Comparison of the title compound, C
20H
28N
2O
5S, with related structures shows that the presence of the alkyl substituents influences the conformation of the rings in the frame fragment. The molecules form hydrogen-bonded centrosymmetric dimers due to an N—H
S intermolecular interaction.
Supporting information
CCDC reference: 673086
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.003 Å
- R factor = 0.038
- wR factor = 0.066
- Data-to-parameter ratio = 14.5
checkCIF/PLATON results
No syntax errors found
Alert level B
PLAT230_ALERT_2_B Hirshfeld Test Diff for O5 - C18 .. 12.21 su
Alert level C
PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 3.17 Ratio
PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.89 Ratio
PLAT230_ALERT_2_C Hirshfeld Test Diff for S1 - C9 .. 6.52 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for O4 - C14 .. 6.02 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for N2 - C16 .. 6.34 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for C1 - C10 .. 5.69 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for C12 - C13 .. 6.57 su
PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C14
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for O5
Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K
PLAT793_ALERT_1_G Check the Absolute Configuration of C1 ..... R
PLAT793_ALERT_1_G Check the Absolute Configuration of C8 ..... R
PLAT793_ALERT_1_G Check the Absolute Configuration of C10 ..... S
0 ALERT level A = In general: serious problem
1 ALERT level B = Potentially serious problem
9 ALERT level C = Check and explain
5 ALERT level G = General alerts; check
5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
9 ALERT type 2 Indicator that the structure model may be wrong or deficient
1 ALERT type 3 Indicator that the structure quality may be low
0 ALERT type 4 Improvement, methodology, query or suggestion
0 ALERT type 5 Informative message, check
checkCIF publication errors
Alert level A
PUBL024_ALERT_1_A The number of authors is greater than 5.
Please specify the role of each of the co-authors
for your paper.
| Author Response: All authors made significant contribution
in this work. The idea of synthesis belong to Kovalenko S. M. and
Chernykh.
The synthesis was performed by Zaremba and Kovalenko S. S..
X-ray diffraction experiment was performed by Baumer.
The analysis of diffraction data was performed by
Konovalova and Shishkin.
|
1 ALERT level A = Data missing that is essential or data in wrong format
0 ALERT level G = General alerts. Data that may be required is missing
The synthesis was carried out according to the Biginelli reaction (Biginelli,
1893). 2-Hydroxy-3-etoxysalicylic aldehyde (0,01 mol),
N-(3-methoxypropyl)-thiourea and ethyl acetoacetate (0,015 mol) were
mixed in 10 ml of ethanol. 3 drops of concentrated HCL were added. Raw
crystals of the title compound were grown during 2 days at room temperature;
they were further filtered, washed in ethanol and dried at room temperature.
Crystals apt for X-ray diffraction were obtained by quick evaporation of a
solution of (I) in dimethylformamide.
All hydrogen atoms were located from electron density difference maps, idealized
and included in the refinement in the riding approximation with Uiso
constrained to be 1.5 times Ueq of the carrier atom for the methyl
groups and 1.2 times Ueq of the carrier atom for the other atoms.
Data collection: P3 (Siemens,1989); cell refinement: P3 (Siemens,1989); data reduction: XDISK (Siemens, 1991); program(s) used to solve structure: SHELXTL (Sheldrick, 1998); program(s) used to refine structure: SHELXTL (Sheldrick, 1998); molecular graphics: XP (Siemens, 1998); software used to prepare material for publication: SHELXTL (Sheldrick, 1998).
Ethyl 6-ethoxy-10-(3-methoxypropyl)-9-methyl-11-thioxo-8-oxa-10,12-
diazatricyclo[7.3.1.0
2,7]trideca-2,4,6-triene-13-carboxylate
top
Crystal data top
C20H28N2O5S | Z = 2 |
Mr = 408.50 | F(000) = 436 |
Triclinic, P1 | Dx = 1.277 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.7612 (16) Å | Cell parameters from 36 reflections |
b = 10.3405 (17) Å | θ = 8–22° |
c = 12.309 (2) Å | µ = 0.19 mm−1 |
α = 107.354 (13)° | T = 293 K |
β = 109.709 (13)° | Block, colourless |
γ = 100.096 (12)° | 0.40 × 0.20 × 0.20 mm |
V = 1062.5 (4) Å3 | |
Data collection top
Siemens P3/PC diffractometer | 2151 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.053 |
Graphite monochromator | θmax = 25.0°, θmin = 2.2° |
Detector resolution: 16.1827 pixels mm-1 | h = −11→10 |
θ/2θ scans | k = −12→11 |
3927 measured reflections | l = 0→14 |
3737 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)] = 0.038 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.066 | H-atom parameters constrained |
S = 0.89 | w = 1/[σ2(Fo2) + (0.0177P)2] where P = (Fo2 + 2Fc2)/3 |
3737 reflections | (Δ/σ)max = 0.001 |
257 parameters | Δρmax = 0.19 e Å−3 |
0 restraints | Δρmin = −0.12 e Å−3 |
Crystal data top
C20H28N2O5S | γ = 100.096 (12)° |
Mr = 408.50 | V = 1062.5 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.7612 (16) Å | Mo Kα radiation |
b = 10.3405 (17) Å | µ = 0.19 mm−1 |
c = 12.309 (2) Å | T = 293 K |
α = 107.354 (13)° | 0.40 × 0.20 × 0.20 mm |
β = 109.709 (13)° | |
Data collection top
Siemens P3/PC diffractometer | 2151 reflections with I > 2σ(I) |
3927 measured reflections | Rint = 0.053 |
3737 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.066 | H-atom parameters constrained |
S = 0.89 | Δρmax = 0.19 e Å−3 |
3737 reflections | Δρmin = −0.12 e Å−3 |
257 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. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S1 | 0.33397 (6) | 0.30050 (6) | 0.46821 (5) | 0.05561 (17) | |
C1 | 0.51711 (19) | 0.33456 (17) | 0.22987 (15) | 0.0366 (4) | |
H1 | 0.5496 | 0.4221 | 0.2172 | 0.044* | |
C2 | 0.64837 (19) | 0.27649 (17) | 0.26528 (15) | 0.0360 (4) | |
C3 | 0.8001 (2) | 0.36494 (19) | 0.33397 (16) | 0.0447 (5) | |
H3 | 0.8220 | 0.4630 | 0.3576 | 0.054* | |
C4 | 0.9156 (2) | 0.3074 (2) | 0.36622 (18) | 0.0559 (6) | |
H4 | 1.0160 | 0.3669 | 0.4110 | 0.067* | |
C5 | 0.8859 (2) | 0.1622 (2) | 0.33345 (18) | 0.0560 (6) | |
H5 | 0.9659 | 0.1246 | 0.3567 | 0.067* | |
C6 | 0.7364 (2) | 0.0724 (2) | 0.26571 (17) | 0.0471 (5) | |
C7 | 0.61870 (19) | 0.13107 (18) | 0.23001 (16) | 0.0365 (4) | |
O1 | 0.47460 (13) | 0.03496 (12) | 0.15539 (11) | 0.0435 (3) | |
C8 | 0.34663 (19) | 0.09174 (18) | 0.13639 (16) | 0.0404 (5) | |
N2 | 0.31829 (16) | 0.12553 (14) | 0.25062 (13) | 0.0401 (4) | |
C9 | 0.37102 (19) | 0.25931 (18) | 0.33937 (16) | 0.0384 (4) | |
N1 | 0.45580 (16) | 0.36240 (14) | 0.32376 (13) | 0.0405 (4) | |
H1N | 0.4750 | 0.4493 | 0.3715 | 0.049* | |
C10 | 0.38594 (19) | 0.22459 (17) | 0.11061 (16) | 0.0382 (4) | |
H10 | 0.4230 | 0.2022 | 0.0446 | 0.046* | |
C11 | 0.2556 (2) | 0.2852 (2) | 0.07013 (18) | 0.0513 (5) | |
O2 | 0.12758 (17) | 0.24063 (17) | 0.06021 (17) | 0.0882 (5) | |
O3 | 0.30182 (15) | 0.39880 (15) | 0.04911 (12) | 0.0590 (4) | |
C12 | 0.1892 (3) | 0.4702 (3) | 0.0106 (2) | 0.0770 (7) | |
H12A | 0.1508 | 0.5006 | 0.0740 | 0.115* | |
H12B | 0.1038 | 0.4057 | −0.0671 | 0.115* | |
C13 | 0.2648 (3) | 0.5951 (3) | −0.0066 (3) | 0.1075 (10) | |
H13A | 0.3445 | 0.6614 | 0.0721 | 0.161* | |
H13B | 0.1910 | 0.6403 | −0.0375 | 0.161* | |
H13C | 0.3081 | 0.5645 | −0.0656 | 0.161* | |
O4 | 0.69411 (16) | −0.07243 (14) | 0.22771 (13) | 0.0640 (4) | |
C14 | 0.7999 (3) | −0.1341 (3) | 0.2869 (3) | 0.1045 (10) | |
H14A | 0.8463 | −0.0810 | 0.3767 | 0.157* | |
H14B | 0.8803 | −0.1313 | 0.2573 | 0.157* | |
C15 | 0.7188 (4) | −0.2819 (3) | 0.2576 (2) | 0.1044 (10) | |
H15A | 0.6465 | −0.2834 | 0.2946 | 0.157* | |
H15B | 0.7909 | −0.3275 | 0.2906 | 0.157* | |
H15C | 0.6658 | −0.3316 | 0.1686 | 0.157* | |
C16 | 0.2414 (2) | 0.0061 (2) | 0.27311 (19) | 0.0579 (6) | |
H16A | 0.1618 | −0.0635 | 0.1944 | 0.087* | |
H16B | 0.1933 | 0.0414 | 0.3282 | 0.087* | |
C17 | 0.3498 (3) | −0.0645 (3) | 0.3302 (2) | 0.0807 (7) | |
H17A | 0.4396 | 0.0082 | 0.3992 | 0.121* | |
H17B | 0.3825 | −0.1153 | 0.2684 | 0.121* | |
C18 | 0.2826 (3) | −0.1691 (3) | 0.3784 (3) | 0.0983 (9) | |
H18A | 0.3637 | −0.1959 | 0.4291 | 0.148* | |
H18B | 0.2353 | −0.1236 | 0.4304 | 0.148* | |
O5 | 0.17768 (19) | −0.28630 (17) | 0.28194 (14) | 0.0856 (5) | |
C19 | 0.1400 (4) | −0.3987 (3) | 0.3224 (3) | 0.1141 (11) | |
H19A | 0.2311 | −0.4201 | 0.3624 | 0.171* | |
H19B | 0.0684 | −0.4819 | 0.2514 | 0.171* | |
H19C | 0.0954 | −0.3692 | 0.3805 | 0.171* | |
C20 | 0.2177 (2) | −0.02969 (19) | 0.02500 (17) | 0.0551 (6) | |
H20A | 0.2327 | −0.0366 | −0.0495 | 0.083* | |
H20B | 0.1220 | −0.0122 | 0.0166 | 0.083* | |
H20C | 0.2168 | −0.1172 | 0.0373 | 0.083* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0581 (3) | 0.0510 (3) | 0.0540 (3) | 0.0063 (3) | 0.0338 (3) | 0.0092 (3) |
C1 | 0.0397 (11) | 0.0283 (9) | 0.0453 (11) | 0.0049 (8) | 0.0210 (9) | 0.0179 (9) |
C2 | 0.0405 (11) | 0.0346 (10) | 0.0368 (10) | 0.0070 (9) | 0.0215 (9) | 0.0151 (8) |
C3 | 0.0422 (12) | 0.0348 (10) | 0.0487 (12) | 0.0044 (9) | 0.0149 (10) | 0.0137 (9) |
C4 | 0.0366 (12) | 0.0634 (15) | 0.0571 (14) | 0.0079 (11) | 0.0116 (10) | 0.0225 (11) |
C5 | 0.0446 (13) | 0.0622 (14) | 0.0630 (14) | 0.0221 (11) | 0.0191 (11) | 0.0268 (11) |
C6 | 0.0553 (13) | 0.0416 (12) | 0.0527 (13) | 0.0192 (11) | 0.0271 (11) | 0.0211 (10) |
C7 | 0.0349 (10) | 0.0351 (10) | 0.0399 (11) | 0.0082 (9) | 0.0162 (9) | 0.0153 (9) |
O1 | 0.0399 (8) | 0.0322 (7) | 0.0547 (8) | 0.0098 (6) | 0.0201 (6) | 0.0120 (6) |
C8 | 0.0342 (11) | 0.0348 (10) | 0.0453 (12) | 0.0045 (9) | 0.0151 (9) | 0.0113 (9) |
N2 | 0.0434 (9) | 0.0289 (8) | 0.0488 (9) | 0.0050 (7) | 0.0250 (8) | 0.0131 (7) |
C9 | 0.0329 (10) | 0.0321 (10) | 0.0455 (11) | 0.0074 (8) | 0.0140 (9) | 0.0129 (9) |
N1 | 0.0485 (10) | 0.0244 (8) | 0.0482 (10) | 0.0090 (7) | 0.0260 (8) | 0.0082 (7) |
C10 | 0.0358 (10) | 0.0355 (10) | 0.0365 (11) | 0.0043 (8) | 0.0128 (9) | 0.0115 (8) |
C11 | 0.0490 (14) | 0.0498 (13) | 0.0529 (13) | 0.0130 (11) | 0.0176 (11) | 0.0222 (10) |
O2 | 0.0411 (9) | 0.0877 (12) | 0.1408 (16) | 0.0196 (8) | 0.0280 (10) | 0.0619 (11) |
O3 | 0.0648 (9) | 0.0600 (9) | 0.0669 (10) | 0.0277 (8) | 0.0284 (8) | 0.0378 (8) |
C12 | 0.102 (2) | 0.0726 (17) | 0.0708 (16) | 0.0537 (16) | 0.0323 (15) | 0.0360 (14) |
C13 | 0.141 (3) | 0.0629 (18) | 0.111 (2) | 0.0521 (18) | 0.035 (2) | 0.0318 (17) |
O4 | 0.0663 (10) | 0.0432 (9) | 0.0851 (11) | 0.0258 (7) | 0.0271 (8) | 0.0281 (8) |
C14 | 0.118 (2) | 0.0620 (18) | 0.132 (2) | 0.0471 (17) | 0.032 (2) | 0.0467 (17) |
C15 | 0.164 (3) | 0.0660 (18) | 0.110 (2) | 0.0559 (18) | 0.068 (2) | 0.0463 (16) |
C16 | 0.0695 (15) | 0.0403 (12) | 0.0606 (14) | 0.0024 (11) | 0.0344 (12) | 0.0147 (10) |
C17 | 0.0720 (16) | 0.0715 (16) | 0.0985 (19) | 0.0092 (14) | 0.0266 (15) | 0.0502 (15) |
C18 | 0.109 (2) | 0.0844 (19) | 0.095 (2) | 0.0057 (17) | 0.0273 (18) | 0.0573 (17) |
O5 | 0.1038 (13) | 0.0639 (11) | 0.0701 (11) | −0.0084 (10) | 0.0246 (10) | 0.0334 (9) |
C19 | 0.164 (3) | 0.0719 (18) | 0.115 (2) | 0.0061 (19) | 0.063 (2) | 0.0579 (17) |
C20 | 0.0458 (12) | 0.0484 (13) | 0.0493 (12) | 0.0006 (10) | 0.0119 (10) | 0.0067 (10) |
Geometric parameters (Å, º) top
S1—C9 | 1.6927 (18) | C12—C13 | 1.481 (3) |
C1—N1 | 1.451 (2) | C12—H12A | 0.9700 |
C1—C2 | 1.497 (2) | C12—H12B | 0.9700 |
C1—C10 | 1.521 (2) | C13—H13A | 0.9600 |
C1—H1 | 0.9800 | C13—H13B | 0.9600 |
C2—C7 | 1.381 (2) | C13—H13C | 0.9600 |
C2—C3 | 1.401 (2) | O4—C14 | 1.416 (3) |
C3—C4 | 1.362 (3) | C14—C15 | 1.466 (3) |
C3—H3 | 0.9300 | C14—H14A | 0.9700 |
C4—C5 | 1.382 (3) | C14—H14B | 0.9700 |
C4—H4 | 0.9300 | C15—H15A | 0.9600 |
C5—C6 | 1.389 (3) | C15—H15B | 0.9600 |
C5—H5 | 0.9300 | C15—H15C | 0.9600 |
C6—O4 | 1.367 (2) | C16—C17 | 1.490 (3) |
C6—C7 | 1.394 (2) | C16—H16A | 0.9700 |
C7—O1 | 1.3798 (19) | C16—H16B | 0.9700 |
O1—C8 | 1.450 (2) | C17—C18 | 1.532 (3) |
C8—N2 | 1.476 (2) | C17—H17A | 0.9700 |
C8—C10 | 1.514 (2) | C17—H17B | 0.9700 |
C8—C20 | 1.515 (2) | C18—O5 | 1.346 (3) |
N2—C9 | 1.357 (2) | C18—H18A | 0.9700 |
N2—C16 | 1.478 (2) | C18—H18B | 0.9700 |
C9—N1 | 1.334 (2) | O5—C19 | 1.432 (2) |
N1—H1N | 0.8600 | C19—H19A | 0.9600 |
C10—C11 | 1.516 (3) | C19—H19B | 0.9600 |
C10—H10 | 0.9800 | C19—H19C | 0.9600 |
C11—O2 | 1.204 (2) | C20—H20A | 0.9600 |
C11—O3 | 1.313 (2) | C20—H20B | 0.9600 |
O3—C12 | 1.456 (2) | C20—H20C | 0.9600 |
| | | |
N1—C1—C2 | 111.76 (14) | O3—C12—H12B | 110.1 |
N1—C1—C10 | 105.55 (13) | C13—C12—H12B | 110.1 |
C2—C1—C10 | 109.75 (14) | H12A—C12—H12B | 108.4 |
N1—C1—H1 | 109.9 | C12—C13—H13A | 109.5 |
C2—C1—H1 | 109.9 | C12—C13—H13B | 109.5 |
C10—C1—H1 | 109.9 | H13A—C13—H13B | 109.5 |
C7—C2—C3 | 118.97 (17) | C12—C13—H13C | 109.5 |
C7—C2—C1 | 118.86 (15) | H13A—C13—H13C | 109.5 |
C3—C2—C1 | 122.17 (16) | H13B—C13—H13C | 109.5 |
C4—C3—C2 | 120.08 (18) | C6—O4—C14 | 118.18 (17) |
C4—C3—H3 | 120.0 | O4—C14—C15 | 108.7 (2) |
C2—C3—H3 | 120.0 | O4—C14—H14A | 109.9 |
C3—C4—C5 | 121.07 (19) | C15—C14—H14A | 109.9 |
C3—C4—H4 | 119.5 | O4—C14—H14B | 109.9 |
C5—C4—H4 | 119.5 | C15—C14—H14B | 109.9 |
C4—C5—C6 | 119.90 (19) | H14A—C14—H14B | 108.3 |
C4—C5—H5 | 120.1 | C14—C15—H15A | 109.5 |
C6—C5—H5 | 120.1 | C14—C15—H15B | 109.5 |
O4—C6—C5 | 124.83 (18) | H15A—C15—H15B | 109.5 |
O4—C6—C7 | 116.18 (17) | C14—C15—H15C | 109.5 |
C5—C6—C7 | 118.97 (18) | H15A—C15—H15C | 109.5 |
O1—C7—C2 | 123.19 (16) | H15B—C15—H15C | 109.5 |
O1—C7—C6 | 115.82 (15) | N2—C16—C17 | 112.23 (17) |
C2—C7—C6 | 120.96 (16) | N2—C16—H16A | 109.2 |
C7—O1—C8 | 117.03 (13) | C17—C16—H16A | 109.2 |
O1—C8—N2 | 108.40 (14) | N2—C16—H16B | 109.2 |
O1—C8—C10 | 108.89 (13) | C17—C16—H16B | 109.2 |
N2—C8—C10 | 110.53 (14) | H16A—C16—H16B | 107.9 |
O1—C8—C20 | 102.78 (14) | C16—C17—C18 | 114.0 (2) |
N2—C8—C20 | 112.72 (15) | C16—C17—H17A | 108.8 |
C10—C8—C20 | 113.09 (15) | C18—C17—H17A | 108.8 |
C9—N2—C8 | 122.51 (14) | C16—C17—H17B | 108.8 |
C9—N2—C16 | 119.32 (15) | C18—C17—H17B | 108.8 |
C8—N2—C16 | 117.94 (14) | H17A—C17—H17B | 107.7 |
N1—C9—N2 | 118.16 (16) | O5—C18—C17 | 110.4 (2) |
N1—C9—S1 | 118.88 (13) | O5—C18—H18A | 109.6 |
N2—C9—S1 | 122.96 (13) | C17—C18—H18A | 109.6 |
C9—N1—C1 | 122.96 (14) | O5—C18—H18B | 109.6 |
C9—N1—H1N | 118.5 | C17—C18—H18B | 109.6 |
C1—N1—H1N | 118.5 | H18A—C18—H18B | 108.1 |
C8—C10—C11 | 115.46 (15) | C18—O5—C19 | 111.30 (18) |
C8—C10—C1 | 106.56 (14) | O5—C19—H19A | 109.5 |
C11—C10—C1 | 110.17 (14) | O5—C19—H19B | 109.5 |
C8—C10—H10 | 108.1 | H19A—C19—H19B | 109.5 |
C11—C10—H10 | 108.1 | O5—C19—H19C | 109.5 |
C1—C10—H10 | 108.1 | H19A—C19—H19C | 109.5 |
O2—C11—O3 | 123.1 (2) | H19B—C19—H19C | 109.5 |
O2—C11—C10 | 126.59 (19) | C8—C20—H20A | 109.5 |
O3—C11—C10 | 110.29 (17) | C8—C20—H20B | 109.5 |
C11—O3—C12 | 116.75 (17) | H20A—C20—H20B | 109.5 |
O3—C12—C13 | 108.0 (2) | C8—C20—H20C | 109.5 |
O3—C12—H12A | 110.1 | H20A—C20—H20C | 109.5 |
C13—C12—H12A | 110.1 | H20B—C20—H20C | 109.5 |
| | | |
N1—C1—C2—C7 | 88.77 (18) | C8—N2—C9—S1 | 177.75 (13) |
C10—C1—C2—C7 | −28.0 (2) | C16—N2—C9—S1 | −7.9 (2) |
N1—C1—C2—C3 | −90.64 (19) | N2—C9—N1—C1 | −11.6 (2) |
C10—C1—C2—C3 | 152.62 (16) | S1—C9—N1—C1 | 168.40 (12) |
C7—C2—C3—C4 | −0.7 (3) | C2—C1—N1—C9 | −74.0 (2) |
C1—C2—C3—C4 | 178.67 (16) | C10—C1—N1—C9 | 45.3 (2) |
C2—C3—C4—C5 | −0.7 (3) | O1—C8—C10—C11 | 171.51 (14) |
C3—C4—C5—C6 | 0.5 (3) | N2—C8—C10—C11 | −69.51 (19) |
C4—C5—C6—O4 | 179.55 (18) | C20—C8—C10—C11 | 57.9 (2) |
C4—C5—C6—C7 | 1.2 (3) | O1—C8—C10—C1 | −65.80 (17) |
C3—C2—C7—O1 | −175.56 (15) | N2—C8—C10—C1 | 53.17 (18) |
C1—C2—C7—O1 | 5.0 (2) | C20—C8—C10—C1 | −179.38 (15) |
C3—C2—C7—C6 | 2.4 (2) | N1—C1—C10—C8 | −63.55 (17) |
C1—C2—C7—C6 | −177.02 (16) | C2—C1—C10—C8 | 57.03 (17) |
O4—C6—C7—O1 | −3.0 (2) | N1—C1—C10—C11 | 62.40 (18) |
C5—C6—C7—O1 | 175.50 (16) | C2—C1—C10—C11 | −177.02 (15) |
O4—C6—C7—C2 | 178.85 (15) | C8—C10—C11—O2 | 2.2 (3) |
C5—C6—C7—C2 | −2.6 (3) | C1—C10—C11—O2 | −118.6 (2) |
C2—C7—O1—C8 | −13.4 (2) | C8—C10—C11—O3 | −179.32 (15) |
C6—C7—O1—C8 | 168.57 (15) | C1—C10—C11—O3 | 59.9 (2) |
C7—O1—C8—N2 | −76.22 (17) | O2—C11—O3—C12 | −0.8 (3) |
C7—O1—C8—C10 | 44.07 (19) | C10—C11—O3—C12 | −179.37 (15) |
C7—O1—C8—C20 | 164.25 (14) | C11—O3—C12—C13 | 179.40 (18) |
O1—C8—N2—C9 | 98.62 (17) | C5—C6—O4—C14 | 17.6 (3) |
C10—C8—N2—C9 | −20.7 (2) | C7—C6—O4—C14 | −164.0 (2) |
C20—C8—N2—C9 | −148.30 (16) | C6—O4—C14—C15 | 164.75 (18) |
O1—C8—N2—C16 | −75.83 (18) | C9—N2—C16—C17 | −92.7 (2) |
C10—C8—N2—C16 | 164.90 (15) | C8—N2—C16—C17 | 81.9 (2) |
C20—C8—N2—C16 | 37.2 (2) | N2—C16—C17—C18 | 168.78 (19) |
C8—N2—C9—N1 | −2.3 (2) | C16—C17—C18—O5 | 70.9 (3) |
C16—N2—C9—N1 | 172.10 (16) | C17—C18—O5—C19 | 166.2 (2) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···S1i | 0.86 | 2.62 | 3.3973 (17) | 152 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Experimental details
Crystal data |
Chemical formula | C20H28N2O5S |
Mr | 408.50 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 9.7612 (16), 10.3405 (17), 12.309 (2) |
α, β, γ (°) | 107.354 (13), 109.709 (13), 100.096 (12) |
V (Å3) | 1062.5 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.19 |
Crystal size (mm) | 0.40 × 0.20 × 0.20 |
|
Data collection |
Diffractometer | Siemens P3/PC diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3927, 3737, 2151 |
Rint | 0.053 |
(sin θ/λ)max (Å−1) | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.066, 0.89 |
No. of reflections | 3737 |
No. of parameters | 257 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.19, −0.12 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···S1i | 0.86 | 2.62 | 3.3973 (17) | 151.6 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Some derivatives of 2,6-methano-2H-1,3,5-benzothiadiazocine and -benzoxadiazocine have been studied due to their biological activity as perspective calcium channel blockers (Baldwin et al., 1986; Kettmann et al., 1996; Kettmann & Svetlík, 1996, 1997). We have performed an X-ray diffraction study of a new member of this group, the title compound C20H28N2O5S1 (I). Tetrahydropyrimidine-2-thione and tetrahydropyran rings adopt in (I) a conformation which is intermediate between half-chair and sofa. Maximum deviations from the tetrahydropyrimidine and the tetrahydropyrane mean planes correspond to atoms C1, C10 (0.28 A°, -0.54 A°) and C8,C10 (0.21 A°, -0.59 A°), respectively. Comparison of the ring conformations in (I) and some of its analogues (Kettmann et al., 1996b; Fu et al., 2002; Kettmann et al., 1997) indicates that the presence of substituent at the nitrogen atoms is probably the reason for some deformation in the heterocycles conformation. The ester substituent in (I) is planar within 0.01 A° and coplanar to the C8—C10 bond (the C8—C10—C11—O2 torsion angle is 2.2 (3) °). The methoxybuthyl substituent adopts instead an orthogonal orientation with respect to the tetrahydropyrimidine ring (the C9—N2—C16—C17 torsion angle is -92.7 (2) °) probably due to the repulsion between some of its atoms and the tione and the methyl groups (as sugested by the short intramolecular contacts C20···H16A 2.43 Å (van der Waals radii sum is 2.87 Å, Zefirov & Zorky, 1995), H16A···H20C 2.12 Å [2.32 Å], S1···H16B is 2.53 Å [3.01 Å]). The ethoxy substituent is turned with respect to the plane of the aromatic ring (the C5—C6—O4—C14 torsion angle is 17.6 (3) °) probably due to the repulsion between atoms of these fragments (shortened intramolecular contacts C14···H5 2.59 Å [van der Waals radii sum is 2.87 Å], C5···H14A 2.71 Å [2.87 Å]). In the crystal phase the molecules of (I) form centrosymmetric dimers due to a weak intermolecular hydrogen bond (Table 1).