2,3,3-Trimethyl-1-[4-(2,3,3-trimethyl-3H-indol-1-ium-1-yl)but­yl]-3H-indol-1-ium diiodide

Wu, D.; Shen, L.-X.; Niu, Y.-Y.; Ng, S.W.

doi:10.1107/S1600536812035234

organic compounds

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ISSN: 2056-9890

Volume 68| Part 9| September 2012| Page o2714

doi:10.1107/S1600536812035234

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2,3,3-Trimethyl-1-[4-(2,3,3-trimethyl-3H-indol-1-ium-1-yl)butyl]-3H-indol-1-ium diiodide

Di Wu,^a Li-Xia Shen,^a Yun-Yin Niu ^a and Seik Weng Ng ^b,^c ^*

^aCollege of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou, People's Republic of China, ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and ^cChemistry Department, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 31 July 2012; accepted 9 August 2012; online 15 August 2012)

In the crystal of the title salt, C₂₆H₃₄N₂²⁺·2I⁻, the dication lies on a center of inversion that exists along the mid-point of the butyl chain; its five-membered ring is approximately planar (r.m.s. deviation = 0.011 Å). In the crystal, the iodide anion is disordered over two positions in a 1:1 ratio.

Related literature

For the synthesis, see: Yang et al. (2005 ). For industrial applications of Mannich products, see: Su et al. (2005 ).

Experimental

Crystal data

C₂₆H₃₄N₂²⁺·2I⁻
M_r = 628.35
Monoclinic, P 2₁ /c
a = 13.9414 (14) Å
b = 7.6013 (8) Å
c = 13.8261 (15) Å
β = 113.011 (2)°
V = 1348.6 (2) Å³
Z = 2
Mo Kα radiation
μ = 2.35 mm⁻¹
T = 293 K
0.35 × 0.30 × 0.25 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.494, T_max = 0.592
8426 measured reflections
3077 independent reflections
2602 reflections with I > 2σ(I)
R_int = 0.017

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.087
S = 1.04
3077 reflections
146 parameters
H-atom parameters constrained
Δρ_max = 0.94 e Å⁻³
Δρ_min = −0.37 e Å⁻³

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, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812035234/xu5603sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812035234/xu5603Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812035234/xu5603Isup3.cml

checkCIF report

Comment top

The salt (Scheme I) can be synthesized in several steps from benzohydrazine, methyl isopropyl ketone and 1,4-diiodobutane, and is an intermediate in the synthesis of a bis-spironaphthoxazine (Yang et al., 2005). It is available commercially in milligram quantities. The methyl group on the carbon atom adjacent to the quarternary nitrogen is acidic, and the methyl group undergoes a Mannich-type of reaction to yield compounds that have been patented for use as high-density recording media (Su et al., 2005).

In the salt, C₂₆H₃₄N₂⁺ 2I^-, the dicationic species lies on a center-of-inversion that exists along the mid-point of the butyl chain; its five-membered ring is planar (r.m.s. deviation 0.011 Å). The iodide anion is disordered over two positions in a 1:1 ratio (Fig. 1).

Related literature top

For the synthesis, see: Yang et al. (2005). For industrial applications of Mannich products, see: Su et al. (2005).

Experimental top

3,3-Dimethyl-3H-indole (40 mmol, 5.81 g), 1,4-dibromobutane (20 mmol, 4.32 g) and potassium iodide (50 mmol, 8.310) were added to acetonitrile (40 ml). The mixture was heated under reflux for 4 days. The mixture was collected and the yellow solid recrystallized from a methanol-ether mixture; yield 40%. The salt is soluble in most organic solvents.

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, 2010).

Figures top

Thermal ellipsoid plot (Barbour, 2001) of C₂₆H₃₄N₂²⁺ 2I^- at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius. The disorder in the iodine atom is not shown.

2,3,3-Trimethyl-1-[4-(2,3,3-trimethyl-3H-indol-1-ium-1-yl)butyl]- 3H-indol-1-ium diiodide top

Crystal data top

C₂₆H₃₄N₂²⁺·2I⁻	F(000) = 620
M_r = 628.35	D_x = 1.547 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3950 reflections
a = 13.9414 (14) Å	θ = 3.0–28.3°
b = 7.6013 (8) Å	µ = 2.35 mm⁻¹
c = 13.8261 (15) Å	T = 293 K
β = 113.011 (2)°	Prism, colorless
V = 1348.6 (2) Å³	0.35 × 0.30 × 0.25 mm
Z = 2

Data collection top

Bruker SMART APEX diffractometer	3077 independent reflections
Radiation source: fine-focus sealed tube	2602 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.017
ω scans	θ_max = 27.5°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→17
T_min = 0.494, T_max = 0.592	k = −8→9
8426 measured reflections	l = −17→14

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.087	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0519P)² + 0.3658P] where P = (F_o² + 2F_c²)/3
3077 reflections	(Δ/σ)_max = 0.001
146 parameters	Δρ_max = 0.94 e Å⁻³
0 restraints	Δρ_min = −0.37 e Å⁻³

Crystal data top

C₂₆H₃₄N₂²⁺·2I⁻	V = 1348.6 (2) Å³
M_r = 628.35	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.9414 (14) Å	µ = 2.35 mm⁻¹
b = 7.6013 (8) Å	T = 293 K
c = 13.8261 (15) Å	0.35 × 0.30 × 0.25 mm
β = 113.011 (2)°

Data collection top

Bruker SMART APEX diffractometer	3077 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2602 reflections with I > 2σ(I)
T_min = 0.494, T_max = 0.592	R_int = 0.017
8426 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	0 restraints
wR(F²) = 0.087	H-atom parameters constrained
S = 1.04	Δρ_max = 0.94 e Å⁻³
3077 reflections	Δρ_min = −0.37 e Å⁻³
146 parameters

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
I1	0.3111 (2)	0.6289 (3)	0.77695 (19)	0.0536 (2)	0.50
I1'	0.3220 (2)	0.6038 (3)	0.7930 (2)	0.0800 (6)	0.50
N2	0.31190 (14)	0.3641 (2)	0.55053 (14)	0.0382 (4)
C1	0.3943 (2)	0.1407 (5)	0.6859 (3)	0.0789 (11)
H1A	0.3772	0.0208	0.6943	0.118*
H1B	0.4081	0.2039	0.7501	0.118*
H1C	0.4550	0.1435	0.6693	0.118*
C2	0.30596 (17)	0.2235 (3)	0.59984 (18)	0.0437 (5)
C3	0.19566 (18)	0.1564 (3)	0.56180 (19)	0.0398 (5)
C4	0.1613 (2)	0.1429 (3)	0.6543 (2)	0.0514 (6)
H4A	0.1669	0.2562	0.6867	0.077*
H4B	0.2051	0.0604	0.7049	0.077*
H4C	0.0902	0.1035	0.6292	0.077*
C5	0.1875 (3)	−0.0238 (4)	0.5086 (2)	0.0621 (7)
H5A	0.2092	−0.0131	0.4510	0.093*
H5B	0.1166	−0.0640	0.4830	0.093*
H5C	0.2316	−0.1067	0.5586	0.093*
C6	0.13926 (16)	0.2961 (3)	0.48332 (16)	0.0358 (4)
C7	0.03506 (19)	0.3190 (3)	0.4208 (2)	0.0484 (5)
H7	−0.0147	0.2402	0.4239	0.058*
C8	0.0064 (2)	0.4603 (4)	0.3539 (2)	0.0585 (7)
H8	−0.0635	0.4773	0.3112	0.070*
C9	0.0803 (3)	0.5787 (4)	0.3488 (2)	0.0585 (7)
H9	0.0590	0.6731	0.3025	0.070*
C10	0.1846 (2)	0.5586 (3)	0.41111 (19)	0.0475 (5)
H10	0.2345	0.6375	0.4084	0.057*
C11	0.21086 (17)	0.4165 (3)	0.47728 (16)	0.0352 (4)
C12	0.40689 (18)	0.4695 (4)	0.56978 (19)	0.0491 (6)
H12	0.4593	0.4384	0.6380	0.059*
H12B	0.3904	0.5931	0.5719	0.059*
C13	0.45182 (18)	0.4435 (3)	0.48771 (18)	0.0435 (5)
H13	0.4001	0.4747	0.4191	0.052*
H13B	0.4699	0.3206	0.4858	0.052*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.0481 (5)	0.0585 (3)	0.0626 (3)	−0.0023 (3)	0.0307 (3)	−0.0126 (3)
I1'	0.0531 (7)	0.0987 (14)	0.1030 (14)	−0.0154 (8)	0.0466 (9)	−0.0430 (8)
N2	0.0294 (9)	0.0511 (10)	0.0395 (9)	−0.0101 (7)	0.0193 (7)	−0.0044 (7)
C1	0.0413 (16)	0.107 (3)	0.083 (2)	0.0150 (15)	0.0190 (15)	0.0413 (18)
C2	0.0320 (11)	0.0575 (14)	0.0466 (12)	0.0011 (9)	0.0206 (9)	0.0075 (10)
C3	0.0342 (11)	0.0396 (11)	0.0514 (12)	−0.0026 (8)	0.0230 (9)	0.0066 (9)
C4	0.0516 (15)	0.0559 (14)	0.0590 (15)	−0.0019 (11)	0.0348 (12)	0.0082 (11)
C5	0.0748 (19)	0.0467 (14)	0.0763 (19)	0.0018 (13)	0.0420 (16)	−0.0007 (13)
C6	0.0317 (10)	0.0376 (10)	0.0406 (10)	−0.0031 (8)	0.0168 (8)	−0.0027 (8)
C7	0.0343 (12)	0.0543 (13)	0.0556 (14)	−0.0054 (10)	0.0166 (10)	−0.0083 (11)
C8	0.0460 (15)	0.0679 (17)	0.0498 (14)	0.0172 (13)	0.0058 (11)	−0.0049 (12)
C9	0.075 (2)	0.0531 (14)	0.0478 (14)	0.0189 (13)	0.0246 (13)	0.0090 (11)
C10	0.0623 (15)	0.0396 (11)	0.0493 (12)	−0.0011 (11)	0.0313 (11)	0.0025 (10)
C11	0.0354 (11)	0.0383 (10)	0.0365 (10)	−0.0052 (8)	0.0191 (8)	−0.0036 (8)
C12	0.0368 (12)	0.0683 (16)	0.0487 (12)	−0.0237 (11)	0.0237 (10)	−0.0136 (11)
C13	0.0343 (11)	0.0568 (13)	0.0459 (12)	−0.0135 (10)	0.0226 (9)	−0.0053 (10)

Geometric parameters (Å, º) top

N2—C2	1.287 (3)	C6—C11	1.381 (3)
N2—C11	1.433 (3)	C6—C7	1.381 (3)
N2—C12	1.480 (3)	C7—C8	1.371 (4)
C1—C2	1.478 (4)	C7—H7	0.9300
C1—H1A	0.9600	C8—C9	1.390 (4)
C1—H1B	0.9600	C8—H8	0.9300
C1—H1C	0.9600	C9—C10	1.378 (4)
C2—C3	1.507 (3)	C9—H9	0.9300
C3—C6	1.502 (3)	C10—C11	1.370 (3)
C3—C4	1.535 (3)	C10—H10	0.9300
C3—C5	1.538 (4)	C12—C13	1.508 (3)
C4—H4A	0.9600	C12—H12	0.9700
C4—H4B	0.9600	C12—H12B	0.9700
C4—H4C	0.9600	C13—C13ⁱ	1.517 (4)
C5—H5A	0.9600	C13—H13	0.9700
C5—H5B	0.9600	C13—H13B	0.9700
C5—H5C	0.9600

C2—N2—C11	110.85 (18)	C11—C6—C7	119.1 (2)
C2—N2—C12	126.3 (2)	C11—C6—C3	109.00 (19)
C11—N2—C12	122.67 (19)	C7—C6—C3	131.9 (2)
C2—C1—H1A	109.5	C8—C7—C6	118.6 (2)
C2—C1—H1B	109.5	C8—C7—H7	120.7
H1A—C1—H1B	109.5	C6—C7—H7	120.7
C2—C1—H1C	109.5	C7—C8—C9	121.0 (2)
H1A—C1—H1C	109.5	C7—C8—H8	119.5
H1B—C1—H1C	109.5	C9—C8—H8	119.5
N2—C2—C1	125.0 (2)	C10—C9—C8	121.2 (2)
N2—C2—C3	111.39 (19)	C10—C9—H9	119.4
C1—C2—C3	123.5 (2)	C8—C9—H9	119.4
C6—C3—C2	100.79 (17)	C11—C10—C9	116.5 (2)
C6—C3—C4	113.8 (2)	C11—C10—H10	121.8
C2—C3—C4	109.9 (2)	C9—C10—H10	121.8
C6—C3—C5	111.4 (2)	C10—C11—C6	123.5 (2)
C2—C3—C5	110.1 (2)	C10—C11—N2	128.6 (2)
C4—C3—C5	110.5 (2)	C6—C11—N2	107.90 (18)
C3—C4—H4A	109.5	N2—C12—C13	113.52 (18)
C3—C4—H4B	109.5	N2—C12—H12	108.9
H4A—C4—H4B	109.5	C13—C12—H12	108.9
C3—C4—H4C	109.5	N2—C12—H12B	108.9
H4A—C4—H4C	109.5	C13—C12—H12B	108.9
H4B—C4—H4C	109.5	H12—C12—H12B	107.7
C3—C5—H5A	109.5	C12—C13—C13ⁱ	110.4 (2)
C3—C5—H5B	109.5	C12—C13—H13	109.6
H5A—C5—H5B	109.5	C13ⁱ—C13—H13	109.6
C3—C5—H5C	109.5	C12—C13—H13B	109.6
H5A—C5—H5C	109.5	C13ⁱ—C13—H13B	109.6
H5B—C5—H5C	109.5	H13—C13—H13B	108.1

C11—N2—C2—C1	−175.6 (3)	C3—C6—C7—C8	−178.7 (2)
C12—N2—C2—C1	−0.1 (4)	C6—C7—C8—C9	−0.1 (4)
C11—N2—C2—C3	2.1 (3)	C7—C8—C9—C10	−0.4 (4)
C12—N2—C2—C3	177.6 (2)	C8—C9—C10—C11	0.2 (4)
N2—C2—C3—C6	−2.7 (3)	C9—C10—C11—C6	0.3 (4)
C1—C2—C3—C6	175.0 (3)	C9—C10—C11—N2	−179.6 (2)
N2—C2—C3—C4	−123.1 (2)	C7—C6—C11—C10	−0.7 (3)
C1—C2—C3—C4	54.6 (3)	C3—C6—C11—C10	178.7 (2)
N2—C2—C3—C5	114.9 (2)	C7—C6—C11—N2	179.17 (19)
C1—C2—C3—C5	−67.3 (3)	C3—C6—C11—N2	−1.4 (2)
C2—C3—C6—C11	2.4 (2)	C2—N2—C11—C10	179.5 (2)
C4—C3—C6—C11	120.0 (2)	C12—N2—C11—C10	3.7 (3)
C5—C3—C6—C11	−114.4 (2)	C2—N2—C11—C6	−0.4 (3)
C2—C3—C6—C7	−178.3 (2)	C12—N2—C11—C6	−176.17 (19)
C4—C3—C6—C7	−60.7 (3)	C2—N2—C12—C13	104.5 (3)
C5—C3—C6—C7	65.0 (3)	C11—N2—C12—C13	−80.5 (3)
C11—C6—C7—C8	0.6 (4)	N2—C12—C13—C13ⁱ	179.6 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₂₆H₃₄N₂²⁺·2I⁻
M_r	628.35
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	13.9414 (14), 7.6013 (8), 13.8261 (15)
β (°)	113.011 (2)
V (Å³)	1348.6 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.35
Crystal size (mm)	0.35 × 0.30 × 0.25

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.494, 0.592
No. of measured, independent and observed [I > 2σ(I)] reflections	8426, 3077, 2602
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.087, 1.04
No. of reflections	3077
No. of parameters	146
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.94, −0.37

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Acknowledgements

We thank the National Natural Science Foundation of China (No. J1103309), the Students' Innovative Undertaking Training Project of Zhengzhou University (No. 121045919) and the Ministry of Higher Education of Malaysia (grant No. UM·C/HIR/MOHE/SC/12) for supporting this study.

References

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