Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010800396X/sk3204sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010800396X/sk3204Isup2.hkl |
CCDC reference: 682830
A mixture of 2,5,6-triaminopyrimidin-4(3H)-one (1.1 mmol) and 1,2'-biindene-1',3,3'(2H)-trione (1.1 mmol) in dry ethanol (10 ml) was heated under reflux with magnetic stirring for 5 h, while the progress of the reaction was monitored by thin-layer chromatography. The reaction mixture was then cooled to ambient temperature, and the resulting precipitate was collected by filtration and washed with ethanol yielding 3-[(2,4-diamino-6-oxo-1,6-dihydropyrimidin-5-yl)amino]-1,2'-biindene-1',3'-dione as a violet solid (m.p. 561–563 K, yield 90%), from which crystals suitable for single-crystal X-ray diffraction have not yet been obtained. The resulting filtrate was evaporated to dryness and the solid residue was crystallized from a mixture of dimethylformamide and ethanol (1:10 v/v) to yield violet crystals of the title compound, (I) (m.p. 616 K), which proved to be suitable for single-crystal X-ray diffraction. When a solution of (III) in an excess of dilute (10%) aqueous hydrochloric acid was heated under reflux for 18 h, compound (I) was produced in 22% yield.
The space group P21/n was uniquely assigned from the systematic absences. All H atoms were located in a difference map and then treated as riding atoms in geometrically idealized positions, with C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C).
Data collection: COLLECT (Nonius, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: OSCAIL (McArdle, 2003) and SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PRPKAPPA (Ferguson, 1999).
C36H16O6 | F(000) = 1120 |
Mr = 544.49 | Dx = 1.456 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 55752 reflections |
a = 8.2209 (11) Å | θ = 3.1–27.5° |
b = 16.552 (3) Å | µ = 0.10 mm−1 |
c = 18.423 (3) Å | T = 120 K |
β = 97.775 (19)° | Needle, violet |
V = 2483.8 (7) Å3 | 0.51 × 0.28 × 0.10 mm |
Z = 4 |
Bruker Nonius KappaCCD diffractometer | 5702 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 4483 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.036 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.1° |
ϕ and ω scans | h = −10→10 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −21→21 |
Tmin = 0.958, Tmax = 0.990 | l = −23→23 |
55752 measured 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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.104 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0281P)2 + 1.8424P] where P = (Fo2 + 2Fc2)/3 |
5702 reflections | (Δ/σ)max < 0.001 |
379 parameters | Δρmax = 0.31 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
C36H16O6 | V = 2483.8 (7) Å3 |
Mr = 544.49 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.2209 (11) Å | µ = 0.10 mm−1 |
b = 16.552 (3) Å | T = 120 K |
c = 18.423 (3) Å | 0.51 × 0.28 × 0.10 mm |
β = 97.775 (19)° |
Bruker Nonius KappaCCD diffractometer | 5702 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 4483 reflections with I > 2σ(I) |
Tmin = 0.958, Tmax = 0.990 | Rint = 0.036 |
55752 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.104 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.31 e Å−3 |
5702 reflections | Δρmin = −0.26 e Å−3 |
379 parameters |
x | y | z | Uiso*/Ueq | ||
O12 | 0.54398 (17) | 0.08532 (9) | 0.81835 (7) | 0.0438 (3) | |
O22 | 0.90296 (17) | 0.12060 (8) | 0.82627 (7) | 0.0410 (3) | |
O32 | 0.68268 (14) | 0.06315 (7) | 0.54259 (7) | 0.0309 (3) | |
O37 | 0.34195 (15) | 0.29388 (7) | 0.53928 (6) | 0.0309 (3) | |
O42 | 0.85081 (17) | 0.21691 (8) | 0.49159 (7) | 0.0387 (3) | |
O47 | 0.58783 (14) | 0.35327 (7) | 0.66940 (6) | 0.0297 (3) | |
C11 | 0.5942 (2) | 0.14293 (9) | 0.70187 (9) | 0.0244 (3) | |
C12 | 0.5007 (2) | 0.09946 (10) | 0.75441 (9) | 0.0291 (4) | |
C12A | 0.3389 (2) | 0.07959 (10) | 0.71099 (10) | 0.0290 (4) | |
C13 | 0.2107 (2) | 0.03504 (11) | 0.73099 (12) | 0.0374 (4) | |
C14 | 0.0742 (2) | 0.02286 (12) | 0.67859 (13) | 0.0420 (5) | |
C15 | 0.0683 (2) | 0.05562 (11) | 0.60996 (12) | 0.0395 (5) | |
C16 | 0.1976 (2) | 0.10180 (11) | 0.58971 (11) | 0.0336 (4) | |
C16A | 0.3342 (2) | 0.11299 (9) | 0.64090 (10) | 0.0259 (3) | |
C17 | 0.4939 (2) | 0.15333 (9) | 0.63809 (9) | 0.0238 (3) | |
C21 | 0.7600 (2) | 0.17309 (10) | 0.71092 (9) | 0.0243 (3) | |
C22 | 0.8975 (2) | 0.16426 (11) | 0.77355 (9) | 0.0289 (4) | |
C22A | 1.0285 (2) | 0.21983 (10) | 0.75535 (9) | 0.0285 (4) | |
C23 | 1.1741 (2) | 0.24119 (12) | 0.79699 (11) | 0.0366 (4) | |
C24 | 1.2740 (2) | 0.29649 (12) | 0.76746 (12) | 0.0396 (5) | |
C25 | 1.2291 (2) | 0.32759 (11) | 0.69832 (11) | 0.0364 (4) | |
C26 | 1.0810 (2) | 0.30604 (11) | 0.65629 (10) | 0.0305 (4) | |
C26A | 0.9800 (2) | 0.25246 (10) | 0.68586 (9) | 0.0249 (3) | |
C27 | 0.81347 (19) | 0.22107 (9) | 0.65968 (9) | 0.0228 (3) | |
C31 | 0.55217 (19) | 0.19108 (9) | 0.57235 (8) | 0.0223 (3) | |
C32 | 0.5963 (2) | 0.11947 (10) | 0.52207 (9) | 0.0245 (3) | |
C32A | 0.4968 (2) | 0.12966 (10) | 0.44945 (9) | 0.0262 (3) | |
C33 | 0.4966 (2) | 0.08225 (11) | 0.38748 (10) | 0.0326 (4) | |
C34 | 0.3800 (3) | 0.09873 (12) | 0.32823 (10) | 0.0370 (4) | |
C35 | 0.2664 (2) | 0.16080 (12) | 0.33046 (10) | 0.0366 (4) | |
C36 | 0.2686 (2) | 0.20951 (11) | 0.39144 (9) | 0.0321 (4) | |
C36A | 0.3870 (2) | 0.19318 (10) | 0.45083 (9) | 0.0264 (3) | |
C37 | 0.4136 (2) | 0.23484 (10) | 0.52183 (9) | 0.0241 (3) | |
C41 | 0.70076 (19) | 0.25015 (9) | 0.59373 (8) | 0.0217 (3) | |
C42 | 0.7876 (2) | 0.26754 (10) | 0.52546 (9) | 0.0264 (3) | |
C42A | 0.7765 (2) | 0.35463 (10) | 0.50979 (9) | 0.0273 (4) | |
C43 | 0.8413 (2) | 0.39652 (12) | 0.45498 (10) | 0.0361 (4) | |
C44 | 0.8213 (3) | 0.47912 (12) | 0.45293 (11) | 0.0427 (5) | |
C45 | 0.7433 (2) | 0.51889 (12) | 0.50419 (12) | 0.0441 (5) | |
C46 | 0.6799 (2) | 0.47796 (11) | 0.55979 (11) | 0.0362 (4) | |
C46A | 0.6960 (2) | 0.39443 (10) | 0.56108 (9) | 0.0268 (4) | |
C47 | 0.6466 (2) | 0.33715 (10) | 0.61488 (8) | 0.0240 (3) | |
H13 | 0.2153 | 0.0133 | 0.7790 | 0.045* | |
H14 | −0.0155 | −0.0084 | 0.6905 | 0.050* | |
H15 | −0.0262 | 0.0467 | 0.5751 | 0.047* | |
H16 | 0.1913 | 0.1247 | 0.5421 | 0.040* | |
H23 | 1.2051 | 0.2188 | 0.8443 | 0.044* | |
H24 | 1.3744 | 0.3130 | 0.7952 | 0.048* | |
H25 | 1.3004 | 0.3645 | 0.6788 | 0.044* | |
H26 | 1.0508 | 0.3278 | 0.6086 | 0.037* | |
H33 | 0.5741 | 0.0399 | 0.3858 | 0.039* | |
H34 | 0.3770 | 0.0671 | 0.2850 | 0.044* | |
H35 | 0.1857 | 0.1698 | 0.2892 | 0.044* | |
H36 | 0.1923 | 0.2524 | 0.3927 | 0.039* | |
H43 | 0.8972 | 0.3693 | 0.4203 | 0.043* | |
H44 | 0.8622 | 0.5093 | 0.4154 | 0.051* | |
H45 | 0.7326 | 0.5760 | 0.5013 | 0.053* | |
H46 | 0.6278 | 0.5058 | 0.5954 | 0.043* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O12 | 0.0439 (8) | 0.0595 (9) | 0.0297 (7) | 0.0003 (7) | 0.0111 (6) | 0.0146 (6) |
O22 | 0.0423 (8) | 0.0443 (8) | 0.0344 (7) | 0.0038 (6) | −0.0019 (6) | 0.0164 (6) |
O32 | 0.0297 (6) | 0.0223 (6) | 0.0399 (7) | 0.0050 (5) | 0.0017 (5) | 0.0017 (5) |
O37 | 0.0356 (7) | 0.0251 (6) | 0.0303 (6) | 0.0082 (5) | −0.0013 (5) | −0.0006 (5) |
O42 | 0.0528 (8) | 0.0312 (7) | 0.0365 (7) | −0.0053 (6) | 0.0215 (6) | −0.0079 (6) |
O47 | 0.0301 (6) | 0.0349 (7) | 0.0239 (6) | 0.0049 (5) | 0.0025 (5) | −0.0048 (5) |
C11 | 0.0266 (8) | 0.0218 (8) | 0.0254 (8) | 0.0031 (6) | 0.0057 (6) | 0.0044 (6) |
C12 | 0.0308 (9) | 0.0273 (9) | 0.0312 (9) | 0.0044 (7) | 0.0111 (7) | 0.0050 (7) |
C12A | 0.0285 (9) | 0.0225 (8) | 0.0381 (10) | 0.0031 (7) | 0.0122 (7) | 0.0008 (7) |
C13 | 0.0378 (10) | 0.0276 (9) | 0.0503 (12) | −0.0018 (8) | 0.0186 (9) | 0.0033 (8) |
C14 | 0.0313 (10) | 0.0300 (10) | 0.0682 (14) | −0.0046 (8) | 0.0197 (10) | −0.0036 (9) |
C15 | 0.0253 (9) | 0.0303 (10) | 0.0627 (13) | −0.0008 (7) | 0.0050 (9) | −0.0061 (9) |
C16 | 0.0284 (9) | 0.0277 (9) | 0.0448 (11) | 0.0025 (7) | 0.0050 (8) | 0.0005 (8) |
C16A | 0.0232 (8) | 0.0194 (8) | 0.0362 (9) | 0.0028 (6) | 0.0079 (7) | 0.0000 (7) |
C17 | 0.0241 (8) | 0.0195 (7) | 0.0282 (8) | 0.0028 (6) | 0.0051 (6) | 0.0024 (6) |
C21 | 0.0259 (8) | 0.0225 (8) | 0.0245 (8) | 0.0048 (6) | 0.0027 (6) | 0.0026 (6) |
C22 | 0.0294 (9) | 0.0294 (9) | 0.0274 (9) | 0.0065 (7) | 0.0014 (7) | 0.0032 (7) |
C22A | 0.0264 (8) | 0.0279 (9) | 0.0304 (9) | 0.0058 (7) | 0.0012 (7) | −0.0005 (7) |
C23 | 0.0302 (9) | 0.0377 (10) | 0.0392 (10) | 0.0079 (8) | −0.0054 (8) | −0.0002 (8) |
C24 | 0.0239 (9) | 0.0374 (10) | 0.0549 (12) | 0.0008 (8) | −0.0043 (8) | −0.0067 (9) |
C25 | 0.0266 (9) | 0.0302 (10) | 0.0529 (12) | −0.0020 (7) | 0.0071 (8) | −0.0047 (8) |
C26 | 0.0278 (9) | 0.0280 (9) | 0.0362 (9) | 0.0002 (7) | 0.0067 (7) | −0.0018 (7) |
C26A | 0.0229 (8) | 0.0231 (8) | 0.0288 (8) | 0.0037 (6) | 0.0033 (6) | −0.0033 (7) |
C27 | 0.0228 (8) | 0.0219 (8) | 0.0240 (8) | 0.0027 (6) | 0.0037 (6) | −0.0007 (6) |
C31 | 0.0244 (8) | 0.0201 (7) | 0.0217 (8) | 0.0022 (6) | 0.0003 (6) | 0.0013 (6) |
C32 | 0.0247 (8) | 0.0209 (8) | 0.0281 (8) | −0.0021 (6) | 0.0039 (6) | 0.0005 (6) |
C32A | 0.0299 (9) | 0.0210 (8) | 0.0276 (8) | −0.0031 (7) | 0.0037 (7) | 0.0007 (6) |
C33 | 0.0440 (10) | 0.0234 (9) | 0.0311 (9) | −0.0032 (8) | 0.0080 (8) | −0.0031 (7) |
C34 | 0.0525 (12) | 0.0334 (10) | 0.0250 (9) | −0.0097 (9) | 0.0051 (8) | −0.0051 (7) |
C35 | 0.0419 (11) | 0.0408 (11) | 0.0252 (9) | −0.0064 (9) | −0.0026 (8) | 0.0025 (8) |
C36 | 0.0350 (10) | 0.0331 (9) | 0.0270 (9) | 0.0015 (8) | −0.0004 (7) | 0.0042 (7) |
C36A | 0.0309 (9) | 0.0237 (8) | 0.0242 (8) | −0.0012 (7) | 0.0021 (7) | 0.0023 (6) |
C37 | 0.0257 (8) | 0.0214 (8) | 0.0246 (8) | 0.0009 (6) | 0.0013 (6) | 0.0031 (6) |
C41 | 0.0257 (8) | 0.0193 (7) | 0.0204 (7) | 0.0005 (6) | 0.0036 (6) | 0.0012 (6) |
C42 | 0.0310 (9) | 0.0258 (8) | 0.0225 (8) | −0.0053 (7) | 0.0041 (7) | −0.0016 (6) |
C42A | 0.0341 (9) | 0.0266 (8) | 0.0198 (8) | −0.0070 (7) | −0.0020 (7) | 0.0015 (6) |
C43 | 0.0449 (11) | 0.0363 (10) | 0.0254 (9) | −0.0154 (8) | −0.0009 (8) | 0.0045 (7) |
C44 | 0.0487 (12) | 0.0401 (11) | 0.0360 (10) | −0.0146 (9) | −0.0060 (9) | 0.0141 (9) |
C45 | 0.0415 (11) | 0.0238 (9) | 0.0619 (14) | −0.0060 (8) | −0.0115 (10) | 0.0155 (9) |
C46 | 0.0355 (10) | 0.0240 (9) | 0.0455 (11) | 0.0023 (7) | −0.0077 (8) | −0.0003 (8) |
C46A | 0.0278 (8) | 0.0234 (8) | 0.0267 (8) | −0.0020 (7) | −0.0060 (7) | 0.0020 (7) |
C47 | 0.0253 (8) | 0.0246 (8) | 0.0205 (8) | 0.0025 (6) | −0.0031 (6) | −0.0015 (6) |
O12—C12 | 1.207 (2) | C25—C26 | 1.399 (3) |
O22—C22 | 1.207 (2) | C25—H25 | 0.9500 |
O32—C32 | 1.2014 (19) | C26—C26A | 1.376 (2) |
O37—C37 | 1.207 (2) | C26—H26 | 0.9500 |
O42—C42 | 1.204 (2) | C26A—C27 | 1.483 (2) |
O47—C47 | 1.2021 (19) | C31—C37 | 1.550 (2) |
C11—C21 | 1.440 (2) | C31—C32 | 1.577 (2) |
C11—C17 | 1.352 (2) | C32—C32A | 1.480 (2) |
C17—C31 | 1.498 (2) | C32A—C33 | 1.385 (2) |
C31—C41 | 1.573 (2) | C32A—C36A | 1.388 (2) |
C21—C27 | 1.352 (2) | C33—C34 | 1.379 (3) |
C27—C41 | 1.504 (2) | C33—H33 | 0.9500 |
C11—C12 | 1.499 (2) | C34—C35 | 1.393 (3) |
C12—C12A | 1.493 (3) | C34—H34 | 0.9500 |
C12A—C13 | 1.376 (2) | C35—C36 | 1.381 (3) |
C12A—C16A | 1.400 (2) | C35—H35 | 0.9500 |
C13—C14 | 1.393 (3) | C36—C36A | 1.389 (2) |
C13—H13 | 0.9500 | C36—H36 | 0.9500 |
C14—C15 | 1.370 (3) | C36A—C37 | 1.469 (2) |
C14—H14 | 0.9500 | C41—C42 | 1.555 (2) |
C15—C16 | 1.400 (3) | C41—C47 | 1.572 (2) |
C15—H15 | 0.9500 | C42—C42A | 1.470 (2) |
C16—C16A | 1.378 (2) | C42A—C43 | 1.389 (2) |
C16—H16 | 0.9500 | C42A—C46A | 1.391 (2) |
C16A—C17 | 1.480 (2) | C43—C44 | 1.377 (3) |
C21—C22 | 1.509 (2) | C43—H43 | 0.9500 |
C22—C22A | 1.489 (2) | C44—C45 | 1.379 (3) |
C22A—C23 | 1.377 (2) | C44—H44 | 0.9500 |
C22A—C26A | 1.397 (2) | C45—C46 | 1.387 (3) |
C23—C24 | 1.389 (3) | C45—H45 | 0.9500 |
C23—H23 | 0.9500 | C46—C46A | 1.389 (2) |
C24—C25 | 1.377 (3) | C46—H46 | 0.9500 |
C24—H24 | 0.9500 | C46A—C47 | 1.468 (2) |
C17—C11—C21 | 120.84 (15) | C17—C31—C32 | 106.60 (13) |
C17—C11—C12 | 108.48 (14) | C37—C31—C32 | 101.98 (12) |
C21—C11—C12 | 130.67 (15) | C41—C31—C32 | 112.45 (13) |
O12—C12—C12A | 127.16 (16) | O32—C32—C32A | 127.14 (15) |
O12—C12—C11 | 127.90 (17) | O32—C32—C31 | 124.86 (15) |
C12A—C12—C11 | 104.90 (14) | C32A—C32—C31 | 107.59 (13) |
C13—C12A—C16A | 122.12 (17) | C33—C32A—C36A | 121.07 (16) |
C13—C12A—C12 | 129.28 (17) | C33—C32A—C32 | 128.24 (16) |
C16A—C12A—C12 | 108.58 (14) | C36A—C32A—C32 | 110.55 (14) |
C12A—C13—C14 | 117.78 (19) | C34—C33—C32A | 117.59 (17) |
C12A—C13—H13 | 121.1 | C34—C33—H33 | 121.2 |
C14—C13—H13 | 121.1 | C32A—C33—H33 | 121.2 |
C15—C14—C13 | 120.46 (18) | C33—C34—C35 | 121.31 (17) |
C15—C14—H14 | 119.8 | C33—C34—H34 | 119.3 |
C13—C14—H14 | 119.8 | C35—C34—H34 | 119.3 |
C14—C15—C16 | 121.91 (19) | C36—C35—C34 | 121.30 (17) |
C14—C15—H15 | 119.0 | C36—C35—H35 | 119.3 |
C16—C15—H15 | 119.0 | C34—C35—H35 | 119.3 |
C16A—C16—C15 | 117.94 (18) | C35—C36—C36A | 117.26 (17) |
C16A—C16—H16 | 121.0 | C35—C36—H36 | 121.4 |
C15—C16—H16 | 121.0 | C36A—C36—H36 | 121.4 |
C16—C16A—C12A | 119.77 (16) | C32A—C36A—C36 | 121.40 (16) |
C16—C16A—C17 | 132.95 (16) | C32A—C36A—C37 | 110.69 (14) |
C12A—C16A—C17 | 107.24 (15) | C36—C36A—C37 | 127.89 (16) |
C11—C17—C16A | 110.58 (14) | O37—C37—C36A | 126.76 (15) |
C11—C17—C31 | 122.14 (14) | O37—C37—C31 | 124.33 (15) |
C16A—C17—C31 | 126.77 (14) | C36A—C37—C31 | 108.91 (13) |
C27—C21—C11 | 121.00 (14) | C27—C41—C42 | 114.37 (13) |
C27—C21—C22 | 108.06 (14) | C27—C41—C47 | 104.90 (12) |
C11—C21—C22 | 130.87 (15) | C42—C41—C47 | 101.96 (12) |
O22—C22—C22A | 127.00 (16) | C27—C41—C31 | 112.10 (13) |
O22—C22—C21 | 128.03 (17) | C42—C41—C31 | 109.79 (12) |
C22A—C22—C21 | 104.95 (14) | C47—C41—C31 | 113.29 (13) |
C23—C22A—C26A | 122.01 (17) | O42—C42—C42A | 126.88 (16) |
C23—C22A—C22 | 129.33 (17) | O42—C42—C41 | 124.61 (15) |
C26A—C22A—C22 | 108.64 (15) | C42A—C42—C41 | 108.51 (14) |
C22A—C23—C24 | 117.80 (18) | C43—C42A—C46A | 121.46 (17) |
C22A—C23—H23 | 121.1 | C43—C42A—C42 | 127.77 (17) |
C24—C23—H23 | 121.1 | C46A—C42A—C42 | 110.70 (14) |
C25—C24—C23 | 120.65 (17) | C44—C43—C42A | 117.36 (19) |
C25—C24—H24 | 119.7 | C44—C43—H43 | 121.3 |
C23—C24—H24 | 119.7 | C42A—C43—H43 | 121.3 |
C24—C25—C26 | 121.41 (18) | C43—C44—C45 | 121.34 (18) |
C24—C25—H25 | 119.3 | C43—C44—H44 | 119.3 |
C26—C25—H25 | 119.3 | C45—C44—H44 | 119.3 |
C26A—C26—C25 | 118.16 (17) | C44—C45—C46 | 121.92 (18) |
C26A—C26—H26 | 120.9 | C44—C45—H45 | 119.0 |
C25—C26—H26 | 120.9 | C46—C45—H45 | 119.0 |
C26—C26A—C22A | 119.95 (16) | C45—C46—C46A | 117.01 (19) |
C26—C26A—C27 | 132.58 (16) | C45—C46—H46 | 121.5 |
C22A—C26A—C27 | 107.41 (14) | C46A—C46—H46 | 121.5 |
C21—C27—C26A | 110.61 (14) | C46—C46A—C42A | 120.88 (17) |
C21—C27—C41 | 121.94 (14) | C46—C46A—C47 | 128.31 (17) |
C26A—C27—C41 | 126.27 (14) | C42A—C46A—C47 | 110.69 (14) |
C17—C31—C37 | 113.02 (13) | O47—C47—C46A | 126.87 (15) |
C17—C31—C41 | 112.28 (13) | O47—C47—C41 | 124.74 (15) |
C37—C31—C41 | 110.06 (12) | C46A—C47—C41 | 108.11 (13) |
C17—C11—C12—O12 | −173.32 (18) | C17—C31—C32—C32A | 122.72 (14) |
C21—C11—C12—O12 | 5.5 (3) | C37—C31—C32—C32A | 4.01 (16) |
C17—C11—C12—C12A | 4.85 (18) | C41—C31—C32—C32A | −113.83 (14) |
C21—C11—C12—C12A | −176.36 (16) | O32—C32—C32A—C33 | −8.5 (3) |
O12—C12—C12A—C13 | −6.8 (3) | C31—C32—C32A—C33 | 178.60 (16) |
C11—C12—C12A—C13 | 175.03 (17) | O32—C32—C32A—C36A | 167.24 (17) |
O12—C12—C12A—C16A | 174.69 (18) | C31—C32—C32A—C36A | −5.64 (18) |
C11—C12—C12A—C16A | −3.51 (18) | C36A—C32A—C33—C34 | −2.2 (3) |
C16A—C12A—C13—C14 | 0.8 (3) | C32—C32A—C33—C34 | 173.18 (17) |
C12—C12A—C13—C14 | −177.60 (17) | C32A—C33—C34—C35 | 0.1 (3) |
C12A—C13—C14—C15 | −1.0 (3) | C33—C34—C35—C36 | 1.6 (3) |
C13—C14—C15—C16 | 0.3 (3) | C34—C35—C36—C36A | −1.0 (3) |
C14—C15—C16—C16A | 0.8 (3) | C33—C32A—C36A—C36 | 2.8 (3) |
C15—C16—C16A—C12A | −1.0 (2) | C32—C32A—C36A—C36 | −173.36 (16) |
C15—C16—C16A—C17 | 176.22 (17) | C33—C32A—C36A—C37 | −178.99 (15) |
C13—C12A—C16A—C16 | 0.3 (3) | C32—C32A—C36A—C37 | 4.90 (19) |
C12—C12A—C16A—C16 | 178.94 (15) | C35—C36—C36A—C32A | −1.1 (3) |
C13—C12A—C16A—C17 | −177.62 (16) | C35—C36—C36A—C37 | −179.01 (17) |
C12—C12A—C16A—C17 | 1.04 (18) | C32A—C36A—C37—O37 | 177.37 (17) |
C21—C11—C17—C16A | 176.67 (14) | C36—C36A—C37—O37 | −4.5 (3) |
C12—C11—C17—C16A | −4.41 (18) | C32A—C36A—C37—C31 | −2.11 (19) |
C12—C11—C17—C31 | −176.72 (14) | C36—C36A—C37—C31 | 176.00 (17) |
C16—C16A—C17—C11 | −175.34 (18) | C17—C31—C37—O37 | 65.2 (2) |
C12A—C16A—C17—C11 | 2.17 (19) | C41—C31—C37—O37 | −61.2 (2) |
C16—C16A—C17—C31 | −3.5 (3) | C32—C31—C37—O37 | 179.22 (16) |
C12A—C16A—C17—C31 | 174.03 (15) | C17—C31—C37—C36A | −115.32 (15) |
C17—C11—C21—C27 | 8.3 (2) | C41—C31—C37—C36A | 118.26 (14) |
C11—C21—C27—C41 | 4.4 (2) | C32—C31—C37—C36A | −1.28 (16) |
C21—C27—C41—C31 | −26.4 (2) | C26A—C27—C41—C42 | 41.4 (2) |
C11—C17—C31—C32 | 97.2 (2) | C21—C27—C41—C47 | 96.96 (17) |
C11—C17—C31—C37 | −151.6 (2) | C26A—C27—C41—C47 | −69.43 (19) |
C17—C31—C41—C27 | 35.27 (18) | C21—C27—C41—C31 | −26.4 (2) |
C21—C11—C17—C31 | 4.4 (2) | C26A—C27—C41—C31 | 167.24 (14) |
C11—C17—C31—C41 | −26.4 (2) | C37—C31—C41—C27 | 162.10 (13) |
C21—C27—C41—C47 | 97.0 (2) | C32—C31—C41—C27 | −84.96 (15) |
C21—C27—C41—C42 | −152.19 (15) | C17—C31—C41—C42 | 163.54 (13) |
C12—C11—C21—C27 | −170.36 (16) | C37—C31—C41—C42 | −69.63 (16) |
C17—C11—C21—C22 | −175.11 (16) | C32—C31—C41—C42 | 43.32 (17) |
C12—C11—C21—C22 | 6.2 (3) | C17—C31—C41—C47 | −83.21 (16) |
C27—C21—C22—O22 | −172.64 (18) | C37—C31—C41—C47 | 43.62 (17) |
C11—C21—C22—O22 | 10.4 (3) | C32—C31—C41—C47 | 156.56 (12) |
C27—C21—C22—C22A | 5.86 (18) | C27—C41—C42—O42 | 66.4 (2) |
C11—C21—C22—C22A | −171.07 (16) | C47—C41—C42—O42 | 179.00 (16) |
O22—C22—C22A—C23 | −8.4 (3) | C31—C41—C42—O42 | −60.6 (2) |
C21—C22—C22A—C23 | 173.10 (18) | C27—C41—C42—C42A | −114.36 (15) |
O22—C22—C22A—C26A | 173.50 (18) | C47—C41—C42—C42A | −1.76 (16) |
C21—C22—C22A—C26A | −5.01 (18) | C31—C41—C42—C42A | 118.62 (14) |
C26A—C22A—C23—C24 | −0.5 (3) | O42—C42—C42A—C43 | −2.6 (3) |
C22—C22A—C23—C24 | −178.40 (17) | C41—C42—C42A—C43 | 178.14 (16) |
C22A—C23—C24—C25 | −1.0 (3) | O42—C42—C42A—C46A | −179.50 (17) |
C23—C24—C25—C26 | 1.3 (3) | C41—C42—C42A—C46A | 1.28 (19) |
C24—C25—C26—C26A | 0.0 (3) | C46A—C42A—C43—C44 | −0.6 (3) |
C25—C26—C26A—C22A | −1.4 (2) | C42—C42A—C43—C44 | −177.18 (17) |
C25—C26—C26A—C27 | 175.41 (17) | C42A—C43—C44—C45 | 1.4 (3) |
C23—C22A—C26A—C26 | 1.8 (3) | C43—C44—C45—C46 | −0.6 (3) |
C22—C22A—C26A—C26 | −179.95 (15) | C44—C45—C46—C46A | −1.0 (3) |
C23—C22A—C26A—C27 | −175.81 (16) | C45—C46—C46A—C42A | 1.8 (3) |
C22—C22A—C26A—C27 | 2.46 (18) | C45—C46—C46A—C47 | 177.30 (16) |
C11—C21—C27—C26A | 172.72 (14) | C43—C42A—C46A—C46 | −1.0 (3) |
C22—C21—C27—C26A | −4.57 (18) | C42—C42A—C46A—C46 | 176.12 (15) |
C22—C21—C27—C41 | −172.87 (14) | C43—C42A—C46A—C47 | −177.24 (15) |
C26—C26A—C27—C21 | −175.76 (18) | C42—C42A—C46A—C47 | −0.15 (19) |
C22A—C26A—C27—C21 | 1.39 (19) | C46—C46A—C47—O47 | −2.8 (3) |
C26—C26A—C27—C41 | −8.1 (3) | C42A—C46A—C47—O47 | 173.10 (16) |
C22A—C26A—C27—C41 | 169.07 (15) | C46—C46A—C47—C41 | −176.94 (17) |
C16A—C17—C31—C37 | 37.4 (2) | C42A—C46A—C47—C41 | −1.03 (18) |
C11—C17—C31—C41 | −26.4 (2) | C27—C41—C47—O47 | −53.1 (2) |
C16A—C17—C31—C41 | 162.61 (14) | C42—C41—C47—O47 | −172.61 (15) |
C16A—C17—C31—C32 | −73.84 (19) | C31—C41—C47—O47 | 69.5 (2) |
C17—C31—C32—O32 | −50.4 (2) | C27—C41—C47—C46A | 121.19 (14) |
C37—C31—C32—O32 | −169.07 (16) | C42—C41—C47—C46A | 1.67 (16) |
C41—C31—C32—O32 | 73.1 (2) | C31—C41—C47—C46A | −116.24 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
C15—H15···O32i | 0.95 | 2.40 | 3.247 (2) | 148 |
C25—H25···O47ii | 0.95 | 2.40 | 3.096 (2) | 130 |
C35—H35···O47iii | 0.95 | 2.28 | 3.136 (2) | 150 |
C43—H43···O12iv | 0.95 | 2.48 | 3.215 (2) | 134 |
C45—H45···O37v | 0.95 | 2.33 | 3.253 (2) | 163 |
C46—H46···O22vi | 0.95 | 2.42 | 3.291 (2) | 152 |
Symmetry codes: (i) x−1, y, z; (ii) x+1, y, z; (iii) x−1/2, −y+1/2, z−1/2; (iv) x+1/2, −y+1/2, z−1/2; (v) −x+1, −y+1, −z+1; (vi) −x+3/2, y+1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | C36H16O6 |
Mr | 544.49 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 120 |
a, b, c (Å) | 8.2209 (11), 16.552 (3), 18.423 (3) |
β (°) | 97.775 (19) |
V (Å3) | 2483.8 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.51 × 0.28 × 0.10 |
Data collection | |
Diffractometer | Bruker Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.958, 0.990 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 55752, 5702, 4483 |
Rint | 0.036 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.104, 1.08 |
No. of reflections | 5702 |
No. of parameters | 379 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.31, −0.26 |
Computer programs: COLLECT (Nonius, 1999), DIRAX/LSQ (Duisenberg et al., 2000), EVALCCD (Duisenberg et al., 2003), SIR2004 (Burla et al., 2005), OSCAIL (McArdle, 2003) and SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003), SHELXL97 (Sheldrick, 2008) and PRPKAPPA (Ferguson, 1999).
C11—C21 | 1.440 (2) | C31—C41 | 1.573 (2) |
C11—C17 | 1.352 (2) | C21—C27 | 1.352 (2) |
C17—C31 | 1.498 (2) | C27—C41 | 1.504 (2) |
C17—C11—C21—C27 | 8.3 (2) | C17—C31—C41—C27 | 35.27 (18) |
C11—C21—C27—C41 | 4.4 (2) | C21—C11—C17—C31 | 4.4 (2) |
C21—C27—C41—C31 | −26.4 (2) | C11—C17—C31—C41 | −26.4 (2) |
C11—C17—C31—C32 | 97.2 (2) | C21—C27—C41—C47 | 97.0 (2) |
C11—C17—C31—C37 | −151.6 (2) | C21—C27—C41—C42 | −152.19 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
C15—H15···O32i | 0.95 | 2.40 | 3.247 (2) | 147.9 |
C25—H25···O47ii | 0.95 | 2.40 | 3.096 (2) | 129.9 |
C35—H35···O47iii | 0.95 | 2.28 | 3.136 (2) | 150.0 |
C43—H43···O12iv | 0.95 | 2.48 | 3.215 (2) | 133.9 |
C45—H45···O37v | 0.95 | 2.33 | 3.253 (2) | 162.5 |
C46—H46···O22vi | 0.95 | 2.42 | 3.291 (2) | 152.4 |
Symmetry codes: (i) x−1, y, z; (ii) x+1, y, z; (iii) x−1/2, −y+1/2, z−1/2; (iv) x+1/2, −y+1/2, z−1/2; (v) −x+1, −y+1, −z+1; (vi) −x+3/2, y+1/2, −z+3/2. |
Benzodiazepines are a class of psychoactive drugs which have found extensive use as minor tranquilisers with a broad range of applications (Pozharskii et al., 1997; Lueddens & Korpi, 2007). Pyrimidobenzodiazepines and their fused derivatives also display similar properties and they have extended the range of pharmaceutical applications (Długosz, 1995). In order to explore synthetic routes to new pyrimido[4,5-b][1,4]diazepine derivatives incorporating fused and/or spiro units linked to the diazepine moiety, we have utilized the chalcone reagent 1,2'-biindene-1',3,3'(2H)-trione, (III), prepared by autocondensation of 1,3-indandione, (II), in reactions with 4,5-diaminopyrimidines. Instead of the expected fused derivative, the reaction between 2,4,5-diaminopyrimidin-4(3H)-one and 1,2'-biindene-1',3,3'(2H)-trione produced 3-[(2,4-diamino-6-oxo-1,6-dihydropyrimidin-5-yl)amino]-1,2'-biindene-1',3'-dione in 90% yield, together with a small quantity of the unexpected dispiro[indene-2,5'-indeno[2,1-a]fluorene-6',2''-indene]-1,1'',3,3'',11',12'-hexaone, (I) (Fig. 1). Subsequently, we found that heating compound (III) in refluxing dilute aqueous hydrochloric acid gave compound (I) in modest, but still useful, yield. The formation of (I) from the indanetrione (III) must involve an oxidative process; the identity of the oxidant has not yet been investigated but plausible mechanisms for the conversion of (III) to (I) in aqueous or ethanolic solutions are not easy to envisage. Here, we report the molecular and supramolecular structure of (I) and briefly compare its supramolecular aggregation with that in some simpler analogues, (II)–(V) (see scheme).
The molecule of (I) exhibits approximate but noncrystallographic twofold rotation symmetry about the line joining the mid-points of the C11—C21 and C31—C41 bonds, as illustrated by the leading torsion angles (Table 1). Within the central ring, the C11—C17 and C21—C27 bonds are both clearly double bonds, while the C31—C41 bond is long, presumably as a consequence of the steric congestion around atoms C31 and C41. Unlike all the other rings in the molecule, the central ring is not planar, as exemplified by the C17—C31—C41—C27 torsion angle. The ring-puckering angles (Cremer & Pople, 1975) for the atom-sequence C11/C17/C31/C41/C27/C21 are θ = 119.3 (3)° and ϕ = 330.2 (4)°, with Q = 0.315 (2) Å, indicating a ring conformation intermediate between half-chair and screw-boat. The ring-puckering may be ascribed to the substitution at atoms C31 and C41. The remaining bond distances and inter-bond angles show no unusual features.
There are six independent C—H.·O hydrogen bonds in the crystal structure of (I), such that each molecule acts as both a sixfold donor and a sixfold acceptor of hydrogen bonds. The resulting aggregation is three-dimensional but it can readily be analysed in terms of four independent one-dimensional substructures. Three of these are very simple, involving only a single hydrogen bond in each substructure, while the fourth substructure is more complex, with three hydrogen bonds involved in its formation.
Atoms C35 and C43 in the molecule at (x, y, z) act as hydrogen-bond donors to, respectively, atom O47 at (-1/2 + x, 1/2 - y, -1/2 + z) and atom O12 at (1/2 + x, 1/2 - y, -1/2 + z), thereby forming a C(9) (Bernstein et al., 1995) chain parallel to the [101] direction and a C(10) chain parallel to the [101] direction, both built from molecules related by the n-glide plane at y = 1/4. In addition, atom C46 in the molecule at (x, y, z) acts as hydrogen-bond donor to atom O22 in the molecule at (3/2 - x, 1/2 + y, 3/2 - z), so forming a second C(9) chain, this time running parallel to the [010] direction and comprising molecules related by the 21 screw axis along (3/4, y, 3/4). These three chains, along [010], [101] and [101], respectively, would in fact suffice to generate a continuous three-dimensional framework.
The more complex motif involves three hydrogen bonds. Atoms C15 and C25 in the molecule at (x, y, z) act as hydrogen-bond donors to, respectively, atom O32 in the molecule at (-1 + x, y, z) and atom O47 in the molecule at (1 + x, y, z). The resulting pair of antiparallel chains generated by translation along [100] combine to form a C(8)C(8)[R22(18)] chain of rings. The final hydrogen bond links pairs of these chains into a complex tubular substructure. Atom C45 in the molecule at (x, y, z) acts as hydrogen-bond donor to atom O37 in the molecule at (1 - x, 1 - y, 1 - z), so forming a complex chain containing three types of ring. In addition to the R22(18) rings generated by translation, there are two types of ring generated by inversion, such that R22(18) rings centred at (n + 1/2, 1/2, 1/2), where n represents zero or an integer, alternate with R44(30) rings centred at (n, 1/2, 1/2), where n represents zero or an integer (Fig. 2).
It is of interest to compare briefly the supramolecular aggregation in the crystal structure of (I) with that of some close analogues, namely compound (II), and compounds (III)–(V), which are all notionally derived from (II) by condensation and/or oxidation. The original reports of compounds (II)–(V) were all concerned with proof of constitution, without discussion of any hydrogen bonding.
The crystal structure of compound (III) [Cambridge Structural Database (CSD; Allen, 2002) refcode BIINDO; Bravic, Bravic et al., 1976], which is a condensation product from the dione, (I), contains a single intermolecular C—H···O hydrogen bond which links molecules related by a 21 screw axis into simple C(4) chains.
Compound (IV) (CSD refcode WEVSUL; Khodorkovsky et al., 1994) is formally an oxidation product of (II) (Kaufmann, 1897), although most reported preparations involving oxidation of (II) are not readily reproducible (Khodorkovsky et al., 1994). The crystal structure of (IV) again contains a single intermolecular C—H···O hydrogen bond which links molecules related by a glide plane into C(6) chains.
By contrast, a single C—H···O hydrogen bond in compound (II) (CSD refcode INDDON; Bravic, Bechtel et al., 1976) links molecules related by a 4 axis into R43(20) tetramers (Fig. 3).
In compound (V) (CSD refcode KETROR; Ji et al., 2006), which was obtained as an unexpected oxidation product during the attempted nitration of (IV), the molecules lie across twofold rotation axes in space group C2/c, and a single C—H···O hydrogen bond links molecules related by translation along this axis into columns of R22(11) rings (Fig. 4).