Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807029157/bv2058sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807029157/bv2058Isup2.hkl |
CCDC reference: 657661
Key indicators
- Single-crystal X-ray study
- T = 113 K
- Mean (C-C) = 0.005 Å
- Disorder in main residue
- R factor = 0.055
- wR factor = 0.139
- Data-to-parameter ratio = 15.7
checkCIF/PLATON results
No syntax errors found
Alert level B ABSMU01_ALERT_1_B The ratio of given/expected absorption coefficient lies outside the range 0.95 <> 1.05 Calculated value of mu = 0.538 Value of mu given = 0.584 PLAT051_ALERT_1_B Mu(calc) and Mu(CIF) Ratio Differs from 1.0 by . 7.88 Perc.
Alert level C CELLV02_ALERT_1_C The supplied cell volume s.u. differs from that calculated from the cell parameter s.u.'s by > 2 Calculated cell volume su = 12.03 Cell volume su given = 9.00 PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 2.81 PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ..... ? PLAT213_ALERT_2_C Atom C24' has ADP max/min Ratio ............. 4.00 oblat PLAT301_ALERT_3_C Main Residue Disorder ......................... 8.00 Perc. PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 5 PLAT412_ALERT_2_C Short Intra XH3 .. XHn H8B .. H15A .. 1.88 Ang. PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ...... 20.10 Deg. C24 -S6 -C24' 1.555 1.555 1.555 PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ...... 16.30 Deg. C22 -N3 -C22' 1.555 1.555 1.555
Alert level G PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 7
0 ALERT level A = In general: serious problem 2 ALERT level B = Potentially serious problem 9 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 5 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 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
A solution of 1-bromo-3,5-bis(bromomethyl)-2,4,6-trimethylbenzene (0.45 g, 1 mmol) in ethanol (5 ml) was added dropwise to a mixture of 5,6-dihydro-4H-1,3-thiazine-2-thiol (0.45 g, 3.4 mmol), KOH (0.19 g, 3.4 mmol) and ethanol (15 ml). The reaction mixture was then stirred for 48 h at room temperature. Then the precipitate was filtered off, washed with water and recrystallized from ethanol and water (yield 62%, m.p. 455–457 K). Crystals of (I) suitable for single-crystal X-ray analysis were grown by slow evaporation of a CH2Cl2 solution.
All H atoms were positioned geometrically and refined as riding with C—H = 0.98 and 0.99 Å). For the CH groups, Uiso(H) values are set equal to 1.2Ueq (carrier atom) and for the methyl groups they are set equal to 1.5Ueq (carrier atom). The C22, C23 and C24 atoms in the thiazinyl ring attached to the S5 atom are disordered over two sites [occupancies 0.462 (2) and 0.538 (2)].
Thioethers are often used as bridging ligands in construction of coordination polymers with soft metal ions. Now, we have a new thiazinyl derivative and present here the crystal structure of 2-(3,5-bis((5,6-dihydro-4H-1,3-thiazin-2-ylthio)methyl)-2,4,6- trimethylbenzylthio)-5,6-dihydro-4H-1,3-thiazine, (I).
There are three 1,3-thiazinyl sulfanyl groups in this molecule. Two 1,3-thiazinyl sulfanyl groups are located on the same side of the planar benzene ring and the other is on the opposite side. In the thiazinyl ring, the C11 atom has an distorted trigonal geometry, with S2—C11—S1 = 108.22 (2) and N1—C11—S2 = 130.7 (2)° deviating significantly from the ideal sp2 value of 120°. The similar results are observed in the other two thiazinyl rings. The C22, C23 and C24 atoms in the thiazinyl ring attached to the S5 atom are disordered over two sites [occupancies 0.462 (2) and 0.538 (2)]. The three methyl groups are almost coplanar with the benzene ring, with an r. m. s. derivation of 0.0272 Å.
Due to π-π conjugation, the Csp2—S bonds distances[S2—C11 = 1.764 (3) Å, S4—C16 = 1.773 (3)Å and S5—C21 = 1.759 (3) Å] are significantly shorter than the Csp3—S bonds distances [S1—C10 = 1.824 (3) Å, S3—C15 = 1.828 (3)Å and S5—C20 = 1.822 (3) Å]. These values are comparable with those in the literature (Wang et al., 2004, 2005). The other bond distances are within normal ranges (Allen et al., 1987).
For related literature, see: Allen et al. (1987); Wang et al. (2004, 2005); Jacobson (1998).
Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 1999); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.
Fig. 1. View of the molecule of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. |
C24H33N3S6 | F(000) = 1176 |
Mr = 555.89 | Dx = 1.400 Mg m−3 |
Monoclinic, P21/c | Melting point: 455 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 17.146 (3) Å | Cell parameters from 5347 reflections |
b = 10.123 (2) Å | θ = 2.3–24.5° |
c = 17.408 (4) Å | µ = 0.58 mm−1 |
β = 119.20 (3)° | T = 113 K |
V = 2637.6 (9) Å3 | Block, colourless |
Z = 4 | 0.20 × 0.18 × 0.02 mm |
Rigaku Saturn diffractometer | 5178 independent reflections |
Radiation source: rotating anode | 4350 reflections with I > 2σ(I) |
Confocal monochromator | Rint = 0.043 |
Detector resolution: 7.31 pixels mm-1 | θmax = 26.0°, θmin = 1.4° |
ω scans | h = −21→20 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −12→12 |
Tmin = 0.900, Tmax = 0.989 | l = −13→21 |
17102 measured reflections |
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)] = 0.055 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.139 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0604P)2 + 3.1576P] where P = (Fo2 + 2Fc2)/3 |
5178 reflections | (Δ/σ)max = 0.002 |
329 parameters | Δρmax = 1.17 e Å−3 |
7 restraints | Δρmin = −0.42 e Å−3 |
C24H33N3S6 | V = 2637.6 (9) Å3 |
Mr = 555.89 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 17.146 (3) Å | µ = 0.58 mm−1 |
b = 10.123 (2) Å | T = 113 K |
c = 17.408 (4) Å | 0.20 × 0.18 × 0.02 mm |
β = 119.20 (3)° |
Rigaku Saturn diffractometer | 5178 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 4350 reflections with I > 2σ(I) |
Tmin = 0.900, Tmax = 0.989 | Rint = 0.043 |
17102 measured reflections |
R[F2 > 2σ(F2)] = 0.055 | 7 restraints |
wR(F2) = 0.139 | H-atom parameters constrained |
S = 1.08 | Δρmax = 1.17 e Å−3 |
5178 reflections | Δρmin = −0.42 e Å−3 |
329 parameters |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
S1 | 0.22603 (7) | 0.49261 (8) | 1.16480 (5) | 0.0391 (2) | |
S2 | 0.21116 (6) | 0.41297 (8) | 1.31502 (5) | 0.0341 (2) | |
S3 | 0.40459 (7) | 0.67273 (8) | 0.89432 (7) | 0.0443 (3) | |
S4 | 0.51695 (7) | 0.75283 (8) | 0.82245 (6) | 0.0389 (2) | |
S5 | 0.04801 (6) | 0.40067 (8) | 0.72402 (5) | 0.0414 (3) | |
S6 | −0.01276 (6) | 0.28553 (9) | 0.55715 (6) | 0.0378 (2) | |
N1 | 0.2901 (2) | 0.2620 (3) | 1.24070 (19) | 0.0378 (7) | |
N2 | 0.44422 (17) | 0.9257 (2) | 0.89238 (17) | 0.0272 (6) | |
N3 | −0.09428 (18) | 0.5017 (3) | 0.58476 (16) | 0.0305 (6) | |
C1 | 0.2251 (2) | 0.5004 (3) | 1.00786 (18) | 0.0262 (7) | |
C2 | 0.2894 (2) | 0.5851 (3) | 1.00776 (19) | 0.0265 (7) | |
C3 | 0.2683 (2) | 0.6612 (3) | 0.93296 (19) | 0.0242 (6) | |
C4 | 0.1851 (2) | 0.6473 (3) | 0.85736 (18) | 0.0229 (6) | |
C5 | 0.1201 (2) | 0.5656 (3) | 0.85905 (18) | 0.0220 (6) | |
C6 | 0.1388 (2) | 0.4930 (3) | 0.93487 (19) | 0.0247 (6) | |
C7 | 0.0681 (2) | 0.4062 (3) | 0.9370 (2) | 0.0365 (8) | |
H7A | 0.0677 | 0.3200 | 0.9112 | 0.055* | |
H7B | 0.0095 | 0.4481 | 0.9032 | 0.055* | |
H7C | 0.0815 | 0.3943 | 0.9981 | 0.055* | |
C8 | 0.3816 (2) | 0.5939 (4) | 1.0879 (2) | 0.0440 (9) | |
H8A | 0.3761 | 0.6214 | 1.1391 | 0.066* | |
H8B | 0.4176 | 0.6586 | 1.0771 | 0.066* | |
H8C | 0.4106 | 0.5072 | 1.0994 | 0.066* | |
C9 | 0.1652 (3) | 0.7181 (3) | 0.7734 (2) | 0.0372 (8) | |
H9A | 0.1291 | 0.7968 | 0.7666 | 0.056* | |
H9B | 0.1322 | 0.6590 | 0.7231 | 0.056* | |
H9C | 0.2214 | 0.7445 | 0.7759 | 0.056* | |
C10 | 0.2502 (2) | 0.4094 (3) | 1.0858 (2) | 0.0327 (7) | |
H10A | 0.3145 | 0.3872 | 1.1139 | 0.039* | |
H10B | 0.2155 | 0.3263 | 1.0657 | 0.039* | |
C11 | 0.2507 (2) | 0.3647 (3) | 1.24276 (19) | 0.0278 (7) | |
C12 | 0.3113 (3) | 0.1601 (4) | 1.3058 (3) | 0.0510 (11) | |
H12A | 0.3651 | 0.1125 | 1.3137 | 0.061* | |
H12B | 0.2614 | 0.0959 | 1.2831 | 0.061* | |
C13 | 0.3284 (3) | 0.2093 (4) | 1.3963 (2) | 0.0487 (10) | |
H13A | 0.3445 | 0.1331 | 1.4368 | 0.058* | |
H13B | 0.3799 | 0.2707 | 1.4205 | 0.058* | |
C14 | 0.2501 (2) | 0.2779 (3) | 1.3929 (2) | 0.0352 (8) | |
H14A | 0.2667 | 0.3123 | 1.4521 | 0.042* | |
H14B | 0.2010 | 0.2135 | 1.3762 | 0.042* | |
C15 | 0.3350 (2) | 0.7569 (3) | 0.9320 (2) | 0.0351 (8) | |
H15A | 0.3731 | 0.7927 | 0.9918 | 0.042* | |
H15B | 0.3033 | 0.8316 | 0.8922 | 0.042* | |
C16 | 0.4551 (2) | 0.8098 (3) | 0.8730 (2) | 0.0264 (6) | |
C17 | 0.4867 (2) | 1.0354 (3) | 0.8727 (2) | 0.0298 (7) | |
H17A | 0.4925 | 1.1106 | 0.9115 | 0.036* | |
H17B | 0.4474 | 1.0639 | 0.8112 | 0.036* | |
C18 | 0.5787 (2) | 1.0031 (3) | 0.8843 (2) | 0.0288 (7) | |
H18A | 0.6060 | 1.0848 | 0.8768 | 0.035* | |
H18B | 0.6175 | 0.9699 | 0.9447 | 0.035* | |
C19 | 0.5739 (2) | 0.9015 (3) | 0.8193 (2) | 0.0318 (7) | |
H19A | 0.6352 | 0.8786 | 0.8322 | 0.038* | |
H19B | 0.5421 | 0.9395 | 0.7593 | 0.038* | |
C20 | 0.0312 (2) | 0.5463 (3) | 0.77578 (19) | 0.0298 (7) | |
H20A | 0.0162 | 0.6243 | 0.7367 | 0.036* | |
H20B | −0.0174 | 0.5315 | 0.7900 | 0.036* | |
C21 | −0.0352 (2) | 0.4136 (3) | 0.61307 (19) | 0.0249 (6) | |
C22 | −0.1721 (8) | 0.5025 (18) | 0.4950 (7) | 0.029 (3) | 0.462 (15) |
H22A | −0.1877 | 0.5951 | 0.4752 | 0.035* | 0.462 (15) |
H22B | −0.2238 | 0.4623 | 0.4968 | 0.035* | 0.462 (15) |
C23 | −0.1552 (8) | 0.4282 (10) | 0.4290 (6) | 0.038 (3) | 0.462 (15) |
H23A | −0.2119 | 0.4218 | 0.3727 | 0.046* | 0.462 (15) |
H23B | −0.1123 | 0.4789 | 0.4179 | 0.046* | 0.462 (15) |
C24 | −0.1187 (7) | 0.2907 (10) | 0.4594 (6) | 0.048 (3) | 0.462 (15) |
H24A | −0.1134 | 0.2460 | 0.4116 | 0.058* | 0.462 (15) |
H24B | −0.1622 | 0.2402 | 0.4696 | 0.058* | 0.462 (15) |
C22' | −0.1523 (9) | 0.5088 (14) | 0.4878 (7) | 0.035 (3) | 0.538 (15) |
H22C | −0.1216 | 0.5628 | 0.4631 | 0.042* | 0.538 (15) |
H22D | −0.2082 | 0.5552 | 0.4749 | 0.042* | 0.538 (15) |
C23' | −0.1763 (5) | 0.3763 (11) | 0.4411 (6) | 0.037 (2) | 0.538 (15) |
H23C | −0.2009 | 0.3173 | 0.4694 | 0.045* | 0.538 (15) |
H23D | −0.2226 | 0.3887 | 0.3789 | 0.045* | 0.538 (15) |
C24' | −0.0947 (6) | 0.3143 (11) | 0.4453 (4) | 0.039 (2) | 0.538 (15) |
H24C | −0.0699 | 0.3736 | 0.4173 | 0.046* | 0.538 (15) |
H24D | −0.1111 | 0.2297 | 0.4126 | 0.046* | 0.538 (15) |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0654 (6) | 0.0283 (4) | 0.0286 (4) | 0.0160 (4) | 0.0268 (4) | 0.0070 (3) |
S2 | 0.0400 (5) | 0.0332 (4) | 0.0363 (4) | 0.0023 (4) | 0.0244 (4) | 0.0006 (3) |
S3 | 0.0469 (6) | 0.0207 (4) | 0.0842 (7) | −0.0071 (4) | 0.0468 (5) | −0.0085 (4) |
S4 | 0.0542 (6) | 0.0262 (4) | 0.0516 (5) | 0.0010 (4) | 0.0378 (5) | −0.0066 (4) |
S5 | 0.0462 (6) | 0.0280 (4) | 0.0292 (4) | 0.0092 (4) | 0.0021 (4) | −0.0067 (3) |
S6 | 0.0474 (6) | 0.0332 (5) | 0.0387 (5) | 0.0019 (4) | 0.0258 (4) | −0.0067 (3) |
N1 | 0.0500 (19) | 0.0335 (16) | 0.0406 (16) | 0.0104 (14) | 0.0305 (14) | 0.0115 (12) |
N2 | 0.0223 (14) | 0.0218 (13) | 0.0410 (15) | −0.0026 (10) | 0.0183 (11) | −0.0038 (10) |
N3 | 0.0304 (15) | 0.0355 (15) | 0.0217 (12) | 0.0004 (12) | 0.0098 (11) | −0.0069 (10) |
C1 | 0.0358 (18) | 0.0241 (15) | 0.0212 (14) | 0.0040 (13) | 0.0158 (13) | 0.0007 (11) |
C2 | 0.0299 (17) | 0.0197 (14) | 0.0250 (15) | −0.0009 (12) | 0.0095 (13) | −0.0038 (11) |
C3 | 0.0250 (16) | 0.0161 (14) | 0.0330 (16) | −0.0027 (12) | 0.0154 (13) | −0.0032 (11) |
C4 | 0.0330 (17) | 0.0174 (14) | 0.0240 (14) | 0.0023 (12) | 0.0184 (13) | 0.0017 (11) |
C5 | 0.0243 (16) | 0.0211 (14) | 0.0210 (14) | 0.0000 (12) | 0.0113 (12) | −0.0019 (11) |
C6 | 0.0323 (17) | 0.0219 (15) | 0.0258 (15) | −0.0012 (13) | 0.0188 (13) | −0.0018 (11) |
C7 | 0.038 (2) | 0.0372 (19) | 0.0442 (19) | −0.0047 (15) | 0.0281 (16) | 0.0030 (15) |
C8 | 0.038 (2) | 0.0313 (19) | 0.042 (2) | −0.0040 (16) | 0.0031 (16) | 0.0008 (15) |
C9 | 0.054 (2) | 0.0321 (18) | 0.0286 (16) | −0.0043 (16) | 0.0223 (16) | 0.0048 (13) |
C10 | 0.044 (2) | 0.0265 (16) | 0.0309 (16) | 0.0085 (15) | 0.0208 (15) | 0.0032 (12) |
C11 | 0.0289 (17) | 0.0292 (16) | 0.0263 (15) | −0.0002 (13) | 0.0144 (13) | 0.0039 (12) |
C12 | 0.069 (3) | 0.0296 (19) | 0.078 (3) | 0.0285 (19) | 0.053 (2) | 0.0235 (18) |
C13 | 0.044 (2) | 0.065 (3) | 0.043 (2) | 0.013 (2) | 0.0264 (18) | 0.0299 (19) |
C14 | 0.044 (2) | 0.0371 (19) | 0.0273 (16) | −0.0063 (16) | 0.0199 (15) | −0.0015 (13) |
C15 | 0.0375 (19) | 0.0236 (16) | 0.053 (2) | −0.0064 (14) | 0.0288 (17) | −0.0063 (14) |
C16 | 0.0228 (16) | 0.0238 (16) | 0.0330 (16) | −0.0010 (12) | 0.0140 (13) | −0.0026 (12) |
C17 | 0.0305 (17) | 0.0217 (15) | 0.0411 (18) | 0.0007 (13) | 0.0206 (14) | −0.0002 (13) |
C18 | 0.0281 (17) | 0.0263 (16) | 0.0354 (17) | 0.0023 (13) | 0.0182 (14) | 0.0026 (12) |
C19 | 0.0309 (18) | 0.0360 (18) | 0.0352 (17) | 0.0037 (14) | 0.0213 (14) | 0.0031 (13) |
C20 | 0.0282 (17) | 0.0282 (16) | 0.0286 (16) | 0.0021 (13) | 0.0105 (13) | −0.0027 (12) |
C21 | 0.0254 (16) | 0.0256 (15) | 0.0264 (15) | −0.0055 (13) | 0.0146 (13) | −0.0041 (11) |
C22 | 0.018 (6) | 0.049 (6) | 0.018 (4) | 0.008 (4) | 0.008 (4) | −0.007 (4) |
C23 | 0.051 (6) | 0.035 (5) | 0.030 (4) | −0.009 (4) | 0.020 (4) | −0.011 (4) |
C24 | 0.097 (9) | 0.036 (5) | 0.030 (5) | 0.007 (6) | 0.045 (6) | 0.002 (4) |
C22' | 0.025 (6) | 0.050 (5) | 0.031 (5) | 0.008 (4) | 0.015 (4) | −0.003 (4) |
C23' | 0.028 (4) | 0.049 (6) | 0.032 (4) | −0.012 (4) | 0.012 (3) | −0.007 (4) |
C24' | 0.059 (5) | 0.049 (5) | 0.010 (3) | 0.001 (4) | 0.019 (3) | −0.006 (3) |
S1—C11 | 1.772 (3) | C9—H9C | 0.9800 |
S1—C10 | 1.824 (3) | C10—H10A | 0.9900 |
S2—C11 | 1.764 (3) | C10—H10B | 0.9900 |
S2—C14 | 1.808 (3) | C12—C13 | 1.537 (6) |
S3—C16 | 1.768 (3) | C12—H12A | 0.9900 |
S3—C15 | 1.828 (3) | C12—H12B | 0.9900 |
S4—C16 | 1.773 (3) | C13—C14 | 1.487 (5) |
S4—C19 | 1.809 (3) | C13—H13A | 0.9900 |
S5—C21 | 1.759 (3) | C13—H13B | 0.9900 |
S5—C20 | 1.822 (3) | C14—H14A | 0.9900 |
S6—C21 | 1.773 (3) | C14—H14B | 0.9900 |
S6—C24 | 1.784 (8) | C15—H15A | 0.9900 |
S6—C24' | 1.784 (6) | C15—H15B | 0.9900 |
N1—C11 | 1.250 (4) | C17—C18 | 1.525 (4) |
N1—C12 | 1.442 (4) | C17—H17A | 0.9900 |
N2—C16 | 1.259 (4) | C17—H17B | 0.9900 |
N2—C17 | 1.458 (4) | C18—C19 | 1.502 (4) |
N3—C21 | 1.256 (4) | C18—H18A | 0.9900 |
N3—C22 | 1.478 (11) | C18—H18B | 0.9900 |
N3—C22' | 1.486 (10) | C19—H19A | 0.9900 |
C1—C2 | 1.397 (4) | C19—H19B | 0.9900 |
C1—C6 | 1.406 (4) | C20—H20A | 0.9900 |
C1—C10 | 1.519 (4) | C20—H20B | 0.9900 |
C2—C3 | 1.400 (4) | C22—C23 | 1.515 (9) |
C2—C8 | 1.517 (4) | C22—H22A | 0.9900 |
C3—C4 | 1.398 (4) | C22—H22B | 0.9900 |
C3—C15 | 1.506 (4) | C23—C24 | 1.511 (9) |
C4—C5 | 1.399 (4) | C23—H23A | 0.9900 |
C4—C9 | 1.511 (4) | C23—H23B | 0.9900 |
C5—C6 | 1.405 (4) | C24—H24A | 0.9900 |
C5—C20 | 1.519 (4) | C24—H24B | 0.9900 |
C6—C7 | 1.511 (4) | C22'—C23' | 1.518 (9) |
C7—H7A | 0.9800 | C22'—H22C | 0.9900 |
C7—H7B | 0.9800 | C22'—H22D | 0.9900 |
C7—H7C | 0.9800 | C23'—C24' | 1.502 (8) |
C8—H8A | 0.9800 | C23'—H23C | 0.9900 |
C8—H8B | 0.9800 | C23'—H23D | 0.9900 |
C8—H8C | 0.9800 | C24'—H24C | 0.9900 |
C9—H9A | 0.9800 | C24'—H24D | 0.9900 |
C9—H9B | 0.9800 | ||
C11—S1—C10 | 100.53 (15) | S2—C14—H14B | 109.1 |
C11—S2—C14 | 101.23 (15) | H14A—C14—H14B | 107.9 |
C16—S3—C15 | 100.44 (15) | C3—C15—S3 | 109.7 (2) |
C16—S4—C19 | 101.96 (15) | C3—C15—H15A | 109.7 |
C21—S5—C20 | 104.09 (14) | S3—C15—H15A | 109.7 |
C21—S6—C24 | 96.3 (4) | C3—C15—H15B | 109.7 |
C21—S6—C24' | 102.3 (3) | S3—C15—H15B | 109.7 |
C24—S6—C24' | 20.1 (3) | H15A—C15—H15B | 108.2 |
C11—N1—C12 | 120.4 (3) | N2—C16—S3 | 121.6 (2) |
C16—N2—C17 | 119.4 (3) | N2—C16—S4 | 129.7 (2) |
C21—N3—C22 | 123.9 (6) | S3—C16—S4 | 108.78 (16) |
C21—N3—C22' | 116.4 (6) | N2—C17—C18 | 114.1 (3) |
C22—N3—C22' | 16.3 (8) | N2—C17—H17A | 108.7 |
C2—C1—C6 | 121.0 (3) | C18—C17—H17A | 108.7 |
C2—C1—C10 | 119.6 (3) | N2—C17—H17B | 108.7 |
C6—C1—C10 | 119.3 (3) | C18—C17—H17B | 108.7 |
C1—C2—C3 | 119.5 (3) | H17A—C17—H17B | 107.6 |
C1—C2—C8 | 120.2 (3) | C19—C18—C17 | 112.0 (3) |
C3—C2—C8 | 120.3 (3) | C19—C18—H18A | 109.2 |
C4—C3—C2 | 120.1 (3) | C17—C18—H18A | 109.2 |
C4—C3—C15 | 119.1 (3) | C19—C18—H18B | 109.2 |
C2—C3—C15 | 120.8 (3) | C17—C18—H18B | 109.2 |
C3—C4—C5 | 119.8 (3) | H18A—C18—H18B | 107.9 |
C3—C4—C9 | 120.5 (3) | C18—C19—S4 | 112.3 (2) |
C5—C4—C9 | 119.7 (3) | C18—C19—H19A | 109.1 |
C4—C5—C6 | 120.7 (3) | S4—C19—H19A | 109.1 |
C4—C5—C20 | 119.6 (3) | C18—C19—H19B | 109.1 |
C6—C5—C20 | 119.4 (3) | S4—C19—H19B | 109.1 |
C5—C6—C1 | 118.5 (3) | H19A—C19—H19B | 107.9 |
C5—C6—C7 | 120.7 (3) | C5—C20—S5 | 104.4 (2) |
C1—C6—C7 | 120.8 (3) | C5—C20—H20A | 110.9 |
C6—C7—H7A | 109.5 | S5—C20—H20A | 110.9 |
C6—C7—H7B | 109.5 | C5—C20—H20B | 110.9 |
H7A—C7—H7B | 109.5 | S5—C20—H20B | 110.9 |
C6—C7—H7C | 109.5 | H20A—C20—H20B | 108.9 |
H7A—C7—H7C | 109.5 | N3—C21—S5 | 123.4 (2) |
H7B—C7—H7C | 109.5 | N3—C21—S6 | 130.8 (2) |
C2—C8—H8A | 109.5 | S5—C21—S6 | 105.75 (17) |
C2—C8—H8B | 109.5 | N3—C22—C23 | 113.0 (9) |
H8A—C8—H8B | 109.5 | N3—C22—H22A | 109.0 |
C2—C8—H8C | 109.5 | C23—C22—H22A | 109.0 |
H8A—C8—H8C | 109.5 | N3—C22—H22B | 109.0 |
H8B—C8—H8C | 109.5 | C23—C22—H22B | 109.0 |
C4—C9—H9A | 109.5 | H22A—C22—H22B | 107.8 |
C4—C9—H9B | 109.5 | C24—C23—C22 | 113.0 (14) |
H9A—C9—H9B | 109.5 | C24—C23—H23A | 109.0 |
C4—C9—H9C | 109.5 | C22—C23—H23A | 109.0 |
H9A—C9—H9C | 109.5 | C24—C23—H23B | 109.0 |
H9B—C9—H9C | 109.5 | C22—C23—H23B | 109.0 |
C1—C10—S1 | 108.9 (2) | H23A—C23—H23B | 107.8 |
C1—C10—H10A | 109.9 | C23—C24—S6 | 114.6 (7) |
S1—C10—H10A | 109.9 | C23—C24—H24A | 108.6 |
C1—C10—H10B | 109.9 | S6—C24—H24A | 108.6 |
S1—C10—H10B | 109.9 | C23—C24—H24B | 108.6 |
H10A—C10—H10B | 108.3 | S6—C24—H24B | 108.6 |
N1—C11—S2 | 130.7 (2) | H24A—C24—H24B | 107.6 |
N1—C11—S1 | 121.1 (2) | N3—C22'—C23' | 115.0 (9) |
S2—C11—S1 | 108.22 (17) | N3—C22'—H22C | 108.5 |
N1—C12—C13 | 115.0 (3) | C23'—C22'—H22C | 108.5 |
N1—C12—H12A | 108.5 | N3—C22'—H22D | 108.5 |
C13—C12—H12A | 108.5 | C23'—C22'—H22D | 108.5 |
N1—C12—H12B | 108.5 | H22C—C22'—H22D | 107.5 |
C13—C12—H12B | 108.5 | C24'—C23'—C22' | 109.9 (11) |
H12A—C12—H12B | 107.5 | C24'—C23'—H23C | 109.7 |
C14—C13—C12 | 113.1 (3) | C22'—C23'—H23C | 109.7 |
C14—C13—H13A | 108.9 | C24'—C23'—H23D | 109.7 |
C12—C13—H13A | 108.9 | C22'—C23'—H23D | 109.7 |
C14—C13—H13B | 108.9 | H23C—C23'—H23D | 108.2 |
C12—C13—H13B | 108.9 | C23'—C24'—S6 | 109.9 (6) |
H13A—C13—H13B | 107.8 | C23'—C24'—H24C | 109.7 |
C13—C14—S2 | 112.3 (2) | S6—C24'—H24C | 109.7 |
C13—C14—H14A | 109.1 | C23'—C24'—H24D | 109.7 |
S2—C14—H14A | 109.1 | S6—C24'—H24D | 109.7 |
C13—C14—H14B | 109.1 | H24C—C24'—H24D | 108.2 |
C6—C1—C2—C3 | −1.7 (4) | C2—C3—C15—S3 | 89.1 (3) |
C10—C1—C2—C3 | 174.9 (3) | C16—S3—C15—C3 | 166.1 (2) |
C6—C1—C2—C8 | 178.7 (3) | C17—N2—C16—S3 | −179.5 (2) |
C10—C1—C2—C8 | −4.7 (4) | C17—N2—C16—S4 | −0.1 (5) |
C1—C2—C3—C4 | −3.3 (4) | C15—S3—C16—N2 | 6.4 (3) |
C8—C2—C3—C4 | 176.2 (3) | C15—S3—C16—S4 | −173.11 (17) |
C1—C2—C3—C15 | 177.9 (3) | C19—S4—C16—N2 | 7.6 (3) |
C8—C2—C3—C15 | −2.5 (4) | C19—S4—C16—S3 | −172.93 (16) |
C2—C3—C4—C5 | 5.5 (4) | C16—N2—C17—C18 | −36.0 (4) |
C15—C3—C4—C5 | −175.7 (3) | N2—C17—C18—C19 | 65.7 (3) |
C2—C3—C4—C9 | −173.6 (3) | C17—C18—C19—S4 | −54.5 (3) |
C15—C3—C4—C9 | 5.2 (4) | C16—S4—C19—C18 | 20.3 (3) |
C3—C4—C5—C6 | −2.6 (4) | C4—C5—C20—S5 | 91.8 (3) |
C9—C4—C5—C6 | 176.5 (3) | C6—C5—C20—S5 | −83.3 (3) |
C3—C4—C5—C20 | −177.6 (3) | C21—S5—C20—C5 | −158.9 (2) |
C9—C4—C5—C20 | 1.5 (4) | C22—N3—C21—S5 | −170.7 (8) |
C4—C5—C6—C1 | −2.4 (4) | C22'—N3—C21—S5 | 172.5 (6) |
C20—C5—C6—C1 | 172.6 (3) | C22—N3—C21—S6 | 11.8 (9) |
C4—C5—C6—C7 | 179.1 (3) | C22'—N3—C21—S6 | −5.0 (7) |
C20—C5—C6—C7 | −5.9 (4) | C20—S5—C21—N3 | −5.3 (3) |
C2—C1—C6—C5 | 4.6 (4) | C20—S5—C21—S6 | 172.78 (16) |
C10—C1—C6—C5 | −172.1 (3) | C24—S6—C21—N3 | −17.4 (5) |
C2—C1—C6—C7 | −176.9 (3) | C24'—S6—C21—N3 | 2.0 (5) |
C10—C1—C6—C7 | 6.4 (4) | C24—S6—C21—S5 | 164.7 (4) |
C2—C1—C10—S1 | 91.8 (3) | C24'—S6—C21—S5 | −175.9 (4) |
C6—C1—C10—S1 | −91.5 (3) | C21—N3—C22—C23 | −25.6 (18) |
C11—S1—C10—C1 | 175.1 (2) | C22'—N3—C22—C23 | 42 (3) |
C12—N1—C11—S2 | −1.0 (5) | N3—C22—C23—C24 | 51 (2) |
C12—N1—C11—S1 | 178.6 (3) | C22—C23—C24—S6 | −62.3 (19) |
C14—S2—C11—N1 | 4.1 (4) | C21—S6—C24—C23 | 40.2 (12) |
C14—S2—C11—S1 | −175.66 (17) | C24'—S6—C24—C23 | −68.8 (15) |
C10—S1—C11—N1 | 11.6 (3) | C21—N3—C22'—C23' | 36.9 (13) |
C10—S1—C11—S2 | −168.71 (17) | C22—N3—C22'—C23' | −84 (4) |
C11—N1—C12—C13 | −30.1 (5) | N3—C22'—C23'—C24' | −68.7 (16) |
N1—C12—C13—C14 | 60.7 (5) | C22'—C23'—C24'—S6 | 61.7 (13) |
C12—C13—C14—S2 | −55.0 (4) | C21—S6—C24'—C23' | −29.7 (11) |
C11—S2—C14—C13 | 24.1 (3) | C24—S6—C24'—C23' | 44.4 (12) |
C4—C3—C15—S3 | −89.7 (3) |
Experimental details
Crystal data | |
Chemical formula | C24H33N3S6 |
Mr | 555.89 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 113 |
a, b, c (Å) | 17.146 (3), 10.123 (2), 17.408 (4) |
β (°) | 119.20 (3) |
V (Å3) | 2637.6 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.58 |
Crystal size (mm) | 0.20 × 0.18 × 0.02 |
Data collection | |
Diffractometer | Rigaku Saturn |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.900, 0.989 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17102, 5178, 4350 |
Rint | 0.043 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.055, 0.139, 1.08 |
No. of reflections | 5178 |
No. of parameters | 329 |
No. of restraints | 7 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.17, −0.42 |
Computer programs: CrystalClear (Molecular Structure Corporation & Rigaku, 1999), CrystalClear, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.
S1—C11 | 1.772 (3) | S3—C15 | 1.828 (3) |
S1—C10 | 1.824 (3) | S5—C21 | 1.759 (3) |
S3—C16 | 1.768 (3) | S5—C20 | 1.822 (3) |
N1—C11—S2 | 130.7 (2) | S3—C16—S4 | 108.78 (16) |
S2—C11—S1 | 108.22 (17) | N3—C21—S6 | 130.8 (2) |
N2—C16—S4 | 129.7 (2) | S5—C21—S6 | 105.75 (17) |
Thioethers are often used as bridging ligands in construction of coordination polymers with soft metal ions. Now, we have a new thiazinyl derivative and present here the crystal structure of 2-(3,5-bis((5,6-dihydro-4H-1,3-thiazin-2-ylthio)methyl)-2,4,6- trimethylbenzylthio)-5,6-dihydro-4H-1,3-thiazine, (I).
There are three 1,3-thiazinyl sulfanyl groups in this molecule. Two 1,3-thiazinyl sulfanyl groups are located on the same side of the planar benzene ring and the other is on the opposite side. In the thiazinyl ring, the C11 atom has an distorted trigonal geometry, with S2—C11—S1 = 108.22 (2) and N1—C11—S2 = 130.7 (2)° deviating significantly from the ideal sp2 value of 120°. The similar results are observed in the other two thiazinyl rings. The C22, C23 and C24 atoms in the thiazinyl ring attached to the S5 atom are disordered over two sites [occupancies 0.462 (2) and 0.538 (2)]. The three methyl groups are almost coplanar with the benzene ring, with an r. m. s. derivation of 0.0272 Å.
Due to π-π conjugation, the Csp2—S bonds distances[S2—C11 = 1.764 (3) Å, S4—C16 = 1.773 (3)Å and S5—C21 = 1.759 (3) Å] are significantly shorter than the Csp3—S bonds distances [S1—C10 = 1.824 (3) Å, S3—C15 = 1.828 (3)Å and S5—C20 = 1.822 (3) Å]. These values are comparable with those in the literature (Wang et al., 2004, 2005). The other bond distances are within normal ranges (Allen et al., 1987).