5-(4-Chlorophenyl)-2-methoxyindeno[1',2':2,3]pyrido[5,6-
d]pyrimidine-4,6(3
H,5
H)-dione crystallizes as a 1:1 dimethylformamide solvate, C
21H
14ClN
3O
3·C
3H
7NO. The heterocyclic molecules contain a planar fused-ring system and they are linked by paired N-H
O hydrogen bonds [H
O = 1.85 Å, N
O = 2.735 (4) Å and N-H
O = 179°] into centrosymmetric dimers, which are themselves linked into chains by a single C-H
(arene) hydrogen bond. 10b-Hydroxy-2-methoxy-5-(4-methoxyphenyl)-5a,10b-dihydroindeno[1',2':2,3]pyrido[5,6-
d]pyrimidine-4,6(3
H,5
H)-dione also crystallizes as a 1:1 dimethylformamide solvate, C
22H
19N
3O
5·C
3H
7NO. The heterocyclic molecules contain a sharply folded fused-ring system and they are linked by two independent N-H
O hydrogen bonds [H
O = 1.92 and 2.18 Å, N
O = 2.801 (2) and 3.051 (2) Å, and N-H
O = 175 and 173°] into chains of rings. In both compounds, the dimethylformamide molecules are pendent from the chains, linked
via N-H
O and O-H
O hydrogen bonds, respectively.
Supporting information
CCDC references: 235339; 235340
For the synthesis of the heterocyclic component of (I), a homogeneous mixture containing equimolar amounts of 6-amino-2-methoxy-3H-4-pyrimidone, 4-chlorobenzaldehyde and indandionewas placed in Pyrex glass open vessels and irradiated in a domestic microwave oven for 5 min (at 600 W). The product of the reaction was recrystallized from absolute ethanol. Yield 71%; m.p. 510 K; MS (EI) m/z: 393, 391 (M+). For the heterocyclic component of (II), a similar mixture, but containing 4-methoxybenzaldehyde in place of 4-chlorobenzaldehyde, was irradiated in a domestic microwave oven for 45 s (at 600 W). The reaction product was filtered off, washed with ethanol and recrystallized from absolute ethanol. Yield 76%; m.p. 455 K. Crystals of solvates (I) and (II) suitable for single-crystal X-ray diffraction were grown from a solution in dimethylformamide.
For (I), space group P21/c was assigned uniquely from the systematic absences. Crystals of (II) are triclinic, and space group P-1 was assigned and confirmed by the successful structure analysis. All H atoms were located from difference maps and subequently treated as riding atoms [C—H = 0.95 (aromatic), 0.98 (methyl) or 1.00 Å (aliphatic C/H), N—H = 0.88 Å and O—H = 0.99 Å), allowed to ride at the distances deduced from the difference maps. The long O—H distance in (II) may be influenced by the short O···O distance in the associated hydrogen bond (Table 3). Examination of the refined structure of (II) using PLATON (Spek, 2003) showed the presence of small voids centred at approximately (1/2, 0, 1/2) and at symmetry-related postions, each having a volume of ca 43 Å3. However, these voids contain negligible electron density.
For both compounds, data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997); data reduction: DENZO–SMN. Program(s) used to solve structure: OSCAIL (MCardle, 2003) and SHELXS97 (Sheldrick, 1997) for (I); OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997) for (II). For both compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).
(I) 5-(4-Chlorophenyl)-2-methoxyindeno[1',2':2,3]pyrido[5,6-
d]pyrimidine- 4,6(3
H,5H)-dione–dimethylformamide (1/1)
top
Crystal data top
C21H14ClN3O3·C3H7NO | F(000) = 968 |
Mr = 464.90 | Dx = 1.398 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 4182 reflections |
a = 10.6850 (6) Å | θ = 3.1–25.7° |
b = 17.6182 (12) Å | µ = 0.21 mm−1 |
c = 12.3774 (8) Å | T = 120 K |
β = 108.523 (4)° | Block, orange |
V = 2209.3 (2) Å3 | 0.08 × 0.04 × 0.02 mm |
Z = 4 | |
Data collection top
Nonius KappaCCD diffractometer | 4182 independent reflections |
Radiation source: rotating anode | 2135 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.123 |
ϕ scans, and ω scans with κ offsets | θmax = 25.7°, θmin = 3.1° |
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997) | h = −13→13 |
Tmin = 0.977, Tmax = 0.996 | k = −21→21 |
8314 measured reflections | l = −15→14 |
Refinement top
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) = 0.157 | w = 1/[σ2(Fo2) + (0.0439P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.96 | (Δ/σ)max = 0.001 |
4182 reflections | Δρmax = 0.27 e Å−3 |
302 parameters | Δρmin = −0.29 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: 0.0104 (12) |
Crystal data top
C21H14ClN3O3·C3H7NO | V = 2209.3 (2) Å3 |
Mr = 464.90 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.6850 (6) Å | µ = 0.21 mm−1 |
b = 17.6182 (12) Å | T = 120 K |
c = 12.3774 (8) Å | 0.08 × 0.04 × 0.02 mm |
β = 108.523 (4)° | |
Data collection top
Nonius KappaCCD diffractometer | 4182 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997) | 2135 reflections with I > 2σ(I) |
Tmin = 0.977, Tmax = 0.996 | Rint = 0.123 |
8314 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.069 | 0 restraints |
wR(F2) = 0.157 | H-atom parameters constrained |
S = 0.96 | Δρmax = 0.27 e Å−3 |
4182 reflections | Δρmin = −0.29 e Å−3 |
302 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | 0.2308 (3) | 0.59710 (19) | 0.6334 (2) | 0.0251 (8) | |
C2 | 0.3516 (4) | 0.5767 (2) | 0.6470 (3) | 0.0263 (10) | |
O2 | 0.4492 (3) | 0.58682 (17) | 0.7444 (2) | 0.0312 (7) | |
N3 | 0.3929 (3) | 0.54392 (19) | 0.5654 (2) | 0.0252 (8) | |
C4 | 0.3057 (4) | 0.5280 (2) | 0.4575 (3) | 0.0261 (10) | |
O4 | 0.3468 (3) | 0.49354 (16) | 0.3872 (2) | 0.0275 (7) | |
C4A | 0.1736 (4) | 0.5525 (2) | 0.4375 (3) | 0.0248 (10) | |
C5A | −0.0583 (4) | 0.5654 (2) | 0.3225 (3) | 0.0256 (10) | |
C5 | 0.0748 (4) | 0.5418 (2) | 0.3174 (3) | 0.0254 (10) | |
C6A | −0.2874 (4) | 0.5921 (2) | 0.2800 (3) | 0.0276 (10) | |
C6 | −0.1859 (4) | 0.5588 (2) | 0.2319 (3) | 0.0290 (10) | |
O6 | −0.2077 (3) | 0.53225 (17) | 0.1356 (2) | 0.0341 (8) | |
C7 | −0.4226 (4) | 0.6002 (3) | 0.2331 (3) | 0.0314 (11) | |
C8 | −0.4908 (4) | 0.6319 (3) | 0.3018 (3) | 0.0347 (11) | |
C9 | −0.4261 (4) | 0.6547 (2) | 0.4124 (3) | 0.0319 (11) | |
C10 | −0.2888 (4) | 0.6461 (2) | 0.4594 (3) | 0.0285 (10) | |
C10A | −0.2216 (4) | 0.6147 (2) | 0.3923 (3) | 0.0266 (10) | |
C10B | −0.0795 (4) | 0.5971 (2) | 0.4155 (3) | 0.0253 (10) | |
N11 | 0.0159 (3) | 0.60870 (19) | 0.5154 (2) | 0.0253 (8) | |
C11A | 0.1426 (4) | 0.5850 (2) | 0.5271 (3) | 0.0234 (9) | |
C21 | 0.4133 (4) | 0.6235 (3) | 0.8348 (3) | 0.0401 (12) | |
C31 | −0.0594 (5) | 0.6568 (3) | 0.7996 (3) | 0.0339 (11) | |
N32 | −0.1610 (4) | 0.6705 (2) | 0.8357 (3) | 0.0328 (9) | |
O31 | −0.0576 (3) | 0.66900 (17) | 0.7009 (2) | 0.0330 (8) | |
C33 | −0.1596 (5) | 0.6509 (3) | 0.9509 (3) | 0.0417 (13) | |
C34 | −0.2831 (4) | 0.6992 (3) | 0.7556 (3) | 0.0366 (12) | |
C51 | 0.1183 (4) | 0.5884 (2) | 0.2314 (3) | 0.0247 (10) | |
C52 | 0.1173 (4) | 0.6671 (2) | 0.2353 (3) | 0.0251 (10) | |
C53 | 0.1629 (4) | 0.7113 (2) | 0.1626 (3) | 0.0273 (10) | |
C54 | 0.2087 (4) | 0.6738 (2) | 0.0840 (3) | 0.0275 (10) | |
Cl54 | 0.27146 (12) | 0.72919 (7) | −0.00552 (9) | 0.0397 (4) | |
C55 | 0.2089 (4) | 0.5961 (2) | 0.0757 (3) | 0.0280 (10) | |
C56 | 0.1630 (4) | 0.5535 (3) | 0.1503 (3) | 0.0282 (10) | |
H21A | 0.3777 | 0.6741 | 0.8097 | 0.060* | |
H21B | 0.4916 | 0.6282 | 0.9023 | 0.060* | |
H21C | 0.3463 | 0.5930 | 0.8536 | 0.060* | |
H3 | 0.4769 | 0.5324 | 0.5808 | 0.030* | |
H5 | 0.0718 | 0.4869 | 0.2962 | 0.030* | |
H52 | 0.0846 | 0.6915 | 0.2893 | 0.030* | |
H53 | 0.1626 | 0.7652 | 0.1665 | 0.033* | |
H55 | 0.2398 | 0.5719 | 0.0204 | 0.034* | |
H56 | 0.1623 | 0.4997 | 0.1454 | 0.034* | |
H7 | −0.4676 | 0.5848 | 0.1570 | 0.038* | |
H8 | −0.5838 | 0.6379 | 0.2717 | 0.042* | |
H9 | −0.4749 | 0.6763 | 0.4569 | 0.038* | |
H10 | −0.2436 | 0.6616 | 0.5353 | 0.034* | |
H11 | −0.0022 | 0.6310 | 0.5723 | 0.030* | |
H31 | 0.0179 | 0.6361 | 0.8528 | 0.051* | |
H33A | −0.0755 | 0.6265 | 0.9920 | 0.063* | |
H33B | −0.2324 | 0.6160 | 0.9466 | 0.063* | |
H33C | −0.1700 | 0.6971 | 0.9913 | 0.063* | |
H34A | −0.2626 | 0.7330 | 0.7007 | 0.055* | |
H34B | −0.3325 | 0.7272 | 0.7972 | 0.055* | |
H34C | −0.3365 | 0.6565 | 0.7151 | 0.055* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.024 (2) | 0.027 (2) | 0.0223 (17) | −0.0003 (17) | 0.0057 (16) | −0.0023 (15) |
C2 | 0.029 (3) | 0.026 (3) | 0.026 (2) | −0.004 (2) | 0.011 (2) | −0.0014 (18) |
O2 | 0.0261 (18) | 0.040 (2) | 0.0261 (15) | 0.0017 (14) | 0.0064 (14) | −0.0053 (13) |
N3 | 0.022 (2) | 0.029 (2) | 0.0271 (18) | 0.0037 (16) | 0.0119 (16) | 0.0007 (15) |
C4 | 0.029 (3) | 0.023 (2) | 0.026 (2) | −0.003 (2) | 0.008 (2) | 0.0015 (19) |
O4 | 0.0287 (18) | 0.0292 (18) | 0.0254 (14) | 0.0004 (14) | 0.0096 (13) | −0.0011 (13) |
C4A | 0.029 (3) | 0.024 (2) | 0.024 (2) | 0.000 (2) | 0.0119 (19) | 0.0006 (18) |
C5A | 0.028 (3) | 0.030 (3) | 0.019 (2) | 0.000 (2) | 0.0081 (19) | 0.0047 (18) |
C5 | 0.028 (2) | 0.026 (2) | 0.022 (2) | 0.002 (2) | 0.0069 (18) | −0.0029 (18) |
C6A | 0.031 (3) | 0.029 (3) | 0.026 (2) | −0.003 (2) | 0.013 (2) | 0.0020 (19) |
C6 | 0.036 (3) | 0.027 (3) | 0.025 (2) | −0.009 (2) | 0.011 (2) | −0.001 (2) |
O6 | 0.0360 (19) | 0.039 (2) | 0.0272 (16) | −0.0048 (15) | 0.0104 (14) | −0.0037 (14) |
C7 | 0.031 (3) | 0.036 (3) | 0.024 (2) | −0.004 (2) | 0.004 (2) | 0.002 (2) |
C8 | 0.025 (3) | 0.039 (3) | 0.037 (2) | 0.003 (2) | 0.007 (2) | 0.010 (2) |
C9 | 0.027 (3) | 0.035 (3) | 0.036 (2) | 0.003 (2) | 0.013 (2) | 0.005 (2) |
C10 | 0.029 (3) | 0.026 (3) | 0.031 (2) | −0.001 (2) | 0.010 (2) | 0.0028 (19) |
C10A | 0.025 (2) | 0.026 (2) | 0.031 (2) | −0.002 (2) | 0.012 (2) | 0.0018 (19) |
C10B | 0.030 (3) | 0.019 (2) | 0.026 (2) | −0.002 (2) | 0.007 (2) | 0.0020 (18) |
N11 | 0.025 (2) | 0.028 (2) | 0.0222 (17) | 0.0051 (17) | 0.0067 (16) | 0.0004 (15) |
C11A | 0.024 (2) | 0.021 (2) | 0.025 (2) | −0.0017 (19) | 0.0074 (19) | −0.0003 (18) |
C21 | 0.037 (3) | 0.059 (3) | 0.026 (2) | −0.006 (3) | 0.013 (2) | −0.017 (2) |
C31 | 0.034 (3) | 0.036 (3) | 0.029 (2) | −0.003 (2) | 0.007 (2) | −0.007 (2) |
N32 | 0.038 (2) | 0.035 (2) | 0.0270 (18) | 0.0039 (19) | 0.0117 (18) | 0.0005 (17) |
O31 | 0.0353 (19) | 0.0374 (19) | 0.0277 (15) | −0.0038 (15) | 0.0118 (14) | −0.0059 (14) |
C33 | 0.054 (3) | 0.040 (3) | 0.036 (2) | 0.004 (3) | 0.021 (2) | 0.003 (2) |
C34 | 0.034 (3) | 0.044 (3) | 0.032 (2) | 0.000 (2) | 0.011 (2) | −0.005 (2) |
C51 | 0.027 (2) | 0.021 (2) | 0.026 (2) | 0.000 (2) | 0.0089 (19) | −0.0024 (18) |
C52 | 0.025 (2) | 0.028 (3) | 0.025 (2) | 0.000 (2) | 0.0106 (18) | −0.0059 (19) |
C53 | 0.026 (2) | 0.025 (3) | 0.029 (2) | 0.003 (2) | 0.0061 (19) | 0.0016 (19) |
C54 | 0.028 (3) | 0.032 (3) | 0.021 (2) | 0.000 (2) | 0.0063 (19) | 0.0040 (19) |
Cl54 | 0.0538 (8) | 0.0369 (7) | 0.0365 (6) | −0.0006 (6) | 0.0258 (6) | 0.0060 (5) |
C55 | 0.028 (3) | 0.032 (3) | 0.023 (2) | 0.007 (2) | 0.0073 (19) | −0.0018 (19) |
C56 | 0.034 (3) | 0.029 (3) | 0.021 (2) | 0.004 (2) | 0.0074 (19) | −0.0020 (19) |
Geometric parameters (Å, º) top
N1—C2 | 1.299 (5) | C56—H56 | 0.95 |
N1—C11A | 1.370 (5) | C6A—C7 | 1.383 (6) |
C2—O2 | 1.332 (4) | C6A—C10A | 1.401 (5) |
C2—N3 | 1.353 (5) | C6A—C6 | 1.512 (6) |
O2—C21 | 1.445 (4) | C6—O6 | 1.232 (4) |
C21—H21A | 0.98 | C7—C8 | 1.400 (6) |
C21—H21B | 0.98 | C7—H7 | 0.95 |
C21—H21C | 0.98 | C8—C9 | 1.383 (5) |
N3—C4 | 1.392 (5) | C8—H8 | 0.95 |
N3—H3 | 0.88 | C9—C10 | 1.404 (6) |
C4—O4 | 1.250 (4) | C9—H9 | 0.95 |
C4—C4A | 1.420 (5) | C10—C10A | 1.374 (5) |
C4A—C11A | 1.378 (5) | C10—H10 | 0.95 |
C4A—C5 | 1.537 (5) | C10A—C10B | 1.486 (6) |
C5A—C10B | 1.361 (5) | C10B—N11 | 1.345 (5) |
C5A—C6 | 1.469 (6) | N11—C11A | 1.380 (5) |
C5A—C5 | 1.502 (5) | N11—H11 | 0.88 |
C5—C51 | 1.529 (5) | C31—O31 | 1.247 (4) |
C5—H5 | 1.00 | C31—N32 | 1.320 (5) |
C51—C56 | 1.385 (5) | C31—H31 | 0.95 |
C51—C52 | 1.388 (5) | N32—C34 | 1.455 (5) |
C52—C53 | 1.390 (5) | N32—C33 | 1.463 (5) |
C52—H52 | 0.95 | C33—H33A | 0.98 |
C53—C54 | 1.387 (5) | C33—H33B | 0.98 |
C53—H53 | 0.95 | C33—H33C | 0.98 |
C54—C55 | 1.373 (6) | C34—H34A | 0.98 |
C54—Cl54 | 1.761 (4) | C34—H34B | 0.98 |
C55—C56 | 1.395 (5) | C34—H34C | 0.98 |
C55—H55 | 0.95 | | |
| | | |
C2—N1—C11A | 115.7 (3) | C7—C6A—C6 | 131.2 (4) |
N1—C2—O2 | 122.7 (3) | C10A—C6A—C6 | 107.7 (4) |
N1—C2—N3 | 124.5 (4) | O6—C6—C5A | 127.8 (4) |
O2—C2—N3 | 112.7 (4) | O6—C6—C6A | 126.2 (4) |
C2—O2—C21 | 115.9 (3) | C5A—C6—C6A | 106.0 (3) |
O2—C21—H21A | 109.5 | C6A—C7—C8 | 117.5 (4) |
O2—C21—H21B | 109.5 | C6A—C7—H7 | 121.3 |
H21A—C21—H21B | 109.5 | C8—C7—H7 | 121.3 |
O2—C21—H21C | 109.5 | C9—C8—C7 | 121.6 (4) |
H21A—C21—H21C | 109.5 | C9—C8—H8 | 119.2 |
H21B—C21—H21C | 109.5 | C7—C8—H8 | 119.2 |
C2—N3—C4 | 121.6 (4) | C8—C9—C10 | 120.4 (4) |
C2—N3—H3 | 119.2 | C8—C9—H9 | 119.8 |
C4—N3—H3 | 119.2 | C10—C9—H9 | 119.8 |
O4—C4—N3 | 119.3 (4) | C10A—C10—C9 | 118.1 (4) |
O4—C4—C4A | 125.1 (4) | C10A—C10—H10 | 121.0 |
N3—C4—C4A | 115.6 (3) | C9—C10—H10 | 121.0 |
C11A—C4A—C4 | 117.7 (4) | C10—C10A—C6A | 121.3 (4) |
C11A—C4A—C5 | 124.2 (4) | C10—C10A—C10B | 131.7 (4) |
C4—C4A—C5 | 118.1 (3) | C6A—C10A—C10B | 107.0 (3) |
C10B—C5A—C6 | 108.4 (4) | N11—C10B—C5A | 124.0 (4) |
C10B—C5A—C5 | 124.2 (4) | N11—C10B—C10A | 125.1 (3) |
C6—C5A—C5 | 127.4 (3) | C5A—C10B—C10A | 110.9 (4) |
C5A—C5—C51 | 112.4 (3) | C10B—N11—C11A | 118.8 (3) |
C5A—C5—C4A | 107.1 (3) | C10B—N11—H11 | 120.6 |
C51—C5—C4A | 109.9 (3) | C11A—N11—H11 | 120.6 |
C5A—C5—H5 | 109.1 | N1—C11A—C4A | 124.7 (4) |
C51—C5—H5 | 109.1 | N1—C11A—N11 | 113.9 (3) |
C4A—C5—H5 | 109.1 | C4A—C11A—N11 | 121.3 (4) |
C56—C51—C52 | 118.5 (4) | O31—C31—N32 | 124.8 (4) |
C56—C51—C5 | 121.1 (4) | O31—C31—H31 | 117.6 |
C52—C51—C5 | 120.3 (3) | N32—C31—H31 | 117.6 |
C51—C52—C53 | 121.9 (4) | C31—N32—C34 | 119.3 (3) |
C51—C52—H52 | 119.0 | C31—N32—C33 | 122.1 (4) |
C53—C52—H52 | 119.0 | C34—N32—C33 | 118.3 (4) |
C54—C53—C52 | 117.5 (4) | N32—C33—H33A | 109.5 |
C54—C53—H53 | 121.3 | N32—C33—H33B | 109.5 |
C52—C53—H53 | 121.3 | H33A—C33—H33B | 109.5 |
C55—C54—C53 | 122.5 (4) | N32—C33—H33C | 109.5 |
C55—C54—Cl54 | 119.7 (3) | H33A—C33—H33C | 109.5 |
C53—C54—Cl54 | 117.9 (3) | H33B—C33—H33C | 109.5 |
C54—C55—C56 | 118.6 (4) | N32—C34—H34A | 109.5 |
C54—C55—H55 | 120.7 | N32—C34—H34B | 109.5 |
C56—C55—H55 | 120.7 | H34A—C34—H34B | 109.5 |
C51—C56—C55 | 121.0 (4) | N32—C34—H34C | 109.5 |
C51—C56—H56 | 119.5 | H34A—C34—H34C | 109.5 |
C55—C56—H56 | 119.5 | H34B—C34—H34C | 109.5 |
C7—C6A—C10A | 121.1 (4) | | |
| | | |
C11A—N1—C2—O2 | 178.0 (4) | C5—C5A—C6—C6A | −178.9 (4) |
C11A—N1—C2—N3 | −1.3 (6) | C7—C6A—C6—O6 | 1.0 (7) |
N1—C2—O2—C21 | −1.0 (6) | C10A—C6A—C6—O6 | 179.1 (4) |
N3—C2—O2—C21 | 178.4 (4) | C7—C6A—C6—C5A | −179.4 (4) |
N1—C2—N3—C4 | −1.1 (6) | C10A—C6A—C6—C5A | −1.2 (4) |
O2—C2—N3—C4 | 179.6 (3) | C10A—C6A—C7—C8 | 0.2 (6) |
C2—N3—C4—O4 | −175.6 (4) | C6—C6A—C7—C8 | 178.2 (4) |
C2—N3—C4—C4A | 3.6 (5) | C6A—C7—C8—C9 | 0.2 (6) |
O4—C4—C4A—C11A | 175.4 (4) | C7—C8—C9—C10 | −0.3 (6) |
N3—C4—C4A—C11A | −3.8 (5) | C8—C9—C10—C10A | 0.0 (6) |
O4—C4—C4A—C5 | −5.2 (6) | C9—C10—C10A—C6A | 0.4 (6) |
N3—C4—C4A—C5 | 175.7 (3) | C9—C10—C10A—C10B | −179.1 (4) |
C10B—C5A—C5—C51 | −115.0 (4) | C7—C6A—C10A—C10 | −0.5 (6) |
C6—C5A—C5—C51 | 65.3 (5) | C6—C6A—C10A—C10 | −178.9 (4) |
C10B—C5A—C5—C4A | 5.8 (5) | C7—C6A—C10A—C10B | 179.1 (4) |
C6—C5A—C5—C4A | −173.9 (4) | C6—C6A—C10A—C10B | 0.7 (4) |
C11A—C4A—C5—C5A | −5.7 (5) | C6—C5A—C10B—N11 | 177.5 (4) |
C4—C4A—C5—C5A | 174.9 (4) | C5—C5A—C10B—N11 | −2.3 (7) |
C11A—C4A—C5—C51 | 116.7 (4) | C6—C5A—C10B—C10A | −0.9 (5) |
C4—C4A—C5—C51 | −62.7 (5) | C5—C5A—C10B—C10A | 179.3 (4) |
C5A—C5—C51—C56 | −129.6 (4) | C10—C10A—C10B—N11 | 1.3 (7) |
C4A—C5—C51—C56 | 111.1 (4) | C6A—C10A—C10B—N11 | −178.3 (4) |
C5A—C5—C51—C52 | 52.2 (5) | C10—C10A—C10B—C5A | 179.7 (4) |
C4A—C5—C51—C52 | −67.0 (5) | C6A—C10A—C10B—C5A | 0.1 (5) |
C56—C51—C52—C53 | −1.7 (6) | C5A—C10B—N11—C11A | −2.4 (6) |
C5—C51—C52—C53 | 176.5 (4) | C10A—C10B—N11—C11A | 175.8 (4) |
C51—C52—C53—C54 | 0.6 (6) | C2—N1—C11A—C4A | 0.9 (6) |
C52—C53—C54—C55 | 0.7 (6) | C2—N1—C11A—N11 | −178.9 (3) |
C52—C53—C54—Cl54 | −178.0 (3) | C4—C4A—C11A—N1 | 1.7 (6) |
C53—C54—C55—C56 | −0.9 (6) | C5—C4A—C11A—N1 | −177.7 (4) |
Cl54—C54—C55—C56 | 177.8 (3) | C4—C4A—C11A—N11 | −178.6 (4) |
C52—C51—C56—C55 | 1.5 (6) | C5—C4A—C11A—N11 | 2.1 (6) |
C5—C51—C56—C55 | −176.7 (4) | C10B—N11—C11A—N1 | −177.8 (3) |
C54—C55—C56—C51 | −0.2 (6) | C10B—N11—C11A—C4A | 2.5 (6) |
C10B—C5A—C6—O6 | −179.0 (4) | O31—C31—N32—C34 | 2.6 (7) |
C5—C5A—C6—O6 | 0.7 (7) | O31—C31—N32—C33 | 176.4 (4) |
C10B—C5A—C6—C6A | 1.3 (5) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O4i | 0.88 | 1.85 | 2.735 (4) | 179 |
N11—H11···O31 | 0.88 | 1.98 | 2.857 (4) | 172 |
C8—H8···Cg1ii | 0.95 | 2.63 | 3.561 (5) | 167 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x−1, y, z. |
(II) (5RS,5aSR,10bSR)-10
b-hydroxy-2-methoxy-5-(4-methoxyphenyl)-5a-10
b- dihydroindeno[1',2':2,3]pyrido[5,6-
d]pyrimidine-4,6(3
H,5H)-dione– dimethylformamide (1/1)
top
Crystal data top
C22H19N3O5·C3H7NO | Z = 2 |
Mr = 478.50 | F(000) = 504 |
Triclinic, P1 | Dx = 1.362 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.4172 (2) Å | Cell parameters from 5297 reflections |
b = 10.8540 (3) Å | θ = 2.9–27.6° |
c = 11.6112 (3) Å | µ = 0.10 mm−1 |
α = 94.2692 (12)° | T = 120 K |
β = 116.0676 (12)° | Block, yellow |
γ = 94.4530 (13)° | 0.20 × 0.10 × 0.04 mm |
V = 1167.08 (5) Å3 | |
Data collection top
Nonius KappaCCD diffractometer | 5297 independent reflections |
Radiation source: rotating anode | 3719 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.073 |
ϕ scans, and ω scans with κ offsets | θmax = 27.6°, θmin = 2.9° |
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997 | h = −13→13 |
Tmin = 0.974, Tmax = 0.996 | k = −14→13 |
5297 measured reflections | l = −15→15 |
Refinement top
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)] = 0.055 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.148 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0589P)2 + 0.5313P] where P = (Fo2 + 2Fc2)/3 |
5297 reflections | (Δ/σ)max < 0.001 |
326 parameters | Δρmax = 0.25 e Å−3 |
0 restraints | Δρmin = −0.37 e Å−3 |
Crystal data top
C22H19N3O5·C3H7NO | γ = 94.4530 (13)° |
Mr = 478.50 | V = 1167.08 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.4172 (2) Å | Mo Kα radiation |
b = 10.8540 (3) Å | µ = 0.10 mm−1 |
c = 11.6112 (3) Å | T = 120 K |
α = 94.2692 (12)° | 0.20 × 0.10 × 0.04 mm |
β = 116.0676 (12)° | |
Data collection top
Nonius KappaCCD diffractometer | 5297 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997 | 3719 reflections with I > 2σ(I) |
Tmin = 0.974, Tmax = 0.996 | Rint = 0.073 |
5297 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.055 | 0 restraints |
wR(F2) = 0.148 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.25 e Å−3 |
5297 reflections | Δρmin = −0.37 e Å−3 |
326 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | 0.35716 (17) | 0.18353 (15) | 0.22434 (15) | 0.0176 (4) | |
C2 | 0.4584 (2) | 0.27369 (18) | 0.29379 (19) | 0.0179 (4) | |
O2 | 0.58146 (14) | 0.28847 (13) | 0.28476 (13) | 0.0220 (3) | |
C4 | 0.3334 (2) | 0.35679 (18) | 0.40663 (18) | 0.0170 (4) | |
N3 | 0.45158 (17) | 0.36083 (15) | 0.37961 (16) | 0.0185 (4) | |
O4 | 0.33167 (14) | 0.43994 (12) | 0.48670 (13) | 0.0198 (3) | |
C4A | 0.2239 (2) | 0.25609 (18) | 0.33839 (18) | 0.0171 (4) | |
C5 | 0.0903 (2) | 0.23997 (18) | 0.35860 (19) | 0.0176 (4) | |
C5A | 0.0276 (2) | 0.10115 (18) | 0.32368 (19) | 0.0177 (4) | |
C6 | 0.1113 (2) | 0.02102 (19) | 0.42837 (19) | 0.0197 (4) | |
O6 | 0.16731 (16) | 0.05430 (14) | 0.54418 (14) | 0.0277 (4) | |
C6A | 0.1088 (2) | −0.10179 (19) | 0.3642 (2) | 0.0206 (4) | |
C7 | 0.1581 (2) | −0.2101 (2) | 0.4181 (2) | 0.0272 (5) | |
C8 | 0.1442 (2) | −0.3147 (2) | 0.3365 (2) | 0.0293 (5) | |
C9 | 0.0819 (2) | −0.3118 (2) | 0.2032 (2) | 0.0285 (5) | |
C10 | 0.0323 (2) | −0.20409 (19) | 0.1487 (2) | 0.0234 (5) | |
C10A | 0.0483 (2) | −0.09871 (18) | 0.23169 (19) | 0.0183 (4) | |
C10B | 0.0182 (2) | 0.03239 (18) | 0.19708 (18) | 0.0171 (4) | |
O10 | −0.11304 (14) | 0.03408 (12) | 0.08569 (13) | 0.0194 (3) | |
N11 | 0.13181 (17) | 0.08555 (15) | 0.16838 (15) | 0.0182 (4) | |
C11A | 0.2381 (2) | 0.17682 (17) | 0.24682 (18) | 0.0166 (4) | |
C21 | 0.6048 (2) | 0.18856 (19) | 0.2077 (2) | 0.0237 (5) | |
C31 | −0.3448 (2) | −0.14912 (19) | 0.18371 (19) | 0.0219 (4) | |
N32 | −0.46330 (19) | −0.17883 (16) | 0.19658 (17) | 0.0229 (4) | |
O31 | −0.33595 (15) | −0.07707 (14) | 0.10888 (14) | 0.0268 (4) | |
C33 | −0.5953 (2) | −0.1251 (2) | 0.1240 (2) | 0.0282 (5) | |
C34 | −0.4635 (3) | −0.2595 (2) | 0.2911 (2) | 0.0347 (6) | |
C51 | −0.0175 (2) | 0.32812 (18) | 0.29006 (19) | 0.0182 (4) | |
C52 | −0.0756 (2) | 0.39835 (18) | 0.3571 (2) | 0.0196 (4) | |
C53 | −0.1745 (2) | 0.47954 (19) | 0.2978 (2) | 0.0225 (5) | |
C54 | −0.2191 (2) | 0.49168 (19) | 0.1679 (2) | 0.0231 (5) | |
O54 | −0.31602 (18) | 0.57484 (15) | 0.11723 (15) | 0.0339 (4) | |
C55 | −0.1636 (2) | 0.42168 (19) | 0.0987 (2) | 0.0246 (5) | |
C56 | −0.0634 (2) | 0.34194 (19) | 0.1605 (2) | 0.0224 (5) | |
C541 | −0.3598 (3) | 0.5935 (3) | −0.0146 (2) | 0.0434 (7) | |
H21A | 0.6220 | 0.1145 | 0.2532 | 0.036* | |
H21B | 0.6887 | 0.2151 | 0.1941 | 0.036* | |
H21C | 0.5195 | 0.1689 | 0.1240 | 0.036* | |
H3 | 0.5230 | 0.4213 | 0.4192 | 0.022* | |
H5 | 0.1219 | 0.2608 | 0.4532 | 0.021* | |
H52 | −0.0465 | 0.3902 | 0.4457 | 0.023* | |
H53 | −0.2118 | 0.5267 | 0.3458 | 0.029 (6)* | |
H54A | −0.2759 | 0.6265 | −0.0251 | 0.065* | |
H54B | −0.4309 | 0.6529 | −0.0394 | 0.065* | |
H54C | −0.4028 | 0.5140 | −0.0696 | 0.065* | |
H55 | −0.1941 | 0.4285 | 0.0096 | 0.037 (7)* | |
H56 | −0.0252 | 0.2955 | 0.1128 | 0.021 (6)* | |
H5A | −0.0725 | 0.0958 | 0.3152 | 0.021* | |
H7 | 0.2002 | −0.2116 | 0.5090 | 0.029 (6)* | |
H8 | 0.1773 | −0.3890 | 0.3712 | 0.032 (6)* | |
H9 | 0.0730 | −0.3847 | 0.1483 | 0.038 (7)* | |
H10 | −0.0110 | −0.2029 | 0.0578 | 0.028* | |
H10B | −0.1942 | −0.0094 | 0.0953 | 0.023* | |
H11 | 0.1317 | 0.0568 | 0.0955 | 0.022* | |
H31 | −0.2612 | −0.1855 | 0.2352 | 0.026* | |
H33A | −0.6741 | −0.1920 | 0.0751 | 0.042* | |
H33B | −0.5816 | −0.0727 | 0.0641 | 0.042* | |
H33C | −0.6189 | −0.0745 | 0.1838 | 0.042* | |
H34A | −0.4806 | −0.2122 | 0.3572 | 0.052* | |
H34B | −0.3701 | −0.2912 | 0.3318 | 0.052* | |
H34C | −0.5399 | −0.3295 | 0.2479 | 0.052* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0160 (8) | 0.0185 (8) | 0.0187 (9) | 0.0010 (7) | 0.0086 (7) | 0.0004 (7) |
C2 | 0.0169 (10) | 0.0189 (10) | 0.0197 (10) | 0.0028 (8) | 0.0096 (8) | 0.0026 (8) |
O2 | 0.0187 (7) | 0.0227 (8) | 0.0266 (8) | −0.0010 (6) | 0.0139 (6) | −0.0056 (6) |
C21 | 0.0227 (11) | 0.0251 (11) | 0.0266 (11) | 0.0028 (9) | 0.0151 (9) | −0.0044 (9) |
N3 | 0.0162 (8) | 0.0171 (8) | 0.0206 (9) | −0.0018 (7) | 0.0084 (7) | −0.0029 (7) |
C4 | 0.0178 (10) | 0.0166 (10) | 0.0165 (10) | 0.0032 (8) | 0.0073 (8) | 0.0029 (8) |
O4 | 0.0208 (7) | 0.0176 (7) | 0.0211 (7) | 0.0009 (6) | 0.0107 (6) | −0.0037 (6) |
C4A | 0.0178 (10) | 0.0172 (10) | 0.0152 (10) | 0.0033 (8) | 0.0065 (8) | 0.0003 (8) |
C5 | 0.0179 (10) | 0.0185 (10) | 0.0167 (10) | 0.0017 (8) | 0.0085 (8) | −0.0008 (8) |
C51 | 0.0170 (10) | 0.0164 (10) | 0.0202 (10) | −0.0017 (8) | 0.0086 (8) | −0.0018 (8) |
C52 | 0.0179 (10) | 0.0202 (10) | 0.0199 (10) | −0.0010 (8) | 0.0089 (9) | −0.0005 (8) |
C53 | 0.0221 (11) | 0.0195 (10) | 0.0264 (11) | 0.0015 (9) | 0.0122 (9) | −0.0023 (9) |
C54 | 0.0197 (10) | 0.0179 (10) | 0.0282 (12) | 0.0034 (8) | 0.0076 (9) | 0.0012 (9) |
O54 | 0.0379 (9) | 0.0317 (9) | 0.0280 (9) | 0.0187 (8) | 0.0088 (7) | 0.0035 (7) |
C541 | 0.0519 (17) | 0.0410 (15) | 0.0286 (13) | 0.0221 (13) | 0.0072 (12) | 0.0076 (11) |
C55 | 0.0276 (11) | 0.0234 (11) | 0.0226 (11) | 0.0040 (9) | 0.0108 (9) | 0.0031 (9) |
C56 | 0.0252 (11) | 0.0223 (11) | 0.0215 (11) | 0.0040 (9) | 0.0123 (9) | −0.0003 (8) |
C5A | 0.0158 (9) | 0.0184 (10) | 0.0200 (10) | −0.0005 (8) | 0.0101 (8) | −0.0011 (8) |
C6 | 0.0164 (10) | 0.0233 (11) | 0.0201 (11) | −0.0011 (8) | 0.0094 (8) | 0.0019 (8) |
O6 | 0.0317 (9) | 0.0296 (8) | 0.0174 (8) | −0.0013 (7) | 0.0081 (7) | 0.0007 (6) |
C6A | 0.0185 (10) | 0.0218 (10) | 0.0217 (11) | 0.0010 (8) | 0.0093 (9) | 0.0029 (8) |
C7 | 0.0282 (12) | 0.0244 (11) | 0.0277 (12) | 0.0021 (9) | 0.0107 (10) | 0.0089 (9) |
C8 | 0.0305 (12) | 0.0220 (11) | 0.0380 (14) | 0.0067 (10) | 0.0164 (11) | 0.0099 (10) |
C9 | 0.0342 (13) | 0.0191 (11) | 0.0371 (13) | 0.0018 (10) | 0.0214 (11) | −0.0013 (10) |
C10 | 0.0281 (11) | 0.0208 (11) | 0.0226 (11) | −0.0004 (9) | 0.0134 (10) | 0.0004 (9) |
C10A | 0.0165 (10) | 0.0190 (10) | 0.0208 (10) | 0.0004 (8) | 0.0101 (8) | 0.0010 (8) |
C10B | 0.0165 (9) | 0.0185 (10) | 0.0148 (9) | 0.0003 (8) | 0.0062 (8) | −0.0001 (8) |
O10 | 0.0145 (7) | 0.0237 (7) | 0.0166 (7) | 0.0000 (6) | 0.0044 (6) | 0.0014 (6) |
N11 | 0.0187 (8) | 0.0201 (9) | 0.0154 (8) | −0.0020 (7) | 0.0085 (7) | −0.0024 (7) |
C11A | 0.0160 (9) | 0.0159 (10) | 0.0171 (10) | 0.0020 (8) | 0.0067 (8) | 0.0021 (8) |
C31 | 0.0219 (11) | 0.0221 (10) | 0.0179 (10) | 0.0030 (9) | 0.0064 (9) | −0.0030 (8) |
N32 | 0.0240 (9) | 0.0222 (9) | 0.0212 (9) | 0.0026 (7) | 0.0090 (8) | 0.0027 (7) |
O31 | 0.0223 (8) | 0.0326 (9) | 0.0247 (8) | 0.0012 (7) | 0.0100 (7) | 0.0048 (7) |
C33 | 0.0222 (11) | 0.0300 (12) | 0.0311 (12) | 0.0037 (9) | 0.0107 (10) | 0.0035 (10) |
C34 | 0.0415 (14) | 0.0348 (13) | 0.0314 (13) | 0.0036 (11) | 0.0187 (12) | 0.0108 (11) |
Geometric parameters (Å, º) top
N1—C2 | 1.302 (2) | C5A—C6 | 1.529 (3) |
N1—C11A | 1.373 (2) | C5A—C10B | 1.558 (3) |
C2—O2 | 1.330 (2) | C5A—H5A | 1.00 |
C2—N3 | 1.351 (2) | C6—O6 | 1.218 (2) |
O2—C21 | 1.457 (2) | C6—C6A | 1.471 (3) |
C21—H21A | 0.98 | C6A—C10A | 1.387 (3) |
C21—H21B | 0.98 | C6A—C7 | 1.400 (3) |
C21—H21C | 0.98 | C7—C8 | 1.379 (3) |
N3—C4 | 1.396 (2) | C7—H7 | 0.95 |
N3—H3 | 0.88 | C8—C9 | 1.394 (3) |
C4—O4 | 1.254 (2) | C8—H8 | 0.95 |
C4—C4A | 1.416 (3) | C9—C10 | 1.397 (3) |
C4A—C11A | 1.383 (3) | C9—H9 | 0.95 |
C4A—C5 | 1.509 (3) | C10—C10A | 1.389 (3) |
C5—C51 | 1.518 (3) | C10—H10 | 0.95 |
C5—C5A | 1.544 (3) | C10A—C10B | 1.526 (3) |
C5—H5 | 1.00 | C10B—O10 | 1.413 (2) |
C51—C56 | 1.388 (3) | C10B—N11 | 1.454 (2) |
C51—C52 | 1.397 (3) | O10—H10B | 0.9894 |
C52—C53 | 1.386 (3) | N11—C11A | 1.358 (2) |
C52—H52 | 0.95 | N11—H11 | 0.88 |
C53—C54 | 1.391 (3) | C31—O31 | 1.239 (2) |
C53—H53 | 0.95 | C31—N32 | 1.326 (3) |
C54—O54 | 1.371 (3) | C31—H31 | 0.95 |
C54—C55 | 1.393 (3) | N32—C34 | 1.454 (3) |
O54—C541 | 1.427 (3) | N32—C33 | 1.456 (3) |
C541—H54A | 0.98 | C33—H33A | 0.98 |
C541—H54B | 0.98 | C33—H33B | 0.98 |
C541—H54C | 0.98 | C33—H33C | 0.98 |
C55—C56 | 1.389 (3) | C34—H34A | 0.98 |
C55—H55 | 0.95 | C34—H34B | 0.98 |
C56—H56 | 0.95 | C34—H34C | 0.98 |
| | | |
C2—N1—C11A | 115.32 (16) | C5—C5A—H5A | 107.2 |
N1—C2—O2 | 121.55 (17) | C10B—C5A—H5A | 107.2 |
N1—C2—N3 | 125.32 (17) | O6—C6—C6A | 126.98 (19) |
O2—C2—N3 | 113.13 (16) | O6—C6—C5A | 125.12 (19) |
C2—O2—C21 | 116.15 (15) | C6A—C6—C5A | 107.89 (16) |
O2—C21—H21A | 109.5 | C10A—C6A—C7 | 121.0 (2) |
O2—C21—H21B | 109.5 | C10A—C6A—C6 | 109.43 (18) |
H21A—C21—H21B | 109.5 | C7—C6A—C6 | 129.53 (19) |
O2—C21—H21C | 109.5 | C8—C7—C6A | 118.5 (2) |
H21A—C21—H21C | 109.5 | C8—C7—H7 | 120.7 |
H21B—C21—H21C | 109.5 | C6A—C7—H7 | 120.7 |
C2—N3—C4 | 121.25 (16) | C7—C8—C9 | 120.3 (2) |
C2—N3—H3 | 119.4 | C7—C8—H8 | 119.8 |
C4—N3—H3 | 119.4 | C9—C8—H8 | 119.8 |
O4—C4—N3 | 118.98 (17) | C8—C9—C10 | 121.4 (2) |
O4—C4—C4A | 125.68 (17) | C8—C9—H9 | 119.3 |
N3—C4—C4A | 115.34 (17) | C10—C9—H9 | 119.3 |
C11A—C4A—C4 | 118.42 (17) | C10A—C10—C9 | 117.9 (2) |
C11A—C4A—C5 | 120.48 (17) | C10A—C10—H10 | 121.1 |
C4—C4A—C5 | 120.98 (17) | C9—C10—H10 | 121.1 |
C4A—C5—C51 | 113.09 (16) | C6A—C10A—C10 | 120.76 (19) |
C4A—C5—C5A | 108.68 (15) | C6A—C10A—C10B | 111.46 (17) |
C51—C5—C5A | 114.10 (16) | C10—C10A—C10B | 127.56 (18) |
C4A—C5—H5 | 106.8 | O10—C10B—N11 | 106.66 (15) |
C51—C5—H5 | 106.8 | O10—C10B—C10A | 113.04 (16) |
C5A—C5—H5 | 106.8 | N11—C10B—C10A | 107.93 (16) |
C56—C51—C52 | 117.36 (19) | O10—C10B—C5A | 115.09 (16) |
C56—C51—C5 | 122.53 (18) | N11—C10B—C5A | 110.99 (15) |
C52—C51—C5 | 120.11 (17) | C10A—C10B—C5A | 102.99 (15) |
C53—C52—C51 | 121.82 (19) | C10B—O10—H10B | 110.8 |
C53—C52—H52 | 119.1 | C11A—N11—C10B | 124.24 (16) |
C51—C52—H52 | 119.1 | C11A—N11—H11 | 117.9 |
C52—C53—C54 | 119.77 (19) | C10B—N11—H11 | 117.9 |
C52—C53—H53 | 120.1 | N11—C11A—N1 | 113.73 (17) |
C54—C53—H53 | 120.1 | N11—C11A—C4A | 122.16 (17) |
O54—C54—C53 | 115.98 (18) | N1—C11A—C4A | 124.10 (17) |
O54—C54—C55 | 124.59 (19) | O31—C31—N32 | 124.3 (2) |
C53—C54—C55 | 119.43 (19) | O31—C31—H31 | 117.9 |
C54—O54—C541 | 117.58 (18) | N32—C31—H31 | 117.9 |
O54—C541—H54A | 109.5 | C31—N32—C34 | 121.12 (19) |
O54—C541—H54B | 109.5 | C31—N32—C33 | 121.58 (17) |
H54A—C541—H54B | 109.5 | C34—N32—C33 | 117.16 (18) |
O54—C541—H54C | 109.5 | N32—C33—H33A | 109.5 |
H54A—C541—H54C | 109.5 | N32—C33—H33B | 109.5 |
H54B—C541—H54C | 109.5 | H33A—C33—H33B | 109.5 |
C56—C55—C54 | 119.7 (2) | N32—C33—H33C | 109.5 |
C56—C55—H55 | 120.1 | H33A—C33—H33C | 109.5 |
C54—C55—H55 | 120.1 | H33B—C33—H33C | 109.5 |
C51—C56—C55 | 121.87 (19) | N32—C34—H34A | 109.5 |
C51—C56—H56 | 119.1 | N32—C34—H34B | 109.5 |
C55—C56—H56 | 119.1 | H34A—C34—H34B | 109.5 |
C6—C5A—C5 | 112.94 (16) | N32—C34—H34C | 109.5 |
C6—C5A—C10B | 104.38 (15) | H34A—C34—H34C | 109.5 |
C5—C5A—C10B | 117.43 (16) | H34B—C34—H34C | 109.5 |
C6—C5A—H5A | 107.2 | | |
| | | |
C11A—N1—C2—O2 | 177.80 (17) | O6—C6—C6A—C10A | −173.56 (19) |
C11A—N1—C2—N3 | −2.7 (3) | C5A—C6—C6A—C10A | 7.6 (2) |
N1—C2—O2—C21 | −8.6 (3) | O6—C6—C6A—C7 | 5.6 (3) |
N3—C2—O2—C21 | 171.84 (17) | C5A—C6—C6A—C7 | −173.3 (2) |
N1—C2—N3—C4 | 3.6 (3) | C10A—C6A—C7—C8 | −0.6 (3) |
O2—C2—N3—C4 | −176.87 (16) | C6—C6A—C7—C8 | −179.6 (2) |
C2—N3—C4—O4 | −179.77 (18) | C6A—C7—C8—C9 | −0.2 (3) |
C2—N3—C4—C4A | 0.1 (3) | C7—C8—C9—C10 | 0.1 (3) |
O4—C4—C4A—C11A | 175.75 (18) | C8—C9—C10—C10A | 0.7 (3) |
N3—C4—C4A—C11A | −4.1 (3) | C7—C6A—C10A—C10 | 1.4 (3) |
O4—C4—C4A—C5 | −0.4 (3) | C6—C6A—C10A—C10 | −179.38 (18) |
N3—C4—C4A—C5 | 179.74 (16) | C7—C6A—C10A—C10B | −173.66 (18) |
C11A—C4A—C5—C51 | −98.9 (2) | C6—C6A—C10A—C10B | 5.6 (2) |
C4—C4A—C5—C51 | 77.1 (2) | C9—C10—C10A—C6A | −1.4 (3) |
C11A—C4A—C5—C5A | 28.8 (2) | C9—C10—C10A—C10B | 172.78 (19) |
C4—C4A—C5—C5A | −155.08 (18) | C6A—C10A—C10B—O10 | −140.67 (17) |
C4A—C5—C51—C56 | 50.3 (2) | C10—C10A—C10B—O10 | 44.7 (3) |
C5A—C5—C51—C56 | −74.6 (2) | C6A—C10A—C10B—N11 | 101.62 (18) |
C4A—C5—C51—C52 | −130.38 (18) | C10—C10A—C10B—N11 | −73.0 (2) |
C5A—C5—C51—C52 | 104.7 (2) | C6A—C10A—C10B—C5A | −15.8 (2) |
C56—C51—C52—C53 | −0.4 (3) | C10—C10A—C10B—C5A | 169.51 (19) |
C5—C51—C52—C53 | −179.82 (17) | C6—C5A—C10B—O10 | 142.61 (16) |
C51—C52—C53—C54 | 0.5 (3) | C5—C5A—C10B—O10 | −91.5 (2) |
C52—C53—C54—O54 | −179.39 (18) | C6—C5A—C10B—N11 | −96.15 (18) |
C52—C53—C54—C55 | 0.1 (3) | C5—C5A—C10B—N11 | 29.8 (2) |
C53—C54—O54—C541 | 177.6 (2) | C6—C5A—C10B—C10A | 19.12 (18) |
C55—C54—O54—C541 | −1.9 (3) | C5—C5A—C10B—C10A | 145.04 (17) |
O54—C54—C55—C56 | 178.64 (19) | O10—C10B—N11—C11A | 130.63 (18) |
C53—C54—C55—C56 | −0.8 (3) | C10A—C10B—N11—C11A | −107.6 (2) |
C52—C51—C56—C55 | −0.3 (3) | C5A—C10B—N11—C11A | 4.6 (3) |
C5—C51—C56—C55 | 179.09 (18) | C10B—N11—C11A—N1 | 159.28 (17) |
C54—C55—C56—C51 | 0.9 (3) | C10B—N11—C11A—C4A | −21.9 (3) |
C4A—C5—C5A—C6 | 76.76 (19) | C2—N1—C11A—N11 | 176.95 (17) |
C51—C5—C5A—C6 | −156.03 (16) | C2—N1—C11A—C4A | −1.8 (3) |
C4A—C5—C5A—C10B | −44.8 (2) | C4—C4A—C11A—N11 | −173.43 (17) |
C51—C5—C5A—C10B | 82.4 (2) | C5—C4A—C11A—N11 | 2.8 (3) |
C5—C5A—C6—O6 | 35.5 (3) | C4—C4A—C11A—N1 | 5.2 (3) |
C10B—C5A—C6—O6 | 164.15 (18) | C5—C4A—C11A—N1 | −178.59 (17) |
C5—C5A—C6—C6A | −145.62 (16) | O31—C31—N32—C34 | −177.0 (2) |
C10B—C5A—C6—C6A | −16.94 (19) | O31—C31—N32—C33 | −1.6 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O10—H10B···O31 | 0.99 | 1.67 | 2.661 (2) | 177 |
N3—H3···O4i | 0.88 | 1.92 | 2.801 (2) | 175 |
N11—H11···O10ii | 0.88 | 2.18 | 3.051 (2) | 173 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y, −z. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C21H14ClN3O3·C3H7NO | C22H19N3O5·C3H7NO |
Mr | 464.90 | 478.50 |
Crystal system, space group | Monoclinic, P21/c | Triclinic, P1 |
Temperature (K) | 120 | 120 |
a, b, c (Å) | 10.6850 (6), 17.6182 (12), 12.3774 (8) | 10.4172 (2), 10.8540 (3), 11.6112 (3) |
α, β, γ (°) | 90, 108.523 (4), 90 | 94.2692 (12), 116.0676 (12), 94.4530 (13) |
V (Å3) | 2209.3 (2) | 1167.08 (5) |
Z | 4 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.21 | 0.10 |
Crystal size (mm) | 0.08 × 0.04 × 0.02 | 0.20 × 0.10 × 0.04 |
|
Data collection |
Diffractometer | Nonius KappaCCD diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995, 1997) | Multi-scan (SORTAV; Blessing, 1995, 1997 |
Tmin, Tmax | 0.977, 0.996 | 0.974, 0.996 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8314, 4182, 2135 | 5297, 5297, 3719 |
Rint | 0.123 | 0.073 |
(sin θ/λ)max (Å−1) | 0.610 | 0.651 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.069, 0.157, 0.96 | 0.055, 0.148, 1.04 |
No. of reflections | 4182 | 5297 |
No. of parameters | 302 | 326 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.27, −0.29 | 0.25, −0.37 |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O4i | 0.88 | 1.85 | 2.735 (4) | 179 |
N11—H11···O31 | 0.88 | 1.98 | 2.857 (4) | 172 |
C8—H8···Cg1ii | 0.95 | 2.63 | 3.561 (5) | 167 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x−1, y, z. |
Selected bond lengths (Å) for compounds (I) and (II) top | (I) | (II) |
N1—C2 | 1.299 (5) | 1.302 (2) |
C2—N3 | 1.353 (5) | 1.351 (2) |
N3—C4 | 1.392 (5) | 1.396 (2) |
C4—C4A | 1.420 (5) | 1.416 (3) |
C4A—C11A | 1.378 (5) | 1.383 (3) |
C11A—N1 | 1.379 (5) | 1.373 (2) |
C4A—C5 | 1.537 (5) | 1.509 (3) |
C5—C5A | 1.502 (5) | 1.544 (3) |
C11A—N11 | 1.380 (5) | 1.358 (2) |
N11—C10B | 1.345 (5) | 1.454 (2) |
C5A—C10B | 1.361 (5) | 1.558 (3) |
C5A—C6 | 1.469 (6) | 1.529 (3) |
C6—C6A | 1.512 (6) | 1.471 (3) |
C6A—C7 | 1.383 (6) | 1.400 (3) |
C7—C8 | 1.400 (6) | 1.379 (3) |
C8—C9 | 1.383 (5) | 1.394 (3) |
C9—C10 | 1.404 (6) | 1.397 (3) |
C10—C10A | 1.374 (5) | 1.389 (3) |
C10A—C10B | 1.486 (6) | 1.526 (3) |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O10—H10B···O31 | 0.99 | 1.67 | 2.661 (2) | 177 |
N3—H3···O4i | 0.88 | 1.92 | 2.801 (2) | 175 |
N11—H11···O10ii | 0.88 | 2.18 | 3.051 (2) | 173 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y, −z. |
As part of our study of the synthesis of new fused heterocyclic systems of potential biological interest using multicomponent condensation reactions under environmentally friendly conditions, we here report on two indeno[1',2':2,3]pyrido[5,6-d]pyrimidinediones obtained from reactions between 6-aminopyrimidinone, aryl aldehydes and indandione activated by microwave radiation (Quiroga et al. 2001) Both of these compounds? form monosolvates, viz. (I) and (II), when crystallized from dimethylformamide solutions.
The fused ring system in (I) (Fig.1) is essentially planar. Although the heterocyclic molecules are chiral, because of the stereogenic centre at atom C5, (I) crystallizes as a racemic mixture in space group P21/c; the reference molecule was selected as having the (R)-configuration at atom C5. Compound (II) (Fig. 2) differs from (I) not only by having a different 4-substituent on the pendent aryl ring but also, more importantly, in having an additional H atom bonded to atom C5A and an OH group bonded to atom C10B. In contrast to the planar ring system in (I), the fused-ring system in (II) is folded sharply along the C5A—C10B bond. The dihedral angle between the planes through the two central rings is 74.9 (2)°. The heterocyclic component of (II) is chiral, with three contiguous stereogenic centres at atoms C5, C5A and C10B. Compound (II) also crystallizes as a racemic mixture, this time in space group P-1. The reference molecule in (II) was again selected to have (R)-configuration at C5, and in this molecule, the configuration at both atom C5A and atom C10B is (S). Hence the racemic mixture consists of molecules whose configurations are (5R,5aS,10bS) and (5S,5aR,10bR). The additional H and OH substituents in (II) are thus attached to the same face of the fused-ring system as the aryl substituent at atom C5.
Within the heterocyclic component in (I), there are alternating C—C bond lengths in the fused benzenoid ring (C6A/C7–C10/C10A) (Table 1); in addition, the N11—C11A and C5A—C6 distances are both significantly shorter than the analogous N1—C2 and C6—C6A bonds, respectively, while the C6—O6 distance is significantly longer in (I) than in (II). On the other hand, there is no evidence for any bond fixation in the fused benzenoid ring of (II), while all the bond distances in (II) that involve atoms C5A or C10B show the expected increases compared with the corresponding distances in (I). Taken together, the metrical data indicate both the polarization of the central conjugated amide unit in (I), which is not possible in (II), and some bond fixation in the fused benzenoid ring of (I). A number of canonical forms can be drawn to represent these two independent effects, of which (Ia) (see the first scheme above) is typical. For (II), the unpolarized form, with a delocalized benzenoid ring in the fused system, is the appropriate representation. The dimethylformamide components show no unusual features.
In the asymmetric unit of (I), the two molecular components are linked by a nearly linear N—H···O hydrogen bond (Table 2). In addition, a second, rather short, N—H···O hydrogen bond generates a centrosymmetric four-molecule aggregate centred at (1/2, 1/2, 1/2) (Fig. 3) and characterized by the graph-set descriptor D33(15)[R22(8)] (Bernstein et al., 1995). The D[R] pattern has been noted (Bernstein et al., 1995) as of common occurrence in centrosymmetric structures containing more than one molecule in the asymmetric unit, for example, where centrosymmetric rings have a second pendent component (Patterson et al., 1998). These centrosymmetric aggregates are linked into chains by a single short C—H···π(arene) hydrogen bond. Atom C8, part of the fused benzenoid ring in the molecule at (x, y, z), which itself lies in the aggregate centred at (1/2, 1/2, 1/2), acts as a hydrogen-bond donor to the corresponding benzenoid ring in the molecule at (−1 + x, y, z), which forms part of the aggregate centred at (−0.5, 1/2, 1/2). Propagation of the hydrogen bonds by translation and inversion then links centrosymmetric aggregates into a rather complex chain of rings running parallel to the [100] direction (Fig. 4). There are no direction-specific interactions between adjacent chains; in particular, aromatic π–π stacking interactions are absent from the structure of (I).
In compound (II), the two independent molecular components (Fig. 2) are linked by a short O—H···O hydrogen bond (Table 3), and two N—H···O hydrogen bonds link the heterocyclic molecules into a chain of rings. In the shorter of the N—H···O hydrogen bonds, amide atom N3 in the molecule at (x, y, z) acts as a hydrogen-bond donor to amide atom O4 in the molecule at (1 − x, 1 − y, 1 − z), so generating a centrosymmetric four-molecule D33(19)[R22(8)] aggregate centred at (1/2, 1/2, 1/2) (Fig. 5) and analogous to the corresponding aggregate formed by (I) (Fig. 3). In addition, atom N11 in the molecule at (x, y, z) acts as a donor in a longer hydrogen bond, to hydroxy atom O10 in the molecule at (-x, −y, −z), so forming a second R22(8) ring, this time centred at (0, 0, 0). The combination of the two ring motifs generates a chain of rings running parallel to the [111] direction (Fig. 6). Both C—H···π(arene) hydrogen bonds and aromatic π–π stacking interactions are absent from the structure of (II).
The constitutions of (I) and (II) and, in particular, the relative stereochemistry of (II), are of importance in the context of a general synthetic method for fused pyridopyrimidinones by means of microwave heating in solvent-free systems (Quiroga et al., 2001). Reaction of an aminopyrimidine with an aromatic aldehyde and benzoylacetonitrile (containing an activated methylene group) yielded firstly the hydrated intermediate (III) (see Scheme 2) followed, upon longer heating, by the loss of water to give (IV). However, the spectral techniques used for the identification of (III) and (IV) did not allow assignment of the relative stereochemistry of the three contiguous stereogenic centres. The synthesis of (I) and (II) are directly related to those of (IV) and (III), respectively, so that the relative stereochemistry in the intermediate (III) can, with reasonable confidence, be assigned as similar to that in (II). In any event, it is clear that the loss of water from intermediates of type (II) to form the new C=C double bond in the type (I) products requires a cis elimination step.
Cg1 is centroid of ring C51—C56.