Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827011204365X/sf3181sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827011204365X/sf3181Isup2.hkl | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S010827011204365X/sf3181Isup3.cml |
CCDC reference: 818064
A solution of diethyl 1,2-phenylenedioxalamate (0.5 g, 1.6 mmol) in methanol (30 ml) and 3-(morpholin-4-yl)propylamine (0.474 ml, 3.2 mmol) was refluxed for 24 h. The suspension was filtered off and the resulting solid was washed with acetone (3 ml) and dried to yield 0.49 g (61%) of a white solid (m.p. 238–440 K). Good quality crystals were grown from DMSO solution by slow evaporation. IR ν (neat) (cm-1): 3272 (N—H), 1667 (C═O). 1H NMR (300 MHz, DMSOd-6): δ 7.27 (m, 2H), 7.59 (m, 2H), 10.52 (s, 2H, Ar–NH), 8.87 (t, 2H, NH–CH2), 3.24 (m, 4H, NH–CH2), 1.64 (m, 4H, NH–CH2–CH2), 2.32 (m, 4H, CH2–N), 2.30 [m, 8H, N–(CH2)2], 3.56 [m, 8H, O–(CH2)2]. 13C NMR (75.46 MHz, DMSOd-6): δ 130.5 (C1,6), 126.2 (C2,5), 126.8 (C3,4), 159.3 (C8), 160.1 (C9), 38.9 (C11), 25.6 (C12), 57.0 (C13), 53.9 (N–CH2), 66.8 (CH2—O). ESI–MS (m/z): calculated 504.27, found 526.9 [M + Na]+.
All H atoms were found by Fourier difference synthesis and refined. The DMSO S atom is disordered over two positions with occupancies of 0.931 (2) and 0.069 (2). The disorder was treated using PART 1, PART 2 and PART 0 SHELXL97 (Sheldrick, 2008) instructions.
Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008) and WinGX (Farrugia, 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: PLATON (Spek, 2009).
The molecular structure of the title DMSO-solvated complex, showing the
atom-labelling scheme. Displacement ellipsoids are drawn at the 30%
probability level and H atoms are shown as small spheres of arbitrary radii. Two molecules of the title DMSO-solvated complex are paired through self-complementary strong N10—H10···O8 hydrogen bonding to form the R22(10) motif characteristic of oxalamides. The linkage of the title DMSO-solvated complex dimer through C35—H35A···O29 soft interactions developing a meso helix along the direction of the c axis. H atoms have been omitted for clarity. |
C24H36N6O6·C2H6OS | Z = 2 |
Mr = 582.72 | F(000) = 624 |
Triclinic, P1 | Dx = 1.318 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.6704 (8) Å | Cell parameters from 600 reflections |
b = 11.0052 (10) Å | θ = 20–25° |
c = 16.3277 (15) Å | µ = 0.16 mm−1 |
α = 107.425 (2)° | T = 173 K |
β = 98.036 (2)° | Block, yellow |
γ = 91.517 (2)° | 0.30 × 0.26 × 0.22 × 0.12 (radius) mm |
V = 1468.0 (2) Å3 |
Bruker APEXII area-detector diffractometer | 5081 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
ϕ and ω scans | θmax = 26.0°, θmin = 1.3° |
Absorption correction: for a sphere (Dwiggins, 1975) | h = −10→10 |
Tmin = 0.861, Tmax = 0.862 | k = −12→13 |
11574 measured reflections | l = −19→20 |
5722 independent reflections |
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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.099 | All H-atom parameters refined |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0453P)2 + 0.6256P] where P = (Fo2 + 2Fc2)/3 |
5722 reflections | (Δ/σ)max = 0.001 |
539 parameters | Δρmax = 0.41 e Å−3 |
0 restraints | Δρmin = −0.28 e Å−3 |
C24H36N6O6·C2H6OS | γ = 91.517 (2)° |
Mr = 582.72 | V = 1468.0 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.6704 (8) Å | Mo Kα radiation |
b = 11.0052 (10) Å | µ = 0.16 mm−1 |
c = 16.3277 (15) Å | T = 173 K |
α = 107.425 (2)° | 0.30 × 0.26 × 0.22 × 0.12 (radius) mm |
β = 98.036 (2)° |
Bruker APEXII area-detector diffractometer | 5722 independent reflections |
Absorption correction: for a sphere (Dwiggins, 1975) | 5081 reflections with I > 2σ(I) |
Tmin = 0.861, Tmax = 0.862 | Rint = 0.021 |
11574 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.099 | All H-atom parameters refined |
S = 1.04 | Δρmax = 0.41 e Å−3 |
5722 reflections | Δρmin = −0.28 e Å−3 |
539 parameters |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su'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 | Occ. (<1) | |
O8 | 0.53574 (12) | 0.60848 (11) | 0.10601 (7) | 0.0264 (3) | |
O9 | 0.17690 (13) | 0.50921 (11) | 0.15060 (7) | 0.0262 (3) | |
O17 | −0.37434 (15) | 0.17201 (13) | 0.08340 (9) | 0.0391 (4) | |
O28 | 0.64360 (13) | 0.75925 (12) | 0.47845 (8) | 0.0302 (4) | |
O29 | 0.25116 (12) | 0.65877 (11) | 0.46500 (7) | 0.0252 (3) | |
O37 | 1.02189 (14) | 0.80083 (12) | 0.67308 (9) | 0.0385 (4) | |
N7 | 0.38959 (15) | 0.70657 (12) | 0.21044 (8) | 0.0187 (4) | |
N10 | 0.31850 (16) | 0.40636 (12) | 0.04669 (9) | 0.0225 (4) | |
N14 | −0.10812 (15) | 0.18090 (12) | −0.00197 (8) | 0.0227 (4) | |
N27 | 0.42871 (15) | 0.79070 (12) | 0.39127 (8) | 0.0188 (3) | |
N30 | 0.46105 (15) | 0.65750 (13) | 0.56521 (9) | 0.0215 (4) | |
N34 | 0.71514 (14) | 0.73241 (12) | 0.69766 (8) | 0.0207 (4) | |
C1 | 0.48849 (16) | 0.81794 (14) | 0.25568 (10) | 0.0185 (4) | |
C2 | 0.56534 (17) | 0.88637 (15) | 0.21224 (10) | 0.0213 (5) | |
C3 | 0.66111 (18) | 0.99471 (15) | 0.25899 (11) | 0.0231 (5) | |
C4 | 0.68062 (18) | 1.03634 (15) | 0.34891 (10) | 0.0221 (4) | |
C5 | 0.60312 (17) | 0.96937 (15) | 0.39263 (10) | 0.0212 (5) | |
C6 | 0.50729 (16) | 0.85992 (14) | 0.34636 (10) | 0.0180 (4) | |
C8 | 0.41987 (17) | 0.61291 (14) | 0.14196 (9) | 0.0194 (4) | |
C9 | 0.29006 (17) | 0.50367 (14) | 0.11262 (10) | 0.0196 (4) | |
C11 | 0.21399 (19) | 0.29092 (15) | 0.01338 (11) | 0.0237 (5) | |
C12 | 0.0849 (2) | 0.29545 (17) | −0.05828 (11) | 0.0274 (5) | |
C13 | −0.0393 (2) | 0.18562 (17) | −0.07818 (10) | 0.0258 (5) | |
C15 | −0.1936 (2) | 0.29349 (17) | 0.03148 (12) | 0.0303 (5) | |
C16 | −0.2704 (2) | 0.28347 (19) | 0.10682 (13) | 0.0369 (6) | |
C18 | −0.2899 (2) | 0.06255 (19) | 0.05283 (14) | 0.0357 (6) | |
C19 | −0.21447 (19) | 0.06680 (16) | −0.02420 (11) | 0.0267 (5) | |
C28 | 0.50291 (17) | 0.74814 (14) | 0.45403 (10) | 0.0201 (4) | |
C29 | 0.39051 (17) | 0.68233 (14) | 0.49543 (10) | 0.0198 (4) | |
C31 | 0.37658 (18) | 0.60791 (16) | 0.62106 (11) | 0.0235 (5) | |
C32 | 0.49037 (18) | 0.58436 (16) | 0.69399 (11) | 0.0235 (5) | |
C33 | 0.59856 (19) | 0.70112 (16) | 0.74713 (10) | 0.0238 (5) | |
C35 | 0.83681 (19) | 0.64169 (16) | 0.68605 (13) | 0.0282 (5) | |
C36 | 0.9470 (2) | 0.67591 (18) | 0.63104 (15) | 0.0364 (6) | |
C38 | 0.9057 (2) | 0.89093 (17) | 0.68587 (14) | 0.0342 (6) | |
C39 | 0.7904 (2) | 0.86114 (16) | 0.73967 (12) | 0.0299 (5) | |
S1A | 0.03282 (4) | 0.22525 (4) | 0.69145 (3) | 0.0201 (1) | 0.931 (2) |
O1 | −0.13537 (12) | 0.21701 (11) | 0.70381 (7) | 0.0256 (3) | |
C40 | 0.0296 (2) | 0.1563 (2) | 0.57760 (12) | 0.0359 (6) | |
C41 | 0.0781 (3) | 0.3874 (2) | 0.69737 (18) | 0.0477 (8) | |
S1B | −0.0121 (11) | 0.3196 (8) | 0.6628 (6) | 0.055 (3) | 0.069 (2) |
H2 | 0.553 (2) | 0.8566 (17) | 0.1505 (12) | 0.025 (4)* | |
H3 | 0.7147 (19) | 1.0425 (16) | 0.2299 (11) | 0.020 (4)* | |
H4 | 0.748 (2) | 1.1113 (17) | 0.3810 (11) | 0.022 (4)* | |
H5 | 0.6172 (19) | 0.9953 (16) | 0.4560 (12) | 0.022 (4)* | |
H7 | 0.304 (2) | 0.6964 (18) | 0.2256 (12) | 0.029 (5)* | |
H10 | 0.392 (2) | 0.4154 (18) | 0.0200 (12) | 0.030 (5)* | |
H11A | 0.1675 (19) | 0.2798 (15) | 0.0609 (11) | 0.016 (4)* | |
H11B | 0.277 (2) | 0.2198 (18) | −0.0084 (12) | 0.026 (4)* | |
H12A | 0.127 (2) | 0.2889 (18) | −0.1108 (12) | 0.029 (5)* | |
H12B | 0.037 (2) | 0.3779 (19) | −0.0421 (12) | 0.030 (5)* | |
H13A | −0.121 (2) | 0.1896 (17) | −0.1243 (12) | 0.027 (5)* | |
H13B | 0.011 (2) | 0.1042 (18) | −0.0995 (11) | 0.024 (4)* | |
H15A | −0.279 (2) | 0.3041 (19) | −0.0144 (13) | 0.039 (5)* | |
H15B | −0.123 (2) | 0.3694 (19) | 0.0496 (12) | 0.031 (5)* | |
H16A | −0.192 (2) | 0.2795 (18) | 0.1533 (13) | 0.033 (5)* | |
H16B | −0.334 (2) | 0.355 (2) | 0.1251 (13) | 0.040 (5)* | |
H18A | −0.364 (2) | −0.011 (2) | 0.0377 (13) | 0.039 (5)* | |
H18B | −0.205 (2) | 0.0586 (18) | 0.0998 (12) | 0.031 (5)* | |
H19A | −0.157 (2) | −0.0075 (18) | −0.0427 (11) | 0.024 (4)* | |
H19B | −0.300 (2) | 0.0644 (17) | −0.0731 (12) | 0.028 (5)* | |
H27 | 0.327 (2) | 0.7744 (17) | 0.3771 (12) | 0.027 (5)* | |
H30 | 0.553 (2) | 0.6837 (18) | 0.5860 (12) | 0.026 (5)* | |
H31A | 0.317 (2) | 0.5292 (19) | 0.5866 (12) | 0.030 (5)* | |
H31B | 0.305 (2) | 0.6694 (17) | 0.6469 (11) | 0.024 (4)* | |
H32A | 0.428 (2) | 0.5591 (18) | 0.7342 (12) | 0.030 (5)* | |
H32B | 0.551 (2) | 0.5113 (17) | 0.6699 (11) | 0.022 (4)* | |
H33A | 0.540 (2) | 0.7767 (19) | 0.7655 (12) | 0.030 (5)* | |
H33B | 0.651 (2) | 0.6867 (17) | 0.8013 (12) | 0.025 (4)* | |
H35A | 0.790 (2) | 0.5578 (19) | 0.6568 (12) | 0.030 (5)* | |
H35B | 0.892 (2) | 0.6453 (18) | 0.7439 (13) | 0.034 (5)* | |
H36A | 1.028 (2) | 0.6189 (19) | 0.6228 (13) | 0.037 (5)* | |
H36B | 0.886 (2) | 0.675 (2) | 0.5718 (14) | 0.044 (6)* | |
H38A | 0.848 (2) | 0.8922 (19) | 0.6298 (13) | 0.036 (5)* | |
H38B | 0.962 (2) | 0.975 (2) | 0.7173 (13) | 0.042 (6)* | |
H39A | 0.846 (2) | 0.8695 (19) | 0.7996 (13) | 0.034 (5)* | |
H39B | 0.707 (2) | 0.9221 (19) | 0.7458 (12) | 0.034 (5)* | |
H40A | −0.001 (3) | 0.059 (3) | 0.5650 (16) | 0.066 (7)* | |
H40B | 0.132 (3) | 0.169 (2) | 0.5635 (13) | 0.043 (6)* | |
H40C | −0.045 (2) | 0.1964 (19) | 0.5472 (13) | 0.035 (5)* | |
H41A | 0.072 (3) | 0.442 (3) | 0.7620 (18) | 0.070 (8)* | |
H41B | −0.005 (3) | 0.414 (3) | 0.6513 (18) | 0.072 (8)* | |
H41C | 0.186 (3) | 0.391 (2) | 0.6899 (16) | 0.065 (7)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O8 | 0.0256 (6) | 0.0259 (6) | 0.0243 (6) | −0.0022 (5) | 0.0091 (5) | 0.0006 (5) |
O9 | 0.0270 (6) | 0.0253 (6) | 0.0255 (6) | −0.0015 (5) | 0.0092 (5) | 0.0046 (5) |
O17 | 0.0332 (7) | 0.0382 (7) | 0.0491 (8) | 0.0076 (6) | 0.0181 (6) | 0.0127 (6) |
O28 | 0.0213 (6) | 0.0423 (7) | 0.0339 (7) | −0.0003 (5) | 0.0026 (5) | 0.0228 (6) |
O29 | 0.0214 (5) | 0.0296 (6) | 0.0251 (6) | −0.0032 (4) | −0.0004 (4) | 0.0115 (5) |
O37 | 0.0247 (6) | 0.0297 (7) | 0.0607 (9) | −0.0060 (5) | 0.0067 (6) | 0.0141 (6) |
N7 | 0.0191 (6) | 0.0204 (7) | 0.0170 (6) | 0.0002 (5) | 0.0049 (5) | 0.0054 (5) |
N10 | 0.0256 (7) | 0.0203 (7) | 0.0210 (7) | −0.0013 (5) | 0.0077 (5) | 0.0037 (5) |
N14 | 0.0259 (7) | 0.0214 (7) | 0.0201 (7) | 0.0011 (5) | 0.0031 (5) | 0.0057 (5) |
N27 | 0.0193 (6) | 0.0198 (6) | 0.0167 (6) | −0.0019 (5) | 0.0025 (5) | 0.0051 (5) |
N30 | 0.0184 (6) | 0.0258 (7) | 0.0219 (7) | −0.0022 (5) | 0.0017 (5) | 0.0108 (6) |
N34 | 0.0215 (6) | 0.0181 (6) | 0.0225 (7) | 0.0009 (5) | 0.0031 (5) | 0.0063 (5) |
C1 | 0.0184 (7) | 0.0176 (7) | 0.0191 (7) | 0.0043 (6) | 0.0031 (6) | 0.0047 (6) |
C2 | 0.0235 (8) | 0.0231 (8) | 0.0189 (8) | 0.0040 (6) | 0.0049 (6) | 0.0078 (6) |
C3 | 0.0237 (8) | 0.0216 (8) | 0.0278 (9) | 0.0027 (6) | 0.0080 (6) | 0.0116 (7) |
C4 | 0.0215 (7) | 0.0167 (7) | 0.0269 (8) | 0.0009 (6) | 0.0033 (6) | 0.0053 (6) |
C5 | 0.0237 (8) | 0.0202 (8) | 0.0187 (8) | 0.0022 (6) | 0.0030 (6) | 0.0044 (6) |
C6 | 0.0186 (7) | 0.0169 (7) | 0.0202 (7) | 0.0035 (5) | 0.0049 (6) | 0.0070 (6) |
C8 | 0.0222 (7) | 0.0203 (8) | 0.0170 (7) | 0.0019 (6) | 0.0023 (6) | 0.0080 (6) |
C9 | 0.0219 (7) | 0.0201 (8) | 0.0179 (7) | 0.0012 (6) | 0.0023 (6) | 0.0079 (6) |
C11 | 0.0290 (8) | 0.0179 (8) | 0.0227 (8) | −0.0019 (6) | 0.0049 (7) | 0.0037 (7) |
C12 | 0.0351 (9) | 0.0279 (9) | 0.0203 (8) | −0.0036 (7) | 0.0041 (7) | 0.0097 (7) |
C13 | 0.0308 (8) | 0.0275 (9) | 0.0172 (8) | −0.0020 (7) | 0.0000 (7) | 0.0060 (7) |
C15 | 0.0345 (9) | 0.0229 (9) | 0.0325 (10) | 0.0034 (7) | 0.0052 (8) | 0.0070 (7) |
C16 | 0.0361 (10) | 0.0357 (10) | 0.0363 (11) | 0.0082 (8) | 0.0110 (8) | 0.0043 (8) |
C18 | 0.0339 (10) | 0.0340 (10) | 0.0464 (12) | 0.0054 (8) | 0.0157 (9) | 0.0186 (9) |
C19 | 0.0267 (8) | 0.0221 (8) | 0.0311 (9) | 0.0009 (7) | 0.0039 (7) | 0.0081 (7) |
C28 | 0.0233 (8) | 0.0187 (7) | 0.0183 (8) | 0.0014 (6) | 0.0048 (6) | 0.0052 (6) |
C29 | 0.0231 (7) | 0.0165 (7) | 0.0189 (8) | 0.0011 (6) | 0.0041 (6) | 0.0039 (6) |
C31 | 0.0217 (8) | 0.0269 (8) | 0.0252 (8) | −0.0012 (7) | 0.0045 (6) | 0.0127 (7) |
C32 | 0.0242 (8) | 0.0265 (8) | 0.0243 (8) | 0.0012 (7) | 0.0066 (6) | 0.0132 (7) |
C33 | 0.0266 (8) | 0.0261 (8) | 0.0198 (8) | 0.0032 (7) | 0.0044 (6) | 0.0083 (7) |
C35 | 0.0220 (8) | 0.0204 (8) | 0.0410 (10) | 0.0013 (6) | 0.0028 (7) | 0.0086 (8) |
C36 | 0.0237 (8) | 0.0263 (9) | 0.0571 (13) | −0.0005 (7) | 0.0133 (9) | 0.0069 (9) |
C38 | 0.0337 (9) | 0.0235 (9) | 0.0447 (11) | −0.0048 (7) | 0.0029 (8) | 0.0116 (8) |
C39 | 0.0349 (9) | 0.0200 (8) | 0.0310 (10) | −0.0011 (7) | 0.0030 (8) | 0.0033 (7) |
S1A | 0.0172 (2) | 0.0196 (2) | 0.0239 (2) | 0.0025 (2) | 0.0024 (2) | 0.0074 (2) |
O1 | 0.0214 (5) | 0.0300 (6) | 0.0243 (6) | 0.0040 (4) | 0.0062 (4) | 0.0053 (5) |
C40 | 0.0313 (10) | 0.0466 (12) | 0.0290 (10) | 0.0066 (9) | 0.0122 (8) | 0.0065 (9) |
C41 | 0.0379 (11) | 0.0256 (10) | 0.0763 (17) | −0.0078 (9) | 0.0077 (11) | 0.0120 (11) |
S1B | 0.066 (6) | 0.037 (5) | 0.065 (6) | −0.005 (4) | 0.021 (5) | 0.017 (4) |
S1A—C41 | 1.788 (2) | C28—C29 | 1.540 (2) |
S1A—O1 | 1.5039 (11) | C31—C32 | 1.526 (2) |
S1A—C40 | 1.7809 (19) | C32—C33 | 1.525 (2) |
S1B—C40 | 1.993 (10) | C35—C36 | 1.512 (3) |
S1B—C41 | 1.039 (10) | C38—C39 | 1.510 (3) |
S1B—O1 | 1.859 (9) | C2—H2 | 0.951 (19) |
S1B—H41B | 1.11 (4) | C3—H3 | 0.957 (18) |
O8—C8 | 1.2274 (18) | C4—H4 | 0.963 (19) |
O9—C9 | 1.2254 (19) | C5—H5 | 0.976 (19) |
O17—C18 | 1.423 (3) | C11—H11A | 0.960 (17) |
O17—C16 | 1.424 (3) | C11—H11B | 0.974 (19) |
O28—C28 | 1.2202 (19) | C12—H12A | 0.962 (18) |
O29—C29 | 1.2298 (18) | C12—H12B | 0.99 (2) |
O37—C36 | 1.430 (3) | C13—H13B | 0.995 (19) |
O37—C38 | 1.425 (2) | C13—H13A | 0.971 (18) |
N7—C8 | 1.3371 (19) | C15—H15B | 0.97 (2) |
N7—C1 | 1.417 (2) | C15—H15A | 1.012 (19) |
N10—C9 | 1.328 (2) | C16—H16A | 0.958 (19) |
N10—C11 | 1.456 (2) | C16—H16B | 0.97 (2) |
N14—C13 | 1.467 (2) | C18—H18B | 0.998 (18) |
N14—C19 | 1.460 (2) | C18—H18A | 0.97 (2) |
N14—C15 | 1.463 (2) | C19—H19A | 0.961 (19) |
N27—C6 | 1.424 (2) | C19—H19B | 1.004 (18) |
N27—C28 | 1.343 (2) | C31—H31B | 0.972 (18) |
N30—C29 | 1.322 (2) | C31—H31A | 0.97 (2) |
N30—C31 | 1.459 (2) | C32—H32B | 0.984 (18) |
N34—C35 | 1.464 (2) | C32—H32A | 1.001 (19) |
N34—C33 | 1.473 (2) | C33—H33B | 0.995 (19) |
N34—C39 | 1.465 (2) | C33—H33A | 0.98 (2) |
N7—H7 | 0.830 (18) | C35—H35B | 0.99 (2) |
N10—H10 | 0.840 (18) | C35—H35A | 0.95 (2) |
N27—H27 | 0.879 (18) | C36—H36B | 1.03 (2) |
N30—H30 | 0.829 (18) | C36—H36A | 0.951 (19) |
C1—C6 | 1.397 (2) | C38—H38B | 0.99 (2) |
C1—C2 | 1.393 (2) | C38—H38A | 0.98 (2) |
C2—C3 | 1.385 (2) | C39—H39B | 0.99 (2) |
C3—C4 | 1.385 (2) | C39—H39A | 1.01 (2) |
C4—C5 | 1.388 (2) | C40—H40B | 0.97 (3) |
C5—C6 | 1.392 (2) | C40—H40C | 0.96 (2) |
C8—C9 | 1.541 (2) | C40—H40A | 1.05 (3) |
C11—C12 | 1.515 (2) | C41—H41B | 1.08 (3) |
C12—C13 | 1.525 (3) | C41—H41C | 0.96 (3) |
C15—C16 | 1.508 (3) | C41—H41A | 1.06 (3) |
C18—C19 | 1.508 (3) | ||
O1—S1A—C40 | 104.66 (7) | C13—C12—H12A | 107.8 (12) |
O1—S1A—C41 | 106.01 (10) | C13—C12—H12B | 110.2 (11) |
C40—S1A—C41 | 97.54 (12) | H13A—C13—H13B | 107.4 (15) |
O1—S1B—C40 | 85.1 (4) | N14—C13—H13A | 109.9 (11) |
O1—S1B—C41 | 128.5 (7) | C12—C13—H13A | 110.5 (11) |
C40—S1B—C41 | 121.3 (7) | C12—C13—H13B | 108.0 (11) |
C41—S1B—H41B | 60.1 (15) | N14—C13—H13B | 107.4 (11) |
O1—S1B—H41B | 142.5 (16) | H15A—C15—H15B | 107.3 (17) |
C40—S1B—H41B | 124.0 (16) | N14—C15—H15A | 111.8 (12) |
C16—O17—C18 | 108.97 (14) | C16—C15—H15A | 107.2 (11) |
C36—O37—C38 | 108.90 (13) | C16—C15—H15B | 109.8 (11) |
C1—N7—C8 | 125.64 (13) | N14—C15—H15B | 109.7 (11) |
C9—N10—C11 | 121.27 (14) | C15—C16—H16B | 110.1 (12) |
C15—N14—C19 | 108.92 (13) | O17—C16—H16A | 108.1 (12) |
C13—N14—C19 | 110.08 (13) | O17—C16—H16B | 105.7 (12) |
C13—N14—C15 | 111.82 (14) | C15—C16—H16A | 109.5 (11) |
C6—N27—C28 | 123.04 (13) | H16A—C16—H16B | 111.6 (17) |
C29—N30—C31 | 122.74 (13) | O17—C18—H18B | 109.6 (11) |
C33—N34—C39 | 111.71 (13) | C19—C18—H18A | 111.0 (12) |
C33—N34—C35 | 112.25 (13) | H18A—C18—H18B | 110.3 (17) |
C35—N34—C39 | 108.39 (13) | O17—C18—H18A | 106.6 (12) |
C8—N7—H7 | 114.6 (13) | C19—C18—H18B | 107.5 (10) |
C1—N7—H7 | 119.8 (14) | H19A—C19—H19B | 107.9 (15) |
C11—N10—H10 | 119.3 (13) | N14—C19—H19A | 109.0 (11) |
C9—N10—H10 | 119.0 (14) | C18—C19—H19B | 107.8 (10) |
C28—N27—H27 | 118.2 (13) | C18—C19—H19A | 109.9 (11) |
C6—N27—H27 | 118.7 (13) | N14—C19—H19B | 111.5 (11) |
C29—N30—H30 | 121.3 (13) | C32—C31—H31B | 108.5 (10) |
C31—N30—H30 | 114.7 (13) | C32—C31—H31A | 110.1 (12) |
N7—C1—C2 | 121.86 (14) | N30—C31—H31B | 109.8 (11) |
C2—C1—C6 | 119.66 (14) | N30—C31—H31A | 109.3 (11) |
N7—C1—C6 | 118.48 (14) | H31A—C31—H31B | 108.8 (15) |
C1—C2—C3 | 120.00 (14) | H32A—C32—H32B | 106.5 (16) |
C2—C3—C4 | 120.53 (15) | C31—C32—H32A | 108.1 (10) |
C3—C4—C5 | 119.80 (15) | C33—C32—H32A | 108.0 (11) |
C4—C5—C6 | 120.19 (14) | C33—C32—H32B | 110.7 (10) |
N27—C6—C5 | 120.17 (14) | C31—C32—H32B | 109.7 (10) |
C1—C6—C5 | 119.83 (14) | C32—C33—H33A | 111.3 (11) |
N27—C6—C1 | 120.00 (14) | N34—C33—H33B | 110.5 (10) |
O8—C8—C9 | 122.06 (13) | N34—C33—H33A | 106.8 (12) |
N7—C8—C9 | 111.30 (13) | C32—C33—H33B | 109.6 (11) |
O8—C8—N7 | 126.63 (15) | H33A—C33—H33B | 106.3 (15) |
N10—C9—C8 | 113.24 (13) | C36—C35—H35A | 108.7 (11) |
O9—C9—N10 | 125.86 (15) | H35A—C35—H35B | 109.8 (17) |
O9—C9—C8 | 120.86 (14) | N34—C35—H35B | 108.4 (11) |
N10—C11—C12 | 113.53 (14) | N34—C35—H35A | 109.4 (11) |
C11—C12—C13 | 111.46 (15) | C36—C35—H35B | 111.4 (11) |
N14—C13—C12 | 113.34 (13) | H36A—C36—H36B | 110.3 (17) |
N14—C15—C16 | 110.94 (16) | O37—C36—H36B | 108.3 (13) |
O17—C16—C15 | 111.85 (16) | C35—C36—H36B | 110.0 (11) |
O17—C18—C19 | 111.82 (17) | O37—C36—H36A | 106.4 (12) |
N14—C19—C18 | 110.72 (14) | C35—C36—H36A | 111.1 (13) |
O28—C28—N27 | 125.74 (15) | C39—C38—H38A | 108.6 (11) |
N27—C28—C29 | 112.80 (13) | O37—C38—H38B | 106.2 (11) |
O28—C28—C29 | 121.46 (14) | O37—C38—H38A | 110.8 (12) |
O29—C29—C28 | 121.55 (14) | H38A—C38—H38B | 110.4 (17) |
N30—C29—C28 | 112.43 (13) | C39—C38—H38B | 109.3 (11) |
O29—C29—N30 | 126.02 (15) | H39A—C39—H39B | 107.6 (16) |
N30—C31—C32 | 110.38 (13) | C38—C39—H39A | 109.4 (11) |
C31—C32—C33 | 113.61 (15) | C38—C39—H39B | 111.0 (11) |
N34—C33—C32 | 112.28 (13) | N34—C39—H39B | 107.7 (11) |
N34—C35—C36 | 109.19 (15) | N34—C39—H39A | 111.0 (12) |
O37—C36—C35 | 110.65 (17) | S1A—C40—H40A | 105.0 (14) |
O37—C38—C39 | 111.71 (16) | S1A—C40—H40B | 109.4 (12) |
N34—C39—C38 | 110.11 (15) | S1A—C40—H40C | 109.0 (12) |
C1—C2—H2 | 119.2 (11) | H40A—C40—H40B | 111 (2) |
C3—C2—H2 | 120.8 (12) | H40A—C40—H40C | 112.5 (19) |
C4—C3—H3 | 118.7 (10) | H40B—C40—H40C | 109.9 (18) |
C2—C3—H3 | 120.8 (10) | S1B—C40—H40B | 106.6 (13) |
C5—C4—H4 | 120.1 (10) | S1B—C40—H40C | 73.1 (13) |
C3—C4—H4 | 120.1 (10) | S1B—C40—H40A | 136.5 (14) |
C6—C5—H5 | 118.4 (11) | S1A—C41—H41A | 105.7 (18) |
C4—C5—H5 | 121.4 (11) | S1A—C41—H41B | 109.5 (17) |
C12—C11—H11A | 108.6 (10) | S1B—C41—H41C | 129.3 (15) |
C12—C11—H11B | 109.6 (11) | H41A—C41—H41B | 112 (2) |
H11A—C11—H11B | 109.9 (16) | H41A—C41—H41C | 107 (2) |
N10—C11—H11A | 107.7 (10) | H41B—C41—H41C | 117 (2) |
N10—C11—H11B | 107.5 (11) | S1A—C41—H41C | 104.8 (14) |
C11—C12—H12B | 110.2 (11) | S1B—C41—H41A | 119.6 (16) |
C11—C12—H12A | 110.1 (11) | S1B—C41—H41B | 63.3 (18) |
H12A—C12—H12B | 107.0 (16) | ||
C18—O17—C16—C15 | 58.2 (2) | C39—N34—C35—C36 | −59.01 (18) |
C16—O17—C18—C19 | −58.57 (19) | N7—C1—C6—N27 | 0.4 (2) |
C38—O37—C36—C35 | −60.2 (2) | C2—C1—C6—N27 | 179.80 (14) |
C36—O37—C38—C39 | 58.5 (2) | N7—C1—C2—C3 | −179.93 (14) |
C8—N7—C1—C6 | −137.65 (16) | C6—C1—C2—C3 | 0.7 (2) |
C1—N7—C8—O8 | −1.4 (3) | N7—C1—C6—C5 | −179.70 (14) |
C8—N7—C1—C2 | 43.0 (2) | C2—C1—C6—C5 | −0.3 (2) |
C1—N7—C8—C9 | 177.00 (14) | C1—C2—C3—C4 | −0.4 (2) |
C11—N10—C9—C8 | 176.20 (13) | C2—C3—C4—C5 | −0.3 (2) |
C11—N10—C9—O9 | −1.4 (3) | C3—C4—C5—C6 | 0.7 (2) |
C9—N10—C11—C12 | 89.77 (18) | C4—C5—C6—N27 | 179.53 (14) |
C19—N14—C13—C12 | −174.58 (14) | C4—C5—C6—C1 | −0.4 (2) |
C15—N14—C13—C12 | 64.21 (18) | N7—C8—C9—O9 | 0.1 (2) |
C15—N14—C19—C18 | −55.40 (18) | N7—C8—C9—N10 | −177.62 (13) |
C19—N14—C15—C16 | 55.15 (18) | O8—C8—C9—O9 | 178.59 (15) |
C13—N14—C19—C18 | −178.32 (14) | O8—C8—C9—N10 | 0.9 (2) |
C13—N14—C15—C16 | 177.03 (14) | N10—C11—C12—C13 | −168.49 (14) |
C6—N27—C28—O28 | −2.3 (3) | C11—C12—C13—N14 | 56.32 (19) |
C28—N27—C6—C5 | −54.0 (2) | N14—C15—C16—O17 | −57.85 (19) |
C6—N27—C28—C29 | 177.02 (13) | O17—C18—C19—N14 | 58.55 (19) |
C28—N27—C6—C1 | 125.88 (16) | O28—C28—C29—N30 | 8.6 (2) |
C31—N30—C29—C28 | 173.34 (14) | O28—C28—C29—O29 | −172.08 (16) |
C29—N30—C31—C32 | 177.84 (15) | N27—C28—C29—O29 | 8.6 (2) |
C31—N30—C29—O29 | −5.9 (3) | N27—C28—C29—N30 | −170.71 (14) |
C33—N34—C35—C36 | 177.14 (14) | N30—C31—C32—C33 | 54.54 (18) |
C39—N34—C33—C32 | 165.05 (14) | C31—C32—C33—N34 | −70.39 (18) |
C35—N34—C39—C38 | 57.35 (18) | N34—C35—C36—O37 | 61.52 (19) |
C33—N34—C39—C38 | −178.47 (14) | O37—C38—C39—N34 | −58.1 (2) |
C35—N34—C33—C32 | −72.96 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
N7—H7···O9 | 0.830 (18) | 2.23 (2) | 2.6620 (18) | 113.1 (16) |
N7—H7···O1i | 0.830 (18) | 2.064 (18) | 2.7896 (17) | 145.8 (19) |
N10—H10···O8 | 0.840 (18) | 2.372 (19) | 2.7224 (18) | 105.8 (15) |
N10—H10···O8ii | 0.840 (18) | 2.177 (18) | 2.9134 (18) | 146.2 (17) |
N27—H27···O29 | 0.879 (18) | 2.329 (19) | 2.7155 (18) | 106.7 (14) |
N27—H27···O1i | 0.879 (18) | 1.996 (18) | 2.7734 (17) | 146.7 (17) |
N30—H30···O28 | 0.829 (18) | 2.370 (19) | 2.6924 (19) | 103.9 (15) |
N30—H30···N34 | 0.829 (18) | 2.061 (18) | 2.7774 (18) | 144.5 (17) |
C4—H4···O37iii | 0.963 (19) | 2.569 (18) | 3.224 (2) | 125.5 (13) |
C11—H11A···N14 | 0.960 (17) | 2.541 (17) | 2.962 (2) | 106.6 (12) |
C35—H35A···O29iv | 0.95 (2) | 2.59 (2) | 3.472 (2) | 155.1 (15) |
C40—H40B···O28iv | 0.97 (3) | 2.34 (3) | 3.290 (2) | 166.7 (19) |
C40—H40C···O29i | 0.96 (2) | 2.45 (2) | 3.345 (2) | 155.0 (16) |
C41—H41B···O29i | 1.08 (3) | 2.58 (3) | 3.527 (3) | 146 (2) |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y+1, −z; (iii) −x+2, −y+2, −z+1; (iv) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C24H36N6O6·C2H6OS |
Mr | 582.72 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 173 |
a, b, c (Å) | 8.6704 (8), 11.0052 (10), 16.3277 (15) |
α, β, γ (°) | 107.425 (2), 98.036 (2), 91.517 (2) |
V (Å3) | 1468.0 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.16 |
Crystal size (mm) | 0.30 × 0.26 × 0.22 × 0.12 (radius) |
Data collection | |
Diffractometer | Bruker APEXII area-detector diffractometer |
Absorption correction | For a sphere (Dwiggins, 1975) |
Tmin, Tmax | 0.861, 0.862 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11574, 5722, 5081 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.099, 1.04 |
No. of reflections | 5722 |
No. of parameters | 539 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.41, −0.28 |
Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008) and WinGX (Farrugia, 1999), SHELXL97 (Sheldrick, 2008), Mercury (Macrae et al., 2006), PLATON (Spek, 2009).
O8—C8 | 1.2274 (18) | N10—C9 | 1.328 (2) |
O17—C16 | 1.424 (3) | N27—C6 | 1.424 (2) |
O28—C28 | 1.2202 (19) | N27—C28 | 1.343 (2) |
O29—C29 | 1.2298 (18) | N30—C29 | 1.322 (2) |
N7—C8 | 1.3371 (19) | N30—C31 | 1.459 (2) |
N7—C1 | 1.417 (2) | C8—C9 | 1.541 (2) |
C1—N7—C8 | 125.64 (13) | N7—C8—C9 | 111.30 (13) |
C9—N10—C11 | 121.27 (14) | O8—C8—N7 | 126.63 (15) |
C15—N14—C19 | 108.92 (13) | N10—C9—C8 | 113.24 (13) |
C6—N27—C28 | 123.04 (13) | O9—C9—N10 | 125.86 (15) |
C29—N30—C31 | 122.74 (13) | O9—C9—C8 | 120.86 (14) |
C33—N34—C39 | 111.71 (13) | N14—C13—C12 | 113.34 (13) |
C33—N34—C35 | 112.25 (13) | O28—C28—N27 | 125.74 (15) |
C35—N34—C39 | 108.39 (13) | N27—C28—C29 | 112.80 (13) |
N7—C1—C2 | 121.86 (14) | O28—C28—C29 | 121.46 (14) |
N7—C1—C6 | 118.48 (14) | O29—C29—C28 | 121.55 (14) |
N27—C6—C5 | 120.17 (14) | N30—C29—C28 | 112.43 (13) |
N27—C6—C1 | 120.00 (14) | O29—C29—N30 | 126.02 (15) |
O8—C8—C9 | 122.06 (13) | N34—C33—C32 | 112.28 (13) |
D—H···A | D—H | H···A | D···A | D—H···A |
N7—H7···O9 | 0.830 (18) | 2.23 (2) | 2.6620 (18) | 113.1 (16) |
N7—H7···O1i | 0.830 (18) | 2.064 (18) | 2.7896 (17) | 145.8 (19) |
N10—H10···O8 | 0.840 (18) | 2.372 (19) | 2.7224 (18) | 105.8 (15) |
N10—H10···O8ii | 0.840 (18) | 2.177 (18) | 2.9134 (18) | 146.2 (17) |
N27—H27···O29 | 0.879 (18) | 2.329 (19) | 2.7155 (18) | 106.7 (14) |
N27—H27···O1i | 0.879 (18) | 1.996 (18) | 2.7734 (17) | 146.7 (17) |
N30—H30···O28 | 0.829 (18) | 2.370 (19) | 2.6924 (19) | 103.9 (15) |
N30—H30···N34 | 0.829 (18) | 2.061 (18) | 2.7774 (18) | 144.5 (17) |
C4—H4···O37iii | 0.963 (19) | 2.569 (18) | 3.224 (2) | 125.5 (13) |
C11—H11A···N14 | 0.960 (17) | 2.541 (17) | 2.962 (2) | 106.6 (12) |
C35—H35A···O29iv | 0.95 (2) | 2.59 (2) | 3.472 (2) | 155.1 (15) |
C40—H40B···O28iv | 0.97 (3) | 2.34 (3) | 3.290 (2) | 166.7 (19) |
C40—H40C···O29i | 0.96 (2) | 2.45 (2) | 3.345 (2) | 155.0 (16) |
C41—H41B···O29i | 1.08 (3) | 2.58 (3) | 3.527 (3) | 146 (2) |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y+1, −z; (iii) −x+2, −y+2, −z+1; (iv) −x+1, −y+1, −z+1. |
In supramolecular chemistry, the design and synthesis of model molecules for donor–acceptor interaction studies continues being an area of interest (Steed & Atwood, 2009). Hydrogen bonding (HB) is the most important noncovalent interaction used in the design of host–guest systems. HB is particularly important from a biological point of view, because of its participation in several biological processes such as the stabilization of the double helix of DNA (Kool, 1997), peptide three-dimensional structures (helices, sheets or turns) (Sewald & Hans-Dieter, 2002), enzyme–substrate interactions (Bugg, 2004), recognition among proteins (Keskin et al., 2008) and drug-acceptor interactions (Sarker & Nahar, 2007). The development of simple hydrogen-bonding motifs for anion recognition, that are easy to make and functionalize, has lead to the design and synthesis of amide, pyrrole and urea-based hosts with conventional hydrogen-bond donors (Brooks et al., 2006; Brooks et al., 2007). The supramolecular versatility of oxalamides has been demonstrated previously as formers of columns, sheets, tapes, helixes and layers (González-González, Martínez-Martínez, García-Báez et al., 2011; González-González, Martínez-Martínez, Peraza-Campos et al., 2011). In this context, the N—H and C═O groups of oxalamides can be exploited as recognition sites in the design of molecular hosts. In this contribution, we report the molecular structure and the helical supramolecular assembly complex, (I) (Fig. 1), formed between N2,N2'-bis[2-(morpholin-4-yl)propyl]-N1,N1'-(1,2-phenylene)dioxalamide and dimethyl sulfoxide (DMSO).
The title compound forms triclinic crystals (P1, Z = 2). Selected bond lengths and angles are listed in Table 1 and are in the normal range found in related structures (Martínez-Martínez et al., 1998). The carbonyl groups are antiperiplanar, with O8—C8—C9—O9 and O28—C28—C29—O29 torsion angles of 178.62 (19) and -171.9 (2)°, respectively. The oxalamide group is almost planar, with N7—C8—C9—N10 and N27—C28—C29—N30 torsion angles of -177.76 (17) and -170.66 (16)°, respectively. These values are in agreement with those reported for oxalamides (Bernés et al., 2010). Both oxalyl arms are twisted from the mean plane of the phenylene ring and adopt an anticlinal conformation with C6—C1—N7—C8 and C1—C6—N27—C28 torsion angles of 137.6 (2) and -126.0 (2)°, respectively. The N7—H and N27—H amide groups point towards the cavity, thus the two oxalamidyl groups are cis-positioned between them, in relation to the mean plane of the phenylene ring. According to graph-set notation (Bernstein et al., 1995), four S(5) rings are formed between amide NH and carbonyl groups, through N7—H7···O9, N10—H10···O8, N27—H27···O29 and N30—H30···O28 interactions, and one S(6) ring is formed between an amide NH group and the N atom of one morpholine residue, through N30—H30···N34 interactions, displaying only one N—H stretch maximum, at 3272 cm-1. N···A distances and N—H···A angles (A = O and N) are in the range of intramolecular hydrogen bonding (HB) (Taylor & Kennard, 1982; Desiraju, 1996), in agreement with similar structures (Desseyn et al., 2004; Martín et al., 2002; Blay et al., 2003) and also in agreement with values reported for intramolecular HB in other systems (Zhu et al., 2007; Yang & Gellman, 1998). The geometric parameters associated with HB interactions are summarized in Table 2. The S(5)S(5)S(6) intramolecular hydrogen-bonded side arm is twisted from the mean aromatic ring plane with N30—C31—C32—C33 and C31—C32—C33—N34 torsion angles values of 54.4 (2) and -70.5 (2)°, respectively, whereas the S(5)S(5) side arm is twisted to the opposite side, with N10—C11—C12—C13 and C11—C12—C13—N14 torsion angles values of -168.58 (16) and 56.5 (2)°, respectively. One molecule of DMSO is situated outside the cavity formed by the pair of oxalamide side arms and bonded to the dioxalamide molecule by means of N7—H7···O1 and N27—H27···O1 HB interactions and C40—H40C···O29 and C41—H41C···O29 soft interactions to form a 1:1 complex. C—H···O interactions are weak HB interactions classified between electrostatic and van der Waals limits (Desiraju, 2002), herein they are called `soft interactions', as suggested by Desiraju (1996).
The zero-dimensional array is given by pairing of two molecules complex (I) (Fig. 2) through self-complementary strong N10—H10···O8 hydrogen bonding, to form the R22(10) motif characteristic of oxalamides. This motif is developed in one-dimensional meso-helix by C35—H35A···O29 soft interaction forming an R22(18) ring motif along the (001) direction. In the crystal lattice, the perfect alignment of the helical molecules of the same chirality in the meso-helix is observed (Fig. 3).
The turn of the helix measured as the spacing between the aromatic rings on neighbouring homochiral molecules is 16.328 (2) Å, which match the exact value of the lattice c parameter. Adjacent meso-helices are interlinked through C4—H4···O37 soft interactions to form an infinite sheet on the [441] family of planes separated by 5.329 (2) Å. DMSO molecules not only act as a template to form the cavity between the two oxalamide arms, but also facilitate the development of the second dimension linking the meso-helices through C40—H40B···O28 soft interactions and fill the voids left between the layers.
The softness of DMSO is not capable interrupting the formation of the typical R22(10) (N—H···O) ring motif of oxalamides, in contrast to that observed with the use of the 2-(4-nitrophenyl)acetic acid (Arman et al., 2012). As a final remark, is worth mentioning that a search was performed in the Cambridge Structural Database (CSD, Version 5.33, November 2011; Allen, 2002) for the 1,2-fenilenedioxalyl moiety and the only hit found was for the crystal structure of ethyl 1,2-fenilenedioxalamate (Martín et al., 2002). Thus, the title compound is the first example of a 1,2-fenilenedioxalamide crystal structure which, in addition, presents a meso-helix supramolecular architecture.