Literature DB >> 21583173

1,3-Bis{(+)-(S)-[1-(1-naphth-yl)eth-yl]imino-meth-yl}benzene dichloro-methane solvate.

Armando Espinosa Leija, Guadalupe Hernández, Sandra Cruz, Sylvain Bernès, René Gutiérrez.

Abstract

In the title compound, C(32)H(28)N(2)·CH(2)Cl(2), the complete Schiff base and solvent molecules are both generated by crystallographic twofold axes, with the two C atoms of the former and the C atom of the latter lying on the rotation axis. The central benzene ring is substituted with two chiral groups including imine functionalities, with the common E configuration. The dihedral angle between the central benzene ring and the terminal naphthalene ring is 45.42 (9)° and that between the two naphthalene rings is 89.16 (8)°. The conformation of the Schiff base allows solvent mol-ecules to fill the voids in the crystal, affording a stable 1:1 solvate, but the solvent inter-acts poorly with the Schiff base, as reflected by its rather high displacement parameters.

Entities: Chemical Disease Gene

Year: 2009 PMID： 21583173 PMCID： PMC2969804 DOI： 10.1107/S1600536809017528

Source DB: PubMed Journal: Acta Crystallogr Sect E Struct Rep Online ISSN： 1600-5368

Related literature

For solvent-free synthesis in organic chemistry, see: Jeon et al. (2005 ▶); Noyori (2005 ▶); Tanaka & Toda (2000 ▶). For related chiral Schiff bases synthesized using similar routes, see: Tovar et al. (2007 ▶).

Experimental

Crystal data

C32H28N2·CH2Cl2 M = 525.49 Orthorhombic, a = 8.550 (2) Å b = 20.706 (6) Å c = 7.972 (3) Å V = 1411.3 (7) Å3 Z = 2 Mo Kα radiation μ = 0.25 mm−1 T = 298 K 0.40 × 0.24 × 0.20 mm

Data collection

Siemens P4 diffractometer Absorption correction: gaussian (XSCANS; Siemens, 1996 ▶) T min = 0.933, T max = 0.954 6308 measured reflections 2497 independent reflections 1428 reflections with I > 2σ(I) R int = 0.060 3 standard reflections every 97 reflections intensity decay: 2.3%

Refinement

R[F 2 > 2σ(F 2)] = 0.060 wR(F 2) = 0.186 S = 1.06 2497 reflections 172 parameters H-atom parameters constrained Δρmax = 0.19 e Å−3 Δρmin = −0.16 e Å−3 Absolute structure: Flack (1983 ▶), 1028 Friedel pairs Flack parameter: 0.0 (2) Data collection: XSCANS (Siemens, 1996 ▶); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXL97. Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809017528/fj2198sup1.cif Structure factors: contains datablocks I. DOI: 10.1107/S1600536809017528/fj2198Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C₃₂H₂₈N₂·CH₂Cl₂	D_x = 1.237 Mg m⁻³
M_r = 525.49	Melting point: 343 K
Orthorhombic, P2₁2₁2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2 2ab	Cell parameters from 51 reflections
a = 8.550 (2) Å	θ = 4.0–11.9°
b = 20.706 (6) Å	µ = 0.25 mm⁻¹
c = 7.972 (3) Å	T = 298 K
V = 1411.3 (7) Å³	Prism, yellow
Z = 2	0.40 × 0.24 × 0.20 mm
F(000) = 552

Siemens P4 diffractometer	1428 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.060
graphite	θ_max = 25.0°, θ_min = 2.0°
2θ/ω scans	h = −10→10
Absorption correction: gaussian (XSCANS; Siemens, 1996)	k = −24→24
T_min = 0.933, T_max = 0.954	l = −9→9
6308 measured reflections	3 standard reflections every 97 reflections
2497 independent reflections	intensity decay: 2.3%

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.060	w = 1/[σ²(F_o²) + (0.0833P)² + 0.2257P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.186	(Δ/σ)_max < 0.001
S = 1.06	Δρ_max = 0.19 e Å⁻³
2497 reflections	Δρ_min = −0.16 e Å⁻³
172 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.036 (6)
0 constraints	Absolute structure: Flack (1983), 1028 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.0 (2)
Secondary atom site location: difference Fourier map

	x	y	z	U_iso*/U_eq
N1	0.8943 (5)	0.38124 (15)	1.0214 (4)	0.0789 (10)
C1	1.0000	0.5000	1.5231 (7)	0.0904 (19)
H1A	1.0000	0.5000	1.6398	0.108*
C2	0.9506 (5)	0.4463 (2)	1.4376 (5)	0.0800 (12)
H2A	0.9166	0.4102	1.4968	0.096*
C3	0.9508 (4)	0.44531 (18)	1.2633 (5)	0.0660 (10)
C4	1.0000	0.5000	1.1777 (7)	0.0682 (14)
H4A	1.0000	0.5000	1.0611	0.082*
C5	0.9004 (5)	0.38667 (18)	1.1771 (5)	0.0711 (10)
H5A	0.8711	0.3514	1.2420	0.085*
C6	0.8370 (5)	0.32020 (18)	0.9537 (5)	0.0747 (11)
H6A	0.8222	0.2897	1.0464	0.090*
C7	0.6791 (5)	0.3332 (2)	0.8717 (6)	0.0947 (14)
H7A	0.6077	0.3499	0.9539	0.142*
H7B	0.6383	0.2937	0.8262	0.142*
H7C	0.6918	0.3642	0.7832	0.142*
C8	0.9507 (5)	0.29178 (16)	0.8309 (5)	0.0646 (9)
C9	1.0643 (5)	0.32880 (18)	0.7563 (5)	0.0760 (11)
H9A	1.0740	0.3720	0.7868	0.091*
C10	1.1656 (6)	0.3034 (2)	0.6361 (6)	0.0924 (14)
H10A	1.2430	0.3295	0.5899	0.111*
C11	1.1527 (6)	0.2419 (2)	0.5865 (5)	0.0851 (12)
H11A	1.2184	0.2263	0.5028	0.102*
C12	1.0413 (5)	0.20049 (19)	0.6592 (5)	0.0751 (11)
C13	1.0297 (6)	0.1351 (2)	0.6116 (6)	0.0911 (13)
H13A	1.0960	0.1188	0.5293	0.109*
C14	0.9225 (6)	0.0957 (2)	0.6848 (7)	0.0973 (15)
H14A	0.9158	0.0527	0.6524	0.117*
C15	0.8233 (5)	0.1194 (2)	0.8073 (7)	0.0909 (14)
H15A	0.7514	0.0919	0.8578	0.109*
C16	0.8295 (5)	0.18255 (17)	0.8549 (6)	0.0749 (11)
H16A	0.7615	0.1975	0.9371	0.090*
C17	0.9380 (4)	0.22579 (17)	0.7812 (5)	0.0652 (9)
C18	0.5000	0.5000	0.8916 (9)	0.123 (3)
H18A	0.4641	0.5349	0.9629	0.148*
Cl1	0.6505 (3)	0.52641 (11)	0.7706 (3)	0.1852 (10)

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.102 (3)	0.0685 (19)	0.067 (2)	−0.0018 (18)	0.003 (2)	0.0003 (16)
C1	0.099 (5)	0.115 (5)	0.057 (3)	0.000 (4)	0.000	0.000
C2	0.084 (3)	0.090 (3)	0.066 (2)	0.004 (3)	0.008 (2)	0.008 (2)
C3	0.062 (2)	0.076 (2)	0.060 (2)	0.0110 (19)	0.0047 (19)	0.0017 (19)
C4	0.073 (3)	0.075 (3)	0.056 (3)	0.015 (3)	0.000	0.000
C5	0.073 (2)	0.070 (2)	0.070 (3)	0.008 (2)	0.007 (2)	0.008 (2)
C6	0.085 (3)	0.070 (2)	0.069 (2)	−0.001 (2)	0.003 (2)	0.0066 (19)
C7	0.080 (3)	0.099 (3)	0.105 (3)	0.016 (3)	0.008 (3)	0.000 (3)
C8	0.069 (2)	0.064 (2)	0.060 (2)	0.0002 (18)	0.003 (2)	0.0087 (17)
C9	0.085 (3)	0.072 (2)	0.071 (2)	−0.006 (2)	0.005 (2)	0.009 (2)
C10	0.091 (3)	0.100 (3)	0.086 (3)	−0.005 (3)	0.026 (3)	0.022 (3)
C11	0.082 (3)	0.102 (3)	0.072 (3)	0.013 (3)	0.011 (2)	0.003 (2)
C12	0.071 (2)	0.081 (2)	0.073 (2)	0.010 (2)	−0.014 (2)	−0.004 (2)
C13	0.089 (3)	0.090 (3)	0.095 (3)	0.020 (3)	−0.019 (3)	−0.019 (3)
C14	0.097 (3)	0.076 (3)	0.120 (4)	0.012 (3)	−0.030 (4)	−0.010 (3)
C15	0.078 (3)	0.075 (3)	0.120 (4)	−0.005 (2)	−0.024 (3)	0.007 (3)
C16	0.066 (2)	0.072 (2)	0.087 (3)	−0.004 (2)	−0.004 (2)	0.002 (2)
C17	0.059 (2)	0.069 (2)	0.068 (2)	0.0022 (18)	−0.007 (2)	0.0072 (18)
C18	0.192 (10)	0.094 (5)	0.084 (4)	−0.003 (5)	0.000	0.000
Cl1	0.1454 (16)	0.208 (2)	0.202 (2)	−0.0442 (14)	0.0100 (17)	0.0547 (16)

N1—C5	1.248 (5)	C9—C10	1.395 (6)
N1—C6	1.459 (5)	C9—H9A	0.9300
C1—C2	1.371 (5)	C10—C11	1.338 (6)
C1—C2ⁱ	1.371 (5)	C10—H10A	0.9300
C1—H1A	0.9300	C11—C12	1.407 (6)
C2—C3	1.390 (5)	C11—H11A	0.9300
C2—H2A	0.9300	C12—C13	1.410 (6)
C3—C4	1.387 (4)	C12—C17	1.414 (5)
C3—C5	1.460 (5)	C13—C14	1.359 (7)
C4—C3ⁱ	1.387 (4)	C13—H13A	0.9300
C4—H4A	0.9300	C14—C15	1.384 (7)
C5—H5A	0.9300	C14—H14A	0.9300
C6—C8	1.500 (5)	C15—C16	1.363 (5)
C6—C7	1.524 (6)	C15—H15A	0.9300
C6—H6A	0.9800	C16—C17	1.416 (5)
C7—H7A	0.9600	C16—H16A	0.9300
C7—H7B	0.9600	C18—Cl1ⁱⁱ	1.699 (5)
C7—H7C	0.9600	C18—Cl1	1.699 (5)
C8—C9	1.373 (5)	C18—H18A	0.9698
C8—C17	1.427 (5)

C5—N1—C6	117.4 (3)	C8—C9—C10	121.8 (4)
C2—C1—C2ⁱ	120.4 (6)	C8—C9—H9A	119.1
C2—C1—H1A	119.8	C10—C9—H9A	119.1
C2ⁱ—C1—H1A	119.8	C11—C10—C9	120.7 (4)
C1—C2—C3	120.6 (4)	C11—C10—H10A	119.7
C1—C2—H2A	119.7	C9—C10—H10A	119.7
C3—C2—H2A	119.7	C10—C11—C12	121.0 (4)
C4—C3—C2	118.7 (4)	C10—C11—H11A	119.5
C4—C3—C5	122.5 (4)	C12—C11—H11A	119.5
C2—C3—C5	118.8 (4)	C11—C12—C13	121.5 (4)
C3—C4—C3ⁱ	121.1 (5)	C11—C12—C17	118.7 (4)
C3—C4—H4A	119.4	C13—C12—C17	119.8 (4)
C3ⁱ—C4—H4A	119.4	C14—C13—C12	120.5 (5)
N1—C5—C3	123.7 (4)	C14—C13—H13A	119.7
N1—C5—H5A	118.1	C12—C13—H13A	119.7
C3—C5—H5A	118.1	C13—C14—C15	120.3 (4)
N1—C6—C8	111.3 (3)	C13—C14—H14A	119.9
N1—C6—C7	107.6 (3)	C15—C14—H14A	119.9
C8—C6—C7	111.3 (3)	C16—C15—C14	120.8 (5)
N1—C6—H6A	108.8	C16—C15—H15A	119.6
C8—C6—H6A	108.8	C14—C15—H15A	119.6
C7—C6—H6A	108.8	C15—C16—C17	121.1 (4)
C6—C7—H7A	109.5	C15—C16—H16A	119.4
C6—C7—H7B	109.5	C17—C16—H16A	119.4
H7A—C7—H7B	109.5	C12—C17—C16	117.4 (4)
C6—C7—H7C	109.5	C12—C17—C8	119.9 (3)
H7A—C7—H7C	109.5	C16—C17—C8	122.7 (4)
H7B—C7—H7C	109.5	Cl1ⁱⁱ—C18—Cl1	110.8 (4)
C9—C8—C17	117.9 (4)	Cl1ⁱⁱ—C18—H18A	109.4
C9—C8—C6	121.5 (3)	Cl1—C18—H18A	109.4
C17—C8—C6	120.5 (3)

C2ⁱ—C1—C2—C3	0.4 (3)	C10—C11—C12—C13	−178.1 (4)
C1—C2—C3—C4	−0.9 (6)	C10—C11—C12—C17	2.7 (6)
C1—C2—C3—C5	178.7 (3)	C11—C12—C13—C14	179.2 (4)
C2—C3—C4—C3ⁱ	0.4 (3)	C17—C12—C13—C14	−1.6 (6)
C5—C3—C4—C3ⁱ	−179.1 (4)	C12—C13—C14—C15	0.0 (7)
C6—N1—C5—C3	−178.2 (4)	C13—C14—C15—C16	1.0 (7)
C4—C3—C5—N1	−1.5 (6)	C14—C15—C16—C17	−0.3 (6)
C2—C3—C5—N1	179.0 (4)	C11—C12—C17—C16	−178.6 (4)
C5—N1—C6—C8	−126.4 (4)	C13—C12—C17—C16	2.2 (5)
C5—N1—C6—C7	111.4 (4)	C11—C12—C17—C8	−1.5 (5)
N1—C6—C8—C9	−19.0 (5)	C13—C12—C17—C8	179.3 (4)
C7—C6—C8—C9	101.1 (4)	C15—C16—C17—C12	−1.3 (6)
N1—C6—C8—C17	164.5 (3)	C15—C16—C17—C8	−178.3 (4)
C7—C6—C8—C17	−75.4 (4)	C9—C8—C17—C12	0.3 (5)
C17—C8—C9—C10	−0.3 (6)	C6—C8—C17—C12	177.0 (3)
C6—C8—C9—C10	−176.9 (4)	C9—C8—C17—C16	177.2 (3)
C8—C9—C10—C11	1.5 (7)	C6—C8—C17—C16	−6.1 (5)
C9—C10—C11—C12	−2.7 (7)

4 in total

1. Solvent-free organic synthesis.

Authors: K Tanaka; F Toda
Journal: Chem Rev Date: 2000-03-08 Impact factor: 60.622

2. Pursuing practical elegance in chemical synthesis.

Authors: Ryoji Noyori
Journal: Chem Commun (Camb) Date: 2005-03-15 Impact factor: 6.222

3. A short history of SHELX.

Authors: George M Sheldrick
Journal: Acta Crystallogr A Date: 2007-12-21 Impact factor: 2.290

4. A green chemistry approach to a more efficient asymmetric catalyst: solvent-free and highly concentrated alkyl additions to ketones.

Authors: Sang-Jin Jeon; Hongmei Li; Patrick J Walsh
Journal: J Am Chem Soc Date: 2005-11-30 Impact factor: 15.419