Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100012440/vj1116sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100012440/vj1116Isup2.hkl |
CCDC reference: 159986
For related literature, see: Hahn (1957); Mostad & Natarajan (1989); Okaya et al. (1966); Prasad & Vijayan (1993); Vijayan (1988).
Colourless single crystals of the title complex were grown as transparent plates from a saturated aqueous solution containing sarcosine and tartaric acid in a 1:1 stoichiometric ratio.
All the H atoms were located from a difference Fourier map and then allowed for as riding atoms (C—H 0.96–0.98, N—H 0.90 and O—H 0.82 Å). The absolute configuration of this light-atom structure was not established by the analysis but is known from the configuration of the starting reagents.
Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: CAD-4 Software; program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1993); molecular graphics: PLATON (Spek, 1999); software used to prepare material for publication: SHELXL97.
Fig. 1. The molecular structure of (I) with the atom-numbering scheme and 50% probability displacement ellipsoids. | |
Fig. 2. A view showing some of the O—H.·O and N—H···O hydrogen bonds in (I). |
C3H8NO2+·C4H5O6− | Z = 1 |
Mr = 239.18 | F(000) = 126 |
Triclinic, P1 | Dx = 1.549 Mg m−3 Dm = 1.54 Mg m−3 Dm measured by flotation in carbon tetrachloride/xylene |
a = 5.0038 (15) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 6.442 (2) Å | Cell parameters from 25 reflections |
c = 8.3179 (11) Å | θ = 4–17° |
α = 78.60 (2)° | µ = 0.14 mm−1 |
β = 80.62 (2)° | T = 293 K |
γ = 79.80 (2)° | Plate, colourless |
V = 256.40 (11) Å3 | 0.45 × 0.30 × 0.20 mm |
Enraf-Nonius sealed tube diffractometer | Rint = 0.032 |
Radiation source: fine-focus sealed tube | θmax = 24.9°, θmin = 2.5° |
Graphite monochromator | h = 0→5 |
/w–2/q scans | k = −7→7 |
1012 measured reflections | l = −9→9 |
897 independent reflections | 2 standard reflections every 200 reflections |
897 reflections with I > 2σ(I) | intensity decay: 0.1% |
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)] = 0.025 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.066 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0497P)2 + 0.0215P] where P = (Fo2 + 2Fc2)/3 |
897 reflections | (Δ/σ)max < 0.001 |
150 parameters | Δρmax = 0.18 e Å−3 |
3 restraints | Δρmin = −0.19 e Å−3 |
C3H8NO2+·C4H5O6− | γ = 79.80 (2)° |
Mr = 239.18 | V = 256.40 (11) Å3 |
Triclinic, P1 | Z = 1 |
a = 5.0038 (15) Å | Mo Kα radiation |
b = 6.442 (2) Å | µ = 0.14 mm−1 |
c = 8.3179 (11) Å | T = 293 K |
α = 78.60 (2)° | 0.45 × 0.30 × 0.20 mm |
β = 80.62 (2)° |
Enraf-Nonius sealed tube diffractometer | Rint = 0.032 |
1012 measured reflections | 2 standard reflections every 200 reflections |
897 independent reflections | intensity decay: 0.1% |
897 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.025 | 3 restraints |
wR(F2) = 0.066 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.18 e Å−3 |
897 reflections | Δρmin = −0.19 e Å−3 |
150 parameters |
Experimental. 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. |
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 | ||
O3 | −0.0485 (3) | 0.4666 (2) | 0.07007 (19) | 0.0354 (4) | |
H3 | −0.1735 | 0.5612 | 0.0933 | 0.053* | |
O4 | 0.0500 (3) | 0.4743 (2) | 0.32013 (18) | 0.0320 (4) | |
O5 | 0.4989 (3) | 0.1832 (2) | 0.28080 (17) | 0.0295 (3) | |
H5 | 0.6556 | 0.1309 | 0.2491 | 0.044* | |
O6 | 0.0631 (3) | −0.0296 (2) | 0.2265 (2) | 0.0328 (4) | |
H6 | 0.0848 | −0.1601 | 0.2336 | 0.049* | |
O7 | 0.5211 (3) | −0.2879 (2) | 0.1359 (2) | 0.0366 (4) | |
O8 | 0.6747 (3) | −0.0335 (3) | −0.0633 (2) | 0.0422 (4) | |
C4 | 0.1002 (4) | 0.4092 (3) | 0.1885 (2) | 0.0230 (4) | |
C5 | 0.3492 (4) | 0.2473 (3) | 0.1451 (2) | 0.0230 (4) | |
H5A | 0.4660 | 0.3158 | 0.0505 | 0.028* | |
C6 | 0.2535 (4) | 0.0579 (3) | 0.0958 (2) | 0.0240 (4) | |
H6A | 0.1600 | 0.1115 | −0.0024 | 0.029* | |
C7 | 0.5052 (4) | −0.1019 (3) | 0.0502 (2) | 0.0249 (4) | |
O1 | 0.1266 (4) | 0.8718 (3) | 0.7568 (3) | 0.0524 (5) | |
H1 | −0.0206 | 0.8733 | 0.8170 | 0.079* | |
O2 | −0.0014 (4) | 0.5979 (3) | 0.6783 (2) | 0.0520 (5) | |
N1 | 0.5001 (4) | 0.4999 (3) | 0.5004 (2) | 0.0308 (4) | |
H1A | 0.3609 | 0.4829 | 0.4503 | 0.037* | |
H1B | 0.6488 | 0.5070 | 0.4236 | 0.037* | |
C1 | 0.1595 (4) | 0.7180 (4) | 0.6725 (3) | 0.0327 (5) | |
C2 | 0.4290 (4) | 0.7057 (3) | 0.5633 (3) | 0.0318 (5) | |
H2A | 0.4208 | 0.8235 | 0.4705 | 0.038* | |
H2B | 0.5711 | 0.7202 | 0.6251 | 0.038* | |
C3 | 0.5565 (6) | 0.3089 (4) | 0.6298 (3) | 0.0431 (6) | |
H3A | 0.6885 | 0.3327 | 0.6935 | 0.065* | |
H3B | 0.6276 | 0.1859 | 0.5784 | 0.065* | |
H3C | 0.3899 | 0.2845 | 0.7014 | 0.065* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O3 | 0.0346 (8) | 0.0313 (8) | 0.0364 (8) | 0.0139 (6) | −0.0082 (6) | −0.0106 (6) |
O4 | 0.0238 (8) | 0.0367 (8) | 0.0361 (8) | 0.0012 (6) | 0.0021 (6) | −0.0178 (6) |
O5 | 0.0193 (7) | 0.0346 (8) | 0.0346 (7) | 0.0026 (6) | −0.0049 (6) | −0.0111 (6) |
O6 | 0.0242 (7) | 0.0231 (7) | 0.0478 (9) | −0.0023 (6) | 0.0054 (6) | −0.0077 (6) |
O7 | 0.0279 (8) | 0.0227 (7) | 0.0523 (9) | 0.0051 (6) | 0.0014 (7) | −0.0033 (6) |
O8 | 0.0397 (9) | 0.0346 (8) | 0.0410 (9) | 0.0064 (7) | 0.0124 (7) | −0.0049 (7) |
C4 | 0.0225 (9) | 0.0171 (8) | 0.0280 (9) | −0.0026 (7) | 0.0017 (7) | −0.0050 (7) |
C5 | 0.0206 (9) | 0.0194 (9) | 0.0274 (9) | 0.0002 (7) | −0.0004 (7) | −0.0057 (7) |
C6 | 0.0234 (9) | 0.0196 (9) | 0.0286 (9) | 0.0006 (7) | −0.0025 (7) | −0.0073 (7) |
C7 | 0.0228 (10) | 0.0216 (9) | 0.0301 (10) | 0.0027 (7) | −0.0039 (7) | −0.0085 (8) |
O1 | 0.0378 (10) | 0.0583 (11) | 0.0659 (13) | −0.0108 (8) | 0.0153 (9) | −0.0371 (10) |
O2 | 0.0260 (8) | 0.0789 (14) | 0.0622 (12) | −0.0182 (8) | 0.0054 (7) | −0.0388 (11) |
N1 | 0.0255 (9) | 0.0354 (9) | 0.0295 (8) | −0.0012 (7) | 0.0010 (7) | −0.0076 (8) |
C1 | 0.0220 (10) | 0.0463 (12) | 0.0310 (11) | −0.0009 (9) | −0.0042 (8) | −0.0127 (9) |
C2 | 0.0272 (11) | 0.0325 (11) | 0.0346 (10) | −0.0024 (9) | 0.0003 (9) | −0.0091 (9) |
C3 | 0.0491 (15) | 0.0362 (12) | 0.0419 (13) | −0.0048 (10) | −0.0103 (11) | 0.0003 (10) |
O3—C4 | 1.288 (3) | O1—C1 | 1.297 (3) |
O3—H3 | 0.82 | O1—H1 | 0.82 |
O4—C4 | 1.222 (3) | O2—C1 | 1.201 (3) |
O5—C5 | 1.410 (2) | N1—C3 | 1.485 (3) |
O5—H5 | 0.82 | N1—C2 | 1.485 (3) |
O6—C6 | 1.421 (2) | N1—H1A | 0.90 |
O6—H6 | 0.82 | N1—H1B | 0.90 |
O7—C7 | 1.264 (3) | C1—C2 | 1.497 (3) |
O8—C7 | 1.230 (3) | C2—H2A | 0.97 |
C4—C5 | 1.521 (2) | C2—H2B | 0.97 |
C5—C6 | 1.535 (3) | C3—H3A | 0.96 |
C5—H5A | 0.98 | C3—H3B | 0.96 |
C6—C7 | 1.526 (3) | C3—H3C | 0.96 |
C6—H6A | 0.98 | ||
C4—O3—H3 | 109.5 | C3—N1—C2 | 114.31 (18) |
C5—O5—H5 | 109.5 | C3—N1—H1A | 108.7 |
C6—O6—H6 | 109.5 | C2—N1—H1A | 108.7 |
O4—C4—O3 | 125.00 (18) | C3—N1—H1B | 108.7 |
O4—C4—C5 | 123.51 (18) | C2—N1—H1B | 108.7 |
O3—C4—C5 | 111.49 (16) | H1A—N1—H1B | 107.6 |
O5—C5—C4 | 109.31 (15) | O2—C1—O1 | 125.7 (2) |
O5—C5—C6 | 112.34 (15) | O2—C1—C2 | 122.8 (2) |
C4—C5—C6 | 109.02 (15) | O1—C1—C2 | 111.4 (2) |
O5—C5—H5A | 108.7 | N1—C2—C1 | 111.55 (18) |
C4—C5—H5A | 108.7 | N1—C2—H2A | 109.3 |
C6—C5—H5A | 108.7 | C1—C2—H2A | 109.3 |
O6—C6—C7 | 113.96 (15) | N1—C2—H2B | 109.3 |
O6—C6—C5 | 109.09 (16) | C1—C2—H2B | 109.3 |
C7—C6—C5 | 108.55 (16) | H2A—C2—H2B | 108.0 |
O6—C6—H6A | 108.4 | N1—C3—H3A | 109.5 |
C7—C6—H6A | 108.4 | N1—C3—H3B | 109.5 |
C5—C6—H6A | 108.4 | H3A—C3—H3B | 109.5 |
O8—C7—O7 | 126.99 (18) | N1—C3—H3C | 109.5 |
O8—C7—C6 | 116.21 (17) | H3A—C3—H3C | 109.5 |
O7—C7—C6 | 116.76 (17) | H3B—C3—H3C | 109.5 |
C1—O1—H1 | 109.5 | ||
O4—C4—C5—O5 | 2.0 (3) | O6—C6—C7—O8 | 179.50 (17) |
O3—C4—C5—O5 | −177.64 (16) | C5—C6—C7—O8 | −58.7 (2) |
O4—C4—C5—C6 | 125.2 (2) | O6—C6—C7—O7 | −2.5 (3) |
O3—C4—C5—C6 | −54.5 (2) | C5—C6—C7—O7 | 119.23 (19) |
O5—C5—C6—O6 | 65.2 (2) | C3—N1—C2—C1 | −67.0 (2) |
C4—C5—C6—O6 | −56.08 (19) | O2—C1—C2—N1 | −14.7 (3) |
O5—C5—C6—C7 | −59.5 (2) | O1—C1—C2—N1 | 165.27 (19) |
C4—C5—C6—C7 | 179.21 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O8i | 0.82 | 1.76 | 2.548 (2) | 161 |
O3—H3···O7ii | 0.82 | 1.68 | 2.488 (2) | 166 |
O5—H5···O6iii | 0.82 | 2.11 | 2.918 (2) | 167 |
O6—H6···O4iv | 0.82 | 2.35 | 3.146 (2) | 163 |
N1—H1A···O4 | 0.90 | 2.05 | 2.946 (2) | 174 |
N1—H1B···O4iii | 0.90 | 2.04 | 2.905 (2) | 160 |
C2—H2B···O2iii | 0.97 | 2.23 | 3.074 (3) | 145 |
Symmetry codes: (i) x−1, y+1, z+1; (ii) x−1, y+1, z; (iii) x+1, y, z; (iv) x, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | C3H8NO2+·C4H5O6− |
Mr | 239.18 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 5.0038 (15), 6.442 (2), 8.3179 (11) |
α, β, γ (°) | 78.60 (2), 80.62 (2), 79.80 (2) |
V (Å3) | 256.40 (11) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.14 |
Crystal size (mm) | 0.45 × 0.30 × 0.20 |
Data collection | |
Diffractometer | Enraf-Nonius sealed tube diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1012, 897, 897 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.593 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.066, 1.09 |
No. of reflections | 897 |
No. of parameters | 150 |
No. of restraints | 3 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.18, −0.19 |
Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software, SHELXS86 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1993), PLATON (Spek, 1999), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O8i | 0.82 | 1.76 | 2.548 (2) | 161 |
O3—H3···O7ii | 0.82 | 1.68 | 2.488 (2) | 166 |
O5—H5···O6iii | 0.82 | 2.11 | 2.918 (2) | 167 |
O6—H6···O4iv | 0.82 | 2.35 | 3.146 (2) | 163 |
N1—H1A···O4 | 0.90 | 2.05 | 2.946 (2) | 174 |
N1—H1B···O4iii | 0.90 | 2.04 | 2.905 (2) | 160 |
C2—H2B···O2iii | 0.97 | 2.23 | 3.074 (3) | 145 |
Symmetry codes: (i) x−1, y+1, z+1; (ii) x−1, y+1, z; (iii) x+1, y, z; (iv) x, y−1, z. |
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Single-crystal X-ray investigations on complexes of amino acids with carboxylic acids are interesting in view of their geometrical features and aggregation patterns that might possibly have occurred in prebiotic polymerization (Vijayan, 1988; Prasad & Vijayan, 1993). The present study reports the crystal structure of a complex, (I), of sarcosine with tartaric acid. Sarcosine (N-methylglycine, CH3NH2+CH2COO-) is an α-amino acid present in several biologically important compounds and its crystal structure was elucidated in our laboratory (Mostad & Natarajan, 1989). \sch
The sarcosine moiety exists in the cationic form with a positively charged amino group and a neutral carboxylic acid group. The C1—C2—N1—C3 chain deviates greatly from planarity as the torsion angle about the C2—N1 bond is -67.2 (2)°, indicating that the methyl group exists in the synclinal conformation with respect to C1.
The tartaric acid molecule (Okaya et al., 1966) exists here as a semi-tartrate ion with a neutral carboxylic acid group and a negatively charged carboxylate ion. The C4—O3 and C4═O4 bond distances [1.288 (3) and 1.222 (3) Å, respectively] of the neutral carboxylic acid group are significantly different from those expected. The decrease in the C—O and increase in the C═O bond lengths may be attributed to a strong O3—H3···O7(x - 1, y + 1, z) hydrogen bond observed in the crystal structure, with an O···O distance of 2.488 (2) Å. This observation is supported by the fact that strong O—H···X hydrogen bonds involving the carboxylic acid group O atom as donor permit some double-bond character to the C—O and some single-bond character to C═O (Hahn, 1957). The angle between the planes of the half molecules (O3/O4/C4/C5/O5 and O7/O8/C6/C7/O6) is 65.10 (7)°, which is somewhat larger than the value of 54.6 (4)° found in the structure of tartaric acid. The carbon skeleton of the semi-tartrate anion is essentially planar [torsion angle C4—C5—C6—C7 179.21 (15)°].
The crystal structure (Fig. 2) is stabilized by hydrogen bonds (Table 1). The semi-tartrate ions aggregate into layers parallel to the ab plane. The layers are interconnected by sarcosinium Ccations which do not directly interact among themselves except for the presence of a weak C—H···O hydrogen bond. The crystal structure can be described as an inclusion compound with the semi-tartrate anion as the host and the sarcosinium cation as the guest.