Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807050374/hy2088sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807050374/hy2088Isup2.hkl |
CCDC reference: 667388
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean (C-C) = 0.002 Å
- R factor = 0.045
- wR factor = 0.106
- Data-to-parameter ratio = 16.1
checkCIF/PLATON results
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Alert level C PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 800 Deg. PLAT369_ALERT_2_C Long C(sp2)-C(sp2) Bond C1 - C2 ... 1.55 Ang.
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
The title compound was synthesized by reacting excess diethyl oxalate with isopropylamine in chloroform at room temperature. Crystals were obtained by the slow evaporation method. After two weeks colourless plate crystals were deposited. The compound was characterized by proton NMR in deuterated chloroform as follows: 1.12 p.p.m. (6H, d, CH3 for anion); 1.13 p.p.m. (6H, m, CH3 for cation); 3.40 p.p.m. (1H, m, CH for cation); 4.18 p.p.m. (1H, m, CH for anion); 7.35 p.p.m. (1H, d, NH for anion); 7.97(1H, br, NH for cation).
H atoms of CH, CH3 and NH3 groups were positiond geometrically and refined as riding, with C—H = 1.00 Å and Uiso(H) = 1.2Ueq(C) for CH groups, and with C—H = 0.98 and 0.91 Å and Uiso(H) = 1.5Ueq(C,N) for CH3 and NH3 groups. H atoms on N1 and on the water molecule were refined isotropically.
Chagas disease, which is caused by Trypanosoma cruzi, is an endemic parasitic disease in Latin America, specially in the Southern part of Mexico (Dumonateil, 1999). The Trypanosoma cruzi enzyme desigenated α-hydroxyacid dehydrogenase (HADH) exhibits two molecular forms (I and II). The trypanocidal activity of N-isopropyloxamate (NIPOx) on cultured epimastigotes (in vitro) and marine trypanosomiasis (in vitro) is used in different Trypanosoma cruzi strains. It is an effective and selective inhibitor of HADH-isozyme II (Chena et al., 2005).
It was serendipitously synthesized during a chromatographic partition of cyclenoxamide. The cyclen and diethyl oxalate were added in an equal molar ratio as starting materials to form the cyclenoxamide at room temperature with stirring for 48 h (Bellouard et al., 1999). The reaction stoichiometry should be one to one, so the excess diethyl oxalate was separated by chromatography on silca (CHCl3:isopropylamine, 5:1). The diethyl oxalate reacted with isopropylamine to produce the title compound at room temperature.
The title compound is a salt, consisting of an N-isopropyloxalamate anion, an isopropylaminium cation and a water molecule (Fig. 1). The C1—C2 bond was 1.549 (2) Å which is longer than the typical C(sp2)—C(sp2) bond length. This is most likely due to the stretching by hydrogen bonds at the two sides of the bond. There is a partial double bond between the C2 and N1 [1.326 (2) Å] in the amide group. The cation, anion and water molecule are connected by intermolecular N—H···O and O—H···O hydrogen bonds, as detailed in Table 1 and Figs. 1 and 2. This hydrogen-bonding network is extended in the ab plane to form a layer. The molecular packing consists of the hydrogen-bonding layers alternating with hydrophobic domains along the c direction.
For related literature, see: Chena et al. (2005); Bellouard et al. (1999); Dumonateil (1999).
Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001; Atwood & Barbour, 2003); software used to prepare material for publication: X-SEED (Barbour, 2001; Atwood & Barbour, 2003).
C3H10N+·C5H8NO3−·H2O | Z = 2 |
Mr = 208.26 | F(000) = 228 |
Triclinic, P1 | Dx = 1.210 Mg m−3 |
Hall symbol: -P 1 | Melting point: 56 K |
a = 7.172 (4) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.154 (5) Å | Cell parameters from 3071 reflections |
c = 9.472 (5) Å | θ = 2.3–26.5° |
α = 104.372 (8)° | µ = 0.10 mm−1 |
β = 105.944 (8)° | T = 100 K |
γ = 94.731 (8)° | Plate, colourless |
V = 571.6 (5) Å3 | 0.38 × 0.19 × 0.08 mm |
Bruker SMART APEX CCD area-detector diffractometer | 2324 independent reflections |
Radiation source: fine-focus sealed tube | 2126 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
φ and ω scans | θmax = 26.4°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −9→8 |
Tmin = 0.962, Tmax = 0.990 | k = −11→11 |
6062 measured reflections | l = −11→11 |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.106 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.16 | w = 1/[σ2(Fo2) + (0.0443P)2 + 0.2432P] where P = (Fo2 + 2Fc2)/3 |
2324 reflections | (Δ/σ)max < 0.001 |
144 parameters | Δρmax = 0.40 e Å−3 |
0 restraints | Δρmin = −0.21 e Å−3 |
C3H10N+·C5H8NO3−·H2O | γ = 94.731 (8)° |
Mr = 208.26 | V = 571.6 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.172 (4) Å | Mo Kα radiation |
b = 9.154 (5) Å | µ = 0.10 mm−1 |
c = 9.472 (5) Å | T = 100 K |
α = 104.372 (8)° | 0.38 × 0.19 × 0.08 mm |
β = 105.944 (8)° |
Bruker SMART APEX CCD area-detector diffractometer | 2324 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | 2126 reflections with I > 2σ(I) |
Tmin = 0.962, Tmax = 0.990 | Rint = 0.023 |
6062 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.106 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.16 | Δρmax = 0.40 e Å−3 |
2324 reflections | Δρmin = −0.21 e Å−3 |
144 parameters |
x | y | z | Uiso*/Ueq | ||
O1 | 0.38400 (15) | 0.13612 (11) | 0.08003 (12) | 0.0186 (2) | |
N1 | 0.36897 (19) | 0.52457 (13) | 0.22589 (14) | 0.0147 (3) | |
C1 | 0.3063 (2) | 0.25345 (16) | 0.09391 (15) | 0.0131 (3) | |
H1 | 0.246 (3) | 0.512 (2) | 0.205 (2) | 0.021 (5)* | |
O2 | 0.12699 (14) | 0.26313 (11) | 0.05100 (11) | 0.0167 (2) | |
N2 | −0.18564 (17) | 0.14413 (13) | 0.13379 (13) | 0.0140 (3) | |
H2A | −0.0868 | 0.1780 | 0.1010 | 0.021* | |
H2B | −0.2743 | 0.2098 | 0.1311 | 0.021* | |
H2C | −0.2463 | 0.0496 | 0.0717 | 0.021* | |
C2 | 0.4503 (2) | 0.40621 (16) | 0.17327 (15) | 0.0131 (3) | |
O3 | 0.62792 (14) | 0.41075 (11) | 0.18756 (12) | 0.0175 (2) | |
C3 | 0.4797 (2) | 0.67704 (16) | 0.31163 (17) | 0.0169 (3) | |
H3 | 0.6232 | 0.6711 | 0.3369 | 0.020* | |
O4 | 0.97028 (16) | 0.59125 (13) | 0.18861 (14) | 0.0211 (3) | |
C4 | 0.4348 (3) | 0.78700 (18) | 0.21497 (19) | 0.0257 (4) | |
H4A | 0.4721 | 0.7511 | 0.1217 | 0.039* | |
H4B | 0.5093 | 0.8888 | 0.2735 | 0.039* | |
H4C | 0.2938 | 0.7921 | 0.1874 | 0.039* | |
C5 | 0.4297 (3) | 0.73017 (19) | 0.45995 (18) | 0.0254 (4) | |
H5A | 0.2892 | 0.7361 | 0.4367 | 0.038* | |
H5B | 0.5061 | 0.8313 | 0.5188 | 0.038* | |
H5C | 0.4616 | 0.6574 | 0.5200 | 0.038* | |
C6 | −0.1027 (2) | 0.13576 (16) | 0.29428 (16) | 0.0161 (3) | |
H6 | −0.2136 | 0.1022 | 0.3300 | 0.019* | |
C7 | −0.0006 (2) | 0.29326 (17) | 0.39773 (17) | 0.0201 (3) | |
H7A | 0.1131 | 0.3254 | 0.3678 | 0.030* | |
H7B | 0.0436 | 0.2897 | 0.5042 | 0.030* | |
H7C | −0.0924 | 0.3664 | 0.3880 | 0.030* | |
C8 | 0.0341 (2) | 0.01765 (18) | 0.29648 (18) | 0.0234 (4) | |
H8A | −0.0399 | −0.0829 | 0.2328 | 0.035* | |
H8B | 0.0909 | 0.0136 | 0.4018 | 0.035* | |
H8C | 0.1397 | 0.0460 | 0.2563 | 0.035* | |
H9 | 0.939 (3) | 0.622 (3) | 0.113 (3) | 0.041 (6)* | |
H10 | 0.859 (3) | 0.539 (2) | 0.184 (2) | 0.033 (5)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0177 (5) | 0.0116 (5) | 0.0241 (6) | 0.0033 (4) | 0.0055 (4) | 0.0013 (4) |
N1 | 0.0106 (6) | 0.0132 (6) | 0.0187 (6) | 0.0023 (5) | 0.0038 (5) | 0.0022 (5) |
C1 | 0.0147 (7) | 0.0148 (7) | 0.0106 (6) | 0.0025 (5) | 0.0053 (5) | 0.0032 (5) |
O2 | 0.0127 (5) | 0.0166 (5) | 0.0203 (5) | 0.0014 (4) | 0.0049 (4) | 0.0046 (4) |
N2 | 0.0122 (6) | 0.0107 (6) | 0.0170 (6) | 0.0016 (4) | 0.0041 (5) | 0.0007 (5) |
C2 | 0.0140 (7) | 0.0142 (7) | 0.0122 (6) | 0.0033 (5) | 0.0040 (5) | 0.0050 (5) |
O3 | 0.0128 (5) | 0.0138 (5) | 0.0248 (6) | 0.0026 (4) | 0.0067 (4) | 0.0021 (4) |
C3 | 0.0131 (7) | 0.0129 (7) | 0.0201 (7) | 0.0006 (5) | 0.0040 (6) | −0.0019 (6) |
O4 | 0.0152 (6) | 0.0239 (6) | 0.0258 (6) | 0.0026 (5) | 0.0048 (5) | 0.0116 (5) |
C4 | 0.0331 (9) | 0.0181 (8) | 0.0276 (9) | 0.0010 (7) | 0.0137 (7) | 0.0056 (7) |
C5 | 0.0281 (9) | 0.0239 (8) | 0.0186 (8) | 0.0001 (7) | 0.0055 (7) | −0.0009 (6) |
C6 | 0.0167 (7) | 0.0168 (7) | 0.0148 (7) | 0.0029 (6) | 0.0060 (6) | 0.0031 (5) |
C7 | 0.0199 (8) | 0.0185 (8) | 0.0178 (7) | 0.0034 (6) | 0.0037 (6) | 0.0001 (6) |
C8 | 0.0288 (9) | 0.0191 (8) | 0.0214 (8) | 0.0092 (6) | 0.0046 (7) | 0.0056 (6) |
O1—C1 | 1.2451 (18) | C4—H4A | 0.9800 |
N1—C2 | 1.3262 (19) | C4—H4B | 0.9800 |
N1—C3 | 1.4623 (19) | C4—H4C | 0.9800 |
N1—H1 | 0.84 (2) | C5—H5A | 0.9800 |
C1—O2 | 1.2554 (18) | C5—H5B | 0.9800 |
C1—C2 | 1.549 (2) | C5—H5C | 0.9800 |
N2—C6 | 1.4963 (19) | C6—C7 | 1.518 (2) |
N2—H2A | 0.9100 | C6—C8 | 1.519 (2) |
N2—H2B | 0.9100 | C6—H6 | 1.0000 |
N2—H2C | 0.9100 | C7—H7A | 0.9800 |
C2—O3 | 1.2394 (18) | C7—H7B | 0.9800 |
C3—C4 | 1.518 (2) | C7—H7C | 0.9800 |
C3—C5 | 1.518 (2) | C8—H8A | 0.9800 |
C3—H3 | 1.0000 | C8—H8B | 0.9800 |
O4—H9 | 0.81 (2) | C8—H8C | 0.9800 |
O4—H10 | 0.88 (2) | ||
C2—N1—C3 | 123.84 (13) | H4A—C4—H4C | 109.5 |
C2—N1—H1 | 118.0 (13) | H4B—C4—H4C | 109.5 |
C3—N1—H1 | 118.1 (13) | C3—C5—H5A | 109.5 |
O1—C1—O2 | 128.18 (13) | C3—C5—H5B | 109.5 |
O1—C1—C2 | 115.46 (12) | H5A—C5—H5B | 109.5 |
O2—C1—C2 | 116.36 (12) | C3—C5—H5C | 109.5 |
C6—N2—H2A | 109.5 | H5A—C5—H5C | 109.5 |
C6—N2—H2B | 109.5 | H5B—C5—H5C | 109.5 |
H2A—N2—H2B | 109.5 | N2—C6—C7 | 109.47 (12) |
C6—N2—H2C | 109.5 | N2—C6—C8 | 109.33 (12) |
H2A—N2—H2C | 109.5 | C7—C6—C8 | 112.50 (13) |
H2B—N2—H2C | 109.5 | N2—C6—H6 | 108.5 |
O3—C2—N1 | 124.74 (13) | C7—C6—H6 | 108.5 |
O3—C2—C1 | 120.31 (12) | C8—C6—H6 | 108.5 |
N1—C2—C1 | 114.92 (12) | C6—C7—H7A | 109.5 |
N1—C3—C4 | 110.08 (13) | C6—C7—H7B | 109.5 |
N1—C3—C5 | 109.27 (12) | H7A—C7—H7B | 109.5 |
C4—C3—C5 | 111.50 (13) | C6—C7—H7C | 109.5 |
N1—C3—H3 | 108.6 | H7A—C7—H7C | 109.5 |
C4—C3—H3 | 108.6 | H7B—C7—H7C | 109.5 |
C5—C3—H3 | 108.6 | C6—C8—H8A | 109.5 |
H9—O4—H10 | 102 (2) | C6—C8—H8B | 109.5 |
C3—C4—H4A | 109.5 | H8A—C8—H8B | 109.5 |
C3—C4—H4B | 109.5 | C6—C8—H8C | 109.5 |
H4A—C4—H4B | 109.5 | H8A—C8—H8C | 109.5 |
C3—C4—H4C | 109.5 | H8B—C8—H8C | 109.5 |
C3—N1—C2—O3 | −1.4 (2) | O1—C1—C2—N1 | −162.00 (12) |
C3—N1—C2—C1 | 176.57 (12) | O2—C1—C2—N1 | 18.40 (17) |
O1—C1—C2—O3 | 16.08 (19) | C2—N1—C3—C4 | 109.88 (15) |
O2—C1—C2—O3 | −163.51 (12) | C2—N1—C3—C5 | −127.36 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H9···O2i | 0.82 (3) | 2.06 (3) | 2.864 (2) | 170 (3) |
O4—H10···O3 | 0.88 (2) | 1.96 (2) | 2.8404 (19) | 173.5 (19) |
N1—H1···O4ii | 0.84 (2) | 2.14 (2) | 2.918 (2) | 153.7 (17) |
N2—H2A···O2 | 0.91 | 1.89 | 2.7957 (19) | 175 |
N2—H2B···O3ii | 0.91 | 2.02 | 2.8808 (19) | 157 |
N2—H2C···O1iii | 0.91 | 1.91 | 2.8182 (18) | 172 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) x−1, y, z; (iii) −x, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | C3H10N+·C5H8NO3−·H2O |
Mr | 208.26 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 100 |
a, b, c (Å) | 7.172 (4), 9.154 (5), 9.472 (5) |
α, β, γ (°) | 104.372 (8), 105.944 (8), 94.731 (8) |
V (Å3) | 571.6 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.38 × 0.19 × 0.08 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2002) |
Tmin, Tmax | 0.962, 0.990 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6062, 2324, 2126 |
Rint | 0.023 |
(sin θ/λ)max (Å−1) | 0.626 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.106, 1.16 |
No. of reflections | 2324 |
No. of parameters | 144 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.40, −0.21 |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), X-SEED (Barbour, 2001; Atwood & Barbour, 2003).
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H9···O2i | 0.82 (3) | 2.06 (3) | 2.864 (2) | 170 (3) |
O4—H10···O3 | 0.88 (2) | 1.96 (2) | 2.8404 (19) | 173.5 (19) |
N1—H1···O4ii | 0.84 (2) | 2.14 (2) | 2.918 (2) | 153.7 (17) |
N2—H2A···O2 | 0.91 | 1.89 | 2.7957 (19) | 174.5 |
N2—H2B···O3ii | 0.91 | 2.02 | 2.8808 (19) | 156.6 |
N2—H2C···O1iii | 0.91 | 1.91 | 2.8182 (18) | 172.4 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) x−1, y, z; (iii) −x, −y, −z. |
Chagas disease, which is caused by Trypanosoma cruzi, is an endemic parasitic disease in Latin America, specially in the Southern part of Mexico (Dumonateil, 1999). The Trypanosoma cruzi enzyme desigenated α-hydroxyacid dehydrogenase (HADH) exhibits two molecular forms (I and II). The trypanocidal activity of N-isopropyloxamate (NIPOx) on cultured epimastigotes (in vitro) and marine trypanosomiasis (in vitro) is used in different Trypanosoma cruzi strains. It is an effective and selective inhibitor of HADH-isozyme II (Chena et al., 2005).
It was serendipitously synthesized during a chromatographic partition of cyclenoxamide. The cyclen and diethyl oxalate were added in an equal molar ratio as starting materials to form the cyclenoxamide at room temperature with stirring for 48 h (Bellouard et al., 1999). The reaction stoichiometry should be one to one, so the excess diethyl oxalate was separated by chromatography on silca (CHCl3:isopropylamine, 5:1). The diethyl oxalate reacted with isopropylamine to produce the title compound at room temperature.
The title compound is a salt, consisting of an N-isopropyloxalamate anion, an isopropylaminium cation and a water molecule (Fig. 1). The C1—C2 bond was 1.549 (2) Å which is longer than the typical C(sp2)—C(sp2) bond length. This is most likely due to the stretching by hydrogen bonds at the two sides of the bond. There is a partial double bond between the C2 and N1 [1.326 (2) Å] in the amide group. The cation, anion and water molecule are connected by intermolecular N—H···O and O—H···O hydrogen bonds, as detailed in Table 1 and Figs. 1 and 2. This hydrogen-bonding network is extended in the ab plane to form a layer. The molecular packing consists of the hydrogen-bonding layers alternating with hydrophobic domains along the c direction.