Electronic effects on crown ether conformation. X-ray crystal structure and 13C NMR study in solution and the solid phase of 4-nitrobenzo-9-crown-3 ether

1994 ◽  
Vol 72 (8) ◽  
pp. 1764-1768 ◽  
Author(s):  
G. W. Buchanan ◽  
A. B. Driega ◽  
A. Moghimi ◽  
C. Bensimon
Keyword(s):  
Crystal Structure ◽  
Crown Ether ◽  
13C Nmr ◽  
Solid Phase ◽  
Electronic Effects ◽  
Nmr Spectrum ◽  
X Ray ◽  
Nmr Study ◽  
C Nmr

The X-ray crystal structure of the title material has been determined and the results are compared to previous findings for benzo-9-crown-3 itself. The 13C NMR spectrum in solution has been unambiguously assigned using COSY and HETCOR methods. The solid phase 13C spectrum has been obtained and the 7, 10-d4 derivative has been examined to aid in spectral assignments.

Solid state stereochemistry of crown ethers: X-ray crystal structure and 13C NMR studies of the LiNCS complex of 1,4,7,11-tetraoxacyclotetradecane

2000 ◽  
Vol 78 (3) ◽  
pp. 316-321
Author(s):  
G W Buchanan ◽  
A B Driega ◽  
G PA Yap
Keyword(s):  
Crystal Structure ◽  
Solid State ◽  
Crown Ether ◽  
13C Nmr ◽  
Title Complex ◽  
Nmr Studies ◽  
Nmr Spectrum ◽  
X Ray ◽  
Large Amplitude Motion ◽  
C Nmr

The title complex is asymmetric in the crystal due to the spatial orientation of the NCS function. The space group has been determined to be P21 with a = 9.496(3), b = 8.736(3), c = 9.676(3) Å, β = 117.859(5)°, and Z = 2. The solid state 13C NMR spectrum is consistent with the lack of symmetry in the crystal and there is little evidence for large amplitude motion in the macrocycle as determined from the dipolar dephased spectrum.Key words: macrocyclic crown ether, lithium complex.

Synthesis, X-ray crystal structure, and solid-state 13C NMR study of tris(9-crown-3)triphenylene

2001 ◽  
Vol 79 (2) ◽  
pp. 195-200 ◽  
Author(s):  
Gerald W Buchanan ◽  
Majid F Rastegar ◽  
Glenn PA Yap
Keyword(s):  
Crystal Structure ◽  
Solid State ◽  
Crown Ether ◽  
Chemical Shifts ◽  
Aromatic Rings ◽  
X Ray ◽  
Nmr Study ◽  
Group A ◽  
C Nmr ◽  
Solid State 13C Nmr

Benzo-9-crown-3 ether trimerizes in the presence of FeCl3 and aqueous H2SO4 to produce tris(9-crown-3)triphenylene in 25.4% yield. This compound crystallizes in the monoclinic P21/c space group: a = 13.759(2) Å, b = 13.318(2) Å, c = 13.399(2) Å, β = 96.883(2)°, with Z = 4. The three 9-crown-3 ether units of the trimer possess different geometries and there is substantial deviation from coplanarity in the three aromatic rings. 13C NMR chemical shifts in the solid state are consistent with this lack of symmetry and are discussed in terms of the X-ray crystal-structure data.Key words: crown ether, trimerization, stereochemistry.

Darstellung, 11B-, 13C-NMR-und Schwingungsspektren von Cyanomethylhexahydro-closo-Hexaborat(Hexaborat(1-), [B6H6(CH2CN)]– sowie Kristallstruktur von [P(C6H5)4][B6H6(CH2CN)] / Preparation, 11B, 13C NMR and Vibrational Spectra of Cyanomethylhexahydro-closohexaborate(1-), [B6H6(CH2CN)]- and the Crystal Structure of [P(C6H5)4][B6H6(CH2CN)]

1994 ◽  
Vol 49 (4) ◽  
pp. 471-476 ◽  
Author(s):  
A. Franken ◽  
W. Preetz
Keyword(s):  
Crystal Structure ◽  
13C Nmr ◽  
Exchange Chromatography ◽  
X Ray Diffraction ◽  
Nmr Spectrum ◽  
Triclinic Space Group ◽  
X Ray ◽  
Diethylaminoethyl Cellulose ◽  
Ir And Raman ◽  
C Nmr

By reaction of [B6H6]2- with chloroacetonitrile in dichloromethane the cyanomethylhexahy-dro-closo-hexaborate(1-), [B6H6(CH2CN)]- is formed. The com pound has been separated from excess [B6H6]2- by ion exchange chromatography on diethylaminoethyl cellulose. The crystal structure of [P(C6H5)4][B6H6(CH2CN)] has been determined by single crystal X-ray diffraction analysis; triclinic, space group P1 with a = 7.503(3), b = 12.0949(8), c = 14.6572(11) Å α = 79.399(6)°, β = 79.19(2)°, γ = 89.2(2)°. The 11B NMR spectrum is consistent with a mono hetero substituted octahedral B6 cage. In the 13C NMR spectrum of Cs2[B6H5(CH2CN)] a singlet at 131.9 ppm (CN) and a quartet at 2.97 ppm with 1J(C,B) = 54.7 Hz (CH2) are observed. The IR and Raman spectra exhibit a very strong CN stretching band at 2218 cm-1.

Darstellung, 11B-, 13C-, 29Si-NMR- und Schwingungsspektren von Trimethylsilylmethyl-hexahydro-closo-hexaborat, [B6H6(CH2Si(CH3)3)]- sowie Kristallstruktur von [P(C6H5)4][B6H6(CH2Si(CH3)3)] / Preparation, 11B, 13C, 29Si NMR and Vibrational Spectra of Trimethylsilylmethyl-hexahydro-clo-hexaborate, [B6H6(CH2Si(CH 3)3)]-and the Crystal Structure of [P(C6H5)4] [B6H6(CH2Si(CH3)3)]

1995 ◽  
Vol 50 (7) ◽  
pp. 1025-1029 ◽  
Author(s):  
J. Baurmeister ◽  
A. Franken ◽  
W. Preetz
Keyword(s):  
Crystal Structure ◽  
Monoclinic Space Group ◽  
29Si Nmr ◽  
X Ray Diffraction ◽  
Nmr Spectrum ◽  
X Ray ◽  
Quadrupole Coupling ◽  
Stretching Vibration ◽  
Ir And Raman ◽  
C Nmr

By reaction of [N(C4H9 )4]2 [B6H6] with iodomethyl-trimethylsilane in acetonitrile a solution with trimethylsilylm ethyl-closo-hexaborate(1-)anions, [B6H6 (CH2Si(CH3)3)]-, is formed. The crystal structure of [P(C6H5 )4][B6H6(CH2Si(CH3)3)] has been determined by single crystal X-ray diffraction analysis; monoclinic, space group P21/n with a = 16.140(2), b = 11.646(8), c = 16.731(3) Å, β 109.664(11)°. The 11B NMR spectrum reveals features of a mono hetero substituted octahedral B6 cage. The 13C NMR spectrum exhibits a quartet at +0.18 ppm with 1J(C,H) = 118 Hz for the three methyl groups and a weak multiplet at -0.65 ppm for the methylene bridge due to quadrupole coupling with the boron atoms. In the 29Si NMR spectrum a decet at +2.25 ppm with 2J(C,H ) = 6.9 Hz is observed. The B -C stretching vibration is observed at 1155 cm-1 in the IR and Raman spectrum.

scholarly journals Darstellung, 11B-, 13C-NMR- und Schwingungsspektren der closo-Hexaborate [B6H5(CN)12- und cis-[B6H4(CN)2]2− sowie Kristallstruktur von Cs2[B6H5(CN)] / Preparation, 11B,13C NMR and Vibrational Spectra of the closo-Hexaborates [B6H5(CN)]2- and cis-[B6H4(CN)2]2-, and the Crystal Structure of Cs2[B6H5(CN)]

1993 ◽  
Vol 48 (5) ◽  
pp. 598-602 ◽  
Author(s):  
W. Preetz ◽  
A. Franken ◽  
M. Rath
Keyword(s):  
Crystal Structure ◽  
13C Nmr ◽  
Exchange Chromatography ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Nmr Spectrum ◽  
Diethylaminoethyl Cellulose ◽  
Ir And Raman ◽  
C Nmr

By reaction of Cs2[B6H6] with in situ generated dicyanogen in aqueous alkaline solution the monocyanohydrohexaborate Cs2[B6H5(CN)] and the dicyanohydrohexaborate cis-Cs2[B6H4(CN)2] are formed. The compounds have been separated by ion exchange chromatography on diethylaminoethyl cellulose. The crystal structure of Cs2[B6H5(CN)] was determined from single crystal X-ray diffraction analysis; monoclinic, space group P21/a with a = 9.540(8), b = 9.977(3), c = 10.578(2)Å, β = 105.06(2)°. The B6 octahedron is compressed in the direction of the nearly linear B—CN bond by about 5%, with bond lengths between 1.71 and 1.76Å. The "B NMR spectra of the two compounds reveal the features of substituted B6 cages with C4v and C2v point symmetry. In the 13C NMR spectrum of Cs2[B6H5(CN)] a quartet at -139 ppm with 1J(C,B) 92 Hz is observed. The IR and Raman spectra exhibit very strong CN stretching bands for Cs2[B6H5(CN)] at 2149, and for cis-Cs2[B6H4(CN)2] at 2170 cm-1.

Variable temperature 13C NMR study of some L(CO)3FeH(SiR3) (L = CO, P(OPh)3; R = Ph, Me, Cl) species. X-ray crystal structure of P(OPh)3(CO)3Fe(H)SiPh3

Polyhedron ◽  
1991 ◽  
Vol 10 (8) ◽  
pp. 841-849 ◽  
Author(s):  
John W. Connolly ◽  
Michael J. Hatlee ◽  
Alan H. Cowley ◽  
Paul R. Sharp
Keyword(s):  
Crystal Structure ◽  
13C Nmr ◽  
Variable Temperature ◽  
X Ray ◽  
Nmr Study

Benzo-9-crown-3 ether: X-ray crystal structure, NMR studies in solution and the solid phase, and ab initio calculations of isotropic 13C chemical shifts using LORG with a D95V basis set

1993 ◽  
Vol 71 (12) ◽  
pp. 1983-1989 ◽  
Author(s):  
G.W. Buchanan ◽  
A.B. Driega ◽  
A. Moghimi ◽  
C. Bensimon ◽  
R.A. Kirby ◽  
...  
Keyword(s):  
Ab Initio ◽  
Solid Phase ◽  
Chemical Shifts ◽  
Basis Set ◽  
Length Variation ◽  
Nmr Studies ◽  
Nmr Spectrum ◽  
X Ray ◽  
Localized Orbital ◽  
C Nmr

Using the X-ray crystal geometry as input, the 13C NMR chemical shifts of benzo-9-crown-3 ether have been calculated via ab initio methods using a localized orbital local origin (LORG) approach. Reasonable agreement is found between the calculated values for an isolated molecule in the gas phase and those obtained in the 13C CPMAS NMR spectrum. Solid phase 13C spectra of the C7,10-d4 derivative confirm the existence of a 7.9 ppm shift difference between these sites in the solid, whereas in solution they are conformationally averaged to one resonance. The effects of C—H bond length variation on calculated 13C shifts have been explored.

Darstellung, 11B-, 13C-NMR-und Schwingungsspektren von Aminom ethylhexahydro-closo-hexaborat(1-), [B6H6(CH2NH2)]- sowie Kristallstrukturen von Cs[B6H6(CH2NH2)] und K[B6H6(CH2NH2)] / Preparation, 11B, 13C NMR and Vibrational Spectra of Aminomethylhexahydro-closo-hexaborate(1-), [B6H6(CH2NH2)]-, and Crystal Structures of Cs[B6H6(CH2NH2)] and K[B6H6(CH2NH2)]

1994 ◽  
Vol 49 (9) ◽  
pp. 1267-1271 ◽  
Author(s):  
A. Franken ◽  
W. Preetz
Keyword(s):  
Single Crystal ◽  
Diffraction Analysis ◽  
Crystal Structures ◽  
13C Nmr ◽  
Vibrational Spectra ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Nmr Spectrum ◽  
X Ray ◽  
C Nmr

By reaction of [B6H6]2- with N-(chloromethyl)phthalimide in dichloromethane the intermediate phthalimidomethylhexahydro-closo-hexaborate(1-), [B6H6(CH2(NC8O2H4)]-, is formed which with an excess of hydrazine reacts to give am inomethylhexahydro-closo-hexaborate(1-). The crystal structures of Cs[Bf,H6(CH2NH2)] and K[B6H6(CH2NH2)] have been determined by single crystal X -ray diffraction analysis. They are monoclinic, space group C2/m with a = 11.123(6), b = 6.8441(11), c = 12.810(7) Å, β = 124.032(5)° for Cs[B6H6(CH2NH2)] and with a = 10.767(2), b = 6.6255(6), c = 12.2648(14) Å, β = 123.880(10")° for K [B6H6(CH2NH2)]. The 11B NMR spectrum is consistent with a monohetero substituted octahedral B6 cage with local C4v symmetry. In the 13C NMR spectrum of Cs[B6H6(CH2NH2)] a quartet at 32.7 ppm with 1J(C,B) 65 Hz is observed. The IR and Ram an spectra exhibit characteristic CH, NH, BH and B6 vibrations

Darstellung, 11B-, 13C-NMR- und Schwingungsspektren von Cs2[B6Cl5(p-C6H4(NI-I2))] sowie Kristallstruktur von (Ph4P)2[B6Cl5(p-C6H4(NH2))]·2CH3CN · 0,5 Et2O / Preparation, 11B, 13C NMR and Vibrational Spectra of Cs2[B6Cl5(p-C6H4(NH2))] and Crystal Structure of (Ph4P)2[B6Cl5(p-C6H4(NH2))]· 2CH3CN · 0.5 Et2O

2001 ◽  
Vol 56 (1) ◽  
pp. 85-89
Author(s):  
S. Zander ◽  
W. Preetz
Keyword(s):  
Crystal Structure ◽  
Single Crystal ◽  
Diffraction Analysis ◽  
13C Nmr ◽  
Vibrational Spectra ◽  
Amino Derivative ◽  
X Ray Diffraction ◽  
Nmr Spectrum ◽  
Triclinic Space Group ◽  
X Ray

Abstract By reduction of [B6Cl5(p-C6H4 (NO2))]2- with hydrazine in the presence of Raney nickel in dichlorom ethane solution the amino derivative [B6Cl5(p-C6H4(NH2)]2-is formed. X -ray diffraction analysis has been performed on a single crystal of (Ph4P)2[B6Cl5(p-C6H4(NH2] ·2CH3CN-0,5Et2O(triclinic, space group P1̅, a = 12.870(6), b = 12.9406(5), c = 35,870(7) Å , a = 91,63(4), ß = 93,22(7), γ = 98,04(8)°, Z = 2). The 11B NMR spectrum is consistent with a monosubstituted B6 cluster. The IR and R am an spectra exhibit characteristic BB, CH , CC, and NH vibrations, respectively.

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