Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106038583/ga3025sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106038583/ga3025Isup2.hkl |
CCDC reference: 258490
The preparation of (I) follows a slightly modified version of the literature procedure. CAUTION! Whilst no problems were encountered in the course of this work, hydrazine and hydrazides are potentially explosive and should therefore be handled with appropriate care. The use of a pure enantiomer of lactic acid, rather than the racemate, is necessary, as the latter always resulted in an oily mixture from which the desired product could not be separated.
Hydrazine hydrate (50 g, 49 ml, 1 mol) was cooled in an ice bath. S-lactic acid (53 g, 0.5 mol, 85% solution in water) was added dropwise with stirring, followed by heating to 373 K overnight. The flask was then equipped for downward distillation and the thermostat temperature was adjusted so as to increase slowly the internal temperature of the flask to 433 K over approximately 3 h (the mixture boils at ca 393 K). The flask was then maintained at 433 K overnight. Upon cooling to room temperature, the resulting straw-coloured oil solidified. The oily solid was dissolved in boiling MeCN (1.5 l). The solution was left to cool, producing a large quantity of white crystalline material, which was washed twice with MeCN (20 ml) and dried under reduced pressure to give a 1:1 mixture of (S,S)-4-amino-3,5-bis(1-hydroxyethyl)-1,2,4-triazole, (1), and (S,S)-1,2-bis(2-hydroxypropionyl)hydrazine, (2). Attempts to obtain a second crop by reducing the volume of the filtrate were unsuccessful, with any additional product oiling out. Use of a greater excess of hydrazine hydrate, longer reaction times or higher temperatures (CAUTION!) did not convert the open-chain intermediate, (2), into the desired triazole derivative, (1) (yield 17.3 g, 40%). Analysis: a 1:1 mixture of C6H12N4O2 and C6H12N2O4 requires: C 41.37, H 6.94, N 24.12%; found: C 41.65, H 6.96, N 24.42%. Suitable single crystals of (I) were grown from a hot dilute acetonitrile solution upon slowly cooling down overnight. Spectroscopic data are available in the archived CIF.
In the absence of significant anomalous scattering, the values of the Flack parameter (Flack, 1983) were indeterminate (Flack & Bernardinelli, 2000). The synthesis started from pure S-lactic acid. All C-bound H atoms were placed in calculated positions, with C—H = 0.98–1.00 Å, and treated as riding on their attached parent atom, with Uiso(H) = 1.2Ueq(C)[Please check added text]. All N– and O-bound H atoms were located in a difference map and their positions were freely refined, with Uiso(H) = 1.2Ueq(N,O).
Data collection: SMART (Bruker, 2000); cell refinement: SMART and SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: enCIFer (Version 1.2; Allen et al., 2004).
C6H12N4O2·C6H12N2O4 | Dx = 1.378 Mg m−3 |
Mr = 348.37 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, P43212 | Cell parameters from 3205 reflections |
a = 9.9296 (1) Å | θ = 3–25.8° |
c = 34.0538 (6) Å | µ = 0.11 mm−1 |
V = 3357.60 (8) Å3 | T = 150 K |
Z = 8 | Fragment, colourless |
F(000) = 1488 | 0.45 × 0.20 × 0.16 mm |
Bruker SMART CCD area-detector diffractometer | 3205 independent reflections |
Radiation source: fine-focus sealed tube | 3084 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.039 |
Type of scans? | θmax = 25.8°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −6→12 |
Tmin = 0.69, Tmax = 1.00 | k = −11→12 |
18817 measured reflections | l = −41→41 |
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)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.082 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0321P)2 + 1.2424P] where P = (Fo2 + 2Fc2)/3 |
3205 reflections | (Δ/σ)max < 0.001 |
245 parameters | Δρmax = 0.19 e Å−3 |
0 restraints | Δρmin = −0.16 e Å−3 |
C6H12N4O2·C6H12N2O4 | Z = 8 |
Mr = 348.37 | Mo Kα radiation |
Tetragonal, P43212 | µ = 0.11 mm−1 |
a = 9.9296 (1) Å | T = 150 K |
c = 34.0538 (6) Å | 0.45 × 0.20 × 0.16 mm |
V = 3357.60 (8) Å3 |
Bruker SMART CCD area-detector diffractometer | 3205 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3084 reflections with I > 2σ(I) |
Tmin = 0.69, Tmax = 1.00 | Rint = 0.039 |
18817 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.082 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | Δρmax = 0.19 e Å−3 |
3205 reflections | Δρmin = −0.16 e Å−3 |
245 parameters |
Experimental. 1H NMR (DMSO-d6, δ, p.p.m.): 1.23 [6H, dd, CH3, (2)], 1.50 [6H, d, CH3, (1)], 4.07 [2H, dq, CH, (2)], 4.92 [2H, dq, CH, (1)], 5.37 [2H, d, OH, (1)], 5.45 [2H, d, OH, (2)], 5.76 [2H, s, NH2, (1)], 9,49 [2H, s, NH, (2)]; 13C NMR (DMSO-d6, δ, p.p.m.): 21.1 [CH3, (2)], 21.2 [CH3, (1)], 59.5 [CH, (1)], 66.7 [CH, (2)], 156.6 [Cq, (1)], 173.1 [CO, (2)]; IR (ν, cm−1): 3378 (O—H), 3325 (N—H), 2984/2936 (C—H), 1681 (C=O), 1140, 1120; m.p. 450 K. |
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. All non-H ANIS. No solvate molecules. No disorder. H's on C's inserted at calculated positions and ride. H's on N's and O's found and xyz freely refined whilst U rides. All N—H and O—H involved in H-bonding. Absolute configuration not reliably determined by Flack x but started from S-lactic acid in the synthesis. Two different molecules in the asymmetric unit: one cyclic and one acyclic. |
x | y | z | Uiso*/Ueq | ||
N1 | 0.28745 (15) | 0.79829 (16) | 0.10999 (4) | 0.0261 (3) | |
N2 | 0.14882 (15) | 0.77320 (16) | 0.10495 (4) | 0.0255 (3) | |
C3 | 0.11056 (19) | 0.83841 (17) | 0.07337 (5) | 0.0235 (4) | |
N3 | 0.21777 (16) | 0.90556 (15) | 0.05782 (4) | 0.0236 (3) | |
N4 | 0.2160 (2) | 0.98844 (19) | 0.02443 (5) | 0.0431 (5) | |
H4X | 0.240 (3) | 0.946 (3) | 0.0015 (8) | 0.052* | |
H4Y | 0.192 (3) | 1.056 (3) | 0.0282 (8) | 0.052* | |
C5 | 0.32550 (17) | 0.87765 (17) | 0.08124 (5) | 0.0233 (4) | |
C6 | 0.46702 (18) | 0.92603 (18) | 0.07249 (5) | 0.0262 (4) | |
H6 | 0.4595 | 1.0124 | 0.0576 | 0.031* | |
C7 | 0.5394 (2) | 0.8248 (2) | 0.04619 (6) | 0.0342 (4) | |
H7A | 0.6284 | 0.8599 | 0.0391 | 0.041* | |
H7B | 0.4864 | 0.8100 | 0.0223 | 0.041* | |
H7C | 0.5498 | 0.7393 | 0.0603 | 0.041* | |
O1 | 0.53839 (13) | 0.95334 (13) | 0.10766 (4) | 0.0277 (3) | |
H1X | 0.562 (2) | 0.881 (2) | 0.1181 (6) | 0.033* | |
C8 | −0.02962 (18) | 0.84651 (18) | 0.05622 (5) | 0.0263 (4) | |
H8 | −0.0199 | 0.8531 | 0.0271 | 0.032* | |
C9 | −0.1000 (2) | 0.9740 (2) | 0.07009 (6) | 0.0362 (5) | |
H9A | −0.1871 | 0.9824 | 0.0568 | 0.043* | |
H9B | −0.0440 | 1.0524 | 0.0639 | 0.043* | |
H9C | −0.1143 | 0.9692 | 0.0985 | 0.043* | |
O2 | −0.10413 (13) | 0.72790 (13) | 0.06432 (4) | 0.0278 (3) | |
H2X | −0.127 (2) | 0.731 (2) | 0.0895 (7) | 0.033* | |
C10 | 0.8270 (2) | 0.9753 (2) | 0.21588 (7) | 0.0382 (5) | |
H10A | 0.8852 | 0.9221 | 0.2332 | 0.046* | |
H10B | 0.8741 | 1.0579 | 0.2081 | 0.046* | |
H10C | 0.8050 | 0.9225 | 0.1924 | 0.046* | |
C11 | 0.69820 (18) | 1.01167 (19) | 0.23748 (5) | 0.0273 (4) | |
H11 | 0.7216 | 1.0663 | 0.2612 | 0.033* | |
O10 | 0.62582 (14) | 0.89525 (15) | 0.24956 (4) | 0.0339 (3) | |
H10X | 0.681 (2) | 0.836 (2) | 0.2619 (6) | 0.041* | |
C12 | 0.60972 (18) | 1.09569 (18) | 0.21053 (5) | 0.0245 (4) | |
O11 | 0.64288 (14) | 1.21192 (13) | 0.20137 (4) | 0.0324 (3) | |
N10 | 0.49882 (16) | 1.03483 (16) | 0.19801 (4) | 0.0261 (3) | |
H10Y | 0.477 (2) | 0.950 (2) | 0.2023 (6) | 0.031* | |
N11 | 0.41675 (16) | 1.09436 (16) | 0.16980 (4) | 0.0276 (3) | |
H11X | 0.429 (2) | 1.069 (2) | 0.1454 (6) | 0.033* | |
C13 | 0.31341 (18) | 1.17292 (17) | 0.18025 (5) | 0.0251 (4) | |
O12 | 0.29042 (14) | 1.20549 (14) | 0.21459 (3) | 0.0313 (3) | |
C14 | 0.22251 (19) | 1.21754 (19) | 0.14684 (5) | 0.0290 (4) | |
H14 | 0.2126 | 1.3177 | 0.1477 | 0.035* | |
O13 | 0.28308 (16) | 1.18017 (16) | 0.11088 (4) | 0.0407 (4) | |
H13X | 0.238 (3) | 1.215 (3) | 0.0933 (7) | 0.049* | |
C15 | 0.0868 (2) | 1.1539 (3) | 0.15214 (7) | 0.0476 (6) | |
H15A | 0.0277 | 1.1807 | 0.1305 | 0.057* | |
H15B | 0.0477 | 1.1837 | 0.1771 | 0.057* | |
H15C | 0.0964 | 1.0557 | 0.1523 | 0.057* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0218 (7) | 0.0296 (8) | 0.0269 (7) | 0.0000 (6) | 0.0007 (6) | 0.0037 (6) |
N2 | 0.0206 (7) | 0.0315 (8) | 0.0245 (7) | 0.0004 (6) | 0.0009 (6) | 0.0033 (7) |
C3 | 0.0253 (9) | 0.0230 (9) | 0.0223 (8) | 0.0035 (7) | 0.0022 (7) | −0.0007 (7) |
N3 | 0.0283 (8) | 0.0225 (7) | 0.0200 (6) | 0.0039 (6) | 0.0023 (6) | 0.0022 (6) |
N4 | 0.0804 (15) | 0.0277 (9) | 0.0211 (8) | 0.0163 (10) | 0.0091 (9) | 0.0084 (7) |
C5 | 0.0247 (9) | 0.0237 (9) | 0.0216 (8) | 0.0017 (7) | 0.0012 (7) | −0.0005 (7) |
C6 | 0.0244 (9) | 0.0292 (10) | 0.0250 (8) | −0.0015 (7) | 0.0020 (7) | 0.0025 (7) |
C7 | 0.0268 (10) | 0.0434 (11) | 0.0324 (10) | −0.0045 (9) | 0.0043 (8) | −0.0055 (9) |
O1 | 0.0291 (7) | 0.0257 (7) | 0.0282 (6) | −0.0002 (5) | −0.0006 (5) | 0.0003 (5) |
C8 | 0.0269 (9) | 0.0267 (9) | 0.0253 (8) | 0.0034 (7) | −0.0016 (7) | 0.0030 (7) |
C9 | 0.0279 (10) | 0.0294 (10) | 0.0513 (12) | 0.0052 (8) | −0.0035 (9) | −0.0027 (9) |
O2 | 0.0268 (7) | 0.0299 (7) | 0.0268 (6) | 0.0006 (5) | 0.0002 (5) | −0.0016 (5) |
C10 | 0.0266 (10) | 0.0374 (11) | 0.0506 (12) | 0.0023 (9) | 0.0034 (9) | −0.0058 (10) |
C11 | 0.0243 (9) | 0.0258 (9) | 0.0318 (9) | −0.0008 (7) | −0.0022 (8) | 0.0003 (7) |
O10 | 0.0270 (7) | 0.0320 (7) | 0.0427 (7) | 0.0013 (6) | −0.0063 (6) | 0.0121 (6) |
C12 | 0.0264 (9) | 0.0267 (9) | 0.0203 (7) | 0.0035 (7) | 0.0064 (7) | −0.0022 (7) |
O11 | 0.0415 (8) | 0.0266 (7) | 0.0292 (6) | −0.0021 (6) | 0.0064 (6) | 0.0017 (6) |
N10 | 0.0280 (8) | 0.0221 (8) | 0.0282 (7) | 0.0041 (6) | −0.0046 (6) | 0.0024 (6) |
N11 | 0.0319 (9) | 0.0301 (8) | 0.0209 (7) | 0.0095 (7) | −0.0039 (6) | −0.0013 (6) |
C13 | 0.0269 (10) | 0.0205 (9) | 0.0278 (9) | −0.0010 (7) | −0.0011 (7) | −0.0016 (7) |
O12 | 0.0325 (7) | 0.0341 (7) | 0.0274 (6) | 0.0072 (6) | 0.0010 (5) | −0.0053 (5) |
C14 | 0.0297 (9) | 0.0264 (9) | 0.0308 (9) | 0.0067 (8) | −0.0032 (8) | −0.0017 (8) |
O13 | 0.0422 (8) | 0.0541 (10) | 0.0258 (6) | 0.0162 (7) | −0.0066 (6) | 0.0031 (6) |
C15 | 0.0329 (12) | 0.0655 (16) | 0.0444 (12) | −0.0044 (11) | −0.0107 (10) | 0.0018 (11) |
N1—C5 | 1.312 (2) | C10—C11 | 1.519 (3) |
N1—N2 | 1.409 (2) | C10—H10A | 0.9800 |
N2—C3 | 1.311 (2) | C10—H10B | 0.9800 |
C3—N3 | 1.363 (2) | C10—H10C | 0.9800 |
C3—C8 | 1.512 (3) | C11—O10 | 1.422 (2) |
N3—C5 | 1.363 (2) | C11—C12 | 1.520 (2) |
N3—N4 | 1.404 (2) | C11—H11 | 1.0000 |
N4—H4X | 0.92 (3) | O10—H10X | 0.91 (2) |
N4—H4Y | 0.72 (3) | C12—O11 | 1.240 (2) |
C5—C6 | 1.515 (2) | C12—N10 | 1.326 (2) |
C6—O1 | 1.418 (2) | N10—N11 | 1.391 (2) |
C6—C7 | 1.526 (3) | N10—H10Y | 0.88 (2) |
C6—H6 | 1.0000 | N11—C13 | 1.337 (2) |
C7—H7A | 0.9800 | N11—H11X | 0.88 (2) |
C7—H7B | 0.9800 | C13—O12 | 1.234 (2) |
C7—H7C | 0.9800 | C13—C14 | 1.518 (2) |
O1—H1X | 0.84 (2) | C14—O13 | 1.414 (2) |
C8—O2 | 1.418 (2) | C14—C15 | 1.499 (3) |
C8—C9 | 1.521 (3) | C14—H14 | 1.0000 |
C8—H8 | 1.0000 | O13—H13X | 0.82 (3) |
C9—H9A | 0.9800 | C15—H15A | 0.9800 |
C9—H9B | 0.9800 | C15—H15B | 0.9800 |
C9—H9C | 0.9800 | C15—H15C | 0.9800 |
O2—H2X | 0.89 (2) | ||
C5—N1—N2 | 107.24 (14) | C8—O2—H2X | 107.2 (15) |
C3—N2—N1 | 107.19 (14) | C11—C10—H10A | 109.5 |
N2—C3—N3 | 109.50 (16) | C11—C10—H10B | 109.5 |
N2—C3—C8 | 127.58 (16) | H10A—C10—H10B | 109.5 |
N3—C3—C8 | 122.88 (15) | C11—C10—H10C | 109.5 |
C5—N3—C3 | 106.63 (14) | H10A—C10—H10C | 109.5 |
C5—N3—N4 | 127.08 (17) | H10B—C10—H10C | 109.5 |
C3—N3—N4 | 126.28 (17) | O10—C11—C10 | 111.87 (16) |
N3—N4—H4X | 114.8 (16) | O10—C11—C12 | 109.19 (15) |
N3—N4—H4Y | 114 (2) | C10—C11—C12 | 108.96 (15) |
H4X—N4—H4Y | 131 (3) | O10—C11—H11 | 108.9 |
N1—C5—N3 | 109.43 (15) | C10—C11—H11 | 108.9 |
N1—C5—C6 | 127.18 (15) | C12—C11—H11 | 108.9 |
N3—C5—C6 | 123.27 (15) | C11—O10—H10X | 110.7 (15) |
O1—C6—C5 | 110.99 (14) | O11—C12—N10 | 124.30 (17) |
O1—C6—C7 | 112.73 (15) | O11—C12—C11 | 120.62 (16) |
C5—C6—C7 | 110.07 (15) | N10—C12—C11 | 115.08 (16) |
O1—C6—H6 | 107.6 | C12—N10—N11 | 120.97 (16) |
C5—C6—H6 | 107.6 | C12—N10—H10Y | 125.8 (14) |
C7—C6—H6 | 107.6 | N11—N10—H10Y | 112.1 (14) |
C6—C7—H7A | 109.5 | C13—N11—N10 | 120.90 (14) |
C6—C7—H7B | 109.5 | C13—N11—H11X | 121.6 (14) |
H7A—C7—H7B | 109.5 | N10—N11—H11X | 117.0 (14) |
C6—C7—H7C | 109.5 | O12—C13—N11 | 123.15 (16) |
H7A—C7—H7C | 109.5 | O12—C13—C14 | 121.56 (16) |
H7B—C7—H7C | 109.5 | N11—C13—C14 | 115.28 (15) |
C6—O1—H1X | 109.5 (15) | O13—C14—C15 | 112.08 (17) |
O2—C8—C3 | 111.17 (14) | O13—C14—C13 | 108.63 (15) |
O2—C8—C9 | 113.01 (15) | C15—C14—C13 | 108.73 (16) |
C3—C8—C9 | 110.33 (15) | O13—C14—H14 | 109.1 |
O2—C8—H8 | 107.4 | C15—C14—H14 | 109.1 |
C3—C8—H8 | 107.4 | C13—C14—H14 | 109.1 |
C9—C8—H8 | 107.4 | C14—O13—H13X | 106.9 (17) |
C8—C9—H9A | 109.5 | C14—C15—H15A | 109.5 |
C8—C9—H9B | 109.5 | C14—C15—H15B | 109.5 |
H9A—C9—H9B | 109.5 | H15A—C15—H15B | 109.5 |
C8—C9—H9C | 109.5 | C14—C15—H15C | 109.5 |
H9A—C9—H9C | 109.5 | H15A—C15—H15C | 109.5 |
H9B—C9—H9C | 109.5 | H15B—C15—H15C | 109.5 |
C5—N1—N2—C3 | 0.17 (19) | N2—C3—C8—O2 | −30.2 (3) |
N1—N2—C3—N3 | −0.46 (19) | N3—C3—C8—O2 | 152.29 (15) |
N1—N2—C3—C8 | −178.23 (16) | N2—C3—C8—C9 | 96.0 (2) |
N2—C3—N3—C5 | 0.57 (19) | N3—C3—C8—C9 | −81.5 (2) |
C8—C3—N3—C5 | 178.46 (16) | O10—C11—C12—O11 | 168.41 (15) |
N2—C3—N3—N4 | −178.73 (16) | C10—C11—C12—O11 | −69.1 (2) |
C8—C3—N3—N4 | −0.8 (3) | O10—C11—C12—N10 | −12.1 (2) |
N2—N1—C5—N3 | 0.18 (19) | C10—C11—C12—N10 | 110.32 (18) |
N2—N1—C5—C6 | −175.98 (16) | O11—C12—N10—N11 | 6.7 (3) |
C3—N3—C5—N1 | −0.45 (19) | C11—C12—N10—N11 | −172.75 (15) |
N4—N3—C5—N1 | 178.84 (16) | C12—N10—N11—C13 | −91.7 (2) |
C3—N3—C5—C6 | 175.89 (16) | N10—N11—C13—O12 | 5.5 (3) |
N4—N3—C5—C6 | −4.8 (3) | N10—N11—C13—C14 | −172.98 (16) |
N1—C5—C6—O1 | −37.8 (2) | O12—C13—C14—O13 | 172.52 (17) |
N3—C5—C6—O1 | 146.55 (16) | N11—C13—C14—O13 | −8.9 (2) |
N1—C5—C6—C7 | 87.7 (2) | O12—C13—C14—C15 | −65.3 (2) |
N3—C5—C6—C7 | −87.9 (2) | N11—C13—C14—C15 | 113.29 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4X···O12i | 0.92 (3) | 2.07 (3) | 2.937 (2) | 158 (2) |
N4—H4Y···O11ii | 0.72 (3) | 2.46 (3) | 3.172 (2) | 170 (3) |
O1—H1X···N2iii | 0.84 (2) | 1.98 (2) | 2.808 (2) | 170 (2) |
O2—H2X···N1iv | 0.89 (2) | 1.94 (2) | 2.8056 (19) | 165 (2) |
O10—H10X···O12v | 0.91 (2) | 1.87 (2) | 2.7740 (18) | 177 (2) |
N10—H10Y···O2iii | 0.88 (2) | 2.02 (2) | 2.833 (2) | 152.4 (19) |
N11—H11X···O1 | 0.88 (2) | 2.04 (2) | 2.810 (2) | 146.2 (19) |
O13—H13X···O11ii | 0.82 (3) | 1.93 (3) | 2.7532 (19) | 175 (2) |
Symmetry codes: (i) −y+3/2, x+1/2, z−1/4; (ii) x−1/2, −y+5/2, −z+1/4; (iii) x+1/2, −y+3/2, −z+1/4; (iv) x−1/2, −y+3/2, −z+1/4; (v) −y+2, −x+1, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C6H12N4O2·C6H12N2O4 |
Mr | 348.37 |
Crystal system, space group | Tetragonal, P43212 |
Temperature (K) | 150 |
a, c (Å) | 9.9296 (1), 34.0538 (6) |
V (Å3) | 3357.60 (8) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.45 × 0.20 × 0.16 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.69, 1.00 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 18817, 3205, 3084 |
Rint | 0.039 |
(sin θ/λ)max (Å−1) | 0.612 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.082, 1.08 |
No. of reflections | 3205 |
No. of parameters | 245 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.19, −0.16 |
Computer programs: SMART (Bruker, 2000), SMART and SAINT (Bruker, 2000), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2000), enCIFer (Version 1.2; Allen et al., 2004).
N1—C5 | 1.312 (2) | N3—N4 | 1.404 (2) |
N1—N2 | 1.409 (2) | C12—N10 | 1.326 (2) |
N2—C3 | 1.311 (2) | N10—N11 | 1.391 (2) |
C3—N3 | 1.363 (2) | N11—C13 | 1.337 (2) |
N1—C5—C6—C7 | 87.7 (2) | C10—C11—C12—N10 | 110.32 (18) |
N2—C3—C8—C9 | 96.0 (2) | C12—N10—N11—C13 | −91.7 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4X···O12i | 0.92 (3) | 2.07 (3) | 2.937 (2) | 158 (2) |
N4—H4Y···O11ii | 0.72 (3) | 2.46 (3) | 3.172 (2) | 170 (3) |
O1—H1X···N2iii | 0.84 (2) | 1.98 (2) | 2.808 (2) | 170 (2) |
O2—H2X···N1iv | 0.89 (2) | 1.94 (2) | 2.8056 (19) | 165 (2) |
O10—H10X···O12v | 0.91 (2) | 1.87 (2) | 2.7740 (18) | 177 (2) |
N10—H10Y···O2iii | 0.88 (2) | 2.02 (2) | 2.833 (2) | 152.4 (19) |
N11—H11X···O1 | 0.88 (2) | 2.04 (2) | 2.810 (2) | 146.2 (19) |
O13—H13X···O11ii | 0.82 (3) | 1.93 (3) | 2.7532 (19) | 175 (2) |
Symmetry codes: (i) −y+3/2, x+1/2, z−1/4; (ii) x−1/2, −y+5/2, −z+1/4; (iii) x+1/2, −y+3/2, −z+1/4; (iv) x−1/2, −y+3/2, −z+1/4; (v) −y+2, −x+1, −z+1/2. |
Triazoles are of special interest as ligands for transition metal ions because of their ability to mediate magnetic exchange and the fact that they can lead to spin-crossover complexes of iron (Klingele et al., 2005; Haasnoot, 2000; Kahn, 1999). We were the first to characterize structurally Schiff base macrocyclic complexes which incorporated triazole moieties in the macrocycle framework. The resulting dimetallic copper(II), nickel(II), cobalt(II) and [Text missing?](III) Schiff base macrocyclic complexes feature double triazolate bridging of the metal ions and exhibit interesting structural, reactivity and magnetic properties (Beckmann & Brooker, 2003; Beckmann, Brooker et al., 2003; Beckmann, Ewing & Brooker, 2003; Depree et al. 2003). The dimetallic [2 + 2] Schiff base macrocyclic complexes were obtained from a metal ion templated condensation reaction of the appropriately derivatized triazole head unit (Alonso et al., 1987; de Mendoza et al., 1992) with an appropriately selected diaminoalkane lateral unit.
In our studies we have used, amongst other compounds, 3,5-diacetyl-1H-1,2,4-triazole as the head unit (Brandt et al., 2006). This compound is obtained via a four-step synthesis (Alonso et al., 1987; de Mendoza et al., 1992). The first step of the published procedure involves heating the reaction mixture to 433 K for 5 h and monitoring the reaction by NMR for the disappearance of open-chain intermediates. However, when following this procedure we found that, even after heating the reaction mixture to 443 K overnight, there is sometimes still an open-chain intermediate, (2), present, in an exact 1:1 ratio with the desired triazole, (1) [step (i) in the scheme; 373–443 K, overnight; dashed lines represent likely hydrogen bonds]. This was indicated by elemental analysis and NMR data and has been confirmed by this study.
Attempts to separate the two products, (1) and (2), by fractional crystallization, even by the addition of small amounts of water to provide an alternative to the intermolecular hydrogen bonds present (see below), failed, and always resulted in analytically pure samples of a 1:1 mixture of (1) and (2). Interestingly, when using mandelic acid instead of lactic acid we observed no open-chain intermediate; this reaction yielded only the corresponding triazole in good yields (Brandt et al., 2006). Fortunately, the presence of (2) does not disturb the next reaction step [deamination of (1)], so (S,S)-3,5-bis-(1-hydroxyethyl)-1,2,4-triazole, (3), can be obtained in high purity and good yield as the hydrochloride salt [step (ii) in the scheme; HCl, NaNO2]. Thus, we do not obtain the free triazole directly but instead first isolate the hydrochloric salt, as this has proved to be the best way to separate the triazole from the open-chain compound (S,S)-1,2-bis(2-hydroxypropionyl)hydrazine, (2).
The structure of the 1:1 adduct, (I), of the title compounds is shown in Fig. 1 and Tables 1 and 2. The structure determination confirms the presence of the expected (S,S)-4-amino-3,5-bis(1-hydroxyethyl)-1,2,4-triazole, (1), and that it has cocrystallized in a 1:1 ratio with the open-chain intermediate (S,S)-1,2-bis(2-hydroxypropionyl)hydrazine, (2). It is important to note that all of the H atoms on N and O were found in a difference map and their coordinates freely refined.
The N—N single bond in (2), N10—N11, is somewhat shorter than those observed in hydrazine (1.46 Å; Collin & Lipscomb, 1951) or in various hydrogen-bonded adducts of hydrazine [e.g. 1.46 Å (Liminga & Sorenson, 1967) and 1.43–1.44 Å (Toda et al., 1995)], but is normal compared with those observed in related C—(C═O)—(NH)—(NH)—(C═ O)—C compounds [e.g. 1.394 (3) Å (Cheng et al., 2006); range observed for 22 such species in the Cambridge Structural Database (Version?; Allen, 2002) 1.251–1.404 Å, average 1.387 Å]. The torsion angle along the N—N axis in (2) is close to 90° (Table 1). As all of the related compounds are also involved in interesting hydrogen-bonding patterns, and some are cyclic, it is not surprising that the torsion angle along this N—N bond is seen to vary extremely widely. In the compound reported by Cheng et al. (2006), the torsion angle is not dissimilar, at 83.1 (2)°.
Within the triazole ring of (1), the N1—N2 distance is somewhat shorter than the N—N single-bond distance observed in hydrazine, but is very close to that observed for N3—N4. As expected, the remaining bonds in the triazole ring of (1) fall into two sets, the first being the C3—N3 and C5—N3 single bonds, which are longer than the second set of C3—N2 and C5—N1 double bonds. In the most closely related triazole-containing structure in the literature, a similar pattern is observed (van Koningsbruggen et al., 1993). Likewise, the C13—N11 and C12—N10 distances in the acyclic component are intermediate between the values expected for a C—N single bond and a C═N double bond, and are similar to previously reported values [e.g. 1.336 (2) Å (Cheng et al., 2006)]. The C12—O11 and C13—O12 bonds are in between the expected values for a C—O single and a C═O double bond. Thus, there is significant delocalization within the amide bonds of the acyclic component, (2). All other dimensions are within expected ranges.
The crystal packing of the 1:1 adduct is stabilized by eight hydrogen bonds, four N—H···O, two O—H···N and two O—H···O (Table 2). Two O—H···N bonds between the hydroxy atoms O1 and O2 of one triazole and atoms N1 and N2 of two neighbouring triazoles (entries 3 and 4 in Table 2) lead to the formation of approximately linear infinite zigzag chains (Fig. 2; note that, due to symmetry, the zigzag chains also run at right angles to this, approximately along b). With two of the four N—H···O bonds, every triazole (1) binds to two acyclic hydrazine (2) molecules (entries 1 and 2 in Table 2). These are the weakest (longest) hydrogen-bond interactions observed in this structure. One hydrazine molecule bridges two triazoles by the other two N—H···O bonds (entries 6 and 7 in Table 2). The two O—H···O bonds are the strongest (shortest) hydrogen bonds observed in this structure. These occur between the hydroxy H atoms on atoms O10 and O13 and the carbonyl atoms O11 and O12 of two neighbouring hydrazine molecules, respectively (entries 5 and 8 in Table 2), to complete the observed three-dimensional molecular framework.