 | Acta Crystallographica Section E Acta Crystallographica Section E CRYSTALLOGRAPHIC COMMUNICATIONS |
journal menu
organic compounds
| CRYSTALLOGRAPHIC COMMUNICATIONS |
accessrac-N,N′-Dimethyl-N,N′-(1,1′-binaphthyl-2,2′-diyl)diformamide
aCollege of Chemistry, Xinjiang Normal University, Urumqi 830054, People's Republic of China, bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and cChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia
*Correspondence e-mail: seikweng@um.edu.my
The molecule of the title compound, C24H20N2O2, lies on a twofold rotation axis that relates one 2-(N-methylformamido)naphthyl unit to the other. The N-methylformamido substituent is twisted by 54.9 (1)° with respect to the naphthalene fused-ring system; the two fused-ring systems are themselves twisted by 70.3 (1)°.
Related literature
For the synthesis of 2,2′-bis(methylamino)-1,1′-binaphthyl, see: Miyano et al. (1984![[Miyano, S., Nawa, M., Mori, A. & Hashimoto, H. (1984). Bull. Chem. Soc. Jpn, 57, 2171-2176.]](../../../../../../logos/arrows/e_arr.gif "Miyano, S., Nawa, M., Mori, A. & Hashimoto, H. (1984). Bull. Chem. Soc. Jpn, 57, 2171-2176.")
).
![[Scheme 1]](xu5377scheme1.gif)
Experimental
Crystal data
|
Data collection: CrystalClear (Rigaku/MSC, 2005); cell CrystalClear; data reduction: CrystalClear; 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
contains datablocks global, I. DOI: https://doi.org/10.1107/S160053681104640X/xu5377sup1.cif
Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681104640X/xu5377Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S160053681104640X/xu5377Isup3.cml
2,2'-Bis(methylamino)-1,1'-binaphthyl was prepared by treatment of racemic 2,2'-diamino-1,1'-binaphthyl (purchased from Aldrich Chemical Company) with ethyl chloroformate in benzene in the presence of pyridine, followed by reduction with lithium aluminium hydride in tetrahydrofuran (Miyano et al., 1984). An ethyl formate solution (10 ml) of 2,2'-bis(methylamino)-1,1'-binaphthyl (156 mg, 0.50 mmol) was heated at 327 K for 10 h. The solvent was removed under reduced pressure and the residue was purified by (eluent: ethyl acetate/petroleum ether 10/1) to give the title compound (158 mg, 86%) as a white solid. Crystals were obtained upon recrystallized from a dichloromethane-hexane mixture.
Carbon-bound H-atoms were placed in calculated positions (C–H 0.95–0.98 Å) and were included in the in the riding model approximation, with Uiso(H) set to 1.2–1.5Ueq(C). In the absence of heavy atoms, 1000 Friedel pairs were merged.
We report here the methylation of commercially available racemic 2,2'-diamino-1,1'-binaphthyl to yield 2,2'-bis(methylamino)-1,1'-binaphthyl. The compound should react with triethyl orthoformate to yield an imidzolium salt. The reaction with ethyl formate, an unintended similar-sounding reagent, gave 2,2'-bis(N-methyformido)-1,1'-binaphthyl (Scheme I) instead.
The C24H20N2O2 molecules lies on a twofold rotation axis that relates one N-methylformamido)-1-naphthyl moiety to the other (Fig. 1). The N-methylformamido substituent is twisted by 54.9 (1) ° with respect to the naphathalene fused-ring; the two fused-rings are themselves twisted by 70.3 (1) °.
For the synthesis of 2,2'-bis(methylamino)-1,1'-binaphthyl, see: Miyano et al. (1984).
Data collection: CrystalClear (Rigaku/MSC, 2005); cell CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 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).
![[Figure 1]](./xu5377fig1thm.gif) | Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of C24H20N2O2 at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius. The unlabeled atoms are related to the labeled one by 2 - x, -y, z. |
| C24H20N2O2 | Dx = 1.294 Mg m−3 |
| Mr = 368.42 | Mo Kα radiation, λ = 0.71070 Å |
| Tetragonal, I41 | Cell parameters from 2958 reflections |
| Hall symbol: I 4bw | θ = 2.3–27.1° |
| a = 11.6548 (12) Å | µ = 0.08 mm−1 |
| c = 13.9171 (15) Å | T = 113 K |
| V = 1890.4 (3) Å3 | Prism, colorless |
| Z = 4 | 0.34 × 0.20 × 0.16 mm |
| F(000) = 776 |
| Rigaku Saturn CCD area-detector diffractometer | 1091 independent reflections |
| Radiation source: rotating anode | 1051 reflections with I > 2σ(I) |
| Confocal monochromator | Rint = 0.044 |
| Detector resolution: 7.31 pixels mm-1 | θmax = 27.1°, θmin = 2.3° |
| ω and φ scans | h = −14→14 |
| Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005) | k = −14→14 |
| Tmin = 0.972, Tmax = 0.987 | l = −17→17 |
| 11169 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)] = 0.038 | H-atom parameters constrained |
| wR(F2) = 0.101 | w = 1/[σ2(Fo2) + (0.0702P)2 + 0.3273P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.07 | (Δ/σ)max = 0.001 |
| 1091 reflections | Δρmax = 0.20 e Å−3 |
| 129 parameters | Δρmin = −0.14 e Å−3 |
| 1 restraint | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.012 (3) |
| C24H20N2O2 | Z = 4 |
| Mr = 368.42 | Mo Kα radiation |
| Tetragonal, I41 | µ = 0.08 mm−1 |
| a = 11.6548 (12) Å | T = 113 K |
| c = 13.9171 (15) Å | 0.34 × 0.20 × 0.16 mm |
| V = 1890.4 (3) Å3 |
| Rigaku Saturn CCD area-detector diffractometer | 1091 independent reflections |
| Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005) | 1051 reflections with I > 2σ(I) |
| Tmin = 0.972, Tmax = 0.987 | Rint = 0.044 |
| 11169 measured reflections |
| R[F2 > 2σ(F2)] = 0.038 | 1 restraint |
| wR(F2) = 0.101 | H-atom parameters constrained |
| S = 1.07 | Δρmax = 0.20 e Å−3 |
| 1091 reflections | Δρmin = −0.14 e Å−3 |
| 129 parameters |
| x | y | z | Uiso*/Ueq | ||
| O1 | 0.8311 (3) | −0.0321 (2) | 0.33342 (16) | 0.0772 (9) | |
| N1 | 0.85923 (17) | 0.00005 (15) | 0.17381 (13) | 0.0284 (5) | |
| C1 | 0.96952 (16) | 0.05699 (16) | 0.03106 (14) | 0.0187 (4) | |
| C2 | 0.89065 (18) | 0.08195 (17) | 0.10211 (15) | 0.0215 (4) | |
| C3 | 0.83669 (17) | 0.19135 (17) | 0.10642 (15) | 0.0220 (4) | |
| H3 | 0.7816 | 0.2067 | 0.1551 | 0.026* | |
| C4 | 0.86360 (17) | 0.27432 (16) | 0.04105 (15) | 0.0199 (4) | |
| H4 | 0.8286 | 0.3477 | 0.0459 | 0.024* | |
| C5 | 0.94283 (16) | 0.25287 (15) | −0.03388 (14) | 0.0176 (4) | |
| C6 | 0.99650 (16) | 0.14242 (15) | −0.03944 (14) | 0.0172 (4) | |
| C7 | 1.07543 (16) | 0.12335 (17) | −0.11571 (15) | 0.0204 (4) | |
| H7 | 1.1138 | 0.0516 | −0.1202 | 0.024* | |
| C8 | 1.09713 (17) | 0.20650 (18) | −0.18289 (15) | 0.0229 (4) | |
| H8 | 1.1490 | 0.1911 | −0.2339 | 0.028* | |
| C9 | 1.04310 (17) | 0.31514 (18) | −0.17716 (16) | 0.0241 (5) | |
| H9 | 1.0591 | 0.3724 | −0.2239 | 0.029* | |
| C10 | 0.96813 (17) | 0.33714 (17) | −0.10433 (16) | 0.0222 (4) | |
| H10 | 0.9322 | 0.4102 | −0.1007 | 0.027* | |
| C11 | 0.8095 (2) | −0.11084 (19) | 0.1472 (2) | 0.0391 (6) | |
| H11A | 0.8619 | −0.1726 | 0.1663 | 0.059* | |
| H11B | 0.7976 | −0.1134 | 0.0775 | 0.059* | |
| H11C | 0.7358 | −0.1208 | 0.1800 | 0.059* | |
| C12 | 0.8630 (3) | 0.0295 (2) | 0.26773 (19) | 0.0475 (8) | |
| H12 | 0.8926 | 0.1030 | 0.2836 | 0.057* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.149 (3) | 0.0543 (14) | 0.0279 (12) | 0.0017 (15) | 0.0288 (14) | 0.0093 (10) |
| N1 | 0.0414 (11) | 0.0224 (9) | 0.0214 (10) | −0.0013 (8) | 0.0095 (8) | 0.0025 (7) |
| C1 | 0.0213 (9) | 0.0166 (9) | 0.0182 (9) | −0.0009 (7) | −0.0013 (7) | −0.0022 (7) |
| C2 | 0.0268 (10) | 0.0200 (9) | 0.0179 (9) | −0.0023 (8) | 0.0009 (8) | −0.0008 (8) |
| C3 | 0.0232 (10) | 0.0226 (10) | 0.0203 (9) | −0.0009 (7) | 0.0022 (8) | −0.0053 (8) |
| C4 | 0.0229 (9) | 0.0173 (9) | 0.0196 (10) | 0.0014 (7) | −0.0029 (8) | −0.0049 (7) |
| C5 | 0.0174 (9) | 0.0166 (9) | 0.0190 (9) | −0.0011 (7) | −0.0042 (7) | −0.0016 (8) |
| C6 | 0.0172 (9) | 0.0163 (9) | 0.0179 (9) | −0.0010 (7) | −0.0035 (7) | −0.0020 (7) |
| C7 | 0.0197 (9) | 0.0195 (9) | 0.0220 (10) | 0.0011 (7) | −0.0021 (8) | −0.0013 (8) |
| C8 | 0.0219 (9) | 0.0255 (10) | 0.0215 (10) | −0.0019 (8) | 0.0035 (8) | −0.0003 (8) |
| C9 | 0.0253 (10) | 0.0211 (10) | 0.0259 (11) | −0.0051 (8) | −0.0012 (8) | 0.0058 (8) |
| C10 | 0.0231 (10) | 0.0188 (10) | 0.0246 (10) | −0.0011 (7) | −0.0052 (8) | −0.0012 (8) |
| C11 | 0.0523 (15) | 0.0288 (12) | 0.0361 (13) | −0.0120 (10) | 0.0130 (12) | 0.0041 (10) |
| C12 | 0.084 (2) | 0.0345 (14) | 0.0237 (12) | 0.0020 (13) | 0.0099 (13) | 0.0022 (10) |
| O1—C12 | 1.220 (4) | C5—C6 | 1.433 (2) |
| N1—C12 | 1.352 (3) | C6—C7 | 1.422 (3) |
| N1—C2 | 1.429 (3) | C7—C8 | 1.370 (3) |
| N1—C11 | 1.464 (3) | C7—H7 | 0.9500 |
| C1—C2 | 1.381 (3) | C8—C9 | 1.416 (3) |
| C1—C6 | 1.433 (3) | C8—H8 | 0.9500 |
| C1—C1i | 1.507 (4) | C9—C10 | 1.363 (3) |
| C2—C3 | 1.423 (3) | C9—H9 | 0.9500 |
| C3—C4 | 1.364 (3) | C10—H10 | 0.9500 |
| C3—H3 | 0.9500 | C11—H11A | 0.9800 |
| C4—C5 | 1.415 (3) | C11—H11B | 0.9800 |
| C4—H4 | 0.9500 | C11—H11C | 0.9800 |
| C5—C10 | 1.419 (3) | C12—H12 | 0.9500 |
| C12—N1—C2 | 119.83 (19) | C8—C7—C6 | 121.21 (18) |
| C12—N1—C11 | 118.8 (2) | C8—C7—H7 | 119.4 |
| C2—N1—C11 | 120.98 (19) | C6—C7—H7 | 119.4 |
| C2—C1—C6 | 119.34 (16) | C7—C8—C9 | 120.79 (19) |
| C2—C1—C1i | 119.98 (15) | C7—C8—H8 | 119.6 |
| C6—C1—C1i | 120.61 (15) | C9—C8—H8 | 119.6 |
| C1—C2—C3 | 120.87 (18) | C10—C9—C8 | 119.68 (19) |
| C1—C2—N1 | 122.00 (17) | C10—C9—H9 | 120.2 |
| C3—C2—N1 | 117.12 (18) | C8—C9—H9 | 120.2 |
| C4—C3—C2 | 120.35 (18) | C9—C10—C5 | 121.14 (18) |
| C4—C3—H3 | 119.8 | C9—C10—H10 | 119.4 |
| C2—C3—H3 | 119.8 | C5—C10—H10 | 119.4 |
| C3—C4—C5 | 121.08 (17) | N1—C11—H11A | 109.5 |
| C3—C4—H4 | 119.5 | N1—C11—H11B | 109.5 |
| C5—C4—H4 | 119.5 | H11A—C11—H11B | 109.5 |
| C4—C5—C10 | 121.50 (16) | N1—C11—H11C | 109.5 |
| C4—C5—C6 | 118.90 (17) | H11A—C11—H11C | 109.5 |
| C10—C5—C6 | 119.59 (18) | H11B—C11—H11C | 109.5 |
| C7—C6—C5 | 117.58 (17) | O1—C12—N1 | 124.4 (3) |
| C7—C6—C1 | 122.99 (16) | O1—C12—H12 | 117.8 |
| C5—C6—C1 | 119.42 (17) | N1—C12—H12 | 117.8 |
| Symmetry code: (i) −x+2, −y, z. |
Experimental details
| Crystal data | |
| Chemical formula | C24H20N2O2 |
| Mr | 368.42 |
| Crystal system, space group | Tetragonal, I41 |
| Temperature (K) | 113 |
| a, c (Å) | 11.6548 (12), 13.9171 (15) |
| V (Å3) | 1890.4 (3) |
| Z | 4 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.08 |
| Crystal size (mm) | 0.34 × 0.20 × 0.16 |
| Data collection | |
| Diffractometer | Rigaku Saturn CCD area-detector |
| Absorption correction | Multi-scan (CrystalClear; Rigaku/MSC, 2005) |
| Tmin, Tmax | 0.972, 0.987 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 11169, 1091, 1051 |
| Rint | 0.044 |
| (sin θ/λ)max (Å−1) | 0.641 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.101, 1.07 |
| No. of reflections | 1091 |
| No. of parameters | 129 |
| No. of restraints | 1 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.20, −0.14 |
Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).
Acknowledgements
We thank Xinjiang Normal University and the University of Malaya for supporting this study.
References
Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Miyano, S., Nawa, M., Mori, A. & Hashimoto, H. (1984). Bull. Chem. Soc. Jpn, 57, 2171–2176. CrossRef CAS Web of Science Google Scholar
Rigaku/MSC (2005). CrystalClear. MSC, The Woodlands, Texas, USA, and Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
| CRYSTALLOGRAPHIC COMMUNICATIONS |
We report here the methylation of commercially available racemic 2,2'-diamino-1,1'-binaphthyl to yield 2,2'-bis(methylamino)-1,1'-binaphthyl. The compound should react with triethyl orthoformate to yield an imidzolium salt. The reaction with ethyl formate, an unintended similar-sounding reagent, gave 2,2'-bis(N-methyformido)-1,1'-binaphthyl (Scheme I) instead.
The C24H20N2O2 molecules lies on a twofold rotation axis that relates one N-methylformamido)-1-naphthyl moiety to the other (Fig. 1). The N-methylformamido substituent is twisted by 54.9 (1) ° with respect to the naphathalene fused-ring; the two fused-rings are themselves twisted by 70.3 (1) °.