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The title compounds, (2
S)-
N-[5-(4-chlorophenyl)-2,3-dihydro-6
H-1,3,4-thiadiazin-2-ylidene]-2-[(phenylsulfonyl)amino]propanamide, C
18H
17ClN
4O
3S
2, (I), (2
R)-
N-[5-(4-fluorophenyl)-6
H-1,3,4-thiadiazin-2-yl]-2-[(phenylsulfonyl)amino]propanamide, C
18H
17FN
4O
3S
2, (II), and (2
S)-
N-[5-(5-chloro-2-thienyl)-6
H-1,3,4-thiadiazin-2-yl]-2-[(phenylsulfonyl)amino]propanamide, C
16H
15ClN
4O
3S
3, (III), are potent inhibitors of matrix metalloproteinases. In all three compounds, the thiadiazine ring adopts a screw-boat conformation. The molecules of compound (I) show a short intramolecular N
Ala—H
N
exo hydrogen bond [N
N 2.661 (3) Å] and are linked into a chain along the
c axis by N
endo—H
S
endo and N
endo—H
O
Ala hydrogen bonds [N
S 3.236 (3) and N
O 3.375 (3) Å] between neighbouring molecules. In compound (II), the molecules are connected antiparallel into a chain along the
a axis by N
exo—H
O
Ala and N
Ala—H
N
endo hydrogen bonds [N
O 2.907 (6) and N
N 2.911 (6) Å]. The molecules of compound (III) are dimerized antiparallel through N
exo—H
N
endo hydrogen bonds [N
N 2.956 (7) and 2.983 (7) Å]. The different hydrogen-bonding patterns can be explained by an amido–imino tautomerism (prototropic shift) shown by different bond lengths within the 6
H-1,3,4-thiadiazine moiety.
Supporting information
CCDC references: 164659; 164660; 164661
The synthesis and spectroscopic data of the title compounds will be published
elsewhere. Crystals of all three compounds suitable for diffraction analysis
were obtained by slow crystallization from solution in methanol/acetonitrile
(5:1).
H atoms on N in (I) and (II) were refined isotropically. Other H atoms in (I)
and (II), and all H atoms in (III), were included in calculated positions
using a riding model, with U(H) = 1.2Ueq for CH2 and CH groups, and
U(H) = 1.5Ueq for CH3 groups, and C—H in the range 0.95–0.99 Å
(Please check - no C—H data in CIF for (III). The torsion angles of the
CH3 groups were refined.
For all compounds, data collection: P3/PC (Siemens, 1993); cell refinement: P3/PC; data reduction: SHELXTL-Plus (Sheldrick, 1990a); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990b); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 1990).
(I) (2
S)-
N-[5-(4-chlorophenyl)-2,3-dihydro-6
H-1,3,4-thiadiazin-2-ylidene]-2- (phenylsulfonyl)amino]propanamide
top
Crystal data top
C18H17ClN4O3S2 | Dx = 1.538 Mg m−3 |
Mr = 436.93 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P21212 | Cell parameters from 21 reflections |
a = 15.600 (4) Å | θ = 2.3–11.3° |
b = 20.764 (6) Å | µ = 0.45 mm−1 |
c = 5.826 (3) Å | T = 173 K |
V = 1887.1 (12) Å3 | Needle, colourless |
Z = 4 | 1.00 × 0.30 × 0.15 mm |
F(000) = 904 | |
Data collection top
Siemens P21 diffractometer | Rint = 0.031 |
Radiation source: normal-focus sealed tube | θmax = 30.0°, θmin = 2.0° |
Graphite monochromator | h = −21→21 |
Wyckoff scan | k = −29→29 |
6296 measured reflections | l = −8→8 |
5491 independent reflections | 3 standard reflections every 100 reflections |
4278 reflections with I > 2σ(I) | intensity decay: none |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.051 | w = 1/[σ2(Fo2) + (0.0588P)2 + 0.3217P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.123 | (Δ/σ)max = 0.001 |
S = 1.02 | Δρmax = 0.33 e Å−3 |
5491 reflections | Δρmin = −0.29 e Å−3 |
263 parameters | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0119 (13) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983) |
Secondary atom site location: difference Fourier map | Absolute structure parameter: −0.09 (9) |
Crystal data top
C18H17ClN4O3S2 | V = 1887.1 (12) Å3 |
Mr = 436.93 | Z = 4 |
Orthorhombic, P21212 | Mo Kα radiation |
a = 15.600 (4) Å | µ = 0.45 mm−1 |
b = 20.764 (6) Å | T = 173 K |
c = 5.826 (3) Å | 1.00 × 0.30 × 0.15 mm |
Data collection top
Siemens P21 diffractometer | Rint = 0.031 |
6296 measured reflections | 3 standard reflections every 100 reflections |
5491 independent reflections | intensity decay: none |
4278 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.051 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.123 | Δρmax = 0.33 e Å−3 |
S = 1.02 | Δρmin = −0.29 e Å−3 |
5491 reflections | Absolute structure: Flack (1983) |
263 parameters | Absolute structure parameter: −0.09 (9) |
0 restraints | |
Special details top
Experimental. A large crystal was taken to obtain sufficient scattering |
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 | |
Cl1 | 0.11511 (5) | 0.02529 (5) | 0.58490 (19) | 0.0520 (2) | |
S1 | 0.59765 (4) | 0.10699 (4) | 0.01091 (11) | 0.03229 (18) | |
S2 | 0.88067 (4) | 0.24019 (3) | 0.42578 (12) | 0.02781 (16) | |
O1 | 0.76848 (13) | 0.11095 (12) | −0.1246 (3) | 0.0368 (5) | |
O2 | 0.93380 (13) | 0.27590 (10) | 0.2705 (4) | 0.0366 (5) | |
O3 | 0.89429 (14) | 0.24560 (11) | 0.6671 (3) | 0.0366 (5) | |
N1 | 0.53506 (15) | 0.08429 (12) | 0.5034 (4) | 0.0314 (5) | |
N2 | 0.61864 (16) | 0.10364 (13) | 0.4584 (4) | 0.0330 (5) | |
H2N | 0.652 (3) | 0.1030 (19) | 0.567 (7) | 0.055 (12)* | |
N3 | 0.74395 (14) | 0.10914 (12) | 0.2667 (4) | 0.0271 (5) | |
N4 | 0.89356 (15) | 0.16405 (12) | 0.3655 (4) | 0.0286 (5) | |
H4N | 0.865 (2) | 0.1395 (15) | 0.468 (6) | 0.028 (8)* | |
C1 | 0.3227 (2) | 0.08555 (18) | 0.2499 (7) | 0.0446 (9) | |
H1 | 0.3350 | 0.1033 | 0.1033 | 0.054* | |
C2 | 0.2383 (2) | 0.0691 (2) | 0.3037 (7) | 0.0500 (10) | |
H2 | 0.1938 | 0.0753 | 0.1947 | 0.060* | |
C3 | 0.22054 (18) | 0.04408 (14) | 0.5135 (6) | 0.0335 (7) | |
C4 | 0.2847 (2) | 0.03333 (17) | 0.6697 (6) | 0.0416 (8) | |
H4 | 0.2719 | 0.0150 | 0.8151 | 0.050* | |
C5 | 0.3687 (2) | 0.04931 (17) | 0.6139 (5) | 0.0380 (7) | |
H5 | 0.4132 | 0.0413 | 0.7216 | 0.046* | |
C6 | 0.38849 (17) | 0.07664 (12) | 0.4045 (5) | 0.0251 (5) | |
C7 | 0.47799 (17) | 0.09696 (12) | 0.3512 (4) | 0.0239 (5) | |
C8 | 0.49870 (19) | 0.13464 (15) | 0.1401 (5) | 0.0335 (7) | |
H8A | 0.5041 | 0.1808 | 0.1800 | 0.040* | |
H8B | 0.4514 | 0.1302 | 0.0281 | 0.040* | |
C9 | 0.65946 (17) | 0.10633 (13) | 0.2565 (5) | 0.0239 (5) | |
C10 | 0.79127 (17) | 0.11970 (13) | 0.0754 (5) | 0.0262 (5) | |
C11 | 0.88237 (17) | 0.14299 (14) | 0.1261 (5) | 0.0286 (6) | |
H11 | 0.8946 | 0.1806 | 0.0240 | 0.034* | |
C12 | 0.9475 (2) | 0.08998 (16) | 0.0706 (7) | 0.0444 (8) | |
H12A | 1.0056 | 0.1057 | 0.1025 | 0.067* | |
H12B | 0.9430 | 0.0783 | −0.0919 | 0.067* | |
H12C | 0.9358 | 0.0521 | 0.1656 | 0.067* | |
C13 | 0.77307 (18) | 0.26187 (14) | 0.3706 (5) | 0.0289 (6) | |
C14 | 0.7503 (2) | 0.28643 (17) | 0.1605 (6) | 0.0421 (8) | |
H14 | 0.7922 | 0.2918 | 0.0437 | 0.051* | |
C15 | 0.6655 (2) | 0.30333 (18) | 0.1204 (7) | 0.0503 (9) | |
H15 | 0.6494 | 0.3205 | −0.0244 | 0.060* | |
C16 | 0.6049 (2) | 0.29535 (16) | 0.2886 (6) | 0.0429 (8) | |
H16 | 0.5473 | 0.3079 | 0.2611 | 0.052* | |
C17 | 0.6274 (2) | 0.26935 (17) | 0.4961 (7) | 0.0445 (8) | |
H17 | 0.5850 | 0.2630 | 0.6108 | 0.053* | |
C18 | 0.7120 (2) | 0.25213 (17) | 0.5398 (5) | 0.0399 (7) | |
H18 | 0.7277 | 0.2340 | 0.6835 | 0.048* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.0271 (4) | 0.0570 (5) | 0.0718 (6) | −0.0076 (4) | 0.0075 (4) | 0.0054 (5) |
S1 | 0.0246 (3) | 0.0544 (4) | 0.0179 (3) | 0.0047 (3) | −0.0008 (3) | −0.0002 (3) |
S2 | 0.0240 (3) | 0.0313 (3) | 0.0281 (3) | −0.0085 (3) | −0.0027 (3) | 0.0017 (3) |
O1 | 0.0293 (10) | 0.0547 (14) | 0.0264 (10) | 0.0002 (10) | 0.0004 (8) | −0.0089 (10) |
O2 | 0.0315 (11) | 0.0356 (12) | 0.0428 (12) | −0.0092 (9) | 0.0016 (10) | 0.0060 (10) |
O3 | 0.0315 (11) | 0.0459 (13) | 0.0324 (10) | −0.0093 (10) | −0.0062 (9) | −0.0051 (10) |
N1 | 0.0264 (11) | 0.0440 (14) | 0.0238 (11) | −0.0122 (10) | 0.0007 (10) | 0.0049 (10) |
N2 | 0.0275 (11) | 0.0516 (15) | 0.0197 (11) | −0.0161 (11) | −0.0027 (9) | 0.0049 (11) |
N3 | 0.0257 (11) | 0.0286 (12) | 0.0270 (11) | −0.0052 (9) | −0.0044 (9) | 0.0039 (10) |
N4 | 0.0263 (12) | 0.0305 (12) | 0.0290 (12) | −0.0044 (10) | −0.0047 (10) | 0.0047 (10) |
C1 | 0.0259 (15) | 0.070 (2) | 0.0378 (17) | 0.0028 (15) | −0.0004 (14) | 0.0202 (17) |
C2 | 0.0267 (16) | 0.070 (3) | 0.053 (2) | −0.0002 (16) | −0.0082 (15) | 0.0186 (19) |
C3 | 0.0267 (13) | 0.0262 (13) | 0.0475 (18) | −0.0024 (10) | 0.0081 (13) | −0.0013 (13) |
C4 | 0.0358 (16) | 0.049 (2) | 0.0401 (18) | −0.0136 (15) | 0.0049 (14) | 0.0092 (16) |
C5 | 0.0337 (16) | 0.0485 (18) | 0.0319 (16) | −0.0090 (14) | −0.0051 (13) | 0.0057 (14) |
C6 | 0.0266 (13) | 0.0223 (11) | 0.0264 (12) | 0.0001 (10) | 0.0014 (12) | −0.0001 (10) |
C7 | 0.0291 (13) | 0.0211 (12) | 0.0213 (11) | 0.0002 (10) | 0.0018 (10) | 0.0011 (10) |
C8 | 0.0268 (13) | 0.0389 (16) | 0.0348 (16) | 0.0081 (12) | 0.0064 (12) | 0.0129 (13) |
C9 | 0.0273 (12) | 0.0227 (12) | 0.0217 (12) | −0.0024 (10) | −0.0048 (10) | 0.0017 (11) |
C10 | 0.0242 (12) | 0.0265 (13) | 0.0279 (12) | 0.0037 (10) | −0.0006 (11) | −0.0008 (12) |
C11 | 0.0232 (12) | 0.0337 (14) | 0.0289 (14) | 0.0008 (11) | −0.0007 (11) | 0.0004 (11) |
C12 | 0.0281 (15) | 0.0490 (19) | 0.056 (2) | 0.0106 (13) | −0.0002 (15) | −0.0101 (18) |
C13 | 0.0277 (13) | 0.0245 (13) | 0.0344 (15) | −0.0036 (11) | −0.0032 (11) | −0.0028 (12) |
C14 | 0.0400 (17) | 0.047 (2) | 0.0390 (17) | 0.0073 (15) | 0.0030 (14) | 0.0105 (16) |
C15 | 0.0460 (19) | 0.058 (2) | 0.047 (2) | 0.0183 (17) | −0.0065 (17) | 0.0144 (18) |
C16 | 0.0352 (17) | 0.0372 (17) | 0.056 (2) | 0.0038 (14) | −0.0058 (16) | −0.0005 (15) |
C17 | 0.0278 (15) | 0.053 (2) | 0.053 (2) | −0.0055 (14) | 0.0048 (15) | 0.0001 (17) |
C18 | 0.0323 (15) | 0.0519 (19) | 0.0354 (17) | −0.0062 (13) | −0.0009 (12) | 0.0065 (16) |
Geometric parameters (Å, º) top
Cl1—C3 | 1.741 (3) | C5—C6 | 1.381 (4) |
S1—C9 | 1.726 (3) | C5—H5 | 0.9500 |
S1—C8 | 1.811 (3) | C6—C7 | 1.491 (4) |
S2—O3 | 1.426 (2) | C7—C8 | 1.493 (4) |
S2—O2 | 1.433 (2) | C8—H8A | 0.9900 |
S2—N4 | 1.632 (3) | C8—H8B | 0.9900 |
S2—C13 | 1.767 (3) | C10—C11 | 1.530 (4) |
O1—C10 | 1.231 (4) | C11—C12 | 1.533 (4) |
N1—C7 | 1.284 (4) | C11—H11 | 1.0000 |
N1—N2 | 1.389 (3) | C12—H12A | 0.9800 |
N2—C9 | 1.338 (3) | C12—H12B | 0.9800 |
N2—H2N | 0.82 (4) | C12—H12C | 0.9800 |
N3—C9 | 1.321 (3) | C13—C14 | 1.373 (4) |
N3—C10 | 1.355 (4) | C13—C18 | 1.385 (4) |
N4—C11 | 1.472 (4) | C14—C15 | 1.388 (5) |
N4—H4N | 0.90 (3) | C14—H14 | 0.9500 |
C1—C6 | 1.378 (4) | C15—C16 | 1.372 (5) |
C1—C2 | 1.396 (5) | C15—H15 | 0.9500 |
C1—H1 | 0.9500 | C16—C17 | 1.370 (5) |
C2—C3 | 1.356 (5) | C16—H16 | 0.9500 |
C2—H2 | 0.9500 | C17—C18 | 1.391 (4) |
C3—C4 | 1.371 (5) | C17—H17 | 0.9500 |
C4—C5 | 1.390 (4) | C18—H18 | 0.9500 |
C4—H4 | 0.9500 | | |
| | | |
C9—S1—C8 | 97.71 (15) | C7—C8—H8B | 109.4 |
O3—S2—O2 | 119.69 (14) | S1—C8—H8B | 109.4 |
O3—S2—N4 | 105.65 (14) | H8A—C8—H8B | 108.0 |
O2—S2—N4 | 107.11 (14) | N3—C9—N2 | 115.9 (2) |
O3—S2—C13 | 107.50 (14) | N3—C9—S1 | 126.5 (2) |
O2—S2—C13 | 107.62 (14) | N2—C9—S1 | 117.6 (2) |
N4—S2—C13 | 108.94 (13) | O1—C10—N3 | 126.7 (3) |
C7—N1—N2 | 117.5 (2) | O1—C10—C11 | 119.8 (3) |
C9—N2—N1 | 128.6 (2) | N3—C10—C11 | 113.5 (2) |
C9—N2—H2N | 112 (3) | N4—C11—C10 | 112.8 (2) |
N1—N2—H2N | 117 (3) | N4—C11—C12 | 109.5 (2) |
C9—N3—C10 | 120.9 (2) | C10—C11—C12 | 110.4 (2) |
C11—N4—S2 | 118.48 (19) | N4—C11—H11 | 108.0 |
C11—N4—H4N | 114 (2) | C10—C11—H11 | 108.0 |
S2—N4—H4N | 110 (2) | C12—C11—H11 | 108.0 |
C6—C1—C2 | 121.5 (3) | C11—C12—H12A | 109.5 |
C6—C1—H1 | 119.2 | C11—C12—H12B | 109.5 |
C2—C1—H1 | 119.2 | H12A—C12—H12B | 109.5 |
C3—C2—C1 | 119.3 (3) | C11—C12—H12C | 109.5 |
C3—C2—H2 | 120.4 | H12A—C12—H12C | 109.5 |
C1—C2—H2 | 120.4 | H12B—C12—H12C | 109.5 |
C2—C3—C4 | 120.7 (3) | C14—C13—C18 | 120.7 (3) |
C2—C3—Cl1 | 119.6 (3) | C14—C13—S2 | 120.2 (2) |
C4—C3—Cl1 | 119.7 (3) | C18—C13—S2 | 119.1 (2) |
C3—C4—C5 | 119.6 (3) | C13—C14—C15 | 119.4 (3) |
C3—C4—H4 | 120.2 | C13—C14—H14 | 120.3 |
C5—C4—H4 | 120.2 | C15—C14—H14 | 120.3 |
C6—C5—C4 | 121.0 (3) | C16—C15—C14 | 120.4 (3) |
C6—C5—H5 | 119.5 | C16—C15—H15 | 119.8 |
C4—C5—H5 | 119.5 | C14—C15—H15 | 119.8 |
C1—C6—C5 | 117.8 (3) | C17—C16—C15 | 120.1 (3) |
C1—C6—C7 | 121.6 (3) | C17—C16—H16 | 119.9 |
C5—C6—C7 | 120.6 (3) | C15—C16—H16 | 119.9 |
N1—C7—C6 | 116.6 (2) | C16—C17—C18 | 120.4 (3) |
N1—C7—C8 | 121.7 (2) | C16—C17—H17 | 119.8 |
C6—C7—C8 | 121.5 (2) | C18—C17—H17 | 119.8 |
C7—C8—S1 | 111.14 (19) | C13—C18—C17 | 119.0 (3) |
C7—C8—H8A | 109.4 | C13—C18—H18 | 120.5 |
S1—C8—H8A | 109.4 | C17—C18—H18 | 120.5 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N···S1i | 0.82 (4) | 2.72 (4) | 3.236 (3) | 122 (3) |
N2—H2N···O1i | 0.82 (4) | 2.56 (4) | 3.375 (3) | 173 (4) |
N4—H4N···N3 | 0.90 (3) | 2.31 (3) | 2.661 (3) | 103 (2) |
Symmetry code: (i) x, y, z+1. |
(II) (2
R)-
N-[5-(4-fluoro-phenyl)-6
H-1,3,4-thiadiazin-2-yl]-2-
[(phenylsulfonyl)amino]propanamide
top
Crystal data top
C18H17FN4O3S2 | Dx = 1.456 Mg m−3 |
Mr = 420.48 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 20 reflections |
a = 9.675 (19) Å | θ = 2.6–11.5° |
b = 12.704 (19) Å | µ = 0.32 mm−1 |
c = 15.606 (15) Å | T = 173 K |
V = 1918 (5) Å3 | Needle, colourless |
Z = 4 | 1.0 × 0.6 × 0.6 mm |
F(000) = 872 | |
Data collection top
Siemens P21 diffractometer | Rint = 0.045 |
Radiation source: normal-focus sealed tube | θmax = 30.1°, θmin = 2.1° |
Graphite monochromator | h = −13→13 |
Wyckoff scan | k = −17→17 |
6306 measured reflections | l = −21→21 |
5271 independent reflections | 3 standard reflections every 100 reflections |
4615 reflections with I > 2σ(I) | intensity decay: none |
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)] = 0.049 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.128 | w = 1/[σ2(Fo2) + (0.0722P)2 + 0.8564P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max = 0.001 |
5271 reflections | Δρmax = 0.34 e Å−3 |
262 parameters | Δρmin = −0.43 e Å−3 |
0 restraints | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.12 (8) |
Crystal data top
C18H17FN4O3S2 | V = 1918 (5) Å3 |
Mr = 420.48 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 9.675 (19) Å | µ = 0.32 mm−1 |
b = 12.704 (19) Å | T = 173 K |
c = 15.606 (15) Å | 1.0 × 0.6 × 0.6 mm |
Data collection top
Siemens P21 diffractometer | Rint = 0.045 |
6306 measured reflections | 3 standard reflections every 100 reflections |
5271 independent reflections | intensity decay: none |
4615 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.049 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.128 | Δρmax = 0.34 e Å−3 |
S = 1.01 | Δρmin = −0.43 e Å−3 |
5271 reflections | Absolute structure: Flack (1983) |
262 parameters | Absolute structure parameter: −0.12 (8) |
0 restraints | |
Special details top
Experimental. A large crystal was taken to obtain sufficient scattering |
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 | 0.09325 (6) | 0.77278 (5) | 0.31052 (4) | 0.02420 (14) | |
S2 | 0.17513 (7) | 0.50883 (5) | 0.58954 (4) | 0.02467 (14) | |
N1 | 0.3671 (2) | 0.8371 (2) | 0.22849 (14) | 0.0289 (5) | |
N2 | 0.3699 (2) | 0.8075 (2) | 0.31511 (14) | 0.0285 (5) | |
N3 | 0.2754 (2) | 0.76999 (19) | 0.44485 (13) | 0.0224 (4) | |
H3N | 0.363 (4) | 0.759 (3) | 0.463 (2) | 0.037 (9)* | |
N4 | 0.1390 (2) | 0.62762 (18) | 0.62024 (13) | 0.0232 (4) | |
H4N | 0.052 (5) | 0.634 (3) | 0.637 (3) | 0.051 (12)* | |
O1 | 0.04966 (18) | 0.77390 (17) | 0.48789 (12) | 0.0279 (4) | |
O2 | 0.3221 (2) | 0.49252 (17) | 0.60224 (12) | 0.0350 (5) | |
O3 | 0.0773 (3) | 0.44185 (17) | 0.63244 (13) | 0.0352 (5) | |
F1 | 0.3034 (3) | 0.9218 (2) | −0.16711 (12) | 0.0593 (7) | |
C1 | 0.2067 (4) | 0.7757 (2) | 0.02291 (18) | 0.0349 (6) | |
H1 | 0.1514 | 0.7170 | 0.0386 | 0.042* | |
C2 | 0.2143 (4) | 0.8060 (3) | −0.06292 (19) | 0.0425 (8) | |
H2 | 0.1649 | 0.7688 | −0.1059 | 0.051* | |
C3 | 0.2953 (4) | 0.8915 (3) | −0.08354 (18) | 0.0375 (7) | |
C4 | 0.3687 (3) | 0.9493 (3) | −0.02380 (18) | 0.0335 (6) | |
H4 | 0.4228 | 1.0083 | −0.0404 | 0.040* | |
C5 | 0.3604 (3) | 0.9181 (2) | 0.06178 (17) | 0.0285 (5) | |
H5 | 0.4100 | 0.9562 | 0.1042 | 0.034* | |
C6 | 0.2797 (3) | 0.8307 (2) | 0.08625 (16) | 0.0238 (5) | |
C7 | 0.2741 (3) | 0.7991 (2) | 0.17787 (16) | 0.0228 (5) | |
C8 | 0.1631 (3) | 0.7255 (2) | 0.20965 (16) | 0.0298 (5) | |
H8A | 0.2024 | 0.6542 | 0.2177 | 0.036* | |
H8B | 0.0882 | 0.7207 | 0.1666 | 0.036* | |
C9 | 0.2571 (3) | 0.7875 (2) | 0.35682 (15) | 0.0212 (4) | |
C10 | 0.1728 (3) | 0.75567 (19) | 0.50393 (15) | 0.0214 (4) | |
C11 | 0.2220 (3) | 0.7174 (2) | 0.59211 (15) | 0.0236 (5) | |
H11 | 0.3211 | 0.6956 | 0.5881 | 0.028* | |
C12 | 0.2083 (4) | 0.8058 (3) | 0.6576 (2) | 0.0392 (7) | |
H12A | 0.1109 | 0.8259 | 0.6630 | 0.059* | |
H12B | 0.2624 | 0.8668 | 0.6387 | 0.059* | |
H12C | 0.2428 | 0.7816 | 0.7133 | 0.059* | |
C13 | 0.1483 (3) | 0.4990 (2) | 0.47732 (15) | 0.0238 (5) | |
C14 | 0.0141 (3) | 0.4948 (2) | 0.44451 (17) | 0.0278 (5) | |
H14 | −0.0637 | 0.5002 | 0.4814 | 0.033* | |
C15 | −0.0030 (3) | 0.4825 (2) | 0.35636 (18) | 0.0316 (6) | |
H15 | −0.0935 | 0.4809 | 0.3327 | 0.038* | |
C16 | 0.1113 (3) | 0.4726 (2) | 0.30260 (17) | 0.0324 (6) | |
H16 | 0.0983 | 0.4627 | 0.2428 | 0.039* | |
C17 | 0.2444 (4) | 0.4770 (3) | 0.33623 (19) | 0.0391 (7) | |
H17 | 0.3221 | 0.4703 | 0.2994 | 0.047* | |
C18 | 0.2639 (3) | 0.4913 (3) | 0.42403 (17) | 0.0361 (6) | |
H18 | 0.3545 | 0.4958 | 0.4473 | 0.043* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0176 (2) | 0.0352 (3) | 0.0198 (3) | −0.0027 (2) | −0.0020 (2) | 0.0014 (2) |
S2 | 0.0276 (3) | 0.0302 (3) | 0.0162 (2) | 0.0046 (3) | −0.0007 (2) | 0.0030 (2) |
N1 | 0.0253 (10) | 0.0446 (13) | 0.0170 (9) | −0.0067 (10) | −0.0006 (8) | 0.0072 (9) |
N2 | 0.0205 (9) | 0.0471 (13) | 0.0180 (9) | −0.0046 (9) | −0.0028 (8) | 0.0079 (9) |
N3 | 0.0173 (8) | 0.0325 (11) | 0.0173 (9) | −0.0011 (9) | −0.0008 (7) | 0.0037 (8) |
N4 | 0.0205 (9) | 0.0310 (10) | 0.0181 (9) | −0.0007 (9) | 0.0041 (8) | 0.0019 (8) |
O1 | 0.0172 (7) | 0.0428 (11) | 0.0237 (8) | 0.0023 (8) | 0.0002 (6) | 0.0060 (8) |
O2 | 0.0312 (9) | 0.0472 (11) | 0.0266 (9) | 0.0166 (10) | −0.0058 (8) | −0.0006 (9) |
O3 | 0.0473 (12) | 0.0334 (10) | 0.0248 (9) | −0.0064 (10) | 0.0043 (9) | 0.0066 (8) |
F1 | 0.0914 (18) | 0.0667 (14) | 0.0197 (9) | −0.0189 (14) | 0.0008 (10) | 0.0077 (9) |
C1 | 0.0509 (18) | 0.0305 (13) | 0.0233 (12) | −0.0073 (13) | −0.0033 (11) | 0.0011 (11) |
C2 | 0.067 (2) | 0.0407 (16) | 0.0201 (12) | −0.0077 (16) | −0.0079 (13) | −0.0029 (11) |
C3 | 0.0500 (19) | 0.0445 (16) | 0.0179 (12) | 0.0002 (14) | 0.0022 (12) | 0.0061 (11) |
C4 | 0.0329 (13) | 0.0420 (15) | 0.0257 (13) | −0.0041 (13) | 0.0043 (11) | 0.0071 (11) |
C5 | 0.0239 (12) | 0.0387 (14) | 0.0228 (11) | −0.0048 (11) | 0.0013 (10) | 0.0032 (10) |
C6 | 0.0250 (11) | 0.0284 (11) | 0.0181 (10) | 0.0015 (10) | 0.0017 (9) | 0.0012 (9) |
C7 | 0.0237 (11) | 0.0262 (11) | 0.0185 (10) | 0.0016 (9) | −0.0001 (8) | 0.0013 (8) |
C8 | 0.0371 (14) | 0.0320 (12) | 0.0202 (11) | −0.0104 (12) | 0.0012 (10) | −0.0028 (10) |
C9 | 0.0217 (10) | 0.0250 (11) | 0.0169 (10) | −0.0002 (9) | −0.0013 (8) | 0.0026 (8) |
C10 | 0.0201 (10) | 0.0278 (11) | 0.0162 (9) | −0.0015 (9) | 0.0001 (8) | 0.0017 (8) |
C11 | 0.0205 (10) | 0.0339 (12) | 0.0165 (9) | −0.0041 (10) | −0.0014 (8) | 0.0033 (10) |
C12 | 0.0525 (19) | 0.0383 (15) | 0.0267 (13) | −0.0128 (14) | −0.0015 (13) | −0.0076 (12) |
C13 | 0.0275 (12) | 0.0265 (11) | 0.0176 (10) | 0.0006 (10) | −0.0011 (8) | 0.0007 (9) |
C14 | 0.0271 (12) | 0.0338 (14) | 0.0225 (11) | −0.0012 (11) | 0.0012 (9) | −0.0021 (10) |
C15 | 0.0360 (14) | 0.0348 (14) | 0.0241 (12) | −0.0094 (12) | −0.0061 (10) | −0.0011 (11) |
C16 | 0.0467 (16) | 0.0328 (13) | 0.0177 (11) | −0.0083 (12) | 0.0003 (11) | −0.0011 (10) |
C17 | 0.0418 (16) | 0.0525 (19) | 0.0229 (12) | −0.0022 (15) | 0.0084 (11) | −0.0041 (12) |
C18 | 0.0290 (13) | 0.0563 (19) | 0.0230 (13) | 0.0036 (14) | 0.0017 (10) | 0.0010 (13) |
Geometric parameters (Å, º) top
S1—C9 | 1.752 (4) | C5—C6 | 1.410 (4) |
S1—C8 | 1.816 (3) | C5—H5 | 0.9500 |
S2—O3 | 1.438 (3) | C6—C7 | 1.486 (4) |
S2—O2 | 1.451 (3) | C7—C8 | 1.508 (4) |
S2—N4 | 1.621 (3) | C8—H8A | 0.9900 |
S2—C13 | 1.775 (3) | C8—H8B | 0.9900 |
N1—C7 | 1.291 (4) | C10—C11 | 1.535 (4) |
N1—N2 | 1.404 (3) | C11—C12 | 1.524 (4) |
N2—C9 | 1.296 (4) | C11—H11 | 1.0000 |
N3—C10 | 1.367 (3) | C12—H12A | 0.9800 |
N3—C9 | 1.403 (3) | C12—H12B | 0.9800 |
N3—H3N | 0.90 (4) | C12—H12C | 0.9800 |
N4—C11 | 1.463 (4) | C13—C14 | 1.397 (4) |
N4—H4N | 0.88 (5) | C13—C18 | 1.397 (4) |
O1—C10 | 1.239 (4) | C14—C15 | 1.394 (4) |
F1—C3 | 1.362 (3) | C14—H14 | 0.9500 |
C1—C2 | 1.396 (4) | C15—C16 | 1.394 (5) |
C1—C6 | 1.401 (4) | C15—H15 | 0.9500 |
C1—H1 | 0.9500 | C16—C17 | 1.392 (5) |
C2—C3 | 1.377 (5) | C16—H16 | 0.9500 |
C2—H2 | 0.9500 | C17—C18 | 1.395 (4) |
C3—C4 | 1.383 (4) | C17—H17 | 0.9500 |
C4—C5 | 1.396 (4) | C18—H18 | 0.9500 |
C4—H4 | 0.9500 | | |
| | | |
C9—S1—C8 | 93.21 (15) | C7—C8—H8B | 109.6 |
O3—S2—O2 | 119.79 (16) | S1—C8—H8B | 109.6 |
O3—S2—N4 | 105.73 (15) | H8A—C8—H8B | 108.1 |
O2—S2—N4 | 107.70 (13) | N2—C9—N3 | 114.6 (2) |
O3—S2—C13 | 108.76 (14) | N2—C9—S1 | 125.2 (2) |
O2—S2—C13 | 105.54 (12) | N3—C9—S1 | 120.08 (18) |
N4—S2—C13 | 109.01 (12) | O1—C10—N3 | 122.5 (2) |
C7—N1—N2 | 120.2 (2) | O1—C10—C11 | 122.6 (2) |
C9—N2—N1 | 121.3 (2) | N3—C10—C11 | 114.9 (2) |
C10—N3—C9 | 126.1 (2) | N4—C11—C12 | 109.0 (2) |
C10—N3—H3N | 117 (2) | N4—C11—C10 | 110.2 (2) |
C9—N3—H3N | 116 (2) | C12—C11—C10 | 109.9 (2) |
C11—N4—S2 | 121.23 (19) | N4—C11—H11 | 109.2 |
C11—N4—H4N | 123 (3) | C12—C11—H11 | 109.2 |
S2—N4—H4N | 112 (3) | C10—C11—H11 | 109.2 |
C2—C1—C6 | 120.9 (3) | C11—C12—H12A | 109.5 |
C2—C1—H1 | 119.6 | C11—C12—H12B | 109.5 |
C6—C1—H1 | 119.6 | H12A—C12—H12B | 109.5 |
C3—C2—C1 | 118.1 (3) | C11—C12—H12C | 109.5 |
C3—C2—H2 | 120.9 | H12A—C12—H12C | 109.5 |
C1—C2—H2 | 120.9 | H12B—C12—H12C | 109.5 |
F1—C3—C2 | 118.6 (3) | C14—C13—C18 | 121.5 (3) |
F1—C3—C4 | 117.8 (3) | C14—C13—S2 | 120.01 (19) |
C2—C3—C4 | 123.6 (3) | C18—C13—S2 | 118.4 (2) |
C3—C4—C5 | 117.7 (3) | C15—C14—C13 | 118.5 (2) |
C3—C4—H4 | 121.2 | C15—C14—H14 | 120.8 |
C5—C4—H4 | 121.2 | C13—C14—H14 | 120.8 |
C4—C5—C6 | 121.0 (3) | C16—C15—C14 | 120.6 (3) |
C4—C5—H5 | 119.5 | C16—C15—H15 | 119.7 |
C6—C5—H5 | 119.5 | C14—C15—H15 | 119.7 |
C1—C6—C5 | 118.7 (2) | C17—C16—C15 | 120.2 (3) |
C1—C6—C7 | 121.7 (2) | C17—C16—H16 | 119.9 |
C5—C6—C7 | 119.6 (2) | C15—C16—H16 | 119.9 |
N1—C7—C6 | 117.5 (2) | C16—C17—C18 | 120.0 (3) |
N1—C7—C8 | 121.8 (2) | C16—C17—H17 | 120.0 |
C6—C7—C8 | 120.7 (2) | C18—C17—H17 | 120.0 |
C7—C8—S1 | 110.18 (19) | C17—C18—C13 | 119.1 (3) |
C7—C8—H8A | 109.6 | C17—C18—H18 | 120.5 |
S1—C8—H8A | 109.6 | C13—C18—H18 | 120.5 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3N···O1i | 0.90 (4) | 2.01 (4) | 2.907 (6) | 174 (3) |
N4—H4N···N2ii | 0.88 (5) | 2.06 (5) | 2.911 (6) | 163 (4) |
Symmetry codes: (i) x+1/2, −y+3/2, −z+1; (ii) x−1/2, −y+3/2, −z+1. |
(III) (2
S)-
N-[5-(5-chloro-2-thienyl)-6
H-1,3,4-thiadiazin-2-yl]-2-
[(phenylsulfonyl)amino]propanamide
top
Crystal data top
C16H15ClN4O3S3 | F(000) = 912 |
Mr = 442.95 | Dx = 1.547 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.613 (4) Å | Cell parameters from 19 reflections |
b = 11.193 (4) Å | θ = 2.2–12.0° |
c = 16.399 (5) Å | µ = 0.56 mm−1 |
β = 102.48 (3)° | T = 173 K |
V = 1902.0 (11) Å3 | Needle, colourless |
Z = 4 | 0.40 × 0.15 × 0.15 mm |
Data collection top
Siemens P21 diffractometer | Rint = 0.054 |
Radiation source: normal-focus sealed tube | θmax = 25.1°, θmin = 2.0° |
Graphite monochromator | h = −12→12 |
Wyckoff scan | k = −13→13 |
7536 measured reflections | l = −19→19 |
6749 independent reflections | 3 standard reflections every 100 reflections |
4676 reflections with I > 2σ(I) | intensity decay: none |
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)] = 0.061 | H-atom parameters constrained |
wR(F2) = 0.125 | w = 1/[σ2(Fo2) + (0.0364P)2 + 0.5602P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max < 0.001 |
6749 reflections | Δρmax = 0.30 e Å−3 |
489 parameters | Δρmin = −0.35 e Å−3 |
1 restraint | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.03 (11) |
Crystal data top
C16H15ClN4O3S3 | V = 1902.0 (11) Å3 |
Mr = 442.95 | Z = 4 |
Monoclinic, P21 | Mo Kα radiation |
a = 10.613 (4) Å | µ = 0.56 mm−1 |
b = 11.193 (4) Å | T = 173 K |
c = 16.399 (5) Å | 0.40 × 0.15 × 0.15 mm |
β = 102.48 (3)° | |
Data collection top
Siemens P21 diffractometer | Rint = 0.054 |
7536 measured reflections | 3 standard reflections every 100 reflections |
6749 independent reflections | intensity decay: none |
4676 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.061 | H-atom parameters constrained |
wR(F2) = 0.125 | Δρmax = 0.30 e Å−3 |
S = 1.02 | Δρmin = −0.35 e Å−3 |
6749 reflections | Absolute structure: Flack (1983) |
489 parameters | Absolute structure parameter: −0.03 (11) |
1 restraint | |
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 | 0.40775 (15) | 0.81849 (19) | 0.58846 (10) | 0.0259 (4) | |
S2 | 0.16364 (15) | 0.81560 (19) | 0.26446 (10) | 0.0235 (4) | |
S3 | 0.28040 (18) | 0.57269 (18) | −0.00242 (12) | 0.0290 (5) | |
Cl1 | 0.3719 (2) | 0.8724 (3) | 0.75937 (14) | 0.0604 (8) | |
O1 | 0.1612 (4) | 0.8569 (5) | 0.1016 (3) | 0.0304 (14) | |
O2 | 0.3633 (5) | 0.4811 (5) | −0.0219 (4) | 0.0458 (17) | |
O3 | 0.1639 (5) | 0.6035 (5) | −0.0615 (3) | 0.0395 (15) | |
N1 | 0.4014 (5) | 0.7993 (5) | 0.4035 (3) | 0.0197 (13) | |
N2 | 0.4201 (5) | 0.7802 (5) | 0.3221 (3) | 0.0174 (13) | |
N3 | 0.3557 (5) | 0.8041 (5) | 0.1809 (3) | 0.0192 (13) | |
H3N | 0.4371 | 0.7925 | 0.1793 | 0.023* | |
N4 | 0.3711 (5) | 0.6881 (5) | 0.0177 (3) | 0.0229 (14) | |
H4N | 0.4543 | 0.6759 | 0.0227 | 0.028* | |
C1 | 0.3059 (7) | 0.8449 (7) | 0.6556 (4) | 0.0274 (18) | |
C2 | 0.1796 (7) | 0.8390 (7) | 0.6185 (5) | 0.0289 (19) | |
H2A | 0.1112 | 0.8523 | 0.6464 | 0.035* | |
C3 | 0.1619 (6) | 0.8107 (7) | 0.5332 (4) | 0.0218 (16) | |
H3A | 0.0796 | 0.8004 | 0.4972 | 0.026* | |
C4 | 0.2763 (6) | 0.7994 (6) | 0.5075 (4) | 0.0174 (15) | |
C5 | 0.2920 (6) | 0.7771 (6) | 0.4220 (4) | 0.0168 (16) | |
C6 | 0.1815 (6) | 0.7287 (7) | 0.3590 (4) | 0.0227 (16) | |
H6A | 0.1015 | 0.7333 | 0.3807 | 0.027* | |
H6B | 0.1975 | 0.6439 | 0.3474 | 0.027* | |
C7 | 0.3258 (6) | 0.7990 (6) | 0.2596 (4) | 0.0160 (15) | |
C8 | 0.2727 (6) | 0.8251 (7) | 0.1059 (4) | 0.0210 (15) | |
C9 | 0.3318 (6) | 0.8119 (7) | 0.0290 (4) | 0.0236 (16) | |
H9A | 0.4126 | 0.8608 | 0.0401 | 0.028* | |
C10 | 0.2422 (7) | 0.8672 (7) | −0.0479 (4) | 0.0341 (19) | |
H10A | 0.2789 | 0.8546 | −0.0972 | 0.051* | |
H10B | 0.2335 | 0.9531 | −0.0389 | 0.051* | |
H10C | 0.1571 | 0.8292 | −0.0567 | 0.051* | |
C11 | 0.2328 (7) | 0.5306 (7) | 0.0920 (5) | 0.0242 (17) | |
C12 | 0.3282 (7) | 0.5117 (8) | 0.1620 (5) | 0.038 (2) | |
H12A | 0.4165 | 0.5235 | 0.1611 | 0.045* | |
C13 | 0.2908 (9) | 0.4745 (8) | 0.2350 (5) | 0.046 (2) | |
H13A | 0.3545 | 0.4614 | 0.2846 | 0.055* | |
C14 | 0.1626 (8) | 0.4568 (8) | 0.2353 (5) | 0.037 (2) | |
H14A | 0.1382 | 0.4306 | 0.2848 | 0.044* | |
C15 | 0.0705 (7) | 0.4767 (7) | 0.1644 (5) | 0.035 (2) | |
H15A | −0.0179 | 0.4659 | 0.1656 | 0.042* | |
C16 | 0.1036 (7) | 0.5128 (7) | 0.0904 (5) | 0.0288 (19) | |
H16A | 0.0397 | 0.5246 | 0.0407 | 0.035* | |
S4 | 0.62260 (17) | 0.65968 (19) | −0.08416 (12) | 0.0313 (5) | |
S5 | 0.87898 (15) | 0.69831 (18) | 0.23384 (11) | 0.0262 (4) | |
S6 | 0.74209 (17) | 0.95360 (17) | 0.49967 (11) | 0.0226 (4) | |
Cl2 | 0.6468 (2) | 0.6173 (2) | −0.25930 (12) | 0.0426 (6) | |
O4 | 0.8880 (4) | 0.6490 (5) | 0.3946 (3) | 0.0303 (13) | |
O5 | 0.8576 (5) | 0.9368 (5) | 0.5643 (3) | 0.0351 (14) | |
O6 | 0.6437 (5) | 1.0353 (5) | 0.5131 (4) | 0.0344 (14) | |
N5 | 0.6363 (5) | 0.7027 (6) | 0.0977 (3) | 0.0211 (14) | |
N6 | 0.6218 (5) | 0.7269 (5) | 0.1804 (3) | 0.0209 (14) | |
N7 | 0.6929 (5) | 0.7152 (5) | 0.3229 (3) | 0.0200 (13) | |
H7N | 0.6139 | 0.7322 | 0.3279 | 0.024* | |
N8 | 0.6715 (5) | 0.8263 (5) | 0.4790 (3) | 0.0204 (12) | |
H8N | 0.5867 | 0.8233 | 0.4685 | 0.025* | |
C17 | 0.7171 (7) | 0.6540 (7) | −0.1580 (5) | 0.0284 (19) | |
C18 | 0.8396 (7) | 0.6827 (7) | −0.1274 (5) | 0.031 (2) | |
H18A | 0.9042 | 0.6840 | −0.1595 | 0.037* | |
C19 | 0.8625 (6) | 0.7114 (7) | −0.0409 (5) | 0.0274 (18) | |
H19A | 0.9450 | 0.7334 | −0.0090 | 0.033* | |
C20 | 0.7558 (6) | 0.7044 (7) | −0.0085 (4) | 0.0221 (16) | |
C21 | 0.7438 (6) | 0.7284 (7) | 0.0769 (4) | 0.0206 (17) | |
C22 | 0.8535 (6) | 0.7838 (8) | 0.1375 (4) | 0.031 (2) | |
H22A | 0.8331 | 0.8679 | 0.1482 | 0.037* | |
H22B | 0.9325 | 0.7825 | 0.1145 | 0.037* | |
C23 | 0.7179 (6) | 0.7134 (7) | 0.2428 (4) | 0.0195 (16) | |
C24 | 0.7823 (6) | 0.6924 (7) | 0.3934 (5) | 0.0220 (17) | |
C25 | 0.7438 (6) | 0.7162 (6) | 0.4773 (4) | 0.0188 (15) | |
H25A | 0.8252 | 0.7229 | 0.5211 | 0.023* | |
C26 | 0.6667 (7) | 0.6109 (6) | 0.5012 (4) | 0.0328 (19) | |
H26A | 0.6527 | 0.6232 | 0.5578 | 0.049* | |
H26B | 0.7149 | 0.5366 | 0.4995 | 0.049* | |
H26C | 0.5832 | 0.6057 | 0.4618 | 0.049* | |
C27 | 0.7938 (7) | 1.0000 (6) | 0.4091 (4) | 0.0196 (16) | |
C28 | 0.9248 (7) | 1.0217 (6) | 0.4133 (5) | 0.0272 (18) | |
H28A | 0.9856 | 1.0142 | 0.4649 | 0.033* | |
C29 | 0.9648 (8) | 1.0542 (7) | 0.3419 (5) | 0.037 (2) | |
H29A | 1.0537 | 1.0684 | 0.3441 | 0.045* | |
C30 | 0.8765 (8) | 1.0664 (7) | 0.2669 (5) | 0.038 (2) | |
H30A | 0.9047 | 1.0901 | 0.2182 | 0.046* | |
C31 | 0.7466 (8) | 1.0441 (8) | 0.2628 (5) | 0.037 (2) | |
H31A | 0.6862 | 1.0516 | 0.2110 | 0.044* | |
C32 | 0.7048 (7) | 1.0108 (6) | 0.3342 (5) | 0.0274 (19) | |
H32A | 0.6159 | 0.9956 | 0.3316 | 0.033* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0224 (9) | 0.0408 (12) | 0.0148 (9) | −0.0048 (9) | 0.0044 (7) | −0.0030 (9) |
S2 | 0.0132 (8) | 0.0401 (12) | 0.0167 (9) | 0.0008 (9) | 0.0023 (7) | 0.0040 (9) |
S3 | 0.0295 (10) | 0.0368 (12) | 0.0221 (10) | −0.0056 (9) | 0.0091 (8) | −0.0076 (9) |
Cl1 | 0.0623 (14) | 0.101 (2) | 0.0210 (12) | −0.0311 (15) | 0.0158 (10) | −0.0204 (13) |
O1 | 0.020 (3) | 0.048 (4) | 0.022 (3) | 0.011 (3) | 0.001 (2) | 0.010 (3) |
O2 | 0.051 (4) | 0.042 (4) | 0.053 (4) | −0.003 (3) | 0.031 (3) | −0.013 (3) |
O3 | 0.033 (3) | 0.060 (4) | 0.020 (3) | −0.017 (3) | −0.007 (2) | 0.002 (3) |
N1 | 0.021 (3) | 0.026 (4) | 0.012 (3) | −0.001 (3) | 0.005 (2) | 0.001 (3) |
N2 | 0.015 (3) | 0.023 (3) | 0.013 (3) | 0.000 (2) | 0.001 (2) | −0.001 (2) |
N3 | 0.018 (3) | 0.031 (4) | 0.010 (3) | 0.003 (3) | 0.006 (2) | 0.001 (3) |
N4 | 0.017 (3) | 0.034 (4) | 0.017 (3) | −0.001 (3) | 0.003 (2) | −0.009 (3) |
C1 | 0.046 (5) | 0.025 (5) | 0.015 (4) | −0.006 (4) | 0.014 (3) | −0.001 (3) |
C2 | 0.026 (4) | 0.033 (5) | 0.033 (5) | −0.003 (4) | 0.019 (3) | −0.001 (4) |
C3 | 0.017 (3) | 0.024 (4) | 0.026 (4) | −0.001 (3) | 0.009 (3) | 0.000 (4) |
C4 | 0.021 (3) | 0.016 (4) | 0.014 (3) | 0.000 (3) | 0.001 (3) | 0.004 (3) |
C5 | 0.016 (3) | 0.019 (4) | 0.015 (4) | 0.002 (3) | 0.002 (3) | 0.004 (3) |
C6 | 0.021 (3) | 0.028 (4) | 0.018 (4) | −0.010 (3) | 0.003 (3) | 0.004 (3) |
C7 | 0.019 (3) | 0.014 (4) | 0.015 (4) | 0.001 (3) | 0.004 (3) | −0.003 (3) |
C8 | 0.024 (4) | 0.022 (4) | 0.016 (4) | −0.003 (3) | 0.003 (3) | 0.005 (3) |
C9 | 0.018 (3) | 0.041 (5) | 0.011 (3) | 0.004 (4) | 0.003 (3) | −0.003 (4) |
C10 | 0.044 (5) | 0.039 (5) | 0.019 (4) | 0.010 (4) | 0.007 (3) | 0.003 (3) |
C11 | 0.030 (4) | 0.021 (4) | 0.022 (4) | −0.001 (3) | 0.007 (3) | −0.008 (3) |
C12 | 0.024 (4) | 0.054 (6) | 0.034 (5) | −0.002 (4) | 0.002 (4) | −0.002 (4) |
C13 | 0.058 (6) | 0.051 (7) | 0.023 (5) | 0.000 (5) | −0.003 (4) | 0.003 (4) |
C14 | 0.062 (6) | 0.028 (5) | 0.026 (5) | −0.011 (5) | 0.023 (4) | 0.000 (4) |
C15 | 0.033 (4) | 0.033 (5) | 0.043 (5) | −0.004 (4) | 0.019 (4) | −0.010 (4) |
C16 | 0.025 (4) | 0.032 (5) | 0.032 (5) | −0.002 (4) | 0.011 (3) | −0.002 (4) |
S4 | 0.0222 (9) | 0.0529 (14) | 0.0189 (10) | −0.0040 (9) | 0.0044 (8) | −0.0066 (9) |
S5 | 0.0135 (8) | 0.0452 (13) | 0.0206 (10) | 0.0016 (9) | 0.0053 (7) | 0.0007 (9) |
S6 | 0.0259 (10) | 0.0238 (10) | 0.0198 (10) | −0.0071 (8) | 0.0088 (8) | −0.0071 (8) |
Cl2 | 0.0547 (13) | 0.0571 (15) | 0.0157 (10) | −0.0008 (11) | 0.0069 (9) | −0.0062 (10) |
O4 | 0.025 (3) | 0.041 (3) | 0.027 (3) | 0.012 (3) | 0.010 (2) | 0.001 (3) |
O5 | 0.040 (3) | 0.045 (4) | 0.020 (3) | −0.019 (3) | 0.005 (2) | −0.002 (3) |
O6 | 0.048 (3) | 0.019 (3) | 0.047 (4) | 0.002 (3) | 0.032 (3) | −0.009 (3) |
N5 | 0.013 (3) | 0.034 (4) | 0.017 (3) | 0.002 (3) | 0.004 (2) | −0.006 (3) |
N6 | 0.019 (3) | 0.034 (4) | 0.011 (3) | 0.000 (3) | 0.007 (2) | −0.006 (3) |
N7 | 0.013 (3) | 0.029 (4) | 0.019 (3) | 0.003 (3) | 0.005 (2) | −0.001 (3) |
N8 | 0.013 (3) | 0.020 (3) | 0.028 (3) | −0.002 (3) | 0.006 (2) | −0.007 (3) |
C17 | 0.032 (4) | 0.035 (5) | 0.021 (4) | 0.001 (4) | 0.014 (3) | −0.002 (4) |
C18 | 0.034 (4) | 0.040 (5) | 0.026 (4) | 0.001 (4) | 0.021 (3) | 0.004 (4) |
C19 | 0.023 (4) | 0.036 (5) | 0.025 (4) | 0.002 (4) | 0.009 (3) | 0.006 (4) |
C20 | 0.018 (3) | 0.030 (4) | 0.020 (4) | 0.002 (3) | 0.005 (3) | 0.002 (4) |
C21 | 0.015 (3) | 0.024 (4) | 0.023 (4) | 0.005 (3) | 0.005 (3) | −0.002 (3) |
C22 | 0.019 (4) | 0.057 (6) | 0.016 (4) | −0.007 (4) | 0.003 (3) | −0.007 (4) |
C23 | 0.009 (3) | 0.031 (4) | 0.019 (4) | 0.001 (3) | 0.003 (3) | 0.004 (3) |
C24 | 0.018 (4) | 0.020 (4) | 0.029 (4) | 0.003 (3) | 0.006 (3) | 0.000 (3) |
C25 | 0.020 (4) | 0.018 (4) | 0.017 (3) | 0.002 (3) | 0.000 (3) | −0.002 (3) |
C26 | 0.045 (5) | 0.023 (4) | 0.038 (5) | −0.002 (4) | 0.026 (4) | 0.006 (4) |
C27 | 0.027 (4) | 0.020 (4) | 0.011 (4) | −0.002 (3) | 0.003 (3) | −0.002 (3) |
C28 | 0.025 (4) | 0.021 (4) | 0.034 (5) | 0.000 (3) | 0.005 (3) | −0.007 (4) |
C29 | 0.042 (5) | 0.037 (5) | 0.041 (5) | −0.004 (4) | 0.023 (4) | 0.002 (4) |
C30 | 0.060 (6) | 0.029 (5) | 0.028 (5) | 0.000 (4) | 0.016 (4) | −0.004 (4) |
C31 | 0.054 (5) | 0.027 (5) | 0.023 (5) | −0.010 (4) | −0.005 (4) | 0.004 (4) |
C32 | 0.033 (4) | 0.019 (4) | 0.029 (5) | −0.002 (3) | 0.004 (4) | 0.005 (4) |
Geometric parameters (Å, º) top
S1—C4 | 1.718 (7) | S4—C17 | 1.732 (7) |
S1—C1 | 1.727 (7) | S4—C20 | 1.741 (7) |
S2—C7 | 1.750 (6) | S5—C23 | 1.755 (6) |
S2—C6 | 1.805 (7) | S5—C22 | 1.817 (7) |
S3—O2 | 1.431 (6) | S6—O6 | 1.440 (5) |
S3—O3 | 1.439 (5) | S6—O5 | 1.449 (5) |
S3—N4 | 1.602 (6) | S6—N8 | 1.611 (6) |
S3—C11 | 1.792 (8) | S6—C27 | 1.769 (7) |
Cl1—C1 | 1.722 (8) | Cl2—C17 | 1.718 (8) |
O1—C8 | 1.223 (7) | O4—C24 | 1.218 (8) |
N1—C5 | 1.286 (8) | N5—C21 | 1.292 (8) |
N1—N2 | 1.407 (7) | N5—N6 | 1.423 (7) |
N2—C7 | 1.286 (8) | N6—C23 | 1.288 (8) |
N3—C8 | 1.369 (8) | N7—C24 | 1.351 (9) |
N3—C7 | 1.395 (8) | N7—C23 | 1.396 (8) |
N4—C9 | 1.470 (9) | N8—C25 | 1.456 (8) |
C1—C2 | 1.349 (10) | C17—C18 | 1.328 (11) |
C2—C3 | 1.406 (10) | C18—C19 | 1.423 (10) |
C3—C4 | 1.375 (8) | C19—C20 | 1.354 (9) |
C4—C5 | 1.469 (9) | C20—C21 | 1.458 (9) |
C5—C6 | 1.487 (9) | C21—C22 | 1.492 (9) |
C8—C9 | 1.533 (8) | C24—C25 | 1.540 (9) |
C9—C10 | 1.536 (9) | C25—C26 | 1.533 (9) |
C11—C12 | 1.373 (10) | C27—C32 | 1.384 (10) |
C11—C16 | 1.380 (9) | C27—C28 | 1.399 (9) |
C12—C13 | 1.404 (11) | C28—C29 | 1.379 (10) |
C13—C14 | 1.376 (11) | C29—C30 | 1.382 (11) |
C14—C15 | 1.366 (11) | C30—C31 | 1.388 (11) |
C15—C16 | 1.395 (10) | C31—C32 | 1.390 (11) |
| | | |
C4—S1—C1 | 89.9 (3) | C17—S4—C20 | 90.3 (3) |
C7—S2—C6 | 93.4 (3) | C23—S5—C22 | 93.3 (3) |
O2—S3—O3 | 120.1 (4) | O6—S6—O5 | 119.8 (3) |
O2—S3—N4 | 104.6 (3) | O6—S6—N8 | 105.9 (3) |
O3—S3—N4 | 109.7 (3) | O5—S6—N8 | 108.7 (3) |
O2—S3—C11 | 107.8 (4) | O6—S6—C27 | 108.0 (3) |
O3—S3—C11 | 106.5 (3) | O5—S6—C27 | 106.6 (3) |
N4—S3—C11 | 107.6 (3) | N8—S6—C27 | 107.3 (3) |
C5—N1—N2 | 120.9 (5) | C21—N5—N6 | 119.5 (5) |
C7—N2—N1 | 119.1 (5) | C23—N6—N5 | 120.3 (5) |
C8—N3—C7 | 127.4 (5) | C24—N7—C23 | 124.1 (5) |
C9—N4—S3 | 127.7 (4) | C25—N8—S6 | 122.0 (4) |
C2—C1—Cl1 | 127.4 (6) | C18—C17—Cl2 | 127.5 (6) |
C2—C1—S1 | 113.7 (6) | C18—C17—S4 | 113.3 (6) |
Cl1—C1—S1 | 118.9 (4) | Cl2—C17—S4 | 119.2 (4) |
C1—C2—C3 | 111.5 (6) | C17—C18—C19 | 111.9 (6) |
C4—C3—C2 | 112.9 (6) | C20—C19—C18 | 113.7 (7) |
C3—C4—C5 | 126.7 (6) | C19—C20—C21 | 128.3 (7) |
C3—C4—S1 | 112.1 (5) | C19—C20—S4 | 110.8 (6) |
C5—C4—S1 | 121.2 (5) | C21—C20—S4 | 120.8 (5) |
N1—C5—C4 | 119.1 (6) | N5—C21—C20 | 118.5 (6) |
N1—C5—C6 | 121.5 (6) | N5—C21—C22 | 121.6 (6) |
C4—C5—C6 | 119.3 (6) | C20—C21—C22 | 119.9 (6) |
C5—C6—S2 | 108.7 (5) | C21—C22—S5 | 107.9 (5) |
N2—C7—N3 | 116.8 (5) | N6—C23—N7 | 117.8 (5) |
N2—C7—S2 | 125.8 (5) | N6—C23—S5 | 124.3 (5) |
N3—C7—S2 | 117.4 (5) | N7—C23—S5 | 117.8 (5) |
O1—C8—N3 | 121.9 (6) | O4—C24—N7 | 124.3 (7) |
O1—C8—C9 | 122.9 (6) | O4—C24—C25 | 118.3 (6) |
N3—C8—C9 | 115.1 (5) | N7—C24—C25 | 117.3 (6) |
N4—C9—C8 | 111.8 (6) | N8—C25—C26 | 109.4 (5) |
N4—C9—C10 | 114.8 (6) | N8—C25—C24 | 114.0 (6) |
C8—C9—C10 | 110.2 (5) | C26—C25—C24 | 110.8 (6) |
C12—C11—C16 | 122.9 (8) | C32—C27—C28 | 120.7 (7) |
C12—C11—S3 | 118.0 (6) | C32—C27—S6 | 119.7 (6) |
C16—C11—S3 | 119.1 (6) | C28—C27—S6 | 119.6 (6) |
C11—C12—C13 | 117.8 (8) | C29—C28—C27 | 119.2 (8) |
C14—C13—C12 | 120.5 (8) | C28—C29—C30 | 120.5 (8) |
C15—C14—C13 | 120.0 (7) | C29—C30—C31 | 120.1 (8) |
C14—C15—C16 | 121.3 (7) | C30—C31—C32 | 120.1 (8) |
C11—C16—C15 | 117.5 (8) | C27—C32—C31 | 119.3 (7) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3N···N6 | 0.88 | 2.09 | 2.956 (7) | 168 |
N4—H4N···S4 | 0.88 | 2.77 | 3.456 (5) | 136 |
N4—H4N···N5 | 0.88 | 2.08 | 2.842 (7) | 145 |
N7—H7N···N2 | 0.88 | 2.11 | 2.983 (7) | 172 |
N8—H8N···N1 | 0.88 | 2.04 | 2.882 (7) | 160 |
Experimental details
| (I) | (II) | (III) |
Crystal data |
Chemical formula | C18H17ClN4O3S2 | C18H17FN4O3S2 | C16H15ClN4O3S3 |
Mr | 436.93 | 420.48 | 442.95 |
Crystal system, space group | Orthorhombic, P21212 | Orthorhombic, P212121 | Monoclinic, P21 |
Temperature (K) | 173 | 173 | 173 |
a, b, c (Å) | 15.600 (4), 20.764 (6), 5.826 (3) | 9.675 (19), 12.704 (19), 15.606 (15) | 10.613 (4), 11.193 (4), 16.399 (5) |
α, β, γ (°) | 90, 90, 90 | 90, 90, 90 | 90, 102.48 (3), 90 |
V (Å3) | 1887.1 (12) | 1918 (5) | 1902.0 (11) |
Z | 4 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.45 | 0.32 | 0.56 |
Crystal size (mm) | 1.00 × 0.30 × 0.15 | 1.0 × 0.6 × 0.6 | 0.40 × 0.15 × 0.15 |
|
Data collection |
Diffractometer | Siemens P21 diffractometer | Siemens P21 diffractometer | Siemens P21 diffractometer |
Absorption correction | – | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6296, 5491, 4278 | 6306, 5271, 4615 | 7536, 6749, 4676 |
Rint | 0.031 | 0.045 | 0.054 |
(sin θ/λ)max (Å−1) | 0.703 | 0.705 | 0.596 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.051, 0.123, 1.02 | 0.049, 0.128, 1.01 | 0.061, 0.125, 1.02 |
No. of reflections | 5491 | 5271 | 6749 |
No. of parameters | 263 | 262 | 489 |
No. of restraints | 0 | 0 | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.33, −0.29 | 0.34, −0.43 | 0.30, −0.35 |
Absolute structure | Flack (1983) | Flack (1983) | Flack (1983) |
Absolute structure parameter | −0.09 (9) | −0.12 (8) | −0.03 (11) |
Selected geometric parameters (Å, º) for (I) topS1—C9 | 1.726 (3) | N2—C9 | 1.338 (3) |
N1—C7 | 1.284 (4) | N3—C9 | 1.321 (3) |
N1—N2 | 1.389 (3) | | |
| | | |
C9—N2—N1 | 128.6 (2) | | |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N···S1i | 0.82 (4) | 2.72 (4) | 3.236 (3) | 122 (3) |
N2—H2N···O1i | 0.82 (4) | 2.56 (4) | 3.375 (3) | 173 (4) |
N4—H4N···N3 | 0.90 (3) | 2.31 (3) | 2.661 (3) | 103 (2) |
Symmetry code: (i) x, y, z+1. |
Selected bond lengths (Å) for (II) topS1—C9 | 1.752 (4) | N1—N2 | 1.404 (3) |
S1—C8 | 1.816 (3) | N2—C9 | 1.296 (4) |
N1—C7 | 1.291 (4) | N3—C9 | 1.403 (3) |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3N···O1i | 0.90 (4) | 2.01 (4) | 2.907 (6) | 174 (3) |
N4—H4N···N2ii | 0.88 (5) | 2.06 (5) | 2.911 (6) | 163 (4) |
Symmetry codes: (i) x+1/2, −y+3/2, −z+1; (ii) x−1/2, −y+3/2, −z+1. |
Selected bond lengths (Å) for (III) topS2—C7 | 1.750 (6) | S5—C23 | 1.755 (6) |
S2—C6 | 1.805 (7) | S5—C22 | 1.817 (7) |
N1—C5 | 1.286 (8) | N5—C21 | 1.292 (8) |
N1—N2 | 1.407 (7) | N5—N6 | 1.423 (7) |
N2—C7 | 1.286 (8) | N6—C23 | 1.288 (8) |
N3—C7 | 1.395 (8) | N7—C23 | 1.396 (8) |
Hydrogen-bond geometry (Å, º) for (III) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3N···N6 | 0.88 | 2.09 | 2.956 (7) | 167.7 |
N4—H4N···S4 | 0.88 | 2.77 | 3.456 (5) | 136.4 |
N4—H4N···N5 | 0.88 | 2.08 | 2.842 (7) | 145.0 |
N7—H7N···N2 | 0.88 | 2.11 | 2.983 (7) | 172.0 |
N8—H8N···N1 | 0.88 | 2.04 | 2.882 (7) | 159.5 |
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Inhibitors of matrix metalloproteinases (MMPs) can provide useful treatments for diseases associated with excessive degradation of the extracellular matrix, such as osteoarthritis (Cawston, 1996), rheumatoid arthritis (Bläser et al., 1996), periodontal disease (Overall et al., 1987), multiple sclerosis (Yong, 1999), and tumour metastasis (Chambers & Matrisian, 1997). Recent efforts by a number of laboratories working in the area have provided several classes of MMP inhibitors, which have been extensively reviewed by Becket & Whittaker (1998). The value of thiadiazines as MMP inhibitors has, however, not hitherto been recognized. To investigate this heterocyclic system further and to establish the inhibitor structures for ligand-protein docking experiments, single-crystal X-ray diffraction studies were carried out on the three title compounds, (I), (II) and (III). \sch
The title compounds (Figs. 1, 2 and 3) consist of a 6H-1,3,4-thiadiazine system, a p-substituted phenyl ring or 5-chloro-substituted thiophene ring, and an amide-linked N-phenylsulfonyl-substituted D– or L-alanine residue. The three rings do not share a common plane and the thiadiazine ring deviates from planarity. The puckering of this ring system may be described by the amplitude and phase coordinates introduced by Cremer & Pople (1975) and Evans & Boeyens (1989). The puckering parameters for (I), (II) and molecules 1 and 2 of (III) are Q = 0.567 (3), 0.618 (2), 0.634 and 0.665 Å, θ = 70.6 (3), 69.9 (2), 109.5 and 70.5°, and ϕ = 39.9 (3), 33.1 (3), 217.1 and 35.9°, respectively. Thus, the thiadiazine moiety assumes a screw-boat conformation in all compounds (Boeyens, 1978). The large ϕ value for molecule 1 in the unit cell of (III) indicates that the direction of the ring distortion is towards an inverted screw-boat conformation.
In compounds (I) and (II) there are two distinct S1—C8 and S1—C9 bond lengths, which can be attributed to typical S-Csp3 and S-Csp2 bonds [average values 1.819 (19) and 1.751 (17) Å; Allen et al., 1992]. The two molecules of compound (III) show similar S—C bond lengths. This corresponds to the 6H tautomeric form of the thiadiazine ring (Novikova et al., 1991). The endocyclic C9—N2 distance in (II) is shorter than the exocyclic C9—N3 distance and corresponds to an N═ Csp2 bond. The same applies to the two molecules of compound (III). In contrast with this trend, the endocyclic C9—N2 distance in (I) is slightly longer than the exocyclic C9—N3 distance and corresponds to an N-Csp2 bond. These systematic bond differences resemble the characteristic pattern of bond length changes introduced by an amido-imino tautomerism (prototropic shift) within the 6H-1,3,4-thiadiazine moiety.
As shown in Scheme 2, the geometry of compounds (II) and (III) is consistent with the tautomer on the left-hand side, while the geometry of (I) is closer to that of the tautomer on the right-hand side. Consequently, the endocyclic N atom close to the exocyclic N atom is a hydrogen-bond acceptor in (II) and (III) and a hydrogen-bond donor in (I). The opposite applies to the exocyclic N atom, which is a hydrogen-bond donor in (II) and (III) and a hydrogen-bond acceptor in (I). This contributes to the different hydrogen-bonding patterns in the crystal structures of the three compounds.