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The structures of the highly substituted title heterocycles, C20H22N2S and C20H22N2O2S, have been determined at 123 (1) K. Both mol­ecules possess exact C2 symmetry and the seven-membered rings have very similar twist-boat conformations. The magnitudes of the C-S-C bond angles, 107.13 (6) and 108.27 (7)°, respectively, are influenced significantly by the four substituent methyl groups on the seven-membered rings.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100020564/fg1607sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100020564/fg1607Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100020564/fg1607IIsup3.hkl
Contains datablock 2

pdf

Portable Document Format (PDF) file https://doi.org/10.1107/S0108270100020564/fg1607sup4.pdf
Supplementary material

CCDC references: 163913; 163914

Computing details top

For both compounds, data collection: SMART (Bruker, 1999); cell refinement: SMART and SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

(I) 2,7–dihydro–2,2,7,7–tetramethyl–3,6–diphenyl–1,4,5–thiadiazepine top
Crystal data top
C20H22N2SDx = 1.235 Mg m3
Mr = 322.46Melting point = 480–481 K
Orthorhombic, PbcnMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2abCell parameters from 4415 reflections
a = 19.4661 (7) Åθ = 3.3–29.3°
b = 10.7312 (4) ŵ = 0.19 mm1
c = 8.3000 (3) ÅT = 123 K
V = 1733.83 (11) Å3Prism, colourless
Z = 40.30 × 0.25 × 0.20 mm
F(000) = 688
Data collection top
Bruker AXS 1K CCD area detector
diffractometer
1856 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.025
Graphite monochromatorθmax = 28.3°, θmin = 2.1°
Detector resolution: 8.192 pixels mm-1h = 2525
narrow frame ω scansk = 1314
15326 measured reflectionsl = 1111
2138 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.122H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.101P)2]
where P = (Fo2 + 2Fc2)/3
2138 reflections(Δ/σ)max < 0.001
118 parametersΔρmax = 0.31 e Å3
0 restraintsΔρmin = 0.26 e Å3
Special details top

Experimental. The data collection for compound 1 nominally covered a sphere of reciprocal space by a combination of three sets of exposures; each set had a different φ angle for the crystal, 0, 120 and 240° repectively. Each exposure covered 0.3° in ω with a 10 second correlated frame time. A total of 600 frames were accumalated in each ω sweep. The crystal to detector distance was 4.805 cm. Coverage of the unique set was 95.0% to 29.13° in θ, (0.73 Å) and 99.4% complete to 28.28° in θ, (0.75 Å). Crystal decay was monitored by repeating the initial 50 frames at the end of data collection and analyzing the duplicate reflections, a further 50 frames of data were collected at positive 2θ to improve cell refinement statistics. A similar data collection protocol was employed for compound 2 with the following minor differences. The correlated frame time set was 30 s and the crystal to detector distance was 4.808 cm. Coverage of the unique set was 95.6% to 29.13° in θ, (0.72 Å) and 99.9% complete to 28.28° in θ, (0.75 Å). The data for both structures were trucatated to 0.75 Å for structure refinement. Area detector scaling and absorption corrections were performed by SADABS. This correction was used to scale the frames of data and to correct for absorption of the primary beam by the crystal support using the method of Blessing (1995). A correction for absorption of the primary beam by the crystal was not applied and as such no transmission factors are quoted.

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
xyzUiso*/Ueq
S10.50000.63132 (3)0.25000.01967 (16)
N10.46419 (5)0.93154 (9)0.24404 (10)0.0205 (2)
C10.31407 (6)0.77649 (11)0.23485 (13)0.0237 (3)
H10.33330.71120.29760.032 (4)*
C20.24317 (6)0.78969 (12)0.22544 (15)0.0281 (3)
H20.21410.73360.28200.044 (4)*
C30.21472 (6)0.88491 (11)0.13337 (14)0.0275 (3)
H30.16620.89380.12670.032 (4)*
C40.25719 (6)0.96681 (11)0.05143 (14)0.0282 (3)
H40.23771.03200.01120.034 (4)*
C50.32849 (5)0.95394 (10)0.06048 (14)0.0241 (3)
H50.35741.01020.00380.033 (4)*
C60.35727 (5)0.85870 (9)0.15253 (12)0.0180 (2)
C70.43389 (5)0.84594 (9)0.16310 (12)0.0177 (2)
C80.46950 (5)0.73379 (10)0.08541 (12)0.0182 (2)
C90.41972 (6)0.65144 (11)0.01157 (14)0.0263 (3)
H9A0.40010.70000.10040.042 (4)*
H9B0.38270.62230.05900.027 (3)*
H9C0.44460.57960.05510.037 (4)*
C100.52761 (5)0.77298 (11)0.02946 (14)0.0249 (3)
H10A0.50990.83310.10800.063 (6)*
H10B0.54510.69940.08620.041 (4)*
H10C0.56490.81130.03260.039 (4)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0234 (2)0.0141 (2)0.0215 (3)0.0000.00039 (12)0.000
N10.0192 (5)0.0174 (5)0.0248 (5)0.0016 (3)0.0052 (3)0.0015 (3)
C10.0231 (6)0.0233 (6)0.0247 (6)0.0031 (4)0.0024 (4)0.0031 (4)
C20.0221 (6)0.0300 (7)0.0322 (6)0.0008 (5)0.0076 (4)0.0017 (5)
C30.0173 (5)0.0321 (6)0.0330 (6)0.0035 (4)0.0018 (4)0.0046 (5)
C40.0232 (5)0.0288 (6)0.0325 (6)0.0056 (4)0.0068 (5)0.0034 (5)
C50.0217 (5)0.0223 (6)0.0284 (6)0.0014 (4)0.0035 (4)0.0034 (4)
C60.0178 (5)0.0185 (5)0.0177 (5)0.0014 (4)0.0025 (4)0.0039 (3)
C70.0183 (5)0.0171 (5)0.0176 (5)0.0006 (4)0.0013 (4)0.0024 (3)
C80.0164 (4)0.0203 (5)0.0178 (5)0.0001 (4)0.0001 (4)0.0012 (4)
C90.0210 (5)0.0299 (6)0.0279 (6)0.0003 (4)0.0028 (4)0.0113 (4)
C100.0234 (5)0.0342 (6)0.0170 (5)0.0028 (4)0.0021 (4)0.0013 (4)
Geometric parameters (Å, º) top
S1—C8i1.8515 (11)C8—C91.5387 (14)
S1—C81.8515 (11)C1—H10.9500
N1—C71.2818 (14)C2—H20.9500
N1—N1i1.3977 (18)C3—H30.9500
C1—C21.3896 (16)C4—H40.9500
C1—C61.3972 (15)C5—H50.9500
C2—C31.3909 (16)C9—H9A0.9800
C3—C41.3850 (17)C9—H9B0.9800
C4—C51.3969 (15)C9—H9C0.9800
C5—C61.3935 (14)C10—H10A0.9800
C6—C71.5004 (13)C10—H10B0.9800
C7—C81.5313 (14)C10—H10C0.9800
C8—C101.5381 (14)
C10···N13.0939 (14)C10···C7i3.2282 (15)
C10···N1i2.9210 (14)
C8i—S1—C8107.13 (6)C1—C2—H2120.0
C7—N1—N1i119.75 (8)C3—C2—H2120.0
C2—C1—C6120.39 (11)C4—C3—H3120.1
C1—C2—C3120.07 (11)C2—C3—H3120.1
C4—C3—C2119.89 (10)C3—C4—H4119.9
C3—C4—C5120.26 (10)C5—C4—H4119.9
C6—C5—C4120.09 (10)C6—C5—H5120.0
C5—C6—C1119.29 (10)C4—C5—H5120.0
C5—C6—C7119.90 (9)C8—C9—H9A109.5
C1—C6—C7120.80 (9)C8—C9—H9B109.5
N1—C7—C6115.01 (9)H9A—C9—H9B109.5
N1—C7—C8125.14 (9)C8—C9—H9C109.5
C6—C7—C8119.81 (8)H9A—C9—H9C109.5
C7—C8—C10112.27 (9)H9B—C9—H9C109.5
C7—C8—C9112.75 (8)C8—C10—H10A109.5
C10—C8—C9107.22 (9)C8—C10—H10B109.5
C7—C8—S1107.53 (7)H10A—C10—H10B109.5
C10—C8—S1112.57 (7)C8—C10—H10C109.5
C9—C8—S1104.29 (7)H10A—C10—H10C109.5
C2—C1—H1119.8H10B—C10—H10C109.5
C6—C1—H1119.8
C6—C1—C2—C30.17 (18)C1—C6—C7—N1109.25 (11)
C1—C2—C3—C40.19 (17)C5—C6—C7—C8111.83 (11)
C2—C3—C4—C50.20 (17)C1—C6—C7—C868.56 (13)
C3—C4—C5—C60.19 (17)N1—C7—C8—C1055.58 (13)
C4—C5—C6—C10.18 (16)C6—C7—C8—C10126.86 (10)
C4—C5—C6—C7179.45 (10)N1—C7—C8—C9176.81 (9)
C2—C1—C6—C50.17 (16)C6—C7—C8—C95.62 (14)
C2—C1—C6—C7179.45 (11)N1—C7—C8—S168.79 (12)
C7i—N1i—N1—C768.75 (17)C6—C7—C8—S1108.78 (9)
N1i—N1—C7—C6177.37 (9)C8i—S1—C8—C737.69 (5)
N1i—N1—C7—C84.96 (16)C8i—S1—C8—C1086.49 (7)
C5—C6—C7—N170.37 (13)C8i—S1—C8—C9157.62 (8)
Symmetry code: (i) x+1, y, z+1/2.
(II) 2,7–dihydro–2,2,7,7–tetramethyl–3,6–diphenyl–1,4,5–thiadiazepine–1,1 –dioxide top
Crystal data top
C20H22N2O2SDx = 1.322 Mg m3
Mr = 354.46Melting point = 470–472 K
Orthorhombic, PbcnMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2abCell parameters from 904 reflections
a = 18.9551 (11) Åθ = 3.2–28.9°
b = 11.4905 (7) ŵ = 0.20 mm1
c = 8.1745 (4) ÅT = 123 K
V = 1780.43 (17) Å3Prism, colourless
Z = 40.30 × 0.25 × 0.10 mm
F(000) = 752
Data collection top
Bruker AXS 1K CCD area detector
diffractometer
1815 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.026
Graphite monochromatorθmax = 28.3°, θmin = 2.1°
Detector resolution: 8.192 pixels mm-1h = 2525
narrow frame ω scansk = 1515
16286 measured reflectionsl = 1010
2214 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.093H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.055P)2 + 0.5P]
where P = (Fo2 + 2Fc2)/3
2214 reflections(Δ/σ)max = 0.001
127 parametersΔρmax = 0.34 e Å3
0 restraintsΔρmin = 0.32 e Å3
Special details top

Experimental. None

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
xyzUiso*/Ueq
S10.50000.65304 (3)0.25000.01915 (13)
O10.56050 (5)0.58857 (8)0.19229 (12)0.0298 (2)
N10.46367 (5)0.93214 (8)0.23939 (12)0.0188 (2)
C10.30821 (7)0.78723 (12)0.20616 (17)0.0254 (3)
H10.32560.72390.26890.034 (4)*
C20.23573 (7)0.80182 (13)0.18545 (19)0.0314 (3)
H20.20390.74820.23410.042 (5)*
C30.21003 (7)0.89407 (13)0.09437 (19)0.0326 (3)
H30.16060.90400.08100.045 (5)*
C40.25638 (7)0.97166 (13)0.02287 (19)0.0341 (3)
H40.23871.03480.04010.049 (5)*
C50.32883 (7)0.95779 (11)0.04264 (18)0.0276 (3)
H50.36051.01140.00690.038 (4)*
C60.35500 (6)0.86563 (10)0.13475 (15)0.0188 (2)
C70.43313 (6)0.85190 (10)0.15586 (14)0.0168 (2)
C80.47082 (6)0.74700 (10)0.08029 (14)0.0180 (2)
C90.42182 (7)0.67004 (12)0.02354 (16)0.0257 (3)
H9A0.40360.71530.11600.033 (4)*
H9B0.38230.64300.04390.028 (4)*
H9C0.44830.60280.06460.037 (4)*
C100.53391 (7)0.78243 (12)0.02785 (15)0.0250 (3)
H10A0.52000.84670.09970.052 (5)*
H10B0.54870.71580.09440.039 (5)*
H10C0.57320.80730.04180.045 (5)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0217 (2)0.0134 (2)0.0224 (2)0.0000.00250 (16)0.000
O10.0311 (5)0.0222 (5)0.0362 (5)0.0099 (4)0.0059 (4)0.0083 (4)
N10.0184 (5)0.0160 (5)0.0219 (5)0.0005 (4)0.0025 (4)0.0019 (4)
C10.0228 (6)0.0268 (7)0.0267 (7)0.0009 (5)0.0029 (5)0.0041 (5)
C20.0217 (6)0.0341 (7)0.0384 (8)0.0036 (5)0.0065 (6)0.0001 (6)
C30.0175 (6)0.0385 (8)0.0419 (8)0.0021 (5)0.0034 (6)0.0062 (7)
C40.0255 (7)0.0338 (7)0.0432 (8)0.0048 (5)0.0099 (6)0.0067 (6)
C50.0220 (6)0.0251 (6)0.0358 (7)0.0015 (5)0.0052 (5)0.0075 (6)
C60.0181 (5)0.0197 (6)0.0185 (5)0.0009 (4)0.0014 (4)0.0023 (5)
C70.0191 (5)0.0158 (5)0.0155 (5)0.0008 (4)0.0003 (4)0.0033 (4)
C80.0193 (5)0.0185 (5)0.0164 (5)0.0003 (4)0.0010 (4)0.0010 (5)
C90.0254 (6)0.0268 (6)0.0248 (6)0.0004 (5)0.0048 (5)0.0089 (5)
C100.0239 (6)0.0342 (7)0.0169 (6)0.0010 (5)0.0032 (5)0.0015 (5)
Geometric parameters (Å, º) top
S1—O11.4444 (9)C8—C91.5379 (16)
S1—O1i1.4444 (9)C8—C101.5419 (16)
S1—C81.8429 (12)C1—H10.9500
S1—C8i1.8429 (12)C2—H20.9500
N1—C71.2850 (15)C3—H30.9500
N1—N1i1.3882 (19)C4—H40.9500
C1—C21.3943 (18)C5—H50.9500
C1—C61.3925 (17)C9—H9A0.9800
C2—C31.384 (2)C9—H9B0.9800
C3—C41.381 (2)C9—H9C0.9800
C4—C51.3920 (18)C10—H10A0.9800
C5—C61.3909 (17)C10—H10B0.9800
C6—C71.4993 (16)C10—H10C0.9800
C7—C81.5313 (16)
C10···N13.0829 (16)C10···C7i3.2053 (17)
C10···N1i2.9191 (16)H9C···O1ii2.4400
O1—S1—O1i118.29 (8)C10—C8—S1110.70 (8)
O1—S1—C8107.03 (5)C2—C1—H1120.0
O1i—S1—C8107.94 (5)C6—C1—H1120.0
O1—S1—C8i107.94 (5)C3—C2—H2119.9
O1i—S1—C8i107.03 (5)C1—C2—H2119.9
C8—S1—C8i108.27 (7)C4—C3—H3120.1
C7—N1—N1i120.88 (9)C2—C3—H3120.1
C2—C1—C6119.93 (12)C3—C4—H4119.9
C3—C2—C1120.28 (13)C5—C4—H4119.9
C4—C3—C2119.88 (12)C6—C5—H5119.9
C3—C4—C5120.29 (13)C4—C5—H5119.9
C6—C5—C4120.13 (12)C8—C9—H9A109.5
C5—C6—C1119.49 (11)C8—C9—H9B109.5
C5—C6—C7119.65 (11)H9A—C9—H9B109.5
C1—C6—C7120.86 (11)C8—C9—H9C109.5
N1—C7—C6115.51 (10)H9A—C9—H9C109.5
N1—C7—C8124.68 (10)H9B—C9—H9C109.5
C6—C7—C8119.81 (10)C8—C10—H10A109.5
C7—C8—C9113.18 (10)C8—C10—H10B109.5
C7—C8—C10112.66 (10)H10A—C10—H10B109.5
C9—C8—C10107.69 (10)C8—C10—H10C109.5
C7—C8—S1107.31 (8)H10A—C10—H10C109.5
C9—C8—S1105.06 (8)H10B—C10—H10C109.5
C6—C1—C2—C30.1 (2)N1—C7—C8—C9175.78 (11)
C1—C2—C3—C40.4 (2)C6—C7—C8—C94.44 (15)
C2—C3—C4—C50.3 (2)N1—C7—C8—C1053.32 (15)
C3—C4—C5—C60.0 (2)C6—C7—C8—C10126.91 (11)
C4—C5—C6—C10.3 (2)N1—C7—C8—S168.78 (13)
C4—C5—C6—C7179.71 (13)C6—C7—C8—S1111.00 (10)
C2—C1—C6—C50.2 (2)O1—S1—C8—C7153.75 (8)
C2—C1—C6—C7179.79 (12)O1i—S1—C8—C777.92 (9)
C7i—N1i—N1—C766.6 (2)C8i—S1—C8—C737.62 (6)
N1i—N1—C7—C6176.82 (11)O1—S1—C8—C985.54 (9)
N1i—N1—C7—C83.39 (19)O1i—S1—C8—C942.79 (9)
C5—C6—C7—N166.64 (15)C8i—S1—C8—C9158.33 (9)
C1—C6—C7—N1113.38 (13)O1—S1—C8—C1030.44 (10)
C5—C6—C7—C8113.56 (13)O1i—S1—C8—C10158.77 (8)
C1—C6—C7—C866.42 (16)C8i—S1—C8—C1085.69 (8)
Symmetry codes: (i) x+1, y, z+1/2; (ii) x+1, y+1, z.
 

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