Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010000809X/sk1378sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010000809X/sk1378Isup2.hkl |
CCDC reference: 150370
Large colourless crystals of tabular form were obtained after one day evaporation of the solution obtained from adding an excess of trifluoroacetic acid (Aldrich, 99%) directly to 1 g of pure sarcosine as purchased from Aldrich (98%). Most of these crystals were too big to be used on the X-ray diffractometer and had to be cut. However, twinned crystals were systematically obtained under application of pressure. Therefore, a small single-crystal cast as grown from the solution was used and checked prior to data collection by photographic methods.
All H atoms were located on a difference Fourier map and refined isotropically.
Examination of the crystal structure with PLATON (Spek, 1995) showed that there are no solvent-accessible voids in the crystal lattice. All calculations were performed on a Pentium 350 MHz PC running LINUX.
Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: HELENA (Spek, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.
C3H8NO2+·C2F3O2− | F(000) = 832 |
Mr = 203.12 | Dx = 1.666 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 14.5912 (19) Å | Cell parameters from 25 reflections |
b = 7.0951 (11) Å | θ = 7.1–18.0° |
c = 15.8414 (13) Å | µ = 0.18 mm−1 |
β = 99.138 (8)° | T = 293 K |
V = 1619.2 (4) Å3 | Block, clear, colourless |
Z = 8 | 0.45 × 0.40 × 0.15 mm |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.011 |
Radiation source: fine-focus sealed tube | θmax = 30.0°, θmin = 3.2° |
Graphite monochromator | h = 0→20 |
profile data from ω–2θ scans | k = 0→9 |
2462 measured reflections | l = −22→22 |
2350 independent reflections | 3 standard reflections every 180 min |
1883 reflections with I > 2σ(I) | intensity decay: 10% |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.056 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.179 | Difmap |
S = 1.04 | w = 1/[σ2(Fo2) + (0.1088P)2 + 1.4397P] where P = (Fo2 + 2Fc2)/3 |
2350 reflections | (Δ/σ)max < 0.001 |
150 parameters | Δρmax = 0.63 e Å−3 |
0 restraints | Δρmin = −0.38 e Å−3 |
C3H8NO2+·C2F3O2− | V = 1619.2 (4) Å3 |
Mr = 203.12 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 14.5912 (19) Å | µ = 0.18 mm−1 |
b = 7.0951 (11) Å | T = 293 K |
c = 15.8414 (13) Å | 0.45 × 0.40 × 0.15 mm |
β = 99.138 (8)° |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.011 |
2462 measured reflections | 3 standard reflections every 180 min |
2350 independent reflections | intensity decay: 10% |
1883 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.056 | 0 restraints |
wR(F2) = 0.179 | Difmap |
S = 1.04 | Δρmax = 0.63 e Å−3 |
2350 reflections | Δρmin = −0.38 e Å−3 |
150 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.25143 (10) | 0.0700 (2) | 0.36853 (10) | 0.0296 (3) | |
O1 | 0.30053 (11) | 0.1504 (2) | 0.43438 (9) | 0.0456 (4) | |
O2 | 0.23728 (10) | 0.1290 (2) | 0.29639 (9) | 0.0427 (3) | |
C2 | 0.21252 (11) | −0.1155 (2) | 0.39371 (10) | 0.0293 (3) | |
N | 0.15374 (11) | −0.2048 (2) | 0.32066 (10) | 0.0327 (3) | |
C3 | 0.12451 (15) | −0.3983 (3) | 0.33993 (16) | 0.0427 (4) | |
H1 | 0.319 (3) | 0.257 (5) | 0.418 (2) | 0.078 (10)* | |
H2 | 0.1784 (17) | −0.098 (3) | 0.4359 (15) | 0.039 (6)* | |
H3 | 0.2669 (18) | −0.199 (4) | 0.4143 (16) | 0.042 (6)* | |
H4 | 0.180 (2) | −0.208 (4) | 0.276 (2) | 0.057 (8)* | |
H5 | 0.105 (2) | −0.140 (4) | 0.3074 (18) | 0.054 (7)* | |
H6 | 0.092 (2) | −0.440 (5) | 0.293 (2) | 0.071 (9)* | |
H7 | 0.181 (3) | −0.466 (6) | 0.355 (2) | 0.087 (11)* | |
H8 | 0.091 (2) | −0.374 (5) | 0.386 (2) | 0.070 (9)* | |
C4 | −0.07118 (11) | 0.0083 (2) | 0.38100 (10) | 0.0305 (3) | |
O3 | −0.14113 (10) | −0.0119 (2) | 0.41607 (11) | 0.0457 (4) | |
O4 | −0.03378 (10) | −0.1039 (2) | 0.33831 (10) | 0.0448 (4) | |
C5 | −0.02818 (12) | 0.2064 (2) | 0.39269 (13) | 0.0384 (4) | |
F1 | 0.06028 (10) | 0.2099 (2) | 0.38432 (17) | 0.0864 (7) | |
F2 | −0.07389 (12) | 0.3281 (2) | 0.33934 (13) | 0.0768 (5) | |
F3 | −0.03152 (16) | 0.2770 (3) | 0.47001 (12) | 0.0853 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0271 (6) | 0.0275 (7) | 0.0365 (7) | −0.0010 (5) | 0.0116 (5) | −0.0013 (5) |
O1 | 0.0550 (8) | 0.0379 (7) | 0.0435 (7) | −0.0171 (6) | 0.0061 (6) | −0.0042 (6) |
O2 | 0.0469 (7) | 0.0416 (7) | 0.0403 (7) | −0.0089 (6) | 0.0091 (5) | 0.0081 (5) |
C2 | 0.0301 (7) | 0.0277 (7) | 0.0306 (7) | −0.0023 (5) | 0.0065 (5) | 0.0010 (5) |
N | 0.0328 (7) | 0.0289 (6) | 0.0365 (7) | −0.0037 (5) | 0.0058 (5) | −0.0016 (5) |
C3 | 0.0417 (9) | 0.0279 (8) | 0.0602 (12) | −0.0076 (7) | 0.0131 (9) | −0.0052 (8) |
C4 | 0.0287 (7) | 0.0274 (7) | 0.0356 (7) | −0.0011 (5) | 0.0059 (6) | −0.0008 (5) |
O3 | 0.0413 (7) | 0.0339 (6) | 0.0681 (9) | −0.0085 (5) | 0.0274 (6) | −0.0072 (6) |
O4 | 0.0413 (7) | 0.0446 (7) | 0.0508 (8) | 0.0036 (6) | 0.0143 (6) | −0.0127 (6) |
C5 | 0.0310 (8) | 0.0301 (8) | 0.0547 (10) | −0.0023 (6) | 0.0083 (7) | 0.0024 (7) |
F1 | 0.0375 (7) | 0.0527 (9) | 0.175 (2) | −0.0101 (6) | 0.0360 (9) | 0.0030 (10) |
F2 | 0.0764 (11) | 0.0464 (8) | 0.1021 (13) | 0.0012 (7) | −0.0026 (9) | 0.0310 (8) |
F3 | 0.1138 (15) | 0.0669 (10) | 0.0770 (11) | −0.0331 (10) | 0.0204 (10) | −0.0331 (9) |
C1—O2 | 1.204 (2) | C3—H6 | 0.87 (4) |
C1—O1 | 1.300 (2) | C3—H7 | 0.95 (4) |
C1—C2 | 1.512 (2) | C3—H8 | 0.96 (4) |
O1—H1 | 0.86 (4) | C4—O4 | 1.227 (2) |
C2—N | 1.470 (2) | C4—O3 | 1.245 (2) |
C2—H2 | 0.90 (3) | C4—C5 | 1.538 (2) |
C2—H3 | 1.00 (3) | C5—F2 | 1.314 (2) |
N—C3 | 1.484 (2) | C5—F1 | 1.319 (2) |
N—H4 | 0.86 (3) | C5—F3 | 1.331 (3) |
N—H5 | 0.84 (3) | ||
O2—C1—O1 | 126.80 (16) | N—C3—H6 | 106 (2) |
O2—C1—C2 | 122.55 (15) | N—C3—H7 | 105 (3) |
O1—C1—C2 | 110.65 (14) | H6—C3—H7 | 112 (3) |
C1—O1—H1 | 108 (2) | N—C3—H8 | 101 (2) |
N—C2—C1 | 111.35 (13) | H6—C3—H8 | 116 (3) |
N—C2—H2 | 108.7 (15) | H7—C3—H8 | 115 (3) |
C1—C2—H2 | 110.4 (16) | O4—C4—O3 | 129.71 (16) |
N—C2—H3 | 109.4 (15) | O4—C4—C5 | 116.77 (15) |
C1—C2—H3 | 106.9 (15) | O3—C4—C5 | 113.51 (15) |
H2—C2—H3 | 110 (2) | F2—C5—F1 | 109.15 (18) |
C2—N—C3 | 112.81 (15) | F2—C5—F3 | 104.80 (19) |
C2—N—H4 | 113 (2) | F1—C5—F3 | 105.36 (19) |
C3—N—H4 | 109 (2) | F2—C5—C4 | 111.55 (15) |
C2—N—H5 | 109 (2) | F1—C5—C4 | 113.09 (16) |
C3—N—H5 | 108 (2) | F3—C5—C4 | 112.39 (16) |
H4—N—H5 | 106 (3) | ||
O2—C1—C2—N | −2.5 (2) | O4—C4—C5—F1 | −24.4 (3) |
O1—C1—C2—N | 177.75 (14) | O3—C4—C5—F1 | 156.8 (2) |
C1—C2—N—C3 | 172.39 (14) | O4—C4—C5—F3 | −143.6 (2) |
O4—C4—C5—F2 | 99.1 (2) | O3—C4—C5—F3 | 37.7 (2) |
O3—C4—C5—F2 | −79.7 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O3i | 0.84 (4) | 1.76 (4) | 2.575 (2) | 163 (4) |
N—H4···O2ii | 0.85 (3) | 2.14 (3) | 2.880 (2) | 146 (3) |
N—H5···O4iii | 0.84 (3) | 2.40 (3) | 2.918 (2) | 121 (3) |
N—H5···O4 | 0.84 (3) | 2.18 (3) | 2.885 (2) | 141 (3) |
Symmetry codes: (i) x+1/2, y+1/2, z; (ii) −x+1/2, y−1/2, −z+1/2; (iii) −x, y, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C3H8NO2+·C2F3O2− |
Mr | 203.12 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 14.5912 (19), 7.0951 (11), 15.8414 (13) |
β (°) | 99.138 (8) |
V (Å3) | 1619.2 (4) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.18 |
Crystal size (mm) | 0.45 × 0.40 × 0.15 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2462, 2350, 1883 |
Rint | 0.011 |
(sin θ/λ)max (Å−1) | 0.704 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.056, 0.179, 1.04 |
No. of reflections | 2350 |
No. of parameters | 150 |
H-atom treatment | Difmap |
Δρmax, Δρmin (e Å−3) | 0.63, −0.38 |
Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software, HELENA (Spek, 1997), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97.
C1—O2 | 1.204 (2) | C4—O3 | 1.245 (2) |
C1—O1 | 1.300 (2) | C4—C5 | 1.538 (2) |
C1—C2 | 1.512 (2) | C5—F2 | 1.314 (2) |
C2—N | 1.470 (2) | C5—F1 | 1.319 (2) |
N—C3 | 1.484 (2) | C5—F3 | 1.331 (3) |
C4—O4 | 1.227 (2) | ||
O2—C1—O1 | 126.80 (16) | O4—C4—O3 | 129.71 (16) |
O2—C1—C2—N | −2.5 (2) | C1—C2—N—C3 | 172.39 (14) |
O1—C1—C2—N | 177.75 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O3i | 0.84 (4) | 1.76 (4) | 2.575 (2) | 163 (4) |
N—H4···O2ii | 0.85 (3) | 2.14 (3) | 2.880 (2) | 146 (3) |
N—H5···O4iii | 0.84 (3) | 2.40 (3) | 2.918 (2) | 121 (3) |
N—H5···O4 | 0.84 (3) | 2.18 (3) | 2.885 (2) | 141 (3) |
Symmetry codes: (i) x+1/2, y+1/2, z; (ii) −x+1/2, y−1/2, −z+1/2; (iii) −x, y, −z+1/2. |
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Sarcosine (N-methylglycine, CH3NH2+CH2COO−) is an α-amino acid found in many biological materials and also used in cosmetics (Meister, 1965).
In pure form sarcosine exists as a zwitterion, where the carboxylic proton has been transferred to the amino group. As most aminoacids, sarcosine has an amphoteric character, being able to accept a proton at the carboxylate group from even moderately weak acids, and to donate the amino proton in basic environments. The anionic form of sarcosine is a well known chelating agent of 3 d and 4 d transition metals (Guha, 1973; Krishnakumar et al., 1994; Darensbourg et al., 1994). On the other hand, structural data on compounds where sarcosine is in the cationic form are rather scarce.
Our main interest in sarcosine compounds relates to their physical properties. The most well known sarcosine compound, tris(sarcosine) calcium chloride (TSCC), undergoes a ferroelectric transition at Tc = 127 K (Pepinsky & Makita, 1962). Its crystal structure both in the paraelectric phase at room temperature (Ashida et al., 1972) and in the ferroelectric phase (Mishima et al., 1984) have been reported. Another closely related compound, which also shows a `devil stair' series of phase transitions is betaine (trimethylglycine) calcium chloride (BCCD) (Almeida et al., 1992). A number of simple salts of betaine show ferroelectric or antiferroelectric phase transitions at low temperature as well as ferroelastic behaviour inducing phase transitions to both commensurate and incommensurate superstructures (Shildkamp & Spilker, 1984; Haussül, 1984, 1988). Therefore it is reasonable to expect that simple salts of sarcosine also show interesting properties at low temperature. The trifluoroacetic acid is a very strong carboxylic acid due to the charge withdrawing effect of the fluorine atoms on the Cα atom. Its dissociation constant is K = 0.66 mol dm−3 (Strehlow & Hildebrandt, 1990), as determined by Raman spectroscopy. Phase transitions at low temperature on crystalline trifluoroacetic acid tetrahydrate have been recently discovered on undeuterated and deuterated samples (Mootz & Schilling, 1992). Thus, sarcosinium trifluoroacetate is expected to be a good candidate to exhibit phase transitions and superstructures at low temperature. This is the first report of a research project on a systematic study of the structural and physical properties of sarcosine compounds. The present study, performed at room temperature, will be completed by other low-temperature structural and spectroscopic studies.
The ionization states of sarcosine and trifluoroacetic acid molecules were determined from the objective localization of the H atoms bonded to the carboxylic groups but could easily be inferred from the bond distances within these groups. The sarcosine molecule exists in cationic form with a mono-positively charged amino group and a neutral carboxylic group in agreement with the large asymmetry between the C–O bond lengths of this functional group. The trifluoroacetate molecules are found in the ionized state, as expected from the strength of the acid and the required charge neutrality of the salt.
The sarcosine carboxy skeleton which includes atoms O1, O2, C1 and C2 is planar within 0.0015 (13) Å. The N atom is slightly displaced out of this plane by −0.0557 (30) Å, corresponding to a small rotation around the single C1–C2 bond. The relevant torsion angles are O1–C1–C2–N [177.75 (14)°] and O2–C1–C2–N [−2.5 (2)°]. These values are to be compared with the corresponding ones in pure sarcosine, 173.7 (2) and −6.8 (2)°, respectively (Mostad & Natarajan, 1989), which is more distorted from planarity. The methyl group breaks the almost perfect planarity of the main chain. The torsional angle C1—C2—N—C3 is 172.39 (14)° and the C3 atom is 0.1256 (46) Å away from the plane, in the opposite direction of the N atom. This deviation of the methyl group from the plane of the main skeleton is, however, smaller than that observed in pure sarcosine for which the torsion angle is −166.3° (Mostad & Natarajan, 1989).
The trifluoroacetate anion has a staggered conformation as indicated by the torsional angle O4—C4—C5—F1 of −24.4 (3)°. The geometry of the CF3 group is similar to that found in other structures (Nahringbauer et al., 1979) with an average C–F bond length and F–C–F angles of 1.32 (12) and 106 (2)°, respectively. The average F–C–C angle is 112 (1)°. The carboxylate group of the anion is planar within 0.0065 (14) Å; the C4—C5 bond length [1.539 (2) Å] is longer than the average Csp3—Csp2 bond but is within the normal range of values found in trifluoroacetic acid and trifluoroacetate compounds (Lundgren, 1978).
It should be pointed out that the atomic displacement tensors of the F atoms have a strong anisotropic character which indicates some disorder, probably of dynamic nature, of these atoms. As is often found in trifluoroacetate compounds, it is plausible that at room temperature the CF3 groups rotate undergoing angular oscillations around the single C–C bond. Such a minor disorder may account for the relatively large final R and wR values.
The sarcosine cations interact directly, via hydrogen-bonds, with two other neighbouring sarcosine molecules and three trifluoroacetate anions. The N atom is only bonded to two H atoms but is engaged in three hydrogen bonds as a donor. One of the two H atoms is shared between two carboxylate O atoms of two distinct trifluoroacetate anions in a bifurcated hydrogen bond. The other H atom is shared with the unprotonated O atom of another sarcosine molecule. The N–H···O distances and angles are in the range 2.880 (2)–2.919 (2) Å and 121 (3)–146 (3)°, respectively, which allows a classification of these hydrogen bonds as relatively weak.
The strongest hydrogen bond in the title compound involves the carboxylic O atom of the cation as a donor and a carboxylate O atom of the anion as an acceptor [O–H···O 2.575 (2) Å; O–H–O 163 (4)°].
Like other carboxylic acid complexes viz. D-tryptophan hydrogen oxalate (Bakke & Mostad, 1980) and L-histidine oxalate and DL-histidine oxalate (Prabu et al., 1996), the present compound has no solvate molecules in which it differs from the more closely related complex sarcosine hydrogen oxalate (Krishnakumar et al., 1998).