Molecules of 1,3-dimethyl-7-(4-methylphenyl)pyrido[2,3-
d]pyrimidine-2,4(1
H,3
H)-dione, C
16H
15N
3O
2, (I), are linked by paired C—H
O hydrogen bonds to form centrosymmetric
R22(10) dimers, which are linked into chains by a single π–π stacking interaction. A single C—H
O hydrogen bond links the molecules of 7-(biphenyl-4-yl)-1,3-dimethylpyrido[2,3-
d]pyrimidine-2,4(1
H,3
H)-dione, C
21H
17N
3O
2, (II), into
C(10) chains, which are weakly linked into sheets by a π–π stacking interaction. In 7-(4-fluorophenyl)-3-methylpyrido[2,3-
d]pyrimidine-2,4(1
H,3
H)-dione, C
14H
10FN
3O
2, (III), an N—H
O hydrogen bond links the molecules into
C(6) chains, which are linked into sheets by a π–π stacking interaction. The molecules of 7-(4-methoxyphenyl)-3-methylpyrido[2,3-
d]pyrimidine-2,4(1
H,3
H)-dione, C
15H
13N
3O
3, (IV), are also linked into
C(6) chains by an N—H
O hydrogen bond, but here the chains are linked into sheets by a combination of two independent C—H
π(arene) hydrogen bonds.
Supporting information
CCDC references: 730090; 730091; 730092; 730093
Equimolar quantities of the appropriate 6-aminopyrimidine-5-carboxaldehyde,
6-amino-1,3-dimethyl-5-formylpyrimidine-2,4(1H,3H)-dione for (I)
and (II) or 6-amino-2-methoxy-3-methyl-5-formylpyrimidine-4(3H)-one for
(III) and (IV), and the appropriate 4-substituted acetophenone
4-RC6H4COCH3, where R is Me for (I), Ph for (II), F for
(III) and MeO for (IV), were mixed in the absence of solvent. Three drops of
BF3–Et2O were added to each mixture, which was then heated in an oil bath
at 443 K for 30 s. The resulting dark-brown liquids were diluted with ethanol
and cooled to ambient temperature. The solid products were collected by
filtration, washed with ethanol and then recrystallized to give the pure
pyrido[2,3-d]pyrimidine derivatives as crystals suitable for
single-crystal X-ray diffraction. For (I), yellow solid, crystallized from
ethanol/DMF, yield 50%, m.p. 458–460 K; HR–MS found: 281.1159;
C16H15N3O2 requires: 281.1164. For (II), yellow solid, purified by
column chromatography using chloroform as eluant, and recrystallized from
ethanol/DMF, yield 60%, m.p. 506–509 K; HR–MS found: 343.1313;
C21H17N3O2 requires: 343.1321. For (III), yellow solid, crystallized
form DMF, yield 60%, m.p. 568–570 K; HRMS found: 271.0752;
C14H10FN3O2 requires: 271.0757. For (IV), yellow solid, crystallized
form DMF, yield 70%, m.p. > 573 K. HR–MS found: 283.0966; C15H13N3O3
requires: 283.0957.
With the exception of the methyl H atoms bonded to C31 in compound (III), all H
atoms were clearly located in difference maps. H atoms bonded to C31 in
compound (III) were placed in calculated positions, and all H atoms were then
treated as riding atoms in geometrically idealized positions. The H atoms
bonded to three-connected C atoms in aromatic or heteroaromatic rings were
placed along the external bisectors of the ring angles, with C—H distances
of 0.95Å and with Uiso(H) = 1.2Ueq(C). H atoms bonded to ring N atoms
were placed along the external bisectors of the ring angles, with N—H
distances of 0.88Å and with Uiso(H) = 1.2Ueq(N). The
methyl groups were all permitted to rotate about the adjacent C—X
bonds (X = C or O) but not to tilt, with all of the X—C—H
and H—C—H angles held fixed in each such group, and with C—H distances
of 0.98Å and with Uiso(H) = 1.5Ueq(C). In the absence of
significant resonant scattering, the Friedel-equivalent reflections were
merged for compounds (III) and (IV). Hence, the absolute configuration of the
molecules in (III), and the correct orientation of the structure of (IV) with
respect to the polar-axis direction are both undetermined.
For all 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: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PRPKAPPA (Ferguson, 1999).
(I) 1,3-dimethyl-7-(4-methylphenyl)pyrido[2,3-
d]pyrimidine-
2,4(1
H,3
H)-dione
top
Crystal data top
C16H15N3O2 | Z = 2 |
Mr = 281.31 | F(000) = 296 |
Triclinic, P1 | Dx = 1.379 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.9953 (5) Å | Cell parameters from 2989 reflections |
b = 7.9221 (7) Å | θ = 3.0–27.6° |
c = 12.5140 (13) Å | µ = 0.09 mm−1 |
α = 93.466 (4)° | T = 120 K |
β = 92.993 (6)° | Lath, yellow |
γ = 101.152 (6)° | 0.20 × 0.10 × 0.02 mm |
V = 677.71 (11) Å3 | |
Data collection top
Bruker–Nonius KappaCCD diffractometer | 2989 independent reflections |
Radiation source: Bruker-Nonius FR591 rotating anode | 1699 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.080 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.6°, θmin = 3.0° |
ϕ & ω scans | h = −8→7 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −10→10 |
Tmin = 0.972, Tmax = 0.998 | l = −16→16 |
11686 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)] = 0.065 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.200 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.1083P)2] where P = (Fo2 + 2Fc2)/3 |
2989 reflections | (Δ/σ)max = 0.001 |
193 parameters | Δρmax = 0.45 e Å−3 |
0 restraints | Δρmin = −0.35 e Å−3 |
Crystal data top
C16H15N3O2 | γ = 101.152 (6)° |
Mr = 281.31 | V = 677.71 (11) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.9953 (5) Å | Mo Kα radiation |
b = 7.9221 (7) Å | µ = 0.09 mm−1 |
c = 12.5140 (13) Å | T = 120 K |
α = 93.466 (4)° | 0.20 × 0.10 × 0.02 mm |
β = 92.993 (6)° | |
Data collection top
Bruker–Nonius KappaCCD diffractometer | 2989 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 1699 reflections with I > 2σ(I) |
Tmin = 0.972, Tmax = 0.998 | Rint = 0.080 |
11686 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.065 | 0 restraints |
wR(F2) = 0.200 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.45 e Å−3 |
2989 reflections | Δρmin = −0.35 e Å−3 |
193 parameters | |
Special details top
Experimental. Mass spectrum: MS (70 eV) m/z (%) = 281 (M+, 100), 252 (51),
169 (50). HR—MS found 281.1159 ? |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | 0.3482 (3) | 0.6338 (3) | 0.60948 (16) | 0.0213 (5) | |
C2 | 0.3500 (3) | 0.5603 (3) | 0.7078 (2) | 0.0228 (6) | |
N3 | 0.2804 (3) | 0.3826 (3) | 0.70606 (16) | 0.0228 (5) | |
C4 | 0.2060 (3) | 0.2754 (3) | 0.6160 (2) | 0.0228 (6) | |
C4A | 0.2009 (3) | 0.3606 (3) | 0.5157 (2) | 0.0207 (6) | |
C5 | 0.1232 (3) | 0.2714 (3) | 0.4197 (2) | 0.0240 (6) | |
H5 | 0.0704 | 0.1512 | 0.4171 | 0.029* | |
C6 | 0.1235 (3) | 0.3597 (3) | 0.3271 (2) | 0.0240 (6) | |
H6 | 0.0681 | 0.3015 | 0.2608 | 0.029* | |
C7 | 0.2066 (3) | 0.5360 (3) | 0.33295 (19) | 0.0197 (5) | |
N8 | 0.2799 (3) | 0.6237 (3) | 0.42589 (16) | 0.0215 (5) | |
C8A | 0.2751 (3) | 0.5372 (3) | 0.51497 (19) | 0.0198 (6) | |
C11 | 0.4114 (4) | 0.8209 (3) | 0.6093 (2) | 0.0282 (6) | |
H11A | 0.5150 | 0.8475 | 0.5596 | 0.042* | |
H11B | 0.4610 | 0.8686 | 0.6817 | 0.042* | |
H11C | 0.3004 | 0.8720 | 0.5864 | 0.042* | |
O2 | 0.4081 (3) | 0.6462 (2) | 0.79085 (15) | 0.0318 (5) | |
C31 | 0.2855 (4) | 0.3030 (3) | 0.8091 (2) | 0.0286 (7) | |
H31A | 0.1547 | 0.2828 | 0.8362 | 0.043* | |
H31B | 0.3767 | 0.3803 | 0.8610 | 0.043* | |
H31C | 0.3286 | 0.1929 | 0.7988 | 0.043* | |
O4 | 0.1474 (2) | 0.1207 (2) | 0.62202 (15) | 0.0305 (5) | |
C71 | 0.2153 (3) | 0.6379 (3) | 0.2370 (2) | 0.0221 (6) | |
C72 | 0.2021 (3) | 0.5621 (3) | 0.1334 (2) | 0.0268 (6) | |
H72 | 0.1851 | 0.4403 | 0.1223 | 0.032* | |
C73 | 0.2133 (4) | 0.6624 (4) | 0.0456 (2) | 0.0302 (6) | |
H73 | 0.2052 | 0.6080 | −0.0247 | 0.036* | |
C74 | 0.2361 (3) | 0.8400 (3) | 0.0589 (2) | 0.0277 (6) | |
C75 | 0.2518 (3) | 0.9174 (3) | 0.1621 (2) | 0.0275 (6) | |
H75 | 0.2698 | 1.0394 | 0.1725 | 0.033* | |
C76 | 0.2415 (3) | 0.8183 (3) | 0.2511 (2) | 0.0238 (6) | |
H76 | 0.2522 | 0.8732 | 0.3214 | 0.029* | |
C77 | 0.2436 (4) | 0.9479 (4) | −0.0370 (2) | 0.0353 (7) | |
H77A | 0.3196 | 0.9021 | −0.0914 | 0.053* | |
H77B | 0.3055 | 1.0675 | −0.0145 | 0.053* | |
H77C | 0.1106 | 0.9441 | −0.0672 | 0.053* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0243 (10) | 0.0185 (11) | 0.0216 (12) | 0.0056 (8) | 0.0012 (8) | 0.0007 (9) |
C2 | 0.0219 (12) | 0.0248 (14) | 0.0229 (15) | 0.0064 (10) | 0.0025 (10) | 0.0032 (11) |
N3 | 0.0233 (10) | 0.0241 (12) | 0.0238 (12) | 0.0090 (9) | 0.0044 (8) | 0.0076 (9) |
C4 | 0.0219 (12) | 0.0232 (14) | 0.0252 (15) | 0.0069 (10) | 0.0080 (10) | 0.0048 (11) |
C4A | 0.0163 (11) | 0.0205 (13) | 0.0261 (15) | 0.0041 (9) | 0.0041 (9) | 0.0036 (11) |
C5 | 0.0210 (12) | 0.0191 (13) | 0.0321 (15) | 0.0037 (10) | 0.0043 (10) | 0.0023 (11) |
C6 | 0.0233 (12) | 0.0226 (14) | 0.0243 (15) | 0.0008 (10) | 0.0008 (10) | −0.0005 (11) |
C7 | 0.0151 (11) | 0.0231 (14) | 0.0217 (14) | 0.0051 (9) | 0.0022 (9) | 0.0017 (11) |
N8 | 0.0198 (10) | 0.0238 (12) | 0.0216 (12) | 0.0052 (9) | 0.0028 (8) | 0.0023 (9) |
C8A | 0.0174 (11) | 0.0218 (14) | 0.0212 (14) | 0.0060 (10) | 0.0012 (9) | 0.0018 (11) |
C11 | 0.0344 (14) | 0.0219 (14) | 0.0280 (16) | 0.0050 (11) | 0.0026 (11) | 0.0008 (11) |
O2 | 0.0411 (11) | 0.0333 (11) | 0.0219 (11) | 0.0095 (8) | 0.0014 (8) | 0.0027 (9) |
C31 | 0.0301 (14) | 0.0326 (16) | 0.0247 (16) | 0.0060 (12) | 0.0039 (11) | 0.0127 (12) |
O4 | 0.0342 (10) | 0.0214 (11) | 0.0370 (12) | 0.0047 (8) | 0.0073 (8) | 0.0090 (8) |
C71 | 0.0179 (12) | 0.0265 (14) | 0.0216 (14) | 0.0031 (10) | −0.0009 (9) | 0.0045 (11) |
C72 | 0.0254 (13) | 0.0260 (15) | 0.0280 (16) | 0.0038 (10) | −0.0007 (10) | 0.0001 (12) |
C73 | 0.0300 (14) | 0.0383 (17) | 0.0209 (15) | 0.0046 (12) | −0.0012 (10) | 0.0015 (12) |
C74 | 0.0221 (13) | 0.0332 (16) | 0.0279 (16) | 0.0040 (11) | −0.0004 (10) | 0.0091 (12) |
C75 | 0.0251 (13) | 0.0263 (15) | 0.0312 (16) | 0.0040 (11) | 0.0014 (10) | 0.0066 (12) |
C76 | 0.0208 (12) | 0.0281 (15) | 0.0217 (14) | 0.0027 (10) | 0.0005 (9) | 0.0023 (11) |
C77 | 0.0350 (15) | 0.0439 (18) | 0.0298 (17) | 0.0107 (13) | 0.0049 (12) | 0.0126 (14) |
Geometric parameters (Å, º) top
N1—C8A | 1.386 (3) | C11—H11B | 0.9800 |
N1—C2 | 1.393 (3) | C11—H11C | 0.9800 |
N1—C11 | 1.463 (3) | C31—H31A | 0.9800 |
C2—O2 | 1.214 (3) | C31—H31B | 0.9800 |
C2—N3 | 1.396 (3) | C31—H31C | 0.9800 |
N3—C4 | 1.383 (3) | C71—C72 | 1.386 (4) |
N3—C31 | 1.472 (3) | C71—C76 | 1.404 (3) |
C4—O4 | 1.223 (3) | C72—C73 | 1.392 (3) |
C4—C4A | 1.463 (3) | C72—H72 | 0.9500 |
C4A—C5 | 1.386 (4) | C73—C74 | 1.384 (4) |
C4A—C8A | 1.395 (3) | C73—H73 | 0.9500 |
C5—C6 | 1.389 (3) | C74—C75 | 1.385 (4) |
C5—H5 | 0.9500 | C74—C77 | 1.513 (3) |
C6—C7 | 1.401 (3) | C75—C76 | 1.398 (3) |
C6—H6 | 0.9500 | C75—H75 | 0.9500 |
C7—N8 | 1.342 (3) | C76—H76 | 0.9500 |
C7—C71 | 1.484 (3) | C77—H77A | 0.9800 |
N8—C8A | 1.342 (3) | C77—H77B | 0.9800 |
C11—H11A | 0.9800 | C77—H77C | 0.9800 |
| | | |
C8A—N1—C2 | 122.0 (2) | H11A—C11—H11C | 109.5 |
C8A—N1—C11 | 120.0 (2) | H11B—C11—H11C | 109.5 |
C2—N1—C11 | 117.9 (2) | N3—C31—H31A | 109.5 |
O2—C2—N1 | 121.8 (2) | N3—C31—H31B | 109.5 |
O2—C2—N3 | 121.6 (2) | H31A—C31—H31B | 109.5 |
N1—C2—N3 | 116.6 (2) | N3—C31—H31C | 109.5 |
C4—N3—C2 | 125.6 (2) | H31A—C31—H31C | 109.5 |
C4—N3—C31 | 117.3 (2) | H31B—C31—H31C | 109.5 |
C2—N3—C31 | 117.1 (2) | C72—C71—C76 | 118.4 (2) |
O4—C4—N3 | 121.2 (2) | C72—C71—C7 | 122.5 (2) |
O4—C4—C4A | 123.4 (2) | C76—C71—C7 | 119.1 (2) |
N3—C4—C4A | 115.4 (2) | C71—C72—C73 | 120.8 (2) |
C5—C4A—C8A | 118.0 (2) | C71—C72—H72 | 119.6 |
C5—C4A—C4 | 122.0 (2) | C73—C72—H72 | 119.6 |
C8A—C4A—C4 | 120.0 (2) | C74—C73—C72 | 121.1 (2) |
C4A—C5—C6 | 119.2 (2) | C74—C73—H73 | 119.5 |
C4A—C5—H5 | 120.4 | C72—C73—H73 | 119.5 |
C6—C5—H5 | 120.4 | C73—C74—C75 | 118.7 (2) |
C5—C6—C7 | 119.0 (2) | C73—C74—C77 | 120.8 (2) |
C5—C6—H6 | 120.5 | C75—C74—C77 | 120.5 (2) |
C7—C6—H6 | 120.5 | C74—C75—C76 | 120.8 (2) |
N8—C7—C6 | 122.1 (2) | C74—C75—H75 | 119.6 |
N8—C7—C71 | 115.9 (2) | C76—C75—H75 | 119.6 |
C6—C7—C71 | 122.0 (2) | C75—C76—C71 | 120.3 (2) |
C7—N8—C8A | 118.1 (2) | C75—C76—H76 | 119.9 |
N8—C8A—N1 | 116.1 (2) | C71—C76—H76 | 119.9 |
N8—C8A—C4A | 123.5 (2) | C74—C77—H77A | 109.5 |
N1—C8A—C4A | 120.4 (2) | C74—C77—H77B | 109.5 |
N1—C11—H11A | 109.5 | H77A—C77—H77B | 109.5 |
N1—C11—H11B | 109.5 | C74—C77—H77C | 109.5 |
H11A—C11—H11B | 109.5 | H77A—C77—H77C | 109.5 |
N1—C11—H11C | 109.5 | H77B—C77—H77C | 109.5 |
| | | |
C8A—N1—C2—O2 | −177.5 (2) | C7—N8—C8A—C4A | 1.1 (3) |
C11—N1—C2—O2 | −2.5 (3) | C2—N1—C8A—N8 | 179.36 (19) |
C8A—N1—C2—N3 | 2.1 (3) | C11—N1—C8A—N8 | 4.4 (3) |
C11—N1—C2—N3 | 177.12 (19) | C2—N1—C8A—C4A | −0.3 (3) |
O2—C2—N3—C4 | 177.9 (2) | C11—N1—C8A—C4A | −175.2 (2) |
N1—C2—N3—C4 | −1.7 (3) | C5—C4A—C8A—N8 | −1.9 (3) |
O2—C2—N3—C31 | −1.7 (3) | C4—C4A—C8A—N8 | 178.4 (2) |
N1—C2—N3—C31 | 178.73 (18) | C5—C4A—C8A—N1 | 177.7 (2) |
C2—N3—C4—O4 | −179.8 (2) | C4—C4A—C8A—N1 | −2.0 (3) |
C31—N3—C4—O4 | −0.2 (3) | N8—C7—C71—C72 | 160.1 (2) |
C2—N3—C4—C4A | −0.5 (3) | C6—C7—C71—C72 | −21.1 (3) |
C31—N3—C4—C4A | 179.10 (18) | N8—C7—C71—C76 | −18.7 (3) |
O4—C4—C4A—C5 | 1.9 (4) | C6—C7—C71—C76 | 160.1 (2) |
N3—C4—C4A—C5 | −177.4 (2) | C76—C71—C72—C73 | −0.4 (3) |
O4—C4—C4A—C8A | −178.4 (2) | C7—C71—C72—C73 | −179.2 (2) |
N3—C4—C4A—C8A | 2.3 (3) | C71—C72—C73—C74 | −0.6 (4) |
C8A—C4A—C5—C6 | 0.5 (3) | C72—C73—C74—C75 | 1.3 (4) |
C4—C4A—C5—C6 | −179.8 (2) | C72—C73—C74—C77 | −178.6 (2) |
C4A—C5—C6—C7 | 1.5 (3) | C73—C74—C75—C76 | −1.1 (3) |
C5—C6—C7—N8 | −2.4 (3) | C77—C74—C75—C76 | 178.8 (2) |
C5—C6—C7—C71 | 178.9 (2) | C74—C75—C76—C71 | 0.1 (3) |
C6—C7—N8—C8A | 1.1 (3) | C72—C71—C76—C75 | 0.6 (3) |
C71—C7—N8—C8A | 179.90 (18) | C7—C71—C76—C75 | 179.5 (2) |
C7—N8—C8A—N1 | −178.52 (18) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···O4i | 0.95 | 2.39 | 3.306 (3) | 161 |
Symmetry code: (i) −x, −y, −z+1. |
(II) 7-(biphenyl-4-yl)-1,3-dimethylpyrido[2,3-
d]pyrimidine-
2,4(1
H,3
H)-dione
top
Crystal data top
C21H17N3O2 | F(000) = 720 |
Mr = 343.38 | Dx = 1.450 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3613 reflections |
a = 7.2314 (5) Å | θ = 3.1–27.5° |
b = 17.5834 (18) Å | µ = 0.10 mm−1 |
c = 12.4864 (15) Å | T = 120 K |
β = 97.782 (8)° | Block, yellow |
V = 1573.1 (3) Å3 | 0.45 × 0.27 × 0.15 mm |
Z = 4 | |
Data collection top
Bruker–Nonius KappaCCD diffractometer | 3612 independent reflections |
Radiation source: Bruker-Nonius FR591 rotating anode | 1851 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.092 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.3° |
ϕ & ω scans | h = −9→9 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −22→22 |
Tmin = 0.947, Tmax = 0.986 | l = −16→16 |
40144 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)] = 0.073 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.244 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.138P)2 + 0.2972P] where P = (Fo2 + 2Fc2)/3 |
3612 reflections | (Δ/σ)max = 0.001 |
237 parameters | Δρmax = 0.48 e Å−3 |
0 restraints | Δρmin = −0.34 e Å−3 |
Crystal data top
C21H17N3O2 | V = 1573.1 (3) Å3 |
Mr = 343.38 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.2314 (5) Å | µ = 0.10 mm−1 |
b = 17.5834 (18) Å | T = 120 K |
c = 12.4864 (15) Å | 0.45 × 0.27 × 0.15 mm |
β = 97.782 (8)° | |
Data collection top
Bruker–Nonius KappaCCD diffractometer | 3612 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 1851 reflections with I > 2σ(I) |
Tmin = 0.947, Tmax = 0.986 | Rint = 0.092 |
40144 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.073 | 0 restraints |
wR(F2) = 0.244 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.48 e Å−3 |
3612 reflections | Δρmin = −0.34 e Å−3 |
237 parameters | |
Special details top
Experimental. Mass spectrum: MS (70 eV) m/z (%) = 343 (M+, 100), 314 (32),
231 (30). HR—MS found 343.1313 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | 0.3564 (3) | 0.34566 (13) | 0.64534 (19) | 0.0311 (6) | |
C2 | 0.3717 (4) | 0.26808 (16) | 0.6605 (2) | 0.0333 (7) | |
N3 | 0.2991 (3) | 0.22236 (13) | 0.57325 (19) | 0.0327 (6) | |
C4 | 0.2240 (4) | 0.24889 (16) | 0.4732 (2) | 0.0338 (7) | |
C4A | 0.2229 (4) | 0.33099 (15) | 0.4611 (2) | 0.0297 (7) | |
C5 | 0.1674 (4) | 0.36487 (17) | 0.3632 (3) | 0.0381 (8) | |
H5 | 0.1293 | 0.3348 | 0.3009 | 0.046* | |
C6 | 0.1674 (4) | 0.44308 (16) | 0.3561 (2) | 0.0361 (7) | |
H6 | 0.1311 | 0.4674 | 0.2886 | 0.043* | |
C7 | 0.2206 (4) | 0.48579 (16) | 0.4482 (2) | 0.0314 (7) | |
N8 | 0.2802 (3) | 0.45337 (13) | 0.54326 (19) | 0.0327 (6) | |
C8A | 0.2842 (3) | 0.37789 (15) | 0.5478 (2) | 0.0290 (7) | |
C11 | 0.4261 (4) | 0.39266 (17) | 0.7378 (2) | 0.0408 (8) | |
H11A | 0.3714 | 0.3755 | 0.8013 | 0.061* | |
H11B | 0.3915 | 0.4458 | 0.7222 | 0.061* | |
H11C | 0.5623 | 0.3883 | 0.7521 | 0.061* | |
O2 | 0.4440 (3) | 0.24105 (11) | 0.74449 (17) | 0.0406 (6) | |
C31 | 0.3064 (4) | 0.14025 (16) | 0.5885 (3) | 0.0396 (8) | |
H31A | 0.1801 | 0.1192 | 0.5734 | 0.059* | |
H32B | 0.3587 | 0.1286 | 0.6633 | 0.059* | |
H33C | 0.3853 | 0.1177 | 0.5390 | 0.059* | |
O4 | 0.1638 (3) | 0.20493 (11) | 0.40182 (17) | 0.0417 (6) | |
C71 | 0.2139 (3) | 0.57038 (16) | 0.4453 (2) | 0.0296 (7) | |
C72 | 0.1204 (4) | 0.60843 (15) | 0.3571 (2) | 0.0346 (7) | |
H72 | 0.0560 | 0.5804 | 0.2985 | 0.041* | |
C73 | 0.1205 (4) | 0.68687 (16) | 0.3538 (2) | 0.0342 (7) | |
H73 | 0.0569 | 0.7121 | 0.2922 | 0.041* | |
C74 | 0.2115 (4) | 0.72988 (16) | 0.4384 (2) | 0.0316 (7) | |
C75 | 0.3013 (4) | 0.69129 (16) | 0.5274 (2) | 0.0342 (7) | |
H75 | 0.3628 | 0.7192 | 0.5869 | 0.041* | |
C76 | 0.3025 (4) | 0.61227 (16) | 0.5308 (2) | 0.0326 (7) | |
H76 | 0.3650 | 0.5869 | 0.5925 | 0.039* | |
C81 | 0.2134 (4) | 0.81360 (16) | 0.4331 (2) | 0.0313 (7) | |
C82 | 0.2154 (4) | 0.85040 (16) | 0.3347 (2) | 0.0349 (7) | |
H82 | 0.2156 | 0.8213 | 0.2707 | 0.042* | |
C83 | 0.2170 (4) | 0.92868 (17) | 0.3291 (3) | 0.0403 (8) | |
H83 | 0.2168 | 0.9531 | 0.2612 | 0.048* | |
C84 | 0.2188 (4) | 0.97151 (17) | 0.4210 (3) | 0.0428 (8) | |
H84 | 0.2207 | 1.0255 | 0.4169 | 0.051* | |
C85 | 0.2180 (4) | 0.93597 (17) | 0.5196 (3) | 0.0417 (8) | |
H85 | 0.2189 | 0.9654 | 0.5835 | 0.050* | |
C86 | 0.2159 (4) | 0.85778 (16) | 0.5248 (2) | 0.0352 (7) | |
H86 | 0.2161 | 0.8337 | 0.5929 | 0.042* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0337 (13) | 0.0273 (13) | 0.0326 (14) | 0.0034 (10) | 0.0059 (11) | −0.0022 (10) |
C2 | 0.0306 (16) | 0.0302 (17) | 0.0399 (18) | 0.0024 (12) | 0.0086 (14) | −0.0009 (14) |
N3 | 0.0336 (13) | 0.0261 (13) | 0.0389 (15) | 0.0013 (10) | 0.0062 (11) | −0.0007 (11) |
C4 | 0.0307 (15) | 0.0320 (17) | 0.0399 (18) | −0.0028 (12) | 0.0099 (13) | 0.0007 (14) |
C4A | 0.0259 (14) | 0.0281 (16) | 0.0354 (17) | 0.0000 (11) | 0.0049 (12) | −0.0005 (12) |
C5 | 0.0356 (16) | 0.0392 (18) | 0.0388 (19) | −0.0012 (13) | 0.0022 (14) | −0.0026 (14) |
C6 | 0.0418 (17) | 0.0320 (17) | 0.0336 (17) | −0.0015 (13) | 0.0013 (14) | −0.0001 (13) |
C7 | 0.0282 (15) | 0.0306 (17) | 0.0360 (17) | −0.0014 (11) | 0.0060 (13) | −0.0010 (13) |
N8 | 0.0288 (13) | 0.0319 (14) | 0.0372 (15) | 0.0013 (10) | 0.0042 (11) | 0.0026 (11) |
C8A | 0.0266 (14) | 0.0261 (15) | 0.0348 (17) | 0.0015 (11) | 0.0059 (13) | 0.0008 (12) |
C11 | 0.0494 (18) | 0.0319 (17) | 0.0392 (18) | 0.0016 (14) | −0.0005 (15) | −0.0070 (13) |
O2 | 0.0463 (13) | 0.0354 (12) | 0.0390 (13) | 0.0064 (9) | 0.0019 (10) | 0.0044 (10) |
C31 | 0.0409 (17) | 0.0275 (17) | 0.051 (2) | 0.0035 (13) | 0.0092 (15) | 0.0019 (14) |
O4 | 0.0429 (12) | 0.0354 (12) | 0.0463 (14) | −0.0044 (9) | 0.0041 (10) | −0.0058 (10) |
C71 | 0.0258 (14) | 0.0283 (16) | 0.0350 (17) | −0.0008 (11) | 0.0052 (12) | 0.0021 (12) |
C72 | 0.0347 (16) | 0.0300 (16) | 0.0386 (18) | −0.0017 (12) | 0.0036 (13) | −0.0035 (13) |
C73 | 0.0307 (15) | 0.0330 (16) | 0.0382 (18) | 0.0031 (12) | 0.0024 (13) | 0.0036 (13) |
C74 | 0.0270 (14) | 0.0272 (16) | 0.0410 (18) | −0.0003 (11) | 0.0063 (13) | −0.0013 (13) |
C75 | 0.0317 (16) | 0.0341 (18) | 0.0374 (18) | −0.0035 (12) | 0.0064 (13) | −0.0008 (13) |
C76 | 0.0280 (15) | 0.0331 (17) | 0.0359 (17) | 0.0011 (12) | 0.0012 (13) | 0.0027 (13) |
C81 | 0.0267 (15) | 0.0300 (16) | 0.0372 (18) | −0.0006 (11) | 0.0046 (13) | −0.0013 (13) |
C82 | 0.0321 (16) | 0.0312 (16) | 0.0401 (18) | 0.0009 (12) | 0.0010 (13) | −0.0024 (13) |
C83 | 0.0395 (17) | 0.0363 (18) | 0.0440 (19) | −0.0003 (13) | 0.0020 (14) | 0.0011 (14) |
C84 | 0.0478 (19) | 0.0269 (16) | 0.053 (2) | −0.0016 (14) | 0.0032 (15) | 0.0021 (15) |
C85 | 0.0478 (19) | 0.0349 (18) | 0.0422 (19) | −0.0013 (14) | 0.0056 (15) | −0.0076 (14) |
C86 | 0.0340 (16) | 0.0334 (17) | 0.0378 (18) | −0.0037 (13) | 0.0038 (13) | 0.0039 (13) |
Geometric parameters (Å, º) top
N1—C2 | 1.380 (4) | C31—H33C | 0.9800 |
N1—C8A | 1.380 (3) | C71—C76 | 1.381 (4) |
N1—C11 | 1.453 (4) | C71—C72 | 1.385 (4) |
C2—O2 | 1.204 (3) | C72—C73 | 1.380 (4) |
C2—N3 | 1.398 (4) | C72—H72 | 0.9500 |
N3—C4 | 1.375 (4) | C73—C74 | 1.391 (4) |
N3—C31 | 1.456 (4) | C73—H73 | 0.9500 |
C4—O4 | 1.215 (3) | C74—C75 | 1.386 (4) |
C4—C4A | 1.451 (4) | C74—C81 | 1.474 (4) |
C4A—C5 | 1.370 (4) | C75—C76 | 1.390 (4) |
C4A—C8A | 1.386 (4) | C75—H75 | 0.9500 |
C5—C6 | 1.378 (4) | C76—H76 | 0.9500 |
C5—H5 | 0.9500 | C81—C86 | 1.382 (4) |
C6—C7 | 1.384 (4) | C81—C82 | 1.390 (4) |
C6—H6 | 0.9500 | C82—C83 | 1.378 (4) |
C7—N8 | 1.335 (3) | C82—H82 | 0.9500 |
C7—C71 | 1.488 (4) | C83—C84 | 1.371 (4) |
N8—C8A | 1.328 (3) | C83—H83 | 0.9500 |
C11—H11A | 0.9800 | C84—C85 | 1.382 (4) |
C11—H11B | 0.9800 | C84—H84 | 0.9500 |
C11—H11C | 0.9800 | C85—C86 | 1.377 (4) |
C31—H31A | 0.9800 | C85—H85 | 0.9500 |
C31—H32B | 0.9800 | C86—H86 | 0.9500 |
| | | |
C2—N1—C8A | 122.8 (2) | H31A—C31—H33C | 109.5 |
C2—N1—C11 | 116.1 (2) | H32B—C31—H33C | 109.5 |
C8A—N1—C11 | 121.1 (2) | C76—C71—C72 | 118.9 (3) |
O2—C2—N1 | 121.8 (3) | C76—C71—C7 | 120.3 (3) |
O2—C2—N3 | 121.6 (3) | C72—C71—C7 | 120.8 (3) |
N1—C2—N3 | 116.5 (3) | C73—C72—C71 | 120.3 (3) |
C4—N3—C2 | 125.0 (2) | C73—C72—H72 | 119.8 |
C4—N3—C31 | 117.3 (2) | C71—C72—H72 | 119.8 |
C2—N3—C31 | 117.7 (2) | C72—C73—C74 | 121.5 (3) |
O4—C4—N3 | 120.6 (3) | C72—C73—H73 | 119.2 |
O4—C4—C4A | 124.0 (3) | C74—C73—H73 | 119.2 |
N3—C4—C4A | 115.4 (3) | C75—C74—C73 | 117.7 (3) |
C5—C4A—C8A | 117.6 (3) | C75—C74—C81 | 121.2 (3) |
C5—C4A—C4 | 121.5 (3) | C73—C74—C81 | 121.0 (3) |
C8A—C4A—C4 | 120.9 (3) | C74—C75—C76 | 121.0 (3) |
C4A—C5—C6 | 119.3 (3) | C74—C75—H75 | 119.5 |
C4A—C5—H5 | 120.4 | C76—C75—H75 | 119.5 |
C6—C5—H5 | 120.4 | C71—C76—C75 | 120.6 (3) |
C5—C6—C7 | 119.4 (3) | C71—C76—H76 | 119.7 |
C5—C6—H6 | 120.3 | C75—C76—H76 | 119.7 |
C7—C6—H6 | 120.3 | C86—C81—C82 | 118.0 (3) |
N8—C7—C6 | 121.8 (3) | C86—C81—C74 | 121.6 (3) |
N8—C7—C71 | 117.0 (3) | C82—C81—C74 | 120.4 (3) |
C6—C7—C71 | 121.2 (3) | C83—C82—C81 | 120.7 (3) |
C8A—N8—C7 | 117.9 (3) | C83—C82—H82 | 119.6 |
N8—C8A—N1 | 116.9 (2) | C81—C82—H82 | 119.6 |
N8—C8A—C4A | 123.9 (3) | C84—C83—C82 | 120.3 (3) |
N1—C8A—C4A | 119.2 (2) | C84—C83—H83 | 119.8 |
N1—C11—H11A | 109.5 | C82—C83—H83 | 119.8 |
N1—C11—H11B | 109.5 | C83—C84—C85 | 119.8 (3) |
H11A—C11—H11B | 109.5 | C83—C84—H84 | 120.1 |
N1—C11—H11C | 109.5 | C85—C84—H84 | 120.1 |
H11A—C11—H11C | 109.5 | C86—C85—C84 | 119.7 (3) |
H11B—C11—H11C | 109.5 | C86—C85—H85 | 120.2 |
N3—C31—H31A | 109.5 | C84—C85—H85 | 120.2 |
N3—C31—H32B | 109.5 | C85—C86—C81 | 121.4 (3) |
H31A—C31—H32B | 109.5 | C85—C86—H86 | 119.3 |
N3—C31—H33C | 109.5 | C81—C86—H86 | 119.3 |
| | | |
C8A—N1—C2—O2 | 176.0 (2) | C4—C4A—C8A—N8 | −177.3 (2) |
C11—N1—C2—O2 | −2.3 (4) | C5—C4A—C8A—N1 | −174.4 (2) |
C8A—N1—C2—N3 | −3.8 (4) | C4—C4A—C8A—N1 | 3.5 (4) |
C11—N1—C2—N3 | 177.9 (2) | N8—C7—C71—C76 | 13.5 (4) |
O2—C2—N3—C4 | −176.2 (3) | C6—C7—C71—C76 | −166.5 (3) |
N1—C2—N3—C4 | 3.6 (4) | N8—C7—C71—C72 | −167.1 (2) |
O2—C2—N3—C31 | 2.6 (4) | C6—C7—C71—C72 | 12.9 (4) |
N1—C2—N3—C31 | −177.5 (2) | C76—C71—C72—C73 | 1.7 (4) |
C2—N3—C4—O4 | −179.9 (2) | C7—C71—C72—C73 | −177.8 (2) |
C31—N3—C4—O4 | 1.2 (4) | C71—C72—C73—C74 | −0.7 (4) |
C2—N3—C4—C4A | 0.0 (4) | C72—C73—C74—C75 | −0.7 (4) |
C31—N3—C4—C4A | −178.9 (2) | C72—C73—C74—C81 | 178.9 (2) |
O4—C4—C4A—C5 | −5.9 (4) | C73—C74—C75—C76 | 1.1 (4) |
N3—C4—C4A—C5 | 174.2 (2) | C81—C74—C75—C76 | −178.5 (2) |
O4—C4—C4A—C8A | 176.3 (3) | C72—C71—C76—C75 | −1.3 (4) |
N3—C4—C4A—C8A | −3.6 (4) | C7—C71—C76—C75 | 178.2 (2) |
C8A—C4A—C5—C6 | −2.6 (4) | C74—C75—C76—C71 | −0.1 (4) |
C4—C4A—C5—C6 | 179.5 (2) | C75—C74—C81—C86 | −32.7 (4) |
C4A—C5—C6—C7 | −1.0 (4) | C73—C74—C81—C86 | 147.7 (3) |
C5—C6—C7—N8 | 3.0 (4) | C75—C74—C81—C82 | 146.4 (3) |
C5—C6—C7—C71 | −177.0 (2) | C73—C74—C81—C82 | −33.2 (4) |
C6—C7—N8—C8A | −1.1 (4) | C86—C81—C82—C83 | −0.9 (4) |
C71—C7—N8—C8A | 178.9 (2) | C74—C81—C82—C83 | 179.9 (2) |
C7—N8—C8A—N1 | 176.3 (2) | C81—C82—C83—C84 | 0.8 (4) |
C7—N8—C8A—C4A | −2.8 (4) | C82—C83—C84—C85 | −0.4 (4) |
C2—N1—C8A—N8 | −178.8 (2) | C83—C84—C85—C86 | 0.2 (4) |
C11—N1—C8A—N8 | −0.6 (4) | C84—C85—C86—C81 | −0.4 (4) |
C2—N1—C8A—C4A | 0.4 (4) | C82—C81—C86—C85 | 0.7 (4) |
C11—N1—C8A—C4A | 178.6 (3) | C74—C81—C86—C85 | 179.9 (3) |
C5—C4A—C8A—N8 | 4.8 (4) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C75—H75···O2i | 0.95 | 2.39 | 3.294 (3) | 158 |
C76—H76···N8 | 0.95 | 2.48 | 2.805 (4) | 100 |
Symmetry code: (i) −x+1, y+1/2, −z+3/2. |
(III) 7-(4-fluorophenyl)-3-methylpyrido[2,3-
d]pyrimidine-
2,4(1
H,3
H)-dione
top
Crystal data top
C14H10FN3O2 | F(000) = 560 |
Mr = 271.25 | Dx = 1.559 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 2636 reflections |
a = 6.7658 (8) Å | θ = 3.4–27.5° |
b = 12.978 (2) Å | µ = 0.12 mm−1 |
c = 13.162 (2) Å | T = 120 K |
V = 1155.7 (3) Å3 | Block, yellow |
Z = 4 | 0.10 × 0.10 × 0.10 mm |
Data collection top
Bruker–Nonius KappaCCD diffractometer | 1538 independent reflections |
Radiation source: Bruker-Nonius FR591 rotating anode | 833 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.164 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.4° |
ϕ & ω scans | h = −8→8 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −14→16 |
Tmin = 0.968, Tmax = 0.988 | l = −16→17 |
11820 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)] = 0.064 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.155 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0734P)2] where P = (Fo2 + 2Fc2)/3 |
1538 reflections | (Δ/σ)max = 0.001 |
182 parameters | Δρmax = 0.29 e Å−3 |
0 restraints | Δρmin = −0.36 e Å−3 |
Crystal data top
C14H10FN3O2 | V = 1155.7 (3) Å3 |
Mr = 271.25 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 6.7658 (8) Å | µ = 0.12 mm−1 |
b = 12.978 (2) Å | T = 120 K |
c = 13.162 (2) Å | 0.10 × 0.10 × 0.10 mm |
Data collection top
Bruker–Nonius KappaCCD diffractometer | 1538 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 833 reflections with I > 2σ(I) |
Tmin = 0.968, Tmax = 0.988 | Rint = 0.164 |
11820 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.064 | 0 restraints |
wR(F2) = 0.155 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.29 e Å−3 |
1538 reflections | Δρmin = −0.36 e Å−3 |
182 parameters | |
Special details top
Experimental. Mass spectrum: MS (70 eV) m/z (%) = 271 (M+, 100), 242 (19),
214 (22), 187 (19), 158 (18), 69 (27). HRMS found 271.0752 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | 0.4355 (5) | 0.3063 (3) | 0.2496 (3) | 0.0293 (10) | |
H1 | 0.4473 | 0.3734 | 0.2574 | 0.035* | |
C2 | 0.4439 (7) | 0.2678 (4) | 0.1534 (4) | 0.0288 (12) | |
N3 | 0.4185 (6) | 0.1613 (3) | 0.1439 (3) | 0.0289 (9) | |
C4 | 0.3932 (6) | 0.0941 (4) | 0.2250 (3) | 0.0277 (11) | |
C4A | 0.3878 (6) | 0.1408 (3) | 0.3250 (3) | 0.0239 (10) | |
C5 | 0.3664 (6) | 0.0822 (4) | 0.4131 (4) | 0.0288 (11) | |
H5 | 0.3537 | 0.0094 | 0.4092 | 0.035* | |
C6 | 0.3638 (7) | 0.1316 (4) | 0.5063 (3) | 0.0304 (12) | |
H6 | 0.3467 | 0.0933 | 0.5672 | 0.036* | |
C7 | 0.3865 (6) | 0.2386 (4) | 0.5097 (3) | 0.0250 (11) | |
N8 | 0.4092 (5) | 0.2959 (3) | 0.4250 (3) | 0.0263 (9) | |
C8A | 0.4096 (6) | 0.2463 (3) | 0.3366 (3) | 0.0250 (11) | |
O2 | 0.4729 (5) | 0.3226 (3) | 0.0793 (3) | 0.0396 (10) | |
C31 | 0.4311 (8) | 0.1208 (4) | 0.0399 (3) | 0.0375 (13) | |
H31A | 0.4326 | 0.0453 | 0.0418 | 0.056* | |
H31B | 0.5526 | 0.1458 | 0.0077 | 0.056* | |
H31C | 0.3165 | 0.1443 | 0.0007 | 0.056* | |
O4 | 0.3753 (4) | 0.0001 (2) | 0.2097 (2) | 0.0345 (8) | |
C71 | 0.3861 (6) | 0.2981 (4) | 0.6059 (3) | 0.0264 (11) | |
C72 | 0.4119 (7) | 0.2510 (4) | 0.7002 (3) | 0.0342 (13) | |
H72 | 0.4283 | 0.1783 | 0.7034 | 0.041* | |
C73 | 0.4141 (6) | 0.3080 (4) | 0.7901 (4) | 0.0339 (12) | |
H73 | 0.4327 | 0.2755 | 0.8541 | 0.041* | |
C74 | 0.3887 (7) | 0.4122 (4) | 0.7827 (4) | 0.0338 (12) | |
C75 | 0.3643 (7) | 0.4628 (4) | 0.6932 (4) | 0.0333 (12) | |
H75 | 0.3487 | 0.5355 | 0.6913 | 0.040* | |
C76 | 0.3630 (7) | 0.4039 (4) | 0.6036 (4) | 0.0301 (12) | |
H76 | 0.3458 | 0.4375 | 0.5401 | 0.036* | |
F74 | 0.3872 (5) | 0.4691 (2) | 0.86986 (19) | 0.0498 (9) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.034 (2) | 0.020 (2) | 0.034 (2) | 0.0022 (17) | −0.0023 (19) | −0.0002 (19) |
C2 | 0.029 (3) | 0.028 (3) | 0.029 (3) | 0.002 (2) | 0.001 (2) | 0.000 (3) |
N3 | 0.034 (2) | 0.025 (2) | 0.027 (2) | 0.0004 (19) | 0.0003 (19) | −0.0028 (18) |
C4 | 0.024 (2) | 0.029 (3) | 0.031 (3) | 0.000 (2) | −0.004 (2) | 0.000 (2) |
C4A | 0.020 (2) | 0.024 (3) | 0.028 (2) | 0.004 (2) | −0.001 (2) | −0.001 (2) |
C5 | 0.028 (2) | 0.022 (3) | 0.037 (3) | 0.001 (2) | −0.002 (2) | 0.002 (2) |
C6 | 0.031 (3) | 0.024 (3) | 0.036 (3) | 0.000 (2) | −0.003 (2) | 0.007 (2) |
C7 | 0.017 (2) | 0.029 (3) | 0.029 (3) | −0.001 (2) | 0.002 (2) | 0.001 (2) |
N8 | 0.026 (2) | 0.023 (2) | 0.030 (2) | −0.0027 (17) | −0.0020 (19) | −0.0034 (19) |
C8A | 0.024 (2) | 0.019 (3) | 0.032 (3) | 0.0035 (19) | 0.000 (2) | 0.005 (2) |
O2 | 0.056 (2) | 0.036 (2) | 0.0266 (18) | −0.0018 (18) | 0.0011 (17) | 0.0016 (18) |
C31 | 0.048 (3) | 0.031 (3) | 0.033 (3) | 0.004 (2) | −0.003 (3) | −0.007 (3) |
O4 | 0.0417 (18) | 0.0234 (18) | 0.0383 (19) | −0.0005 (17) | −0.0011 (16) | −0.0025 (17) |
C71 | 0.020 (2) | 0.032 (3) | 0.027 (2) | −0.002 (2) | 0.003 (2) | 0.000 (2) |
C72 | 0.033 (3) | 0.031 (3) | 0.038 (3) | −0.002 (2) | −0.001 (2) | 0.000 (3) |
C73 | 0.028 (3) | 0.043 (3) | 0.031 (3) | −0.005 (3) | −0.001 (2) | 0.003 (3) |
C74 | 0.035 (3) | 0.042 (3) | 0.024 (3) | −0.008 (3) | 0.005 (2) | −0.012 (3) |
C75 | 0.032 (2) | 0.025 (3) | 0.043 (3) | −0.004 (2) | 0.007 (2) | −0.011 (2) |
C76 | 0.027 (2) | 0.026 (3) | 0.038 (3) | −0.002 (2) | 0.010 (2) | −0.001 (2) |
F74 | 0.0562 (18) | 0.056 (2) | 0.0373 (17) | −0.0062 (17) | 0.0028 (15) | −0.0146 (16) |
Geometric parameters (Å, º) top
N1—C2 | 1.362 (6) | C7—C71 | 1.483 (7) |
N1—C8A | 1.395 (5) | N8—C8A | 1.329 (5) |
N1—H1 | 0.8800 | C31—H31A | 0.9800 |
C2—O2 | 1.222 (5) | C31—H31B | 0.9800 |
C2—N3 | 1.399 (6) | C31—H31C | 0.9800 |
N3—C4 | 1.389 (6) | C71—C76 | 1.383 (6) |
N3—C31 | 1.468 (5) | C71—C72 | 1.394 (6) |
C4—O4 | 1.242 (5) | C72—C73 | 1.395 (7) |
C4—C4A | 1.449 (6) | C72—H72 | 0.9500 |
C4A—C8A | 1.386 (6) | C73—C74 | 1.367 (7) |
C4A—C5 | 1.395 (6) | C73—H73 | 0.9500 |
C5—C6 | 1.384 (7) | C74—C75 | 1.359 (6) |
C5—H5 | 0.9500 | C74—F74 | 1.364 (5) |
C6—C7 | 1.398 (6) | C75—C76 | 1.405 (7) |
C6—H6 | 0.9500 | C75—H75 | 0.9500 |
C7—N8 | 1.349 (5) | C76—H76 | 0.9500 |
| | | |
C2—N1—C8A | 124.3 (4) | N8—C8A—N1 | 116.7 (4) |
C2—N1—H1 | 117.9 | C4A—C8A—N1 | 118.3 (4) |
C8A—N1—H1 | 117.9 | N3—C31—H31A | 109.5 |
O2—C2—N1 | 122.3 (4) | N3—C31—H31B | 109.5 |
O2—C2—N3 | 121.5 (4) | H31A—C31—H31B | 109.5 |
N1—C2—N3 | 116.2 (4) | N3—C31—H31C | 109.5 |
C4—N3—C2 | 124.5 (4) | H31A—C31—H31C | 109.5 |
C4—N3—C31 | 120.0 (4) | H31B—C31—H31C | 109.5 |
C2—N3—C31 | 115.5 (4) | C76—C71—C72 | 118.0 (5) |
O4—C4—N3 | 120.2 (4) | C76—C71—C7 | 119.9 (4) |
O4—C4—C4A | 123.7 (4) | C72—C71—C7 | 122.1 (4) |
N3—C4—C4A | 116.0 (4) | C71—C72—C73 | 121.6 (5) |
C8A—C4A—C5 | 117.3 (4) | C71—C72—H72 | 119.2 |
C8A—C4A—C4 | 120.7 (4) | C73—C72—H72 | 119.2 |
C5—C4A—C4 | 122.0 (4) | C74—C73—C72 | 117.6 (5) |
C6—C5—C4A | 119.1 (4) | C74—C73—H73 | 121.2 |
C6—C5—H5 | 120.5 | C72—C73—H73 | 121.2 |
C4A—C5—H5 | 120.5 | C75—C74—F74 | 117.8 (4) |
C5—C6—C7 | 119.1 (5) | C75—C74—C73 | 123.7 (4) |
C5—C6—H6 | 120.4 | F74—C74—C73 | 118.5 (5) |
C7—C6—H6 | 120.4 | C74—C75—C76 | 117.7 (4) |
N8—C7—C6 | 122.2 (4) | C74—C75—H75 | 121.1 |
N8—C7—C71 | 114.8 (4) | C76—C75—H75 | 121.1 |
C6—C7—C71 | 122.9 (4) | C71—C76—C75 | 121.4 (5) |
C8A—N8—C7 | 117.2 (4) | C71—C76—H76 | 119.3 |
N8—C8A—C4A | 125.0 (4) | C75—C76—H76 | 119.3 |
| | | |
C8A—N1—C2—O2 | −177.7 (4) | C7—N8—C8A—N1 | −179.3 (4) |
C8A—N1—C2—N3 | 1.9 (6) | C5—C4A—C8A—N8 | −0.9 (7) |
O2—C2—N3—C4 | 177.2 (4) | C4—C4A—C8A—N8 | −179.1 (4) |
N1—C2—N3—C4 | −2.4 (6) | C5—C4A—C8A—N1 | 178.6 (4) |
O2—C2—N3—C31 | 0.5 (7) | C4—C4A—C8A—N1 | 0.4 (6) |
N1—C2—N3—C31 | −179.1 (4) | C2—N1—C8A—N8 | 178.5 (4) |
C2—N3—C4—O4 | −178.7 (4) | C2—N1—C8A—C4A | −1.0 (6) |
C31—N3—C4—O4 | −2.1 (6) | N8—C7—C71—C76 | 14.6 (6) |
C2—N3—C4—C4A | 1.8 (6) | C6—C7—C71—C76 | −165.0 (4) |
C31—N3—C4—C4A | 178.4 (4) | N8—C7—C71—C72 | −164.3 (4) |
O4—C4—C4A—C8A | 179.7 (4) | C6—C7—C71—C72 | 16.1 (7) |
N3—C4—C4A—C8A | −0.8 (6) | C76—C71—C72—C73 | 0.1 (7) |
O4—C4—C4A—C5 | 1.6 (7) | C7—C71—C72—C73 | 179.1 (4) |
N3—C4—C4A—C5 | −178.9 (4) | C71—C72—C73—C74 | 0.5 (7) |
C8A—C4A—C5—C6 | 1.3 (6) | C72—C73—C74—C75 | −1.0 (7) |
C4—C4A—C5—C6 | 179.5 (4) | C72—C73—C74—F74 | 179.0 (4) |
C4A—C5—C6—C7 | −1.2 (7) | F74—C74—C75—C76 | −179.1 (4) |
C5—C6—C7—N8 | 0.6 (7) | C73—C74—C75—C76 | 0.8 (7) |
C5—C6—C7—C71 | −179.8 (4) | C72—C71—C76—C75 | −0.3 (7) |
C6—C7—N8—C8A | −0.1 (6) | C7—C71—C76—C75 | −179.2 (4) |
C71—C7—N8—C8A | −179.7 (4) | C74—C75—C76—C71 | −0.2 (6) |
C7—N8—C8A—C4A | 0.2 (7) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O4i | 0.88 | 2.08 | 2.874 (4) | 149 |
C76—H76···N8 | 0.95 | 2.42 | 2.755 (7) | 100 |
Symmetry code: (i) −x+1, y+1/2, −z+1/2. |
Crystal data top
C15H13N3O3 | F(000) = 592 |
Mr = 283.28 | Dx = 1.506 Mg m−3 |
Orthorhombic, Pca21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2c-2ac | Cell parameters from 1439 reflections |
a = 6.6312 (11) Å | θ = 3.0–27.5° |
b = 6.8121 (15) Å | µ = 0.11 mm−1 |
c = 27.653 (7) Å | T = 120 K |
V = 1249.2 (5) Å3 | Block, yellow |
Z = 4 | 0.28 × 0.24 × 0.22 mm |
Data collection top
Bruker–Nonius KappaCCD diffractometer | 1439 independent reflections |
Radiation source: Bruker-Nonius FR591 rotating anode | 1181 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.051 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.0° |
ϕ & ω scans | h = −8→8 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −8→8 |
Tmin = 0.961, Tmax = 0.977 | l = −35→24 |
8019 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) = 0.147 | H-atom parameters constrained |
S = 1.14 | w = 1/[σ2(Fo2) + (0.0462P)2 + 1.8263P] where P = (Fo2 + 2Fc2)/3 |
1439 reflections | (Δ/σ)max = 0.001 |
192 parameters | Δρmax = 0.36 e Å−3 |
1 restraint | Δρmin = −0.39 e Å−3 |
Crystal data top
C15H13N3O3 | V = 1249.2 (5) Å3 |
Mr = 283.28 | Z = 4 |
Orthorhombic, Pca21 | Mo Kα radiation |
a = 6.6312 (11) Å | µ = 0.11 mm−1 |
b = 6.8121 (15) Å | T = 120 K |
c = 27.653 (7) Å | 0.28 × 0.24 × 0.22 mm |
Data collection top
Bruker–Nonius KappaCCD diffractometer | 1439 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 1181 reflections with I > 2σ(I) |
Tmin = 0.961, Tmax = 0.977 | Rint = 0.051 |
8019 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.057 | 1 restraint |
wR(F2) = 0.147 | H-atom parameters constrained |
S = 1.14 | Δρmax = 0.36 e Å−3 |
1439 reflections | Δρmin = −0.39 e Å−3 |
192 parameters | |
Special details top
Experimental. Mass spectrum: MS (70 eV) m/z (%) = 283 (M+, 100), 254 (10),
226 (20), 155 (8). HR—MS found 283.0966 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | 0.4060 (6) | 0.2722 (6) | 0.12467 (14) | 0.0249 (9) | |
H1 | 0.5364 | 0.2894 | 0.1287 | 0.030* | |
C2 | 0.3255 (8) | 0.2656 (8) | 0.07964 (17) | 0.0273 (11) | |
N3 | 0.1173 (6) | 0.2446 (6) | 0.07641 (14) | 0.0250 (9) | |
C4 | −0.0076 (7) | 0.2280 (7) | 0.11555 (17) | 0.0231 (10) | |
C4A | 0.0882 (7) | 0.2336 (7) | 0.16283 (18) | 0.0226 (9) | |
C5 | −0.0217 (7) | 0.2147 (7) | 0.20436 (17) | 0.0225 (10) | |
H5 | −0.1642 | 0.2013 | 0.2032 | 0.027* | |
C6 | 0.0785 (8) | 0.2155 (7) | 0.24795 (16) | 0.0222 (10) | |
H6 | 0.0061 | 0.2011 | 0.2774 | 0.027* | |
C7 | 0.2882 (7) | 0.2380 (7) | 0.24835 (15) | 0.0176 (9) | |
N8 | 0.3962 (6) | 0.2585 (6) | 0.20775 (14) | 0.0216 (8) | |
C8A | 0.2960 (7) | 0.2552 (7) | 0.16624 (17) | 0.0211 (9) | |
O2 | 0.4287 (6) | 0.2763 (6) | 0.04349 (11) | 0.0355 (10) | |
C31 | 0.0296 (8) | 0.2343 (8) | 0.02801 (16) | 0.0288 (11) | |
H31A | 0.0433 | 0.1004 | 0.0154 | 0.043* | |
H31B | 0.1003 | 0.3259 | 0.0066 | 0.043* | |
H31C | −0.1135 | 0.2695 | 0.0296 | 0.043* | |
O4 | −0.1875 (5) | 0.2024 (7) | 0.11046 (13) | 0.0358 (10) | |
C71 | 0.3976 (8) | 0.2384 (7) | 0.29459 (15) | 0.0204 (11) | |
C72 | 0.3115 (7) | 0.1589 (7) | 0.33615 (15) | 0.0211 (10) | |
H72 | 0.1820 | 0.0999 | 0.3342 | 0.025* | |
C73 | 0.4093 (7) | 0.1639 (6) | 0.37970 (15) | 0.0198 (10) | |
H73 | 0.3475 | 0.1080 | 0.4075 | 0.024* | |
C74 | 0.5977 (7) | 0.2497 (7) | 0.38355 (15) | 0.0193 (10) | |
C75 | 0.6861 (7) | 0.3325 (7) | 0.34289 (15) | 0.0216 (10) | |
H75 | 0.8144 | 0.3940 | 0.3452 | 0.026* | |
C76 | 0.5862 (7) | 0.3248 (7) | 0.29893 (15) | 0.0194 (10) | |
H76 | 0.6482 | 0.3800 | 0.2711 | 0.023* | |
O7 | 0.6810 (5) | 0.2436 (5) | 0.42776 (12) | 0.0241 (8) | |
C77 | 0.8726 (8) | 0.3323 (8) | 0.43432 (19) | 0.0304 (11) | |
H77A | 0.9709 | 0.2699 | 0.4128 | 0.046* | |
H77C | 0.9157 | 0.3158 | 0.4680 | 0.046* | |
H77B | 0.8636 | 0.4726 | 0.4267 | 0.046* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0127 (17) | 0.040 (2) | 0.0217 (19) | −0.0025 (17) | 0.0008 (15) | 0.0036 (17) |
C2 | 0.025 (2) | 0.041 (3) | 0.016 (2) | 0.001 (2) | 0.000 (2) | 0.004 (2) |
N3 | 0.019 (2) | 0.035 (2) | 0.0209 (19) | 0.0017 (17) | −0.0045 (16) | 0.0007 (16) |
C4 | 0.021 (2) | 0.027 (2) | 0.022 (2) | 0.0028 (19) | 0.0014 (19) | −0.003 (2) |
C4A | 0.018 (2) | 0.025 (2) | 0.025 (2) | 0.0007 (19) | 0.000 (2) | −0.001 (2) |
C5 | 0.015 (2) | 0.025 (2) | 0.028 (2) | 0.0005 (18) | 0.0025 (19) | −0.007 (2) |
C6 | 0.020 (2) | 0.023 (2) | 0.023 (2) | 0.001 (2) | 0.0042 (18) | −0.0005 (18) |
C7 | 0.019 (2) | 0.019 (2) | 0.0155 (19) | −0.0004 (18) | 0.0006 (16) | 0.0004 (16) |
N8 | 0.0171 (17) | 0.028 (2) | 0.0196 (18) | 0.0001 (16) | 0.0001 (16) | 0.0020 (16) |
C8A | 0.018 (2) | 0.026 (2) | 0.019 (2) | 0.0005 (18) | 0.0021 (19) | −0.0001 (17) |
O2 | 0.0204 (17) | 0.069 (3) | 0.0172 (17) | −0.0022 (18) | 0.0024 (14) | 0.0054 (18) |
C31 | 0.025 (2) | 0.045 (3) | 0.017 (2) | 0.000 (2) | −0.0033 (19) | 0.002 (2) |
O4 | 0.0154 (16) | 0.067 (3) | 0.0252 (17) | 0.0009 (16) | −0.0007 (13) | −0.0022 (18) |
C71 | 0.018 (2) | 0.023 (3) | 0.021 (2) | 0.0020 (19) | 0.0001 (17) | −0.0015 (18) |
C72 | 0.019 (2) | 0.021 (2) | 0.023 (2) | −0.0018 (18) | 0.0024 (18) | 0.0000 (17) |
C73 | 0.023 (2) | 0.020 (2) | 0.016 (2) | 0.0000 (19) | 0.0063 (17) | 0.0010 (16) |
C74 | 0.019 (2) | 0.019 (2) | 0.019 (2) | 0.0024 (18) | 0.0016 (18) | −0.0021 (18) |
C75 | 0.018 (2) | 0.026 (3) | 0.021 (2) | −0.0008 (19) | −0.0009 (18) | 0.0007 (18) |
C76 | 0.020 (2) | 0.020 (2) | 0.018 (2) | 0.0031 (19) | 0.0027 (17) | −0.0002 (17) |
O7 | 0.0208 (17) | 0.033 (2) | 0.0180 (14) | −0.0026 (14) | −0.0007 (13) | −0.0001 (14) |
C77 | 0.026 (2) | 0.037 (3) | 0.028 (2) | −0.008 (2) | −0.0030 (19) | 0.002 (2) |
Geometric parameters (Å, º) top
N1—C2 | 1.356 (6) | C31—H31A | 0.9800 |
N1—C8A | 1.366 (6) | C31—H31B | 0.9800 |
N1—H1 | 0.8800 | C31—H31C | 0.9800 |
C2—O2 | 1.213 (6) | C71—C76 | 1.387 (7) |
C2—N3 | 1.391 (6) | C71—C72 | 1.393 (6) |
N3—C4 | 1.368 (6) | C72—C73 | 1.368 (6) |
N3—C31 | 1.461 (6) | C72—H72 | 0.9500 |
C4—O4 | 1.214 (6) | C73—C74 | 1.383 (6) |
C4—C4A | 1.454 (6) | C73—H73 | 0.9500 |
C4A—C5 | 1.366 (6) | C74—O7 | 1.342 (5) |
C4A—C8A | 1.389 (6) | C74—C75 | 1.388 (6) |
C5—C6 | 1.376 (6) | C75—C76 | 1.386 (6) |
C5—H5 | 0.9500 | C75—H75 | 0.9500 |
C6—C7 | 1.399 (7) | C76—H76 | 0.9500 |
C6—H6 | 0.9500 | O7—C77 | 1.419 (6) |
C7—N8 | 1.339 (6) | C77—H77A | 0.9800 |
C7—C71 | 1.470 (6) | C77—H77C | 0.9800 |
N8—C8A | 1.326 (6) | C77—H77B | 0.9800 |
| | | |
C2—N1—C8A | 124.1 (4) | H31A—C31—H31B | 109.5 |
C2—N1—H1 | 120.4 | N3—C31—H31C | 109.5 |
C8A—N1—H1 | 115.5 | H31A—C31—H31C | 109.5 |
O2—C2—N1 | 122.2 (4) | H31B—C31—H31C | 109.5 |
O2—C2—N3 | 120.8 (4) | C76—C71—C72 | 117.6 (4) |
N1—C2—N3 | 116.9 (4) | C76—C71—C7 | 121.4 (4) |
C4—N3—C2 | 124.0 (4) | C72—C71—C7 | 121.0 (4) |
C4—N3—C31 | 118.7 (4) | C73—C72—C71 | 121.5 (4) |
C2—N3—C31 | 117.3 (4) | C73—C72—H72 | 119.3 |
O4—C4—N3 | 121.0 (4) | C71—C72—H72 | 119.3 |
O4—C4—C4A | 122.5 (4) | C72—C73—C74 | 120.4 (4) |
N3—C4—C4A | 116.4 (4) | C72—C73—H73 | 119.8 |
C5—C4A—C8A | 118.8 (5) | C74—C73—H73 | 119.8 |
C5—C4A—C4 | 121.4 (4) | O7—C74—C73 | 115.4 (4) |
C8A—C4A—C4 | 119.8 (4) | O7—C74—C75 | 125.2 (4) |
C4A—C5—C6 | 118.6 (4) | C73—C74—C75 | 119.4 (4) |
C4A—C5—H5 | 120.7 | C76—C75—C74 | 119.5 (4) |
C6—C5—H5 | 120.7 | C76—C75—H75 | 120.2 |
C5—C6—C7 | 119.1 (4) | C74—C75—H75 | 120.2 |
C5—C6—H6 | 120.4 | C75—C76—C71 | 121.6 (4) |
C7—C6—H6 | 120.4 | C75—C76—H76 | 119.2 |
N8—C7—C6 | 122.4 (4) | C71—C76—H76 | 119.2 |
N8—C7—C71 | 117.7 (4) | C74—O7—C77 | 118.1 (4) |
C6—C7—C71 | 119.8 (4) | O7—C77—H77A | 109.5 |
C8A—N8—C7 | 117.1 (4) | O7—C77—H77C | 109.5 |
N8—C8A—N1 | 117.3 (4) | H77A—C77—H77C | 109.5 |
N8—C8A—C4A | 123.9 (4) | O7—C77—H77B | 109.5 |
N1—C8A—C4A | 118.8 (4) | H77A—C77—H77B | 109.5 |
N3—C31—H31A | 109.5 | H77C—C77—H77B | 109.5 |
N3—C31—H31B | 109.5 | | |
| | | |
C8A—N1—C2—O2 | −178.1 (5) | C2—N1—C8A—N8 | 178.0 (4) |
C8A—N1—C2—N3 | 1.5 (7) | C2—N1—C8A—C4A | −1.3 (7) |
O2—C2—N3—C4 | 178.7 (5) | C5—C4A—C8A—N8 | 0.1 (8) |
N1—C2—N3—C4 | −0.9 (7) | C4—C4A—C8A—N8 | −178.9 (5) |
O2—C2—N3—C31 | 0.6 (8) | C5—C4A—C8A—N1 | 179.4 (5) |
N1—C2—N3—C31 | −179.1 (5) | C4—C4A—C8A—N1 | 0.4 (7) |
C2—N3—C4—O4 | −177.1 (5) | N8—C7—C71—C76 | 22.9 (6) |
C31—N3—C4—O4 | 1.0 (7) | C6—C7—C71—C76 | −157.4 (5) |
C2—N3—C4—C4A | 0.1 (7) | N8—C7—C71—C72 | −159.8 (4) |
C31—N3—C4—C4A | 178.3 (4) | C6—C7—C71—C72 | 19.9 (7) |
O4—C4—C4A—C5 | −1.6 (8) | C76—C71—C72—C73 | −0.5 (7) |
N3—C4—C4A—C5 | −178.8 (5) | C7—C71—C72—C73 | −178.0 (4) |
O4—C4—C4A—C8A | 177.3 (5) | C71—C72—C73—C74 | 0.3 (7) |
N3—C4—C4A—C8A | 0.1 (6) | C72—C73—C74—O7 | −179.0 (4) |
C8A—C4A—C5—C6 | −0.8 (7) | C72—C73—C74—C75 | 0.6 (6) |
C4—C4A—C5—C6 | 178.2 (4) | O7—C74—C75—C76 | 178.4 (4) |
C4A—C5—C6—C7 | 0.8 (7) | C73—C74—C75—C76 | −1.2 (7) |
C5—C6—C7—N8 | −0.1 (8) | C74—C75—C76—C71 | 0.9 (7) |
C5—C6—C7—C71 | −179.8 (4) | C72—C71—C76—C75 | −0.1 (7) |
C6—C7—N8—C8A | −0.6 (7) | C7—C71—C76—C75 | 177.3 (4) |
C71—C7—N8—C8A | 179.1 (4) | C73—C74—O7—C77 | −178.8 (4) |
C7—N8—C8A—N1 | −178.7 (4) | C75—C74—O7—C77 | 1.6 (7) |
C7—N8—C8A—C4A | 0.6 (7) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O4i | 0.88 | 1.99 | 2.765 (5) | 146 |
C72—H72···Cgii | 0.95 | 2.65 | 3.448 (5) | 142 |
C75—H75···Cgiii | 0.95 | 2.75 | 3.548 (5) | 142 |
Symmetry codes: (i) x+1, y, z; (ii) x−1/2, −y, z; (iii) x+1/2, −y+1, z. |
Experimental details
| (I) | (II) | (III) | (IV) |
Crystal data |
Chemical formula | C16H15N3O2 | C21H17N3O2 | C14H10FN3O2 | C15H13N3O3 |
Mr | 281.31 | 343.38 | 271.25 | 283.28 |
Crystal system, space group | Triclinic, P1 | Monoclinic, P21/c | Orthorhombic, P212121 | Orthorhombic, Pca21 |
Temperature (K) | 120 | 120 | 120 | 120 |
a, b, c (Å) | 6.9953 (5), 7.9221 (7), 12.5140 (13) | 7.2314 (5), 17.5834 (18), 12.4864 (15) | 6.7658 (8), 12.978 (2), 13.162 (2) | 6.6312 (11), 6.8121 (15), 27.653 (7) |
α, β, γ (°) | 93.466 (4), 92.993 (6), 101.152 (6) | 90, 97.782 (8), 90 | 90, 90, 90 | 90, 90, 90 |
V (Å3) | 677.71 (11) | 1573.1 (3) | 1155.7 (3) | 1249.2 (5) |
Z | 2 | 4 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.09 | 0.10 | 0.12 | 0.11 |
Crystal size (mm) | 0.20 × 0.10 × 0.02 | 0.45 × 0.27 × 0.15 | 0.10 × 0.10 × 0.10 | 0.28 × 0.24 × 0.22 |
|
Data collection |
Diffractometer | Bruker–Nonius KappaCCD diffractometer | Bruker–Nonius KappaCCD diffractometer | Bruker–Nonius KappaCCD diffractometer | Bruker–Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.972, 0.998 | 0.947, 0.986 | 0.968, 0.988 | 0.961, 0.977 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11686, 2989, 1699 | 40144, 3612, 1851 | 11820, 1538, 833 | 8019, 1439, 1181 |
Rint | 0.080 | 0.092 | 0.164 | 0.051 |
(sin θ/λ)max (Å−1) | 0.652 | 0.650 | 0.649 | 0.650 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.065, 0.200, 1.03 | 0.073, 0.244, 1.03 | 0.064, 0.155, 1.00 | 0.057, 0.147, 1.14 |
No. of reflections | 2989 | 3612 | 1538 | 1439 |
No. of parameters | 193 | 237 | 182 | 192 |
No. of restraints | 0 | 0 | 0 | 1 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.45, −0.35 | 0.48, −0.34 | 0.29, −0.36 | 0.36, −0.39 |
Selected interplanar angles (°) for (I)–(IV) topAngle | (I) | (II) | (III) | (IV) |
Pyridine/C71–C76 | 19.7 (2) | 12.8 (2) | 15.3 (2) | 21.7 (2) |
C71–C76/C81–C86 | | 33.0 (2) | | |
Pyridine/C81–C86 | | 20.3 (2) | | |
Hydrogen bonds and short intramolecular contacts (Å, °)
for (I)–(IV) topCompound | D—H···A | D—H | H···A | D···A | D—H···A |
(I) | C5—H5···O4i | 0.95 | 2.39 | 3.306 (3) | 161 |
(II) | C75—H75···O2ii | 0.95 | 2.39 | 3.294 (3) | 158 |
| C76—H76···N8 | 0.95 | 2.48 | 2.805 (4) | 100 |
(III) | N1—H1···O4iii | 0.88 | 2.08 | 2.874 (4) | 149 |
| C76—H76···N8 | 0.95 | 2.42 | 2.753 (5) | 100 |
(IV) | N1—H1···O4iv | 0.88 | 1.99 | 2.765 (5) | 146 |
| C72—H72···Cgv | 0.95 | 2.65 | 3.448 (5) | 142 |
| C75—H75···Cgvi | 0.95 | 2.75 | 3.548 (5) | 142 |
Cg represents the centroid of the C71–C76 ring. Symmetry codes:
(i) -x, -y, -z+1; (ii) -x+1, y+1/2, -z+3/2;
(iii) -x+1, y+1/2, -z+1/2;
(iv) x+1, y, z; (v) x-0.5, -y, z;
(vi) x+1/2, -y+1, z. |
Pyrido[2,3-d]pyrimidine heterocycles (also known as 5-deazapteridines) have received considerable attention over the past decade as a result of the wide range of biological activity that they exhibit (Devi et al., 2003; Tu et al., 2008), including for example bronchodilator, vasodilator, antiallergic, cardiotonic, antihypertensive or hepatoprotective activities, as well as for their role in the treatment of proliferative diseases (Devi et al., 2004). As part of a wide-ranging project on the synthesis and characterization of fused pyrimidine systems under solvent-free conditions, we report here the structures of four examples of 7-arylpyrido[2,3-d]pyrimidine derivatives prepared by cyclocondensation reactions between 6-aminopyrimidin-5-carboxaldehydes and acetophenones, utilizing solvent-free fusion reactions promoted by BF3–Et2O catalysis.
While the molecular structures of the pair of compounds 1,3-dimethyl-7-(4-methylphenyl)pyrido[2,3-d]pyrimidine-2,4(1H,3H)-dione, (I), and 7-(1,1'-biphenyl-4-yl)-1,3-dimethylpyrido[2,3-d]pyrimidine-2,4(1H,3H)-dione, (II) (Figs. 1 and 2), are broadly similar in constitution and very similar in conformation, they exhibit significant differences in their crystal structures, in particular in their space groups and in their pattern of supramolecular aggregation. Similarly, the pair of compounds 7-(4-fluorophenyl)-3-methylpyrido[2,3-d]pyrimidine-2,4(1H,3H)-dione, (III), and 7-(4-methoxyphenyl)-3-methylpyrido[2,3-d]pyrimidine-2,4(1H,3H)-dione, (IV) (Figs. 3 and 4), which are closely related to (I) and (II), have similar constitutions and conformations, but again they crystallize in different space groups and they exhibit different patterns of supramolecular aggregation. Overall, no two of the compounds reported here crystallize in the same space group or have similar unit-cell dimensions or exhibit the same pattern of direction-specific intermolecular interactions.
The molecular conformations are straightforwardly definable in terms of the interplanar angle between the pyridine ring and the pendent aryl ring (C71–C76), with an additional angle between the two rings of the biphenyl-4-yl substituent in (II) (Table1). These angles indicate that the molecular skeletons do not much deviate from overall planarity, a point emphasized by the very small deviation, 0.012 (5) Å, of the methoxy C atom from the plane of the adjacent aryl ring in (IV). The bond distances and angles show no unexpected values.
In our analysis of the intermolecular interactions, we have discounted all intermolecular contacts involving methyl C—H bonds, on the usual grounds that these bonds are of low acidity, while the rotation about the adjacent C—C bonds of methyl groups bonded to planar rings are hindered by extremely low barriers, typically a few joules per mole (Tannenbaum et al., 1956; Naylor & Wilson, 1957), and so are likely to be undergoing very fast rotation about the adjacent C—C bonds.
In (I), there is a single C—H···O hydrogen bond utilizing a pyridine C—H bond as the donor (Table 2), and this links pairs of molecules into centrosymmetric dimers characterized by an R22(10) (Bernstein et al., 1995) motif. In addition, the pyridine rings of the molecules at (x, y, z) and (-x, -y + 1, -z + 1) are strictly parallel, with an interplanar spacing of 3.439 (2) Å; the corresponding ring-centroid separation is 3.693 (2) Å, with a near-ideal ring-centroid offset of 1.345 (2) Å. The combined effect of these two interactions is to link the molecules into a π-stacked chain of hydrogen-bonded dimers, running parallel to the [010] direction, with R22(10) rings centred at (0, n, 1/2), where n represents an integer, alternating with π–π stacking interactions across (0, n + 1/2, 1/2), where n represents an integer (Fig. 5).
The crystal structure of (II) also contains just one intermolecular C—H···O hydrogen bond, but this now involves an aryl C—H bond as the donor (Table 2), and its effect is to link molecules related by the 21 screw axis along (1/2, y, 3/4) into a C(10) chain running parallel to the [010] direction. The pyridine and phenyl rings in the molecules at (x, y, z) and (-x, -y + 1, -z + 1), respectively, are not parallel, but the dihedral angle between them is only 12.8 (2)°; the ring-centroid separation is 3.718 (2) Å and the interplanar distance is ca 3.53 Å, corresponding to a ring-centroid offset of ca 1.17 Å. Thus, these centrosymmetrically related molecules are weakly linked by the π–π stacking interaction and the overall effect of this is to link the hydrogen-bonded chain into a sheet parallel to (102) (Fig. 6).
In each of (III) and (IV), a single N—H···O hydrogen-bond links the molecules into a C(6) chain. Although the same hydrogen-bond donor and acceptor are utilized in each structure, the construction and orientation of the chains is different. In (III), the chain consists of molecules related by a 21 screw axis parallel to the [010] direction, while the chain in (IV) consists of molecules related by translation along [100]. In addition, the subsequent linking of the chains is different in the two structures. The pyridine ring in the molecule of (III) at (x, y, z) makes angles of 1.1 (2)° with the phenyl ring in each of the molecules at (x + 1/2, -y + 1/2, -z + 1) and (x - 1/2, -y + 1/2, -z + 1), with ring-centroid separations of 3.759 (2) Å and 3.748 (2) Å respectively. The interplanar spacings are ca 3.315 and ca 3.39 Å, respectively, corresponding to ring centroid offsets of ca 1.77 and ca 1.60 Å, respectively. The cooperative action of these two independent stacking interactions along [100] links the hydrogen-bonded chains along [010] into a sheet parallel to (001) (Fig. 7). In the structure of (IV), by contrast, the chains generated by the C—H···O hydrogen bond are linked by two independent C—H···π(arene) hydrogen bonds, both involving the same ring as the acceptor. The C71–C76 ring in the molecule at (x, y, z) acts as a hydrogen-bond acceptor from C72 in the molecule at (x + 1/2, -y, z) and from C75 in the molecule at (x - 1/2, -y + 1, z), so forming a chain running parallel to the [110] direction; the two C—H···π hydrogen bonds lie on opposite faces of the ring, with C···Cg···C and H···Cg···H angles of 179 and 177°, respectively. The combination of the [100] and [110] chains then generates a sheet parallel to (001) (Fig. 8).
In view of the different patterns of supramolecular aggregation found here for (I)–(IV), it is of interest briefly to compare these structures with those of the closely related compounds (V) [Cambridge Structural Database (Allen, 2002) refcode QOQQIW (Sarkhel et al., 2001)] and (VI) (XEBCUD; Wang et al., 2006). The crystal structure of (V) was described (Sarkhel et al., 2001) as containing C—H···O and C—H···Br hydrogen bonds and π–π stacking interactions, although the structural effects of these interactions were not specified. However, it is now well established that Br and Cl bonded to C are both exceptionally poor acceptors of hydrogen bonds, even from O—H and N—H units, so that the C—H···Br contacts in (V) and the C—H···Cl contacts in (VI) are likely to be no more than normal van der Waals contacts (Brammer et al., 2001; Thallypally & Nangia, 2001). Accordingly, the structure of (V) consists of C(10) hydrogen-bonded chains, running parallel to the [001] direction and built from a single C—H···O hydrogen bond; antiparallel pairs of these chains, related by inversion, are linked by the π—π stacking interaction (Fig. 9). The original report on (VI) (Wang et al., 2006) stated that `the crystal structure is stabilized by N—H···O, C—H···O and C—H···Cl hydrogen bonds', but it gave no information as to the actions of these interactions. Re-examination of this structure shows that most of the so-called hydrogen bonds listed by the authors have H···A distances far too long to be of structural significance. In the event, only two hydrogen bonds linking the heterocyclic components are significant, and they link these molecules into chains of centrosymmetric rings running parallel to the [001] direction: the dimethylformamide molecules are pendent from the chain, but they play no other role in the hydrogen bonding. Within the chain, R22(8) rings containing paired N—H···O hydrogen bonds are centred at (0, 0, n), where n represents an integer, and these alternate with R22(16) rings containing paired C—H···O hydrogen bonds, which are centred at (0, 0, 1/2 + n), where n represents an integer (Fig. 10). These chains are further linked by a π–π stacking interaction to form a sheet parallel to (100).