organic compounds
2,3,3-Trimethyl-1-[4-(2,3,3-trimethyl-3H-indol-1-ium-1-yl)butyl]-3H-indol-1-ium diiodide
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
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
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Data collection: APEX2 (Bruker, 2005); cell 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
10.1107/S1600536812035234/xu5603sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812035234/xu5603Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812035234/xu5603Isup3.cml
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.
Carbon-, nitrogen- and oxygen-bound H-atoms were placed in calculated positions (C–H 0.93 to 0.97, N–H 0.88, O–H 0.84 Å) and were included in the
in the riding model approximation, with U(H) set to 1.2 to 1.5U(C,N,O).The iodine atom is disordered over two positions; as the disorder refined to a nearly 1:1 ratio, the occupancy was then fixed as exactly 0.5.
Data collection: APEX2 (Bruker, 2005); cell
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).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. |
C26H34N22+·2I− | F(000) = 620 |
Mr = 628.35 | Dx = 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 |
Bruker SMART APEX diffractometer | 3077 independent reflections |
Radiation source: fine-focus sealed tube | 2602 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.017 |
ω scans | θmax = 27.5°, θmin = 3.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −13→17 |
Tmin = 0.494, Tmax = 0.592 | k = −8→9 |
8426 measured reflections | l = −17→14 |
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(Fo2) + (0.0519P)2 + 0.3658P] where P = (Fo2 + 2Fc2)/3 |
3077 reflections | (Δ/σ)max = 0.001 |
146 parameters | Δρmax = 0.94 e Å−3 |
0 restraints | Δρmin = −0.37 e Å−3 |
C26H34N22+·2I− | V = 1348.6 (2) Å3 |
Mr = 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)° |
Bruker SMART APEX diffractometer | 3077 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2602 reflections with I > 2σ(I) |
Tmin = 0.494, Tmax = 0.592 | Rint = 0.017 |
8426 measured reflections |
R[F2 > 2σ(F2)] = 0.027 | 0 restraints |
wR(F2) = 0.087 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.94 e Å−3 |
3077 reflections | Δρmin = −0.37 e Å−3 |
146 parameters |
x | y | z | Uiso*/Ueq | 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* |
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) |
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− |
Mr | 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) |
Tmin, Tmax | 0.494, 0.592 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8426, 3077, 2602 |
Rint | 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 |
Δρmax, Δρmin (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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Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Su, J.-H., Meng, F.-S., Tian, H., Li, C., Wang, H.-L. & Chen, K.-C. (2005). Faming Zhuanli Shenqing (Chin. Patent) 1563201 A 20050112. Google Scholar
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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).