The title solvates, (I) and (II), both C
18H
16N
6O
3·C
2H
6OS, are isomeric. The conformations adopted by the 6-substituent are significantly different, with the 6-aminophenyl unit remote from the nitrophenyl ring in methoxypyrimidine (I) but adjacent to it in pyrimidinone (II). Pairs of pyrimidine molecules in (I) are linked by N-H
N hydrogen bonds to form cyclic centrosymmetric dimers from which the dimethyl sulfoxide molecules are pendent, while in (II) a combination of three independent N-H
O hydrogen bonds links the components into a chain containing both
R22(8) and
R42(8) rings, in which the dimethyl sulfoxide component acts as a double acceptor of hydrogen bonds. The significance of this study lies in its observation of different conformations for the pyrimidine components in (I) and (II), and different hydrogen-bonded structures, apparently dominated by the different roles adopted by the dimethyl sulfoxide components.
Supporting information
CCDC references: 728219; 728220
For the synthesis of (I), a mixture of
2,5-amino-4-methoxy-6-(phenylamino)pyrimidine (0.856 mmol) and
4-nitrobenzaldehyde (0.860 mmol) was added to a mixture of methanol (10 ml)
and acetic acid (0.5 ml), and the resulting solution was stirred overnight
(ca 12 h) at ambient temperature. The resulting orange product
2-amino-6-anilino-4-methoxy-5-[(E)-4-nitrobenzylideneamino]pyrimidine,
was collected by filtration, washed several times with water and then dried
(yield 99%, m.p. 487–489 K). For the synthesis of (II), a mixture of
2,5-diamino-6-[methyl(phenyl)amino]-pyrimidin-4(3H)-one (0.822 mmol)
and 4-nitrobenzaldehyde (0.827 mmol) was added to a mixture of methanol (10 ml) and acetic acid (0.5 ml), and the resulting solution was stirred overnight
(ca 12 h) at ambient temperature. The resulting dark-red
product,2-amino-6-[methyl(phenyl)amino]-5-[(E)-4-nitrobenzylideneamino]pyrimidin-4(3H)-one, was collected by
filtration, washed several times with water and then dried (yield 83%, m.p.
510–512 K). Recrystallization of both compounds from dimethyl sulfoxide gave
crystals of the monosolvates suitable for single-crystal X-ray diffraction.
Crystals of (I) and (II) are triclinic; for each, the space group P1
was chosen, and confirmed by the structure analysis. All H atoms were located
in difference maps and then treated as riding atoms in geometrically idealized
positions with C—H distances of 0.95 Å (aromatic and methylidene) or 0.98 Å (methyl) and N—H distances of 0.88 Å, with Uiso(H) =
kUeq(carrier), where k = 1.5 for the methyl groups and
k = 1.2 for all other H atoms.
For both compounds, data collection: COLLECT (Hooft, 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, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PRPKAPPA (Ferguson, 1999).
(I) 2-amino-6-anilino-4-methoxy-5-[(E)-4-nitrobenzylideneamino]pyrimidine
dimethyl sulfoxide solvate
top
Crystal data top
C18H16N6O3·C2H6OS | Z = 2 |
Mr = 442.50 | F(000) = 464 |
Triclinic, P1 | Dx = 1.461 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.0386 (8) Å | Cell parameters from 4614 reflections |
b = 10.6862 (14) Å | θ = 2.7–27.5° |
c = 12.8856 (13) Å | µ = 0.20 mm−1 |
α = 71.007 (11)° | T = 120 K |
β = 74.463 (9)° | Plate, orange |
γ = 88.672 (12)° | 0.45 × 0.32 × 0.08 mm |
V = 1005.9 (2) Å3 | |
Data collection top
Bruker–Nonius KappaCCD diffractometer | 4614 independent reflections |
Radiation source: Bruker–Nonius FR591 rotating anode | 2569 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.089 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 2.7° |
ϕ and ω scans | h = −10→10 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −13→13 |
Tmin = 0.944, Tmax = 0.984 | l = −16→16 |
29080 measured reflections | |
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)] = 0.057 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.154 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0637P)2 + 0.6801P] where P = (Fo2 + 2Fc2)/3 |
4614 reflections | (Δ/σ)max = 0.001 |
283 parameters | Δρmax = 0.38 e Å−3 |
0 restraints | Δρmin = −0.47 e Å−3 |
Crystal data top
C18H16N6O3·C2H6OS | γ = 88.672 (12)° |
Mr = 442.50 | V = 1005.9 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.0386 (8) Å | Mo Kα radiation |
b = 10.6862 (14) Å | µ = 0.20 mm−1 |
c = 12.8856 (13) Å | T = 120 K |
α = 71.007 (11)° | 0.45 × 0.32 × 0.08 mm |
β = 74.463 (9)° | |
Data collection top
Bruker–Nonius KappaCCD diffractometer | 4614 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2569 reflections with I > 2σ(I) |
Tmin = 0.944, Tmax = 0.984 | Rint = 0.089 |
29080 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.057 | 0 restraints |
wR(F2) = 0.154 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.38 e Å−3 |
4614 reflections | Δρmin = −0.47 e Å−3 |
283 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | 0.7112 (3) | 0.2112 (2) | 0.61976 (19) | 0.0267 (5) | |
C2 | 0.6449 (3) | 0.3173 (3) | 0.5598 (2) | 0.0249 (6) | |
N3 | 0.5928 (3) | 0.3306 (2) | 0.46596 (19) | 0.0257 (5) | |
C4 | 0.6184 (3) | 0.2297 (3) | 0.4279 (2) | 0.0256 (6) | |
C5 | 0.6977 (3) | 0.1163 (3) | 0.4759 (2) | 0.0252 (6) | |
C6 | 0.7369 (3) | 0.1128 (3) | 0.5773 (2) | 0.0248 (6) | |
N2 | 0.6292 (3) | 0.4192 (2) | 0.59872 (19) | 0.0293 (6) | |
H21 | 0.6444 | 0.4110 | 0.6657 | 0.035* | |
H22 | 0.5734 | 0.4887 | 0.5716 | 0.035* | |
O4 | 0.5623 (2) | 0.23074 (18) | 0.33871 (16) | 0.0291 (5) | |
C41 | 0.4634 (4) | 0.3396 (3) | 0.2958 (2) | 0.0333 (7) | |
H41A | 0.3663 | 0.3461 | 0.3584 | 0.050* | |
H41B | 0.4189 | 0.3248 | 0.2367 | 0.050* | |
H41C | 0.5375 | 0.4223 | 0.2631 | 0.050* | |
N5 | 0.7357 (3) | 0.0055 (2) | 0.44428 (19) | 0.0268 (5) | |
C57 | 0.7052 (3) | −0.0193 (3) | 0.3605 (2) | 0.0267 (6) | |
H57 | 0.6477 | 0.0416 | 0.3121 | 0.032* | |
C51 | 0.7595 (3) | −0.1421 (3) | 0.3397 (2) | 0.0270 (6) | |
C52 | 0.7093 (4) | −0.1783 (3) | 0.2582 (2) | 0.0318 (7) | |
H52 | 0.6403 | −0.1223 | 0.2155 | 0.038* | |
C53 | 0.7580 (4) | −0.2940 (3) | 0.2383 (3) | 0.0357 (7) | |
H53 | 0.7219 | −0.3198 | 0.1834 | 0.043* | |
C54 | 0.8603 (4) | −0.3716 (3) | 0.3000 (3) | 0.0340 (7) | |
C55 | 0.9123 (4) | −0.3395 (3) | 0.3816 (3) | 0.0327 (7) | |
H55 | 0.9820 | −0.3958 | 0.4235 | 0.039* | |
C56 | 0.8615 (3) | −0.2246 (3) | 0.4011 (2) | 0.0291 (6) | |
H56 | 0.8963 | −0.2005 | 0.4574 | 0.035* | |
N51 | 0.9171 (3) | −0.4936 (3) | 0.2770 (3) | 0.0438 (7) | |
O51 | 0.8807 (3) | −0.5157 (2) | 0.1980 (2) | 0.0562 (7) | |
O52 | 0.9990 (3) | −0.5657 (3) | 0.3366 (3) | 0.0578 (7) | |
N6 | 0.8016 (3) | 0.0000 (2) | 0.63230 (19) | 0.0298 (6) | |
H6 | 0.8158 | −0.0575 | 0.5954 | 0.036* | |
C61 | 0.8406 (3) | −0.0433 (3) | 0.7369 (2) | 0.0256 (6) | |
C62 | 0.9050 (3) | −0.1676 (3) | 0.7648 (2) | 0.0295 (7) | |
H62 | 0.9191 | −0.2171 | 0.7140 | 0.035* | |
C63 | 0.9486 (4) | −0.2195 (3) | 0.8661 (3) | 0.0327 (7) | |
H63 | 0.9936 | −0.3045 | 0.8846 | 0.039* | |
C64 | 0.9275 (4) | −0.1492 (3) | 0.9404 (3) | 0.0337 (7) | |
H64 | 0.9574 | −0.1850 | 1.0103 | 0.040* | |
C65 | 0.8625 (4) | −0.0264 (3) | 0.9122 (2) | 0.0319 (7) | |
H65 | 0.8480 | 0.0225 | 0.9635 | 0.038* | |
C66 | 0.8179 (4) | 0.0276 (3) | 0.8115 (2) | 0.0287 (6) | |
H66 | 0.7721 | 0.1124 | 0.7937 | 0.034* | |
S1 | 0.70572 (10) | 0.31598 (8) | 0.92073 (6) | 0.0351 (2) | |
O1 | 0.6022 (4) | 0.3805 (3) | 0.8414 (2) | 0.0620 (7) | |
C11 | 0.7263 (5) | 0.4279 (4) | 0.9929 (4) | 0.0590 (11) | |
H11A | 0.7971 | 0.5077 | 0.9386 | 0.089* | |
H11B | 0.7819 | 0.3855 | 1.0534 | 0.089* | |
H11C | 0.6113 | 0.4525 | 1.0266 | 0.089* | |
C12 | 0.5621 (5) | 0.1958 (4) | 1.0365 (3) | 0.0555 (10) | |
H12A | 0.4549 | 0.2360 | 1.0623 | 0.083* | |
H12B | 0.6158 | 0.1622 | 1.0993 | 0.083* | |
H12C | 0.5357 | 0.1224 | 1.0123 | 0.083* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0268 (12) | 0.0282 (13) | 0.0266 (12) | 0.0049 (10) | −0.0101 (10) | −0.0091 (11) |
C2 | 0.0203 (14) | 0.0302 (16) | 0.0227 (14) | 0.0024 (11) | −0.0056 (11) | −0.0069 (12) |
N3 | 0.0257 (12) | 0.0264 (13) | 0.0248 (12) | 0.0014 (9) | −0.0086 (10) | −0.0068 (10) |
C4 | 0.0232 (14) | 0.0328 (16) | 0.0203 (14) | −0.0018 (12) | −0.0061 (11) | −0.0078 (12) |
C5 | 0.0241 (14) | 0.0263 (15) | 0.0247 (15) | 0.0027 (11) | −0.0066 (12) | −0.0080 (12) |
C6 | 0.0207 (14) | 0.0278 (15) | 0.0241 (14) | 0.0006 (11) | −0.0057 (11) | −0.0065 (12) |
N2 | 0.0373 (14) | 0.0299 (13) | 0.0245 (12) | 0.0099 (10) | −0.0130 (11) | −0.0109 (11) |
O4 | 0.0347 (11) | 0.0295 (11) | 0.0260 (10) | 0.0063 (8) | −0.0138 (9) | −0.0089 (9) |
C41 | 0.0384 (17) | 0.0365 (17) | 0.0282 (16) | 0.0118 (13) | −0.0159 (14) | −0.0101 (14) |
N5 | 0.0241 (12) | 0.0301 (13) | 0.0250 (13) | 0.0004 (10) | −0.0049 (10) | −0.0091 (11) |
C57 | 0.0249 (15) | 0.0292 (15) | 0.0224 (14) | −0.0009 (11) | −0.0059 (12) | −0.0045 (12) |
C51 | 0.0238 (14) | 0.0327 (16) | 0.0223 (14) | −0.0042 (12) | −0.0020 (12) | −0.0093 (12) |
C52 | 0.0331 (16) | 0.0372 (17) | 0.0233 (15) | −0.0040 (13) | −0.0073 (13) | −0.0075 (13) |
C53 | 0.0377 (17) | 0.0397 (18) | 0.0300 (17) | −0.0082 (14) | −0.0026 (14) | −0.0166 (15) |
C54 | 0.0298 (16) | 0.0336 (17) | 0.0379 (17) | −0.0029 (13) | 0.0021 (14) | −0.0200 (15) |
C55 | 0.0295 (16) | 0.0314 (16) | 0.0356 (17) | −0.0007 (12) | −0.0048 (13) | −0.0121 (14) |
C56 | 0.0268 (15) | 0.0347 (17) | 0.0283 (15) | 0.0028 (12) | −0.0078 (12) | −0.0135 (13) |
N51 | 0.0284 (15) | 0.0453 (17) | 0.0581 (19) | −0.0069 (13) | 0.0056 (14) | −0.0310 (16) |
O51 | 0.0599 (16) | 0.0610 (17) | 0.0585 (16) | −0.0068 (12) | −0.0035 (13) | −0.0434 (14) |
O52 | 0.0429 (14) | 0.0506 (16) | 0.096 (2) | 0.0155 (12) | −0.0210 (15) | −0.0455 (16) |
N6 | 0.0385 (14) | 0.0285 (13) | 0.0273 (13) | 0.0080 (11) | −0.0146 (11) | −0.0115 (11) |
C61 | 0.0234 (14) | 0.0283 (15) | 0.0241 (14) | 0.0013 (11) | −0.0081 (12) | −0.0061 (12) |
C62 | 0.0299 (15) | 0.0285 (16) | 0.0309 (16) | 0.0043 (12) | −0.0095 (13) | −0.0102 (13) |
C63 | 0.0355 (17) | 0.0278 (16) | 0.0345 (17) | 0.0052 (12) | −0.0157 (14) | −0.0056 (13) |
C64 | 0.0375 (17) | 0.0346 (17) | 0.0286 (16) | 0.0017 (13) | −0.0154 (14) | −0.0049 (14) |
C65 | 0.0361 (17) | 0.0317 (16) | 0.0284 (16) | 0.0014 (13) | −0.0121 (13) | −0.0081 (13) |
C66 | 0.0314 (16) | 0.0271 (15) | 0.0279 (15) | 0.0023 (12) | −0.0098 (13) | −0.0084 (13) |
S1 | 0.0371 (4) | 0.0369 (5) | 0.0301 (4) | 0.0043 (3) | −0.0081 (3) | −0.0105 (3) |
O1 | 0.096 (2) | 0.0627 (17) | 0.0363 (14) | 0.0343 (15) | −0.0358 (14) | −0.0156 (13) |
C11 | 0.047 (2) | 0.071 (3) | 0.074 (3) | −0.0007 (18) | −0.015 (2) | −0.046 (2) |
C12 | 0.055 (2) | 0.044 (2) | 0.050 (2) | 0.0007 (17) | −0.0005 (18) | −0.0033 (18) |
Geometric parameters (Å, º) top
N1—C6 | 1.324 (3) | C55—C56 | 1.364 (4) |
N1—C2 | 1.337 (3) | C55—H55 | 0.9500 |
C2—N2 | 1.330 (4) | C56—H56 | 0.9500 |
C2—N3 | 1.347 (3) | N51—O52 | 1.216 (4) |
N3—C4 | 1.313 (3) | N51—O51 | 1.225 (4) |
C4—O4 | 1.340 (3) | N6—C61 | 1.394 (3) |
C4—C5 | 1.395 (4) | N6—H6 | 0.8800 |
C5—N5 | 1.375 (3) | C61—C66 | 1.380 (4) |
C5—C6 | 1.413 (4) | C61—C62 | 1.386 (4) |
C6—N6 | 1.356 (3) | C62—C63 | 1.378 (4) |
N2—H21 | 0.8800 | C62—H62 | 0.9500 |
N2—H22 | 0.8800 | C63—C64 | 1.373 (4) |
O4—C41 | 1.437 (3) | C63—H63 | 0.9500 |
C41—H41A | 0.9800 | C64—C65 | 1.374 (4) |
C41—H41B | 0.9800 | C64—H64 | 0.9500 |
C41—H41C | 0.9800 | C65—C66 | 1.378 (4) |
N5—C57 | 1.276 (3) | C65—H65 | 0.9500 |
C57—C51 | 1.457 (4) | C66—H66 | 0.9500 |
C57—H57 | 0.9500 | S1—O1 | 1.477 (2) |
C51—C52 | 1.383 (4) | S1—C12 | 1.763 (3) |
C51—C56 | 1.392 (4) | S1—C11 | 1.771 (3) |
C52—C53 | 1.370 (4) | C11—H11A | 0.9800 |
C52—H52 | 0.9500 | C11—H11B | 0.9800 |
C53—C54 | 1.372 (4) | C11—H11C | 0.9800 |
C53—H53 | 0.9500 | C12—H12A | 0.9800 |
C54—C55 | 1.370 (4) | C12—H12B | 0.9800 |
C54—N51 | 1.465 (4) | C12—H12C | 0.9800 |
| | | |
C6—N1—C2 | 115.6 (2) | C55—C56—C51 | 120.9 (3) |
N2—C2—N1 | 115.4 (2) | C55—C56—H56 | 119.6 |
N2—C2—N3 | 117.6 (2) | C51—C56—H56 | 119.6 |
N1—C2—N3 | 127.0 (3) | O52—N51—O51 | 124.0 (3) |
C4—N3—C2 | 115.2 (2) | O52—N51—C54 | 118.2 (3) |
N3—C4—O4 | 119.5 (2) | O51—N51—C54 | 117.8 (3) |
N3—C4—C5 | 124.6 (2) | C6—N6—C61 | 132.3 (2) |
O4—C4—C5 | 115.8 (2) | C6—N6—H6 | 112.3 |
N5—C5—C4 | 130.9 (3) | C61—N6—H6 | 115.3 |
N5—C5—C6 | 115.2 (2) | C66—C61—C62 | 119.9 (3) |
C4—C5—C6 | 113.9 (2) | C66—C61—N6 | 124.8 (3) |
N1—C6—N6 | 120.3 (2) | C62—C61—N6 | 115.3 (2) |
N1—C6—C5 | 123.5 (2) | C63—C62—C61 | 120.0 (3) |
N6—C6—C5 | 116.2 (2) | C63—C62—H62 | 120.0 |
C2—N2—H21 | 121.1 | C61—C62—H62 | 120.0 |
C2—N2—H22 | 122.3 | C64—C63—C62 | 120.4 (3) |
H21—N2—H22 | 114.0 | C64—C63—H63 | 119.8 |
C4—O4—C41 | 116.8 (2) | C62—C63—H63 | 119.8 |
O4—C41—H41A | 109.5 | C63—C64—C65 | 119.1 (3) |
O4—C41—H41B | 109.5 | C63—C64—H64 | 120.5 |
H41A—C41—H41B | 109.5 | C65—C64—H64 | 120.5 |
O4—C41—H41C | 109.5 | C64—C65—C66 | 121.6 (3) |
H41A—C41—H41C | 109.5 | C64—C65—H65 | 119.2 |
H41B—C41—H41C | 109.5 | C66—C65—H65 | 119.2 |
C57—N5—C5 | 127.8 (3) | C65—C66—C61 | 119.0 (3) |
N5—C57—C51 | 119.4 (3) | C65—C66—H66 | 120.5 |
N5—C57—H57 | 120.3 | C61—C66—H66 | 120.5 |
C51—C57—H57 | 120.3 | O1—S1—C12 | 105.52 (18) |
C52—C51—C56 | 119.0 (3) | O1—S1—C11 | 106.08 (17) |
C52—C51—C57 | 120.1 (3) | C12—S1—C11 | 97.49 (19) |
C56—C51—C57 | 120.9 (2) | S1—C11—H11A | 109.5 |
C53—C52—C51 | 120.8 (3) | S1—C11—H11B | 109.5 |
C53—C52—H52 | 119.6 | H11A—C11—H11B | 109.5 |
C51—C52—H52 | 119.6 | S1—C11—H11C | 109.5 |
C52—C53—C54 | 118.2 (3) | H11A—C11—H11C | 109.5 |
C52—C53—H53 | 120.9 | H11B—C11—H11C | 109.5 |
C54—C53—H53 | 120.9 | S1—C12—H12A | 109.5 |
C55—C54—C53 | 122.8 (3) | S1—C12—H12B | 109.5 |
C55—C54—N51 | 118.6 (3) | H12A—C12—H12B | 109.5 |
C53—C54—N51 | 118.6 (3) | S1—C12—H12C | 109.5 |
C56—C55—C54 | 118.3 (3) | H12A—C12—H12C | 109.5 |
C56—C55—H55 | 120.9 | H12B—C12—H12C | 109.5 |
C54—C55—H55 | 120.9 | | |
| | | |
C6—N1—C2—N2 | −176.0 (2) | C51—C52—C53—C54 | −1.2 (4) |
C6—N1—C2—N3 | 4.3 (4) | C52—C53—C54—C55 | 1.4 (4) |
N2—C2—N3—C4 | 176.9 (2) | C52—C53—C54—N51 | −178.3 (3) |
N1—C2—N3—C4 | −3.4 (4) | C53—C54—C55—C56 | −0.8 (4) |
C2—N3—C4—O4 | 176.4 (2) | N51—C54—C55—C56 | 178.8 (3) |
C2—N3—C4—C5 | −1.8 (4) | C54—C55—C56—C51 | 0.0 (4) |
N3—C4—C5—N5 | −178.6 (3) | C52—C51—C56—C55 | 0.2 (4) |
O4—C4—C5—N5 | 3.2 (4) | C57—C51—C56—C55 | −180.0 (3) |
N3—C4—C5—C6 | 5.0 (4) | C55—C54—N51—O52 | 4.6 (4) |
O4—C4—C5—C6 | −173.2 (2) | C53—C54—N51—O52 | −175.7 (3) |
C2—N1—C6—N6 | −179.2 (2) | C55—C54—N51—O51 | −174.5 (3) |
C2—N1—C6—C5 | −0.3 (4) | C53—C54—N51—O51 | 5.1 (4) |
N5—C5—C6—N1 | 179.1 (2) | N1—C6—N6—C61 | 5.2 (4) |
C4—C5—C6—N1 | −3.9 (4) | C5—C6—N6—C61 | −173.7 (3) |
N5—C5—C6—N6 | −2.0 (4) | C6—N6—C61—C66 | 0.2 (5) |
C4—C5—C6—N6 | 175.0 (2) | C6—N6—C61—C62 | 179.6 (3) |
N3—C4—O4—C41 | −5.0 (4) | C66—C61—C62—C63 | −0.9 (4) |
C5—C4—O4—C41 | 173.3 (2) | N6—C61—C62—C63 | 179.6 (2) |
C4—C5—N5—C57 | −0.2 (5) | C61—C62—C63—C64 | 0.5 (4) |
C6—C5—N5—C57 | 176.2 (2) | C62—C63—C64—C65 | −0.1 (4) |
C5—N5—C57—C51 | 178.7 (2) | C63—C64—C65—C66 | 0.1 (4) |
N5—C57—C51—C52 | 172.1 (2) | C64—C65—C66—C61 | −0.6 (4) |
N5—C57—C51—C56 | −7.7 (4) | C62—C61—C66—C65 | 1.0 (4) |
C56—C51—C52—C53 | 0.4 (4) | N6—C61—C66—C65 | −179.7 (2) |
C57—C51—C52—C53 | −179.4 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H21···O1 | 0.88 | 2.11 | 2.966 (3) | 163 |
N2—H22···N3i | 0.88 | 2.32 | 3.186 (3) | 170 |
N6—H6···N5 | 0.88 | 2.11 | 2.598 (3) | 114 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
(II) 2-amino-6-[methyl(phenyl)amino]-5-[(E)-4-nitrobenzylideneamino]pyrimidin-
4(3
H)-one dimethyl sulfoxide solvate
top
Crystal data top
C18H16N6O3·C2H6OS | Z = 2 |
Mr = 442.50 | F(000) = 464 |
Triclinic, P1 | Dx = 1.481 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.2601 (8) Å | Cell parameters from 4556 reflections |
b = 10.4555 (6) Å | θ = 3.0–27.5° |
c = 11.4537 (14) Å | µ = 0.21 mm−1 |
α = 113.230 (7)° | T = 120 K |
β = 112.295 (8)° | Plate, red |
γ = 96.709 (8)° | 0.35 × 0.26 × 0.08 mm |
V = 992.0 (2) Å3 | |
Data collection top
Bruker–Nonius KappaCCD diffractometer | 4556 independent reflections |
Radiation source: Bruker-Nonius FR591 rotating anode | 2896 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.074 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.0° |
ϕ and ω scans | h = −13→13 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −13→13 |
Tmin = 0.941, Tmax = 0.984 | l = −14→14 |
29046 measured reflections | |
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)] = 0.057 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.161 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0676P)2 + 1.0668P] where P = (Fo2 + 2Fc2)/3 |
4556 reflections | (Δ/σ)max = 0.001 |
283 parameters | Δρmax = 0.40 e Å−3 |
0 restraints | Δρmin = −0.66 e Å−3 |
Crystal data top
C18H16N6O3·C2H6OS | γ = 96.709 (8)° |
Mr = 442.50 | V = 992.0 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.2601 (8) Å | Mo Kα radiation |
b = 10.4555 (6) Å | µ = 0.21 mm−1 |
c = 11.4537 (14) Å | T = 120 K |
α = 113.230 (7)° | 0.35 × 0.26 × 0.08 mm |
β = 112.295 (8)° | |
Data collection top
Bruker–Nonius KappaCCD diffractometer | 4556 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2896 reflections with I > 2σ(I) |
Tmin = 0.941, Tmax = 0.984 | Rint = 0.074 |
29046 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.057 | 0 restraints |
wR(F2) = 0.161 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.40 e Å−3 |
4556 reflections | Δρmin = −0.66 e Å−3 |
283 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | 0.4034 (2) | 0.6213 (2) | 0.1845 (2) | 0.0202 (5) | |
C2 | 0.4609 (3) | 0.6622 (3) | 0.3230 (3) | 0.0199 (6) | |
N3 | 0.4525 (3) | 0.5672 (2) | 0.3729 (2) | 0.0224 (5) | |
H3 | 0.5030 | 0.6000 | 0.4660 | 0.027* | |
C4 | 0.3799 (3) | 0.4195 (3) | 0.2843 (3) | 0.0203 (6) | |
C5 | 0.3097 (3) | 0.3722 (3) | 0.1344 (3) | 0.0197 (6) | |
C6 | 0.3260 (3) | 0.4785 (3) | 0.0914 (3) | 0.0198 (6) | |
N2 | 0.5310 (3) | 0.8042 (2) | 0.4185 (2) | 0.0258 (5) | |
H21 | 0.5160 | 0.8655 | 0.3835 | 0.031* | |
H22 | 0.5431 | 0.8304 | 0.5059 | 0.031* | |
O4 | 0.3818 (2) | 0.3384 (2) | 0.33964 (19) | 0.0247 (4) | |
N5 | 0.2329 (2) | 0.2282 (2) | 0.0290 (2) | 0.0200 (5) | |
C57 | 0.2049 (3) | 0.1195 (3) | 0.0503 (3) | 0.0209 (6) | |
H57 | 0.2416 | 0.1320 | 0.1450 | 0.025* | |
C51 | 0.1149 (3) | −0.0251 (3) | −0.0746 (3) | 0.0203 (6) | |
C52 | 0.1086 (3) | −0.1508 (3) | −0.0601 (3) | 0.0240 (6) | |
H52 | 0.1636 | −0.1430 | 0.0317 | 0.029* | |
C53 | 0.0240 (3) | −0.2868 (3) | −0.1767 (3) | 0.0267 (6) | |
H53 | 0.0219 | −0.3730 | −0.1668 | 0.032* | |
C54 | −0.0575 (3) | −0.2952 (3) | −0.3082 (3) | 0.0248 (6) | |
C55 | −0.0585 (3) | −0.1733 (3) | −0.3267 (3) | 0.0252 (6) | |
H55 | −0.1183 | −0.1819 | −0.4178 | 0.030* | |
C56 | 0.0298 (3) | −0.0379 (3) | −0.2094 (3) | 0.0241 (6) | |
H56 | 0.0326 | 0.0475 | −0.2205 | 0.029* | |
N51 | −0.1490 (3) | −0.4388 (3) | −0.4325 (3) | 0.0319 (6) | |
O51 | −0.1545 (3) | −0.5454 (2) | −0.4130 (3) | 0.0545 (7) | |
O52 | −0.2188 (3) | −0.4460 (2) | −0.5495 (2) | 0.0397 (6) | |
N6 | 0.2700 (3) | 0.4454 (2) | −0.0507 (2) | 0.0216 (5) | |
C61 | 0.1260 (3) | 0.3456 (3) | −0.1574 (3) | 0.0207 (6) | |
C62 | 0.0105 (3) | 0.3350 (3) | −0.1250 (3) | 0.0229 (6) | |
H62 | 0.0278 | 0.3909 | −0.0291 | 0.027* | |
C63 | −0.1310 (3) | 0.2433 (3) | −0.2312 (3) | 0.0255 (6) | |
H63 | −0.2100 | 0.2360 | −0.2077 | 0.031* | |
C64 | −0.1572 (3) | 0.1623 (3) | −0.3714 (3) | 0.0284 (7) | |
H64 | −0.2542 | 0.0999 | −0.4446 | 0.034* | |
C65 | −0.0422 (3) | 0.1727 (3) | −0.4038 (3) | 0.0274 (6) | |
H65 | −0.0598 | 0.1170 | −0.5000 | 0.033* | |
C66 | 0.0995 (3) | 0.2634 (3) | −0.2979 (3) | 0.0240 (6) | |
H66 | 0.1785 | 0.2695 | −0.3214 | 0.029* | |
C67 | 0.3280 (3) | 0.5553 (3) | −0.0822 (3) | 0.0265 (6) | |
H67A | 0.2957 | 0.6409 | −0.0471 | 0.040* | |
H67B | 0.2907 | 0.5137 | −0.1862 | 0.040* | |
H67C | 0.4367 | 0.5850 | −0.0344 | 0.040* | |
S1 | 0.50481 (9) | 1.00119 (8) | 0.19238 (8) | 0.0311 (2) | |
O1 | 0.4690 (2) | 1.0149 (2) | 0.3099 (2) | 0.0311 (5) | |
C11 | 0.6266 (4) | 1.1739 (3) | 0.2533 (4) | 0.0357 (7) | |
H11A | 0.7070 | 1.2069 | 0.3497 | 0.054* | |
H11B | 0.5720 | 1.2450 | 0.2565 | 0.054* | |
H11C | 0.6684 | 1.1654 | 0.1875 | 0.054* | |
C12 | 0.6310 (4) | 0.9017 (3) | 0.1989 (4) | 0.0345 (7) | |
H12A | 0.5841 | 0.8046 | 0.1821 | 0.052* | |
H12B | 0.7186 | 0.9540 | 0.2936 | 0.052* | |
H12C | 0.6610 | 0.8907 | 0.1247 | 0.052* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0219 (12) | 0.0184 (11) | 0.0161 (11) | 0.0041 (9) | 0.0071 (9) | 0.0067 (9) |
C2 | 0.0195 (13) | 0.0204 (13) | 0.0181 (13) | 0.0056 (11) | 0.0083 (11) | 0.0083 (11) |
N3 | 0.0258 (12) | 0.0202 (12) | 0.0134 (11) | 0.0037 (9) | 0.0044 (9) | 0.0066 (9) |
C4 | 0.0217 (14) | 0.0198 (13) | 0.0190 (13) | 0.0058 (11) | 0.0092 (11) | 0.0092 (11) |
C5 | 0.0213 (14) | 0.0188 (13) | 0.0171 (13) | 0.0062 (11) | 0.0083 (11) | 0.0074 (11) |
C6 | 0.0201 (13) | 0.0208 (13) | 0.0175 (13) | 0.0063 (11) | 0.0094 (11) | 0.0078 (11) |
N2 | 0.0337 (14) | 0.0197 (12) | 0.0178 (12) | 0.0041 (10) | 0.0092 (11) | 0.0072 (10) |
O4 | 0.0295 (11) | 0.0213 (10) | 0.0175 (10) | 0.0035 (8) | 0.0065 (8) | 0.0097 (8) |
N5 | 0.0202 (11) | 0.0183 (11) | 0.0195 (11) | 0.0061 (9) | 0.0091 (10) | 0.0076 (9) |
C57 | 0.0201 (13) | 0.0232 (14) | 0.0187 (13) | 0.0069 (11) | 0.0086 (11) | 0.0097 (11) |
C51 | 0.0204 (13) | 0.0203 (13) | 0.0196 (14) | 0.0057 (11) | 0.0095 (11) | 0.0091 (11) |
C52 | 0.0256 (15) | 0.0236 (14) | 0.0228 (14) | 0.0072 (12) | 0.0109 (12) | 0.0116 (12) |
C53 | 0.0275 (15) | 0.0239 (15) | 0.0304 (16) | 0.0069 (12) | 0.0133 (13) | 0.0150 (13) |
C54 | 0.0248 (15) | 0.0198 (14) | 0.0222 (14) | 0.0024 (11) | 0.0100 (12) | 0.0055 (11) |
C55 | 0.0252 (15) | 0.0273 (15) | 0.0206 (14) | 0.0046 (12) | 0.0094 (12) | 0.0114 (12) |
C56 | 0.0274 (15) | 0.0224 (14) | 0.0230 (14) | 0.0063 (12) | 0.0122 (12) | 0.0113 (12) |
N51 | 0.0367 (15) | 0.0230 (13) | 0.0275 (14) | 0.0036 (11) | 0.0124 (12) | 0.0083 (11) |
O51 | 0.0718 (19) | 0.0218 (12) | 0.0401 (14) | 0.0021 (11) | 0.0045 (13) | 0.0121 (11) |
O52 | 0.0503 (14) | 0.0301 (12) | 0.0202 (11) | −0.0020 (10) | 0.0079 (10) | 0.0074 (9) |
N6 | 0.0254 (12) | 0.0195 (11) | 0.0145 (11) | 0.0010 (9) | 0.0065 (10) | 0.0076 (9) |
C61 | 0.0234 (14) | 0.0199 (13) | 0.0170 (13) | 0.0065 (11) | 0.0068 (11) | 0.0098 (11) |
C62 | 0.0246 (14) | 0.0225 (14) | 0.0206 (14) | 0.0086 (11) | 0.0089 (12) | 0.0107 (11) |
C63 | 0.0229 (14) | 0.0286 (15) | 0.0283 (15) | 0.0088 (12) | 0.0104 (12) | 0.0178 (13) |
C64 | 0.0214 (14) | 0.0272 (15) | 0.0268 (16) | 0.0025 (12) | 0.0029 (12) | 0.0134 (13) |
C65 | 0.0288 (16) | 0.0262 (15) | 0.0180 (14) | 0.0045 (12) | 0.0060 (12) | 0.0080 (12) |
C66 | 0.0266 (15) | 0.0252 (14) | 0.0184 (14) | 0.0073 (12) | 0.0097 (12) | 0.0099 (11) |
C67 | 0.0322 (16) | 0.0256 (15) | 0.0203 (14) | 0.0034 (12) | 0.0094 (12) | 0.0140 (12) |
S1 | 0.0304 (4) | 0.0334 (4) | 0.0283 (4) | 0.0076 (3) | 0.0134 (3) | 0.0146 (3) |
O1 | 0.0437 (13) | 0.0296 (11) | 0.0329 (12) | 0.0159 (10) | 0.0257 (10) | 0.0179 (10) |
C11 | 0.0406 (19) | 0.0278 (16) | 0.044 (2) | 0.0094 (14) | 0.0245 (16) | 0.0171 (15) |
C12 | 0.0362 (18) | 0.0245 (16) | 0.0383 (18) | 0.0049 (13) | 0.0227 (15) | 0.0072 (14) |
Geometric parameters (Å, º) top
N1—C2 | 1.319 (3) | N51—O51 | 1.220 (3) |
N1—C6 | 1.350 (3) | N51—O52 | 1.223 (3) |
C2—N3 | 1.337 (3) | N6—C61 | 1.425 (3) |
C2—N2 | 1.338 (3) | N6—C67 | 1.461 (3) |
N3—C4 | 1.375 (3) | C61—C62 | 1.375 (4) |
N3—H3 | 0.8799 | C61—C66 | 1.387 (4) |
C4—O4 | 1.241 (3) | C62—C63 | 1.386 (4) |
C4—C5 | 1.421 (4) | C62—H62 | 0.9500 |
C5—N5 | 1.382 (3) | C63—C64 | 1.383 (4) |
C5—C6 | 1.399 (4) | C63—H63 | 0.9500 |
C6—N6 | 1.378 (3) | C64—C65 | 1.370 (4) |
N2—H21 | 0.8800 | C64—H64 | 0.9500 |
N2—H22 | 0.8800 | C65—C66 | 1.384 (4) |
N5—C57 | 1.276 (3) | C65—H65 | 0.9500 |
C57—C51 | 1.467 (4) | C66—H66 | 0.9500 |
C57—H57 | 0.9500 | C67—H67A | 0.9800 |
C51—C52 | 1.386 (4) | C67—H67B | 0.9800 |
C51—C56 | 1.396 (4) | C67—H67C | 0.9800 |
C52—C53 | 1.376 (4) | S1—O1 | 1.484 (2) |
C52—H52 | 0.9500 | S1—C12 | 1.752 (3) |
C53—C54 | 1.378 (4) | S1—C11 | 1.768 (3) |
C53—H53 | 0.9500 | C11—H11A | 0.9800 |
C54—C55 | 1.372 (4) | C11—H11B | 0.9800 |
C54—N51 | 1.460 (4) | C11—H11C | 0.9800 |
C55—C56 | 1.380 (4) | C12—H12A | 0.9800 |
C55—H55 | 0.9500 | C12—H12B | 0.9800 |
C56—H56 | 0.9500 | C12—H12C | 0.9800 |
| | | |
C2—N1—C6 | 117.7 (2) | O52—N51—C54 | 118.8 (2) |
N1—C2—N3 | 122.7 (2) | C6—N6—C61 | 122.5 (2) |
N1—C2—N2 | 119.4 (2) | C6—N6—C67 | 117.4 (2) |
N3—C2—N2 | 118.0 (2) | C61—N6—C67 | 115.3 (2) |
C2—N3—C4 | 122.8 (2) | C62—C61—C66 | 119.2 (3) |
C2—N3—H3 | 117.9 | C62—C61—N6 | 121.0 (2) |
C4—N3—H3 | 119.0 | C66—C61—N6 | 119.7 (2) |
O4—C4—N3 | 118.5 (2) | C61—C62—C63 | 120.6 (3) |
O4—C4—C5 | 125.2 (2) | C61—C62—H62 | 119.7 |
N3—C4—C5 | 116.2 (2) | C63—C62—H62 | 119.7 |
N5—C5—C6 | 118.2 (2) | C64—C63—C62 | 120.0 (3) |
N5—C5—C4 | 124.5 (2) | C64—C63—H63 | 120.0 |
C6—C5—C4 | 117.2 (2) | C62—C63—H63 | 120.0 |
N1—C6—N6 | 113.8 (2) | C65—C64—C63 | 119.5 (3) |
N1—C6—C5 | 123.3 (2) | C65—C64—H64 | 120.2 |
N6—C6—C5 | 122.8 (2) | C63—C64—H64 | 120.2 |
C2—N2—H21 | 115.5 | C64—C65—C66 | 120.6 (3) |
C2—N2—H22 | 116.1 | C64—C65—H65 | 119.7 |
H21—N2—H22 | 119.5 | C66—C65—H65 | 119.7 |
C57—N5—C5 | 125.8 (2) | C65—C66—C61 | 120.1 (3) |
N5—C57—C51 | 118.5 (2) | C65—C66—H66 | 120.0 |
N5—C57—H57 | 120.7 | C61—C66—H66 | 120.0 |
C51—C57—H57 | 120.7 | N6—C67—H67A | 109.5 |
C52—C51—C56 | 118.8 (2) | N6—C67—H67B | 109.5 |
C52—C51—C57 | 120.6 (2) | H67A—C67—H67B | 109.5 |
C56—C51—C57 | 120.5 (2) | N6—C67—H67C | 109.5 |
C53—C52—C51 | 121.0 (3) | H67A—C67—H67C | 109.5 |
C53—C52—H52 | 119.5 | H67B—C67—H67C | 109.5 |
C51—C52—H52 | 119.5 | O1—S1—C12 | 105.48 (14) |
C52—C53—C54 | 118.5 (3) | O1—S1—C11 | 106.46 (14) |
C52—C53—H53 | 120.8 | C12—S1—C11 | 98.81 (15) |
C54—C53—H53 | 120.8 | S1—C11—H11A | 109.5 |
C55—C54—C53 | 122.5 (3) | S1—C11—H11B | 109.5 |
C55—C54—N51 | 118.5 (3) | H11A—C11—H11B | 109.5 |
C53—C54—N51 | 119.0 (3) | S1—C11—H11C | 109.5 |
C54—C55—C56 | 118.3 (3) | H11A—C11—H11C | 109.5 |
C54—C55—H55 | 120.9 | H11B—C11—H11C | 109.5 |
C56—C55—H55 | 120.9 | S1—C12—H12A | 109.5 |
C55—C56—C51 | 120.8 (3) | S1—C12—H12B | 109.5 |
C55—C56—H56 | 119.6 | H12A—C12—H12B | 109.5 |
C51—C56—H56 | 119.6 | S1—C12—H12C | 109.5 |
O51—N51—O52 | 123.3 (3) | H12A—C12—H12C | 109.5 |
O51—N51—C54 | 117.9 (3) | H12B—C12—H12C | 109.5 |
| | | |
C6—N1—C2—N3 | 3.9 (4) | C53—C54—C55—C56 | 2.2 (4) |
C6—N1—C2—N2 | −176.2 (2) | N51—C54—C55—C56 | −179.1 (3) |
N1—C2—N3—C4 | −1.7 (4) | C54—C55—C56—C51 | −1.6 (4) |
N2—C2—N3—C4 | 178.3 (2) | C52—C51—C56—C55 | −0.5 (4) |
C2—N3—C4—O4 | 177.6 (3) | C57—C51—C56—C55 | −178.2 (3) |
C2—N3—C4—C5 | −1.6 (4) | C55—C54—N51—O51 | −175.5 (3) |
O4—C4—C5—N5 | 0.2 (4) | C53—C54—N51—O51 | 3.4 (4) |
N3—C4—C5—N5 | 179.3 (2) | C55—C54—N51—O52 | 2.6 (4) |
O4—C4—C5—C6 | −176.6 (3) | C53—C54—N51—O52 | −178.5 (3) |
N3—C4—C5—C6 | 2.5 (4) | N1—C6—N6—C61 | −140.1 (2) |
C2—N1—C6—N6 | −180.0 (2) | C5—C6—N6—C61 | 42.6 (4) |
C2—N1—C6—C5 | −2.8 (4) | N1—C6—N6—C67 | 14.0 (3) |
N5—C5—C6—N1 | −177.5 (2) | C5—C6—N6—C67 | −163.3 (3) |
C4—C5—C6—N1 | −0.4 (4) | C6—N6—C61—C62 | 34.1 (4) |
N5—C5—C6—N6 | −0.5 (4) | C67—N6—C61—C62 | −120.4 (3) |
C4—C5—C6—N6 | 176.5 (2) | C6—N6—C61—C66 | −149.4 (3) |
C6—C5—N5—C57 | −178.0 (3) | C67—N6—C61—C66 | 56.0 (3) |
C4—C5—N5—C57 | 5.3 (4) | C66—C61—C62—C63 | 0.0 (4) |
C5—N5—C57—C51 | 176.8 (2) | N6—C61—C62—C63 | 176.5 (2) |
N5—C57—C51—C52 | 165.6 (3) | C61—C62—C63—C64 | −0.5 (4) |
N5—C57—C51—C56 | −16.8 (4) | C62—C63—C64—C65 | 0.5 (4) |
C56—C51—C52—C53 | 2.1 (4) | C63—C64—C65—C66 | −0.1 (4) |
C57—C51—C52—C53 | 179.7 (3) | C64—C65—C66—C61 | −0.3 (4) |
C51—C52—C53—C54 | −1.6 (4) | C62—C61—C66—C65 | 0.4 (4) |
C52—C53—C54—C55 | −0.6 (4) | N6—C61—C66—C65 | −176.2 (2) |
C52—C53—C54—N51 | −179.4 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O4i | 0.88 | 1.86 | 2.739 (3) | 176 |
N2—H21···O1 | 0.88 | 2.07 | 2.949 (3) | 175 |
N2—H22···O1ii | 0.88 | 2.15 | 2.935 (3) | 148 |
C56—H56···Cg | 0.95 | 2.46 | 3.397 (4) | 168 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+2, −z+1. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C18H16N6O3·C2H6OS | C18H16N6O3·C2H6OS |
Mr | 442.50 | 442.50 |
Crystal system, space group | Triclinic, P1 | Triclinic, P1 |
Temperature (K) | 120 | 120 |
a, b, c (Å) | 8.0386 (8), 10.6862 (14), 12.8856 (13) | 10.2601 (8), 10.4555 (6), 11.4537 (14) |
α, β, γ (°) | 71.007 (11), 74.463 (9), 88.672 (12) | 113.230 (7), 112.295 (8), 96.709 (8) |
V (Å3) | 1005.9 (2) | 992.0 (2) |
Z | 2 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.20 | 0.21 |
Crystal size (mm) | 0.45 × 0.32 × 0.08 | 0.35 × 0.26 × 0.08 |
|
Data collection |
Diffractometer | Bruker–Nonius KappaCCD diffractometer | Bruker–Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.944, 0.984 | 0.941, 0.984 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 29080, 4614, 2569 | 29046, 4556, 2896 |
Rint | 0.089 | 0.074 |
(sin θ/λ)max (Å−1) | 0.650 | 0.650 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.057, 0.154, 1.05 | 0.057, 0.161, 1.07 |
No. of reflections | 4614 | 4556 |
No. of parameters | 283 | 283 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.38, −0.47 | 0.40, −0.66 |
Selected torsion angles (°) for compounds (I) and (II) topParameter | (I) | (II) |
N1—C6—N6—C61 | 5.2 (4) | -140.1 |
C6—N6—C61—C62 | 179.6 (3) | 34.1 (4) |
C6—C5—N5—C57 | 176.2 (2) | -178.0 (3) |
C5—N5—C57—C51 | 178.7 (2) | 176.8 (2) |
N5—C57—C51—C52 | 172.1 (2) | 165.6 (3) |
C53—C54—N51—O51 | 5.1 (4) | 3.4 (4) |
N3—C4—O4—C41 | -5.0 (4) | – |
Hydrogen bonds and short intramolecular contacts (Å, °)
for (I) and (II) topCompound | D—H···A | D—H | H···A | D···A | D—H···A |
(I) | N2—H21···O1 | 0.88 | 2.11 | 2.966 (3) | 163 |
| N2—H22···N3i | 0.88 | 2.32 | 3.186 (3) | 170 |
| N6—H6···N5 | 0.88 | 2.11 | 2.598 (3) | 114 |
| | | | | |
(II) | N2—H21···O1 | 0.88 | 2.07 | 2.949 (3) | 175 |
| N2—H22···O1ii | 0.88 | 2.15 | 2.935 (3) | 148 |
| N3—H3···O4i | 0.88 | 1.86 | 2.739 (3) | 176 |
| C56—H56···Cg | 0.95 | 2.46 | 3.397 (4) | 168 |
Cg represents the centroid of the C61–C66 ring. Symmetry codes:
(i) -x+1, -y+1, -z+1; (ii) -x+1, -y+2, -z+1. |
Pyrimidodiazepines belong to the so-called bicyclic privileged structures, which may be useful in the field of medicinal chemistry. (Horton et al., 2003). We have already reported the preparations (Cobo et al., 2008) and structures (Rodríguez et al., 2008) of some 6-aryl-2-amino-4-methoxy-11H-pyrimido[4,5-b][1,4]benzodiazepines using as final key step a Bischler–Napieralski cyclocondensation involving reaction of 2-amino-6-(methoxy)-5-amino-4-phenylaminopyrimidine with acid derivatives. We have now modified this procedure, replacing the aromatic acid used previously (Cobo et al., 2008) with an aromatic aldehyde, in the expectation of producing the corresponding dihydropyrimidobenzo[4,5-b][1,4]diazepine analogue. By the use of 4-nitrobenzaldehyde in the absence of phosphoryl choride, so preventing the cyclization step, we have isolated the intermediate Schiff bases (I) and (II), whose molecular and supramolecular structures we report here, both of them as stoichiometric monosolvates with dimethyl sulfoxide. The Schiff base components of the title solvates, 2-amino-6-anilino-4-methoxy-5-[(E)-4-nitrobenzylideneamino]pyrimidine dimethyl sulfoxide solvate, (I), and 2-amino-6-[methyl(phenyl)amino]-5-[(E)-4-nitrobenzylideneamino]pyrimidin-4(3H)-one dimethyl sulfoxide solvate, (II), are isomeric, and they were prepared by the acid-promoted condensation of 4-nitrobenzaldehyde with the isomeric heterocycles (A) for the formation of (I), and (B) for the formation of (II) (see scheme).
The molecular conformations can be defined in terms of a rather small number of torsion angles (Table 1): these show that the Schiff base backbone, running from the amino atom N2 to the nitro atom N51, has the (E) configuration, and that is does not deviate markedly from planarity: similarly the nitro group in each compound deviates only a little from the plane of the adjacent aryl ring, as does the methoxy atom C41 in compound (I). On the other hand the substituent at N6 shows some differences between (I) and (II), particularly in the location and orientation of the C61–C66 aryl ring. The location of this ring in (II) may be influenced both by the intramolecular C—H···π(arene) interaction in the compound and, perhaps more significantly, by the necessity to locate the neighbouring methyl group containing atom C67 away from the C51–C56 ring, in particular away from atom H56. The location of the C61–C66 ring in (I) may be a consequence of the intramolecular N—H···N interaction.
The Schiff base frameworks of compounds (I) and (II) can be regarded as chain-extended homologues of 4-nitroaniline but, despite the near planarity of these frameworks in both compounds, the bond distances provide no evidence for any significant polarization of the electronic structure, with its concomitant development of quinonoid character in the nitro-aryl ring, The distances in both (I) and (II) show no significant deviations from the expected values for unperturbed systems (Allen et al., 1987). Although the development of such quinonoid character is particularly marked in 4-nitroaniline itself (Qian et al., 2006), it is scarcely apparent in the homologous 4-amino-4'-nitrobiphenyl, although more developed in the similarly substituted biphenyl analogues where the two rings are separated by acetylene spacer units (Graham et al., 1989).
In each compound, the two independent components are linked within the selected asymmetric units (Figs. 1 and 2) by a fairly short, and nearly linear, N—H···O hydrogen bond (Table 2). Despite this, the further linking of these bimolecular aggregates differs significantly between the two compounds. In (I), paired N—H···N hydrogen bonds, having one of the pyrimidine N atoms as the acceptor, form a centrosymmetric R22(8) (Bernstein et al., 1995) motif, but there are no further direction-specific intermolecular interactions. The hydrogen-bonded structure thus consists of a four-component aggregate (Fig. 1), whose overall graph-set descriptor is D33(9)[R22(8)]. By contrast, the structure of (II) contains no N—H···N hydrogen bonds and the solvent atom O1 acts as a double acceptor in N—H···O hydrogen bonds (Table 2). The reference atom O1 at (x, y, z) accepts hydrogen bonds from atoms N2 at (x, y, z), via H21, and at (1 - x, 2 - y, 1 - z), via H22. The combined effect of the three independent N—H···O hydrogen bonds is the formation of a C33(12)[R22(8)][R42(8)] chain of rings running parallel to the [010] direction, in which the R22(8) rings formed by paired amide units are centred at (1/2, n + 1/2, 1/2), and the R42(8) rings are centred at (1/2, n, 1/2), where in both cases n represents an integer (Fig. 3). There are no direction-specific interactions between the four-component aggregates in (I), or between the chains in (II). The only C—H···π interaction observed is the intramolecular contact in (II) (Table 2).
The principal differences between the hydrogen-bonded structures of (I) and (II) arise from the nature of the hydrogen-bonds deployed and from the role of the dimethyl sulfoxide components. The formation of an N—H..N hydrogen bond with the pyrimidine ring atom N3, as found in (I), is not feasible in (II) because N3 now carries an H atom; the alternative ring site N1 is very effectively shielded in (II), by the adjacent amine and methyl substituents, while the Schiff base atom N5 is shielded by the C61–C66 aryl ring, so that formation of N—H···N hydrogen bonds is wholly impeded. On the other hand, in (II) not only are there three N—H bonds readily available as donors, but also atom O4 is available as a hydrogen-bond acceptor. Finally, the dimethyl sulfoxide component acts only as a single acceptor of hydrogen bonds in (I), and thus it plays only a marginal role in the supramolecular aggregation, possibly by simply filling space which would otherwise be empty. In contrast, this component acts as a double acceptor in (II), where it plays a key role in the chain formation, by acting as the sole link between R22(8) dimer units built from paired N—H···O═C hydrogen bonds.