organic compounds
(1E,2E)-1,2-Bis[(1-benzyloxymethyl-1H-indol-3-yl)methylidene]hydrazine
aDepartment of Chemistry, Louisiana State University, Baton Rouge, LA 70803-1804, USA
*Correspondence e-mail: ffroncz@lsu.edu
The title compound, C34H30N4O2, lies on an inversion center and consists of two 3-substituted-1H-indole units linked by a 1,2-dimethylenehydrazine bridge. It is one of numerous examples in which two aromatic ring systems are joined by this 4-atom bridge. The geometry of the centrosymmetric bridge is: C(arom)—C = 1.444 (3), C=N = 1.284 (3), N—N = 1.414 (4) Å, C(arom)—C=N = 122.6 (2) and C=N—N = 111.9 (2)°. The nine non-H atoms of the indole unit lie in a plane (δr.m.s. = 0.0089 Å) which is twisted 6.0 (2)° with respect to the hydrazine bridge plane. The benzyloxymethyl substituents do not lie in the plane of the rest of the molecule and are in a folded rather than an extended conformation. This is described by the three torsion angles in the middle of the C=N—C—O—CBz group, viz. 98.5 (3), −62.1 (3), and −66.3 (2)°.
Related literature
For the synthesis, see: Shui (1994). For related structures, see: Burke-Laing & Laing (1976); Mom & de With (1978); Biswas et al. (1999); Rizal et al. (2008). For a description of the Cambridge Structural Database, see: Allen (2002).
Experimental
Crystal data
|
Data collection: COLLECT (Nonius, 2000); cell HKL SCALEPACK (Otwinowski & Minor 1997); data reduction: HKL DENZO and SCALEPACK (Otwinowski & Minor 1997); program(s) used to solve structure: SHELXS86 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999).
Supporting information
10.1107/S1600536812042493/pk2449sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812042493/pk2449Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812042493/pk2449Isup3.cml
The synthesis of I is detailed by Shui (1994), who prepared a suitable single-crystal by recrystallization from dichloromethane.
All H atoms were placed in calculated positions, guided by difference maps, with C—H bond distances 0.95 (aromatic C) and 0.99 (alkyl C) Å, and Uiso=1.2Ueq, thereafter refined as riding.
Data collection: COLLECT (Nonius, 2000); cell
HKL SCALEPACK (Otwinowski & Minor 1997); data reduction: HKL DENZO and SCALEPACK (Otwinowski & Minor 1997); program(s) used to solve structure: SHELXS86 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999).C34H30N4O2 | F(000) = 556 |
Mr = 526.62 | Dx = 1.285 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 2472 reflections |
a = 12.8518 (10) Å | θ = 2.6–26.0° |
b = 7.9663 (9) Å | µ = 0.08 mm−1 |
c = 13.6810 (12) Å | T = 90 K |
β = 103.672 (5)° | Fragment, colorless |
V = 1361.0 (2) Å3 | 0.18 × 0.10 × 0.05 mm |
Z = 2 |
Nonius KappaCCD diffractometer | 2678 independent reflections |
Radiation source: sealed tube | 1481 reflections with I > 2σ(I) |
Horizonally mounted graphite crystal monochromator | Rint = 0.067 |
Detector resolution: 9 pixels mm-1 | θmax = 26.0°, θmin = 3.0° |
CCD rotation images, thick slices scans | h = −15→15 |
Absorption correction: multi-scan (HKL SCALEPACK; Otwinowski & Minor 1997) | k = −8→9 |
Tmin = 0.986, Tmax = 0.996 | l = −16→16 |
4340 measured reflections |
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)] = 0.056 | H-atom parameters constrained |
wR(F2) = 0.126 | w = 1/[σ2(Fo2) + (0.0483P)2 + 0.249P] where P = (Fo2 + 2Fc2)/3 |
S = 0.99 | (Δ/σ)max = 0.001 |
2678 reflections | Δρmax = 0.25 e Å−3 |
182 parameters | Δρmin = −0.25 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 constraints | Extinction coefficient: 0.0062 (13) |
Primary atom site location: structure-invariant direct methods |
C34H30N4O2 | V = 1361.0 (2) Å3 |
Mr = 526.62 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 12.8518 (10) Å | µ = 0.08 mm−1 |
b = 7.9663 (9) Å | T = 90 K |
c = 13.6810 (12) Å | 0.18 × 0.10 × 0.05 mm |
β = 103.672 (5)° |
Nonius KappaCCD diffractometer | 2678 independent reflections |
Absorption correction: multi-scan (HKL SCALEPACK; Otwinowski & Minor 1997) | 1481 reflections with I > 2σ(I) |
Tmin = 0.986, Tmax = 0.996 | Rint = 0.067 |
4340 measured reflections |
R[F2 > 2σ(F2)] = 0.056 | 0 restraints |
wR(F2) = 0.126 | H-atom parameters constrained |
S = 0.99 | Δρmax = 0.25 e Å−3 |
2678 reflections | Δρmin = −0.25 e Å−3 |
182 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. |
x | y | z | Uiso*/Ueq | ||
N1 | 0.02086 (15) | 0.0030 (3) | 0.55263 (14) | 0.0211 (5) | |
C1 | 0.11765 (18) | −0.0511 (3) | 0.57786 (17) | 0.0206 (6) | |
H1 | 0.15 | −0.0917 | 0.5268 | 0.025* | |
C2 | 0.17927 (18) | −0.0526 (3) | 0.68083 (16) | 0.0191 (6) | |
C3 | 0.14858 (18) | −0.0067 (3) | 0.77188 (17) | 0.0180 (6) | |
C4 | 0.05355 (19) | 0.0445 (3) | 0.79619 (18) | 0.0207 (6) | |
H4 | −0.0108 | 0.0538 | 0.7452 | 0.025* | |
C5 | 0.05426 (19) | 0.0813 (3) | 0.89494 (18) | 0.0236 (6) | |
H5 | −0.0098 | 0.1178 | 0.9115 | 0.028* | |
C6 | 0.14857 (19) | 0.0654 (3) | 0.97152 (19) | 0.0258 (7) | |
H6 | 0.147 | 0.0915 | 1.0389 | 0.031* | |
C7 | 0.24299 (19) | 0.0127 (3) | 0.95068 (17) | 0.0226 (6) | |
H7 | 0.3066 | 0.0011 | 1.0023 | 0.027* | |
C8 | 0.24147 (18) | −0.0229 (3) | 0.85072 (17) | 0.0182 (6) | |
N2 | 0.32454 (15) | −0.0785 (3) | 0.81007 (14) | 0.0190 (5) | |
C9 | 0.28592 (19) | −0.0961 (3) | 0.70805 (17) | 0.0205 (6) | |
H9 | 0.3269 | −0.133 | 0.6628 | 0.025* | |
C10 | 0.43362 (18) | −0.1094 (3) | 0.86494 (18) | 0.0218 (6) | |
H10A | 0.4327 | −0.1657 | 0.9293 | 0.026* | |
H10B | 0.468 | −0.1866 | 0.8254 | 0.026* | |
O1 | 0.49589 (12) | 0.0398 (2) | 0.88566 (11) | 0.0225 (4) | |
C11 | 0.50844 (19) | 0.1279 (3) | 0.79804 (18) | 0.0241 (6) | |
H11A | 0.5435 | 0.237 | 0.8194 | 0.029* | |
H11B | 0.4365 | 0.152 | 0.7552 | 0.029* | |
C12 | 0.57299 (18) | 0.0365 (3) | 0.73523 (18) | 0.0219 (6) | |
C13 | 0.5658 (2) | 0.0890 (3) | 0.63721 (18) | 0.0276 (7) | |
H13 | 0.5168 | 0.1754 | 0.6092 | 0.033* | |
C14 | 0.6293 (2) | 0.0168 (4) | 0.57959 (19) | 0.0329 (7) | |
H14 | 0.6248 | 0.0562 | 0.5132 | 0.039* | |
C15 | 0.6992 (2) | −0.1122 (4) | 0.6180 (2) | 0.0352 (7) | |
H15 | 0.7423 | −0.1619 | 0.5782 | 0.042* | |
C16 | 0.7056 (2) | −0.1679 (4) | 0.71520 (19) | 0.0328 (7) | |
H16 | 0.7525 | −0.2576 | 0.7419 | 0.039* | |
C17 | 0.64369 (19) | −0.0929 (3) | 0.77379 (19) | 0.0263 (7) | |
H17 | 0.6497 | −0.1304 | 0.8408 | 0.032* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0247 (12) | 0.0193 (12) | 0.0164 (10) | 0.0004 (11) | −0.0011 (9) | −0.0027 (10) |
C1 | 0.0221 (14) | 0.0174 (15) | 0.0212 (13) | −0.0012 (12) | 0.0030 (11) | −0.0005 (11) |
C2 | 0.0203 (12) | 0.0162 (14) | 0.0186 (13) | 0.0005 (11) | 0.0004 (10) | −0.0009 (11) |
C3 | 0.0209 (12) | 0.0141 (14) | 0.0185 (13) | −0.0019 (12) | 0.0038 (10) | 0.0015 (11) |
C4 | 0.0190 (12) | 0.0189 (14) | 0.0225 (14) | −0.0022 (12) | 0.0017 (10) | 0.0011 (12) |
C5 | 0.0235 (13) | 0.0229 (16) | 0.0272 (14) | −0.0017 (12) | 0.0116 (11) | 0.0002 (12) |
C6 | 0.0292 (15) | 0.0261 (17) | 0.0228 (14) | −0.0024 (13) | 0.0074 (12) | −0.0007 (12) |
C7 | 0.0253 (13) | 0.0217 (15) | 0.0189 (13) | 0.0000 (13) | 0.0016 (11) | −0.0007 (12) |
C8 | 0.0196 (12) | 0.0136 (14) | 0.0218 (13) | −0.0007 (12) | 0.0059 (10) | 0.0000 (11) |
N2 | 0.0198 (11) | 0.0198 (13) | 0.0161 (11) | 0.0003 (9) | 0.0013 (8) | −0.0012 (9) |
C9 | 0.0237 (13) | 0.0197 (15) | 0.0172 (13) | 0.0002 (12) | 0.0031 (10) | −0.0017 (11) |
C10 | 0.0214 (13) | 0.0179 (15) | 0.0242 (14) | 0.0003 (12) | 0.0016 (11) | 0.0000 (12) |
O1 | 0.0240 (9) | 0.0201 (10) | 0.0220 (9) | −0.0030 (8) | 0.0025 (7) | −0.0021 (8) |
C11 | 0.0241 (13) | 0.0227 (15) | 0.0252 (14) | −0.0006 (12) | 0.0052 (11) | 0.0048 (12) |
C12 | 0.0209 (13) | 0.0204 (14) | 0.0224 (13) | −0.0035 (12) | 0.0016 (11) | −0.0009 (12) |
C13 | 0.0292 (14) | 0.0246 (16) | 0.0274 (15) | −0.0002 (13) | 0.0031 (12) | 0.0045 (13) |
C14 | 0.0357 (15) | 0.0386 (19) | 0.0251 (15) | −0.0055 (15) | 0.0088 (12) | −0.0007 (14) |
C15 | 0.0326 (16) | 0.0410 (19) | 0.0348 (17) | 0.0004 (15) | 0.0136 (13) | −0.0079 (15) |
C16 | 0.0295 (15) | 0.0346 (18) | 0.0324 (16) | 0.0066 (14) | 0.0036 (12) | −0.0025 (14) |
C17 | 0.0229 (14) | 0.0330 (17) | 0.0218 (14) | 0.0017 (13) | 0.0030 (11) | −0.0008 (13) |
N1—C1 | 1.284 (3) | C9—H9 | 0.95 |
N1—N1i | 1.414 (4) | C10—O1 | 1.424 (3) |
C1—C2 | 1.444 (3) | C10—H10A | 0.99 |
C1—H1 | 0.95 | C10—H10B | 0.99 |
C2—C9 | 1.377 (3) | O1—C11 | 1.431 (3) |
C2—C3 | 1.440 (3) | C11—C12 | 1.514 (3) |
C3—C4 | 1.400 (3) | C11—H11A | 0.99 |
C3—C8 | 1.413 (3) | C11—H11B | 0.99 |
C4—C5 | 1.380 (3) | C12—C13 | 1.387 (3) |
C4—H4 | 0.95 | C12—C17 | 1.393 (4) |
C5—C6 | 1.408 (3) | C13—C14 | 1.386 (3) |
C5—H5 | 0.95 | C13—H13 | 0.95 |
C6—C7 | 1.376 (3) | C14—C15 | 1.384 (4) |
C6—H6 | 0.95 | C14—H14 | 0.95 |
C7—C8 | 1.392 (3) | C15—C16 | 1.385 (4) |
C7—H7 | 0.95 | C15—H15 | 0.95 |
C8—N2 | 1.388 (3) | C16—C17 | 1.391 (3) |
N2—C9 | 1.373 (3) | C16—H16 | 0.95 |
N2—C10 | 1.446 (3) | C17—H17 | 0.95 |
C1—N1—N1i | 111.9 (2) | O1—C10—N2 | 113.05 (19) |
N1—C1—C2 | 122.6 (2) | O1—C10—H10A | 109 |
N1—C1—H1 | 118.7 | N2—C10—H10A | 109 |
C2—C1—H1 | 118.7 | O1—C10—H10B | 109 |
C9—C2—C3 | 106.77 (19) | N2—C10—H10B | 109 |
C9—C2—C1 | 123.2 (2) | H10A—C10—H10B | 107.8 |
C3—C2—C1 | 130.0 (2) | C10—O1—C11 | 114.34 (17) |
C4—C3—C8 | 118.2 (2) | O1—C11—C12 | 115.2 (2) |
C4—C3—C2 | 135.4 (2) | O1—C11—H11A | 108.5 |
C8—C3—C2 | 106.41 (19) | C12—C11—H11A | 108.5 |
C5—C4—C3 | 119.3 (2) | O1—C11—H11B | 108.5 |
C5—C4—H4 | 120.3 | C12—C11—H11B | 108.5 |
C3—C4—H4 | 120.3 | H11A—C11—H11B | 107.5 |
C4—C5—C6 | 121.0 (2) | C13—C12—C17 | 118.5 (2) |
C4—C5—H5 | 119.5 | C13—C12—C11 | 118.9 (2) |
C6—C5—H5 | 119.5 | C17—C12—C11 | 122.5 (2) |
C7—C6—C5 | 121.3 (2) | C12—C13—C14 | 120.8 (2) |
C7—C6—H6 | 119.4 | C12—C13—H13 | 119.6 |
C5—C6—H6 | 119.4 | C14—C13—H13 | 119.6 |
C6—C7—C8 | 117.2 (2) | C15—C14—C13 | 120.5 (2) |
C6—C7—H7 | 121.4 | C15—C14—H14 | 119.7 |
C8—C7—H7 | 121.4 | C13—C14—H14 | 119.7 |
N2—C8—C7 | 128.7 (2) | C16—C15—C14 | 119.3 (3) |
N2—C8—C3 | 108.3 (2) | C16—C15—H15 | 120.4 |
C7—C8—C3 | 123.0 (2) | C14—C15—H15 | 120.4 |
C9—N2—C8 | 108.20 (19) | C15—C16—C17 | 120.2 (3) |
C9—N2—C10 | 125.7 (2) | C15—C16—H16 | 119.9 |
C8—N2—C10 | 126.11 (19) | C17—C16—H16 | 119.9 |
N2—C9—C2 | 110.3 (2) | C16—C17—C12 | 120.7 (2) |
N2—C9—H9 | 124.9 | C16—C17—H17 | 119.6 |
C2—C9—H9 | 124.9 | C12—C17—H17 | 119.6 |
C1i—N1i—N1—C1 | 180 | C7—C8—N2—C10 | −1.0 (4) |
N1i—N1—C1—C2 | 177.9 (2) | C3—C8—N2—C10 | 179.2 (2) |
N1—C1—C2—C9 | −174.1 (2) | C8—N2—C9—C2 | 0.2 (3) |
N1—C1—C2—C3 | 3.4 (4) | C10—N2—C9—C2 | −178.6 (2) |
C9—C2—C3—C4 | −178.3 (3) | C3—C2—C9—N2 | −0.8 (3) |
C1—C2—C3—C4 | 4.0 (5) | C1—C2—C9—N2 | 177.2 (2) |
C9—C2—C3—C8 | 1.0 (3) | C9—N2—C10—O1 | 98.5 (3) |
C1—C2—C3—C8 | −176.8 (2) | C8—N2—C10—O1 | −80.1 (3) |
C8—C3—C4—C5 | 1.6 (4) | N2—C10—O1—C11 | −62.1 (3) |
C2—C3—C4—C5 | −179.2 (3) | C10—O1—C11—C12 | −66.3 (2) |
C3—C4—C5—C6 | −1.0 (4) | O1—C11—C12—C13 | 163.0 (2) |
C4—C5—C6—C7 | 0.0 (4) | O1—C11—C12—C17 | −20.4 (3) |
C5—C6—C7—C8 | 0.5 (4) | C17—C12—C13—C14 | −1.4 (4) |
C6—C7—C8—N2 | −179.5 (2) | C11—C12—C13—C14 | 175.3 (2) |
C6—C7—C8—C3 | 0.2 (4) | C12—C13—C14—C15 | 1.7 (4) |
C4—C3—C8—N2 | 178.5 (2) | C13—C14—C15—C16 | −0.4 (4) |
C2—C3—C8—N2 | −0.9 (3) | C14—C15—C16—C17 | −1.0 (4) |
C4—C3—C8—C7 | −1.2 (4) | C15—C16—C17—C12 | 1.3 (4) |
C2—C3—C8—C7 | 179.4 (2) | C13—C12—C17—C16 | 0.0 (4) |
C7—C8—N2—C9 | −179.8 (3) | C11—C12—C17—C16 | −176.7 (2) |
C3—C8—N2—C9 | 0.4 (3) |
Symmetry code: (i) −x, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C34H30N4O2 |
Mr | 526.62 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 90 |
a, b, c (Å) | 12.8518 (10), 7.9663 (9), 13.6810 (12) |
β (°) | 103.672 (5) |
V (Å3) | 1361.0 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.18 × 0.10 × 0.05 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (HKL SCALEPACK; Otwinowski & Minor 1997) |
Tmin, Tmax | 0.986, 0.996 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4340, 2678, 1481 |
Rint | 0.067 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.056, 0.126, 0.99 |
No. of reflections | 2678 |
No. of parameters | 182 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.25, −0.25 |
Computer programs: COLLECT (Nonius, 2000), HKL SCALEPACK (Otwinowski & Minor 1997), HKL DENZO and SCALEPACK (Otwinowski & Minor 1997), SHELXS86 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX publication routines (Farrugia, 1999).
Acknowledgements
The purchase of the diffractometer was made possible by grant No. LEQSF(1999–2000)-ENH-TR-13, administered by the Louisiana Board of Regents. We thank Dr Lee Shui for kindly providing the sample.
References
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Title compound I was synthesized as part of a project targeting the synthesis of tryptophan and other tyrosine derivatives (Shui, 1994). The molecule occupies a crystallographic inversion center and consists of two 3-substituted 1H-indole moieties linked by a (1E,2E)-1,2-dimethylenehydrazine bridge, one of numerous examples in which two aromatic ring systems are joined by this 4-atom bridge. The bridge geometry is consistent with that found, for example, in Ph—CH═N—N═CH—Ph [CAS:1048662–10-7, Mom & de With (1978); Burke-Laing & Laing (1976); CSD:BZAZIN02, BZAZIN11, respectively, Allen (2002)]. The geometry of the indole is also consistent with that found in other 1,3-disubstituted indoles [e.g., CSD:OBAVIW, CAS:256391–53-4, Biswas et al. (1999)].