)	168.1
N1—H1C···O3^v	0.89	2.02	2.899 (2)	169.1

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

Acknowledgements

The author thanks an anonymous advisor from the Ordered Matter Science Research Centre, Southeast University, for great help in the revision of this paper.

References

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