2-[2-(1H-indol-3-yl)ethyl­iminiomethyl]-4-nitro­phenolate

Ali, H.M.; Mohamed Mustafa, M.I.; Rizal, M.R.; Ng, S.W.

doi:10.1107/S1600536808011185

organic compounds

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ISSN: 2056-9890

Volume 64| Part 5| May 2008| Page o913

doi:10.1107/S1600536808011185

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2-[2-(1H-indol-3-yl)ethyliminiomethyl]-4-nitrophenolate

Hapipah M. Ali,^a M. I. Mohamed Mustafa,^a M. Razali Rizal ^a and Seik Weng Ng ^a ^*

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 7 January 2008; accepted 20 April 2008; online 26 April 2008)

The title Schiff base, C₁₇H₁₅N₃O₃, exists in the zwitterionic form with the phenol H atom transferred to the imine group. Adjacent zwitterions are linked into a linear chain running along the a axis by an indole–hydroxy N—H⋯O hydrogen bond [3.100 (2) Å].

Related literature

For the structure of the zwitterionic 2-{[3-(indol-3-yl)propenyl]methylammonio}-4-methylphenolate, see: Ali et al. (2007 ).

Experimental

Crystal data

C₁₇H₁₅N₃O₃
M_r = 309.32
Monoclinic, C 2/c
a = 14.5990 (7) Å
b = 9.5027 (5) Å
c = 21.5373 (10) Å
β = 95.712 (2)°
V = 2973.0 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 139 (2) K
0.51 × 0.30 × 0.19 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: none
6383 measured reflections
3312 independent reflections
2403 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.161
S = 1.06
3312 reflections
216 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.18 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2n⋯O1	0.88 (1)	1.87 (2)	2.602 (2)	139 (2)
N3—H3n⋯O2ⁱ	0.88 (1)	2.36 (2)	3.027 (2)	133 (2)
N3—H3n⋯O3ⁱ	0.88 (1)	2.23 (1)	3.100 (2)	171 (2)
Symmetry code: (i) x-1, y, z.

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2008 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808011185/bv2090sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808011185/bv2090Isup2.hkl

checkCIF report

Related literature top

For the structure of the zwitterionic 2-{[3-(indol-3-yl)propenyl]methylammonio}-4-methylphenolate, see: Ali et al. (2007).

Experimental top

Tryptamine (0.32 g, 2 mmol) and 5-nitrosalisylaldehyde (0.33 g, 21.9 mmol) were refluxed in ethanol (50 ml) for 2 h. The solvent was removed to give the product Schiff base, and crystals were obtained by recrystallization from THF.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2008).

Figures top

Fig. 1. Thermal ellipsoid plot of C₁₇H₁₅N₃O₃. Displacement ellipsoids are drawn at the 70% probability level, and H atoms are shown as spheres of arbitrary radii.

2-[2-(1H-indol-3-yl)ethyliminiomethyl]-4-nitrophenolate top

Crystal data top

C₁₇H₁₅N₃O₃	F(000) = 1296
M_r = 309.32	D_x = 1.382 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -c 2yc	Cell parameters from 2068 reflections
a = 14.5990 (7) Å	θ = 5.1–59.5°
b = 9.5027 (5) Å	µ = 0.10 mm⁻¹
c = 21.5373 (10) Å	T = 139 K
β = 95.712 (2)°	Irregular, yellow
V = 2973.0 (3) Å³	0.51 × 0.30 × 0.19 mm
Z = 8

Data collection top

Bruker APEXII diffractometer	2403 reflections with I > 2σ(I)
Radiation source: medium-focus sealed tube	R_int = 0.023
Graphite monochromator	θ_max = 27.5°, θ_min = 1.9°
ϕ and ω scans	h = −14→18
6383 measured reflections	k = −12→9
3312 independent reflections	l = −27→26

Refinement top

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.161	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0911P)² + 1.065P] where P = (F_o² + 2F_c²)/3
3312 reflections	(Δ/σ)_max = 0.001
216 parameters	Δρ_max = 1.18 e Å⁻³
2 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₁₇H₁₅N₃O₃	V = 2973.0 (3) Å³
M_r = 309.32	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 14.5990 (7) Å	µ = 0.10 mm⁻¹
b = 9.5027 (5) Å	T = 139 K
c = 21.5373 (10) Å	0.51 × 0.30 × 0.19 mm
β = 95.712 (2)°

Data collection top

Bruker APEXII diffractometer	2403 reflections with I > 2σ(I)
6383 measured reflections	R_int = 0.023
3312 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	2 restraints
wR(F²) = 0.161	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 1.18 e Å⁻³
3312 reflections	Δρ_min = −0.27 e Å⁻³
216 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
O1	0.60196 (9)	0.52975 (15)	0.49373 (6)	0.0348 (3)
O2	1.01389 (10)	0.6546 (2)	0.56727 (9)	0.0596 (5)
O3	0.95763 (10)	0.75509 (18)	0.64477 (7)	0.0501 (5)
N1	0.94781 (11)	0.68697 (19)	0.59563 (8)	0.0377 (4)
N2	0.53650 (11)	0.61992 (16)	0.59452 (7)	0.0278 (4)
N3	0.16678 (11)	0.81046 (17)	0.64386 (8)	0.0308 (4)
C1	0.68118 (12)	0.56415 (18)	0.51803 (8)	0.0254 (4)
C2	0.76150 (13)	0.54714 (19)	0.48512 (8)	0.0286 (4)
H2	0.7547	0.5085	0.4442	0.034*
C3	0.84661 (13)	0.58457 (19)	0.51059 (9)	0.0283 (4)
H3	0.8986	0.5705	0.4880	0.034*
C4	0.85759 (12)	0.64418 (19)	0.57044 (9)	0.0273 (4)
C5	0.78428 (12)	0.66384 (18)	0.60489 (8)	0.0258 (4)
H5	0.7935	0.7037	0.6455	0.031*
C6	0.69633 (12)	0.62481 (18)	0.57975 (8)	0.0241 (4)
C7	0.62047 (12)	0.65009 (18)	0.61477 (8)	0.0258 (4)
H7	0.6321	0.6911	0.6550	0.031*
C8	0.45617 (12)	0.6528 (2)	0.62664 (9)	0.0285 (4)
H8A	0.4761	0.6835	0.6698	0.034*
H8B	0.4177	0.5675	0.6288	0.034*
C9	0.39951 (13)	0.7694 (2)	0.59244 (9)	0.0303 (4)
H9A	0.4375	0.8556	0.5918	0.036*
H9B	0.3823	0.7402	0.5487	0.036*
C10	0.31404 (12)	0.80148 (19)	0.62293 (8)	0.0253 (4)
C11	0.22563 (13)	0.77101 (19)	0.60122 (9)	0.0298 (4)
H11	0.2072	0.7284	0.5621	0.036*
C12	0.21685 (12)	0.86790 (19)	0.69435 (9)	0.0269 (4)
C13	0.18875 (15)	0.9262 (2)	0.74883 (10)	0.0391 (5)
H13	0.1259	0.9262	0.7567	0.047*
C14	0.25584 (18)	0.9837 (3)	0.79057 (10)	0.0482 (6)
H14	0.2387	1.0238	0.8281	0.058*
C15	0.34794 (18)	0.9848 (2)	0.77940 (10)	0.0467 (6)
H15	0.3923	1.0267	0.8090	0.056*
C16	0.37574 (14)	0.9260 (2)	0.72603 (9)	0.0349 (5)
H16	0.4389	0.9265	0.7188	0.042*
C17	0.30999 (12)	0.86553 (18)	0.68270 (8)	0.0240 (4)
H2N	0.5301 (16)	0.578 (2)	0.5578 (6)	0.047 (7)*
H3N	0.1078 (8)	0.790 (3)	0.6400 (11)	0.052 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0221 (7)	0.0421 (8)	0.0390 (8)	−0.0044 (6)	−0.0020 (6)	−0.0080 (6)
O2	0.0177 (8)	0.0831 (13)	0.0789 (12)	−0.0053 (8)	0.0097 (8)	−0.0235 (10)
O3	0.0286 (9)	0.0690 (12)	0.0514 (9)	−0.0109 (8)	−0.0022 (7)	−0.0173 (8)
N1	0.0197 (9)	0.0436 (10)	0.0493 (10)	−0.0028 (7)	0.0012 (7)	−0.0020 (8)
N2	0.0194 (8)	0.0308 (8)	0.0334 (8)	0.0039 (6)	0.0040 (6)	−0.0015 (6)
N3	0.0162 (8)	0.0303 (8)	0.0452 (9)	−0.0007 (6)	0.0001 (7)	−0.0016 (7)
C1	0.0211 (9)	0.0229 (8)	0.0316 (9)	0.0007 (7)	−0.0006 (7)	0.0002 (7)
C2	0.0290 (10)	0.0274 (9)	0.0298 (9)	0.0004 (8)	0.0041 (8)	−0.0010 (7)
C3	0.0229 (9)	0.0273 (9)	0.0357 (10)	0.0014 (7)	0.0076 (7)	0.0024 (8)
C4	0.0164 (9)	0.0269 (9)	0.0378 (10)	−0.0005 (7)	−0.0007 (7)	0.0025 (7)
C5	0.0216 (9)	0.0243 (9)	0.0311 (9)	−0.0001 (7)	0.0004 (7)	0.0001 (7)
C6	0.0194 (9)	0.0224 (8)	0.0305 (9)	0.0013 (7)	0.0020 (7)	0.0017 (7)
C7	0.0225 (10)	0.0241 (8)	0.0305 (9)	0.0029 (7)	0.0013 (7)	0.0016 (7)
C8	0.0202 (10)	0.0343 (10)	0.0319 (9)	0.0042 (7)	0.0069 (7)	0.0022 (7)
C9	0.0269 (10)	0.0329 (10)	0.0319 (9)	0.0082 (8)	0.0063 (8)	0.0027 (8)
C10	0.0226 (9)	0.0255 (8)	0.0275 (9)	0.0044 (7)	0.0012 (7)	0.0012 (7)
C11	0.0281 (10)	0.0276 (9)	0.0323 (9)	0.0039 (8)	−0.0047 (8)	−0.0027 (7)
C12	0.0209 (9)	0.0258 (9)	0.0341 (9)	0.0029 (7)	0.0031 (7)	0.0033 (7)
C13	0.0362 (12)	0.0413 (11)	0.0422 (11)	0.0092 (9)	0.0162 (9)	0.0023 (9)
C14	0.0619 (16)	0.0498 (13)	0.0336 (11)	0.0158 (12)	0.0087 (11)	−0.0085 (10)
C15	0.0499 (14)	0.0478 (13)	0.0388 (11)	0.0072 (11)	−0.0129 (10)	−0.0144 (10)
C16	0.0262 (10)	0.0361 (10)	0.0406 (11)	0.0029 (8)	−0.0063 (8)	−0.0047 (8)
C17	0.0190 (9)	0.0239 (8)	0.0286 (9)	0.0034 (7)	0.0005 (7)	0.0006 (7)

Geometric parameters (Å, º) top

O1—C1	1.264 (2)	C7—H7	0.9500
O2—N1	1.231 (2)	C8—C9	1.527 (3)
O3—N1	1.237 (2)	C8—H8A	0.9900
N1—C4	1.433 (2)	C8—H8B	0.9900
N2—C7	1.292 (2)	C9—C10	1.498 (2)
N2—C8	1.454 (2)	C9—H9A	0.9900
N2—H2N	0.883 (10)	C9—H9B	0.9900
N3—C12	1.363 (3)	C10—C11	1.359 (3)
N3—C11	1.371 (2)	C10—C17	1.430 (2)
N3—H3N	0.879 (10)	C11—H11	0.9500
C1—C2	1.439 (2)	C12—C13	1.396 (3)
C1—C6	1.446 (3)	C12—C17	1.407 (2)
C2—C3	1.355 (3)	C13—C14	1.375 (3)
C2—H2	0.9500	C13—H13	0.9500
C3—C4	1.402 (3)	C14—C15	1.389 (4)
C3—H3	0.9500	C14—H14	0.9500
C4—C5	1.375 (2)	C15—C16	1.375 (3)
C5—C6	1.393 (3)	C15—H15	0.9500
C5—H5	0.9500	C16—C17	1.394 (3)
C6—C7	1.421 (2)	C16—H16	0.9500

O2—N1—O3	121.71 (18)	N2—C8—H8B	109.5
O2—N1—C4	118.51 (17)	C9—C8—H8B	109.5
O3—N1—C4	119.78 (16)	H8A—C8—H8B	108.1
C7—N2—C8	125.09 (16)	C10—C9—C8	111.78 (14)
C7—N2—H2N	114.5 (16)	C10—C9—H9A	109.3
C8—N2—H2N	120.4 (16)	C8—C9—H9A	109.3
C12—N3—C11	108.79 (15)	C10—C9—H9B	109.3
C12—N3—H3N	127.4 (16)	C8—C9—H9B	109.3
C11—N3—H3N	123.3 (16)	H9A—C9—H9B	107.9
O1—C1—C2	121.60 (16)	C11—C10—C17	106.10 (15)
O1—C1—C6	122.27 (16)	C11—C10—C9	127.56 (17)
C2—C1—C6	116.12 (16)	C17—C10—C9	126.29 (17)
C3—C2—C1	122.05 (17)	C10—C11—N3	110.38 (16)
C3—C2—H2	119.0	C10—C11—H11	124.8
C1—C2—H2	119.0	N3—C11—H11	124.8
C2—C3—C4	119.64 (16)	N3—C12—C13	130.60 (18)
C2—C3—H3	120.2	N3—C12—C17	107.60 (15)
C4—C3—H3	120.2	C13—C12—C17	121.76 (19)
C5—C4—C3	121.81 (17)	C14—C13—C12	117.22 (19)
C5—C4—N1	119.53 (17)	C14—C13—H13	121.4
C3—C4—N1	118.65 (16)	C12—C13—H13	121.4
C4—C5—C6	119.41 (17)	C13—C14—C15	121.91 (19)
C4—C5—H5	120.3	C13—C14—H14	119.0
C6—C5—H5	120.3	C15—C14—H14	119.0
C5—C6—C7	119.05 (16)	C16—C15—C14	120.9 (2)
C5—C6—C1	120.95 (16)	C16—C15—H15	119.6
C7—C6—C1	119.97 (16)	C14—C15—H15	119.6
N2—C7—C6	123.14 (17)	C15—C16—C17	119.08 (19)
N2—C7—H7	118.4	C15—C16—H16	120.5
C6—C7—H7	118.4	C17—C16—H16	120.5
N2—C8—C9	110.52 (14)	C16—C17—C12	119.15 (17)
N2—C8—H8A	109.5	C16—C17—C10	133.65 (16)
C9—C8—H8A	109.5	C12—C17—C10	107.12 (16)

O1—C1—C2—C3	179.54 (17)	C8—C9—C10—C11	−108.7 (2)
C6—C1—C2—C3	0.6 (3)	C8—C9—C10—C17	68.3 (2)
C1—C2—C3—C4	−1.2 (3)	C17—C10—C11—N3	−0.7 (2)
C2—C3—C4—C5	1.2 (3)	C9—C10—C11—N3	176.80 (17)
C2—C3—C4—N1	−178.08 (17)	C12—N3—C11—C10	0.1 (2)
O2—N1—C4—C5	172.08 (18)	C11—N3—C12—C13	178.3 (2)
O3—N1—C4—C5	−8.1 (3)	C11—N3—C12—C17	0.5 (2)
O2—N1—C4—C3	−8.7 (3)	N3—C12—C13—C14	−176.5 (2)
O3—N1—C4—C3	171.20 (18)	C17—C12—C13—C14	1.0 (3)
C3—C4—C5—C6	−0.5 (3)	C12—C13—C14—C15	0.2 (3)
N1—C4—C5—C6	178.68 (16)	C13—C14—C15—C16	−0.9 (4)
C4—C5—C6—C7	−177.79 (16)	C14—C15—C16—C17	0.4 (3)
C4—C5—C6—C1	−0.1 (3)	C15—C16—C17—C12	0.8 (3)
O1—C1—C6—C5	−178.92 (17)	C15—C16—C17—C10	177.4 (2)
C2—C1—C6—C5	0.1 (2)	N3—C12—C17—C16	176.45 (17)
O1—C1—C6—C7	−1.2 (3)	C13—C12—C17—C16	−1.5 (3)
C2—C1—C6—C7	177.77 (16)	N3—C12—C17—C10	−0.9 (2)
C8—N2—C7—C6	−175.39 (16)	C13—C12—C17—C10	−178.93 (18)
C5—C6—C7—N2	178.55 (16)	C11—C10—C17—C16	−175.9 (2)
C1—C6—C7—N2	0.8 (3)	C9—C10—C17—C16	6.6 (3)
C7—N2—C8—C9	109.1 (2)	C11—C10—C17—C12	1.0 (2)
N2—C8—C9—C10	177.58 (15)	C9—C10—C17—C12	−176.53 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2n···O1	0.88 (1)	1.87 (2)	2.602 (2)	139 (2)
N3—H3n···O2ⁱ	0.88 (1)	2.36 (2)	3.027 (2)	133 (2)
N3—H3n···O3ⁱ	0.88 (1)	2.23 (1)	3.100 (2)	171 (2)

Symmetry code: (i) x−1, y, z.

Experimental details

Crystal data
Chemical formula	C₁₇H₁₅N₃O₃
M_r	309.32
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	139
a, b, c (Å)	14.5990 (7), 9.5027 (5), 21.5373 (10)
β (°)	95.712 (2)
V (Å³)	2973.0 (3)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.51 × 0.30 × 0.19

Data collection
Diffractometer	Bruker APEXII diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	6383, 3312, 2403
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.161, 1.06
No. of reflections	3312
No. of parameters	216
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.18, −0.27

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2n···O1	0.88 (1)	1.87 (2)	2.602 (2)	139 (2)
N3—H3n···O2ⁱ	0.88 (1)	2.36 (2)	3.027 (2)	133 (2)
N3—H3n···O3ⁱ	0.88 (1)	2.23 (1)	3.100 (2)	171 (2)

Symmetry code: (i) x−1, y, z.

Acknowledgements

The authors thank the University of Canterbury, New Zealand, for the diffraction measurements, and the Science Fund (12–02-03–2031) and the Fundamental Research Grant Scheme (FP064/2006 A) for supporting this study.

References

Ali, H. M., Emmy Maryati, O. & Ng, S. W. (2007). Acta Cryst. E63, o3458. Web of Science CSD CrossRef IUCr Journals Google Scholar
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