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The molecules of 2-amino-4,6-bis[
N-methyl-
N-(4-methylphenyl)amino]pyrimidine-5-carbaldehyde, C
21H
23N
5O, (I), and 2-amino-4-(indolin-1-yl)-6-methoxypyrimidine-5-carbaldehyde, C
14H
14N
4O
2, (II), which crystallizes with
Z' = 2 in the space group
P, exhibit polarized electronic structures. Molecules of (I) are linked by a combination of N-H
O, C-H
O and C-H
(arene) hydrogen bonds into a three-dimensional framework structure, while those of (II) are linked into sheets by a combination of two N-H
O hydrogen bonds and one N-H
(arene) hydrogen bond.
Supporting information
CCDC references: 669202; 669203
For the synthesis of (I), a solution of 2-amino-4,6-dichloro-5-formylpyrimidine (1 mmol), N-methyltoluidine (2 mmol) and triethylamine (2 mmol) in ethanol (5.0 ml) was heated under reflux for 3 h. The solution was cooled to ambient temperature, and the resulting solid product was collected by filtration, washed with ethanol and dried under atmospheric pressure to provide a yellow crystalline solid (yield 50%, m.p. 494–495 K).
For the synthesis of (II), a solution of 2-amino-4,6-dichloro-5-formylpyrimidine (1 mmol), indoline (1 mmol) and a catalytic quantity of sodium hydroxide (one pellet) in methanol (5.0 ml) was stirred at room temperature for 1 h. The resulting solid product was collected by filtration, washed with methanol and dried at atmospheric pressure to provide a colourless solid (yield 60%, m.p. 446–447 K).
Crystals of (I) and (II) suitable for single-crystal X-ray diffraction were grown by slow evaporation of solutions in ethanol.
Crystals of both (I) and (II) are triclinic. For each, the space group P1 was selected and confirmed by the subsequent structure analysis. All H atoms were located in difference maps and then treated as riding atoms in geometrically idealized positions, with distances C—H = 0.95 (aromatic and formyl), 0.86 [0.98?] (CH3) or 0.99 Å (CH2), and N—H = 0.86 Å, and with Uiso(H) = kUeq(carrier), where k = 1.5 for the methyl groups and 1.2 for all other H atoms.
For both compounds, data collection: COLLECT (Nonius, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: OSCAIL (McArdle, 2003) and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and PRPKAPPA (Ferguson, 1999).
(I) 2-amino-4,6-bis[
N-methyl-
N-(4-methylphenyl)amino]pyrimidine-5-carbaldehyde
top
Crystal data top
C21H23N5O | Z = 2 |
Mr = 361.44 | F(000) = 384 |
Triclinic, P1 | Dx = 1.289 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.6844 (6) Å | Cell parameters from 4249 reflections |
b = 10.7807 (19) Å | θ = 3.1–27.5° |
c = 10.8903 (10) Å | µ = 0.08 mm−1 |
α = 69.998 (14)° | T = 120 K |
β = 88.918 (7)° | Block, pale yellow |
γ = 76.822 (13)° | 0.31 × 0.24 × 0.21 mm |
V = 930.9 (2) Å3 | |
Data collection top
Bruker Nonius KappaCCD area-detector diffractometer | 4249 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 2988 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.046 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.1° |
ϕ and ω scans | h = −11→11 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −13→13 |
Tmin = 0.965, Tmax = 0.983 | l = −13→14 |
24528 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)] = 0.060 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.153 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0498P)2 + 0.9799P] where P = (Fo2 + 2Fc2)/3 |
4249 reflections | (Δ/σ)max < 0.001 |
248 parameters | Δρmax = 0.51 e Å−3 |
0 restraints | Δρmin = −0.35 e Å−3 |
Crystal data top
C21H23N5O | γ = 76.822 (13)° |
Mr = 361.44 | V = 930.9 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.6844 (6) Å | Mo Kα radiation |
b = 10.7807 (19) Å | µ = 0.08 mm−1 |
c = 10.8903 (10) Å | T = 120 K |
α = 69.998 (14)° | 0.31 × 0.24 × 0.21 mm |
β = 88.918 (7)° | |
Data collection top
Bruker Nonius KappaCCD area-detector diffractometer | 4249 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2988 reflections with I > 2σ(I) |
Tmin = 0.965, Tmax = 0.983 | Rint = 0.046 |
24528 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.060 | 0 restraints |
wR(F2) = 0.153 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.51 e Å−3 |
4249 reflections | Δρmin = −0.35 e Å−3 |
248 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O51 | 0.45664 (19) | 0.24611 (16) | 0.02414 (15) | 0.0302 (4) | |
N1 | −0.0523 (2) | 0.37964 (18) | 0.16743 (17) | 0.0230 (4) | |
N2 | −0.2446 (2) | 0.2764 (2) | 0.1403 (2) | 0.0329 (5) | |
N3 | 0.0124 (2) | 0.15860 (18) | 0.14617 (18) | 0.0250 (4) | |
N4 | 0.2709 (2) | 0.04097 (19) | 0.14906 (18) | 0.0273 (4) | |
N6 | 0.1444 (2) | 0.48684 (18) | 0.18302 (17) | 0.0220 (4) | |
C2 | −0.0891 (3) | 0.2718 (2) | 0.1497 (2) | 0.0245 (5) | |
C4 | 0.1659 (2) | 0.1597 (2) | 0.14363 (19) | 0.0214 (4) | |
C5 | 0.2165 (2) | 0.2801 (2) | 0.1315 (2) | 0.0209 (4) | |
C6 | 0.1005 (2) | 0.3810 (2) | 0.16149 (19) | 0.0200 (4) | |
C41 | 0.4289 (3) | 0.0048 (2) | 0.2085 (2) | 0.0255 (5) | |
C42 | 0.5501 (3) | −0.0805 (2) | 0.1694 (2) | 0.0358 (6) | |
C43 | 0.7003 (3) | −0.1183 (3) | 0.2292 (3) | 0.0411 (6) | |
C44 | 0.7380 (3) | −0.0734 (2) | 0.3271 (2) | 0.0354 (6) | |
C45 | 0.6154 (3) | 0.0109 (2) | 0.3648 (2) | 0.0313 (5) | |
C46 | 0.4628 (3) | 0.0473 (2) | 0.3088 (2) | 0.0273 (5) | |
C47 | 0.2144 (3) | −0.0624 (3) | 0.1217 (3) | 0.0357 (6) | |
C51 | 0.3530 (3) | 0.3178 (2) | 0.0634 (2) | 0.0239 (4) | |
C61 | 0.2931 (2) | 0.4608 (2) | 0.2551 (2) | 0.0210 (4) | |
C62 | 0.3294 (3) | 0.3548 (2) | 0.3741 (2) | 0.0255 (5) | |
C63 | 0.4722 (3) | 0.3291 (2) | 0.4439 (2) | 0.0279 (5) | |
C64 | 0.5800 (3) | 0.4091 (2) | 0.3972 (2) | 0.0266 (5) | |
C65 | 0.5392 (3) | 0.5180 (2) | 0.2796 (2) | 0.0262 (5) | |
C66 | 0.3977 (2) | 0.5435 (2) | 0.2085 (2) | 0.0232 (4) | |
C67 | 0.0233 (3) | 0.6002 (2) | 0.1913 (2) | 0.0290 (5) | |
C441 | 0.9027 (3) | −0.1135 (3) | 0.3899 (3) | 0.0497 (8) | |
C641 | 0.7369 (3) | 0.3777 (3) | 0.4707 (3) | 0.0394 (6) | |
H2A | −0.3101 | 0.3406 | 0.1571 | 0.039* | |
H2B | −0.2742 | 0.2073 | 0.1355 | 0.039* | |
H42 | 0.5292 | −0.1125 | 0.1018 | 0.043* | |
H43 | 0.7811 | −0.1775 | 0.2022 | 0.049* | |
H45 | 0.6369 | 0.0446 | 0.4311 | 0.038* | |
H46 | 0.3806 | 0.1019 | 0.3396 | 0.033* | |
H47A | 0.1056 | −0.0251 | 0.0827 | 0.054* | |
H47B | 0.2165 | −0.1387 | 0.2032 | 0.054* | |
H47C | 0.2825 | −0.0940 | 0.0603 | 0.054* | |
H51 | 0.3627 | 0.4079 | 0.0478 | 0.029* | |
H62 | 0.2565 | 0.2996 | 0.4078 | 0.031* | |
H63 | 0.4966 | 0.2556 | 0.5249 | 0.034* | |
H65 | 0.6098 | 0.5758 | 0.2476 | 0.031* | |
H66 | 0.3724 | 0.6176 | 0.1281 | 0.028* | |
H67A | −0.0656 | 0.6198 | 0.1280 | 0.044* | |
H67B | 0.0675 | 0.6803 | 0.1715 | 0.044* | |
H67C | −0.0142 | 0.5774 | 0.2799 | 0.044* | |
H44A | 0.9518 | −0.2074 | 0.3975 | 0.075* | |
H44B | 0.8979 | −0.1063 | 0.4773 | 0.075* | |
H44C | 0.9659 | −0.0530 | 0.3360 | 0.075* | |
H64A | 0.7374 | 0.3086 | 0.5571 | 0.059* | |
H64B | 0.7538 | 0.4605 | 0.4812 | 0.059* | |
H64C | 0.8219 | 0.3436 | 0.4217 | 0.059* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O51 | 0.0299 (9) | 0.0301 (8) | 0.0298 (8) | −0.0076 (7) | 0.0071 (7) | −0.0093 (7) |
N1 | 0.0189 (9) | 0.0217 (9) | 0.0264 (9) | −0.0052 (7) | 0.0000 (7) | −0.0054 (7) |
N2 | 0.0226 (10) | 0.0331 (11) | 0.0442 (12) | −0.0119 (8) | −0.0008 (8) | −0.0115 (9) |
N3 | 0.0265 (10) | 0.0226 (9) | 0.0264 (9) | −0.0096 (7) | −0.0002 (7) | −0.0064 (7) |
N4 | 0.0278 (10) | 0.0248 (9) | 0.0262 (10) | −0.0013 (8) | 0.0004 (8) | −0.0080 (8) |
N6 | 0.0181 (9) | 0.0225 (9) | 0.0247 (9) | −0.0055 (7) | −0.0017 (7) | −0.0067 (7) |
C2 | 0.0230 (11) | 0.0259 (11) | 0.0224 (10) | −0.0088 (9) | −0.0019 (8) | −0.0036 (9) |
C4 | 0.0264 (11) | 0.0199 (10) | 0.0165 (9) | −0.0059 (8) | 0.0001 (8) | −0.0041 (8) |
C5 | 0.0187 (10) | 0.0218 (10) | 0.0205 (10) | −0.0037 (8) | −0.0016 (8) | −0.0059 (8) |
C6 | 0.0207 (10) | 0.0186 (10) | 0.0169 (9) | −0.0047 (8) | −0.0017 (8) | −0.0011 (8) |
C41 | 0.0291 (12) | 0.0187 (10) | 0.0239 (11) | −0.0035 (9) | 0.0038 (9) | −0.0028 (8) |
C42 | 0.0447 (15) | 0.0267 (12) | 0.0308 (12) | 0.0013 (11) | 0.0058 (11) | −0.0098 (10) |
C43 | 0.0374 (14) | 0.0331 (13) | 0.0399 (14) | 0.0064 (11) | 0.0111 (11) | −0.0064 (11) |
C44 | 0.0272 (12) | 0.0287 (12) | 0.0354 (13) | −0.0032 (10) | 0.0056 (10) | 0.0051 (10) |
C45 | 0.0320 (13) | 0.0261 (11) | 0.0297 (12) | −0.0067 (10) | 0.0000 (10) | −0.0022 (9) |
C46 | 0.0273 (12) | 0.0235 (11) | 0.0267 (11) | −0.0015 (9) | 0.0021 (9) | −0.0061 (9) |
C47 | 0.0375 (14) | 0.0330 (13) | 0.0395 (14) | −0.0099 (11) | 0.0053 (11) | −0.0152 (11) |
C51 | 0.0274 (11) | 0.0223 (10) | 0.0221 (10) | −0.0065 (9) | −0.0005 (8) | −0.0074 (8) |
C61 | 0.0209 (10) | 0.0206 (10) | 0.0220 (10) | −0.0042 (8) | −0.0005 (8) | −0.0085 (8) |
C62 | 0.0302 (12) | 0.0225 (11) | 0.0239 (11) | −0.0097 (9) | 0.0008 (9) | −0.0059 (9) |
C63 | 0.0339 (13) | 0.0250 (11) | 0.0209 (11) | −0.0023 (9) | −0.0035 (9) | −0.0055 (9) |
C64 | 0.0230 (11) | 0.0327 (12) | 0.0253 (11) | −0.0018 (9) | −0.0018 (8) | −0.0143 (9) |
C65 | 0.0237 (11) | 0.0296 (11) | 0.0283 (11) | −0.0109 (9) | 0.0044 (9) | −0.0108 (9) |
C66 | 0.0251 (11) | 0.0206 (10) | 0.0227 (10) | −0.0062 (8) | −0.0006 (8) | −0.0054 (8) |
C67 | 0.0270 (12) | 0.0225 (11) | 0.0369 (13) | −0.0038 (9) | −0.0045 (9) | −0.0105 (9) |
C441 | 0.0287 (14) | 0.0476 (16) | 0.0497 (17) | −0.0026 (12) | 0.0017 (12) | 0.0079 (13) |
C641 | 0.0282 (13) | 0.0509 (16) | 0.0385 (14) | −0.0025 (11) | −0.0083 (10) | −0.0188 (12) |
Geometric parameters (Å, º) top
N1—C2 | 1.347 (3) | C45—H45 | 0.95 |
C2—N3 | 1.345 (3) | C46—H46 | 0.95 |
N3—C4 | 1.336 (3) | C47—H47A | 0.98 |
C4—C5 | 1.426 (3) | C47—H47B | 0.98 |
C5—C6 | 1.427 (3) | C47—H47C | 0.98 |
C6—N1 | 1.330 (3) | C51—H51 | 0.95 |
C2—N2 | 1.345 (3) | C61—C66 | 1.386 (3) |
C4—N4 | 1.376 (3) | C61—C62 | 1.387 (3) |
C6—N6 | 1.374 (3) | C62—C63 | 1.389 (3) |
C5—C51 | 1.450 (3) | C62—H62 | 0.95 |
C51—O51 | 1.219 (3) | C63—C64 | 1.390 (3) |
N2—H2A | 0.86 | C63—H63 | 0.95 |
N2—H2B | 0.86 | C64—C65 | 1.394 (3) |
N4—C47 | 1.433 (3) | C64—C641 | 1.503 (3) |
N4—C41 | 1.439 (3) | C65—C66 | 1.386 (3) |
N6—C61 | 1.444 (3) | C65—H65 | 0.95 |
N6—C67 | 1.447 (3) | C66—H66 | 0.95 |
C41—C46 | 1.380 (3) | C67—H67A | 0.98 |
C41—C42 | 1.394 (3) | C67—H67B | 0.98 |
C42—C43 | 1.378 (4) | C67—H67C | 0.98 |
C42—H42 | 0.95 | C441—H44A | 0.98 |
C43—C44 | 1.384 (4) | C441—H44B | 0.98 |
C43—H43 | 0.95 | C441—H44C | 0.98 |
C44—C45 | 1.388 (3) | C641—H64A | 0.98 |
C44—C441 | 1.502 (4) | C641—H64B | 0.98 |
C45—C46 | 1.383 (3) | C641—H64C | 0.98 |
| | | |
C6—N1—C2 | 115.12 (18) | H47A—C47—H47B | 109.5 |
C2—N2—H2A | 117.8 | N4—C47—H47C | 109.5 |
C2—N2—H2B | 119.4 | H47A—C47—H47C | 109.5 |
H2A—N2—H2B | 121.2 | H47B—C47—H47C | 109.5 |
C4—N3—C2 | 116.53 (18) | O51—C51—C5 | 126.8 (2) |
C4—N4—C47 | 119.62 (19) | O51—C51—H51 | 116.6 |
C4—N4—C41 | 121.34 (19) | C5—C51—H51 | 116.6 |
C47—N4—C41 | 117.67 (19) | C66—C61—C62 | 119.62 (19) |
C6—N6—C61 | 119.05 (17) | C66—C61—N6 | 120.59 (18) |
C6—N6—C67 | 119.41 (17) | C62—C61—N6 | 119.75 (19) |
C61—N6—C67 | 115.44 (17) | C61—C62—C63 | 120.1 (2) |
N2—C2—N3 | 116.9 (2) | C61—C62—H62 | 120.0 |
N2—C2—N1 | 115.9 (2) | C63—C62—H62 | 120.0 |
N3—C2—N1 | 127.11 (19) | C62—C63—C64 | 121.0 (2) |
N3—C4—N4 | 116.73 (19) | C62—C63—H63 | 119.5 |
N3—C4—C5 | 121.09 (19) | C64—C63—H63 | 119.5 |
N4—C4—C5 | 122.15 (19) | C63—C64—C65 | 118.1 (2) |
C4—C5—C6 | 114.34 (18) | C63—C64—C641 | 120.8 (2) |
C4—C5—C51 | 124.86 (19) | C65—C64—C641 | 121.1 (2) |
C6—C5—C51 | 118.96 (19) | C66—C65—C64 | 121.2 (2) |
N1—C6—N6 | 117.20 (18) | C66—C65—H65 | 119.4 |
N1—C6—C5 | 122.81 (19) | C64—C65—H65 | 119.4 |
N6—C6—C5 | 119.98 (18) | C61—C66—C65 | 119.9 (2) |
C46—C41—C42 | 118.5 (2) | C61—C66—H66 | 120.0 |
C46—C41—N4 | 121.5 (2) | C65—C66—H66 | 120.0 |
C42—C41—N4 | 119.9 (2) | N6—C67—H67A | 109.5 |
C43—C42—C41 | 119.9 (2) | N6—C67—H67B | 109.5 |
C43—C42—H42 | 120.1 | H67A—C67—H67B | 109.5 |
C41—C42—H42 | 120.1 | N6—C67—H67C | 109.5 |
C42—C43—C44 | 122.5 (2) | H67A—C67—H67C | 109.5 |
C42—C43—H43 | 118.7 | H67B—C67—H67C | 109.5 |
C44—C43—H43 | 118.7 | C44—C441—H44A | 109.5 |
C43—C44—C45 | 116.6 (2) | C44—C441—H44B | 109.5 |
C43—C44—C441 | 122.1 (2) | H44A—C441—H44B | 109.5 |
C45—C44—C441 | 121.3 (3) | C44—C441—H44C | 109.5 |
C46—C45—C44 | 121.9 (2) | H44A—C441—H44C | 109.5 |
C46—C45—H45 | 119.1 | H44B—C441—H44C | 109.5 |
C44—C45—H45 | 119.1 | C64—C641—H64A | 109.5 |
C41—C46—C45 | 120.5 (2) | C64—C641—H64B | 109.5 |
C41—C46—H46 | 119.8 | H64A—C641—H64B | 109.5 |
C45—C46—H46 | 119.8 | C64—C641—H64C | 109.5 |
N4—C47—H47A | 109.5 | H64A—C641—H64C | 109.5 |
N4—C47—H47B | 109.5 | H64B—C641—H64C | 109.5 |
| | | |
C4—N3—C2—N2 | 174.15 (19) | C47—N4—C41—C42 | 39.3 (3) |
C4—N3—C2—N1 | −9.0 (3) | C46—C41—C42—C43 | −1.2 (3) |
C6—N1—C2—N2 | −172.62 (19) | N4—C41—C42—C43 | −178.1 (2) |
C6—N1—C2—N3 | 10.5 (3) | C41—C42—C43—C44 | −0.8 (4) |
C2—N3—C4—N4 | 175.68 (18) | C42—C43—C44—C45 | 1.1 (4) |
C2—N3—C4—C5 | −6.3 (3) | C42—C43—C44—C441 | −179.0 (2) |
C47—N4—C4—N3 | 16.8 (3) | C43—C44—C45—C46 | 0.7 (3) |
C41—N4—C4—N3 | −149.56 (19) | C441—C44—C45—C46 | −179.2 (2) |
C47—N4—C4—C5 | −161.2 (2) | C42—C41—C46—C45 | 3.0 (3) |
C41—N4—C4—C5 | 32.5 (3) | N4—C41—C46—C45 | 179.8 (2) |
N3—C4—C5—C6 | 17.7 (3) | C44—C45—C46—C41 | −2.8 (3) |
N4—C4—C5—C6 | −164.39 (19) | C4—C5—C51—O51 | −11.6 (3) |
N3—C4—C5—C51 | −146.6 (2) | C6—C5—C51—O51 | −175.3 (2) |
N4—C4—C5—C51 | 31.3 (3) | C6—N6—C61—C66 | 132.2 (2) |
C2—N1—C6—N6 | −178.03 (18) | C67—N6—C61—C66 | −75.4 (3) |
C2—N1—C6—C5 | 3.3 (3) | C6—N6—C61—C62 | −49.9 (3) |
C61—N6—C6—N1 | 142.17 (19) | C67—N6—C61—C62 | 102.5 (2) |
C67—N6—C6—N1 | −9.1 (3) | C66—C61—C62—C63 | −2.1 (3) |
C61—N6—C6—C5 | −39.1 (3) | N6—C61—C62—C63 | 180.0 (2) |
C67—N6—C6—C5 | 169.59 (19) | C61—C62—C63—C64 | 0.6 (3) |
C4—C5—C6—N1 | −16.3 (3) | C62—C63—C64—C65 | 1.5 (3) |
C51—C5—C6—N1 | 149.0 (2) | C62—C63—C64—C641 | −177.7 (2) |
C4—C5—C6—N6 | 165.06 (18) | C63—C64—C65—C66 | −2.2 (3) |
C51—C5—C6—N6 | −29.7 (3) | C641—C64—C65—C66 | 177.0 (2) |
C4—N4—C41—C46 | 29.1 (3) | C62—C61—C66—C65 | 1.4 (3) |
C47—N4—C41—C46 | −137.5 (2) | N6—C61—C66—C65 | 179.33 (19) |
C4—N4—C41—C42 | −154.2 (2) | C64—C65—C66—C61 | 0.7 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2B···O51i | 0.86 | 2.53 | 3.038 (3) | 118 |
C42—H42···O51ii | 0.95 | 2.29 | 3.203 (3) | 162 |
C66—H66···O51iii | 0.95 | 2.52 | 3.228 (3) | 131 |
C63—H63···Cg1iv | 0.95 | 2.87 | 3.736 (2) | 152 |
Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y, −z; (iii) −x+1, −y+1, −z; (iv) −x+1, −y, −z+1. |
(II) 2-amino-4-(indolin-1-yl)-6-methoxypyrimidine-5-carbaldehyde
top
Crystal data top
C14H14N4O2 | Z = 4 |
Mr = 270.29 | F(000) = 568 |
Triclinic, P1 | Dx = 1.407 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.2846 (4) Å | Cell parameters from 5864 reflections |
b = 11.2710 (4) Å | θ = 3.0–27.5° |
c = 15.0024 (7) Å | µ = 0.10 mm−1 |
α = 108.983 (4)° | T = 120 K |
β = 95.403 (4)° | Plate, colourless |
γ = 101.908 (3)° | 0.52 × 0.41 × 0.14 mm |
V = 1276.35 (10) Å3 | |
Data collection top
Bruker Nonius KappaCCD area-detector diffractometer | 5864 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 3790 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.045 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.0° |
ϕ and ω scans | h = −10→10 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −14→14 |
Tmin = 0.967, Tmax = 0.986 | l = −19→19 |
31946 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)] = 0.055 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.164 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0832P)2 + 0.5084P] where P = (Fo2 + 2Fc2)/3 |
5864 reflections | (Δ/σ)max = 0.001 |
363 parameters | Δρmax = 0.30 e Å−3 |
0 restraints | Δρmin = −0.38 e Å−3 |
Crystal data top
C14H14N4O2 | γ = 101.908 (3)° |
Mr = 270.29 | V = 1276.35 (10) Å3 |
Triclinic, P1 | Z = 4 |
a = 8.2846 (4) Å | Mo Kα radiation |
b = 11.2710 (4) Å | µ = 0.10 mm−1 |
c = 15.0024 (7) Å | T = 120 K |
α = 108.983 (4)° | 0.52 × 0.41 × 0.14 mm |
β = 95.403 (4)° | |
Data collection top
Bruker Nonius KappaCCD area-detector diffractometer | 5864 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 3790 reflections with I > 2σ(I) |
Tmin = 0.967, Tmax = 0.986 | Rint = 0.045 |
31946 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.055 | 0 restraints |
wR(F2) = 0.164 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.30 e Å−3 |
5864 reflections | Δρmin = −0.38 e Å−3 |
363 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N11 | 0.1123 (2) | 0.21765 (17) | 0.94923 (12) | 0.0218 (4) | |
C12 | 0.2619 (3) | 0.19018 (19) | 0.95139 (15) | 0.0215 (4) | |
N12 | 0.3465 (2) | 0.20113 (17) | 0.88162 (13) | 0.0250 (4) | |
N13 | 0.3405 (2) | 0.15560 (17) | 1.01878 (12) | 0.0239 (4) | |
C14 | 0.2547 (3) | 0.1430 (2) | 1.08612 (15) | 0.0232 (5) | |
O14 | 0.32080 (18) | 0.10218 (16) | 1.15269 (11) | 0.0286 (4) | |
C141 | 0.4708 (3) | 0.0588 (3) | 1.13729 (18) | 0.0335 (6) | |
C15 | 0.0961 (2) | 0.1702 (2) | 1.09502 (14) | 0.0216 (4) | |
C151 | 0.0039 (3) | 0.1288 (2) | 1.16083 (15) | 0.0247 (5) | |
O151 | −0.14254 (18) | 0.12705 (15) | 1.16863 (11) | 0.0282 (4) | |
C16 | 0.0360 (2) | 0.2171 (2) | 1.02430 (15) | 0.0220 (4) | |
N21 | −0.1009 (2) | 0.26789 (17) | 1.03052 (12) | 0.0232 (4) | |
C22 | −0.1337 (3) | 0.3505 (2) | 1.12282 (15) | 0.0258 (5) | |
C23 | −0.1729 (3) | 0.4679 (2) | 1.10309 (15) | 0.0259 (5) | |
C23a | −0.2266 (3) | 0.4161 (2) | 0.99630 (15) | 0.0228 (5) | |
C24 | −0.3113 (3) | 0.4643 (2) | 0.93744 (16) | 0.0264 (5) | |
C25 | −0.3441 (3) | 0.3985 (2) | 0.83944 (16) | 0.0265 (5) | |
C26 | −0.2934 (3) | 0.2849 (2) | 0.80039 (16) | 0.0258 (5) | |
C27 | −0.2096 (3) | 0.2351 (2) | 0.85884 (15) | 0.0240 (5) | |
C27a | −0.1767 (2) | 0.3022 (2) | 0.95651 (15) | 0.0214 (4) | |
N31 | −0.0291 (2) | 0.19891 (17) | 0.43799 (12) | 0.0233 (4) | |
C32 | −0.1572 (3) | 0.0949 (2) | 0.41639 (15) | 0.0219 (4) | |
N32 | −0.2335 (2) | 0.03817 (18) | 0.32449 (13) | 0.0272 (4) | |
N33 | −0.2252 (2) | 0.04228 (17) | 0.47789 (13) | 0.0236 (4) | |
C34 | −0.1436 (3) | 0.0938 (2) | 0.56673 (15) | 0.0226 (5) | |
O34 | −0.19847 (18) | 0.04248 (14) | 0.63094 (10) | 0.0267 (4) | |
C341 | −0.3425 (3) | −0.0666 (2) | 0.59653 (17) | 0.0297 (5) | |
C35 | 0.0019 (2) | 0.1983 (2) | 0.59979 (14) | 0.0214 (4) | |
C351 | 0.1048 (3) | 0.2173 (2) | 0.68859 (15) | 0.0250 (5) | |
O351 | 0.25403 (18) | 0.27528 (15) | 0.71601 (11) | 0.0273 (4) | |
C36 | 0.0437 (3) | 0.2560 (2) | 0.53065 (15) | 0.0217 (4) | |
N41 | 0.1558 (2) | 0.37265 (17) | 0.55452 (12) | 0.0235 (4) | |
C42 | 0.1924 (3) | 0.4725 (2) | 0.65157 (15) | 0.0267 (5) | |
C43 | 0.2289 (3) | 0.6021 (2) | 0.63562 (16) | 0.0283 (5) | |
C43a | 0.2674 (3) | 0.5658 (2) | 0.53581 (15) | 0.0244 (5) | |
C44 | 0.3415 (3) | 0.6436 (2) | 0.48904 (16) | 0.0281 (5) | |
C45 | 0.3673 (3) | 0.5873 (2) | 0.39637 (17) | 0.0318 (5) | |
C46 | 0.3155 (3) | 0.4537 (2) | 0.35030 (17) | 0.0316 (5) | |
C47 | 0.2390 (3) | 0.3744 (2) | 0.39613 (16) | 0.0283 (5) | |
C47a | 0.2171 (3) | 0.4320 (2) | 0.48942 (15) | 0.0233 (5) | |
H12A | 0.3119 | 0.2371 | 0.8436 | 0.030* | |
H12B | 0.4492 | 0.1973 | 0.8907 | 0.030* | |
H14A | 0.5588 | 0.1295 | 1.1342 | 0.050* | |
H14B | 0.4479 | −0.0151 | 1.0769 | 0.050* | |
H14C | 0.5079 | 0.0322 | 1.1902 | 0.050* | |
H151 | 0.0634 | 0.0994 | 1.2032 | 0.030* | |
H22A | −0.0342 | 0.3780 | 1.1737 | 0.031* | |
H22B | −0.2300 | 0.3035 | 1.1427 | 0.031* | |
H23A | −0.2639 | 0.4958 | 1.1362 | 0.031* | |
H23B | −0.0724 | 0.5418 | 1.1234 | 0.031* | |
H24 | −0.3464 | 0.5416 | 0.9640 | 0.032* | |
H25 | −0.4017 | 0.4310 | 0.7985 | 0.032* | |
H26 | −0.3163 | 0.2409 | 0.7330 | 0.031* | |
H27 | −0.1758 | 0.1572 | 0.8324 | 0.029* | |
H32A | −0.1999 | 0.0644 | 0.2800 | 0.033* | |
H32B | −0.3076 | −0.0337 | 0.3112 | 0.033* | |
H34A | −0.3197 | −0.1357 | 0.5435 | 0.045* | |
H34B | −0.4392 | −0.0399 | 0.5741 | 0.045* | |
H34C | −0.3667 | −0.0986 | 0.6485 | 0.045* | |
H351 | 0.0520 | 0.1811 | 0.7307 | 0.030* | |
H42A | 0.2907 | 0.4652 | 0.6905 | 0.032* | |
H42B | 0.0951 | 0.4635 | 0.6846 | 0.032* | |
H43A | 0.1303 | 0.6393 | 0.6403 | 0.034* | |
H43B | 0.3258 | 0.6654 | 0.6826 | 0.034* | |
H44 | 0.3746 | 0.7351 | 0.5201 | 0.034* | |
H45 | 0.4206 | 0.6402 | 0.3642 | 0.038* | |
H46 | 0.3327 | 0.4161 | 0.2865 | 0.038* | |
H47 | 0.2026 | 0.2831 | 0.3644 | 0.034* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N11 | 0.0214 (9) | 0.0242 (9) | 0.0210 (9) | 0.0069 (7) | 0.0050 (7) | 0.0085 (7) |
C12 | 0.0232 (10) | 0.0190 (10) | 0.0212 (11) | 0.0040 (8) | 0.0029 (8) | 0.0068 (9) |
N12 | 0.0227 (9) | 0.0331 (10) | 0.0248 (10) | 0.0099 (8) | 0.0055 (7) | 0.0153 (8) |
N13 | 0.0224 (9) | 0.0284 (10) | 0.0237 (10) | 0.0071 (8) | 0.0053 (7) | 0.0120 (8) |
C14 | 0.0236 (11) | 0.0234 (11) | 0.0226 (11) | 0.0056 (9) | 0.0007 (9) | 0.0092 (9) |
O14 | 0.0248 (8) | 0.0421 (9) | 0.0272 (8) | 0.0161 (7) | 0.0066 (6) | 0.0180 (7) |
C141 | 0.0272 (12) | 0.0476 (15) | 0.0384 (14) | 0.0182 (11) | 0.0108 (10) | 0.0248 (12) |
C15 | 0.0197 (10) | 0.0250 (11) | 0.0199 (11) | 0.0055 (8) | 0.0034 (8) | 0.0079 (9) |
C151 | 0.0267 (11) | 0.0275 (12) | 0.0219 (11) | 0.0091 (9) | 0.0056 (9) | 0.0097 (9) |
O151 | 0.0233 (8) | 0.0338 (9) | 0.0314 (9) | 0.0074 (7) | 0.0079 (7) | 0.0159 (7) |
C16 | 0.0188 (10) | 0.0224 (11) | 0.0229 (11) | 0.0037 (8) | 0.0027 (8) | 0.0066 (9) |
N21 | 0.0236 (9) | 0.0289 (10) | 0.0205 (9) | 0.0095 (8) | 0.0045 (7) | 0.0111 (8) |
C22 | 0.0296 (11) | 0.0294 (12) | 0.0210 (11) | 0.0118 (9) | 0.0080 (9) | 0.0086 (9) |
C23 | 0.0273 (11) | 0.0263 (11) | 0.0243 (11) | 0.0082 (9) | 0.0057 (9) | 0.0079 (9) |
C23a | 0.0211 (10) | 0.0232 (11) | 0.0240 (11) | 0.0037 (8) | 0.0065 (8) | 0.0088 (9) |
C24 | 0.0289 (11) | 0.0231 (11) | 0.0299 (12) | 0.0082 (9) | 0.0075 (9) | 0.0113 (10) |
C25 | 0.0258 (11) | 0.0296 (12) | 0.0285 (12) | 0.0086 (9) | 0.0045 (9) | 0.0153 (10) |
C26 | 0.0254 (11) | 0.0307 (12) | 0.0215 (11) | 0.0076 (9) | 0.0037 (9) | 0.0093 (9) |
C27 | 0.0224 (10) | 0.0267 (11) | 0.0238 (11) | 0.0064 (9) | 0.0058 (9) | 0.0093 (9) |
C27a | 0.0189 (10) | 0.0263 (11) | 0.0211 (11) | 0.0049 (8) | 0.0040 (8) | 0.0115 (9) |
N31 | 0.0241 (9) | 0.0242 (9) | 0.0208 (9) | 0.0048 (7) | 0.0037 (7) | 0.0078 (8) |
C32 | 0.0231 (10) | 0.0226 (11) | 0.0220 (11) | 0.0090 (9) | 0.0052 (8) | 0.0081 (9) |
N32 | 0.0297 (10) | 0.0273 (10) | 0.0223 (10) | 0.0018 (8) | 0.0031 (8) | 0.0091 (8) |
N33 | 0.0232 (9) | 0.0245 (9) | 0.0234 (10) | 0.0054 (7) | 0.0050 (7) | 0.0089 (8) |
C34 | 0.0242 (10) | 0.0230 (11) | 0.0246 (11) | 0.0099 (9) | 0.0091 (9) | 0.0097 (9) |
O34 | 0.0282 (8) | 0.0289 (8) | 0.0242 (8) | 0.0033 (6) | 0.0071 (6) | 0.0128 (7) |
C341 | 0.0284 (11) | 0.0286 (12) | 0.0325 (13) | 0.0005 (9) | 0.0082 (10) | 0.0145 (10) |
C35 | 0.0217 (10) | 0.0231 (11) | 0.0201 (11) | 0.0063 (8) | 0.0049 (8) | 0.0077 (9) |
C351 | 0.0270 (11) | 0.0257 (11) | 0.0250 (11) | 0.0075 (9) | 0.0067 (9) | 0.0115 (9) |
O351 | 0.0250 (8) | 0.0281 (8) | 0.0288 (9) | 0.0051 (6) | 0.0005 (6) | 0.0120 (7) |
C36 | 0.0241 (10) | 0.0211 (10) | 0.0219 (11) | 0.0087 (8) | 0.0059 (8) | 0.0078 (9) |
N41 | 0.0283 (9) | 0.0218 (9) | 0.0195 (9) | 0.0033 (8) | 0.0047 (7) | 0.0079 (7) |
C42 | 0.0327 (12) | 0.0252 (11) | 0.0214 (11) | 0.0067 (9) | 0.0050 (9) | 0.0075 (9) |
C43 | 0.0339 (12) | 0.0236 (11) | 0.0255 (12) | 0.0051 (9) | 0.0043 (10) | 0.0079 (9) |
C43a | 0.0239 (11) | 0.0258 (11) | 0.0249 (11) | 0.0052 (9) | 0.0027 (9) | 0.0115 (9) |
C44 | 0.0280 (11) | 0.0245 (11) | 0.0306 (12) | 0.0029 (9) | 0.0009 (9) | 0.0115 (10) |
C45 | 0.0311 (12) | 0.0350 (13) | 0.0339 (13) | 0.0034 (10) | 0.0061 (10) | 0.0210 (11) |
C46 | 0.0352 (13) | 0.0357 (13) | 0.0252 (12) | 0.0065 (10) | 0.0078 (10) | 0.0134 (10) |
C47 | 0.0323 (12) | 0.0254 (11) | 0.0243 (12) | 0.0040 (9) | 0.0044 (9) | 0.0073 (9) |
C47a | 0.0236 (10) | 0.0243 (11) | 0.0233 (11) | 0.0041 (9) | 0.0033 (9) | 0.0116 (9) |
Geometric parameters (Å, º) top
N11—C12 | 1.338 (3) | N31—C32 | 1.334 (3) |
C12—N13 | 1.355 (3) | C32—N33 | 1.355 (3) |
N13—C14 | 1.317 (3) | N33—C34 | 1.317 (3) |
C14—C15 | 1.418 (3) | C34—C35 | 1.417 (3) |
C15—C16 | 1.423 (3) | C35—C36 | 1.425 (3) |
C16—N11 | 1.343 (3) | C36—N31 | 1.345 (3) |
C12—N12 | 1.337 (3) | C32—N32 | 1.343 (3) |
C14—O14 | 1.345 (2) | C34—O34 | 1.344 (2) |
C16—N21 | 1.370 (3) | C36—N41 | 1.359 (3) |
C15—C151 | 1.439 (3) | C35—C351 | 1.440 (3) |
C151—O151 | 1.226 (3) | C351—O351 | 1.233 (3) |
N12—H12A | 0.86 | N32—H32A | 0.86 |
N12—H12B | 0.86 | N32—H32B | 0.86 |
O14—C141 | 1.438 (3) | O34—C341 | 1.438 (3) |
C141—H14A | 0.98 | C341—H34A | 0.98 |
C141—H14B | 0.98 | C341—H34B | 0.98 |
C141—H14C | 0.98 | C341—H34C | 0.98 |
C151—H151 | 0.95 | C351—H351 | 0.95 |
N21—C27a | 1.423 (3) | N41—C47a | 1.427 (3) |
N21—C22 | 1.481 (3) | N41—C42 | 1.479 (3) |
C22—C23 | 1.536 (3) | C42—C43 | 1.531 (3) |
C22—H22A | 0.99 | C42—H42A | 0.99 |
C22—H22B | 0.99 | C42—H42B | 0.99 |
C23—C23a | 1.502 (3) | C43—C43a | 1.502 (3) |
C23—H23A | 0.99 | C43—H43A | 0.99 |
C23—H23B | 0.99 | C43—H43B | 0.99 |
C23a—C24 | 1.385 (3) | C43a—C44 | 1.378 (3) |
C23a—C27a | 1.395 (3) | C43a—C47a | 1.391 (3) |
C24—C25 | 1.385 (3) | C44—C45 | 1.385 (3) |
C24—H24 | 0.95 | C44—H44 | 0.95 |
C25—C26 | 1.393 (3) | C45—C46 | 1.389 (3) |
C25—H25 | 0.95 | C45—H45 | 0.95 |
C26—C27 | 1.390 (3) | C46—C47 | 1.386 (3) |
C26—H26 | 0.95 | C46—H46 | 0.95 |
C27—C27a | 1.383 (3) | C47—C47a | 1.385 (3) |
C27—H27 | 0.95 | C47—H47 | 0.95 |
| | | |
C12—N11—C16 | 116.41 (18) | C32—N31—C36 | 116.56 (18) |
N12—C12—N11 | 117.39 (18) | N31—C32—N32 | 117.36 (19) |
N12—C12—N13 | 115.71 (18) | N31—C32—N33 | 127.17 (19) |
N11—C12—N13 | 126.88 (19) | N32—C32—N33 | 115.39 (18) |
C12—N12—H12A | 119.4 | C32—N32—H32A | 122.5 |
C12—N12—H12B | 115.1 | C32—N32—H32B | 115.5 |
H12A—N12—H12B | 121.7 | H32A—N32—H32B | 121.2 |
C14—N13—C12 | 115.09 (18) | C34—N33—C32 | 114.80 (18) |
N13—C14—O14 | 118.54 (18) | N33—C34—O34 | 118.33 (18) |
N13—C14—C15 | 125.00 (19) | N33—C34—C35 | 124.76 (19) |
O14—C14—C15 | 116.45 (18) | O34—C34—C35 | 116.90 (18) |
C14—O14—C141 | 116.64 (17) | C34—O34—C341 | 116.86 (17) |
O14—C141—H14A | 109.5 | O34—C341—H34A | 109.5 |
O14—C141—H14B | 109.5 | O34—C341—H34B | 109.5 |
H14A—C141—H14B | 109.5 | H34A—C341—H34B | 109.5 |
O14—C141—H14C | 109.5 | O34—C341—H34C | 109.5 |
H14A—C141—H14C | 109.5 | H34A—C341—H34C | 109.5 |
H14B—C141—H14C | 109.5 | H34B—C341—H34C | 109.5 |
C14—C15—C16 | 113.58 (18) | C34—C35—C36 | 113.86 (18) |
C14—C15—C151 | 118.31 (18) | C34—C35—C351 | 117.54 (18) |
C16—C15—C151 | 127.22 (18) | C36—C35—C351 | 127.43 (19) |
O151—C151—C15 | 127.6 (2) | O351—C351—C35 | 127.1 (2) |
O151—C151—H151 | 116.2 | O351—C351—H351 | 116.4 |
C15—C151—H151 | 116.2 | C35—C351—H351 | 116.4 |
N11—C16—N21 | 116.05 (18) | N31—C36—N41 | 116.13 (18) |
N11—C16—C15 | 122.28 (18) | N31—C36—C35 | 121.61 (19) |
N21—C16—C15 | 121.65 (18) | N41—C36—C35 | 122.24 (19) |
C16—N21—C27a | 123.53 (17) | C36—N41—C47a | 126.13 (17) |
C16—N21—C22 | 122.32 (17) | C36—N41—C42 | 122.96 (17) |
C27a—N21—C22 | 107.93 (16) | C47a—N41—C42 | 108.67 (16) |
N21—C22—C23 | 104.66 (16) | N41—C42—C43 | 105.03 (17) |
N21—C22—H22A | 110.8 | N41—C42—H42A | 110.7 |
C23—C22—H22A | 110.8 | C43—C42—H42A | 110.7 |
N21—C22—H22B | 110.8 | N41—C42—H42B | 110.7 |
C23—C22—H22B | 110.8 | C43—C42—H42B | 110.7 |
H22A—C22—H22B | 108.9 | H42A—C42—H42B | 108.8 |
C23a—C23—C22 | 102.53 (17) | C43a—C43—C42 | 102.93 (18) |
C23a—C23—H23A | 111.3 | C43a—C43—H43A | 111.2 |
C22—C23—H23A | 111.3 | C42—C43—H43A | 111.2 |
C23a—C23—H23B | 111.3 | C43a—C43—H43B | 111.2 |
C22—C23—H23B | 111.3 | C42—C43—H43B | 111.2 |
H23A—C23—H23B | 109.2 | H43A—C43—H43B | 109.1 |
C24—C23a—C27a | 119.86 (19) | C44—C43a—C47a | 120.0 (2) |
C24—C23a—C23 | 130.4 (2) | C44—C43a—C43 | 129.7 (2) |
C27a—C23a—C23 | 109.77 (18) | C47a—C43a—C43 | 110.34 (18) |
C25—C24—C23a | 119.2 (2) | C43a—C44—C45 | 119.4 (2) |
C25—C24—H24 | 120.4 | C43a—C44—H44 | 120.3 |
C23a—C24—H24 | 120.4 | C45—C44—H44 | 120.3 |
C24—C25—C26 | 120.5 (2) | C44—C45—C46 | 120.3 (2) |
C24—C25—H25 | 119.7 | C44—C45—H45 | 119.9 |
C26—C25—H25 | 119.7 | C46—C45—H45 | 119.9 |
C27—C26—C25 | 120.8 (2) | C47—C46—C45 | 120.9 (2) |
C27—C26—H26 | 119.6 | C47—C46—H46 | 119.5 |
C25—C26—H26 | 119.6 | C45—C46—H46 | 119.5 |
C27a—C27—C26 | 118.2 (2) | C47a—C47—C46 | 118.1 (2) |
C27a—C27—H27 | 120.9 | C47a—C47—H47 | 120.9 |
C26—C27—H27 | 120.9 | C46—C47—H47 | 120.9 |
C27—C27a—C23a | 121.49 (19) | C47—C47a—C43a | 121.3 (2) |
C27—C27a—N21 | 128.57 (19) | C47—C47a—N41 | 129.2 (2) |
C23a—C27a—N21 | 109.85 (18) | C43a—C47a—N41 | 109.34 (18) |
| | | |
C16—N11—C12—N12 | −174.35 (18) | C36—N31—C32—N32 | 178.75 (18) |
C16—N11—C12—N13 | 3.6 (3) | C36—N31—C32—N33 | 2.0 (3) |
N12—C12—N13—C14 | −178.88 (18) | N31—C32—N33—C34 | −7.0 (3) |
N11—C12—N13—C14 | 3.2 (3) | N32—C32—N33—C34 | 176.19 (18) |
C12—N13—C14—O14 | 176.52 (18) | C32—N33—C34—O34 | −176.69 (17) |
C12—N13—C14—C15 | −4.0 (3) | C32—N33—C34—C35 | 1.7 (3) |
N13—C14—O14—C141 | −8.1 (3) | N33—C34—O34—C341 | 0.7 (3) |
C15—C14—O14—C141 | 172.34 (19) | C35—C34—O34—C341 | −177.80 (18) |
N13—C14—C15—C16 | −1.5 (3) | N33—C34—C35—C36 | 7.3 (3) |
O14—C14—C15—C16 | 177.98 (18) | O34—C34—C35—C36 | −174.29 (18) |
N13—C14—C15—C151 | 168.4 (2) | N33—C34—C35—C351 | −161.2 (2) |
O14—C14—C15—C151 | −12.1 (3) | O34—C34—C35—C351 | 17.1 (3) |
C14—C15—C151—O151 | −168.9 (2) | C34—C35—C351—O351 | 158.1 (2) |
C16—C15—C151—O151 | −0.5 (4) | C36—C35—C351—O351 | −8.7 (4) |
C12—N11—C16—N21 | 168.48 (18) | C32—N31—C36—N41 | −170.04 (18) |
C12—N11—C16—C15 | −9.7 (3) | C32—N31—C36—C35 | 8.4 (3) |
C14—C15—C16—N11 | 8.7 (3) | C34—C35—C36—N31 | −12.5 (3) |
C151—C15—C16—N11 | −160.1 (2) | C351—C35—C36—N31 | 154.7 (2) |
C14—C15—C16—N21 | −169.37 (19) | C34—C35—C36—N41 | 165.82 (19) |
C151—C15—C16—N21 | 21.8 (3) | C351—C35—C36—N41 | −27.0 (3) |
N11—C16—N21—C27a | 9.2 (3) | N31—C36—N41—C47a | −7.9 (3) |
C15—C16—N21—C27a | −172.59 (19) | C35—C36—N41—C47a | 173.67 (19) |
N11—C16—N21—C22 | −139.7 (2) | N31—C36—N41—C42 | 153.14 (19) |
C15—C16—N21—C22 | 38.5 (3) | C35—C36—N41—C42 | −25.3 (3) |
C16—N21—C22—C23 | 131.9 (2) | C36—N41—C42—C43 | −146.42 (19) |
C27a—N21—C22—C23 | −21.2 (2) | C47a—N41—C42—C43 | 17.5 (2) |
N21—C22—C23—C23a | 22.3 (2) | N41—C42—C43—C43a | −18.8 (2) |
C22—C23—C23a—C24 | 164.2 (2) | C42—C43—C43a—C44 | −165.3 (2) |
C22—C23—C23a—C27a | −16.4 (2) | C42—C43—C43a—C47a | 14.4 (2) |
C27a—C23a—C24—C25 | −0.4 (3) | C47a—C43a—C44—C45 | −0.9 (3) |
C23—C23a—C24—C25 | 178.9 (2) | C43—C43a—C44—C45 | 178.8 (2) |
C23a—C24—C25—C26 | 0.3 (3) | C43a—C44—C45—C46 | 1.4 (3) |
C24—C25—C26—C27 | 0.3 (3) | C44—C45—C46—C47 | −0.7 (4) |
C25—C26—C27—C27a | −0.6 (3) | C45—C46—C47—C47a | −0.6 (3) |
C26—C27—C27a—C23a | 0.5 (3) | C46—C47—C47a—C43a | 1.1 (3) |
C26—C27—C27a—N21 | 176.66 (19) | C46—C47—C47a—N41 | −174.2 (2) |
C24—C23a—C27a—C27 | 0.0 (3) | C44—C43a—C47a—C47 | −0.4 (3) |
C23—C23a—C27a—C27 | −179.43 (18) | C43—C43a—C47a—C47 | 179.89 (19) |
C24—C23a—C27a—N21 | −176.79 (18) | C44—C43a—C47a—N41 | 175.77 (19) |
C23—C23a—C27a—N21 | 3.7 (2) | C43—C43a—C47a—N41 | −3.9 (2) |
C16—N21—C27a—C27 | 42.2 (3) | C36—N41—C47a—C47 | −29.8 (3) |
C22—N21—C27a—C27 | −165.2 (2) | C42—N41—C47a—C47 | 166.9 (2) |
C16—N21—C27a—C23a | −141.3 (2) | C36—N41—C47a—C43a | 154.4 (2) |
C22—N21—C27a—C23a | 11.4 (2) | C42—N41—C47a—C43a | −8.8 (2) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N12—H12A···O351 | 0.86 | 2.13 | 2.952 (2) | 160 |
N32—H32A···O151i | 0.86 | 2.07 | 2.930 (3) | 175 |
N12—H12B···Cg2ii | 0.86 | 2.61 | 3.294 (4) | 136 |
Symmetry codes: (i) x, y, z−1; (ii) x+1, y, z. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C21H23N5O | C14H14N4O2 |
Mr | 361.44 | 270.29 |
Crystal system, space group | Triclinic, P1 | Triclinic, P1 |
Temperature (K) | 120 | 120 |
a, b, c (Å) | 8.6844 (6), 10.7807 (19), 10.8903 (10) | 8.2846 (4), 11.2710 (4), 15.0024 (7) |
α, β, γ (°) | 69.998 (14), 88.918 (7), 76.822 (13) | 108.983 (4), 95.403 (4), 101.908 (3) |
V (Å3) | 930.9 (2) | 1276.35 (10) |
Z | 2 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.08 | 0.10 |
Crystal size (mm) | 0.31 × 0.24 × 0.21 | 0.52 × 0.41 × 0.14 |
|
Data collection |
Diffractometer | Bruker Nonius KappaCCD area-detector diffractometer | Bruker Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.965, 0.983 | 0.967, 0.986 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 24528, 4249, 2988 | 31946, 5864, 3790 |
Rint | 0.046 | 0.045 |
(sin θ/λ)max (Å−1) | 0.650 | 0.650 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.060, 0.153, 1.08 | 0.055, 0.164, 1.08 |
No. of reflections | 4249 | 5864 |
No. of parameters | 248 | 363 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.51, −0.35 | 0.30, −0.38 |
Selected bond lengths (Å) for (I) topN1—C2 | 1.347 (3) | C2—N2 | 1.345 (3) |
C2—N3 | 1.345 (3) | C4—N4 | 1.376 (3) |
N3—C4 | 1.336 (3) | C6—N6 | 1.374 (3) |
C4—C5 | 1.426 (3) | C5—C51 | 1.450 (3) |
C5—C6 | 1.427 (3) | C51—O51 | 1.219 (3) |
C6—N1 | 1.330 (3) | | |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2B···O51i | 0.86 | 2.53 | 3.038 (3) | 118 |
C42—H42···O51ii | 0.95 | 2.29 | 3.203 (3) | 162 |
C66—H66···O51iii | 0.95 | 2.52 | 3.228 (3) | 131 |
C63—H63···Cg1iv | 0.95 | 2.87 | 3.736 (2) | 152 |
Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y, −z; (iii) −x+1, −y+1, −z; (iv) −x+1, −y, −z+1. |
Selected bond lengths (Å) for (II) topN11—C12 | 1.338 (3) | N31—C32 | 1.334 (3) |
C12—N13 | 1.355 (3) | C32—N33 | 1.355 (3) |
N13—C14 | 1.317 (3) | N33—C34 | 1.317 (3) |
C14—C15 | 1.418 (3) | C34—C35 | 1.417 (3) |
C15—C16 | 1.423 (3) | C35—C36 | 1.425 (3) |
C16—N11 | 1.343 (3) | C36—N31 | 1.345 (3) |
C12—N12 | 1.337 (3) | C32—N32 | 1.343 (3) |
C14—O14 | 1.345 (2) | C34—O34 | 1.344 (2) |
C16—N21 | 1.370 (3) | C36—N41 | 1.359 (3) |
C15—C151 | 1.439 (3) | C35—C351 | 1.440 (3) |
C151—O151 | 1.226 (3) | C351—O351 | 1.233 (3) |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N12—H12A···O351 | 0.86 | 2.13 | 2.952 (2) | 160 |
N32—H32A···O151i | 0.86 | 2.07 | 2.930 (3) | 175 |
N12—H12B···Cg2ii | 0.86 | 2.61 | 3.294 (4) | 136 |
Symmetry codes: (i) x, y, z−1; (ii) x+1, y, z. |
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Substituted 6-amino-5-nitrosopyrimidines, (A), often form intramolecular N—H···O hydrogen bonds and thus are interesting mimics of purines, (B). We have found that such pyrimidines often exhibit markedly polarized molecular electronic structures (Low et al., 2000), leading to the formation of very strong charge-assisted intermolecular hydrogen bonds (Gilli et al., 1994). Bearing in mind the close analogies between nitrosyl and formyl groups, we have recently initiated a study of the analogous formylpyrimidines, (C). Compounds (I) and (II) (Figs. 1 and 2) were first obtained during attempts to prepare the corresponding 4-chloro analogues, (III) and (IV), respectively, by selective amino substitution at the 6-position in the precursor 2-amino-4,6-dichloro-5-formylpyrimidine (Taylor & Gillespie, 1992). In the event, we observed competition between solvolysis or aminolysis in the second substitution step, which appears to be dependent on the nucleophilic character of the reaction medium. Accordingly, we have now optimized the reaction conditions which generate compounds (I) and (II). For the formation of (I), 2-amino-4,6-dichloro-5-formylpyrimidine was reacted in ethanol with a twofold molar excess of N-methyltoluidine and with a twofold molar excess of triethylamine acting as a base. For the formation of (II), the same pyrimidine was reacted in methanol with an equimolar quantity of indoline in the presence of sodium hydroxide.
In both compounds, the pyrimidine rings deviate from planarity. In (I), the puckering amplitude (Cremer & Pople, 1975) is 0.167 (2) Å, with puckering angles θ = 75.7 (7)° and ϕ = 234.0 (8)°, so that the boat conformation [where the ideal values are θ = 90° and ϕ = (60n)°, where n represents zero or an integer] is the best approximate description. For the two independent molecules of (II), the puckering amplitudes for the pyrimidine rings are less than those in (I), at 0.078 (4) and 0.0108 (50) Å, respectively, for molecules of types 1 and 2 (containing atoms N11 and N31, respectively). The ring-puckering angles θ and ϕ are 110 (3) and 128 (3)°, respectively, in the type 1 molecule, and 74 (2) and 272 (2)°, respectively, in the type 2 molecule. These values correspond to a screw-boat conformation for the type 2 molecule, and a conformation intermediate between boat and envelope for the type 1 molecule. The five-membered rings in the two molecules of (II) both adopt envelope conformations, folded across the lines Ny1···Cy3 for y = 2 or 4. The asymmetric unit of compound (II) was selected such that the two independent molecules within it are linked by an N—H···O hydrogen bond (see below), and subject to this the two molecules in the asymmetric unit are very approximately enantiomeric.
The bond distances in the molecules of both compounds (Tables 1 and 3) show some unusual features, consistent with a degree of polarization in their overall molecular electronic structures; this is more marked in (II) than in (I), and thus we discuss only (II) in any detail. In each molecule of compound (II), the C—O bond is long for its type (mean value 1.192 Å; Allen et al., 1987), and the adjacent C5—C51 bond is short (mean value 1.488 Å). Similarly, the C—NH2 bond length lies towards the shorter end of the range for such bonds (mean value 1.355 Å, lower quartile 1.340 Å). The data indicate a significant contribution from the polarized form, (IIa), with a more modest contribution from the analogous form in (I).
The molecules of compound (I) are linked into a three-dimensional framework structure by a combination of N—H···O and C—H···O hydrogen bonds (Table 2), although only one N—H bond of the amino group containing atom N2 participates in the hydrogen bonding. The formation of the framework is analysed in terms of a simple chain generated by the weak N—H···O hydrogen bond, followed by the linking of different inversion-related pairs of chains to form the overall structure. Atom N2 in the molecule at (x, y, z) acts as hydrogen-bond donor to atom O51 in the molecule at (−1 + x, y, z), so generating by translation a C(8) (Bernstein et al., 1995) chain running parallel to the [100] direction (Fig. 3). The shorter of the C—H···O hydrogen bonds links an antiparallel pair of C(8) chains into a chain of edge-fused R22(16) and R24(20) rings running along the line (x, 0, 0) (Fig. 3). The longer of the C—H···O hydrogen bonds links this chain to those along (x, 1, 0) and (x, −1, 0), while the C—H···π(arene) hydrogen bond links the chain along (x, 0, 0) to those along (x, 0, 1) and (x, 0, −1). Hence, all of the [100] chains are linked into a single three-dimensional array.
In compound (II), the molecules are linked into sheets by a combination of two independent N—H···O hydrogen bonds and one N—H···π(arene) hydrogen bond (Table 4). Within the selected asymmetric unit, atom N12 acts as hydrogen-bond donor, via atom H12A, to atom O351. Similarly, atom N32 at (x, y, z) acts as hydrogen-bond donor to atom O151 at (x, y, −1 + z), so that the combination of these two hydrogen bonds generates by translation a C22(16) chain running parallel to the [001] direction (Fig. 4). Only one of the other two N—H bonds participates in the hydrogen bonding. Atom N12 in the type 1 molecule at (x, y, z) acts as hydrogen-bond donor, via atom H12B, to the aryl ring (C23a/C24–C27/C27a) in the type 1 molecule at (1 + x, y, z), so generating by translation a chain of type 1 molecules running parallel to the [100] direction (Fig. 5). There are no potential hydrogen-bond acceptors within bonding distance of the corresponding N—H bond of the type 2 molecule. The combination of the [100] and [001] chains generates a sheet parallel to (010), but there are no direction-specific interactions between adjacent sheets.
In view of the variety of C—H···O and C—H···π(arene) hydrogen bonds evident in the structures of compounds (I) and (II), it is surprising to note that, in each compound, one of the N—H bonds plays no role in the hydrogen bonding.