Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101007041/sk1478sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101007041/sk1478Isup2.hkl |
CCDC reference: 146382
%T Details of the synthesis of the title compound, (I), are described elsewhere (Makarević {ιt et al.}., 2001).
%T The Flack parameter [-0.1 (4); Flack, 1983] only weakly supports the absolute structure chosen on the basis of the known absolute configuration of the starting materials. The structure contains disordered molecules of dimethylsulphoxide. Electron density of dimethylsulphoxide was taken into account with the SQUEEZE procedure in PLATON (Spek, 1999), based on iterative difference Fourier syntheses (van der Sluis \& Spek, 1990). After two cycles of the SQUEEZE procedure and least-squares refinement, the convergence was reached. The total number of electrons in the solvent region (576 AA$3$ in one unit cell) is 173 electrons, calculated by SQUEEZE on data corrected for the absorption. This number of electrons is in agreement with the result of thermogravimetric analysis. The experimental weight loss by heating the sample from 323 to 510 K was 16.4°. It corresponds to one molecule of dimethylsulphoxide per formula unit. Thus, one molecule of dimethylsulphoxide was added in the chemical formula, chemical formula weight, crystal density and linear absorption coeficient ($µu$). The contribution of dimethylsulphoxide to the observed structure factors was removed by the SQUEEZE procedure and last refinement cycles were performed without atoms of dimethylsulphoxide. The H atoms were calculated at ideal positions and constrained to ride on atoms to which they are bonded. Exceptions are H atoms involved in hydrogen bonds which were refined without restraints. Final F$_o$, F$_c$ tables were calculated with the program PLATON (Spek, 1999) and include the solvent contribution.
Data collection: CAD-4 EXPRESS (Enraf Nonius, 1992); cell refinement: CAD-4 EXPRESS; data reduction: HELENA (Spek, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997) and PLATON (Spek, 1999); molecular graphics: PLATON; software used to prepare material for publication: PLATON.
C20H22N4O4·C2H6OS | F(000) = 976 |
Mr = 460.54 | Dx = 1.309 Mg m−3 |
Orthorhombic, P212121 | Cu Kα radiation, λ = 1.54178 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 21 reflections |
a = 5.1830 (5) Å | θ = 9.1–18.9° |
b = 15.220 (3) Å | µ = 1.57 mm−1 |
c = 29.63 (1) Å | T = 295 K |
V = 2337.4 (9) Å3 | Needle, colourless |
Z = 4 | 0.32 × 0.14 × 0.04 mm |
Enraf-Nonius CAD4 diffractometer | 1888 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.000 |
Graphite monochromator | θmax = 74.2°, θmin = 3.0° |
ω/2θ scans | h = 0→6 |
Absorption correction: analytical (PLATON; Spek, 1999) | k = 0→18 |
Tmin = 0.744, Tmax = 0.943 | l = 0→36 |
2786 measured reflections | 3 standard reflections every 180 min |
2786 independent reflections | intensity decay: 1% |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.043 | w = 1/[σ2(Fo2) + (0.0722P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.120 | (Δ/σ)max < 0.001 |
S = 1.01 | Δρmax = 0.15 e Å−3 |
2786 reflections | Δρmin = −0.19 e Å−3 |
277 parameters |
C20H22N4O4·C2H6OS | V = 2337.4 (9) Å3 |
Mr = 460.54 | Z = 4 |
Orthorhombic, P212121 | Cu Kα radiation |
a = 5.1830 (5) Å | µ = 1.57 mm−1 |
b = 15.220 (3) Å | T = 295 K |
c = 29.63 (1) Å | 0.32 × 0.14 × 0.04 mm |
Enraf-Nonius CAD4 diffractometer | 1888 reflections with I > 2σ(I) |
Absorption correction: analytical (PLATON; Spek, 1999) | Rint = 0.000 |
Tmin = 0.744, Tmax = 0.943 | 3 standard reflections every 180 min |
2786 measured reflections | intensity decay: 1% |
2786 independent reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.120 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 0.15 e Å−3 |
2786 reflections | Δρmin = −0.19 e Å−3 |
277 parameters |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'s are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
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 | ||
O1 | 0.0101 (4) | 0.31193 (14) | 0.13748 (9) | 0.0480 (8) | |
O2 | 0.6532 (4) | 0.1835 (2) | 0.22139 (7) | 0.0540 (9) | |
O11 | 0.5276 (4) | 0.45631 (14) | 0.12294 (9) | 0.0489 (8) | |
O21 | −0.1323 (4) | 0.63358 (16) | 0.17801 (7) | 0.0434 (7) | |
N1 | 0.4386 (4) | 0.28348 (15) | 0.13896 (8) | 0.0290 (7) | |
N3 | 0.2207 (6) | 0.1868 (2) | 0.22616 (10) | 0.0491 (10) | |
N11 | 0.0978 (5) | 0.48334 (15) | 0.12064 (8) | 0.0301 (7) | |
N31 | 0.2990 (6) | 0.6309 (2) | 0.18461 (10) | 0.0475 (10) | |
C1 | 0.2362 (5) | 0.33556 (19) | 0.13436 (9) | 0.0303 (8) | |
C2 | 0.4142 (5) | 0.19069 (17) | 0.15207 (8) | 0.0300 (8) | |
C3 | 0.4399 (5) | 0.18538 (19) | 0.20337 (9) | 0.0329 (8) | |
C4 | 0.6154 (6) | 0.13388 (18) | 0.12854 (9) | 0.0353 (9) | |
C5 | 0.5664 (6) | 0.12703 (18) | 0.07820 (10) | 0.0362 (9) | |
C6 | 0.7188 (7) | 0.1702 (2) | 0.04730 (10) | 0.0510 (11) | |
C7 | 0.6720 (9) | 0.1657 (3) | 0.00190 (10) | 0.0627 (15) | |
C8 | 0.4676 (9) | 0.1158 (3) | −0.01395 (10) | 0.0592 (13) | |
C9 | 0.3123 (8) | 0.0710 (3) | 0.01630 (10) | 0.0557 (11) | |
C10 | 0.3626 (7) | 0.0766 (2) | 0.06209 (10) | 0.0486 (11) | |
C11 | 0.3027 (5) | 0.43168 (19) | 0.12493 (10) | 0.0315 (8) | |
C21 | 0.1134 (5) | 0.57889 (17) | 0.11512 (8) | 0.0272 (7) | |
C31 | 0.0821 (6) | 0.61840 (19) | 0.16235 (9) | 0.0315 (8) | |
C41 | −0.0924 (6) | 0.61047 (18) | 0.08178 (9) | 0.0337 (8) | |
C51 | −0.0968 (6) | 0.70878 (18) | 0.07470 (9) | 0.0332 (8) | |
C61 | −0.2827 (7) | 0.7602 (2) | 0.09371 (10) | 0.0553 (11) | |
C71 | −0.2928 (8) | 0.8508 (3) | 0.08571 (10) | 0.0643 (14) | |
C81 | −0.1131 (8) | 0.8889 (2) | 0.05805 (10) | 0.0553 (11) | |
C91 | 0.0727 (9) | 0.8389 (2) | 0.03904 (10) | 0.0607 (12) | |
C101 | 0.0840 (8) | 0.7486 (2) | 0.04696 (10) | 0.0510 (11) | |
H1 | 0.597 (8) | 0.306 (3) | 0.1361 (11) | 0.054 (10)* | |
H2 | 0.24213 | 0.16987 | 0.14348 | 0.0360* | |
H6 | 0.85760 | 0.20334 | 0.05757 | 0.0611* | |
H7 | 0.77696 | 0.19602 | −0.01823 | 0.0753* | |
H8 | 0.43494 | 0.11236 | −0.04476 | 0.0711* | |
H9 | 0.17488 | 0.03730 | 0.00592 | 0.0667* | |
H10 | 0.25864 | 0.04625 | 0.08236 | 0.0584* | |
H11 | −0.049 (6) | 0.4596 (19) | 0.1248 (9) | 0.026 (7)* | |
H21 | 0.28438 | 0.59423 | 0.10339 | 0.0327* | |
H31 | 0.228 (6) | 0.181 (2) | 0.2545 (12) | 0.041 (9)* | |
H32 | 0.073 (10) | 0.179 (3) | 0.2131 (14) | 0.089 (16)* | |
H41 | 0.78520 | 0.15882 | 0.13353 | 0.0424* | |
H42 | 0.61328 | 0.07549 | 0.14165 | 0.0424* | |
H61 | −0.40548 | 0.73447 | 0.11240 | 0.0663* | |
H71 | −0.42060 | 0.88486 | 0.09909 | 0.0773* | |
H81 | −0.11905 | 0.94891 | 0.05238 | 0.0666* | |
H91 | 0.19490 | 0.86505 | 0.02040 | 0.0726* | |
H101 | 0.21308 | 0.71503 | 0.03359 | 0.0610* | |
H311 | 0.279 (7) | 0.645 (2) | 0.2138 (11) | 0.040 (9)* | |
H312 | 0.440 (7) | 0.616 (2) | 0.1772 (10) | 0.037 (9)* | |
H411 | −0.06316 | 0.58211 | 0.05291 | 0.0404* | |
H412 | −0.26037 | 0.59192 | 0.09262 | 0.0404* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0220 (9) | 0.0357 (12) | 0.0864 (17) | −0.0024 (9) | −0.0024 (11) | 0.0123 (12) |
O2 | 0.0279 (11) | 0.095 (2) | 0.0391 (12) | 0.0000 (12) | −0.0079 (9) | 0.0132 (13) |
O11 | 0.0180 (10) | 0.0362 (11) | 0.0926 (18) | −0.0016 (9) | −0.0010 (11) | 0.0117 (11) |
O21 | 0.0265 (11) | 0.0632 (15) | 0.0405 (12) | 0.0045 (10) | 0.0050 (9) | −0.0104 (11) |
N1 | 0.0200 (11) | 0.0302 (12) | 0.0367 (12) | −0.0015 (10) | 0.0018 (11) | 0.0083 (10) |
N3 | 0.0280 (14) | 0.084 (2) | 0.0352 (15) | 0.0043 (16) | 0.0029 (12) | 0.0048 (16) |
N11 | 0.0211 (11) | 0.0273 (12) | 0.0420 (13) | −0.0029 (10) | −0.0016 (11) | 0.0031 (10) |
N31 | 0.0261 (14) | 0.079 (2) | 0.0375 (16) | 0.0030 (15) | −0.0033 (12) | −0.0158 (16) |
C1 | 0.0242 (14) | 0.0326 (14) | 0.0341 (14) | −0.0012 (12) | −0.0034 (12) | 0.0014 (12) |
C2 | 0.0233 (12) | 0.0318 (14) | 0.0350 (14) | −0.0006 (13) | −0.0022 (12) | 0.0059 (11) |
C3 | 0.0280 (14) | 0.0368 (15) | 0.0338 (14) | 0.0028 (14) | 0.0006 (12) | 0.0091 (12) |
C4 | 0.0315 (15) | 0.0325 (14) | 0.0420 (16) | 0.0044 (13) | −0.0017 (14) | 0.0048 (12) |
C5 | 0.0361 (16) | 0.0314 (14) | 0.0410 (15) | 0.0096 (14) | 0.0033 (14) | −0.0026 (12) |
C6 | 0.0436 (18) | 0.056 (2) | 0.0533 (18) | −0.0052 (18) | 0.0095 (16) | 0.0019 (17) |
C7 | 0.074 (3) | 0.070 (3) | 0.0440 (18) | −0.003 (2) | 0.0186 (19) | 0.0048 (19) |
C8 | 0.077 (3) | 0.059 (2) | 0.0417 (18) | 0.007 (2) | 0.0023 (19) | −0.0088 (16) |
C9 | 0.066 (2) | 0.051 (2) | 0.0500 (19) | −0.008 (2) | −0.0060 (19) | −0.0110 (17) |
C10 | 0.057 (2) | 0.0403 (17) | 0.0484 (18) | −0.0065 (17) | 0.0061 (17) | −0.0021 (15) |
C11 | 0.0248 (13) | 0.0290 (14) | 0.0406 (15) | −0.0002 (12) | −0.0013 (12) | 0.0031 (13) |
C21 | 0.0226 (12) | 0.0258 (12) | 0.0332 (13) | −0.0006 (12) | 0.0013 (12) | 0.0008 (11) |
C31 | 0.0287 (14) | 0.0323 (14) | 0.0335 (14) | −0.0012 (14) | 0.0001 (13) | 0.0013 (11) |
C41 | 0.0316 (15) | 0.0294 (14) | 0.0400 (15) | −0.0007 (14) | −0.0050 (14) | 0.0014 (12) |
C51 | 0.0298 (14) | 0.0344 (15) | 0.0354 (14) | −0.0033 (13) | −0.0059 (14) | 0.0039 (11) |
C61 | 0.047 (2) | 0.0380 (18) | 0.081 (2) | 0.0034 (17) | 0.015 (2) | 0.0115 (18) |
C71 | 0.053 (2) | 0.045 (2) | 0.095 (3) | 0.0110 (19) | 0.012 (2) | 0.007 (2) |
C81 | 0.055 (2) | 0.0290 (16) | 0.082 (2) | −0.0021 (18) | −0.002 (2) | 0.0112 (16) |
C91 | 0.062 (2) | 0.051 (2) | 0.069 (2) | −0.011 (2) | 0.014 (2) | 0.0143 (18) |
C101 | 0.053 (2) | 0.0436 (18) | 0.0563 (18) | −0.0005 (19) | 0.0103 (19) | 0.0042 (15) |
O1—C1 | 1.229 (3) | C21—C41 | 1.531 (3) |
O2—C3 | 1.228 (3) | C21—C31 | 1.532 (4) |
O11—C11 | 1.226 (3) | C41—C51 | 1.511 (4) |
O21—C31 | 1.226 (3) | C51—C101 | 1.386 (4) |
N1—C1 | 1.322 (3) | C51—C61 | 1.363 (4) |
N1—C2 | 1.470 (3) | C61—C71 | 1.400 (5) |
N3—C3 | 1.322 (4) | C71—C81 | 1.369 (5) |
N11—C11 | 1.327 (4) | C81—C91 | 1.350 (5) |
N11—C21 | 1.466 (3) | C91—C101 | 1.395 (4) |
N31—C31 | 1.317 (4) | C2—H2 | 0.9801 |
N1—H1 | 0.89 (4) | C4—H41 | 0.9698 |
N3—H32 | 0.87 (5) | C4—H42 | 0.9699 |
N3—H31 | 0.85 (4) | C6—H6 | 0.9298 |
N11—H11 | 0.85 (3) | C7—H7 | 0.9299 |
N31—H311 | 0.90 (3) | C8—H8 | 0.9299 |
N31—H312 | 0.80 (4) | C9—H9 | 0.9300 |
C1—C11 | 1.529 (4) | C10—H10 | 0.9297 |
C2—C4 | 1.524 (4) | C21—H21 | 0.9801 |
C2—C3 | 1.528 (4) | C41—H411 | 0.9701 |
C4—C5 | 1.517 (3) | C41—H412 | 0.9699 |
C5—C10 | 1.390 (5) | C61—H61 | 0.9301 |
C5—C6 | 1.376 (4) | C71—H71 | 0.9299 |
C6—C7 | 1.369 (4) | C81—H81 | 0.9292 |
C7—C8 | 1.386 (6) | C91—H91 | 0.9298 |
C8—C9 | 1.384 (6) | C101—H101 | 0.9304 |
C9—C10 | 1.384 (4) | ||
O1···N1i | 2.994 (3) | C101···C61iii | 3.567 (5) |
O1···N11 | 2.695 (3) | C3···H311ii | 2.92 (3) |
O1···C4i | 3.406 (4) | C7···H7vii | 2.9759 |
O2···N1 | 3.085 (2) | C8···H6vii | 3.0940 |
O2···N31ii | 2.909 (3) | C9···H81viii | 3.0974 |
O2···N3iii | 2.945 (4) | C10···H2 | 2.8672 |
O11···C41iii | 3.297 (4) | C31···H31iv | 3.09 (3) |
O11···N11iii | 2.985 (3) | C91···H101ix | 2.9630 |
O11···N1 | 2.712 (3) | C101···H21 | 3.0650 |
O21···N3iv | 2.988 (3) | H1···O1iii | 2.14 (4) |
O21···N11 | 3.089 (3) | H1···O11 | 2.35 (5) |
O21···C61 | 3.250 (4) | H1···H41 | 2.4444 |
O21···N31i | 2.954 (4) | H2···O1 | 2.4805 |
O21···C51 | 3.273 (4) | H2···C10 | 2.8672 |
O1···H1i | 2.14 (4) | H2···H32 | 2.2457 |
O1···H11 | 2.30 (3) | H2···H41i | 2.3925 |
O1···H2 | 2.4805 | H6···H41 | 2.3802 |
O1···H41i | 2.6082 | H6···C8x | 3.0940 |
O2···H42 | 2.8858 | H7···C7x | 2.9759 |
O2···H41 | 2.7178 | H8···N11x | 2.8087 |
O2···H32iii | 2.19 (5) | H9···H81viii | 2.4547 |
O2···H311ii | 2.04 (3) | H10···H42 | 2.5813 |
O11···H11iii | 2.20 (3) | H11···O1 | 2.30 (3) |
O11···H412iii | 2.5050 | H11···O11i | 2.20 (3) |
O11···H1 | 2.35 (5) | H11···H412 | 2.4830 |
O11···H21 | 2.5162 | H21···O11 | 2.5162 |
O21···H312i | 2.23 (4) | H21···C101 | 3.0650 |
O21···H412 | 2.6915 | H21···H312 | 2.3544 |
O21···H61 | 2.8534 | H21···H412iii | 2.3813 |
O21···H31iv | 2.18 (3) | H31···O21v | 2.18 (3) |
N1···O1iii | 2.994 (3) | H31···C31v | 3.09 (3) |
N1···O2 | 3.085 (2) | H32···O2i | 2.19 (5) |
N1···O11 | 2.712 (3) | H32···H2 | 2.2457 |
N1···N3 | 3.181 (3) | H41···O1iii | 2.6082 |
N3···O2i | 2.945 (4) | H41···O2 | 2.7178 |
N3···N1 | 3.181 (3) | H41···H1 | 2.4444 |
N3···O21v | 2.988 (3) | H41···H2iii | 2.3925 |
N11···O1 | 2.695 (3) | H41···H6 | 2.3802 |
N11···O11i | 2.985 (3) | H42···O2 | 2.8858 |
N11···O21 | 3.089 (3) | H42···H10 | 2.5813 |
N11···N31 | 3.118 (4) | H61···O21 | 2.8534 |
N31···O2vi | 2.909 (3) | H61···H412 | 2.3699 |
N31···O21iii | 2.954 (4) | H81···C9xi | 3.0974 |
N31···N11 | 3.118 (4) | H81···H9xi | 2.4547 |
N11···H8vii | 2.8087 | H101···H411 | 2.5437 |
C4···O1iii | 3.406 (4) | H101···C91xii | 2.9630 |
C6···C9iii | 3.548 (6) | H311···O2vi | 2.04 (3) |
C9···C6i | 3.548 (6) | H311···C3vi | 2.92 (3) |
C31···C61 | 3.517 (4) | H312···O21iii | 2.23 (4) |
C41···O11i | 3.297 (4) | H312···H21 | 2.3544 |
C51···O21 | 3.273 (4) | H411···H101 | 2.5437 |
C61···C101i | 3.567 (5) | H412···O11i | 2.5050 |
C61···C31 | 3.517 (4) | H412···O21 | 2.6915 |
C61···O21 | 3.250 (4) | H412···H11 | 2.4830 |
C71···C91i | 3.572 (6) | H412···H21i | 2.3813 |
C91···C71iii | 3.572 (6) | H412···H61 | 2.3699 |
C1—N1—C2 | 122.3 (2) | C41—C51—C101 | 120.3 (2) |
C11—N11—C21 | 123.7 (2) | C51—C61—C71 | 121.5 (3) |
C2—N1—H1 | 118 (3) | C61—C71—C81 | 119.5 (4) |
C1—N1—H1 | 119 (3) | C71—C81—C91 | 119.7 (3) |
C3—N3—H32 | 122 (3) | C81—C91—C101 | 121.0 (3) |
C3—N3—H31 | 118 (2) | C51—C101—C91 | 120.1 (3) |
H31—N3—H32 | 118 (4) | N1—C2—H2 | 108.68 |
C21—N11—H11 | 119 (2) | C3—C2—H2 | 108.70 |
C11—N11—H11 | 117 (2) | C4—C2—H2 | 108.69 |
H311—N31—H312 | 116 (3) | C2—C4—H41 | 109.22 |
C31—N31—H311 | 115 (2) | C2—C4—H42 | 109.21 |
C31—N31—H312 | 127 (2) | C5—C4—H41 | 109.20 |
O1—C1—C11 | 120.6 (2) | C5—C4—H42 | 109.21 |
O1—C1—N1 | 125.0 (3) | H41—C4—H42 | 107.93 |
N1—C1—C11 | 114.4 (2) | C5—C6—H6 | 119.04 |
N1—C2—C3 | 107.83 (17) | C7—C6—H6 | 119.07 |
N1—C2—C4 | 111.43 (17) | C6—C7—H7 | 120.13 |
C3—C2—C4 | 111.44 (18) | C8—C7—H7 | 120.13 |
O2—C3—C2 | 120.81 (18) | C7—C8—H8 | 120.18 |
N3—C3—C2 | 115.6 (2) | C9—C8—H8 | 120.14 |
O2—C3—N3 | 123.5 (3) | C8—C9—H9 | 120.19 |
C2—C4—C5 | 112.0 (2) | C10—C9—H9 | 120.15 |
C4—C5—C6 | 121.7 (3) | C5—C10—H10 | 119.53 |
C4—C5—C10 | 120.2 (3) | C9—C10—H10 | 119.57 |
C6—C5—C10 | 118.1 (3) | N11—C21—H21 | 109.01 |
C5—C6—C7 | 121.9 (3) | C31—C21—H21 | 109.04 |
C6—C7—C8 | 119.7 (3) | C41—C21—H21 | 109.04 |
C7—C8—C9 | 119.7 (3) | C21—C41—H411 | 108.69 |
C8—C9—C10 | 119.7 (4) | C21—C41—H412 | 108.68 |
C5—C10—C9 | 120.9 (3) | C51—C41—H411 | 108.70 |
O11—C11—N11 | 125.1 (3) | C51—C41—H412 | 108.70 |
O11—C11—C1 | 121.1 (2) | H411—C41—H412 | 107.62 |
N11—C11—C1 | 113.8 (2) | C51—C61—H61 | 119.21 |
C31—C21—C41 | 113.1 (2) | C71—C61—H61 | 119.33 |
N11—C21—C31 | 106.36 (13) | C61—C71—H71 | 120.23 |
N11—C21—C41 | 110.18 (19) | C81—C71—H71 | 120.24 |
O21—C31—N31 | 123.83 (16) | C71—C81—H81 | 120.12 |
O21—C31—C21 | 121.0 (2) | C91—C81—H81 | 120.14 |
N31—C31—C21 | 115.1 (3) | C81—C91—H91 | 119.49 |
C21—C41—C51 | 114.3 (2) | C101—C91—H91 | 119.53 |
C61—C51—C101 | 118.2 (3) | C51—C101—H101 | 119.90 |
C41—C51—C61 | 121.5 (2) | C91—C101—H101 | 119.96 |
C2—N1—C1—O1 | −4.9 (4) | C4—C5—C10—C9 | 178.8 (3) |
C11—C1—N1—C2 | 174.50 (13) | C4—C5—C6—C7 | −178.6 (3) |
C1—N1—C2—C3 | −92.83 (18) | C5—C6—C7—C8 | −0.7 (6) |
C1—N1—C2—C4 | 144.6 (3) | C6—C7—C8—C9 | 0.1 (7) |
C21—N11—C11—O11 | −3.2 (3) | C7—C8—C9—C10 | 0.1 (7) |
C11—N11—C21—C41 | 141.8 (2) | C8—C9—C10—C5 | 0.3 (6) |
O1—C1—C11—N11 | −0.2 (3) | C31—C21—C41—C51 | 59.6 (3) |
N1—C1—C11—O11 | −1.4 (3) | C41—C21—C31—N31 | −147.9 (3) |
O1—C1—C11—O11 | 178.06 (16) | N11—C21—C31—N31 | 91.0 (3) |
N1—C1—C11—N11 | −179.64 (14) | N11—C21—C41—C51 | 178.46 (16) |
C4—C2—C3—O2 | 39.4 (4) | C41—C21—C31—O21 | 34.6 (3) |
N1—C2—C3—O2 | −83.2 (3) | N11—C21—C31—O21 | −86.5 (3) |
N1—C2—C3—N3 | 94.1 (3) | C21—C41—C51—C61 | −104.3 (3) |
C3—C2—C4—C5 | 171.0 (2) | C21—C41—C51—C101 | 78.4 (2) |
N1—C2—C4—C5 | −68.5 (3) | C41—C51—C101—C91 | 177.3 (3) |
C1—C11—N11—C21 | 174.95 (10) | C61—C51—C101—C91 | −0.1 (4) |
C11—N11—C21—C31 | −95.3 (2) | C41—C51—C61—C71 | −177.4 (3) |
C4—C2—C3—N3 | −143.3 (3) | C101—C51—C61—C71 | 0.0 (4) |
C2—C4—C5—C10 | −72.7 (3) | C51—C61—C71—C81 | 0.3 (5) |
C2—C4—C5—C6 | 106.9 (3) | C61—C71—C81—C91 | −0.4 (5) |
C6—C5—C10—C9 | −0.9 (5) | C71—C81—C91—C101 | 0.3 (5) |
C10—C5—C6—C7 | 1.1 (5) | C81—C91—C101—C51 | 0.0 (5) |
Symmetry codes: (i) x−1, y, z; (ii) −x+1, y−1/2, −z+1/2; (iii) x+1, y, z; (iv) −x, y+1/2, −z+1/2; (v) −x, y−1/2, −z+1/2; (vi) −x+1, y+1/2, −z+1/2; (vii) x−1/2, −y+1/2, −z; (viii) x, y−1, z; (ix) x−1/2, −y+3/2, −z; (x) x+1/2, −y+1/2, −z; (xi) x, y+1, z; (xii) x+1/2, −y+3/2, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1iii | 0.89 (4) | 2.14 (4) | 2.994 (3) | 159 (4) |
N1—H1···O11 | 0.89 (4) | 2.35 (5) | 2.712 (3) | 104 (3) |
N11—H11···O1 | 0.85 (3) | 2.30 (3) | 2.695 (3) | 109 (2) |
N11—H11···O11i | 0.85 (3) | 2.20 (3) | 2.985 (3) | 154 (3) |
N3—H31···O21v | 0.85 (4) | 2.18 (3) | 2.988 (3) | 159 (3) |
N3—H32···O2i | 0.87 (5) | 2.19 (5) | 2.945 (4) | 145 (4) |
N31—H311···O2vi | 0.90 (3) | 2.04 (3) | 2.909 (3) | 163 (3) |
N31—H312···O21iii | 0.80 (4) | 2.23 (4) | 2.954 (4) | 151 (3) |
Symmetry codes: (i) x−1, y, z; (iii) x+1, y, z; (v) −x, y−1/2, −z+1/2; (vi) −x+1, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C20H22N4O4·C2H6OS |
Mr | 460.54 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 295 |
a, b, c (Å) | 5.1830 (5), 15.220 (3), 29.63 (1) |
V (Å3) | 2337.4 (9) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 1.57 |
Crystal size (mm) | 0.32 × 0.14 × 0.04 |
Data collection | |
Diffractometer | Enraf-Nonius CAD4 diffractometer |
Absorption correction | Analytical (PLATON; Spek, 1999) |
Tmin, Tmax | 0.744, 0.943 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2786, 2786, 1888 |
Rint | 0.000 |
(sin θ/λ)max (Å−1) | 0.624 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.120, 1.01 |
No. of reflections | 2786 |
No. of parameters | 277 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.15, −0.19 |
Absolute structure parameter | −0.1 (4) |
Computer programs: CAD-4 EXPRESS (Enraf Nonius, 1992), CAD-4 EXPRESS, HELENA (Spek, 1997), SIR97 (Altomare et al., 1997), SHELXL97 (Sheldrick, 1997) and PLATON (Spek, 1999), PLATON.
C11—C1—N1—C2 | 174.50 (13) | C1—C11—N11—C21 | 174.95 (10) |
C1—N1—C2—C3 | −92.83 (18) | C11—N11—C21—C31 | −95.3 (2) |
N1—C2—C3—N3 | 94.1 (3) | N11—C21—C31—N31 | 91.0 (3) |
N1—C2—C4—C5 | −68.5 (3) | N11—C21—C41—C51 | 178.46 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.89 (4) | 2.14 (4) | 2.994 (3) | 159 (4) |
N1—H1···O11 | 0.89 (4) | 2.35 (5) | 2.712 (3) | 104 (3) |
N11—H11···O1 | 0.85 (3) | 2.30 (3) | 2.695 (3) | 109 (2) |
N11—H11···O11ii | 0.85 (3) | 2.20 (3) | 2.985 (3) | 154 (3) |
N3—H31···O21iii | 0.85 (4) | 2.18 (3) | 2.988 (3) | 159 (3) |
N3—H32···O2ii | 0.87 (5) | 2.19 (5) | 2.945 (4) | 145 (4) |
N31—H311···O2iv | 0.90 (3) | 2.04 (3) | 2.909 (3) | 163 (3) |
N31—H312···O21i | 0.80 (4) | 2.23 (4) | 2.954 (4) | 151 (3) |
Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z; (iii) −x, y−1/2, −z+1/2; (iv) −x+1, y+1/2, −z+1/2. |
%T In recent years, there is an increased interest for the investigation of retro-bipeptides with an oxalamide unit (–NH–CO–CO–NH–) for two reasons: a) to modify peptides in order to gain peptidomimetics useful for medical treatment (Karle {ιt et al.}., 1994; Karle \& Ranganathan, 1995) and b) to model synthons which generate supramolecular aggregates (Coe {ιt et al.}., 1997; Nguyen {ιt et al.}., 1998). Our interest has been focused on the retro-bipeptides, which serve as gelators of many organic solvents and water (Joki\'{c} {ιt et al.}., 1995; Makarević {ιt et al.}., 2001). Gelling properties of these compounds depend on stereochemistry of amino acids substituted at the ends of the oxalamide units. Generally, it appears that retro-bipeptide containing amino acids of the same chirality are good gelators, whereas {ιt meso}-forms or racemates are found to be poor gelators or they are not gelators at all. Therefore, detailed analysis of hydrogen-bond systems in crystal structures of these retro-bipeptides and other molecules closely related to them is required. The analysis points out to the interactions responsible for the aggregation and to reveal holes, which can serve as the solvent traps during gel formation. σch
In this paper the molecular structure of the title compound, (I), is presented. The ORTEPII (Johnson, 1976) plot (Fig 1) shows that primary amide groups, as well as phenylalanine side chains, are oriented to the same side of the central oxalamide unit. The pairs of torsion angles ($πhi$,$πsi$) and ($πhi'$,$πsi'$) are close to those found in the parellel $βeta$-sheets in peptides (Table 1). Torsion angles $οmega$, $οmega'$, $πhi$, $πhi'$, $πsi$, $πsi'$, $χhi$ and $χhi'$ are labelled according to the literature (Karle {ιt et al.}., 1994). The large difference in the angles $χhi$ and $χhi'$ (Table 1), reveals perpendicular and parallel orientations of amino acid moieties toward the central oxalamide unit, respectively (Fig. 1).
Crystal packing is realised by hydrogen bonds connecting: a) oxalamide $χdots$ oxalamide units and b) terminal amide $χdots$ terminal amide groups [Table 2, Fig 2 a) and b), respectively]. The former hydrogen bonds form fourth level pattern with the graph-set descriptor $R_22(4)$ (Bernstein {ιt et al.}., 1995) connecting molecules translated along the axis $a$ (Fig. 2a). These interactions include two intramolecular hydrogen bonds N1–H1$χdots$O11 and N11–H11$χdots$O1, and two intermolecular hydogen bonds N1–H1$χdots$O1${i}$ and N11–H11$χdots$O11${ii}$ (Table 2). The pattern formed is also stabilised by $πi$$χdots$$πi$ interactions between the phenyl rings. The later hydrogen bond pattern involves terminal primary amide groups with both of their hydrogens {ιt syn} and {ιt anti}. {ιt Anti}-hydrogen atoms of both terminal amide groups act as proton donors to oxygen atoms of amide groups of the molecules translated along $a$ (N3–H32$χdots$O2${ii}$ and N31–H312$χdots$O21${i}$, Table 2). {ιt Syn}-hydrogen atoms participate in hydrogen bonds with oxygen atoms of primary amide groups operated by the symmetry $2_1$ along $b$ (N3–H31$χdots$O21${iii}$ and N31–H311$χdots$O2${iv}$, Table 2). The pattern described here is different to the one discused Chang {ιt et al.}., 1993, the one which is the most common hydrogen bonding pattern formed by primary amides (Lieserovitz \& Schmidt, 1969). However, fragmental similarity can be seen in the crystal structure of adipamide (Hospital \& Housty, 1966) with primary amide groups hydrogen bonded along the two-fold screw axis. On the contrary, in the title molecule the hydrogen-bonded pattern is perpendicular to the two-fold screw axis along $b$. The rest of adipamide molecule develops a centrosymmetric arrangement. In the crystal of the title molecule, the wave-shaped pattern of two-dimensional system of hydrogen bonds forms holes occupied by disordered dimethylsulphoxide molecules (Fig 3). Such packing also brings phenyl rings of neighbouring molecules in a perpendicular orientation enabling C–H$χdots$$πi$ interactions. One of these interactions [C81-H81$χdots$Ph(1), H$χdots$centroid, 3.286 AA] connects molecules along $b$ whereas C7–H7$χdots$Ph(1) [H$χdots$centroid 3.076 AA] and C101-H101$χdots$Ph(2) [H$χdots$centroid 3.116 AA] connect layers along $c$ (Fig. 3). Thus, C–H$χdots$$πi$ interactions complete the three-dimensional network.