Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103021310/gg1184sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103021310/gg1184Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103021310/gg1184IIsup3.hkl |
CCDC references: 204757; 204758
For (I), a 2:1 molar ratio of piperidine (0.71 g, 8.33 mmol) and 5,7-dimethyl-2-phenyl-1-oxo-1H-pyrazolo[1,2-a]pyrazol-4-ylium-3-olate (1.00 g, 4.20 mmol) was refluxed in tetrahydrofuran (THF, 100 ml) for 48 h. Upon cooling the reaction, the solvent was removed under reduced pressure. The crude product was redissolved in minimal THF and precipitated by pouring into cool deionized water (100 ml). Collection in vacuo yielded an off-white powder (0.94 g, 72%; m.p. 416–419 K). Spectroscopic analysis, IR (νmax, KBr, cm−1: 1647 (s) and 1626 (s) (CO); 1H NMR (400 MHz, d6-DMSO, Me4Si, p.p.m.): 1.40 (m, 12H, CH2), 3.40 (m, 8H, NCH2), 5.40 (s, 1H), 7.30 (m, 5H, ArH); m/z (ES): 315 (MH+, 15%), 337 (M + Na, 39%), 651 (2M + Na, 100%). Compound (II) was produced using a method analogous to that used for (I), using morpholine (1.45 g, 1.67 mmol) and 5,7-dimethyl-2-phenyl-1-oxo-1H-pyrazolo[1,2-a]pyrazol-4-ylium-3-olate (2.00 g, 8.33 mmol). The final product was collected in vacuo as a white powder (2.33 g, 88%, m.p. 459–461 K). Spectroscopic analysis, IR (νmax, KBr, cm−1: 1658 (s) and 1633 (s) (CO); 1H NMR (400 MHz, d6-DMSO, Me4Si, p.p.m.): 3.27–3.63 (br m, 16H, NCH2 & OCH2), 5.51 (s, 1H), 7.21–7.39 (m, 5H, ArH); m/z (ES): 319 (MH+, 30%), 341 (M + Na, 100%), 659 (2M + Na, 73%). Crystals of both were grown from CHCl3 solutions.
All H atoms were included in the refinement, at calculated positions, in the riding-model approximation, with C—H set at 0.95 (aryl H), 0.99 (CH2) and 1.00 Å (C—H). The isotropic displacement parameters were set equal to 1.25Ueq of the carrier atom. The high Rint value for (I) was the result of weak high-angle data. The numbers of Friedel pairs for (I) and (II) are 1386 and 1195, respectively. In the absence of large atoms in both structures or strong anomalous dispersion effects, the Friedel opposites were merged prior to refinement.
For both compounds, data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Nonius, 1998); cell refinement: DENZO and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLUTON94 (Spek, 1994) and PLATON97 (Spek, 1997); software used to prepare material for publication: SHELXL97.
C19H26N2O2 | Dx = 1.259 Mg m−3 |
Mr = 314.42 | Melting point: 416-419 K K |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 6419 reflections |
a = 6.1652 (3) Å | θ = 2.9–27.5° |
b = 10.2718 (5) Å | µ = 0.08 mm−1 |
c = 26.1962 (17) Å | T = 120 K |
V = 1658.95 (16) Å3 | Plate, colourless |
Z = 4 | 0.15 × 0.10 × 0.04 mm |
F(000) = 680 |
Bruker Nonius KappaCCD area-detector diffractometer | 2177 independent reflections |
Radiation source: Bruker–Nonius FR591 rotating anode | 1013 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.176 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.1° |
ϕ and ω scans | h = −7→7 |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | k = −9→13 |
Tmin = 0.988, Tmax = 0.997 | l = −34→25 |
6936 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.069 | H-atom parameters constrained |
wR(F2) = 0.177 | w = 1/[σ2(Fo2) + (0.0705P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.94 | (Δ/σ)max < 0.001 |
2177 reflections | Δρmax = 0.34 e Å−3 |
209 parameters | Δρmin = −0.34 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.012 (3) |
C19H26N2O2 | V = 1658.95 (16) Å3 |
Mr = 314.42 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 6.1652 (3) Å | µ = 0.08 mm−1 |
b = 10.2718 (5) Å | T = 120 K |
c = 26.1962 (17) Å | 0.15 × 0.10 × 0.04 mm |
Bruker Nonius KappaCCD area-detector diffractometer | 2177 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 1013 reflections with I > 2σ(I) |
Tmin = 0.988, Tmax = 0.997 | Rint = 0.176 |
6936 measured reflections |
R[F2 > 2σ(F2)] = 0.069 | 0 restraints |
wR(F2) = 0.177 | H-atom parameters constrained |
S = 0.94 | Δρmax = 0.34 e Å−3 |
2177 reflections | Δρmin = −0.34 e Å−3 |
209 parameters |
x | y | z | Uiso*/Ueq | ||
C1 | 0.9803 (9) | 0.2467 (6) | 0.1834 (2) | 0.0289 (14) | |
O1 | 0.9011 (6) | 0.3469 (4) | 0.19950 (14) | 0.0328 (10) | |
C2 | 1.1346 (8) | 0.2493 (5) | 0.1361 (2) | 0.0242 (13) | |
H2 | 1.2586 | 0.1884 | 0.1421 | 0.030* | |
C3 | 1.0037 (9) | 0.2022 (5) | 0.0903 (2) | 0.0276 (14) | |
O3 | 0.8046 (6) | 0.2120 (4) | 0.09015 (15) | 0.0364 (12) | |
N4 | 0.9471 (7) | 0.1286 (4) | 0.20548 (17) | 0.0287 (12) | |
C5 | 0.7861 (10) | 0.1181 (7) | 0.2474 (2) | 0.0370 (17) | |
H51 | 0.7481 | 0.2060 | 0.2600 | 0.046* | |
H52 | 0.8488 | 0.0680 | 0.2761 | 0.046* | |
C6 | 0.5838 (10) | 0.0500 (6) | 0.2278 (2) | 0.0372 (16) | |
H61 | 0.4764 | 0.0420 | 0.2557 | 0.047* | |
H62 | 0.5178 | 0.1020 | 0.2000 | 0.047* | |
C7 | 0.6426 (10) | −0.0836 (6) | 0.2080 (2) | 0.0424 (17) | |
H71 | 0.6956 | −0.1379 | 0.2367 | 0.053* | |
H72 | 0.5116 | −0.1258 | 0.1937 | 0.053* | |
C8 | 0.8154 (9) | −0.0758 (6) | 0.1673 (2) | 0.0379 (16) | |
H81 | 0.7548 | −0.0336 | 0.1365 | 0.047* | |
H82 | 0.8621 | −0.1648 | 0.1579 | 0.047* | |
C9 | 1.0098 (10) | 0.0014 (5) | 0.1861 (2) | 0.0365 (16) | |
H91 | 1.0838 | −0.0480 | 0.2134 | 0.046* | |
H92 | 1.1138 | 0.0128 | 0.1576 | 0.046* | |
N10 | 1.1110 (7) | 0.1500 (4) | 0.04983 (17) | 0.0266 (12) | |
C11 | 0.9889 (9) | 0.0865 (5) | 0.0089 (2) | 0.0309 (15) | |
H111 | 1.0442 | 0.1156 | −0.0247 | 0.039* | |
H112 | 0.8337 | 0.1107 | 0.0113 | 0.039* | |
C12 | 1.0134 (10) | −0.0602 (5) | 0.0138 (2) | 0.0313 (15) | |
H121 | 0.9479 | −0.0896 | 0.0463 | 0.039* | |
H122 | 0.9352 | −0.1034 | −0.0146 | 0.039* | |
C13 | 1.2499 (10) | −0.0990 (6) | 0.0124 (2) | 0.0385 (16) | |
H131 | 1.3102 | −0.0801 | −0.0219 | 0.048* | |
H132 | 1.2628 | −0.1937 | 0.0185 | 0.048* | |
C14 | 1.3803 (10) | −0.0252 (6) | 0.0528 (2) | 0.0354 (16) | |
H141 | 1.3343 | −0.0537 | 0.0872 | 0.044* | |
H142 | 1.5363 | −0.0457 | 0.0489 | 0.044* | |
C15 | 1.3465 (9) | 0.1212 (6) | 0.0476 (2) | 0.0317 (15) | |
H151 | 1.4227 | 0.1672 | 0.0755 | 0.040* | |
H152 | 1.4070 | 0.1518 | 0.0147 | 0.040* | |
C16 | 1.2215 (9) | 0.3858 (5) | 0.1280 (2) | 0.0246 (14) | |
C17 | 1.4316 (9) | 0.4170 (6) | 0.1421 (2) | 0.0275 (14) | |
H17 | 1.5256 | 0.3514 | 0.1549 | 0.034* | |
C18 | 1.5047 (10) | 0.5438 (6) | 0.1375 (2) | 0.0333 (16) | |
H18 | 1.6483 | 0.5650 | 0.1477 | 0.042* | |
C19 | 1.3699 (10) | 0.6408 (6) | 0.1180 (2) | 0.0355 (16) | |
H19 | 1.4202 | 0.7279 | 0.1148 | 0.044* | |
C20 | 1.1603 (10) | 0.6076 (6) | 0.1034 (2) | 0.0363 (16) | |
H20 | 1.0660 | 0.6726 | 0.0903 | 0.045* | |
C21 | 1.0878 (10) | 0.4805 (6) | 0.1078 (2) | 0.0313 (15) | |
H21 | 0.9455 | 0.4585 | 0.0969 | 0.039* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.028 (3) | 0.033 (4) | 0.025 (3) | 0.001 (3) | −0.008 (3) | −0.005 (3) |
O1 | 0.037 (2) | 0.029 (2) | 0.032 (2) | 0.000 (2) | 0.001 (2) | −0.007 (2) |
C2 | 0.022 (3) | 0.023 (3) | 0.028 (3) | 0.005 (3) | −0.011 (2) | 0.000 (3) |
C3 | 0.032 (3) | 0.020 (3) | 0.030 (4) | −0.003 (3) | −0.004 (3) | 0.009 (3) |
O3 | 0.017 (2) | 0.053 (3) | 0.040 (3) | 0.0046 (19) | −0.0048 (19) | −0.007 (2) |
N4 | 0.033 (3) | 0.024 (3) | 0.029 (3) | 0.006 (2) | 0.001 (2) | −0.005 (3) |
C5 | 0.044 (4) | 0.043 (4) | 0.024 (3) | 0.002 (3) | 0.008 (3) | 0.004 (3) |
C6 | 0.032 (3) | 0.050 (4) | 0.030 (3) | 0.001 (3) | 0.001 (3) | 0.000 (3) |
C7 | 0.036 (4) | 0.049 (5) | 0.042 (4) | −0.007 (4) | −0.003 (3) | −0.004 (4) |
C8 | 0.035 (3) | 0.041 (4) | 0.038 (4) | −0.002 (3) | −0.001 (3) | 0.000 (3) |
C9 | 0.038 (4) | 0.031 (4) | 0.041 (4) | 0.008 (3) | 0.001 (3) | −0.003 (3) |
N10 | 0.022 (2) | 0.026 (3) | 0.031 (3) | 0.000 (2) | −0.001 (2) | −0.006 (2) |
C11 | 0.028 (3) | 0.036 (4) | 0.029 (3) | −0.004 (3) | 0.000 (3) | 0.000 (3) |
C12 | 0.039 (4) | 0.026 (3) | 0.029 (3) | −0.005 (3) | 0.007 (3) | −0.005 (3) |
C13 | 0.049 (4) | 0.024 (4) | 0.042 (4) | 0.002 (3) | 0.011 (3) | 0.006 (3) |
C14 | 0.031 (4) | 0.038 (4) | 0.037 (4) | 0.009 (3) | 0.008 (3) | 0.011 (3) |
C15 | 0.029 (3) | 0.033 (4) | 0.033 (3) | 0.004 (3) | 0.001 (3) | −0.001 (3) |
C16 | 0.032 (3) | 0.021 (4) | 0.021 (3) | −0.001 (3) | −0.002 (3) | −0.006 (3) |
C17 | 0.022 (3) | 0.034 (4) | 0.026 (3) | −0.002 (3) | −0.002 (3) | −0.009 (3) |
C18 | 0.027 (3) | 0.044 (4) | 0.029 (3) | −0.006 (3) | 0.006 (3) | −0.012 (3) |
C19 | 0.055 (4) | 0.027 (4) | 0.025 (3) | 0.001 (3) | 0.009 (3) | −0.002 (3) |
C20 | 0.039 (4) | 0.043 (5) | 0.027 (3) | 0.003 (3) | −0.002 (3) | 0.007 (3) |
C21 | 0.034 (3) | 0.033 (4) | 0.027 (3) | −0.010 (3) | −0.006 (3) | 0.002 (3) |
C3—O3 | 1.231 (6) | C5—C6 | 1.519 (8) |
C3—N10 | 1.361 (7) | C5—H51 | 0.99 |
C3—C2 | 1.524 (7) | C5—H52 | 0.99 |
C2—C16 | 1.516 (7) | C6—C7 | 1.510 (8) |
C2—C1 | 1.562 (8) | C6—H61 | 0.99 |
C2—H2 | 1.00 | C6—H62 | 0.99 |
C1—O1 | 1.215 (6) | C7—C8 | 1.509 (8) |
C1—N4 | 1.360 (7) | C7—H71 | 0.99 |
N10—C11 | 1.464 (7) | C7—H72 | 0.99 |
N10—C15 | 1.483 (7) | C8—C9 | 1.518 (8) |
C11—C12 | 1.520 (8) | C8—H81 | 0.99 |
C11—H111 | 0.99 | C8—H82 | 0.99 |
C11—H112 | 0.99 | C9—H91 | 0.99 |
C12—C13 | 1.512 (8) | C9—H92 | 0.99 |
C12—H121 | 0.99 | C16—C21 | 1.380 (8) |
C12—H122 | 0.99 | C16—C17 | 1.384 (7) |
C13—C14 | 1.530 (8) | C17—C18 | 1.384 (8) |
C13—H131 | 0.99 | C17—H17 | 0.95 |
C13—H132 | 0.99 | C18—C19 | 1.394 (8) |
C14—C15 | 1.524 (8) | C18—H18 | 0.95 |
C14—H141 | 0.99 | C19—C20 | 1.390 (8) |
C14—H142 | 0.99 | C19—H19 | 0.95 |
C15—H151 | 0.99 | C20—C21 | 1.384 (8) |
C15—H152 | 0.99 | C20—H20 | 0.95 |
N4—C9 | 1.454 (7) | C21—H21 | 0.95 |
N4—C5 | 1.484 (7) | ||
O3—C3—N10 | 121.0 (5) | N4—C5—C6 | 109.4 (5) |
O3—C3—C2 | 120.3 (5) | N4—C5—H51 | 109.8 |
N10—C3—C2 | 118.7 (5) | C6—C5—H51 | 109.8 |
C16—C2—C3 | 111.8 (4) | N4—C5—H52 | 109.8 |
C16—C2—C1 | 110.0 (5) | C6—C5—H52 | 109.8 |
C3—C2—C1 | 107.2 (4) | H51—C5—H52 | 108.2 |
C16—C2—H2 | 109.3 | C7—C6—C5 | 109.7 (5) |
C3—C2—H2 | 109.3 | C7—C6—H61 | 109.7 |
C1—C2—H2 | 109.3 | C5—C6—H61 | 109.7 |
O1—C1—N4 | 123.2 (5) | C7—C6—H62 | 109.7 |
O1—C1—C2 | 120.4 (5) | C5—C6—H62 | 109.7 |
N4—C1—C2 | 116.4 (5) | H61—C6—H62 | 108.2 |
C3—N10—C11 | 119.8 (4) | C8—C7—C6 | 111.3 (5) |
C3—N10—C15 | 125.9 (4) | C8—C7—H71 | 109.4 |
C11—N10—C15 | 112.7 (4) | C6—C7—H71 | 109.4 |
N10—C11—C12 | 109.2 (5) | C8—C7—H72 | 109.4 |
N10—C11—H111 | 109.8 | C6—C7—H72 | 109.4 |
C12—C11—H111 | 109.8 | H71—C7—H72 | 108.0 |
N10—C11—H112 | 109.8 | C7—C8—C9 | 110.9 (5) |
C12—C11—H112 | 109.8 | C7—C8—H81 | 109.5 |
H111—C11—H112 | 108.3 | C9—C8—H81 | 109.5 |
C13—C12—C11 | 110.8 (5) | C7—C8—H82 | 109.5 |
C13—C12—H121 | 109.5 | C9—C8—H82 | 109.5 |
C11—C12—H121 | 109.5 | H81—C8—H82 | 108.0 |
C13—C12—H122 | 109.5 | N4—C9—C8 | 111.8 (5) |
C11—C12—H122 | 109.5 | N4—C9—H91 | 109.2 |
H121—C12—H122 | 108.1 | C8—C9—H91 | 109.2 |
C12—C13—C14 | 111.1 (5) | N4—C9—H92 | 109.2 |
C12—C13—H131 | 109.4 | C8—C9—H92 | 109.2 |
C14—C13—H131 | 109.4 | H91—C9—H92 | 107.9 |
C12—C13—H132 | 109.4 | C21—C16—C17 | 119.8 (5) |
C14—C13—H132 | 109.4 | C21—C16—C2 | 119.6 (5) |
H131—C13—H132 | 108.0 | C17—C16—C2 | 120.5 (5) |
C15—C14—C13 | 110.8 (5) | C16—C17—C18 | 119.9 (6) |
C15—C14—H141 | 109.5 | C16—C17—H17 | 120.0 |
C13—C14—H141 | 109.5 | C18—C17—H17 | 120.0 |
C15—C14—H142 | 109.5 | C17—C18—C19 | 120.7 (6) |
C13—C14—H142 | 109.5 | C17—C18—H18 | 119.6 |
H141—C14—H142 | 108.1 | C19—C18—H18 | 119.6 |
N10—C15—C14 | 109.1 (4) | C20—C19—C18 | 118.6 (6) |
N10—C15—H151 | 109.9 | C20—C19—H19 | 120.7 |
C14—C15—H151 | 109.9 | C18—C19—H19 | 120.7 |
N10—C15—H152 | 109.9 | C21—C20—C19 | 120.6 (6) |
C14—C15—H152 | 109.9 | C21—C20—H20 | 119.7 |
H151—C15—H152 | 108.3 | C19—C20—H20 | 119.7 |
C1—N4—C9 | 127.8 (5) | C16—C21—C20 | 120.3 (5) |
C1—N4—C5 | 118.7 (5) | C16—C21—H21 | 119.9 |
C9—N4—C5 | 111.8 (5) | C20—C21—H21 | 119.9 |
O1—C1—C2—C16 | 19.1 (7) | O1—C1—N4—C5 | 7.7 (8) |
N4—C1—C2—C16 | −159.0 (5) | C2—C1—N4—C5 | −174.3 (4) |
O1—C1—C2—C3 | −102.6 (6) | C1—N4—C5—C6 | 106.2 (6) |
N4—C1—C2—C3 | 79.3 (5) | C9—N4—C5—C6 | −60.1 (6) |
C16—C2—C3—O3 | −96.3 (6) | N4—C5—C6—C7 | 58.8 (7) |
C1—C2—C3—O3 | 24.2 (7) | C5—C6—C7—C8 | −56.3 (7) |
C16—C2—C3—N10 | 83.4 (6) | C6—C7—C8—C9 | 52.9 (7) |
C1—C2—C3—N10 | −156.1 (5) | C1—N4—C9—C8 | −107.4 (6) |
O3—C3—N10—C11 | −9.4 (8) | C5—N4—C9—C8 | 57.3 (6) |
C2—C3—N10—C11 | 170.9 (4) | C7—C8—C9—N4 | −53.1 (7) |
O3—C3—N10—C15 | −173.6 (5) | C3—C2—C16—C21 | 44.3 (7) |
C2—C3—N10—C15 | 6.7 (7) | C1—C2—C16—C21 | −74.6 (6) |
C3—N10—C11—C12 | −104.9 (5) | C3—C2—C16—C17 | −137.5 (5) |
C15—N10—C11—C12 | 61.3 (6) | C1—C2—C16—C17 | 103.6 (6) |
N10—C11—C12—C13 | −57.2 (6) | C21—C16—C17—C18 | 2.2 (8) |
C11—C12—C13—C14 | 54.3 (7) | C2—C16—C17—C18 | −176.0 (5) |
C12—C13—C14—C15 | −53.6 (6) | C16—C17—C18—C19 | −1.0 (8) |
C3—N10—C15—C14 | 104.7 (6) | C17—C18—C19—C20 | 0.1 (8) |
C11—N10—C15—C14 | −60.5 (6) | C18—C19—C20—C21 | −0.4 (9) |
C13—C14—C15—N10 | 55.2 (6) | C17—C16—C21—C20 | −2.5 (9) |
O1—C1—N4—C9 | 171.5 (5) | C2—C16—C21—C20 | 175.7 (5) |
C2—C1—N4—C9 | −10.5 (7) | C19—C20—C21—C16 | 1.6 (9) |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H51···O1 | 0.99 | 2.34 | 2.757 (7) | 104 |
C9—H91···O1i | 0.99 | 2.52 | 3.436 (7) | 153 |
C11—H112···O3 | 0.99 | 2.32 | 2.735 (7) | 104 |
C15—H151···O3ii | 0.99 | 2.43 | 3.177 (7) | 132 |
C17—H17···O1ii | 0.95 | 2.59 | 3.340 (7) | 136 |
Symmetry codes: (i) −x+2, y−1/2, −z+1/2; (ii) x+1, y, z. |
C17H22N2O4 | Dx = 1.360 Mg m−3 |
Mr = 318.37 | Melting point: 459-461 K K |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 6411 reflections |
a = 8.3900 (1) Å | θ = 1.0–30.5° |
b = 10.8464 (2) Å | µ = 0.10 mm−1 |
c = 17.0838 (4) Å | T = 120 K |
V = 1554.65 (5) Å3 | Block, colourless |
Z = 4 | 0.60 × 0.40 × 0.26 mm |
F(000) = 680 |
Bruker–Nonius KappaCCD area-detector diffractometer | 2032 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 1909 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.066 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 2.2° |
ϕ and ω scans | h = −9→10 |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | k = −11→14 |
Tmin = 0.944, Tmax = 0.975 | l = −18→22 |
9999 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.039 | H-atom parameters constrained |
wR(F2) = 0.103 | w = 1/[σ2(Fo2) + (0.0639P)2 + 0.2187P] where P = (Fo2 + 2Fc2)/3 |
S = 1.12 | (Δ/σ)max < 0.001 |
2032 reflections | Δρmax = 0.38 e Å−3 |
209 parameters | Δρmin = −0.35 e Å−3 |
0 restraints | Extinction correction: SHELXL07, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.067 (7) |
C17H22N2O4 | V = 1554.65 (5) Å3 |
Mr = 318.37 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 8.3900 (1) Å | µ = 0.10 mm−1 |
b = 10.8464 (2) Å | T = 120 K |
c = 17.0838 (4) Å | 0.60 × 0.40 × 0.26 mm |
Bruker–Nonius KappaCCD area-detector diffractometer | 2032 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 1909 reflections with I > 2σ(I) |
Tmin = 0.944, Tmax = 0.975 | Rint = 0.066 |
9999 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.103 | H-atom parameters constrained |
S = 1.12 | Δρmax = 0.38 e Å−3 |
2032 reflections | Δρmin = −0.35 e Å−3 |
209 parameters |
x | y | z | Uiso*/Ueq | ||
C1 | 0.9933 (2) | 0.34874 (16) | 0.78954 (10) | 0.0154 (4) | |
O1 | 1.02680 (19) | 0.24983 (11) | 0.75851 (8) | 0.0231 (3) | |
C2 | 0.9005 (2) | 0.44671 (17) | 0.74398 (10) | 0.0147 (4) | |
H2 | 0.9537 | 0.5285 | 0.7507 | 0.018* | |
C3 | 0.9009 (2) | 0.41155 (17) | 0.65666 (10) | 0.0174 (4) | |
O3 | 0.78446 (18) | 0.36214 (15) | 0.62747 (8) | 0.0273 (4) | |
N4 | 1.03130 (19) | 0.37393 (14) | 0.86451 (9) | 0.0170 (3) | |
C5 | 1.1032 (2) | 0.27872 (18) | 0.91380 (11) | 0.0207 (4) | |
H51 | 1.2087 | 0.3066 | 0.9327 | 0.026* | |
H52 | 1.1183 | 0.2022 | 0.8831 | 0.026* | |
C6 | 0.9946 (3) | 0.25402 (18) | 0.98249 (12) | 0.0255 (5) | |
H61 | 0.8921 | 0.2205 | 0.9632 | 0.032* | |
H62 | 1.0440 | 0.1912 | 1.0168 | 0.032* | |
O7 | 0.9653 (2) | 0.36275 (13) | 1.02649 (8) | 0.0276 (4) | |
C8 | 0.8912 (2) | 0.45425 (19) | 0.97879 (12) | 0.0232 (4) | |
H81 | 0.8726 | 0.5295 | 1.0103 | 0.029* | |
H82 | 0.7865 | 0.4235 | 0.9606 | 0.029* | |
C9 | 0.9936 (2) | 0.48630 (16) | 0.90849 (10) | 0.0178 (4) | |
H91 | 0.9360 | 0.5450 | 0.8743 | 0.022* | |
H92 | 1.0934 | 0.5262 | 0.9262 | 0.022* | |
N10 | 1.0324 (2) | 0.44033 (16) | 0.61470 (9) | 0.0201 (4) | |
C11 | 1.0427 (3) | 0.4011 (2) | 0.53262 (11) | 0.0242 (5) | |
H111 | 1.0619 | 0.4736 | 0.4987 | 0.030* | |
H112 | 0.9408 | 0.3626 | 0.5165 | 0.030* | |
C12 | 1.1765 (3) | 0.30997 (19) | 0.52314 (12) | 0.0260 (5) | |
H121 | 1.1533 | 0.2352 | 0.5544 | 0.033* | |
H122 | 1.1847 | 0.2853 | 0.4675 | 0.033* | |
O13 | 1.32469 (18) | 0.36189 (15) | 0.54814 (8) | 0.0277 (4) | |
C14 | 1.3176 (3) | 0.3948 (2) | 0.62909 (11) | 0.0248 (4) | |
H141 | 1.4207 | 0.4313 | 0.6452 | 0.031* | |
H142 | 1.2995 | 0.3198 | 0.6609 | 0.031* | |
C15 | 1.1845 (2) | 0.48672 (17) | 0.64430 (11) | 0.0190 (4) | |
H151 | 1.1757 | 0.5021 | 0.7013 | 0.024* | |
H152 | 1.2101 | 0.5659 | 0.6184 | 0.024* | |
C16 | 0.7307 (2) | 0.45459 (17) | 0.77398 (10) | 0.0159 (4) | |
C17 | 0.6589 (2) | 0.56884 (18) | 0.78233 (10) | 0.0192 (4) | |
H17 | 0.7158 | 0.6413 | 0.7684 | 0.024* | |
C18 | 0.5037 (2) | 0.57841 (19) | 0.81094 (11) | 0.0226 (4) | |
H18 | 0.4554 | 0.6571 | 0.8171 | 0.028* | |
C19 | 0.4205 (2) | 0.4727 (2) | 0.83027 (11) | 0.0228 (4) | |
H19 | 0.3145 | 0.4789 | 0.8495 | 0.028* | |
C20 | 0.4906 (2) | 0.3580 (2) | 0.82179 (11) | 0.0222 (4) | |
H20 | 0.4329 | 0.2855 | 0.8349 | 0.028* | |
C21 | 0.6463 (2) | 0.34934 (18) | 0.79396 (11) | 0.0192 (4) | |
H21 | 0.6949 | 0.2707 | 0.7886 | 0.024* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0131 (8) | 0.0174 (8) | 0.0157 (8) | 0.0004 (7) | 0.0019 (6) | −0.0005 (7) |
O1 | 0.0298 (8) | 0.0184 (7) | 0.0209 (7) | 0.0062 (6) | 0.0015 (6) | −0.0029 (5) |
C2 | 0.0164 (9) | 0.0158 (8) | 0.0120 (8) | −0.0003 (7) | 0.0009 (6) | −0.0022 (6) |
C3 | 0.0183 (9) | 0.0201 (9) | 0.0139 (8) | 0.0014 (7) | −0.0010 (7) | −0.0021 (7) |
O3 | 0.0233 (7) | 0.0400 (8) | 0.0188 (7) | −0.0058 (7) | −0.0020 (6) | −0.0085 (6) |
N4 | 0.0153 (7) | 0.0197 (7) | 0.0160 (7) | 0.0031 (6) | −0.0010 (6) | −0.0001 (6) |
C5 | 0.0195 (9) | 0.0249 (9) | 0.0178 (9) | 0.0047 (8) | −0.0002 (7) | 0.0028 (8) |
C6 | 0.0309 (11) | 0.0237 (9) | 0.0219 (9) | −0.0008 (9) | 0.0051 (9) | 0.0034 (8) |
O7 | 0.0405 (9) | 0.0254 (7) | 0.0169 (6) | 0.0004 (7) | 0.0052 (6) | 0.0015 (6) |
C8 | 0.0236 (10) | 0.0241 (9) | 0.0218 (9) | −0.0013 (9) | 0.0041 (8) | −0.0026 (8) |
C9 | 0.0194 (9) | 0.0179 (8) | 0.0161 (8) | −0.0008 (7) | −0.0017 (7) | −0.0025 (7) |
N10 | 0.0203 (8) | 0.0274 (8) | 0.0127 (7) | −0.0012 (7) | 0.0010 (6) | −0.0038 (6) |
C11 | 0.0292 (11) | 0.0313 (10) | 0.0121 (8) | −0.0013 (9) | 0.0025 (7) | −0.0045 (8) |
C12 | 0.0343 (12) | 0.0220 (9) | 0.0218 (9) | −0.0026 (9) | 0.0080 (9) | −0.0029 (8) |
O13 | 0.0265 (8) | 0.0341 (8) | 0.0225 (7) | 0.0016 (7) | 0.0082 (6) | −0.0021 (6) |
C14 | 0.0238 (10) | 0.0318 (11) | 0.0187 (9) | 0.0014 (8) | 0.0032 (8) | 0.0009 (8) |
C15 | 0.0196 (9) | 0.0207 (9) | 0.0167 (8) | −0.0030 (7) | 0.0022 (7) | −0.0008 (7) |
C16 | 0.0173 (9) | 0.0195 (8) | 0.0109 (7) | 0.0000 (7) | −0.0009 (6) | −0.0015 (7) |
C17 | 0.0195 (9) | 0.0191 (9) | 0.0189 (8) | −0.0002 (7) | 0.0019 (7) | 0.0013 (7) |
C18 | 0.0198 (9) | 0.0256 (10) | 0.0224 (9) | 0.0064 (8) | 0.0019 (8) | 0.0012 (8) |
C19 | 0.0152 (9) | 0.0359 (11) | 0.0173 (9) | −0.0029 (9) | 0.0016 (6) | −0.0004 (8) |
C20 | 0.0222 (10) | 0.0277 (9) | 0.0168 (8) | −0.0083 (9) | −0.0007 (7) | 0.0005 (8) |
C21 | 0.0207 (9) | 0.0192 (9) | 0.0178 (8) | −0.0012 (8) | −0.0026 (7) | −0.0015 (7) |
C1—O1 | 1.229 (2) | C11—C12 | 1.505 (3) |
C1—N4 | 1.348 (2) | C11—H111 | 0.99 |
C1—C2 | 1.530 (2) | C11—H112 | 0.99 |
C2—C16 | 1.516 (2) | C12—O13 | 1.430 (3) |
C2—C3 | 1.540 (2) | C12—H121 | 0.99 |
C2—H2 | 1.00 | C12—H122 | 0.99 |
C3—O3 | 1.220 (2) | O13—C14 | 1.429 (2) |
C3—N10 | 1.353 (3) | C14—C15 | 1.519 (3) |
N4—C5 | 1.463 (2) | C14—H141 | 0.99 |
N4—C9 | 1.466 (2) | C14—H142 | 0.99 |
C5—C6 | 1.509 (3) | C15—H151 | 0.99 |
C5—H51 | 0.99 | C15—H152 | 0.99 |
C5—H52 | 0.99 | C16—C17 | 1.385 (3) |
C6—O7 | 1.420 (2) | C16—C21 | 1.386 (3) |
C6—H61 | 0.99 | C17—C18 | 1.395 (3) |
C6—H62 | 0.99 | C17—H17 | 0.95 |
O7—C8 | 1.427 (3) | C18—C19 | 1.382 (3) |
C8—C9 | 1.517 (3) | C18—H18 | 0.95 |
C8—H81 | 0.99 | C19—C20 | 1.384 (3) |
C8—H82 | 0.99 | C19—H19 | 0.95 |
C9—H91 | 0.99 | C20—C21 | 1.393 (3) |
C9—H92 | 0.99 | C20—H20 | 0.95 |
N10—C15 | 1.462 (2) | C21—H21 | 0.95 |
N10—C11 | 1.468 (2) | ||
O1—C1—N4 | 122.18 (17) | N10—C11—C12 | 109.69 (17) |
O1—C1—C2 | 120.21 (16) | N10—C11—H111 | 109.7 |
N4—C1—C2 | 117.57 (15) | C12—C11—H111 | 109.7 |
C16—C2—C1 | 110.20 (14) | N10—C11—H112 | 109.7 |
C16—C2—C3 | 110.07 (15) | C12—C11—H112 | 109.7 |
C1—C2—C3 | 108.65 (14) | H111—C11—H112 | 108.2 |
C16—C2—H2 | 109.3 | O13—C12—C11 | 110.98 (16) |
C1—C2—H2 | 109.3 | O13—C12—H121 | 109.4 |
C3—C2—H2 | 109.3 | C11—C12—H121 | 109.4 |
O3—C3—N10 | 122.54 (16) | O13—C12—H122 | 109.4 |
O3—C3—C2 | 120.20 (17) | C11—C12—H122 | 109.4 |
N10—C3—C2 | 117.24 (16) | H121—C12—H122 | 108.0 |
C1—N4—C5 | 120.09 (16) | C14—O13—C12 | 110.55 (15) |
C1—N4—C9 | 127.19 (15) | O13—C14—C15 | 111.10 (16) |
C5—N4—C9 | 112.38 (15) | O13—C14—H141 | 109.4 |
N4—C5—C6 | 108.92 (16) | C15—C14—H141 | 109.4 |
N4—C5—H51 | 109.9 | O13—C14—H142 | 109.4 |
C6—C5—H51 | 109.9 | C15—C14—H142 | 109.4 |
N4—C5—H52 | 109.9 | H141—C14—H142 | 108.0 |
C6—C5—H52 | 109.9 | N10—C15—C14 | 110.89 (15) |
H51—C5—H52 | 108.3 | N10—C15—H151 | 109.5 |
O7—C6—C5 | 111.64 (16) | C14—C15—H151 | 109.5 |
O7—C6—H61 | 109.3 | N10—C15—H152 | 109.5 |
C5—C6—H61 | 109.3 | C14—C15—H152 | 109.5 |
O7—C6—H62 | 109.3 | H151—C15—H152 | 108.0 |
C5—C6—H62 | 109.3 | C17—C16—C21 | 119.26 (16) |
H61—C6—H62 | 108.0 | C17—C16—C2 | 119.60 (16) |
C6—O7—C8 | 110.54 (16) | C21—C16—C2 | 121.13 (17) |
O7—C8—C9 | 111.40 (16) | C16—C17—C18 | 120.59 (18) |
O7—C8—H81 | 109.3 | C16—C17—H17 | 119.7 |
C9—C8—H81 | 109.3 | C18—C17—H17 | 119.7 |
O7—C8—H82 | 109.3 | C19—C18—C17 | 119.57 (18) |
C9—C8—H82 | 109.3 | C19—C18—H18 | 120.2 |
H81—C8—H82 | 108.0 | C17—C18—H18 | 120.2 |
N4—C9—C8 | 109.71 (15) | C18—C19—C20 | 120.39 (17) |
N4—C9—H91 | 109.7 | C18—C19—H19 | 119.8 |
C8—C9—H91 | 109.7 | C20—C19—H19 | 119.8 |
N4—C9—H92 | 109.7 | C19—C20—C21 | 119.66 (19) |
C8—C9—H92 | 109.7 | C19—C20—H20 | 120.2 |
H91—C9—H92 | 108.2 | C21—C20—H20 | 120.2 |
C3—N10—C15 | 127.47 (14) | C16—C21—C20 | 120.52 (19) |
C3—N10—C11 | 119.14 (16) | C16—C21—H21 | 119.7 |
C15—N10—C11 | 112.29 (15) | C20—C21—H21 | 119.7 |
O1—C1—C2—C16 | 106.91 (18) | O3—C3—N10—C11 | −5.7 (3) |
N4—C1—C2—C16 | −71.0 (2) | C2—C3—N10—C11 | 175.85 (16) |
O1—C1—C2—C3 | −13.8 (2) | C3—N10—C11—C12 | −115.2 (2) |
N4—C1—C2—C3 | 168.29 (15) | C15—N10—C11—C12 | 53.7 (2) |
C16—C2—C3—O3 | −20.3 (2) | N10—C11—C12—O13 | −57.7 (2) |
C1—C2—C3—O3 | 100.5 (2) | C11—C12—O13—C14 | 60.9 (2) |
C16—C2—C3—N10 | 158.25 (16) | C12—O13—C14—C15 | −58.5 (2) |
C1—C2—C3—N10 | −81.0 (2) | C3—N10—C15—C14 | 115.8 (2) |
O1—C1—N4—C5 | −5.1 (3) | C11—N10—C15—C14 | −52.0 (2) |
C2—C1—N4—C5 | 172.81 (15) | O13—C14—C15—N10 | 54.0 (2) |
O1—C1—N4—C9 | −177.95 (17) | C1—C2—C16—C17 | 139.41 (17) |
C2—C1—N4—C9 | 0.0 (3) | C3—C2—C16—C17 | −100.77 (19) |
C1—N4—C5—C6 | −119.06 (19) | C1—C2—C16—C21 | −40.0 (2) |
C9—N4—C5—C6 | 54.8 (2) | C3—C2—C16—C21 | 79.8 (2) |
N4—C5—C6—O7 | −57.5 (2) | C21—C16—C17—C18 | 0.4 (3) |
C5—C6—O7—C8 | 60.1 (2) | C2—C16—C17—C18 | −179.03 (15) |
C6—O7—C8—C9 | −58.5 (2) | C16—C17—C18—C19 | −0.7 (3) |
C1—N4—C9—C8 | 119.39 (19) | C17—C18—C19—C20 | 0.3 (3) |
C5—N4—C9—C8 | −53.9 (2) | C18—C19—C20—C21 | 0.3 (3) |
O7—C8—C9—N4 | 55.0 (2) | C17—C16—C21—C20 | 0.3 (3) |
O3—C3—N10—C15 | −172.72 (18) | C2—C16—C21—C20 | 179.70 (16) |
C2—C3—N10—C15 | 8.8 (3) | C19—C20—C21—C16 | −0.6 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O1i | 1.00 | 2.41 | 3.344 (2) | 155 |
C17—H17···O1i | 0.95 | 2.50 | 3.361 (2) | 150 |
C5—H52···O1 | 0.99 | 2.32 | 2.747 (2) | 105 |
C9—H92···O13ii | 0.99 | 2.51 | 3.275 (2) | 134 |
C11—H112···O3 | 0.99 | 2.31 | 2.738 (3) | 105 |
C12—H122···O3iii | 0.99 | 2.43 | 3.305 (2) | 148 |
Symmetry codes: (i) −x+2, y+1/2, −z+3/2; (ii) −x+5/2, −y+1, z+1/2; (iii) x+1/2, −y+1/2, −z+1. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C19H26N2O2 | C17H22N2O4 |
Mr | 314.42 | 318.37 |
Crystal system, space group | Orthorhombic, P212121 | Orthorhombic, P212121 |
Temperature (K) | 120 | 120 |
a, b, c (Å) | 6.1652 (3), 10.2718 (5), 26.1962 (17) | 8.3900 (1), 10.8464 (2), 17.0838 (4) |
V (Å3) | 1658.95 (16) | 1554.65 (5) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.08 | 0.10 |
Crystal size (mm) | 0.15 × 0.10 × 0.04 | 0.60 × 0.40 × 0.26 |
Data collection | ||
Diffractometer | Bruker Nonius KappaCCD area-detector diffractometer | Bruker–Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995) | Multi-scan (SORTAV; Blessing, 1995) |
Tmin, Tmax | 0.988, 0.997 | 0.944, 0.975 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6936, 2177, 1013 | 9999, 2032, 1909 |
Rint | 0.176 | 0.066 |
(sin θ/λ)max (Å−1) | 0.650 | 0.650 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.069, 0.177, 0.94 | 0.039, 0.103, 1.12 |
No. of reflections | 2177 | 2032 |
No. of parameters | 209 | 209 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.34, −0.34 | 0.38, −0.35 |
Computer programs: DENZO (Otwinowski & Minor, 1997) and COLLECT (Nonius, 1998), DENZO and COLLECT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLUTON94 (Spek, 1994) and PLATON97 (Spek, 1997), SHELXL97.
O1—C1—C2—C16 | 19.1 (7) | C16—C2—C3—O3 | −96.3 (6) |
N4—C1—C2—C16 | −159.0 (5) | C1—C2—C3—O3 | 24.2 (7) |
O1—C1—C2—C3 | −102.6 (6) | C16—C2—C3—N10 | 83.4 (6) |
N4—C1—C2—C3 | 79.3 (5) | C1—C2—C3—N10 | −156.1 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H51···O1 | 0.99 | 2.34 | 2.757 (7) | 104 |
C9—H91···O1i | 0.99 | 2.52 | 3.436 (7) | 153 |
C11—H112···O3 | 0.99 | 2.32 | 2.735 (7) | 104 |
C15—H151···O3ii | 0.99 | 2.43 | 3.177 (7) | 132 |
C17—H17···O1ii | 0.95 | 2.59 | 3.340 (7) | 136 |
Symmetry codes: (i) −x+2, y−1/2, −z+1/2; (ii) x+1, y, z. |
O1—C1—C2—C16 | 106.91 (18) | C16—C2—C3—O3 | −20.3 (2) |
N4—C1—C2—C16 | −71.0 (2) | C1—C2—C3—O3 | 100.5 (2) |
O1—C1—C2—C3 | −13.8 (2) | C16—C2—C3—N10 | 158.25 (16) |
N4—C1—C2—C3 | 168.29 (15) | C1—C2—C3—N10 | −81.0 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O1i | 1.00 | 2.41 | 3.344 (2) | 155 |
C17—H17···O1i | 0.95 | 2.50 | 3.361 (2) | 150 |
C5—H52···O1 | 0.99 | 2.32 | 2.747 (2) | 105 |
C9—H92···O13ii | 0.99 | 2.51 | 3.275 (2) | 134 |
C11—H112···O3 | 0.99 | 2.31 | 2.738 (3) | 105 |
C12—H122···O3iii | 0.99 | 2.43 | 3.305 (2) | 148 |
Symmetry codes: (i) −x+2, y+1/2, −z+3/2; (ii) −x+5/2, −y+1, z+1/2; (iii) x+1/2, −y+1/2, −z+1. |
Symmetrical malonamides can be prepared by two classical methods (Burgada, 1964) with both involving the reaction of two molar equivalents of an amine with either diethyl malonate or malonyldichloride. A third, more modern but less efficient, synthesis involves the reaction of a two molar equivalence of a base or amine with 3-oxopyrazolo[1,2-a]pyrazol-8-ylium-1-olate (Zvilichovsky & David, 1982), a compound also derived from either diethyl malonate or malonyldichloride. The nucleophilic cleavage of derivatives of 3-oxopyrazolo[1,2-a]pyrazol-8-ylium-1-olate to produce symmetrical malonamides was also investigated by Potts et al. (1988), who studied their decomposition using morpholine, aniline or water. Experimental runs were performed in tetrahydrofuran at 298 K and took from a few s to several days for a complete reaction, depending on the substituents of the initial pyrazolo[1,2a]pyrazole with one of the slowest reactants being seen for 5,7-dimethyl-2-phenyl-1-oxo-1H-pyrazolo[1,2-a]pyrazol-4-ylium-3-olate. We decided to continue investigating the nucleophilic cleavage of this specific compound using a variety of nucleophiles including both piperidine and morpholine with all resultant products being 2-phenylmalonamide derivatives. Interestingly, a search of the April 2003 release of the Cambridge Structural Database (Allen, 2002) reveals that there are 37 reported structures of malonamides, including both symmetrical and unsymmetrical analogues, yet of these there is only one 2-phenylmalonamide derivative, that being the amide itself (Sakamoto et al., 2000). Reported here are the crystal structures of both 2-phenylmalonpiperadide, (I), and 2-phenylmalonmorpholide, (II).
Compounds (I) and (II) share crystallographic similarities by both packing in the same non-centrosymmetric space group and sharing similar cell dimensions and cell volumes. The only chemical difference between the two is the substitution of the piperidyl 4-position CH2 groups in (I) for the morpholine O atoms in (II), with the loss of ca 104 Å3 in cell volume. However, these two O atoms have the potential to cause a difference in the solid-state packing of (II), as opposed to (I), because exposed O atoms can act as hydrogen-bond acceptors, in addition to the two malonamide carbonyl O atoms. Comparative molecular conformations for (I) and (II) are shown in Figs 1 and 2, respectively, while selected torsion angles are listed in Tables 1 and 3.
With both the saturated heterocyclic rings systems in the chair conformation and the carbonyl groups orientated in the same direction for both molecules, the important torsion angles become those containing the C16—C2 bond, specifically N4—C1—C2—C16 and C16—C2—C3—N10, because the backbone torsion angles for the two compounds, N4—C1—C2—C3 and C1—C2—C3—N10, are inversely similar. The conformation of 2-phenylmalonamide itself differs from both (I) and (II), with the carbonyl groups arranged in opposing directions and the backbone chain being much flatter. Comparative torsion angles are 98.15 (N1—C1—C2—C4), 101.16 (C4—C2—C3—N2), −26.26 (N1—C1—C2—C3) and 134.11° (C1—C2—C3—N4) (note that in 2-phenylmalonamide atom C4 = C16).
The C—H···O hydrogen-bonding associations for compounds (I) and (II) are listed in Tables 2 and 4, respectively, and although both compounds arrange very differently the malonamide carbonyl O atoms in each are involved in the same number of intermolecular C—H···O associations. In addition, there is only one listed association to a morpholine O atom (O13) indicating that the morpholine O atoms do not have much effect on the difference in molecular packing. The unit cells for (I) and (II), both viewed down the a axis, are shown in Figs 3 and 4. Interestingly, the phenyl rings in both compounds are arranged almost perpendicular to the c axis orientating the main length of the backbone in the same direction as the c axis. However, apart from these general packing similarities the two structures remain considerably different. The occurrence of crystallographic differences between chemically similar compounds, such as (I) and (II), is interesting and in the structures discussed in this paper have no apparent cause. Additional comparative compounds would be those containing thiomorpholine, piperazine or any minor 4-position derivative of piperidine or piperazine.