The combined study of electron-density features in three substituted hydropyrimidines of the Biginelli compound family has been fulfilled. Results of the low-temperature X-ray diffraction measurements and density functional theory (DFT) B3LYP/6-311++G** calculations of these compounds are described. The experimentally derived atomic and bonding characteristics determined within the quantum-topological theory of atoms in molecules and crystals (QTAIMC) were demonstrated to be fully transferable within chemically similar structures such as the Biginelli compounds. However, for certain covalent bonds they differ significantly from the theoretical results because of insufficient flexibility of the atom-centered multipole electron density model. It was concluded that currently analysis of the theoretical electron density provides a more reliable basis for the determination of the transferability of QTAIMC descriptors for molecular structures. Empirical corrections making the experimentally derived QTAIMC bond descriptors more transferable are proposed.
Supporting information
CCDC references: 849847; 849848
Data collection: CrystalClear,(2005) for (I), (II). Cell refinement: Otwinowski & Minor (1997) for (I), (II). Data reduction: SORTAV (Blessing, 1987, 1989,1995) for (I); SORTAV (Blessing, 1987,1989) for (II). Program(s) used to solve structure: SHELXS97 (Sheldrick, 2008) for (I), (II). Program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) for (I), (II); Protas, J. (1997). MOLDOS97/MOLLY IBM PC-DOS for Imult, IImult.
Crystal data top
C9H14N2OS | Z = 2 |
Mr = 198.28 | F(000) = 212 |
Triclinic, P1 | Dx = 1.303 Mg m−3 |
a = 7.2533 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 7.8212 (3) Å | Cell parameters from 9999 reflections |
c = 9.1837 (3) Å | θ = 2.3–55.6° |
α = 97.187 (1)° | µ = 0.28 mm−1 |
β = 100.674 (1)° | T = 110 K |
γ = 94.106 (1)° | Prism, colorless |
V = 505.54 (2) Å3 | 0.40 × 0.22 × 0.14 mm |
Data collection top
Bruker diffractometer with a SMART 6000 CCD detector | 10974 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.042 |
ω scans | θmax = 55.6°, θmin = 2.3° |
Absorption correction: multi-scan R.H. Blessing, Acta Cryst. (1995), A51, 33-38 | h = −15→16 |
Tmin = 0.909, Tmax = 1.106 | k = −18→17 |
57560 measured reflections | l = −21→21 |
12868 independent 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)] = 0.030 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.092 | All H-atom parameters refined |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0459P)2 + 0.0256P] where P = (Fo2 + 2Fc2)/3 |
12868 reflections | (Δ/σ)max = 0.001 |
174 parameters | Δρmax = 0.81 e Å−3 |
0 restraints | Δρmin = −0.58 e Å−3 |
Crystal data top
C9H14N2OS | γ = 94.106 (1)° |
Mr = 198.28 | V = 505.54 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.2533 (2) Å | Mo Kα radiation |
b = 7.8212 (3) Å | µ = 0.28 mm−1 |
c = 9.1837 (3) Å | T = 110 K |
α = 97.187 (1)° | 0.40 × 0.22 × 0.14 mm |
β = 100.674 (1)° | |
Data collection top
Bruker diffractometer with a SMART 6000 CCD detector | 12868 independent reflections |
Absorption correction: multi-scan R.H. Blessing, Acta Cryst. (1995), A51, 33-38 | 10974 reflections with I > 2σ(I) |
Tmin = 0.909, Tmax = 1.106 | Rint = 0.042 |
57560 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.092 | All H-atom parameters refined |
S = 1.08 | Δρmax = 0.81 e Å−3 |
12868 reflections | Δρmin = −0.58 e Å−3 |
174 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S | 0.257791 (11) | 0.417146 (11) | 0.100343 (9) | 0.01531 (2) | |
O | 1.09288 (4) | 0.22556 (6) | 0.42300 (4) | 0.02704 (7) | |
N1 | 0.44346 (3) | 0.27510 (4) | 0.32474 (3) | 0.01352 (3) | |
N3 | 0.62324 (4) | 0.36956 (4) | 0.16492 (3) | 0.01422 (3) | |
C2 | 0.45354 (4) | 0.35047 (4) | 0.19876 (3) | 0.01240 (3) | |
C4 | 0.77766 (4) | 0.27105 (4) | 0.22534 (3) | 0.01324 (3) | |
C4' | 0.76443 (5) | 0.09252 (4) | 0.13056 (4) | 0.01648 (4) | |
C4'' | 0.77977 (6) | 0.10447 (5) | −0.03140 (4) | 0.01948 (5) | |
C5 | 0.77282 (4) | 0.25825 (4) | 0.38786 (3) | 0.01344 (4) | |
C5' | 0.95553 (4) | 0.24516 (5) | 0.48341 (4) | 0.01607 (4) | |
C5" | 0.98389 (5) | 0.25638 (6) | 0.65112 (4) | 0.02109 (6) | |
C6 | 0.60141 (4) | 0.25116 (4) | 0.42923 (3) | 0.01260 (3) | |
C6' | 0.55530 (5) | 0.21774 (5) | 0.57679 (3) | 0.01675 (4) | |
H1 | 0.3349 (16) | 0.2604 (13) | 0.3451 (11) | 0.040 (3)* | |
H3 | 0.6343 (14) | 0.4217 (12) | 0.0892 (11) | 0.034 (2)* | |
H4 | 0.8945 (13) | 0.3399 (11) | 0.2145 (10) | 0.026 (2)* | |
H41' | 0.8667 (14) | 0.0271 (12) | 0.1758 (11) | 0.032 (2)* | |
H42' | 0.6494 (13) | 0.0269 (11) | 0.1332 (10) | 0.029 (2)* | |
H41" | 0.8970 (13) | 0.1695 (12) | −0.0374 (10) | 0.031 (2)* | |
H42" | 0.7764 (13) | −0.0103 (11) | −0.0853 (10) | 0.028 (2)* | |
H43" | 0.6778 (15) | 0.1612 (13) | −0.0814 (12) | 0.038 (3)* | |
H51" | 1.1192 (15) | 0.2792 (13) | 0.6970 (11) | 0.037 (2)* | |
H52" | 0.9177 (13) | 0.3497 (12) | 0.6930 (11) | 0.030 (2)* | |
H53" | 0.9361 (15) | 0.1501 (13) | 0.6763 (12) | 0.040 (3)* | |
H61' | 0.5918 (14) | 0.3127 (12) | 0.6537 (11) | 0.034 (2)* | |
H62' | 0.4222 (13) | 0.1842 (12) | 0.5678 (10) | 0.027 (2)* | |
H63' | 0.6188 (13) | 0.1226 (12) | 0.6197 (11) | 0.029 (2)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S | 0.01181 (3) | 0.01940 (3) | 0.01626 (3) | 0.00409 (2) | 0.00269 (2) | 0.00708 (2) |
O | 0.01109 (8) | 0.0521 (2) | 0.02109 (11) | 0.00633 (10) | 0.00525 (7) | 0.01214 (12) |
N1 | 0.01003 (7) | 0.01882 (9) | 0.01295 (7) | 0.00205 (6) | 0.00312 (5) | 0.00540 (6) |
N3 | 0.01197 (7) | 0.01831 (9) | 0.01487 (8) | 0.00390 (6) | 0.00476 (6) | 0.00728 (6) |
C2 | 0.01125 (8) | 0.01405 (8) | 0.01279 (8) | 0.00246 (6) | 0.00296 (6) | 0.00371 (6) |
C4 | 0.01071 (8) | 0.01747 (9) | 0.01298 (8) | 0.00278 (6) | 0.00360 (6) | 0.00499 (7) |
C4' | 0.01802 (11) | 0.01742 (10) | 0.01571 (9) | 0.00457 (8) | 0.00502 (8) | 0.00471 (8) |
C4'' | 0.02268 (13) | 0.02163 (12) | 0.01444 (10) | 0.00266 (10) | 0.00474 (9) | 0.00180 (8) |
C5 | 0.01024 (8) | 0.01875 (9) | 0.01232 (8) | 0.00238 (6) | 0.00278 (6) | 0.00463 (7) |
C5' | 0.01074 (8) | 0.02340 (12) | 0.01483 (9) | 0.00230 (7) | 0.00218 (7) | 0.00572 (8) |
C5" | 0.01588 (11) | 0.03289 (17) | 0.01427 (10) | 0.00558 (10) | 0.00048 (8) | 0.00429 (10) |
C6 | 0.01072 (8) | 0.01633 (9) | 0.01147 (7) | 0.00169 (6) | 0.00283 (6) | 0.00354 (6) |
C6' | 0.01504 (10) | 0.02391 (12) | 0.01236 (8) | 0.00149 (8) | 0.00416 (7) | 0.00472 (8) |
Geometric parameters (Å, º) top
S—C2 | 1.6892 (3) | C4''—H41" | 0.973 (9) |
O—C5' | 1.2365 (4) | C4''—H42" | 0.966 (9) |
N1—C2 | 1.3738 (4) | C4''—H43" | 0.963 (10) |
N1—C6 | 1.3917 (4) | C5—C6 | 1.3651 (4) |
N1—H1 | 0.845 (11) | C5—C5' | 1.4656 (4) |
N3—C2 | 1.3270 (4) | C5'—C5" | 1.5061 (5) |
N3—C4 | 1.4684 (4) | C5"—H51" | 0.988 (11) |
N3—H3 | 0.862 (10) | C5"—H52" | 0.979 (9) |
C4—C5 | 1.5150 (4) | C5"—H53" | 0.950 (10) |
C4—C4' | 1.5370 (5) | C6—C6' | 1.5036 (4) |
C4—H4 | 0.999 (9) | C6'—H61' | 0.945 (9) |
C4'—C4'' | 1.5257 (5) | C6'—H62' | 0.967 (9) |
C4'—H41' | 0.989 (10) | C6'—H63' | 0.988 (9) |
C4'—H42' | 0.954 (9) | | |
| | | |
C2—N1—C6 | 123.30 (2) | C4'—C4''—H43" | 111.5 (6) |
C2—N1—H1 | 116.0 (7) | H41"—C4''—H43" | 107.4 (8) |
C6—N1—H1 | 119.8 (7) | H42"—C4''—H43" | 108.4 (8) |
C2—N3—C4 | 122.42 (2) | C6—C5—C5' | 126.60 (3) |
C2—N3—H3 | 117.6 (7) | C6—C5—C4 | 117.92 (2) |
C4—N3—H3 | 118.2 (7) | C5'—C5—C4 | 115.39 (2) |
N3—C2—N1 | 115.93 (2) | O—C5'—C5 | 118.15 (3) |
N3—C2—S | 124.15 (2) | O—C5'—C5" | 118.70 (3) |
N1—C2—S | 119.90 (2) | C5—C5'—C5" | 123.14 (3) |
N3—C4—C5 | 108.80 (2) | C5'—C5"—H51" | 110.6 (6) |
N3—C4—C4' | 110.64 (3) | C5'—C5"—H52" | 110.9 (6) |
C5—C4—C4' | 112.46 (2) | H51"—C5"—H52" | 108.3 (8) |
N3—C4—H4 | 104.6 (5) | C5'—C5"—H53" | 109.4 (7) |
C5—C4—H4 | 111.8 (5) | H51"—C5"—H53" | 108.9 (8) |
C4'—C4—H4 | 108.3 (5) | H52"—C5"—H53" | 108.7 (9) |
C4''—C4'—C4 | 112.76 (3) | C5—C6—N1 | 118.47 (2) |
C4''—C4'—H41' | 108.9 (6) | C5—C6—C6' | 128.51 (3) |
C4—C4'—H41' | 109.1 (5) | N1—C6—C6' | 113.02 (2) |
C4''—C4'—H42' | 109.8 (6) | C6—C6'—H61' | 113.7 (6) |
C4—C4'—H42' | 110.1 (5) | C6—C6'—H62' | 111.5 (5) |
H41'—C4'—H42' | 106.0 (8) | H61'—C6'—H62' | 108.6 (8) |
C4'—C4''—H41" | 111.5 (6) | C6—C6'—H63' | 114.3 (6) |
C4'—C4''—H42" | 109.8 (5) | H61'—C6'—H63' | 103.2 (8) |
H41"—C4''—H42" | 108.1 (8) | H62'—C6'—H63' | 104.7 (8) |
Crystal data top
? | β = ?° |
Mr = ? | γ = ?° |
?, ? | V = ? Å3 |
a = ? Å | Z = ? |
b = ? Å | ? radiation, λ = ? Å |
c = ? Å | × × mm |
α = ?° | |
Refinement top
Refinement on F2 | 10418 reflections |
Least-squares matrix: full | 275 parameters |
R[F2 > 2σ(F2)] = 0.019 | 0 restraints |
wR(F2) = 0.030 | ' w = 1/[σ2(Fo2) + (0.03P)2 + 2.56P] where P = (Fo2 + 2Fc2)/3' |
S = 1.43 | |
Crystal data top
? | β = ?° |
Mr = ? | γ = ?° |
?, ? | V = ? Å3 |
a = ? Å | Z = ? |
b = ? Å | ? radiation, λ = ? Å |
c = ? Å | × × mm |
α = ?° | |
Refinement top
R[F2 > 2σ(F2)] = 0.019 | 10418 reflections |
wR(F2) = 0.030 | 275 parameters |
S = 1.43 | 0 restraints |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S | 0.25777 (1) | 0.41714 (1) | 0.10035 (1) | 0.016 | |
O | 1.09233 (4) | 0.22310 (8) | 0.42246 (4) | 0.028 | |
N1 | 0.44344 (3) | 0.27514 (4) | 0.32472 (3) | 0.014 | |
N3 | 0.62331 (3) | 0.36956 (4) | 0.16490 (3) | 0.015 | |
C2 | 0.45356 (4) | 0.35041 (4) | 0.19873 (3) | 0.013 | |
C4 | 0.77758 (4) | 0.27107 (4) | 0.22533 (3) | 0.014 | |
C4' | 0.76432 (5) | 0.09243 (5) | 0.13048 (4) | 0.017 | |
C4" | 0.77987 (6) | 0.10450 (6) | −0.03143 (4) | 0.020 | |
C5 | 0.77280 (4) | 0.25834 (4) | 0.38787 (3) | 0.014 | |
C5' | 0.95558 (4) | 0.24494 (5) | 0.48338 (4) | 0.016 | |
C5" | 0.98376 (6) | 0.25615 (7) | 0.65110 (4) | 0.021 | |
C6 | 0.60130 (4) | 0.25115 (4) | 0.42918 (3) | 0.013 | |
C6' | 0.55524 (5) | 0.21770 (5) | 0.57670 (3) | 0.017 | |
H1 | 0.31362 | 0.25734 | 0.34869 | 0.022 | |
H3 | 0.63708 | 0.43228 | 0.07725 | 0.028 | |
H4 | 0.90513 | 0.34615 | 0.21347 | 0.025 | |
H41' | 0.88092 | 0.02488 | 0.18078 | 0.039 | |
H42' | 0.63226 | 0.02052 | 0.13670 | 0.036 | |
H41" | 0.90492 | 0.17842 | −0.03961 | 0.041 | |
H42" | 0.76508 | −0.02106 | −0.09356 | 0.044 | |
H43" | 0.66278 | 0.16308 | −0.08403 | 0.053 | |
H51" | 1.12924 | 0.28047 | 0.69950 | 0.047 | |
H52" | 0.91432 | 0.35938 | 0.69547 | 0.039 | |
H53" | 0.92992 | 0.13727 | 0.67854 | 0.044 | |
H61' | 0.60105 | 0.32259 | 0.66397 | 0.041 | |
H62' | 0.41059 | 0.17941 | 0.57092 | 0.043 | |
H63' | 0.62107 | 0.11366 | 0.62117 | 0.042 | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S | 0.01187 (2) | 0.01929 (3) | 0.01616 (2) | 0.00406 (2) | 0.00274 (2) | 0.00702 (2) |
O | 0.01106 (7) | 0.0518 (3) | 0.02027 (10) | 0.00620 (9) | 0.00499 (6) | 0.01159 (12) |
N1 | 0.01004 (5) | 0.01874 (8) | 0.01291 (6) | 0.00200 (5) | 0.00315 (4) | 0.00531 (5) |
N3 | 0.01207 (6) | 0.01825 (8) | 0.01465 (6) | 0.00390 (5) | 0.00479 (5) | 0.00720 (6) |
C2 | 0.01102 (6) | 0.01442 (7) | 0.01278 (6) | 0.00253 (5) | 0.00300 (5) | 0.00398 (5) |
C4 | 0.01087 (6) | 0.01736 (8) | 0.01275 (6) | 0.00261 (5) | 0.00364 (5) | 0.00484 (6) |
C4' | 0.01814 (9) | 0.01736 (9) | 0.01559 (8) | 0.00455 (7) | 0.00510 (7) | 0.00468 (7) |
C4" | 0.02284 (12) | 0.02143 (11) | 0.01429 (8) | 0.00252 (9) | 0.00477 (8) | 0.00181 (8) |
C5 | 0.01022 (6) | 0.01898 (8) | 0.01221 (6) | 0.00242 (5) | 0.00284 (5) | 0.00466 (6) |
C5' | 0.01054 (7) | 0.02415 (11) | 0.01441 (8) | 0.00249 (6) | 0.00222 (6) | 0.00576 (7) |
C5" | 0.01592 (10) | 0.03289 (17) | 0.01424 (8) | 0.00570 (10) | 0.00064 (7) | 0.00434 (9) |
C6 | 0.01052 (6) | 0.01677 (8) | 0.01130 (6) | 0.00169 (5) | 0.00289 (5) | 0.00370 (5) |
C6' | 0.01517 (8) | 0.02387 (11) | 0.01220 (7) | 0.00151 (7) | 0.00417 (6) | 0.00473 (7) |
Crystal data top
C8H12N2O2 | F(000) = 720 |
Mr = 168.20 | Dx = 1.355 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 14.2785 (1) Å | Cell parameters from 9999 reflections |
b = 6.9187 (1) Å | θ = 2.4–51.5° |
c = 17.1827 (2) Å | µ = 0.10 mm−1 |
β = 103.642 (1)° | T = 110 K |
V = 1649.56 (1) Å3 | Prism, colorless |
Z = 8 | 0.42 × 0.34 × 0.22 mm |
Data collection top
Bruker diffractometer with a SMART 6000 CCD detector | Rint = 0.048 |
Graphite monochromator | θmax = 51.5°, θmin = 2.4° |
ω scans | h = 0→29 |
46839 measured reflections | k = 0→15 |
8718 independent reflections | l = −37→36 |
7330 reflections with I > 2σ(I) | |
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)] = 0.037 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.116 | All H-atom parameters refined |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0787P)2] where P = (Fo2 + 2Fc2)/3 |
8718 reflections | (Δ/σ)max = 0.001 |
157 parameters | Δρmax = 0.81 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
Crystal data top
C8H12N2O2 | V = 1649.56 (1) Å3 |
Mr = 168.20 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 14.2785 (1) Å | µ = 0.10 mm−1 |
b = 6.9187 (1) Å | T = 110 K |
c = 17.1827 (2) Å | 0.42 × 0.34 × 0.22 mm |
β = 103.642 (1)° | |
Data collection top
Bruker diffractometer with a SMART 6000 CCD detector | 7330 reflections with I > 2σ(I) |
46839 measured reflections | Rint = 0.048 |
8718 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.116 | All H-atom parameters refined |
S = 1.08 | Δρmax = 0.81 e Å−3 |
8718 reflections | Δρmin = −0.25 e Å−3 |
157 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.31998 (2) | 0.72688 (4) | 0.427659 (15) | 0.01857 (5) | |
O2 | 0.11751 (2) | −0.01312 (4) | 0.278433 (17) | 0.02043 (5) | |
N1 | 0.19285 (2) | 0.53867 (4) | 0.440001 (15) | 0.01468 (4) | |
N3 | 0.272344 (18) | 0.47801 (4) | 0.340460 (14) | 0.01372 (4) | |
C2 | 0.26456 (2) | 0.59029 (4) | 0.402018 (15) | 0.01342 (4) | |
C4 | 0.19485 (2) | 0.34889 (4) | 0.299860 (15) | 0.01320 (4) | |
C4' | 0.12283 (3) | 0.45513 (5) | 0.233209 (19) | 0.01869 (5) | |
C5 | 0.14602 (2) | 0.25923 (4) | 0.360596 (16) | 0.01279 (4) | |
C5' | 0.10425 (2) | 0.06699 (4) | 0.339243 (17) | 0.01410 (4) | |
C5" | 0.04508 (3) | −0.03817 (5) | 0.38795 (2) | 0.01790 (5) | |
C6 | 0.14326 (2) | 0.36476 (4) | 0.427177 (15) | 0.01277 (4) | |
C6' | 0.09215 (2) | 0.31871 (5) | 0.492226 (18) | 0.01685 (5) | |
H1 | 0.1881 (6) | 0.6101 (13) | 0.4794 (5) | 0.0277 (19)* | |
H3 | 0.3178 (7) | 0.5094 (13) | 0.3103 (6) | 0.033 (2)* | |
H4 | 0.2272 (6) | 0.2468 (12) | 0.2744 (5) | 0.0216 (17)* | |
H41' | 0.1564 (7) | 0.5016 (12) | 0.1901 (5) | 0.0275 (19)* | |
H42' | 0.0703 (7) | 0.3669 (13) | 0.2076 (6) | 0.034 (2)* | |
H43' | 0.0951 (7) | 0.5628 (13) | 0.2548 (6) | 0.0283 (19)* | |
H51" | 0.0187 (7) | −0.1557 (13) | 0.3579 (6) | 0.034 (2)* | |
H52" | 0.0841 (7) | −0.0625 (14) | 0.4437 (5) | 0.032 (2)* | |
H53" | −0.0089 (6) | 0.0475 (12) | 0.3969 (5) | 0.0229 (18)* | |
H61' | 0.1189 (7) | 0.2005 (14) | 0.5217 (5) | 0.034 (2)* | |
H62' | 0.0979 (7) | 0.4359 (15) | 0.5300 (6) | 0.036 (2)* | |
H63' | 0.0242 (7) | 0.3088 (14) | 0.4690 (6) | 0.035 (2)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.02115 (10) | 0.01990 (10) | 0.01561 (8) | −0.00738 (7) | 0.00625 (7) | −0.00466 (7) |
O2 | 0.02474 (11) | 0.01969 (10) | 0.02038 (10) | −0.00641 (8) | 0.01239 (8) | −0.00705 (8) |
N1 | 0.01733 (9) | 0.01469 (9) | 0.01370 (8) | −0.00178 (6) | 0.00702 (6) | −0.00235 (6) |
N3 | 0.01381 (8) | 0.01625 (9) | 0.01208 (7) | −0.00214 (6) | 0.00500 (6) | −0.00176 (6) |
C2 | 0.01452 (9) | 0.01469 (9) | 0.01130 (8) | −0.00130 (6) | 0.00359 (6) | −0.00053 (7) |
C4 | 0.01480 (9) | 0.01425 (9) | 0.01161 (8) | −0.00169 (6) | 0.00523 (6) | −0.00161 (7) |
C4' | 0.01891 (12) | 0.02324 (13) | 0.01291 (9) | −0.00327 (9) | 0.00173 (8) | 0.00177 (8) |
C5 | 0.01396 (9) | 0.01336 (9) | 0.01202 (8) | −0.00062 (6) | 0.00501 (6) | −0.00046 (6) |
C5' | 0.01461 (9) | 0.01457 (9) | 0.01403 (9) | −0.00124 (7) | 0.00523 (7) | −0.00082 (7) |
C5" | 0.02060 (12) | 0.01768 (11) | 0.01691 (10) | −0.00430 (8) | 0.00742 (8) | 0.00061 (8) |
C6 | 0.01362 (9) | 0.01391 (9) | 0.01158 (8) | 0.00046 (6) | 0.00461 (6) | 0.00014 (6) |
C6' | 0.01978 (12) | 0.01864 (11) | 0.01456 (9) | −0.00031 (8) | 0.00889 (8) | 0.00024 (8) |
Geometric parameters (Å, º) top
O1—C2 | 1.2446 (4) | C4'—H42' | 0.986 (9) |
O2—C5' | 1.2361 (4) | C4'—H43' | 0.958 (9) |
N1—C2 | 1.3845 (4) | C5—C6 | 1.3656 (4) |
N1—C6 | 1.3872 (4) | C5—C5' | 1.4684 (4) |
N1—H1 | 0.853 (9) | C5'—C5" | 1.5091 (4) |
N3—C2 | 1.3379 (4) | C5"—H51" | 0.989 (9) |
N3—C4 | 1.4645 (4) | C5"—H52" | 1.002 (9) |
N3—H3 | 0.946 (10) | C5"—H53" | 1.012 (8) |
C4—C5 | 1.5177 (4) | C6—C6' | 1.5060 (4) |
C4—C4' | 1.5342 (4) | C6'—H61' | 0.990 (9) |
C4—H4 | 1.000 (8) | C6'—H62' | 1.030 (10) |
C4'—H41' | 1.024 (9) | C6'—H63' | 0.960 (10) |
| | | |
C2—N1—C6 | 123.74 (2) | C6—C5—C5' | 127.11 (2) |
C2—N1—H1 | 115.5 (6) | C6—C5—C4 | 117.79 (2) |
C6—N1—H1 | 119.7 (6) | C5'—C5—C4 | 115.07 (2) |
C2—N3—C4 | 122.44 (2) | O2—C5'—C5 | 118.90 (3) |
C2—N3—H3 | 119.7 (6) | O2—C5'—C5" | 118.04 (3) |
C4—N3—H3 | 114.7 (6) | C5—C5'—C5" | 123.07 (2) |
O1—C2—N3 | 123.80 (3) | C5'—C5"—H51" | 107.5 (5) |
O1—C2—N1 | 120.54 (3) | C5'—C5"—H52" | 110.7 (5) |
N3—C2—N1 | 115.56 (3) | H51"—C5"—H52" | 114.7 (8) |
N3—C4—C5 | 109.86 (2) | C5'—C5"—H53" | 110.3 (5) |
N3—C4—C4' | 111.19 (2) | H51"—C5"—H53" | 110.6 (7) |
C5—C4—C4' | 111.92 (2) | H52"—C5"—H53" | 103.1 (7) |
N3—C4—H4 | 105.3 (5) | C5—C6—N1 | 118.84 (2) |
C5—C4—H4 | 110.3 (5) | C5—C6—C6' | 128.57 (3) |
C4'—C4—H4 | 108.1 (5) | N1—C6—C6' | 112.59 (2) |
C4—C4'—H41' | 110.2 (5) | C6—C6'—H61' | 111.0 (5) |
C4—C4'—H42' | 109.9 (5) | C6—C6'—H62' | 108.7 (6) |
H41'—C4'—H42' | 107.9 (7) | H61'—C6'—H62' | 111.3 (8) |
C4—C4'—H43' | 110.4 (6) | C6—C6'—H63' | 109.0 (6) |
H41'—C4'—H43' | 110.0 (7) | H61'—C6'—H63' | 112.6 (8) |
H42'—C4'—H43' | 108.3 (8) | H62'—C6'—H63' | 103.9 (8) |
Crystal data top
? | β = ?° |
Mr = ? | γ = ?° |
?, ? | V = ? Å3 |
a = ? Å | Z = ? |
b = ? Å | ? radiation, λ = ? Å |
c = ? Å | × × mm |
α = ?° | |
Refinement top
Refinement on F | 6921 reflections |
Least-squares matrix: full | 228 parameters |
R[F2 > 2σ(F2)] = 0.019 | 0 restraints |
wR(F2) = 0.022 | ' w = 1/[σ2(Fo2) + (0.00015)2] |
S = 1.07 | |
Crystal data top
? | β = ?° |
Mr = ? | γ = ?° |
?, ? | V = ? Å3 |
a = ? Å | Z = ? |
b = ? Å | ? radiation, λ = ? Å |
c = ? Å | × × mm |
α = ?° | |
Refinement top
R[F2 > 2σ(F2)] = 0.019 | 6921 reflections |
wR(F2) = 0.022 | 228 parameters |
S = 1.07 | 0 restraints |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.32001 (2) | 0.72664 (4) | 0.42766 (1) | 0.019 | |
O2 | 0.11744 (2) | −0.01319 (4) | 0.27846 (1) | 0.022 | |
N1 | 0.19289 (2) | 0.53861 (3) | 0.44001 (1) | 0.015 | |
N3 | 0.27227 (1) | 0.47811 (3) | 0.34040 (1) | 0.014 | |
C2 | 0.26452 (2) | 0.59020 (4) | 0.40198 (1) | 0.014 | |
C4 | 0.19490 (2) | 0.34905 (4) | 0.29991 (1) | 0.013 | |
C4' | 0.12286 (2) | 0.45506 (5) | 0.23320 (1) | 0.018 | |
C5 | 0.14605 (2) | 0.25924 (3) | 0.36061 (1) | 0.013 | |
C5' | 0.10429 (2) | 0.06699 (4) | 0.33928 (1) | 0.014 | |
C5" | 0.04502 (2) | −0.03810 (4) | 0.38796 (2) | 0.018 | |
C6 | 0.14326 (2) | 0.36489 (3) | 0.42720 (1) | 0.013 | |
C6' | 0.09221 (2) | 0.31865 (4) | 0.49226 (1) | 0.018 | |
H1 | 0.18717 | 0.62302 | 0.48657 | 0.025 | |
H3 | 0.32411 | 0.51271 | 0.31178 | 0.024 | |
H4 | 0.22930 | 0.23497 | 0.27249 | 0.029 | |
H41' | 0.15866 | 0.49964 | 0.18891 | 0.043 | |
H42' | 0.06537 | 0.36276 | 0.20594 | 0.039 | |
H43' | 0.09554 | 0.57766 | 0.25732 | 0.043 | |
H51" | 0.01985 | −0.16809 | 0.35773 | 0.047 | |
H52" | 0.08649 | −0.07860 | 0.44511 | 0.044 | |
H53" | −0.01475 | 0.04542 | 0.39440 | 0.038 | |
H61' | 0.12043 | 0.19080 | 0.52269 | 0.049 | |
H62' | 0.10272 | 0.43330 | 0.53418 | 0.049 | |
H63' | 0.01690 | 0.30331 | 0.46998 | 0.043 | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.02112 (8) | 0.01998 (8) | 0.01524 (5) | −0.00748 (6) | 0.00650 (5) | −0.00485 (5) |
O2 | 0.02535 (9) | 0.01968 (8) | 0.02022 (7) | −0.00709 (6) | 0.01297 (7) | −0.00739 (6) |
N1 | 0.01743 (7) | 0.01472 (7) | 0.01338 (5) | −0.00191 (5) | 0.00702 (5) | −0.00250 (5) |
N3 | 0.01374 (6) | 0.01627 (7) | 0.01178 (5) | −0.00230 (4) | 0.00497 (4) | −0.00174 (5) |
C2 | 0.01466 (7) | 0.01466 (7) | 0.01121 (5) | −0.00178 (5) | 0.00377 (5) | −0.00103 (5) |
C4 | 0.01464 (7) | 0.01432 (7) | 0.01145 (5) | −0.00155 (5) | 0.00519 (5) | −0.00152 (5) |
C4' | 0.01877 (8) | 0.02333 (10) | 0.01287 (6) | −0.00322 (7) | 0.00166 (6) | 0.00193 (6) |
C5 | 0.01422 (7) | 0.01340 (7) | 0.01178 (5) | −0.00078 (5) | 0.00516 (5) | −0.00065 (5) |
C5' | 0.01509 (7) | 0.01429 (7) | 0.01393 (6) | −0.00166 (5) | 0.00577 (5) | −0.00122 (5) |
C5" | 0.02068 (9) | 0.01773 (9) | 0.01675 (7) | −0.00433 (6) | 0.00740 (6) | 0.00054 (6) |
C6 | 0.01379 (6) | 0.01381 (7) | 0.01128 (5) | 0.00019 (5) | 0.00490 (4) | −0.00012 (5) |
C6' | 0.01956 (9) | 0.01876 (9) | 0.01448 (6) | −0.00048 (6) | 0.00880 (6) | 0.00021 (6) |
Experimental details
| (I) | (Imult) | (II) | (IImult) |
Crystal data |
Chemical formula | C9H14N2OS | ? | C8H12N2O2 | ? |
Mr | 198.28 | ? | 168.20 | ? |
Crystal system, space group | Triclinic, P1 | ?, ? | Monoclinic, C2/c | ?, ? |
Temperature (K) | 110 | ? | 110 | ? |
a, b, c (Å) | 7.2533 (2), 7.8212 (3), 9.1837 (3) | ?, ?, ? | 14.2785 (1), 6.9187 (1), 17.1827 (2) | ?, ?, ? |
α, β, γ (°) | 97.187 (1), 100.674 (1), 94.106 (1) | ?, ?, ? | 90, 103.642 (1), 90 | ?, ?, ? |
V (Å3) | 505.54 (2) | ? | 1649.56 (1) | ? |
Z | 2 | ? | 8 | ? |
Radiation type | Mo Kα | ?, λ = ? Å | Mo Kα | ?, λ = ? Å |
µ (mm−1) | 0.28 | ? | 0.10 | ? |
Crystal size (mm) | 0.40 × 0.22 × 0.14 | × × | 0.42 × 0.34 × 0.22 | × × |
|
Data collection |
Diffractometer | Bruker diffractometer with a SMART 6000 CCD detector | ? | Bruker diffractometer with a SMART 6000 CCD detector | ? |
Absorption correction | Multi-scan R.H. Blessing, Acta Cryst. (1995), A51, 33-38 | ? | – | ? |
Tmin, Tmax | 0.909, 1.106 | ?, ? | – | ?, ? |
No. of measured, independent and observed reflections | 57560, 12868, 10974 [I > 2σ(I)] | ?, ?, ? (?) | 46839, 8718, 7330 [I > 2σ(I)] | ?, ?, ? (?) |
Rint | 0.042 | ? | 0.048 | ? |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.092, 1.08 | 0.019, 0.030, 1.43 | 0.037, 0.116, 1.08 | 0.019, 0.022, 1.07 |
No. of reflections | 12868 | 10418 | 8718 | 6921 |
No. of parameters | 174 | 275 | 157 | 228 |
H-atom treatment | All H-atom parameters refined | – | All H-atom parameters refined | – |
Δρmax, Δρmin (e Å−3) | 0.81, −0.58 | ?, ? | 0.81, −0.25 | ?, ? |