The room-temperature crystal structures of four new thio derivatives of N-methylphenobarbital [systematic name: 5-ethyl-1-methyl-5-phenylpyrimidine-2,4,6(1H,3H,5H)-trione], C13H14N2O3, are compared with the structure of the parent compound. The sulfur substituents in N-methyl-2-thiophenobarbital [5-ethyl-1-methyl-5-phenyl-2-thioxo-1,2-dihydropyrimidine-4,6(3H,5H)-dione], C13H14N2O2S, N-methyl-4-thiophenobarbital [5-ethyl-1-methyl-5-phenyl-4-thioxo-3,4-dihydropyrimidine-2,6(1H,5H)-dione], C13H14N2O2S, and N-methyl-2,4,6-trithiophenobarbital [5-ethyl-1-methyl-5-phenylpyrimidine-2,4,6(1H,3H,5H)-trithione], C13H14N2S3, preserve the heterocyclic ring puckering observed for N-methylphenobarbital (a half-chair conformation), whereas in N-methyl-2,4-dithiophenobarbital [5-ethyl-1-methyl-5-phenyl-2,4-dithioxo-1,2,3,4-tetrahydropyrimidine-6(5H)-one], C13H14N2OS2, significant flattening of the ring was detected. The number and positions of the sulfur substituents influence the packing and hydrogen-bonding patterns of the derivatives. In the cases of the 2-thio, 4-thio and 2,4,6-trithio derivatives, there is a preference for the formation of a ring motif of the R22(8) type, which is also a characteristic of N-methylphenobarbital, whereas a C(6) chain forms in the 2,4-dithio derivative. The preferences for hydrogen-bond formation, which follow the sequence of acceptor position 4 > 2 > 6, confirm the differences in the nucleophilic properties of the C atoms of the heterocyclic ring and are consistent with the course of N-methylphenobarbital thionation reactions.
Supporting information
| Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108043060/ln3120sup1.cif Contains datablocks global, 2-TP, 4-TP, 2,4-DTP, 2,4,6-TTP, P |
| Structure factor file (CIF format) https://doi.org/10.1107/S0108270108043060/ln31202-TPsup2.hkl Contains datablock 2-TP |
| Structure factor file (CIF format) https://doi.org/10.1107/S0108270108043060/ln31204-TPsup3.hkl Contains datablock 4-TP |
| Structure factor file (CIF format) https://doi.org/10.1107/S0108270108043060/ln31202,4-DTPsup4.hkl Contains datablock 2,4-DTP |
| Structure factor file (CIF format) https://doi.org/10.1107/S0108270108043060/ln31202,4,6-TTPsup5.hkl Contains datablock 2,4,6-TTP |
| Structure factor file (CIF format) https://doi.org/10.1107/S0108270108043060/ln3120Psup6.hkl Contains datablock P |
CCDC references: 724210; 724211; 724212; 724213; 724214
The compunds were obtained by the thionation of N-methylphenobarbital
with Lawesson's reagent (Stasiewicz-Urban et al., 2004).
Crystals
suitable for X-ray diffraction were grown by slow evaporation at room
temperature from the following solvents: (2-TP) and (4-TP) from a mixture of
n-hexane and ethyl acetate in the ratio 3:1, (2,4-DTP) from
cyclohexane, (2,4,6-TTP) from n-hexane and (P) from ethanol.
Although all the derivatives studied have a chiral centre at the C5 atom, their
crystal structures are centrosymmetric and so the crystals contain racemates.
All H atoms were initially located in difference Fourier maps. The H atoms of
the methyl (C1, C8) and methylene (C7) groups and those of the phenyl ring
(C10–C14) were subsequently included in the refinement in geometrically
idealised positions with C—H = 0.96, 0.97 and 0.93 Å, respectively, and
refined using the riding model with isotropic displacement factors of
Uiso(H) = 1.2Ueq (parent atom). The H atom attached to atom
N3 was constrained to an idealised position for (2-TP) with N—H = 0.86 Å,
restrained assuming a target N—H distance of 0.86 (1) Å for (2,4,6-TTP) and
with Uiso(H) = 1.2Ueq(N) in both cases. For the remaining
structures, the positional and displacement parameters of this H atom were
refined freely.
In the last stage of the refinement, a few reflections, probably affected by
absorption, wer omitted [(4-TP): reflections 200 and 153; (2,4-DTP): 032,
0121, 793 and 210; (2,4,6-TTP): 200; (P): 413, 620 and 114]. Additionally, in
the case of (2,4-DTP) the θmax was also reduced from 27.41 to 27.00° (97
reflections omitted) which improved the data completeness (0.976 to 0.986).
For all compounds, data collection: COLLECT (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: HKL DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); ORTEP-3 for Windows (Farrugia, 1997); Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
(2-TP) 5-ethyl-1-methyl-5-phenyl-2-thioxo-1,2-dihydropyrimidine-
4,6(3
H,5
H)-dione
top
Crystal data top
C13H14N2O2S | F(000) = 552 |
Mr = 262.32 | Dx = 1.339 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 12.9315 (3) Å | Cell parameters from 2315 reflections |
b = 7.1804 (2) Å | θ = 1.0–27.5° |
c = 15.2362 (5) Å | µ = 0.24 mm−1 |
β = 113.077 (1)° | T = 293 K |
V = 1301.52 (6) Å3 | Block, yellow |
Z = 4 | 0.35 × 0.30 × 0.12 mm |
Data collection top
KappaCCD diffractometer | 2978 independent reflections |
Radiation source: fine-focus sealed tube | 2293 reflections with I > 2σ(I) |
Horizontally mounted graphite crystal monochromator | Rint = 0.021 |
Detector resolution: 9 pixels mm-1 | θmax = 27.5°, θmin = 2.9° |
ϕ scans and ω scans to fill asymmetric unit | h = −16→16 |
Absorption correction: multi-scan (HKL DENZO and SCALEPACK; Otwinowski & Minor, 1997) | k = −9→9 |
Tmin = 0.924, Tmax = 0.976 | l = −19→19 |
4964 measured reflections | |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.045 | H-atom parameters constrained |
wR(F2) = 0.111 | w = 1/[σ2(Fo2) + (0.0382P)2 + 0.5601P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max < 0.001 |
2978 reflections | Δρmax = 0.24 e Å−3 |
164 parameters | Δρmin = −0.28 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.010 (3) |
Crystal data top
C13H14N2O2S | V = 1301.52 (6) Å3 |
Mr = 262.32 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 12.9315 (3) Å | µ = 0.24 mm−1 |
b = 7.1804 (2) Å | T = 293 K |
c = 15.2362 (5) Å | 0.35 × 0.30 × 0.12 mm |
β = 113.077 (1)° | |
Data collection top
KappaCCD diffractometer | 2978 independent reflections |
Absorption correction: multi-scan (HKL DENZO and SCALEPACK; Otwinowski & Minor, 1997) | 2293 reflections with I > 2σ(I) |
Tmin = 0.924, Tmax = 0.976 | Rint = 0.021 |
4964 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.111 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.24 e Å−3 |
2978 reflections | Δρmin = −0.28 e Å−3 |
164 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | 0.69598 (11) | 0.20338 (18) | −0.15072 (9) | 0.0340 (3) | |
C1 | 0.61802 (17) | 0.1000 (3) | −0.23340 (13) | 0.0491 (5) | |
H1A | 0.5427 | 0.1147 | −0.2370 | 0.059* | |
H1B | 0.6377 | −0.0297 | −0.2265 | 0.059* | |
H1C | 0.6228 | 0.1473 | −0.2906 | 0.059* | |
C2 | 0.80863 (15) | 0.2009 (2) | −0.13225 (12) | 0.0370 (4) | |
S2 | 0.86488 (5) | 0.07263 (8) | −0.19133 (4) | 0.0633 (2) | |
N3 | 0.87524 (12) | 0.3196 (2) | −0.06250 (10) | 0.0382 (4) | |
H3 | 0.9433 | 0.3321 | −0.0579 | 0.046* | |
C4 | 0.84634 (13) | 0.4202 (2) | 0.00043 (11) | 0.0326 (4) | |
O4 | 0.91342 (10) | 0.52423 (19) | 0.05753 (9) | 0.0480 (3) | |
C5 | 0.72875 (13) | 0.3900 (2) | −0.00387 (11) | 0.0290 (3) | |
C6 | 0.64935 (13) | 0.3179 (2) | −0.10122 (12) | 0.0332 (4) | |
O6 | 0.54948 (10) | 0.3441 (2) | −0.13142 (9) | 0.0507 (4) | |
C7 | 0.68492 (15) | 0.5742 (2) | 0.02065 (13) | 0.0384 (4) | |
H7A | 0.6112 | 0.5526 | 0.0213 | 0.046* | |
H7B | 0.7346 | 0.6123 | 0.0844 | 0.046* | |
C8 | 0.6764 (2) | 0.7322 (3) | −0.04828 (16) | 0.0556 (5) | |
H8A | 0.6486 | 0.8419 | −0.0288 | 0.067* | |
H8B | 0.6259 | 0.6972 | −0.1114 | 0.067* | |
H8C | 0.7494 | 0.7572 | −0.0482 | 0.067* | |
C9 | 0.73075 (13) | 0.2338 (2) | 0.06672 (11) | 0.0294 (3) | |
C10 | 0.82660 (15) | 0.1345 (2) | 0.11969 (12) | 0.0408 (4) | |
H10 | 0.8938 | 0.1612 | 0.1136 | 0.049* | |
C11 | 0.82360 (18) | −0.0042 (3) | 0.18170 (14) | 0.0528 (5) | |
H11 | 0.8890 | −0.0690 | 0.2171 | 0.063* | |
C12 | 0.7254 (2) | −0.0470 (3) | 0.19144 (14) | 0.0524 (5) | |
H12 | 0.7238 | −0.1400 | 0.2334 | 0.063* | |
C13 | 0.62957 (19) | 0.0491 (3) | 0.13846 (16) | 0.0555 (5) | |
H13 | 0.5624 | 0.0200 | 0.1442 | 0.067* | |
C14 | 0.63141 (15) | 0.1886 (3) | 0.07675 (14) | 0.0444 (5) | |
H14 | 0.5657 | 0.2528 | 0.0416 | 0.053* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0381 (8) | 0.0330 (7) | 0.0300 (7) | −0.0067 (6) | 0.0124 (6) | −0.0024 (6) |
C1 | 0.0555 (12) | 0.0490 (11) | 0.0389 (10) | −0.0171 (9) | 0.0143 (9) | −0.0107 (9) |
C2 | 0.0438 (10) | 0.0330 (8) | 0.0383 (9) | −0.0035 (7) | 0.0206 (8) | −0.0005 (7) |
S2 | 0.0720 (4) | 0.0593 (4) | 0.0726 (4) | 0.0001 (3) | 0.0434 (3) | −0.0232 (3) |
N3 | 0.0308 (7) | 0.0462 (8) | 0.0432 (8) | −0.0080 (6) | 0.0207 (6) | −0.0094 (7) |
C4 | 0.0311 (8) | 0.0356 (8) | 0.0335 (9) | −0.0059 (7) | 0.0155 (7) | −0.0022 (7) |
O4 | 0.0378 (7) | 0.0607 (8) | 0.0491 (8) | −0.0205 (6) | 0.0211 (6) | −0.0202 (7) |
C5 | 0.0281 (8) | 0.0308 (8) | 0.0307 (8) | −0.0016 (6) | 0.0142 (6) | −0.0009 (6) |
C6 | 0.0319 (8) | 0.0338 (8) | 0.0341 (9) | −0.0036 (7) | 0.0130 (7) | 0.0041 (7) |
O6 | 0.0294 (7) | 0.0648 (9) | 0.0499 (8) | 0.0008 (6) | 0.0069 (6) | −0.0003 (7) |
C7 | 0.0436 (10) | 0.0328 (9) | 0.0446 (10) | 0.0014 (7) | 0.0235 (8) | −0.0010 (7) |
C8 | 0.0749 (15) | 0.0348 (10) | 0.0637 (14) | 0.0049 (10) | 0.0342 (12) | 0.0053 (9) |
C9 | 0.0309 (8) | 0.0285 (7) | 0.0294 (8) | −0.0031 (6) | 0.0125 (7) | −0.0018 (6) |
C10 | 0.0365 (9) | 0.0435 (9) | 0.0399 (10) | −0.0004 (8) | 0.0124 (8) | 0.0044 (8) |
C11 | 0.0561 (12) | 0.0468 (11) | 0.0448 (11) | 0.0063 (9) | 0.0082 (9) | 0.0111 (9) |
C12 | 0.0790 (15) | 0.0399 (10) | 0.0423 (11) | −0.0045 (10) | 0.0280 (11) | 0.0079 (9) |
C13 | 0.0584 (13) | 0.0552 (12) | 0.0660 (14) | −0.0078 (10) | 0.0383 (11) | 0.0103 (11) |
C14 | 0.0375 (9) | 0.0457 (10) | 0.0565 (12) | 0.0015 (8) | 0.0254 (9) | 0.0115 (9) |
Geometric parameters (Å, º) top
N1—C2 | 1.371 (2) | C7—H7A | 0.9700 |
N1—C6 | 1.402 (2) | C7—H7B | 0.9700 |
N1—C1 | 1.469 (2) | C8—H8A | 0.9600 |
C1—H1A | 0.9600 | C8—H8B | 0.9600 |
C1—H1B | 0.9600 | C8—H8C | 0.9600 |
C1—H1C | 0.9600 | C9—C10 | 1.383 (2) |
C2—N3 | 1.371 (2) | C9—C14 | 1.390 (2) |
C2—S2 | 1.6436 (17) | C10—C11 | 1.384 (3) |
N3—C4 | 1.364 (2) | C10—H10 | 0.9300 |
N3—H3 | 0.8600 | C11—C12 | 1.370 (3) |
C4—O4 | 1.2147 (19) | C11—H11 | 0.9300 |
C4—C5 | 1.512 (2) | C12—C13 | 1.371 (3) |
C5—C6 | 1.526 (2) | C12—H12 | 0.9300 |
C5—C7 | 1.542 (2) | C13—C14 | 1.380 (3) |
C5—C9 | 1.547 (2) | C13—H13 | 0.9300 |
C6—O6 | 1.2039 (19) | C14—H14 | 0.9300 |
C7—C8 | 1.520 (2) | | |
| | | |
C2—N1—C6 | 122.93 (14) | C5—C7—H7A | 108.8 |
C2—N1—C1 | 119.09 (15) | C8—C7—H7B | 108.8 |
C6—N1—C1 | 117.54 (14) | C5—C7—H7B | 108.8 |
N1—C1—H1A | 109.5 | H7A—C7—H7B | 107.6 |
N1—C1—H1B | 109.5 | C7—C8—H8A | 109.5 |
H1A—C1—H1B | 109.5 | C7—C8—H8B | 109.5 |
N1—C1—H1C | 109.5 | H8A—C8—H8B | 109.5 |
H1A—C1—H1C | 109.5 | C7—C8—H8C | 109.5 |
H1B—C1—H1C | 109.5 | H8A—C8—H8C | 109.5 |
N3—C2—N1 | 116.44 (14) | H8B—C8—H8C | 109.5 |
N3—C2—S2 | 119.63 (13) | C10—C9—C14 | 118.10 (15) |
N1—C2—S2 | 123.87 (13) | C10—C9—C5 | 123.12 (14) |
C4—N3—C2 | 127.72 (14) | C14—C9—C5 | 118.77 (14) |
C4—N3—H3 | 116.1 | C9—C10—C11 | 120.73 (17) |
C2—N3—H3 | 116.1 | C9—C10—H10 | 119.6 |
O4—C4—N3 | 120.89 (14) | C11—C10—H10 | 119.6 |
O4—C4—C5 | 122.89 (14) | C12—C11—C10 | 120.72 (19) |
N3—C4—C5 | 116.20 (13) | C12—C11—H11 | 119.6 |
C4—C5—C6 | 111.91 (13) | C10—C11—H11 | 119.6 |
C4—C5—C7 | 109.00 (13) | C11—C12—C13 | 119.04 (17) |
C6—C5—C7 | 110.83 (13) | C11—C12—H12 | 120.5 |
C4—C5—C9 | 109.35 (13) | C13—C12—H12 | 120.5 |
C6—C5—C9 | 104.53 (12) | C12—C13—C14 | 120.89 (18) |
C7—C5—C9 | 111.17 (12) | C12—C13—H13 | 119.6 |
O6—C6—N1 | 120.63 (15) | C14—C13—H13 | 119.6 |
O6—C6—C5 | 122.05 (15) | C13—C14—C9 | 120.51 (17) |
N1—C6—C5 | 117.04 (14) | C13—C14—H14 | 119.7 |
C8—C7—C5 | 113.99 (14) | C9—C14—H14 | 119.7 |
C8—C7—H7A | 108.8 | | |
| | | |
C6—N1—C2—N3 | −0.8 (2) | C4—C5—C6—N1 | 32.14 (18) |
C1—N1—C2—N3 | 171.37 (15) | C7—C5—C6—N1 | 154.04 (13) |
C6—N1—C2—S2 | −178.15 (12) | C9—C5—C6—N1 | −86.11 (15) |
C1—N1—C2—S2 | −6.0 (2) | C4—C5—C7—C8 | 61.7 (2) |
N1—C2—N3—C4 | 10.4 (3) | C6—C5—C7—C8 | −61.94 (19) |
S2—C2—N3—C4 | −172.09 (14) | C9—C5—C7—C8 | −177.74 (15) |
C2—N3—C4—O4 | −178.22 (17) | C4—C5—C9—C10 | −3.4 (2) |
C2—N3—C4—C5 | 3.4 (2) | C6—C5—C9—C10 | 116.58 (17) |
O4—C4—C5—C6 | 157.90 (16) | C7—C5—C9—C10 | −123.80 (17) |
N3—C4—C5—C6 | −23.72 (19) | C4—C5—C9—C14 | 177.55 (15) |
O4—C4—C5—C7 | 35.0 (2) | C6—C5—C9—C14 | −62.48 (18) |
N3—C4—C5—C7 | −146.67 (14) | C7—C5—C9—C14 | 57.1 (2) |
O4—C4—C5—C9 | −86.76 (19) | C14—C9—C10—C11 | −0.8 (3) |
N3—C4—C5—C9 | 91.62 (16) | C5—C9—C10—C11 | −179.87 (16) |
C2—N1—C6—O6 | 165.03 (16) | C9—C10—C11—C12 | 0.5 (3) |
C1—N1—C6—O6 | −7.3 (2) | C10—C11—C12—C13 | 0.3 (3) |
C2—N1—C6—C5 | −20.9 (2) | C11—C12—C13—C14 | −0.7 (3) |
C1—N1—C6—C5 | 166.77 (14) | C12—C13—C14—C9 | 0.3 (3) |
C4—C5—C6—O6 | −153.92 (16) | C10—C9—C14—C13 | 0.4 (3) |
C7—C5—C6—O6 | −32.0 (2) | C5—C9—C14—C13 | 179.51 (17) |
C9—C5—C6—O6 | 87.84 (18) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O4i | 0.86 | 2.12 | 2.927 (2) | 157 |
Symmetry code: (i) −x+2, −y+1, −z. |
(4-TP) 5-ethyl-1-methyl-5-phenyl-4-thioxo-3,4-dihydropyrimidine-
2,6(1
H,5
H)-dione
top
Crystal data top
C13H14N2O2S | F(000) = 552 |
Mr = 262.32 | Dx = 1.373 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 11.5609 (3) Å | Cell parameters from 3185 reflections |
b = 9.5538 (3) Å | θ = 1.0–29.1° |
c = 11.7268 (3) Å | µ = 0.25 mm−1 |
β = 101.521 (2)° | T = 293 K |
V = 1269.13 (6) Å3 | Plate, yellow |
Z = 4 | 0.32 × 0.30 × 0.07 mm |
Data collection top
KappaCCD diffractometer | 3381 independent reflections |
Radiation source: fine-focus sealed tube | 2494 reflections with I > 2σ(I) |
Horizontally mounted graphite crystal monochromator | Rint = 0.021 |
Detector resolution: 9 pixels mm-1 | θmax = 29.2°, θmin = 2.8° |
ϕ scans and ω scans to fill asymmetric unit | h = −15→15 |
Absorption correction: multi-scan (HKL DENZO and SCALEPACK; Otwinowski & Minor, 1997) | k = −13→13 |
Tmin = 0.929, Tmax = 0.980 | l = −15→15 |
5542 measured reflections | |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.050 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.145 | w = 1/[σ2(Fo2) + (0.0603P)2 + 0.5723P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.001 |
3381 reflections | Δρmax = 0.37 e Å−3 |
168 parameters | Δρmin = −0.41 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.011 (4) |
Crystal data top
C13H14N2O2S | V = 1269.13 (6) Å3 |
Mr = 262.32 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.5609 (3) Å | µ = 0.25 mm−1 |
b = 9.5538 (3) Å | T = 293 K |
c = 11.7268 (3) Å | 0.32 × 0.30 × 0.07 mm |
β = 101.521 (2)° | |
Data collection top
KappaCCD diffractometer | 3381 independent reflections |
Absorption correction: multi-scan (HKL DENZO and SCALEPACK; Otwinowski & Minor, 1997) | 2494 reflections with I > 2σ(I) |
Tmin = 0.929, Tmax = 0.980 | Rint = 0.021 |
5542 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.145 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.37 e Å−3 |
3381 reflections | Δρmin = −0.41 e Å−3 |
168 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | 0.85462 (13) | 0.71786 (15) | 0.28315 (13) | 0.0354 (3) | |
C1 | 0.91162 (18) | 0.7383 (2) | 0.18288 (17) | 0.0463 (5) | |
H1A | 0.9817 | 0.6820 | 0.1926 | 0.056* | |
H1B | 0.9322 | 0.8351 | 0.1778 | 0.056* | |
H1C | 0.8582 | 0.7110 | 0.1128 | 0.056* | |
C2 | 0.91090 (14) | 0.63196 (17) | 0.37193 (15) | 0.0339 (4) | |
O2 | 1.00795 (11) | 0.58274 (14) | 0.37125 (12) | 0.0441 (3) | |
N3 | 0.85203 (13) | 0.60342 (17) | 0.45992 (13) | 0.0368 (3) | |
H3 | 0.888 (2) | 0.542 (3) | 0.5037 (19) | 0.050 (6)* | |
C4 | 0.73952 (15) | 0.64272 (18) | 0.46494 (15) | 0.0365 (4) | |
S4 | 0.66585 (5) | 0.55954 (7) | 0.54871 (5) | 0.0586 (2) | |
C5 | 0.69586 (15) | 0.77289 (18) | 0.39368 (15) | 0.0352 (4) | |
C6 | 0.75149 (15) | 0.78918 (18) | 0.28659 (15) | 0.0367 (4) | |
O6 | 0.70851 (13) | 0.86645 (17) | 0.20761 (12) | 0.0567 (4) | |
C9 | 0.73504 (15) | 0.90006 (19) | 0.47446 (16) | 0.0379 (4) | |
C10 | 0.82075 (19) | 0.9933 (2) | 0.45587 (19) | 0.0521 (5) | |
H10 | 0.8603 | 0.9775 | 0.3954 | 0.063* | |
C11 | 0.8486 (2) | 1.1100 (3) | 0.5261 (2) | 0.0666 (7) | |
H11 | 0.9055 | 1.1725 | 0.5114 | 0.080* | |
C12 | 0.7929 (2) | 1.1340 (3) | 0.6171 (2) | 0.0669 (7) | |
H12 | 0.8110 | 1.2131 | 0.6633 | 0.080* | |
C13 | 0.7100 (2) | 1.0399 (3) | 0.6393 (2) | 0.0651 (7) | |
H13 | 0.6731 | 1.0545 | 0.7018 | 0.078* | |
C14 | 0.68137 (18) | 0.9236 (3) | 0.56891 (19) | 0.0540 (5) | |
H14 | 0.6255 | 0.8604 | 0.5850 | 0.065* | |
C7 | 0.56027 (16) | 0.7752 (2) | 0.35226 (18) | 0.0442 (4) | |
H7A | 0.5242 | 0.7650 | 0.4197 | 0.053* | |
H7B | 0.5375 | 0.8660 | 0.3181 | 0.053* | |
C8 | 0.5106 (2) | 0.6631 (3) | 0.2645 (2) | 0.0634 (6) | |
H8A | 0.4263 | 0.6726 | 0.2437 | 0.076* | |
H8B | 0.5302 | 0.5724 | 0.2980 | 0.076* | |
H8C | 0.5438 | 0.6735 | 0.1962 | 0.076* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0316 (7) | 0.0385 (8) | 0.0374 (7) | 0.0050 (6) | 0.0103 (6) | 0.0031 (6) |
C1 | 0.0433 (10) | 0.0539 (11) | 0.0460 (10) | 0.0031 (8) | 0.0190 (8) | 0.0047 (9) |
C2 | 0.0294 (8) | 0.0311 (8) | 0.0406 (9) | 0.0004 (6) | 0.0055 (6) | −0.0019 (7) |
O2 | 0.0298 (6) | 0.0460 (7) | 0.0575 (8) | 0.0068 (5) | 0.0111 (6) | 0.0067 (6) |
N3 | 0.0348 (8) | 0.0365 (7) | 0.0389 (8) | 0.0074 (6) | 0.0072 (6) | 0.0062 (6) |
C4 | 0.0348 (9) | 0.0376 (9) | 0.0377 (9) | 0.0026 (7) | 0.0087 (7) | 0.0007 (7) |
S4 | 0.0571 (4) | 0.0625 (4) | 0.0636 (4) | 0.0053 (3) | 0.0301 (3) | 0.0195 (3) |
C5 | 0.0299 (8) | 0.0373 (8) | 0.0391 (9) | 0.0040 (7) | 0.0088 (6) | 0.0010 (7) |
C6 | 0.0336 (8) | 0.0375 (9) | 0.0392 (9) | 0.0059 (7) | 0.0075 (7) | 0.0033 (7) |
O6 | 0.0558 (9) | 0.0666 (10) | 0.0494 (8) | 0.0229 (7) | 0.0146 (7) | 0.0224 (7) |
C9 | 0.0310 (8) | 0.0389 (9) | 0.0427 (9) | 0.0074 (7) | 0.0052 (7) | −0.0010 (7) |
C10 | 0.0523 (12) | 0.0494 (11) | 0.0558 (12) | −0.0050 (9) | 0.0138 (9) | −0.0034 (9) |
C11 | 0.0696 (16) | 0.0535 (13) | 0.0725 (16) | −0.0118 (12) | 0.0043 (13) | −0.0113 (12) |
C12 | 0.0626 (15) | 0.0608 (14) | 0.0676 (15) | 0.0114 (12) | −0.0106 (12) | −0.0237 (12) |
C13 | 0.0507 (13) | 0.0850 (17) | 0.0575 (13) | 0.0163 (12) | 0.0058 (10) | −0.0281 (12) |
C14 | 0.0407 (10) | 0.0679 (14) | 0.0554 (12) | 0.0020 (10) | 0.0146 (9) | −0.0145 (10) |
C7 | 0.0304 (9) | 0.0506 (11) | 0.0508 (10) | 0.0048 (8) | 0.0065 (7) | −0.0006 (9) |
C8 | 0.0457 (12) | 0.0707 (15) | 0.0697 (15) | −0.0070 (11) | 0.0019 (10) | −0.0100 (12) |
Geometric parameters (Å, º) top
N1—C6 | 1.381 (2) | C9—C14 | 1.392 (3) |
N1—C2 | 1.382 (2) | C10—C11 | 1.385 (3) |
N1—C1 | 1.471 (2) | C10—H10 | 0.9300 |
C1—H1A | 0.9600 | C11—C12 | 1.371 (4) |
C1—H1B | 0.9600 | C11—H11 | 0.9300 |
C1—H1C | 0.9600 | C12—C13 | 1.376 (4) |
C2—O2 | 1.218 (2) | C12—H12 | 0.9300 |
C2—N3 | 1.372 (2) | C13—C14 | 1.384 (3) |
N3—C4 | 1.366 (2) | C13—H13 | 0.9300 |
N3—H3 | 0.83 (2) | C14—H14 | 0.9300 |
C4—C5 | 1.527 (2) | C7—C8 | 1.516 (3) |
C4—S4 | 1.6297 (18) | C7—H7A | 0.9700 |
C5—C6 | 1.529 (2) | C7—H7B | 0.9700 |
C5—C7 | 1.546 (2) | C8—H8A | 0.9600 |
C5—C9 | 1.551 (2) | C8—H8B | 0.9600 |
C6—O6 | 1.211 (2) | C8—H8C | 0.9600 |
C9—C10 | 1.382 (3) | | |
| | | |
C6—N1—C2 | 123.39 (14) | C14—C9—C5 | 119.37 (17) |
C6—N1—C1 | 119.02 (15) | C9—C10—C11 | 120.9 (2) |
C2—N1—C1 | 117.53 (14) | C9—C10—H10 | 119.5 |
N1—C1—H1A | 109.5 | C11—C10—H10 | 119.5 |
N1—C1—H1B | 109.5 | C12—C11—C10 | 120.5 (2) |
H1A—C1—H1B | 109.5 | C12—C11—H11 | 119.7 |
N1—C1—H1C | 109.5 | C10—C11—H11 | 119.7 |
H1A—C1—H1C | 109.5 | C11—C12—C13 | 119.4 (2) |
H1B—C1—H1C | 109.5 | C11—C12—H12 | 120.3 |
O2—C2—N3 | 121.61 (16) | C13—C12—H12 | 120.3 |
O2—C2—N1 | 121.33 (16) | C12—C13—C14 | 120.3 (2) |
N3—C2—N1 | 117.06 (14) | C12—C13—H13 | 119.9 |
C4—N3—C2 | 126.67 (15) | C14—C13—H13 | 119.9 |
C4—N3—H3 | 121.7 (16) | C13—C14—C9 | 120.8 (2) |
C2—N3—H3 | 110.2 (16) | C13—C14—H14 | 119.6 |
N3—C4—C5 | 114.43 (15) | C9—C14—H14 | 119.6 |
N3—C4—S4 | 120.57 (14) | C8—C7—C5 | 115.22 (16) |
C5—C4—S4 | 124.87 (13) | C8—C7—H7A | 108.5 |
C4—C5—C6 | 112.66 (14) | C5—C7—H7A | 108.5 |
C4—C5—C7 | 112.77 (15) | C8—C7—H7B | 108.5 |
C6—C5—C7 | 107.87 (15) | C5—C7—H7B | 108.5 |
C4—C5—C9 | 106.23 (14) | H7A—C7—H7B | 107.5 |
C6—C5—C9 | 107.60 (14) | C7—C8—H8A | 109.5 |
C7—C5—C9 | 109.56 (14) | C7—C8—H8B | 109.5 |
O6—C6—N1 | 120.22 (16) | H8A—C8—H8B | 109.5 |
O6—C6—C5 | 120.98 (16) | C7—C8—H8C | 109.5 |
N1—C6—C5 | 118.75 (14) | H8A—C8—H8C | 109.5 |
C10—C9—C14 | 117.97 (19) | H8B—C8—H8C | 109.5 |
C10—C9—C5 | 122.66 (17) | | |
| | | |
C6—N1—C2—O2 | −172.10 (17) | C4—C5—C6—N1 | −19.2 (2) |
C1—N1—C2—O2 | 5.0 (2) | C7—C5—C6—N1 | −144.29 (16) |
C6—N1—C2—N3 | 8.6 (2) | C9—C5—C6—N1 | 97.58 (18) |
C1—N1—C2—N3 | −174.25 (16) | C4—C5—C9—C10 | 111.14 (19) |
O2—C2—N3—C4 | −174.07 (17) | C6—C5—C9—C10 | −9.7 (2) |
N1—C2—N3—C4 | 5.2 (3) | C7—C5—C9—C10 | −126.76 (19) |
C2—N3—C4—C5 | −25.1 (3) | C4—C5—C9—C14 | −69.7 (2) |
C2—N3—C4—S4 | 158.79 (15) | C6—C5—C9—C14 | 169.37 (17) |
N3—C4—C5—C6 | 30.1 (2) | C7—C5—C9—C14 | 52.3 (2) |
S4—C4—C5—C6 | −154.03 (14) | C14—C9—C10—C11 | −2.8 (3) |
N3—C4—C5—C7 | 152.49 (16) | C5—C9—C10—C11 | 176.3 (2) |
S4—C4—C5—C7 | −31.6 (2) | C9—C10—C11—C12 | 1.2 (4) |
N3—C4—C5—C9 | −87.48 (17) | C10—C11—C12—C13 | 0.9 (4) |
S4—C4—C5—C9 | 88.41 (17) | C11—C12—C13—C14 | −1.3 (4) |
C2—N1—C6—O6 | 177.60 (18) | C12—C13—C14—C9 | −0.4 (4) |
C1—N1—C6—O6 | 0.5 (3) | C10—C9—C14—C13 | 2.4 (3) |
C2—N1—C6—C5 | −0.1 (3) | C5—C9—C14—C13 | −176.76 (19) |
C1—N1—C6—C5 | −177.13 (16) | C4—C5—C7—C8 | −66.7 (2) |
C4—C5—C6—O6 | 163.18 (18) | C6—C5—C7—C8 | 58.3 (2) |
C7—C5—C6—O6 | 38.1 (2) | C9—C5—C7—C8 | 175.17 (18) |
C9—C5—C6—O6 | −80.1 (2) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O2i | 0.83 (3) | 2.08 (3) | 2.902 (2) | 170 (2) |
Symmetry code: (i) −x+2, −y+1, −z+1. |
(2,4-DTP) 5-ethyl-1-methyl-5-phenyl-2,4-dithioxo-1,2,3,4-tetrahydropyrimidine-
6(5
H)-one
top
Crystal data top
C13H14N2OS2 | F(000) = 584 |
Mr = 278.38 | Dx = 1.390 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 6.9600 (3) Å | Cell parameters from 4532 reflections |
b = 14.9407 (7) Å | θ = 1.0–27.5° |
c = 13.1556 (10) Å | µ = 0.39 mm−1 |
β = 103.454 (2)° | T = 293 K |
V = 1330.47 (13) Å3 | Block, orange |
Z = 4 | 0.25 × 0.15 × 0.10 mm |
Data collection top
KappaCCD diffractometer | 2856 independent reflections |
Radiation source: fine-focus sealed tube | 2309 reflections with I > 2σ(I) |
Horizontally mounted graphite crystal monochromator | Rint = 0.032 |
Detector resolution: 9 pixels mm-1 | θmax = 27.0°, θmin = 3.2° |
ϕ scans and ω scans to fill asymmetric unit | h = −8→8 |
Absorption correction: multi-scan HKL DENZO and SCALEPACK (Otwinowski & Minor, 1997) | k = −19→18 |
Tmin = 0.916, Tmax = 0.955 | l = −16→16 |
5152 measured reflections | |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.046 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.114 | w = 1/[σ2(Fo2) + (0.0338P)2 + 0.759P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max < 0.001 |
2856 reflections | Δρmax = 0.21 e Å−3 |
168 parameters | Δρmin = −0.29 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.017 (4) |
Crystal data top
C13H14N2OS2 | V = 1330.47 (13) Å3 |
Mr = 278.38 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 6.9600 (3) Å | µ = 0.39 mm−1 |
b = 14.9407 (7) Å | T = 293 K |
c = 13.1556 (10) Å | 0.25 × 0.15 × 0.10 mm |
β = 103.454 (2)° | |
Data collection top
KappaCCD diffractometer | 2856 independent reflections |
Absorption correction: multi-scan HKL DENZO and SCALEPACK (Otwinowski & Minor, 1997) | 2309 reflections with I > 2σ(I) |
Tmin = 0.916, Tmax = 0.955 | Rint = 0.032 |
5152 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.114 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.21 e Å−3 |
2856 reflections | Δρmin = −0.29 e Å−3 |
168 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S2 | 0.94383 (10) | 0.93906 (5) | 0.10023 (5) | 0.0561 (2) | |
S4 | 1.11881 (8) | 0.74572 (5) | 0.43563 (5) | 0.0590 (2) | |
O6 | 0.4119 (2) | 0.84689 (13) | 0.26619 (13) | 0.0534 (5) | |
N1 | 0.6625 (2) | 0.89136 (12) | 0.19642 (12) | 0.0376 (4) | |
C2 | 0.8574 (3) | 0.88936 (15) | 0.19196 (15) | 0.0377 (5) | |
N3 | 0.9852 (3) | 0.84383 (13) | 0.27062 (14) | 0.0400 (4) | |
H3 | 1.103 (4) | 0.8445 (16) | 0.2669 (17) | 0.040 (6)* | |
C4 | 0.9435 (3) | 0.79720 (15) | 0.35175 (16) | 0.0381 (5) | |
C5 | 0.7277 (3) | 0.79573 (15) | 0.35849 (15) | 0.0368 (5) | |
C6 | 0.5877 (3) | 0.84601 (15) | 0.27097 (15) | 0.0371 (5) | |
C1 | 0.5201 (3) | 0.94113 (18) | 0.11563 (17) | 0.0486 (6) | |
H1A | 0.3906 | 0.9364 | 0.1290 | 0.058* | |
H1B | 0.5187 | 0.9164 | 0.0481 | 0.058* | |
H1C | 0.5582 | 1.0030 | 0.1172 | 0.058* | |
C9 | 0.7144 (3) | 0.84385 (16) | 0.46001 (16) | 0.0396 (5) | |
C10 | 0.7546 (4) | 0.93509 (18) | 0.46874 (19) | 0.0509 (6) | |
H10 | 0.7900 | 0.9650 | 0.4138 | 0.061* | |
C11 | 0.7429 (4) | 0.9822 (2) | 0.5576 (2) | 0.0615 (7) | |
H11 | 0.7676 | 1.0434 | 0.5616 | 0.074* | |
C12 | 0.6947 (4) | 0.9381 (2) | 0.6398 (2) | 0.0658 (8) | |
H12 | 0.6880 | 0.9692 | 0.7001 | 0.079* | |
C13 | 0.6564 (4) | 0.8478 (2) | 0.6326 (2) | 0.0672 (8) | |
H13 | 0.6241 | 0.8182 | 0.6885 | 0.081* | |
C14 | 0.6652 (4) | 0.8001 (2) | 0.54332 (19) | 0.0543 (6) | |
H14 | 0.6382 | 0.7390 | 0.5394 | 0.065* | |
C7 | 0.6558 (3) | 0.69729 (16) | 0.35046 (18) | 0.0452 (5) | |
H7A | 0.7326 | 0.6639 | 0.4093 | 0.054* | |
H7B | 0.5188 | 0.6958 | 0.3550 | 0.054* | |
C8 | 0.6738 (4) | 0.65186 (19) | 0.2495 (2) | 0.0597 (7) | |
H8A | 0.6280 | 0.5912 | 0.2489 | 0.072* | |
H8B | 0.8095 | 0.6521 | 0.2450 | 0.072* | |
H8C | 0.5952 | 0.6836 | 0.1909 | 0.072* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S2 | 0.0537 (4) | 0.0706 (5) | 0.0493 (4) | 0.0020 (3) | 0.0226 (3) | 0.0215 (3) |
S4 | 0.0332 (3) | 0.0825 (5) | 0.0606 (4) | 0.0105 (3) | 0.0094 (2) | 0.0329 (3) |
O6 | 0.0278 (7) | 0.0726 (12) | 0.0601 (10) | 0.0041 (7) | 0.0111 (7) | 0.0197 (8) |
N1 | 0.0327 (8) | 0.0461 (11) | 0.0338 (8) | 0.0036 (8) | 0.0073 (6) | 0.0083 (7) |
C2 | 0.0377 (10) | 0.0406 (12) | 0.0358 (10) | −0.0008 (9) | 0.0108 (8) | 0.0028 (8) |
N3 | 0.0282 (9) | 0.0514 (12) | 0.0420 (9) | 0.0006 (8) | 0.0116 (7) | 0.0115 (8) |
C4 | 0.0301 (10) | 0.0445 (12) | 0.0407 (11) | 0.0004 (9) | 0.0102 (8) | 0.0081 (9) |
C5 | 0.0271 (9) | 0.0452 (12) | 0.0386 (10) | 0.0011 (9) | 0.0088 (8) | 0.0106 (9) |
C6 | 0.0303 (10) | 0.0427 (12) | 0.0380 (10) | −0.0002 (8) | 0.0075 (8) | 0.0055 (8) |
C1 | 0.0427 (12) | 0.0590 (15) | 0.0421 (12) | 0.0106 (11) | 0.0056 (9) | 0.0156 (10) |
C9 | 0.0281 (9) | 0.0508 (13) | 0.0398 (10) | 0.0005 (9) | 0.0074 (8) | 0.0072 (9) |
C10 | 0.0488 (13) | 0.0539 (15) | 0.0498 (13) | −0.0032 (11) | 0.0115 (10) | 0.0042 (11) |
C11 | 0.0567 (15) | 0.0627 (18) | 0.0619 (16) | 0.0004 (13) | 0.0074 (12) | −0.0094 (13) |
C12 | 0.0532 (15) | 0.094 (2) | 0.0505 (15) | 0.0135 (15) | 0.0121 (12) | −0.0091 (15) |
C13 | 0.0691 (18) | 0.090 (2) | 0.0495 (14) | 0.0065 (16) | 0.0282 (12) | 0.0092 (14) |
C14 | 0.0521 (14) | 0.0640 (17) | 0.0517 (13) | 0.0027 (12) | 0.0220 (11) | 0.0123 (12) |
C7 | 0.0362 (11) | 0.0428 (13) | 0.0563 (13) | −0.0025 (9) | 0.0105 (9) | 0.0098 (10) |
C8 | 0.0539 (15) | 0.0530 (16) | 0.0720 (17) | −0.0060 (12) | 0.0143 (12) | −0.0048 (13) |
Geometric parameters (Å, º) top
S2—C2 | 1.646 (2) | C9—C10 | 1.391 (3) |
S4—C4 | 1.635 (2) | C10—C11 | 1.383 (4) |
O6—C6 | 1.210 (2) | C10—H10 | 0.9300 |
N1—C2 | 1.371 (2) | C11—C12 | 1.374 (4) |
N1—C6 | 1.389 (3) | C11—H11 | 0.9300 |
N1—C1 | 1.475 (3) | C12—C13 | 1.374 (5) |
C2—N3 | 1.377 (3) | C12—H12 | 0.9300 |
N3—C4 | 1.361 (3) | C13—C14 | 1.388 (4) |
N3—H3 | 0.83 (2) | C13—H13 | 0.9300 |
C4—C5 | 1.525 (3) | C14—H14 | 0.9300 |
C5—C6 | 1.522 (3) | C7—C8 | 1.522 (3) |
C5—C9 | 1.538 (3) | C7—H7A | 0.9700 |
C5—C7 | 1.549 (3) | C7—H7B | 0.9700 |
C1—H1A | 0.9600 | C8—H8A | 0.9600 |
C1—H1B | 0.9600 | C8—H8B | 0.9600 |
C1—H1C | 0.9600 | C8—H8C | 0.9600 |
C9—C14 | 1.386 (3) | | |
| | | |
C2—N1—C6 | 123.81 (17) | C10—C9—C5 | 118.56 (19) |
C2—N1—C1 | 119.06 (17) | C11—C10—C9 | 121.2 (2) |
C6—N1—C1 | 117.08 (17) | C11—C10—H10 | 119.4 |
N1—C2—N3 | 116.82 (17) | C9—C10—H10 | 119.4 |
N1—C2—S2 | 123.75 (15) | C12—C11—C10 | 119.6 (3) |
N3—C2—S2 | 119.42 (15) | C12—C11—H11 | 120.2 |
C4—N3—C2 | 128.56 (18) | C10—C11—H11 | 120.2 |
C4—N3—H3 | 116.4 (16) | C13—C12—C11 | 119.7 (3) |
C2—N3—H3 | 115.0 (16) | C13—C12—H12 | 120.1 |
N3—C4—C5 | 116.46 (17) | C11—C12—H12 | 120.1 |
N3—C4—S4 | 120.54 (15) | C12—C13—C14 | 121.1 (3) |
C5—C4—S4 | 123.00 (15) | C12—C13—H13 | 119.4 |
C6—C5—C4 | 114.50 (16) | C14—C13—H13 | 119.4 |
C6—C5—C9 | 105.59 (17) | C9—C14—C13 | 119.7 (3) |
C4—C5—C9 | 107.62 (17) | C9—C14—H14 | 120.2 |
C6—C5—C7 | 106.09 (17) | C13—C14—H14 | 120.2 |
C4—C5—C7 | 108.45 (18) | C8—C7—C5 | 113.08 (19) |
C9—C5—C7 | 114.78 (17) | C8—C7—H7A | 109.0 |
O6—C6—N1 | 119.89 (18) | C5—C7—H7A | 109.0 |
O6—C6—C5 | 120.41 (18) | C8—C7—H7B | 109.0 |
N1—C6—C5 | 119.70 (16) | C5—C7—H7B | 109.0 |
N1—C1—H1A | 109.5 | H7A—C7—H7B | 107.8 |
N1—C1—H1B | 109.5 | C7—C8—H8A | 109.5 |
H1A—C1—H1B | 109.5 | C7—C8—H8B | 109.5 |
N1—C1—H1C | 109.5 | H8A—C8—H8B | 109.5 |
H1A—C1—H1C | 109.5 | C7—C8—H8C | 109.5 |
H1B—C1—H1C | 109.5 | H8A—C8—H8C | 109.5 |
C14—C9—C10 | 118.6 (2) | H8B—C8—H8C | 109.5 |
C14—C9—C5 | 122.8 (2) | | |
| | | |
C6—N1—C2—N3 | −4.1 (3) | C4—C5—C6—N1 | −2.7 (3) |
C1—N1—C2—N3 | 178.5 (2) | C9—C5—C6—N1 | 115.5 (2) |
C6—N1—C2—S2 | 176.88 (17) | C7—C5—C6—N1 | −122.3 (2) |
C1—N1—C2—S2 | −0.5 (3) | C6—C5—C9—C14 | 124.0 (2) |
N1—C2—N3—C4 | 2.4 (3) | C4—C5—C9—C14 | −113.3 (2) |
S2—C2—N3—C4 | −178.54 (19) | C7—C5—C9—C14 | 7.5 (3) |
C2—N3—C4—C5 | −1.0 (3) | C6—C5—C9—C10 | −56.4 (2) |
C2—N3—C4—S4 | 178.57 (19) | C4—C5—C9—C10 | 66.3 (2) |
N3—C4—C5—C6 | 1.1 (3) | C7—C5—C9—C10 | −172.83 (19) |
S4—C4—C5—C6 | −178.51 (17) | C14—C9—C10—C11 | −1.1 (3) |
N3—C4—C5—C9 | −116.0 (2) | C5—C9—C10—C11 | 179.3 (2) |
S4—C4—C5—C9 | 64.4 (2) | C9—C10—C11—C12 | 1.3 (4) |
N3—C4—C5—C7 | 119.3 (2) | C10—C11—C12—C13 | −0.7 (4) |
S4—C4—C5—C7 | −60.3 (2) | C11—C12—C13—C14 | −0.1 (4) |
C2—N1—C6—O6 | −175.8 (2) | C10—C9—C14—C13 | 0.2 (3) |
C1—N1—C6—O6 | 1.7 (3) | C5—C9—C14—C13 | 179.9 (2) |
C2—N1—C6—C5 | 4.5 (3) | C12—C13—C14—C9 | 0.4 (4) |
C1—N1—C6—C5 | −178.1 (2) | C6—C5—C7—C8 | 64.5 (2) |
C4—C5—C6—O6 | 177.5 (2) | C4—C5—C7—C8 | −58.9 (2) |
C9—C5—C6—O6 | −64.3 (3) | C9—C5—C7—C8 | −179.30 (19) |
C7—C5—C6—O6 | 57.9 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O6i | 0.83 (2) | 2.15 (2) | 2.984 (2) | 176 (2) |
Symmetry code: (i) x+1, y, z. |
(2,4,6-TTP) 5-ethyl-1-methyl-5-phenyl-2,4,6(1
H,3H,5
H)-pyrimidinetrithione
top
Crystal data top
C13H14N2S3 | F(000) = 616 |
Mr = 294.44 | Dx = 1.390 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 13.8686 (2) Å | Cell parameters from 5864 reflections |
b = 7.2346 (4) Å | θ = 1.0–27.5° |
c = 14.9844 (5) Å | µ = 0.51 mm−1 |
β = 110.681 (1)° | T = 293 K |
V = 1406.56 (9) Å3 | Plate, red |
Z = 4 | 0.19 × 0.15 × 0.05 mm |
Data collection top
KappaCCD diffractometer | 3201 independent reflections |
Radiation source: fine-focus sealed tube | 2587 reflections with I > 2σ(I) |
Horizontally mounted graphite crystal monochromator | Rint = 0.025 |
Detector resolution: 9 pixels mm-1 | θmax = 27.5°, θmin = 3.2° |
ϕ scans and ω scans to fill asymmetric unit | h = −17→17 |
Absorption correction: multi-scan (HKL DENZO and SCALEPACK; Otwinowski & Minor, 1997) | k = −9→8 |
Tmin = 0.905, Tmax = 0.975 | l = −19→18 |
5585 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)] = 0.048 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.116 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0378P)2 + 0.9914P] where P = (Fo2 + 2Fc2)/3 |
3201 reflections | (Δ/σ)max < 0.001 |
166 parameters | Δρmax = 0.32 e Å−3 |
1 restraint | Δρmin = −0.38 e Å−3 |
Crystal data top
C13H14N2S3 | V = 1406.56 (9) Å3 |
Mr = 294.44 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 13.8686 (2) Å | µ = 0.51 mm−1 |
b = 7.2346 (4) Å | T = 293 K |
c = 14.9844 (5) Å | 0.19 × 0.15 × 0.05 mm |
β = 110.681 (1)° | |
Data collection top
KappaCCD diffractometer | 3201 independent reflections |
Absorption correction: multi-scan (HKL DENZO and SCALEPACK; Otwinowski & Minor, 1997) | 2587 reflections with I > 2σ(I) |
Tmin = 0.905, Tmax = 0.975 | Rint = 0.025 |
5585 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.048 | 1 restraint |
wR(F2) = 0.116 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.32 e Å−3 |
3201 reflections | Δρmin = −0.38 e Å−3 |
166 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S2 | 0.62364 (7) | 0.57579 (12) | 0.67308 (7) | 0.0697 (3) | |
S4 | 0.59290 (5) | 1.07522 (10) | 0.41969 (5) | 0.0516 (2) | |
S6 | 0.97026 (5) | 0.84366 (11) | 0.65166 (5) | 0.0541 (2) | |
N1 | 0.79393 (14) | 0.7041 (3) | 0.64856 (12) | 0.0367 (4) | |
C2 | 0.68854 (18) | 0.7062 (3) | 0.62460 (16) | 0.0395 (5) | |
N3 | 0.63592 (14) | 0.8345 (3) | 0.55717 (14) | 0.0399 (4) | |
H3 | 0.5714 (9) | 0.849 (4) | 0.5512 (18) | 0.048* | |
C4 | 0.67072 (16) | 0.9342 (3) | 0.49844 (15) | 0.0331 (5) | |
C5 | 0.78160 (15) | 0.8976 (3) | 0.50722 (14) | 0.0293 (4) | |
C6 | 0.84561 (16) | 0.8160 (3) | 0.60545 (15) | 0.0333 (5) | |
C1 | 0.8537 (2) | 0.5882 (4) | 0.73020 (19) | 0.0559 (7) | |
H1A | 0.9257 | 0.5982 | 0.7399 | 0.067* | |
H1B | 0.8323 | 0.4618 | 0.7174 | 0.067* | |
H1C | 0.8420 | 0.6292 | 0.7865 | 0.067* | |
C9 | 0.78163 (16) | 0.7428 (3) | 0.43490 (14) | 0.0311 (4) | |
C10 | 0.69749 (18) | 0.6297 (3) | 0.39136 (16) | 0.0400 (5) | |
H10 | 0.6375 | 0.6460 | 0.4047 | 0.048* | |
C11 | 0.7015 (2) | 0.4927 (4) | 0.32819 (18) | 0.0493 (6) | |
H11 | 0.6442 | 0.4180 | 0.2998 | 0.059* | |
C12 | 0.7891 (2) | 0.4662 (4) | 0.30713 (18) | 0.0537 (7) | |
H12 | 0.7915 | 0.3745 | 0.2645 | 0.064* | |
C13 | 0.8734 (2) | 0.5772 (4) | 0.3501 (2) | 0.0579 (7) | |
H13 | 0.9330 | 0.5603 | 0.3361 | 0.069* | |
C14 | 0.87040 (18) | 0.7135 (4) | 0.41367 (18) | 0.0466 (6) | |
H14 | 0.9283 | 0.7865 | 0.4426 | 0.056* | |
C7 | 0.82923 (17) | 1.0775 (3) | 0.48562 (16) | 0.0368 (5) | |
H7A | 0.8986 | 1.0507 | 0.4878 | 0.044* | |
H7B | 0.7894 | 1.1161 | 0.4211 | 0.044* | |
C8 | 0.8343 (2) | 1.2379 (4) | 0.5529 (2) | 0.0533 (7) | |
H8A | 0.8649 | 1.3431 | 0.5342 | 0.064* | |
H8B | 0.8752 | 1.2029 | 0.6169 | 0.064* | |
H8C | 0.7659 | 1.2687 | 0.5499 | 0.064* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S2 | 0.0742 (5) | 0.0664 (5) | 0.0840 (6) | 0.0054 (4) | 0.0471 (5) | 0.0349 (4) |
S4 | 0.0363 (3) | 0.0645 (4) | 0.0569 (4) | 0.0160 (3) | 0.0201 (3) | 0.0288 (3) |
S6 | 0.0332 (3) | 0.0706 (5) | 0.0492 (4) | 0.0058 (3) | 0.0028 (3) | 0.0019 (3) |
N1 | 0.0441 (10) | 0.0361 (10) | 0.0289 (9) | 0.0100 (8) | 0.0118 (8) | 0.0058 (8) |
C2 | 0.0495 (13) | 0.0373 (12) | 0.0378 (12) | 0.0054 (10) | 0.0230 (10) | 0.0064 (10) |
N3 | 0.0345 (9) | 0.0477 (11) | 0.0436 (11) | 0.0077 (9) | 0.0212 (8) | 0.0125 (9) |
C4 | 0.0322 (10) | 0.0355 (11) | 0.0346 (11) | 0.0037 (9) | 0.0153 (9) | 0.0022 (9) |
C5 | 0.0272 (9) | 0.0331 (10) | 0.0284 (10) | 0.0034 (8) | 0.0108 (8) | 0.0000 (8) |
C6 | 0.0352 (11) | 0.0348 (11) | 0.0286 (10) | 0.0070 (9) | 0.0097 (8) | −0.0033 (9) |
C1 | 0.0652 (17) | 0.0536 (15) | 0.0441 (14) | 0.0184 (13) | 0.0133 (12) | 0.0182 (12) |
C9 | 0.0349 (10) | 0.0306 (10) | 0.0275 (10) | 0.0026 (9) | 0.0107 (8) | 0.0019 (8) |
C10 | 0.0416 (12) | 0.0405 (12) | 0.0359 (12) | −0.0045 (10) | 0.0111 (10) | 0.0007 (10) |
C11 | 0.0596 (16) | 0.0399 (13) | 0.0382 (13) | −0.0060 (12) | 0.0043 (11) | −0.0036 (11) |
C12 | 0.079 (2) | 0.0407 (14) | 0.0380 (13) | 0.0095 (13) | 0.0168 (13) | −0.0084 (11) |
C13 | 0.0588 (16) | 0.0606 (17) | 0.0608 (17) | 0.0096 (14) | 0.0293 (14) | −0.0173 (14) |
C14 | 0.0397 (12) | 0.0506 (14) | 0.0528 (15) | −0.0006 (11) | 0.0205 (11) | −0.0149 (12) |
C7 | 0.0367 (11) | 0.0333 (11) | 0.0425 (12) | −0.0015 (9) | 0.0166 (10) | 0.0000 (9) |
C8 | 0.0607 (16) | 0.0377 (13) | 0.0591 (16) | 0.0003 (12) | 0.0184 (13) | −0.0064 (12) |
Geometric parameters (Å, º) top
S2—C2 | 1.640 (2) | C9—C14 | 1.392 (3) |
S4—C4 | 1.643 (2) | C10—C11 | 1.385 (3) |
S6—C6 | 1.632 (2) | C10—H10 | 0.9300 |
N1—C2 | 1.377 (3) | C11—C12 | 1.372 (4) |
N1—C6 | 1.383 (3) | C11—H11 | 0.9300 |
N1—C1 | 1.473 (3) | C12—C13 | 1.376 (4) |
C2—N3 | 1.376 (3) | C12—H12 | 0.9300 |
N3—C4 | 1.352 (3) | C13—C14 | 1.382 (3) |
N3—H3 | 0.873 (10) | C13—H13 | 0.9300 |
C4—C5 | 1.520 (3) | C14—H14 | 0.9300 |
C5—C6 | 1.543 (3) | C7—C8 | 1.522 (3) |
C5—C7 | 1.544 (3) | C7—H7A | 0.9700 |
C5—C9 | 1.558 (3) | C7—H7B | 0.9700 |
C1—H1A | 0.9600 | C8—H8A | 0.9600 |
C1—H1B | 0.9600 | C8—H8B | 0.9600 |
C1—H1C | 0.9600 | C8—H8C | 0.9600 |
C9—C10 | 1.385 (3) | | |
| | | |
C2—N1—C6 | 123.34 (18) | C14—C9—C5 | 119.05 (19) |
C2—N1—C1 | 117.2 (2) | C9—C10—C11 | 120.9 (2) |
C6—N1—C1 | 119.2 (2) | C9—C10—H10 | 119.5 |
N3—C2—N1 | 115.95 (19) | C11—C10—H10 | 119.5 |
N3—C2—S2 | 118.78 (18) | C12—C11—C10 | 120.6 (2) |
N1—C2—S2 | 125.21 (17) | C12—C11—H11 | 119.7 |
C4—N3—C2 | 128.24 (19) | C10—C11—H11 | 119.7 |
C4—N3—H3 | 117.2 (17) | C11—C12—C13 | 119.0 (2) |
C2—N3—H3 | 114.5 (18) | C11—C12—H12 | 120.5 |
N3—C4—C5 | 115.71 (18) | C13—C12—H12 | 120.5 |
N3—C4—S4 | 120.26 (16) | C12—C13—C14 | 120.8 (3) |
C5—C4—S4 | 123.94 (16) | C12—C13—H13 | 119.6 |
C4—C5—C6 | 111.90 (16) | C14—C13—H13 | 119.6 |
C4—C5—C7 | 109.25 (17) | C13—C14—C9 | 120.7 (2) |
C6—C5—C7 | 112.20 (17) | C13—C14—H14 | 119.7 |
C4—C5—C9 | 108.28 (16) | C9—C14—H14 | 119.7 |
C6—C5—C9 | 104.30 (16) | C8—C7—C5 | 115.24 (19) |
C7—C5—C9 | 110.76 (16) | C8—C7—H7A | 108.5 |
N1—C6—C5 | 116.81 (18) | C5—C7—H7A | 108.5 |
N1—C6—S6 | 121.32 (16) | C8—C7—H7B | 108.5 |
C5—C6—S6 | 121.62 (16) | C5—C7—H7B | 108.5 |
N1—C1—H1A | 109.5 | H7A—C7—H7B | 107.5 |
N1—C1—H1B | 109.5 | C7—C8—H8A | 109.5 |
H1A—C1—H1B | 109.5 | C7—C8—H8B | 109.5 |
N1—C1—H1C | 109.5 | H8A—C8—H8B | 109.5 |
H1A—C1—H1C | 109.5 | C7—C8—H8C | 109.5 |
H1B—C1—H1C | 109.5 | H8A—C8—H8C | 109.5 |
C10—C9—C14 | 117.9 (2) | H8B—C8—H8C | 109.5 |
C10—C9—C5 | 123.02 (19) | | |
| | | |
C6—N1—C2—N3 | −3.1 (3) | C4—C5—C6—S6 | −153.62 (16) |
C1—N1—C2—N3 | 171.2 (2) | C7—C5—C6—S6 | −30.4 (2) |
C6—N1—C2—S2 | 179.65 (17) | C9—C5—C6—S6 | 89.54 (19) |
C1—N1—C2—S2 | −6.0 (3) | C4—C5—C9—C10 | −15.5 (3) |
N1—C2—N3—C4 | 13.8 (4) | C6—C5—C9—C10 | 103.8 (2) |
S2—C2—N3—C4 | −168.8 (2) | C7—C5—C9—C10 | −135.3 (2) |
C2—N3—C4—C5 | 0.9 (3) | C4—C5—C9—C14 | 165.6 (2) |
C2—N3—C4—S4 | 177.6 (2) | C6—C5—C9—C14 | −75.1 (2) |
N3—C4—C5—C6 | −23.0 (3) | C7—C5—C9—C14 | 45.8 (3) |
S4—C4—C5—C6 | 160.47 (16) | C14—C9—C10—C11 | −0.4 (3) |
N3—C4—C5—C7 | −147.9 (2) | C5—C9—C10—C11 | −179.4 (2) |
S4—C4—C5—C7 | 35.6 (2) | C9—C10—C11—C12 | −0.1 (4) |
N3—C4—C5—C9 | 91.4 (2) | C10—C11—C12—C13 | 0.3 (4) |
S4—C4—C5—C9 | −85.1 (2) | C11—C12—C13—C14 | 0.1 (4) |
C2—N1—C6—C5 | −19.9 (3) | C12—C13—C14—C9 | −0.7 (4) |
C1—N1—C6—C5 | 165.8 (2) | C10—C9—C14—C13 | 0.8 (4) |
C2—N1—C6—S6 | 165.80 (17) | C5—C9—C14—C13 | 179.8 (2) |
C1—N1—C6—S6 | −8.4 (3) | C4—C5—C7—C8 | 61.5 (2) |
C4—C5—C6—N1 | 32.1 (2) | C6—C5—C7—C8 | −63.2 (2) |
C7—C5—C6—N1 | 155.33 (18) | C9—C5—C7—C8 | −179.32 (19) |
C9—C5—C6—N1 | −84.7 (2) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···S4i | 0.87 (1) | 2.53 (1) | 3.376 (2) | 164 (2) |
Symmetry code: (i) −x+1, −y+2, −z+1. |
(P) 5-ethyl-1-methyl-5-phenylpyrimidine-2,4,6(1
H,3
H,5
H)-trione
top
Crystal data top
C13H14N2O3 | F(000) = 520 |
Mr = 246.26 | Dx = 1.349 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 13.7063 (5) Å | Cell parameters from 2505 reflections |
b = 7.2553 (2) Å | θ = 1.0–27.5° |
c = 12.6606 (4) Å | µ = 0.10 mm−1 |
β = 105.565 (2)° | T = 293 K |
V = 1212.84 (7) Å3 | Block, colourless |
Z = 4 | 0.30 × 0.30 × 0.30 mm |
Data collection top
KappaCCD diffractometer | 2756 independent reflections |
Radiation source: fine-focus sealed tube | 2230 reflections with I > 2σ(I) |
Horizontally mounted graphite crystal monochromator | Rint = 0.019 |
Detector resolution: 9 pixels mm-1 | θmax = 27.5°, θmin = 3.2° |
ϕ scans and ω scans to fill asymmetric unit | h = −17→17 |
Absorption correction: multi-scan (HKL DENZO and SCALEPACK; Otwinowski & Minor, 1997) | k = −9→9 |
Tmin = 0.972, Tmax = 0.975 | l = −16→15 |
4931 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)] = 0.051 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.143 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0669P)2 + 0.4169P] where P = (Fo2 + 2Fc2)/3 |
2756 reflections | (Δ/σ)max < 0.001 |
167 parameters | Δρmax = 0.37 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
Crystal data top
C13H14N2O3 | V = 1212.84 (7) Å3 |
Mr = 246.26 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.7063 (5) Å | µ = 0.10 mm−1 |
b = 7.2553 (2) Å | T = 293 K |
c = 12.6606 (4) Å | 0.30 × 0.30 × 0.30 mm |
β = 105.565 (2)° | |
Data collection top
KappaCCD diffractometer | 2756 independent reflections |
Absorption correction: multi-scan (HKL DENZO and SCALEPACK; Otwinowski & Minor, 1997) | 2230 reflections with I > 2σ(I) |
Tmin = 0.972, Tmax = 0.975 | Rint = 0.019 |
4931 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.051 | 0 restraints |
wR(F2) = 0.143 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.37 e Å−3 |
2756 reflections | Δρmin = −0.23 e Å−3 |
167 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | 0.15281 (10) | −0.06849 (18) | 0.83089 (11) | 0.0391 (3) | |
H3 | 0.0159 (18) | −0.093 (3) | 0.5891 (17) | 0.058 (6)* | |
C1 | 0.14919 (18) | −0.1211 (3) | 0.94219 (15) | 0.0614 (5) | |
H1A | 0.0954 | −0.2080 | 0.9375 | 0.074* | |
H1B | 0.1373 | −0.0134 | 0.9811 | 0.074* | |
H1C | 0.2125 | −0.1761 | 0.9805 | 0.074* | |
C2 | 0.07740 (11) | −0.1379 (2) | 0.74425 (13) | 0.0365 (3) | |
O2 | 0.01695 (9) | −0.25137 (17) | 0.75646 (11) | 0.0523 (3) | |
N3 | 0.07344 (10) | −0.06910 (18) | 0.64185 (11) | 0.0355 (3) | |
C4 | 0.13138 (11) | 0.0701 (2) | 0.61907 (12) | 0.0348 (3) | |
O4 | 0.10742 (9) | 0.15042 (18) | 0.53145 (9) | 0.0483 (3) | |
C5 | 0.23105 (11) | 0.1068 (2) | 0.70516 (12) | 0.0353 (3) | |
C6 | 0.22523 (12) | 0.0571 (2) | 0.82031 (13) | 0.0403 (4) | |
O6 | 0.28554 (11) | 0.1204 (2) | 0.90135 (10) | 0.0605 (4) | |
C7 | 0.26374 (12) | 0.3102 (2) | 0.70232 (15) | 0.0429 (4) | |
H7A | 0.3302 | 0.3252 | 0.7530 | 0.051* | |
H7B | 0.2698 | 0.3378 | 0.6294 | 0.051* | |
C8 | 0.19227 (15) | 0.4488 (3) | 0.73127 (18) | 0.0557 (5) | |
H8A | 0.2178 | 0.5711 | 0.7275 | 0.067* | |
H8B | 0.1872 | 0.4253 | 0.8042 | 0.067* | |
H8C | 0.1265 | 0.4377 | 0.6804 | 0.067* | |
C9 | 0.31005 (11) | −0.0196 (2) | 0.67368 (13) | 0.0381 (4) | |
C10 | 0.32720 (14) | 0.0015 (3) | 0.57093 (15) | 0.0505 (4) | |
H10 | 0.2913 | 0.0897 | 0.5226 | 0.061* | |
C11 | 0.39780 (16) | −0.1089 (3) | 0.54037 (19) | 0.0644 (6) | |
H11 | 0.4091 | −0.0936 | 0.4717 | 0.077* | |
C12 | 0.45120 (16) | −0.2404 (3) | 0.6106 (2) | 0.0698 (6) | |
H12 | 0.4978 | −0.3149 | 0.5894 | 0.084* | |
C13 | 0.43520 (15) | −0.2606 (3) | 0.7122 (2) | 0.0674 (6) | |
H13 | 0.4716 | −0.3488 | 0.7601 | 0.081* | |
C14 | 0.36524 (13) | −0.1510 (3) | 0.74434 (17) | 0.0511 (5) | |
H14 | 0.3554 | −0.1660 | 0.8137 | 0.061* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0419 (7) | 0.0365 (7) | 0.0395 (7) | 0.0017 (6) | 0.0121 (6) | 0.0022 (6) |
C1 | 0.0712 (13) | 0.0705 (13) | 0.0462 (10) | −0.0034 (11) | 0.0218 (9) | 0.0065 (10) |
C2 | 0.0334 (7) | 0.0278 (7) | 0.0500 (9) | 0.0035 (6) | 0.0142 (6) | 0.0001 (6) |
O2 | 0.0467 (7) | 0.0438 (7) | 0.0693 (8) | −0.0094 (6) | 0.0208 (6) | 0.0057 (6) |
N3 | 0.0285 (6) | 0.0325 (7) | 0.0427 (7) | −0.0049 (5) | 0.0049 (5) | −0.0025 (5) |
C4 | 0.0289 (7) | 0.0324 (7) | 0.0407 (8) | −0.0017 (6) | 0.0050 (6) | −0.0004 (6) |
O4 | 0.0378 (6) | 0.0532 (7) | 0.0468 (7) | −0.0103 (5) | −0.0011 (5) | 0.0106 (5) |
C5 | 0.0292 (7) | 0.0314 (7) | 0.0421 (8) | −0.0039 (6) | 0.0038 (6) | 0.0005 (6) |
C6 | 0.0390 (8) | 0.0360 (8) | 0.0426 (8) | −0.0007 (7) | 0.0054 (7) | −0.0030 (7) |
O6 | 0.0655 (9) | 0.0639 (9) | 0.0455 (7) | −0.0161 (7) | 0.0035 (6) | −0.0079 (6) |
C7 | 0.0342 (8) | 0.0319 (8) | 0.0588 (10) | −0.0062 (6) | 0.0060 (7) | −0.0013 (7) |
C8 | 0.0496 (10) | 0.0359 (9) | 0.0808 (13) | −0.0021 (8) | 0.0160 (9) | −0.0074 (9) |
C9 | 0.0278 (7) | 0.0319 (7) | 0.0508 (9) | −0.0039 (6) | 0.0040 (6) | −0.0030 (7) |
C10 | 0.0446 (9) | 0.0532 (11) | 0.0522 (10) | −0.0005 (8) | 0.0103 (8) | −0.0049 (8) |
C11 | 0.0491 (11) | 0.0775 (14) | 0.0689 (12) | −0.0032 (11) | 0.0197 (9) | −0.0195 (11) |
C12 | 0.0458 (11) | 0.0621 (13) | 0.1042 (18) | 0.0087 (10) | 0.0249 (11) | −0.0185 (13) |
C13 | 0.0454 (10) | 0.0513 (12) | 0.1042 (18) | 0.0133 (9) | 0.0176 (11) | 0.0103 (12) |
C14 | 0.0376 (9) | 0.0457 (10) | 0.0682 (11) | 0.0035 (7) | 0.0114 (8) | 0.0116 (8) |
Geometric parameters (Å, º) top
N1—C6 | 1.380 (2) | C7—H7A | 0.9700 |
N1—C2 | 1.384 (2) | C7—H7B | 0.9700 |
N1—C1 | 1.473 (2) | C8—H8A | 0.9600 |
C1—H1A | 0.9600 | C8—H8B | 0.9600 |
C1—H1B | 0.9600 | C8—H8C | 0.9600 |
C1—H1C | 0.9600 | C9—C14 | 1.385 (2) |
C2—O2 | 1.2072 (19) | C9—C10 | 1.391 (2) |
C2—N3 | 1.377 (2) | C10—C11 | 1.388 (3) |
N3—C4 | 1.363 (2) | C10—H10 | 0.9300 |
N3—H3 | 0.90 (2) | C11—C12 | 1.374 (3) |
C4—O4 | 1.2176 (19) | C11—H11 | 0.9300 |
C4—C5 | 1.525 (2) | C12—C13 | 1.369 (3) |
C5—C6 | 1.525 (2) | C12—H12 | 0.9300 |
C5—C7 | 1.545 (2) | C13—C14 | 1.388 (3) |
C5—C9 | 1.550 (2) | C13—H13 | 0.9300 |
C6—O6 | 1.221 (2) | C14—H14 | 0.9300 |
C7—C8 | 1.516 (2) | | |
| | | |
C6—N1—C2 | 124.52 (13) | C5—C7—H7A | 108.6 |
C6—N1—C1 | 118.25 (15) | C8—C7—H7B | 108.6 |
C2—N1—C1 | 117.00 (15) | C5—C7—H7B | 108.6 |
N1—C1—H1A | 109.5 | H7A—C7—H7B | 107.6 |
N1—C1—H1B | 109.5 | C7—C8—H8A | 109.5 |
H1A—C1—H1B | 109.5 | C7—C8—H8B | 109.5 |
N1—C1—H1C | 109.5 | H8A—C8—H8B | 109.5 |
H1A—C1—H1C | 109.5 | C7—C8—H8C | 109.5 |
H1B—C1—H1C | 109.5 | H8A—C8—H8C | 109.5 |
O2—C2—N3 | 120.86 (15) | H8B—C8—H8C | 109.5 |
O2—C2—N1 | 122.60 (15) | C14—C9—C10 | 118.66 (16) |
N3—C2—N1 | 116.54 (13) | C14—C9—C5 | 122.63 (15) |
C4—N3—C2 | 126.16 (13) | C10—C9—C5 | 118.70 (14) |
C4—N3—H3 | 115.5 (14) | C11—C10—C9 | 120.17 (19) |
C2—N3—H3 | 115.6 (13) | C11—C10—H10 | 119.9 |
O4—C4—N3 | 121.16 (13) | C9—C10—H10 | 119.9 |
O4—C4—C5 | 122.59 (13) | C12—C11—C10 | 120.7 (2) |
N3—C4—C5 | 116.05 (13) | C12—C11—H11 | 119.7 |
C6—C5—C4 | 112.05 (13) | C10—C11—H11 | 119.7 |
C6—C5—C7 | 109.75 (13) | C13—C12—C11 | 119.38 (19) |
C4—C5—C7 | 111.08 (12) | C13—C12—H12 | 120.3 |
C6—C5—C9 | 108.98 (12) | C11—C12—H12 | 120.3 |
C4—C5—C9 | 105.46 (12) | C12—C13—C14 | 120.8 (2) |
C7—C5—C9 | 109.39 (12) | C12—C13—H13 | 119.6 |
O6—C6—N1 | 120.59 (15) | C14—C13—H13 | 119.6 |
O6—C6—C5 | 121.14 (15) | C9—C14—C13 | 120.34 (19) |
N1—C6—C5 | 118.19 (13) | C9—C14—H14 | 119.8 |
C8—C7—C5 | 114.69 (14) | C13—C14—H14 | 119.8 |
C8—C7—H7A | 108.6 | | |
| | | |
C6—N1—C2—O2 | 177.98 (15) | C4—C5—C6—N1 | 22.8 (2) |
C1—N1—C2—O2 | −7.6 (2) | C7—C5—C6—N1 | 146.72 (14) |
C6—N1—C2—N3 | −2.8 (2) | C9—C5—C6—N1 | −93.50 (16) |
C1—N1—C2—N3 | 171.68 (15) | C6—C5—C7—C8 | −60.70 (18) |
O2—C2—N3—C4 | 173.84 (15) | C4—C5—C7—C8 | 63.76 (19) |
N1—C2—N3—C4 | −5.4 (2) | C9—C5—C7—C8 | 179.78 (15) |
C2—N3—C4—O4 | −162.54 (15) | C6—C5—C9—C14 | −1.3 (2) |
C2—N3—C4—C5 | 22.5 (2) | C4—C5—C9—C14 | −121.73 (16) |
O4—C4—C5—C6 | 155.70 (15) | C7—C5—C9—C14 | 118.73 (17) |
N3—C4—C5—C6 | −29.38 (19) | C6—C5—C9—C10 | 179.63 (14) |
O4—C4—C5—C7 | 32.5 (2) | C4—C5—C9—C10 | 59.16 (18) |
N3—C4—C5—C7 | −152.53 (14) | C7—C5—C9—C10 | −60.38 (18) |
O4—C4—C5—C9 | −85.87 (18) | C14—C9—C10—C11 | 0.5 (3) |
N3—C4—C5—C9 | 89.06 (16) | C5—C9—C10—C11 | 179.67 (16) |
C2—N1—C6—O6 | 175.48 (15) | C9—C10—C11—C12 | 0.3 (3) |
C1—N1—C6—O6 | 1.1 (3) | C10—C11—C12—C13 | −0.8 (3) |
C2—N1—C6—C5 | −7.5 (2) | C11—C12—C13—C14 | 0.5 (3) |
C1—N1—C6—C5 | 178.11 (15) | C10—C9—C14—C13 | −0.8 (3) |
C4—C5—C6—O6 | −160.18 (16) | C5—C9—C14—C13 | −179.91 (16) |
C7—C5—C6—O6 | −36.3 (2) | C12—C13—C14—C9 | 0.3 (3) |
C9—C5—C6—O6 | 83.49 (19) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O4i | 0.90 (2) | 1.99 (2) | 2.896 (2) | 178 (2) |
Symmetry code: (i) −x, −y, −z+1. |
Experimental details
| (2-TP) | (4-TP) | (2,4-DTP) | (2,4,6-TTP) |
Crystal data |
Chemical formula | C13H14N2O2S | C13H14N2O2S | C13H14N2OS2 | C13H14N2S3 |
Mr | 262.32 | 262.32 | 278.38 | 294.44 |
Crystal system, space group | Monoclinic, P21/n | Monoclinic, P21/n | Monoclinic, P21/n | Monoclinic, P21/n |
Temperature (K) | 293 | 293 | 293 | 293 |
a, b, c (Å) | 12.9315 (3), 7.1804 (2), 15.2362 (5) | 11.5609 (3), 9.5538 (3), 11.7268 (3) | 6.9600 (3), 14.9407 (7), 13.1556 (10) | 13.8686 (2), 7.2346 (4), 14.9844 (5) |
β (°) | 113.077 (1) | 101.521 (2) | 103.454 (2) | 110.681 (1) |
V (Å3) | 1301.52 (6) | 1269.13 (6) | 1330.47 (13) | 1406.56 (9) |
Z | 4 | 4 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.24 | 0.25 | 0.39 | 0.51 |
Crystal size (mm) | 0.35 × 0.30 × 0.12 | 0.32 × 0.30 × 0.07 | 0.25 × 0.15 × 0.10 | 0.19 × 0.15 × 0.05 |
|
Data collection |
Diffractometer | KappaCCD diffractometer | KappaCCD diffractometer | KappaCCD diffractometer | KappaCCD diffractometer |
Absorption correction | Multi-scan (HKL DENZO and SCALEPACK; Otwinowski & Minor, 1997) | Multi-scan (HKL DENZO and SCALEPACK; Otwinowski & Minor, 1997) | Multi-scan HKL DENZO and SCALEPACK (Otwinowski & Minor, 1997) | Multi-scan (HKL DENZO and SCALEPACK; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.924, 0.976 | 0.929, 0.980 | 0.916, 0.955 | 0.905, 0.975 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4964, 2978, 2293 | 5542, 3381, 2494 | 5152, 2856, 2309 | 5585, 3201, 2587 |
Rint | 0.021 | 0.021 | 0.032 | 0.025 |
(sin θ/λ)max (Å−1) | 0.650 | 0.686 | 0.639 | 0.649 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.111, 1.02 | 0.050, 0.145, 1.04 | 0.046, 0.114, 1.06 | 0.048, 0.116, 1.06 |
No. of reflections | 2978 | 3381 | 2856 | 3201 |
No. of parameters | 164 | 168 | 168 | 166 |
No. of restraints | 0 | 0 | 0 | 1 |
H-atom treatment | H-atom parameters constrained | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.24, −0.28 | 0.37, −0.41 | 0.21, −0.29 | 0.32, −0.38 |
| (P) |
Crystal data |
Chemical formula | C13H14N2O3 |
Mr | 246.26 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 13.7063 (5), 7.2553 (2), 12.6606 (4) |
β (°) | 105.565 (2) |
V (Å3) | 1212.84 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.30 × 0.30 × 0.30 |
|
Data collection |
Diffractometer | KappaCCD diffractometer |
Absorption correction | Multi-scan (HKL DENZO and SCALEPACK; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.972, 0.975 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4931, 2756, 2230 |
Rint | 0.019 |
(sin θ/λ)max (Å−1) | 0.649 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.051, 0.143, 1.05 |
No. of reflections | 2756 |
No. of parameters | 167 |
No. of restraints | 0 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.37, −0.23 |
Table 1. A comparison of selected geometric parameters and ring-puckering
parameters* (Å, °) for the thio derivatives of N-methylphenobarbital
with
N-methylphenobarbital (P) itself. top | (2–TP) | (4–TP) | (2,4–DTP) | (2,4,6–TTP) | (P) | (P) at 163 K** |
N1—C2 | 1.371 (2) | 1.382 (2) | 1.371 (2) | 1.377 (3) | 1.384 (2) | 1.391 (2) |
C2—N3 | 1.371 (2) | 1.372 (2) | 1.377 (3) | 1.376 (3) | 1.377 (2) | 1.379 (2) |
N3—C4 | 1.364 (2) | 1.366 (2) | 1.361 (3) | 1.352 (3) | 1.363 (2) | 1.365 (2) |
C4—C5 | 1.512 (2) | 1.527 (2) | 1.525 (3) | 1.520 (3) | 1.525 (2) | 1.528 (2) |
C5—C6 | 1.526 (2) | 1.529 (2) | 1.523 (3) | 1.543 (3) | 1.525 (2) | 1.528 (2) |
N1—C6 | 1.402 (2) | 1.381 (2) | 1.389 (3) | 1.383 (3) | 1.380 (2) | 1.386 (2) |
C2—O2 / S2 | 1.6436 (17) | 1.218 (2) | 1.646 (2) | 1.640 (2) | 1.2072 (19) | 1.2095 (19) |
C4—O4 / S4 | 1.2147 (19) | 1.6297 (18) | 1.635 (2) | 1.643 (2) | 1.2176 (19) | 1.2184 (19) |
C6—O6 / S6 | 1.2039 (19) | 1.211 (2) | 1.210 (2) | 1.632 (2) | 1.221 (2) | 1.2126 (19) |
| | | | | | |
C2—N1—C6 | 122.93 (14) | 123.39 (14) | 123.81 (17) | 123.34 (18) | 124.52 (13) | 124.39 (13) |
N1—C2—N3 | 116.44 (14) | 117.06 (14) | 116.82 (17) | 115.95 (19) | 116.54 (13) | 116.52 (13) |
C2—N3—C4 | 127.72 (14) | 126.67 (15) | 128.56 (18) | 128.24 (19) | 126.16 (13) | 126.06 (13) |
N3—C4—C5 | 116.20 (13) | 114.43 (15) | 116.46 (17) | 115.71 (18) | 116.05 (13) | 116.23 (13) |
C4—C5—C6 | 111.91 (13) | 112.66 (14) | 114.50 (16) | 111.90 (16) | 112.05 (13) | 111.91 (13) |
N1—C6—C5 | 117.04 (14) | 118.75 (14) | 119.70 (16) | 116.81 (18) | 118.19 (13) | 118.20 (13) |
| | | | | | |
N1—C2—N3—C4 | 10.4 (3) | 5.2 (3) | 2.4 (3) | 13.8 (4) | -5.4 (2) | 5.9 (2) |
C2—N3—C4—C5 | 3.4 (2) | -25.1 (3) | -1.0 (3) | 0.9 (3) | 22.5 (2) | -23.0 (2) |
N3—C4—C5—C6 | -23.72 (19) | 30.1 (2) | 1.1 (3) | -23.0 (3) | -29.38 (19) | 29.84 (18) |
C4—C5—C6—N1 | 32.14 (18) | -19.2 (2) | -2.7 (3) | 32.1 (2) | 22.8 (2) | -23.27 (19) |
C5—C6—N1—C2 | -20.9 (2) | -0.1 (3) | 4.5 (3) | -19.9 (3) | -7.5 (2) | 8.1 (2) |
C6—N1—C2—N3 | -0.8 (2) | 8.6 (2) | -4.1 (3) | -3.1 (3) | -2.8 (2) | 2.2 (2) |
C4—C5—C7—C8 | 61.7 (2) | -66.7 (2) | -58.9 (2) | 61.5 (2) | 63.76 (19) | -63.03 (19) |
C4—C5—C9—C10 | -3.4 (2) | 111.14 (19) | 66.3 (2) | -15.5 (3) | 59.16 (18) | -59.21 (17) |
C4—C5—C9—C14 | 177.55 (15) | -69.7 (2) | -113.3 (2) | 165.6 (2) | -121.73 (16) | -121.60 (15) |
| | | | | | |
q2 | 0.251 (1) | 0.232 (2) | 0.019 (2) | 0.269 (2) | 0.198 (1) | |
q3 | 0.120 (2) | 0.117 (2) | 0.023 (2) | -0.107 (2) | -0.136 (2) | |
phi2 | 80.9 (4) | -154.1 (4) | -11 (5) | 80.8 (5) | 37.5 (5) | |
QT | 0.278 (2) | 0.260 (2) | 0.030 (2) | 0.289 (2) | 0.240 (2) | |
theta2 | 115.5 (3) | 63.3 (4) | 39 (4) | 111.8 (4) | 124.6 (3) | |
* Ring-puckering parameters defined according Cremer & Pople (1975) and
calculated using the PARST program (Nardelli, 1983).
** Crystal structure of N-methylphenobarbital reported erlier by Lewis
et al. (2005) with R = 4.21% Refcode: MEPBAB01 (Allen,
2002). |
Table 2. Hydrogen-bond geometry (Å, °). topD—H···A | Acceptor position | D—H | H···A | D···A | D—H···A |
(2-TP) | | | | | |
N3—H3···O4 | -x+2, -y+1, -z | 0.86 | 2.12 | 2.927 (2) | 157 |
(4-TP) | | | | | |
N3—H3···O2 | -x+2, -y+1, -z+1 | 0.83 (3) | 2.08 (3) | 2.902 (2) | 170 (2) |
(2,4-DTP) | | | | | |
N3—H3···O6 | x+1, y, z | 0.83 (2) | 2.15 (2) | 2.984 (2) | 176 (2) |
(2,4,6-TTP) | | | | | |
N3—H3···S4 | -x+1, -y+2, -z+1 | 0.87 (1) | 2.53 (1) | 3.376 (2) | 164 (2) |
(P) | | | | | |
N3—H3···O4 | -x, -y, -z+1 | 0.90 (2) | 1.99 (2) | 2.896 (2) | 178 (2) |
Table 3. Weak interactions (Å, °) and contacts (Å) for the
analyzed crystal
structures. topCg1 is the centre of gravity of C9 - C14 benzene ring, Cg2 is the centre of
gravity of heterocyclic ring. |
D—H···A | Acceptor position | D—H | H···A | D···A | D—H···A | Remarks |
(2-TP) | | | | | | |
C1—H1a···O6 | | 0.96 | 2.28 | 2.712 (3) | 106 | Intra |
C8—H8a···Cg1 | x, y+1, z | 0.96 | 2.85 | 3.610 (2) | 136 | III* |
C12—H12···Cg1 | -x+3/2, y-1/2, -z+1/2 | 0.93 | 2.73 | 3.639 (2) | 167 | Edge to face, I* |
| | | | | | |
(4-TP) | | | | | | |
C1—H1a···O2 | | 0.96 | 2.26 | 2.710 (2) | 107 | Intra |
C1—H1c···Cg1 | -x+3/2, y-1/2, -z+1/2 | 0.96 | 2.81 | 3.702 (2) | 154 | II* |
O6···C2 | -x+3/2, y+1/2, -z+1/2 | | | 2.949 (2) | | |
O6···Cg2 | -x+3/2, y+1/2, -z+1/2 | | | 3.214 (2) | | |
| | | | | | |
(2,4-DTP) | | | | | | |
C1—H1a···O6 | | 0.96 | 2.22 | 2.677 (3) | 108 | Intra |
C1—H1b···S4 | x-1/2, -y+3/2, z-1/2 | 0.96 | 3.00 | 3.824 | 144 | |
| | | | | | |
(2,4,6-TTP) | | | | | | |
C1—H1a···S6 | | 0.96 | 2.42 | 2.959 (3) | 115 | Intra |
C8—H8c···S4 | | 0.96 | 2.87 | 3.444 (3) | 120 | Intra |
C8—H8a···Cg1 | x, y+1, z | 0.96 | 2.98 | 3.687 (3) | 132 | III* |
C12—H12···Cg1 | -x+3/2, y-1/2, -z+1/2 | 0.93 | 2.75 | 3.620 (3) | 156 | Edge to face, I* |
| | | | | | |
(P) | | | | | | |
C1—H1a···O2 | | 0.96 | 2.28 | 2.724 | 108 | Intra |
C1—H1c···Cg1 | x, -y-1/2, z+1/2 | 0.96 | 3.00 | 3.931 | 165 | II* |
C10—H10···O4 | | 0.93 | 2.59 | 3.112 (2) | 116 | Intra |
C10—H10···O6 | x, -y+1/2, z-1/2 | 0.93 | 2.59 | 3.436 (2) | 151 | |
C13—H13···Cg1 | -x+1, y-1/2, -z+3/2 | 0.93 | 2.90 | 3.798 (2) | 162 | Edge to face, I* |
O2···C2 | -x, y-1/2, -z+3/2 | | | 3.087 (2) | | |
O2···Cg2 | -x, y-1/2, -z+3/2 | | | 2.921 (2) | | |
* Category of weak H···π interaction according to the classification of Malone
et al. (1997). |
Barbiturates are a widespread group of compounds with various pharmacological activities. In particular, phenobarbital, thiopental and pentobarbital have been the subjects of extensive research due to their anaesthetic, sedative, hypnotic, amnesiac and anticonvulsant properties (Kushikata et al., 2003; Huber et al., 2008). The structures of numerous barbituric acid derivatives, such as phenobarbital, have been studied with respect to their ability to form polymorphs (Williams, 1973, 1974; Platteau et al., 2005; Day et al., 2007). However, there are only a few examples of sulfur analogues of barbiturates. Recently, the crystal structure of 5-benzyl-1,3,5-trimethyltrithiobarbiturate was reported (Takechi et al., 2007).
In this paper, we present the crystal structures of four thio derivatives of 5-ethyl-1-methyl-5-phenyl-2,4,6(1H,3H,5H)-pyrimidinetrione, of common name N-methylphenobarbital, all crystallizing in the centrosymmetric space group P21/n. The structural formulae of the derivatives are given in the scheme. The asymmetric units of N-methyl-2-thiophenobarbital, (2-TP), N-methyl-4-thiophenobarbital, (4-TP), N-methyl-2,4-dithiophenobarbital, (2,4-DTP), N-methyl-2,4,6-trithiophenobarbital, (2,4,6-TTP), and N-methylphenobarbital, (P), are shown in Fig. 1. The structure of the latter compound was redetermined at 293 (2) K, so as to enable all five structures to be compared under the same conditions. The previously published data for N-methylphenobarbital were obtained at 163 K by Lewis et al. (2005) and refined to R = 0.042. A determination at 295 K by Bideau et al. (1969) was a low-quality determination with R = 0.107.
Selected geometric parameters at 293 (2) K for the crystal structures of the thio derivatives are given in Table 1, together with the values observed for N-methylphenobarbital at 293 (2) K and also at 163 (2) K (Lewis et al., 2005). The C—N bond lengths are similar to those found in β-lactams (Csp2–Nsp2= 1.385 Å; Allen et al., 1995), indicating that the lone pairs of the N1 and N3 atoms are conjugated with the carbonyl or thiocarbonyl groups, which results in the C2—N1—C6 and C2—N3—C4 angles being greater than 120° [the average values are 123.4 (3) and 127.8 (7)°, respectively], whereas the mean value of the C4—C5—C6 angle at the chiral centre is 112.8 (11)°. The heterocyclic ring in all crystal structures adopts a half-chair conformation, with the torsion angles and ring-puckering parameters given in Table 1. The set of torsion angles defining the heterocyclic ring conformation was found to be similar for (2-TP), (2,4,6-TTP), (4-TP) and (P), whereas for (2,4-DTP) all the torsion angles are close to zero, which indicates that the ring is significantly flattened. The geometric parameters of (P) at 293 (2) K are comparable with those found at 163 (2) K.
The C═S bond lengths in the thio derivatives are significantly shortened [range 1.630–1.646 Å; 1.639 (6) Å on average, see Table 1] when compared with the value characteristic for thioureas (1.681 Å; Allen et al., 1995) and are similar to those observed in 5-benzyl-1,3,5-trimethylpyrimidine-2,4,6(1H,3H,5H)-trithione (Takechi et al., 2007). The average value of the C═O bond lengths was found to be 1.212 (5) Å, which is also relatively short compared with the values observed in ureas (Allen et al., 1995).
Both (P) and its thio derivatives possess only one hydrogen-bond donor (the N3—H3 amide group), despite an excess of acceptor groups, which limits the number of possible moderate hydrogen bonds. The analysis of the hydrogen-bond parameters (Table 2) indicates the preferential acceptor properties of the O atom in position 4. If position 4 is occupied by an S atom, the role of the acceptor is taken over by the O atom in position 2 [as in (4-TP)]. In the case of the 2,4-dithio derivative, only the O atom in position 6 is available as the strong acceptor (the electronegativity of the O atom is 3.44 whereas that for the S atom is 2.58, which is comparable with that of a C atom, 2.55). When all the O atoms are replaced by S atoms in (2,4,6-TTP), position 4 is preferred again for the N—H···S hydrogen bond.
As can be seen in Fig. 2, the structures of (2-TP), (4-TP) and (2,4,6-TTP) contain centrosymmetric hydrogen-bonded dimers – like that observed in (P) – formed by the intermolecular N3—H3···O or N3—H3···S interactions across a centre of inversion. This hydrogen-bond motif can be recognized as the typical R22(8) type according to the graph-set approach (Etter et al., 1990; Bernstein et al., 1995). The type of hydrogen-bond system determines the specific packing pattern in the structures of the thio derivatives. The R22(8) ring composed of N3—H3···O4(2 - x, 1 - y, -z) hydrogen bonds in (2-TP) and that of N3—H3···S4(1 - x, 2 - y, 1 - z) in (2,4,6-TTP) enforces the same molecular packing arrangement shown in Figs. 3 and 6, respectively. Although the R22(8) system is also observed in the structure of (4-TP), the packing of the molecules is different (Fig. 4) because of the different acceptor type in the N3—H3···O2(2 - x, 1 - y, 1 - z) hydrogen bond. In (2,4-DTP) the R22(8) ring is not preserved because the donor and acceptor functional groups are not in adjacent positions on the heterocyclic ring. Instead, the packing of the molecules (Fig. 5) is dominated by a C(6) chain formed by the N3—H3···O6(x + 1, y, z) hydrogen bond (Fig. 2).
The preference of the moderate hydrogen-bond formation seems to follow the acceptor atom position in the heterocyclic ring according to the sequence 4 > 2 > 6, which corresponds with the nucleophilic properties of the heterocyclic ring C atoms. This finding is consistent with the order of the S atom substitution in the reaction of N-methyphenobarbital thionation, in which the amount of the thio derivatives of (P) in the reaction product was found to be: (4-TP) - 26% > (2,4-DTP) - 22% > (2-TP) - 16% (Stasiewicz-Urban et al., 2004).
Because the moderate hydrogen bonds form only discrete dimers or one-dimensional chains, the three-dimensional architecture of the molecular packing has to be provided by weak intermolecular interactions, the geometric parameters of which are summarized in Table 3. In the structures of (2-TP) and (2,4,6-TTP), with the substituent in position 4 (O4 and S4, respectively) serving as the acceptor for the N—H group, the hydrophobic layers (depicted in Figs. 7 and 8) are formed due to weak C—H···π edge-to-face interactions between the benzene rings of the adjacent molecules. A similar behaviour of the molecules is observed in the structure of (P).
In all the structures studied, the methyl group in position 1 seems to be engaged as the donor in weak intramolecular C—H···O or C—H···S hydrogen bonds. The differences in the values of the torsion angle defining the spatial arrangement of the substituents at position 5 (C4—C5—C7—C8 and C4—C5—C9—C10, Table 1), observed even in the structures with similar packing patterns, may be attributed to the resultant effect of the different set of weak attractive, weak repulsive and steric interactions. In the structure of (4-TP), the O6 atom is close to the centre of the neighbouring pyrimidine heterocyclic ring [Cg2 at -x + 3/2, y + 1/2, -z + 1/2; 3.214 (2) Å]. A similar observation can be made for atom O2 in the structure of (P) [Cg2 at -x, y - 1/2, -z + 3/2; 2.921 (2) Å].