(1E,2E)-1,2-Bis[(1-benzyloxymethyl-1H-indol-3-yl)methylidene]hydrazine

Myers, J.A.; Fronczek, F.R.; Watkins, S.F.

doi:10.1107/S1600536812042493

organic compounds

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ISSN: 2056-9890

Volume 68| Part 11| November 2012| Page o3158

doi:10.1107/S1600536812042493

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(1E,2E)-1,2-Bis[(1-benzyloxymethyl-1H-indol-3-yl)methylidene]hydrazine

Jacob A. Myers,^a Frank R. Fronczek ^a ^* and Steven F. Watkins ^a

^aDepartment of Chemistry, Louisiana State University, Baton Rouge, LA 70803-1804, USA
^*Correspondence e-mail: ffroncz@lsu.edu

(Received 8 October 2012; accepted 10 October 2012; online 20 October 2012)

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 (δ_r.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—C_Bz 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

C₃₄H₃₀N₄O₂
M_r = 526.62
Monoclinic, P 2₁ /n
a = 12.8518 (10) Å
b = 7.9663 (9) Å
c = 13.6810 (12) Å
β = 103.672 (5)°
V = 1361.0 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 90 K
0.18 × 0.10 × 0.05 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (HKL SCALEPACK; Otwinowski & Minor 1997 ) T_min = 0.986, T_max = 0.996
4340 measured reflections
2678 independent reflections
1481 reflections with I > 2σ(I)
R_int = 0.067

Refinement

R[F² > 2σ(F²)] = 0.056
wR(F²) = 0.126
S = 0.99
2678 reflections
182 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: COLLECT (Nonius, 2000 ); cell refinement: 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

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812042493/pk2449sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812042493/pk2449Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812042493/pk2449Isup3.cml

checkCIF report

Comment top

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)].

Related literature top

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 top

The synthesis of I is detailed by Shui (1994), who prepared a suitable single-crystal by recrystallization from dichloromethane.

Computing details top

Data collection: COLLECT (Nonius, 2000); cell refinement: 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).

Figures top

Fig. 1. View of (I) (50% probability displacement ellipsoids)

(1E,2E)-1,2-Bis[(1-benzyloxymethyl-1H-indol- 3-yl)methylidene]hydrazine top

Crystal data top

C₃₄H₃₀N₄O₂	F(000) = 556
M_r = 526.62	D_x = 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

Data collection top

Nonius KappaCCD diffractometer	2678 independent reflections
Radiation source: sealed tube	1481 reflections with I > 2σ(I)
Horizonally mounted graphite crystal monochromator	R_int = 0.067
Detector resolution: 9 pixels mm^-1	θ_max = 26.0°, θ_min = 3.0°
CCD rotation images, thick slices scans	h = −15→15
Absorption correction: multi-scan (HKL SCALEPACK; Otwinowski & Minor 1997)	k = −8→9
T_min = 0.986, T_max = 0.996	l = −16→16
4340 measured reflections

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)] = 0.056	H-atom parameters constrained
wR(F²) = 0.126	w = 1/[σ²(F_o²) + (0.0483P)² + 0.249P] where P = (F_o² + 2F_c²)/3
S = 0.99	(Δ/σ)_max = 0.001
2678 reflections	Δρ_max = 0.25 e Å⁻³
182 parameters	Δρ_min = −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

Crystal data top

C₃₄H₃₀N₄O₂	V = 1361.0 (2) Å³
M_r = 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)°

Data collection top

Nonius KappaCCD diffractometer	2678 independent reflections
Absorption correction: multi-scan (HKL SCALEPACK; Otwinowski & Minor 1997)	1481 reflections with I > 2σ(I)
T_min = 0.986, T_max = 0.996	R_int = 0.067
4340 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	0 restraints
wR(F²) = 0.126	H-atom parameters constrained
S = 0.99	Δρ_max = 0.25 e Å⁻³
2678 reflections	Δρ_min = −0.25 e Å⁻³
182 parameters

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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
M_r	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)
T_min, T_max	0.986, 0.996
No. of measured, independent and observed [I > 2σ(I)] reflections	4340, 2678, 1481
R_int	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
Δρ_max, Δρ_min (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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