rac-N,N′-Dimethyl-N,N′-(1,1′-binaphthyl-2,2′-di­yl)diformamide

Jing Zeng; Seik Weng Ng

doi:10.1107/S160053681104640X

. 2011 Nov 9;67(Pt 12):o3227. doi: 10.1107/S160053681104640X

rac-N,N′-Dimethyl-N,N′-(1,1′-binaphthyl-2,2′-diyl)diformamide

Jing Zeng ^a, Seik Weng Ng ^b,^c,^*

PMCID: PMC3238889 PMID: 22199742

Abstract

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 ▶).

Experimental

Crystal data

C₂₄H₂₀N₂O₂
M _r = 368.42
Tetragonal,
a = 11.6548 (12) Å
c = 13.9171 (15) Å
V = 1890.4 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 113 K
0.34 × 0.20 × 0.16 mm

Data collection

Rigaku Saturn CCD area-detector diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ▶) T _min = 0.972, T _max = 0.987
11169 measured reflections
1091 independent reflections
1051 reflections with I > 2σ(I)
R _int = 0.044

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.101
S = 1.07
1091 reflections
129 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Data collection: CrystalClear (Rigaku/MSC, 2005 ▶); cell refinement: 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 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681104640X/xu5377sup1.cif

e-67-o3227-sup1.cif^{(13KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681104640X/xu5377Isup2.hkl

e-67-o3227-Isup2.hkl^{(54.1KB, hkl)}

Supplementary material file. DOI: 10.1107/S160053681104640X/xu5377Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

We thank Xinjiang Normal University and the University of Malaya for supporting this study.

supplementary crystallographic information

Comment

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) °.

Experimental

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 column chromatography (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.

Figures

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.

Crystal data

C₂₄H₂₀N₂O₂	D_x = 1.294 Mg m⁻³
M_r = 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

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Data collection

Rigaku Saturn CCD area-detector diffractometer	1091 independent reflections
Radiation source: rotating anode	1051 reflections with I > 2σ(I)
confocal	R_int = 0.044
Detector resolution: 7.31 pixels mm^-1	θ_max = 27.1°, θ_min = 2.3°
ω and φ scans	h = −14→14
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −14→14
T_min = 0.972, T_max = 0.987	l = −17→17
11169 measured reflections

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Refinement

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(F_o²) + (0.0702P)² + 0.3273P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
1091 reflections	Δρ_max = 0.20 e Å⁻³
129 parameters	Δρ_min = −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)

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

	x	y	z	U_iso*/U_eq
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*

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Atomic displacement parameters (Å²)

	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)

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Geometric parameters (Å, °)

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

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Symmetry codes: (i) −x+2, −y, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: XU5377).

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.
Miyano, S., Nawa, M., Mori, A. & Hashimoto, H. (1984). Bull. Chem. Soc. Jpn, 57, 2171–2176.
Rigaku/MSC (2005). CrystalClear MSC, The Woodlands, Texas, USA, and Rigaku Corporation, Tokyo, Japan.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [DOI] [PubMed]
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.

Associated Data

This section collects any data citations, data availability statements, or supplementary materials included in this article.

Supplementary Materials

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681104640X/xu5377sup1.cif

e-67-o3227-sup1.cif^{(13KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681104640X/xu5377Isup2.hkl

e-67-o3227-Isup2.hkl^{(54.1KB, hkl)}

Supplementary material file. DOI: 10.1107/S160053681104640X/xu5377Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[bb1] Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.

[bb2] Miyano, S., Nawa, M., Mori, A. & Hashimoto, H. (1984). Bull. Chem. Soc. Jpn, 57, 2171–2176.

[bb3] Rigaku/MSC (2005). CrystalClear MSC, The Woodlands, Texas, USA, and Rigaku Corporation, Tokyo, Japan.

[bb4] Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [DOI] [PubMed]

[bb5] Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.

PERMALINK

rac-N,N′-Dimethyl-N,N′-(1,1′-binaphthyl-2,2′-diyl)diformamide

Jing Zeng

Seik Weng Ng

Abstract

Related literature

Experimental

Crystal data

Data collection

Refinement

Supplementary Material

Acknowledgments

supplementary crystallographic information

Comment

Experimental

Refinement

Figures

Fig. 1.

Crystal data

Data collection

Refinement

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

Atomic displacement parameters (Å²)

Geometric parameters (Å, °)

Footnotes

References

Associated Data

Supplementary Materials

ACTIONS

PERMALINK

RESOURCES

Cite

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PERMALINK

rac-N,N′-Dimethyl-N,N′-(1,1′-binaphthyl-2,2′-di­yl)diformamide

Jing Zeng

Seik Weng Ng

Abstract

Related literature

Experimental

Crystal data

Data collection

Refinement

Supplementary Material

Acknowledgments

supplementary crystallographic information

Comment

Experimental

Refinement

Figures

Fig. 1.

Crystal data

Data collection

Refinement

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

Atomic displacement parameters (Å2)

Geometric parameters (Å, °)

Footnotes

References

Associated Data

Supplementary Materials

ACTIONS

PERMALINK

RESOURCES

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rac-N,N′-Dimethyl-N,N′-(1,1′-binaphthyl-2,2′-diyl)diformamide

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

Atomic displacement parameters (Å²)