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The crystal structures of 4-methyl-2-[N-(3,4-methylenedioxybenzylidene)hydrazino]thiazole, C12H11N3O2S, and its reduction product 4-methyl-2-[N-(3,4-methylenedioxybenzylidene)hydrazono]-4,5-dihydrothiazole, C12H13N3O2S, have been determined and compared. In the reduction product, the tautomer observed bears an H atom on the exocyclic N atom. Both compounds form hydrogen-bonded dimers over centers of inversion.
Supporting information
CCDC references: 182015; 182016
Description of the synthesis of the title compounds is given in Mazzone et
al. (1992), Pignatello et al. (1994) and Cambria et al.
(1996).
H atoms on N3 or N6 were located at the end of the refinement by Fourier
difference synthesis. Once located, they were refined using the riding model
method.
Program(s) used to solve structure: SHELXS97 (Sheldrick, 1997) for (I); SHELXS97 (Sheldrick, 1990) for (IIb). For both compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: PLATON (Spek, 1990).
Crystal data top
C12H11N3O2S | F(000) = 544 |
Mr = 261.31 | Dx = 1.447 Mg m−3 |
Monoclinic, P21/n | Cu Kα radiation, λ = 1.54178 Å |
Hall symbol: -P 2yn | Cell parameters from 25 reflections |
a = 6.219 (1) Å | θ = 35–45° |
b = 12.163 (2) Å | µ = 2.40 mm−1 |
c = 15.855 (1) Å | T = 293 K |
β = 91.13 (1)° | Plate, yellow |
V = 1199.1 (3) Å3 | 0.6 × 0.4 × 0.09 mm |
Z = 4 | |
Data collection top
Enraf Nonius CAD 4 diffractometer | 2066 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.015 |
Graphite monochromator | θmax = 71.9°, θmin = 4.6° |
θ/2θ scans | h = 0→7 |
Absorption correction: analytical North et al. (1968) | k = −11→14 |
Tmin = 0.393, Tmax = 0.805 | l = −19→19 |
3882 measured reflections | 3 standard reflections every 60 min |
2356 independent reflections | intensity decay: 1% |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H-atom parameters not refined |
R[F2 > 2σ(F2)] = 0.038 | Calculated w = 1/[σ2(Fo2) + (0.0521P)2 + 0.2929P]
where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.106 | (Δ/σ)max = 0.001 |
S = 1.09 | Δρmax = 0.23 e Å−3 |
2356 reflections | Δρmin = −0.28 e Å−3 |
164 parameters | |
Crystal data top
C12H11N3O2S | V = 1199.1 (3) Å3 |
Mr = 261.31 | Z = 4 |
Monoclinic, P21/n | Cu Kα radiation |
a = 6.219 (1) Å | µ = 2.40 mm−1 |
b = 12.163 (2) Å | T = 293 K |
c = 15.855 (1) Å | 0.6 × 0.4 × 0.09 mm |
β = 91.13 (1)° | |
Data collection top
Enraf Nonius CAD 4 diffractometer | 2066 reflections with I > 2σ(I) |
Absorption correction: analytical North et al. (1968) | Rint = 0.015 |
Tmin = 0.393, Tmax = 0.805 | 3 standard reflections every 60 min |
3882 measured reflections | intensity decay: 1% |
2356 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.106 | H-atom parameters not refined |
S = 1.09 | Δρmax = 0.23 e Å−3 |
2356 reflections | Δρmin = −0.28 e Å−3 |
164 parameters | |
Special details top
Geometry. Bond distances, angles etc. have been calculated using the rounded
fractional coordinates. All e.s.d.'s are estimated from the variances of the
(full) variance-covariance matrix. The cell e.s.d.'s are taken into account in
the estimation of distances, angles and torsion angles |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S5 | 0.79678 (8) | 0.14782 (4) | 0.29729 (3) | 0.0618 (2) | |
O12 | −0.09986 (19) | 0.39953 (11) | 0.40256 (8) | 0.0611 (4) | |
O14 | −0.26993 (19) | 0.41203 (10) | 0.53016 (9) | 0.0581 (4) | |
N3 | 1.0512 (2) | 0.01641 (11) | 0.37999 (8) | 0.0455 (4) | |
N6 | 0.7658 (2) | 0.08673 (11) | 0.45879 (9) | 0.0479 (4) | |
N7 | 0.5847 (2) | 0.15092 (11) | 0.45379 (9) | 0.0458 (4) | |
C0 | 1.3144 (3) | −0.04372 (19) | 0.27277 (14) | 0.0727 (8) | |
C1 | 1.0092 (3) | 0.08857 (18) | 0.24570 (11) | 0.0627 (7) | |
C2 | 1.1240 (3) | 0.02250 (15) | 0.29753 (11) | 0.0518 (5) | |
C4 | 0.8793 (2) | 0.07730 (13) | 0.38701 (10) | 0.0429 (5) | |
C8 | 0.4753 (3) | 0.15987 (13) | 0.52066 (11) | 0.0464 (5) | |
C9 | 0.2798 (2) | 0.22569 (13) | 0.52381 (10) | 0.0429 (5) | |
C10 | 0.1948 (2) | 0.27923 (13) | 0.45198 (10) | 0.0449 (5) | |
C11 | 0.0113 (2) | 0.33899 (13) | 0.46195 (11) | 0.0443 (5) | |
C13 | −0.2898 (3) | 0.43654 (16) | 0.44252 (13) | 0.0568 (6) | |
C15 | −0.0907 (2) | 0.34695 (13) | 0.53856 (11) | 0.0458 (5) | |
C16 | −0.0125 (3) | 0.29586 (14) | 0.60916 (11) | 0.0508 (5) | |
C17 | 0.1753 (3) | 0.23447 (14) | 0.60032 (11) | 0.0484 (5) | |
H0A | 1.34333 | −0.03118 | 0.21431 | 0.1091* | |
H0B | 1.28525 | −0.12034 | 0.28153 | 0.1091* | |
H0C | 1.43715 | −0.02228 | 0.30655 | 0.1091* | |
H1 | 1.04029 | 0.10075 | 0.18933 | 0.0753* | |
H6 | 0.80514 | 0.05435 | 0.50478 | 0.0575* | |
H8 | 0.52195 | 0.12312 | 0.56909 | 0.0558* | |
H10 | 0.26074 | 0.27416 | 0.39999 | 0.0539* | |
H13A | −0.30716 | 0.51511 | 0.43438 | 0.0682* | |
H13B | −0.41484 | 0.39973 | 0.41829 | 0.0682* | |
H16 | −0.08072 | 0.30160 | 0.66064 | 0.0610* | |
H17 | 0.23261 | 0.19814 | 0.64722 | 0.0581* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S5 | 0.0541 (3) | 0.0811 (4) | 0.0499 (3) | 0.0050 (2) | −0.0033 (2) | 0.0081 (2) |
O12 | 0.0469 (7) | 0.0730 (8) | 0.0638 (8) | 0.0118 (6) | 0.0103 (6) | 0.0139 (6) |
O14 | 0.0409 (6) | 0.0627 (8) | 0.0710 (8) | 0.0090 (5) | 0.0116 (6) | −0.0015 (6) |
N3 | 0.0426 (7) | 0.0479 (7) | 0.0463 (7) | −0.0012 (6) | 0.0102 (5) | −0.0017 (6) |
N6 | 0.0401 (7) | 0.0547 (8) | 0.0493 (7) | 0.0078 (6) | 0.0081 (6) | 0.0041 (6) |
N7 | 0.0347 (7) | 0.0474 (7) | 0.0553 (8) | 0.0013 (5) | 0.0038 (6) | −0.0011 (6) |
C0 | 0.0717 (13) | 0.0837 (14) | 0.0640 (12) | 0.0061 (11) | 0.0307 (10) | −0.0048 (11) |
C1 | 0.0608 (11) | 0.0839 (14) | 0.0436 (9) | −0.0082 (10) | 0.0068 (8) | 0.0002 (9) |
C2 | 0.0488 (9) | 0.0598 (10) | 0.0472 (9) | −0.0080 (8) | 0.0123 (7) | −0.0056 (8) |
C4 | 0.0377 (8) | 0.0455 (8) | 0.0456 (8) | −0.0066 (6) | 0.0032 (6) | −0.0027 (6) |
C8 | 0.0381 (8) | 0.0487 (9) | 0.0526 (9) | 0.0003 (7) | 0.0030 (7) | −0.0016 (7) |
C9 | 0.0336 (7) | 0.0427 (8) | 0.0526 (9) | −0.0050 (6) | 0.0052 (6) | −0.0047 (6) |
C10 | 0.0365 (8) | 0.0492 (9) | 0.0494 (8) | −0.0046 (6) | 0.0088 (6) | −0.0022 (7) |
C11 | 0.0348 (8) | 0.0446 (8) | 0.0537 (9) | −0.0051 (6) | 0.0042 (7) | 0.0006 (7) |
C13 | 0.0357 (8) | 0.0593 (10) | 0.0755 (12) | 0.0019 (7) | 0.0031 (8) | 0.0002 (9) |
C15 | 0.0323 (7) | 0.0453 (8) | 0.0600 (10) | −0.0044 (6) | 0.0091 (7) | −0.0078 (7) |
C16 | 0.0452 (9) | 0.0579 (10) | 0.0499 (9) | −0.0024 (7) | 0.0124 (7) | −0.0068 (8) |
C17 | 0.0439 (9) | 0.0525 (9) | 0.0490 (8) | −0.0015 (7) | 0.0034 (7) | −0.0028 (7) |
Geometric parameters (Å, º) top
S5—C4 | 1.7303 (17) | C8—C9 | 1.457 (2) |
S5—C1 | 1.725 (2) | C9—C10 | 1.406 (2) |
O12—C11 | 1.372 (2) | C9—C17 | 1.392 (2) |
O12—C13 | 1.424 (2) | C10—C11 | 1.3648 (19) |
O14—C13 | 1.424 (3) | C11—C15 | 1.385 (2) |
O14—C15 | 1.3715 (18) | C15—C16 | 1.362 (2) |
N3—C4 | 1.3071 (19) | C16—C17 | 1.396 (3) |
N3—C2 | 1.394 (2) | C1—H1 | 0.9300 |
N6—N7 | 1.3714 (18) | C8—H8 | 0.9300 |
N6—C4 | 1.356 (2) | C10—H10 | 0.9299 |
N7—C8 | 1.276 (2) | C13—H13A | 0.9701 |
N6—H6 | 0.8600 | C13—H13B | 0.9700 |
C0—C2 | 1.491 (3) | C16—H16 | 0.9299 |
C1—C2 | 1.345 (3) | C17—H17 | 0.9299 |
| | | |
C1—S5—C4 | 88.01 (8) | C10—C11—C15 | 122.50 (15) |
C11—O12—C13 | 105.99 (13) | O12—C13—O14 | 108.12 (14) |
C13—O14—C15 | 105.68 (14) | O14—C15—C16 | 128.29 (16) |
C2—N3—C4 | 109.33 (14) | O14—C15—C11 | 109.92 (14) |
N7—N6—C4 | 116.11 (13) | C11—C15—C16 | 121.79 (14) |
N6—N7—C8 | 116.83 (14) | C15—C16—C17 | 116.59 (16) |
C4—N6—H6 | 121.93 | C9—C17—C16 | 122.33 (16) |
N7—N6—H6 | 121.96 | S5—C1—H1 | 124.38 |
S5—C1—C2 | 111.24 (14) | C2—C1—H1 | 124.38 |
N3—C2—C1 | 115.26 (16) | N7—C8—H8 | 118.84 |
N3—C2—C0 | 119.51 (16) | C9—C8—H8 | 118.86 |
C0—C2—C1 | 125.23 (17) | C9—C10—H10 | 121.46 |
S5—C4—N6 | 119.82 (11) | C11—C10—H10 | 121.49 |
S5—C4—N3 | 116.15 (12) | O12—C13—H13A | 110.08 |
N3—C4—N6 | 124.03 (14) | O12—C13—H13B | 110.08 |
N7—C8—C9 | 122.30 (15) | O14—C13—H13A | 110.08 |
C8—C9—C17 | 118.44 (15) | O14—C13—H13B | 110.08 |
C10—C9—C17 | 119.73 (13) | H13A—C13—H13B | 108.41 |
C8—C9—C10 | 121.82 (14) | C15—C16—H16 | 121.70 |
C9—C10—C11 | 117.05 (14) | C17—C16—H16 | 121.70 |
O12—C11—C15 | 109.35 (12) | C9—C17—H17 | 118.84 |
O12—C11—C10 | 128.15 (15) | C16—C17—H17 | 118.83 |
| | | |
C1—S5—C4—N6 | −178.59 (14) | S5—C1—C2—N3 | −0.5 (2) |
C4—S5—C1—C2 | −0.19 (15) | S5—C1—C2—C0 | 178.26 (16) |
C1—S5—C4—N3 | 0.96 (14) | N7—C8—C9—C10 | 3.0 (2) |
C11—O12—C13—O14 | 9.60 (18) | N7—C8—C9—C17 | −177.43 (16) |
C13—O12—C11—C10 | 174.33 (16) | C10—C9—C17—C16 | −0.5 (2) |
C13—O12—C11—C15 | −6.17 (17) | C8—C9—C17—C16 | 179.90 (18) |
C15—O14—C13—O12 | −9.36 (17) | C8—C9—C10—C11 | −179.83 (14) |
C13—O14—C15—C16 | −175.03 (17) | C17—C9—C10—C11 | 0.6 (2) |
C13—O14—C15—C11 | 5.61 (17) | C9—C10—C11—C15 | −0.6 (2) |
C4—N3—C2—C1 | 1.2 (2) | C9—C10—C11—O12 | 178.85 (15) |
C2—N3—C4—S5 | −1.39 (17) | O12—C11—C15—C16 | −179.05 (15) |
C2—N3—C4—N6 | 178.13 (15) | O12—C11—C15—O14 | 0.36 (17) |
C4—N3—C2—C0 | −177.65 (16) | C10—C11—C15—C16 | 0.5 (2) |
N7—N6—C4—S5 | 1.98 (19) | C10—C11—C15—O14 | 179.88 (18) |
N7—N6—C4—N3 | −177.53 (14) | C11—C15—C16—C17 | −0.3 (2) |
C4—N6—N7—C8 | 179.46 (15) | O14—C15—C16—C17 | −179.63 (15) |
N6—N7—C8—C9 | 179.9 (2) | C15—C16—C17—C9 | 0.4 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N6—H6···N3i | 0.86 | 2.19 | 3.048 (2) | 172 |
Symmetry code: (i) −x+2, −y, −z+1. |
Crystal data top
C12H13N3O2S | F(000) = 552 |
Mr = 263.32 | Dx = 1.344 Mg m−3 |
Monoclinic, P21/c | Cu Kα radiation, λ = 1.54178 Å |
Hall symbol: -P 2ybc | Cell parameters from 25 reflections |
a = 14.738 (1) Å | θ = 35–45° |
b = 5.750 (1) Å | µ = 2.21 mm−1 |
c = 15.898 (1) Å | T = 293 K |
β = 105.02 (1)° | Prism, yellow |
V = 1301.2 (3) Å3 | 0.6 × 0.4 × 0.21 mm |
Z = 4 | |
Data collection top
Enraf Nonius CAD 4 diffractometer | 2333 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.030 |
Graphite monochromator | θmax = 71.9°, θmin = 3.1° |
θ/2θ scans | h = −18→17 |
Absorption correction: analytical North et al. (1968) | k = −7→5 |
Tmin = 0.336, Tmax = 0.660 | l = 0→19 |
3758 measured reflections | 3 standard reflections every 60 min |
2540 independent reflections | intensity decay: 1% |
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)] = 0.042 | H-atom parameters not refined |
wR(F2) = 0.135 | Calculated w = 1/[σ2(Fo2) + (0.0703P)2 + 0.3517P]
where P = (Fo2 + 2Fc2)/3 |
S = 1.11 | (Δ/σ)max = 0.001 |
2540 reflections | Δρmax = 0.30 e Å−3 |
167 parameters | Δρmin = −0.25 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0035 (5) |
Crystal data top
C12H13N3O2S | V = 1301.2 (3) Å3 |
Mr = 263.32 | Z = 4 |
Monoclinic, P21/c | Cu Kα radiation |
a = 14.738 (1) Å | µ = 2.21 mm−1 |
b = 5.750 (1) Å | T = 293 K |
c = 15.898 (1) Å | 0.6 × 0.4 × 0.21 mm |
β = 105.02 (1)° | |
Data collection top
Enraf Nonius CAD 4 diffractometer | 2333 reflections with I > 2σ(I) |
Absorption correction: analytical North et al. (1968) | Rint = 0.030 |
Tmin = 0.336, Tmax = 0.660 | 3 standard reflections every 60 min |
3758 measured reflections | intensity decay: 1% |
2540 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.135 | H-atom parameters not refined |
S = 1.11 | Δρmax = 0.30 e Å−3 |
2540 reflections | Δρmin = −0.25 e Å−3 |
167 parameters | |
Special details top
Geometry. Bond distances, angles etc. have been calculated using the rounded
fractional coordinates. All e.s.d.'s are estimated from the variances of the
(full) variance-covariance matrix. The cell e.s.d.'s are taken into account in
the estimation of distances, angles and torsion angles |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C0 | −0.19889 (19) | 0.2577 (7) | 0.0887 (2) | 0.1012 (11) | |
H0A | −0.2273 | 0.1440 | 0.0457 | 0.152* | |
H0B | −0.2469 | 0.3537 | 0.1015 | 0.152* | |
H0C | −0.1648 | 0.1803 | 0.1408 | 0.152* | |
C1 | −0.08248 (17) | 0.5943 (5) | 0.11810 (16) | 0.0692 (6) | |
H1A | −0.1205 | 0.6380 | 0.1571 | 0.074 (7)* | |
H1B | −0.0718 | 0.7317 | 0.0866 | 0.092 (9)* | |
C2 | −0.13261 (16) | 0.4067 (5) | 0.05427 (16) | 0.0672 (6) | |
H2 | −0.1673 | 0.4809 | 0.0000 | 0.085 (9)* | |
N3 | −0.05820 (12) | 0.2663 (3) | 0.03746 (12) | 0.0596 (5) | |
H3 | −0.0687 | 0.1533 | −0.0003 | 0.050* | |
C4 | 0.02269 (13) | 0.2579 (4) | 0.09979 (12) | 0.0495 (4) | |
S5 | 0.02832 (4) | 0.47341 (10) | 0.17933 (3) | 0.0597 (2) | |
N6 | 0.08724 (11) | 0.1051 (3) | 0.10000 (11) | 0.0548 (4) | |
N7 | 0.16639 (11) | 0.1413 (3) | 0.16895 (10) | 0.0514 (4) | |
C8 | 0.22709 (13) | −0.0193 (3) | 0.17883 (13) | 0.0506 (4) | |
H8 | 0.2158 | −0.1543 | 0.1389 | 0.050* | |
C9 | 0.31637 (13) | −0.0098 (3) | 0.24518 (12) | 0.0458 (4) | |
C10 | 0.33979 (13) | 0.1817 (3) | 0.30242 (12) | 0.0475 (4) | |
H10 | 0.2984 | 0.3049 | 0.3005 | 0.057* | |
C11 | 0.42579 (13) | 0.1774 (3) | 0.36064 (11) | 0.0469 (4) | |
O12 | 0.46423 (10) | 0.3403 (3) | 0.42296 (10) | 0.0628 (4) | |
C13 | 0.55967 (15) | 0.2700 (4) | 0.45742 (14) | 0.0612 (5) | |
H13A | 0.6013 | 0.3749 | 0.4376 | 0.073* | |
H13B | 0.5758 | 0.2741 | 0.5206 | 0.073* | |
O14 | 0.56982 (11) | 0.0399 (3) | 0.42813 (10) | 0.0639 (4) | |
C15 | 0.48911 (13) | −0.0032 (3) | 0.36400 (12) | 0.0485 (4) | |
C16 | 0.46836 (14) | −0.1908 (4) | 0.31048 (12) | 0.0522 (5) | |
H16 | 0.5107 | −0.3123 | 0.3134 | 0.063* | |
C17 | 0.38013 (13) | −0.1920 (3) | 0.25082 (12) | 0.0501 (4) | |
H17 | 0.3633 | −0.3185 | 0.2136 | 0.060* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C0 | 0.0680 (15) | 0.128 (3) | 0.112 (2) | −0.0048 (17) | 0.0307 (16) | −0.036 (2) |
C1 | 0.0724 (13) | 0.0618 (13) | 0.0698 (14) | 0.0151 (11) | 0.0118 (11) | −0.0135 (12) |
C2 | 0.0606 (12) | 0.0721 (14) | 0.0626 (12) | 0.0180 (11) | 0.0046 (10) | −0.0121 (11) |
N3 | 0.0522 (9) | 0.0648 (10) | 0.0561 (9) | 0.0057 (8) | 0.0039 (7) | −0.0207 (8) |
C4 | 0.0517 (9) | 0.0518 (10) | 0.0446 (9) | −0.0034 (8) | 0.0121 (8) | −0.0083 (8) |
S5 | 0.0721 (4) | 0.0556 (3) | 0.0467 (3) | 0.0055 (2) | 0.0065 (2) | −0.0135 (2) |
N6 | 0.0482 (8) | 0.0623 (10) | 0.0503 (9) | 0.0018 (7) | 0.0062 (7) | −0.0169 (8) |
N7 | 0.0485 (8) | 0.0574 (9) | 0.0459 (8) | −0.0021 (7) | 0.0078 (6) | −0.0106 (7) |
C8 | 0.0520 (10) | 0.0534 (10) | 0.0478 (10) | −0.0019 (8) | 0.0152 (8) | −0.0099 (8) |
C9 | 0.0503 (9) | 0.0478 (9) | 0.0426 (9) | −0.0016 (7) | 0.0177 (7) | −0.0013 (7) |
C10 | 0.0499 (9) | 0.0455 (9) | 0.0488 (9) | 0.0019 (7) | 0.0157 (7) | −0.0025 (8) |
C11 | 0.0543 (9) | 0.0465 (9) | 0.0414 (9) | −0.0034 (8) | 0.0151 (7) | 0.0007 (7) |
O12 | 0.0641 (8) | 0.0574 (9) | 0.0595 (8) | −0.0015 (7) | 0.0025 (7) | −0.0105 (7) |
C13 | 0.0597 (11) | 0.0718 (14) | 0.0477 (10) | −0.0055 (10) | 0.0058 (9) | 0.0014 (10) |
O14 | 0.0588 (8) | 0.0718 (10) | 0.0537 (8) | 0.0068 (7) | 0.0014 (6) | 0.0044 (7) |
C15 | 0.0517 (10) | 0.0545 (10) | 0.0399 (9) | 0.0029 (8) | 0.0132 (7) | 0.0094 (8) |
C16 | 0.0610 (11) | 0.0530 (11) | 0.0461 (9) | 0.0121 (8) | 0.0202 (8) | 0.0074 (8) |
C17 | 0.0613 (11) | 0.0479 (10) | 0.0447 (9) | 0.0027 (8) | 0.0203 (8) | −0.0020 (8) |
Geometric parameters (Å, º) top
C0—C2 | 1.504 (4) | C8—H8 | 0.9890 |
C0—H0A | 0.9600 | C9—C17 | 1.395 (3) |
C0—H0B | 0.9600 | C9—C10 | 1.413 (3) |
C0—H0C | 0.9600 | C10—C11 | 1.362 (3) |
C1—C2 | 1.533 (3) | C10—H10 | 0.9300 |
C1—S5 | 1.809 (2) | C11—O12 | 1.375 (2) |
C1—H1A | 0.9700 | C11—C15 | 1.388 (3) |
C1—H1B | 0.9700 | O12—C13 | 1.429 (3) |
C2—N3 | 1.441 (3) | C13—O14 | 1.424 (3) |
C2—H2 | 0.9800 | C13—H13A | 0.9700 |
N3—C4 | 1.339 (3) | C13—H13B | 0.9700 |
N3—H3 | 0.8707 | O14—C15 | 1.374 (2) |
C4—N6 | 1.294 (3) | C15—C16 | 1.359 (3) |
C4—S5 | 1.7569 (19) | C16—C17 | 1.397 (3) |
N6—N7 | 1.394 (2) | C16—H16 | 0.9300 |
N7—C8 | 1.267 (3) | C17—H17 | 0.9300 |
C8—C9 | 1.459 (3) | | |
| | | |
C2—C0—H0A | 109.5 | N7—C8—H8 | 119.8 |
C2—C0—H0B | 109.5 | C9—C8—H8 | 117.6 |
H0A—C0—H0B | 109.5 | C17—C9—C10 | 119.73 (18) |
C2—C0—H0C | 109.5 | C17—C9—C8 | 118.99 (17) |
H0A—C0—H0C | 109.5 | C10—C9—C8 | 121.28 (17) |
H0B—C0—H0C | 109.5 | C11—C10—C9 | 116.90 (17) |
C2—C1—S5 | 107.37 (16) | C11—C10—H10 | 121.5 |
C2—C1—H1A | 110.2 | C9—C10—H10 | 121.5 |
S5—C1—H1A | 110.2 | C10—C11—O12 | 127.91 (17) |
C2—C1—H1B | 110.2 | C10—C11—C15 | 122.53 (18) |
S5—C1—H1B | 110.2 | O12—C11—C15 | 109.56 (16) |
H1A—C1—H1B | 108.5 | C11—O12—C13 | 105.32 (16) |
N3—C2—C0 | 110.2 (2) | O14—C13—O12 | 108.30 (17) |
N3—C2—C1 | 104.93 (18) | O14—C13—H13A | 110.0 |
C0—C2—C1 | 114.0 (2) | O12—C13—H13A | 110.0 |
N3—C2—H2 | 109.2 | O14—C13—H13B | 110.0 |
C0—C2—H2 | 109.2 | O12—C13—H13B | 110.0 |
C1—C2—H2 | 109.2 | H13A—C13—H13B | 108.4 |
C4—N3—C2 | 117.19 (17) | C15—O14—C13 | 105.43 (15) |
C4—N3—H3 | 116.7 | C16—C15—O14 | 128.22 (18) |
C2—N3—H3 | 122.5 | C16—C15—C11 | 122.00 (18) |
N6—C4—N3 | 122.62 (17) | O14—C15—C11 | 109.77 (17) |
N6—C4—S5 | 125.39 (14) | C15—C16—C17 | 116.59 (18) |
N3—C4—S5 | 111.99 (15) | C15—C16—H16 | 121.7 |
C4—S5—C1 | 90.92 (10) | C17—C16—H16 | 121.7 |
C4—N6—N7 | 111.45 (16) | C9—C17—C16 | 122.22 (18) |
C8—N7—N6 | 114.15 (16) | C9—C17—H17 | 118.9 |
N7—C8—C9 | 122.54 (17) | C16—C17—H17 | 118.9 |
| | | |
S5—C1—C2—N3 | −27.7 (3) | C9—C10—C11—O12 | −179.43 (17) |
S5—C1—C2—C0 | 92.9 (2) | C9—C10—C11—C15 | 0.8 (3) |
C0—C2—N3—C4 | −96.2 (3) | C10—C11—O12—C13 | −171.82 (19) |
C1—C2—N3—C4 | 26.9 (3) | C15—C11—O12—C13 | 7.9 (2) |
C2—N3—C4—N6 | 166.1 (2) | C11—O12—C13—O14 | −12.6 (2) |
C2—N3—C4—S5 | −13.1 (3) | O12—C13—O14—C15 | 12.4 (2) |
N6—C4—S5—C1 | 176.1 (2) | C13—O14—C15—C16 | 173.63 (19) |
N3—C4—S5—C1 | −4.62 (18) | C13—O14—C15—C11 | −7.5 (2) |
C2—C1—S5—C4 | 19.02 (19) | C10—C11—C15—C16 | −1.6 (3) |
N3—C4—N6—N7 | 176.72 (19) | O12—C11—C15—C16 | 178.65 (17) |
S5—C4—N6—N7 | −4.1 (3) | C10—C11—C15—O14 | 179.45 (17) |
C4—N6—N7—C8 | 171.73 (18) | O12—C11—C15—O14 | −0.3 (2) |
N6—N7—C8—C9 | 177.58 (17) | O14—C15—C16—C17 | 179.53 (18) |
N7—C8—C9—C17 | −178.90 (18) | C11—C15—C16—C17 | 0.8 (3) |
N7—C8—C9—C10 | 0.0 (3) | C10—C9—C17—C16 | −1.4 (3) |
C17—C9—C10—C11 | 0.6 (3) | C8—C9—C17—C16 | 177.57 (17) |
C8—C9—C10—C11 | −178.33 (17) | C15—C16—C17—C9 | 0.7 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···N6i | 0.87 | 2.139 | 3.005 (2) | 174.6 |
Symmetry code: (i) −x, −y, −z. |
Experimental details
| (I) | (IIb) |
Crystal data |
Chemical formula | C12H11N3O2S | C12H13N3O2S |
Mr | 261.31 | 263.32 |
Crystal system, space group | Monoclinic, P21/n | Monoclinic, P21/c |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 6.219 (1), 12.163 (2), 15.855 (1) | 14.738 (1), 5.750 (1), 15.898 (1) |
β (°) | 91.13 (1) | 105.02 (1) |
V (Å3) | 1199.1 (3) | 1301.2 (3) |
Z | 4 | 4 |
Radiation type | Cu Kα | Cu Kα |
µ (mm−1) | 2.40 | 2.21 |
Crystal size (mm) | 0.6 × 0.4 × 0.09 | 0.6 × 0.4 × 0.21 |
|
Data collection |
Diffractometer | Enraf Nonius CAD 4 diffractometer | Enraf Nonius CAD 4 diffractometer |
Absorption correction | Analytical North et al. (1968) | Analytical North et al. (1968) |
Tmin, Tmax | 0.393, 0.805 | 0.336, 0.660 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3882, 2356, 2066 | 3758, 2540, 2333 |
Rint | 0.015 | 0.030 |
(sin θ/λ)max (Å−1) | 0.616 | 0.616 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.106, 1.09 | 0.042, 0.135, 1.11 |
No. of reflections | 2356 | 2540 |
No. of parameters | 164 | 167 |
H-atom treatment | H-atom parameters not refined | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.23, −0.28 | 0.30, −0.25 |
Selected geometric parameters (Å, º) for (I) topN3—C4 | 1.3071 (19) | N7—C8 | 1.276 (2) |
N3—C2 | 1.394 (2) | C1—C2 | 1.345 (3) |
N6—N7 | 1.3714 (18) | C8—C9 | 1.457 (2) |
N6—C4 | 1.356 (2) | | |
| | | |
C2—N3—C4 | 109.33 (14) | N3—C2—C1 | 115.26 (16) |
N7—N6—C4 | 116.11 (13) | N3—C4—N6 | 124.03 (14) |
N6—N7—C8 | 116.83 (14) | N7—C8—C9 | 122.30 (15) |
S5—C1—C2 | 111.24 (14) | | |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N6—H6···N3i | 0.86 | 2.194 | 3.048 (2) | 172.0 |
Symmetry code: (i) −x+2, −y, −z+1. |
Selected geometric parameters (Å, º) for (IIb) topC1—C2 | 1.533 (3) | N6—N7 | 1.394 (2) |
C2—N3 | 1.441 (3) | N7—C8 | 1.267 (3) |
N3—C4 | 1.339 (3) | C8—C9 | 1.459 (3) |
C4—N6 | 1.294 (3) | | |
| | | |
C2—C1—S5 | 107.37 (16) | C8—N7—N6 | 114.15 (16) |
C4—N3—C2 | 117.19 (17) | N7—C8—C9 | 122.54 (17) |
N6—C4—N3 | 122.62 (17) | | |
Hydrogen-bond geometry (Å, º) for (IIb) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···N6i | 0.87 | 2.139 | 3.005 (2) | 174.6 |
Symmetry code: (i) −x, −y, −z. |
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Reduction of N-(3,4-methylenedioxy) benzylidene hydrazino methylthiazole (1) has been reported to lead to the corresponding benzyl analogue (2) (Mazzone et al., 1992; Pignatello et al., 1994; Cambria et al., 1996; Gritsch et al., 2001). Determination of the crystal structures of both compounds has been undertaken in order to clarify the mechanism of reduction of (1). The structural evidence given in this work demonstrates that the product of the reaction is the (2 b) isomer. The crystal structure further establishes that the tautomeric form of this product is the one with an H on the endocyclic N3 nitrogen.
Both compounds adopt an extended conformation (Fig. 1) with torsion angles N3—C4—N6—N7 [-177.53 (14) and 176.72 (19)° for (1) and (2) respectively], C4—N6—N7—C8 [179.46 (15) and 171.73 (18)°], and N6—N7—C8—C9 [179.9 (2) and 177.6 (2)°] close to 180°. A similar anti E conformation is observed for related substituted thiazol-2-yl hydrazines in solution as demonstrated by NMR data and ab initio calculations in water (Wouters et al., 2001).
For the fully oxidized molecule (1), analysis of the bond lengths and angles confirm an sp2 hybridation of all C and N atoms of the benzylidene hydrazino thiazole fragment. The C1—C2 [1.345 (3) Å], C2—N3 [1.394 (2) Å], N3—C4 [1.3071 (19) Å], C4—N6 [1.356 (2) Å], N6—N7 [1.3714 (18) Å], and N7—C8 (1.276 (2) Å) bond lengths are intermediate between C—C or C—N single and double bonds. The alternation of shorter and longer bonds further confirms electron delocalization along the whole molecule.
In the reduced product (2), C1 and C2 adopt a (sp3) tetrahedral geometry as demonstrated by the C2—C1—S5 [107.37 (15)°] and C1—C2—N3 [104.93 (18)°] valence angles. The C1—C2 bond [1.533 (3) Å] is significantly longer that the corresponding bond in molecule (1). In (2), the C4—N3 bond [1.339 (3) Å] is also longer than the C4—N6 bond [1.294 (3) Å]. The opposite is observed in (1). Analysis of the geometry therefore strongly suggests that the structure of the reduction product of (1) is the (2 b) isomer and not (2a).
Unambiguous localization from the difference Fourier map of an hydrogen on endocyclic N3 nitrogen in (2) establishes the tautomeric preference of the reduction product. Recent results obtained by energy calculations at the HF/6–31 G(d) and MP2/6–31 G(d) levels confirm the stability of the endocyclic N3 tautomeric form (Wouters et al., 2001).
In compound (2), the hydrogen on endocyclic nitrogen N3 is involved in an H bond connecting N3 to N6 [N3···N6 = 3.005 (2) Å, Table 1]. As a consequence of this H bond, molecules form interesting dimers in the crystal packing as illustrated in the ORTEP plot (Fig. 1).
A similar dimeric assembly is observed in the crystal structure of compound (1). The same nitrogen atoms are involved in the stabilization via H bond. In contrast to structure (2), the H donor in (1) is the exocyclic nitrogen N6 [N6···N3 = 3.048 (2) Å, Table 1].