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organic compounds
While trying to prepare mesoionic thiazolo[3,2-a]pyridinium-2-thiolate by reaction of 2-bromo-1-(ethoxycarbonylmethyl)pyridinium bromide with CS2, an unexpected product was formed, namely (ethoxycarbonyl)[3-(ethoxycarbonyl)-1,3-thiazolo[3,2-a]pyridin-4-ium-2-yl](2-thioxo-1,2-dihydropyridin-1-yl)methanide, C19H18N2O4S2. The structure of the product corresponds to a previously unknown subclass of mesoionic thiazolo[3,2-a]pyridinium-2-methylides.
Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536806011135/sj2004sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536806011135/sj20042sup2.hkl |
CCDC reference: 608484
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean (C-C)= 0.002 Å
- R factor = 0.032
- wR factor = 0.077
- Data-to-parameter ratio = 17.5
checkCIF/PLATON results
No syntax errors found No errors found in this datablock
Computing details top
Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
(ethoxycarbonyl)[3-(ethoxycarbonyl)-1,3-thiazolo[3,2-a]pyridin-4-ium-2-
yl](2-thioxo-1,2-dihydropyridin-1-yl)methanide top
Crystal data top
C19H18N2O4S2 | Z = 2 |
Mr = 402.47 | F(000) = 420 |
Triclinic, P1 | Dx = 1.508 Mg m−3 |
Hall symbol: -P 1 | Melting point: 465 K |
a = 6.8600 (14) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.0710 (18) Å | Cell parameters from 6851 reflections |
c = 14.634 (3) Å | θ = 3.5–31° |
α = 82.66 (3)° | µ = 0.33 mm−1 |
β = 80.06 (3)° | T = 100 K |
γ = 84.11 (3)° | Plate, dark-red |
V = 886.6 (3) Å3 | 0.40 × 0.40 × 0.14 mm |
Data collection top
Stoe IPDS diffractometer | 3810 reflections with I > 2σ(I) |
Radiation source: Fine-focus sealed tube | Rint = 0.020 |
Graphite monochromator | θmax = 29.1°, θmin = 3.4° |
ω scans | h = −8→9 |
6851 measured reflections | k = −12→12 |
4780 independent reflections | l = −20→20 |
Refinement top
Refinement on F2 | Primary atom site location: Direct |
Least-squares matrix: Full | Secondary atom site location: Difmap |
R[F2 > 2σ(F2)] = 0.032 | Hydrogen site location: Geom |
wR(F2) = 0.077 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0359P)2 + 0.5422P] where P = (Fo2 + 2Fc2)/3 |
4308 reflections | (Δ/σ)max = 0.002 |
246 parameters | Δρmax = 0.46 e Å−3 |
0 restraints | Δρmin = −0.29 e Å−3 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
x | y | z | Uiso*/Ueq | ||
N1 | 0.73931 (17) | 0.06684 (12) | 0.43307 (7) | 0.0117 (2) | |
C2 | 0.7116 (2) | 0.17442 (14) | 0.35650 (8) | 0.0118 (2) | |
C3 | 0.71296 (19) | 0.10997 (13) | 0.27377 (8) | 0.0103 (2) | |
S4 | 0.72642 (5) | −0.08644 (3) | 0.29787 (2) | 0.01191 (8) | |
C5 | 0.7457 (2) | −0.07683 (14) | 0.41281 (9) | 0.0123 (2) | |
C6 | 0.7664 (2) | −0.19789 (15) | 0.48086 (9) | 0.0158 (3) | |
H6 | 0.7701 | −0.2970 | 0.4657 | 0.019* | |
C7 | 0.7814 (2) | −0.17233 (16) | 0.57020 (9) | 0.0171 (3) | |
H7 | 0.7968 | −0.2531 | 0.6173 | 0.021* | |
C8 | 0.7736 (2) | −0.02521 (16) | 0.58988 (9) | 0.0164 (3) | |
H8 | 0.7826 | −0.0060 | 0.6513 | 0.020* | |
C9 | 0.7531 (2) | 0.09251 (15) | 0.52230 (9) | 0.0144 (3) | |
H9 | 0.7484 | 0.1919 | 0.5372 | 0.017* | |
C10 | 0.7207 (2) | 0.17242 (13) | 0.18132 (8) | 0.0109 (2) | |
C11 | 0.71795 (19) | 0.07723 (13) | 0.11059 (8) | 0.0107 (2) | |
O11 | 0.69820 (15) | −0.05712 (10) | 0.12827 (6) | 0.01452 (19) | |
O12 | 0.74345 (15) | 0.14595 (10) | 0.02199 (6) | 0.01253 (19) | |
C13 | 0.7638 (2) | 0.04543 (13) | −0.04991 (8) | 0.0122 (2) | |
H13A | 0.6475 | −0.0143 | −0.0398 | 0.015* | |
H13B | 0.8849 | −0.0236 | −0.0477 | 0.015* | |
C14 | 0.7777 (2) | 0.13942 (15) | −0.14321 (9) | 0.0166 (3) | |
H14A | 0.6575 | 0.2076 | −0.1445 | 0.025* | |
H14B | 0.7906 | 0.0745 | −0.1929 | 0.025* | |
H14C | 0.8941 | 0.1972 | −0.1528 | 0.025* | |
C15 | 0.6679 (2) | 0.33087 (14) | 0.37343 (9) | 0.0144 (3) | |
O15 | 0.7262 (2) | 0.38675 (12) | 0.43391 (8) | 0.0270 (3) | |
O16 | 0.54618 (16) | 0.40277 (10) | 0.31738 (7) | 0.0161 (2) | |
C17 | 0.4825 (2) | 0.55892 (14) | 0.32733 (10) | 0.0203 (3) | |
H17A | 0.5449 | 0.6233 | 0.2725 | 0.024* | |
H17B | 0.5225 | 0.5875 | 0.3841 | 0.024* | |
C18 | 0.2601 (3) | 0.57815 (16) | 0.33466 (11) | 0.0234 (3) | |
H18A | 0.2204 | 0.5324 | 0.2843 | 0.035* | |
H18B | 0.2160 | 0.6847 | 0.3293 | 0.035* | |
H18C | 0.1991 | 0.5299 | 0.3951 | 0.035* | |
N19 | 0.76306 (17) | 0.32462 (11) | 0.15110 (7) | 0.0108 (2) | |
C20 | 0.9490 (2) | 0.37005 (13) | 0.15285 (8) | 0.0115 (2) | |
S20 | 1.13386 (5) | 0.25380 (3) | 0.19116 (2) | 0.01423 (8) | |
C21 | 0.9756 (2) | 0.52220 (14) | 0.11827 (9) | 0.0151 (3) | |
H21 | 1.0980 | 0.5607 | 0.1208 | 0.018* | |
C22 | 0.8313 (2) | 0.61450 (14) | 0.08165 (9) | 0.0174 (3) | |
H22 | 0.8550 | 0.7147 | 0.0580 | 0.021* | |
C23 | 0.6475 (2) | 0.56066 (15) | 0.07906 (9) | 0.0171 (3) | |
H23 | 0.5467 | 0.6229 | 0.0527 | 0.021* | |
C24 | 0.6171 (2) | 0.41725 (14) | 0.11514 (9) | 0.0139 (2) | |
H24 | 0.4921 | 0.3806 | 0.1154 | 0.017* |
Atomic displacement parameters (Å2) top
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0112 (5) | 0.0138 (5) | 0.0100 (5) | −0.0027 (4) | −0.0006 (4) | −0.0016 (4) |
C2 | 0.0146 (6) | 0.0117 (5) | 0.0092 (5) | −0.0028 (4) | −0.0009 (5) | −0.0012 (4) |
C3 | 0.0097 (6) | 0.0097 (5) | 0.0119 (5) | −0.0023 (4) | −0.0007 (4) | −0.0024 (4) |
S4 | 0.01615 (17) | 0.00926 (13) | 0.01042 (14) | −0.00289 (10) | −0.00121 (11) | −0.00123 (10) |
C5 | 0.0118 (6) | 0.0130 (5) | 0.0119 (5) | −0.0027 (4) | −0.0005 (5) | −0.0013 (4) |
C6 | 0.0160 (7) | 0.0151 (6) | 0.0160 (6) | −0.0041 (5) | −0.0029 (5) | 0.0020 (5) |
C7 | 0.0150 (7) | 0.0212 (6) | 0.0143 (6) | −0.0038 (5) | −0.0034 (5) | 0.0040 (5) |
C8 | 0.0134 (7) | 0.0248 (7) | 0.0110 (5) | −0.0033 (5) | −0.0021 (5) | −0.0009 (5) |
C9 | 0.0135 (7) | 0.0198 (6) | 0.0104 (5) | −0.0022 (5) | −0.0015 (5) | −0.0036 (4) |
C10 | 0.0137 (6) | 0.0086 (5) | 0.0109 (5) | −0.0025 (4) | −0.0010 (5) | −0.0025 (4) |
C11 | 0.0101 (6) | 0.0119 (5) | 0.0104 (5) | −0.0012 (4) | −0.0017 (4) | −0.0025 (4) |
O11 | 0.0196 (5) | 0.0107 (4) | 0.0141 (4) | −0.0037 (3) | −0.0026 (4) | −0.0030 (3) |
O12 | 0.0188 (5) | 0.0107 (4) | 0.0088 (4) | −0.0016 (3) | −0.0023 (4) | −0.0033 (3) |
C13 | 0.0156 (6) | 0.0114 (5) | 0.0106 (5) | −0.0014 (4) | −0.0019 (5) | −0.0050 (4) |
C14 | 0.0241 (8) | 0.0144 (6) | 0.0110 (5) | 0.0000 (5) | −0.0020 (5) | −0.0030 (4) |
C15 | 0.0186 (7) | 0.0137 (5) | 0.0108 (5) | −0.0033 (5) | 0.0001 (5) | −0.0030 (4) |
O15 | 0.0479 (8) | 0.0165 (5) | 0.0219 (5) | −0.0020 (5) | −0.0170 (5) | −0.0072 (4) |
O16 | 0.0225 (5) | 0.0097 (4) | 0.0173 (4) | 0.0013 (3) | −0.0051 (4) | −0.0055 (3) |
C17 | 0.0326 (9) | 0.0090 (5) | 0.0198 (6) | 0.0004 (5) | −0.0041 (6) | −0.0054 (5) |
C18 | 0.0327 (9) | 0.0168 (6) | 0.0213 (7) | 0.0071 (6) | −0.0089 (6) | −0.0057 (5) |
N19 | 0.0144 (6) | 0.0089 (4) | 0.0094 (4) | −0.0017 (4) | −0.0013 (4) | −0.0023 (3) |
C20 | 0.0146 (6) | 0.0112 (5) | 0.0092 (5) | −0.0027 (4) | −0.0008 (5) | −0.0033 (4) |
S20 | 0.01343 (17) | 0.01290 (14) | 0.01683 (15) | −0.00174 (11) | −0.00421 (12) | −0.00047 (11) |
C21 | 0.0195 (7) | 0.0112 (5) | 0.0151 (6) | −0.0048 (5) | −0.0016 (5) | −0.0026 (4) |
C22 | 0.0265 (8) | 0.0101 (5) | 0.0153 (6) | −0.0019 (5) | −0.0018 (5) | −0.0020 (4) |
C23 | 0.0225 (7) | 0.0133 (6) | 0.0151 (6) | 0.0039 (5) | −0.0045 (5) | −0.0018 (4) |
C24 | 0.0149 (7) | 0.0146 (6) | 0.0128 (5) | 0.0003 (4) | −0.0034 (5) | −0.0033 (4) |
Geometric parameters (Å, º) top
N1—C5 | 1.3677 (16) | C14—H14A | 0.9800 |
N1—C9 | 1.3758 (16) | C14—H14B | 0.9800 |
N1—C2 | 1.4143 (17) | C14—H14C | 0.9800 |
C2—C3 | 1.4082 (17) | C15—O15 | 1.2160 (17) |
C2—C15 | 1.4636 (17) | C15—O16 | 1.3356 (18) |
C3—C10 | 1.3928 (17) | O16—C17 | 1.4567 (16) |
C3—S4 | 1.7675 (13) | C17—C18 | 1.504 (2) |
S4—C5 | 1.7237 (14) | C17—H17A | 0.9900 |
C5—C6 | 1.3983 (18) | C17—H17B | 0.9900 |
C6—C7 | 1.3793 (19) | C18—H18A | 0.9800 |
C6—H6 | 0.9500 | C18—H18B | 0.9800 |
C7—C8 | 1.395 (2) | C18—H18C | 0.9800 |
C7—H7 | 0.9500 | N19—C24 | 1.3717 (18) |
C8—C9 | 1.373 (2) | N19—C20 | 1.3852 (17) |
C8—H8 | 0.9500 | C20—C21 | 1.4268 (17) |
C9—H9 | 0.9500 | C20—S20 | 1.6897 (15) |
C10—C11 | 1.4337 (17) | C21—C22 | 1.366 (2) |
C10—N19 | 1.4381 (15) | C21—H21 | 0.9500 |
C11—O11 | 1.2295 (15) | C22—C23 | 1.406 (2) |
C11—O12 | 1.3557 (15) | C22—H22 | 0.9500 |
O12—C13 | 1.4581 (14) | C23—C24 | 1.3626 (19) |
C13—C14 | 1.5081 (18) | C23—H23 | 0.9500 |
C13—H13A | 0.9900 | C24—H24 | 0.9500 |
C13—H13B | 0.9900 | ||
C5—N1—C9 | 119.24 (11) | C13—C14—H14B | 109.5 |
C5—N1—C2 | 113.37 (11) | H14A—C14—H14B | 109.5 |
C9—N1—C2 | 127.35 (11) | C13—C14—H14C | 109.5 |
C3—C2—N1 | 112.66 (11) | H14A—C14—H14C | 109.5 |
C3—C2—C15 | 128.68 (12) | H14B—C14—H14C | 109.5 |
N1—C2—C15 | 118.38 (11) | O15—C15—O16 | 124.07 (12) |
C10—C3—C2 | 131.70 (11) | O15—C15—C2 | 124.55 (13) |
C10—C3—S4 | 118.39 (9) | O16—C15—C2 | 111.28 (11) |
C2—C3—S4 | 109.70 (9) | C15—O16—C17 | 118.33 (11) |
C5—S4—C3 | 91.55 (7) | O16—C17—C18 | 107.97 (12) |
N1—C5—C6 | 121.32 (12) | O16—C17—H17A | 110.1 |
N1—C5—S4 | 112.47 (10) | C18—C17—H17A | 110.1 |
C6—C5—S4 | 126.20 (10) | O16—C17—H17B | 110.1 |
C7—C6—C5 | 119.50 (12) | C18—C17—H17B | 110.1 |
C7—C6—H6 | 120.3 | H17A—C17—H17B | 108.4 |
C5—C6—H6 | 120.3 | C17—C18—H18A | 109.5 |
C6—C7—C8 | 118.49 (13) | C17—C18—H18B | 109.5 |
C6—C7—H7 | 120.8 | H18A—C18—H18B | 109.5 |
C8—C7—H7 | 120.8 | C17—C18—H18C | 109.5 |
C9—C8—C7 | 121.33 (13) | H18A—C18—H18C | 109.5 |
C9—C8—H8 | 119.3 | H18B—C18—H18C | 109.5 |
C7—C8—H8 | 119.3 | C24—N19—C20 | 122.52 (11) |
C8—C9—N1 | 120.12 (12) | C24—N19—C10 | 116.97 (11) |
C8—C9—H9 | 119.9 | C20—N19—C10 | 120.35 (11) |
N1—C9—H9 | 119.9 | N19—C20—C21 | 115.31 (12) |
C3—C10—C11 | 119.18 (11) | N19—C20—S20 | 122.81 (9) |
C3—C10—N19 | 122.55 (11) | C21—C20—S20 | 121.88 (11) |
C11—C10—N19 | 117.51 (11) | C22—C21—C20 | 122.31 (13) |
O11—C11—O12 | 122.22 (11) | C22—C21—H21 | 118.8 |
O11—C11—C10 | 122.90 (12) | C20—C21—H21 | 118.8 |
O12—C11—C10 | 114.87 (10) | C21—C22—C23 | 119.75 (12) |
C11—O12—C13 | 114.42 (9) | C21—C22—H22 | 120.1 |
O12—C13—C14 | 107.74 (10) | C23—C22—H22 | 120.1 |
O12—C13—H13A | 110.2 | C24—C23—C22 | 118.59 (13) |
C14—C13—H13A | 110.2 | C24—C23—H23 | 120.7 |
O12—C13—H13B | 110.2 | C22—C23—H23 | 120.7 |
C14—C13—H13B | 110.2 | C23—C24—N19 | 121.43 (13) |
H13A—C13—H13B | 108.5 | C23—C24—H24 | 119.3 |
C13—C14—H14A | 109.5 | N19—C24—H24 | 119.3 |
C5—N1—C2—C3 | −4.91 (16) | N19—C10—C11—O11 | 174.38 (12) |
C9—N1—C2—C3 | 177.33 (12) | C3—C10—C11—O12 | −174.49 (12) |
C5—N1—C2—C15 | 169.58 (12) | N19—C10—C11—O12 | −4.18 (18) |
C9—N1—C2—C15 | −8.2 (2) | O11—C11—O12—C13 | −5.43 (18) |
N1—C2—C3—C10 | −169.10 (14) | C10—C11—O12—C13 | 173.14 (11) |
C15—C2—C3—C10 | 17.1 (2) | C11—O12—C13—C14 | 176.47 (11) |
N1—C2—C3—S4 | 5.39 (14) | C3—C2—C15—O15 | −156.16 (15) |
C15—C2—C3—S4 | −168.39 (12) | N1—C2—C15—O15 | 30.4 (2) |
C10—C3—S4—C5 | 171.73 (12) | C3—C2—C15—O16 | 27.39 (19) |
C2—C3—S4—C5 | −3.60 (10) | N1—C2—C15—O16 | −146.08 (12) |
C9—N1—C5—C6 | −0.2 (2) | O15—C15—O16—C17 | 1.6 (2) |
C2—N1—C5—C6 | −178.12 (12) | C2—C15—O16—C17 | 178.04 (11) |
C9—N1—C5—S4 | −179.99 (10) | C15—O16—C17—C18 | −129.94 (13) |
C2—N1—C5—S4 | 2.05 (14) | C3—C10—N19—C24 | −117.42 (14) |
C3—S4—C5—N1 | 0.92 (10) | C11—C10—N19—C24 | 72.62 (15) |
C3—S4—C5—C6 | −178.90 (13) | C3—C10—N19—C20 | 66.97 (17) |
N1—C5—C6—C7 | −0.2 (2) | C11—C10—N19—C20 | −102.99 (14) |
S4—C5—C6—C7 | 179.57 (11) | C24—N19—C20—C21 | 2.59 (17) |
C5—C6—C7—C8 | 0.6 (2) | C10—N19—C20—C21 | 177.95 (10) |
C6—C7—C8—C9 | −0.5 (2) | C24—N19—C20—S20 | −176.29 (9) |
C7—C8—C9—N1 | 0.2 (2) | C10—N19—C20—S20 | −0.94 (16) |
C5—N1—C9—C8 | 0.2 (2) | N19—C20—C21—C22 | −3.16 (18) |
C2—N1—C9—C8 | 177.84 (13) | S20—C20—C21—C22 | 175.74 (10) |
C2—C3—C10—C11 | −179.37 (14) | C20—C21—C22—C23 | 1.3 (2) |
S4—C3—C10—C11 | 6.53 (18) | C21—C22—C23—C24 | 1.23 (19) |
C2—C3—C10—N19 | 10.8 (2) | C22—C23—C24—N19 | −1.82 (19) |
S4—C3—C10—N19 | −163.27 (10) | C20—N19—C24—C23 | −0.19 (18) |
C3—C10—C11—O11 | 4.1 (2) | C10—N19—C24—C23 | −175.69 (11) |
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