Comparative analysis of hydrogen bonding with participation of the nitrogen, oxygen and sulfur atoms in the 2(2'-heteroaryl)pyrroles and their trifluoroacetyl derivatives based on the 1H, 13C, 15N spectroscopy and DFT calculations

The N-H...X (X = N,O,S) intramolecular hydrogen bond in the series of 2(2'-heteroaryl)pyrroles and their trifluoroacetyl derivatives is examined by the (1)H, (13)C, (15)N spectroscopy and density functional theory (DFT) calculations. The influence of the hydrogen bond on coupling and shielding constants is considered. It is shown that the N-H...N intramolecular hydrogen bond causes a larger increase in the absolute size of the (1)J(N,H) coupling constant and a larger deshielding of the bridge proton than the N-H...O hydrogen bond. The effect of the N-H...S interaction on the (1)J(N,H) coupling constant and the shielding of the bridge proton is small. The NMR parameter changes in the series of the 2(2'-heteroaryl)pyrroles due to N-H...X hydrogen bond and the series of the 1-vinyl-2-(2'-heteroaryl)-pyrroles due to C-H...X hydrogen bond have the same order. The proximity of the nitrogen, oxygen or sulfur lone pair to the F...H hydrogen bridge quenches the trans-hydrogen bond spin-spin couplings (1h)J(F,H-1) and (2h)J(F,N).     

1H, 13C and 15N NMR spectral characterization of twenty-seven 1,2-diaryl-(4E)-arylidene-2-imidazolin-5-ones

1H, 13C and 15N NMR chemical shifts and couplings (n)J(H,C) in DMSO-d(6) at 30 degrees C have been determined for 1,2-diaryl-(4E)-arylidene-2-imidazolin-5-one derivatives 1-27. Their chemical shift assignments are based on PFG DQF 1H,1H COSY, PFG 1H,13C HMQC as well as PFG 1H,13C and 1H,15N HMBC experiments. For compounds 1-10 including aryl fluorine substituent(s) also the couplings (n)J(F,C) (n = 1 - 4) are reported.     

Eremophilane esters of Robinsonecio gerberifolius and their rearranged products. Study of the coupling constants (2)J(H, H), (3)J(H, H) and (4)J(H, H)

In the course of the basic hydrolysis of four eremophilane esters isolated from Robinsonecio gerberifolius, some rearrangements, eliminations, and additions occurred. Five compounds were obtained, three of them not previously described. Additionally, a new sesquiterpene was produced by autooxidation of compound 1. The (1)H and (13)C NMR spectra of these compounds were completely assigned by utilization of HMQC, HMBC, COSY, DEPT, and NOESY techniques. The long-range coupling constants of the peroxide 10 are reported, and all its coupling constants (2)J(H, H), (3)J(H, H), and (4)J(H, H) are calculated at the B3LYP/6-31G(d,p) level of theory. Their magnitude is explained in terms of electronic delocalization and the additivity of stereoelectronic effects.     

Complete assignment of 19F, 1H and 13C NMR spectra of monomers and precursors towards bridge trifluoromethylated poly(p-phenylenevinylene)

The complete assignment of 19F, 1H and 13C NMR spectra of 11 trifluoromethylated and four bistrifluoromethylated monomers for bridge trifluoromethylated poly(p-phenylenevinylene) is described. The combination of one-dimensional 19F, 1H and 13C spectra, long-range fluorine couplings and the two-dimensional techniques of direct and long-range HETCOR (J = 140 and 8 Hz) permitted full resonance assignment.     

Substituent effects on scalar J(13C, 13C) couplings in pyrimidines. An experimental and DFT study

One- two- and three 13C, 13C (n = 1, 2, 3) scalar couplings, (n)J(C,C) in a set of pyrimidine derivatives were studied both experimentally at natural abundance and theoretically by their DFT calculation of all four contributions. Trends of non-contact terms are discussed and substituent effects are rationalized, comparing some of them with the corresponding values in benzene and pyridine. Although substituent effects on non-contact terms are relatively important, the whole trend is dominated by the Fermi contact term. According to the current literature, substituent effects on 1J(C,C) couplings in benzene derivatives are dominated by the inductive effect, which, apparently, is also the case in nitrogen heteroaromatic compounds. However, some differences observed in this work for substituent effects on 1J(C,C) couplings in pyrimidine derivatives suggest that in the latter type of compounds substituent effects can be affected by the orientation of the ring nitrogen lone pairs.     

Hydrogen Bonding of Fluorinated Saccharides in Solution: F Acting as H‐Bond Acceptor in a Bifurcated H‐Bond of 4‐Fluorinated Levoglucosans

4‐Fluorinated levoglucosans were synthesised to test if OH???F H‐bonds are feasible even when the O???F distance is increased. The fluorinated 1,6‐anhydro‐β‐D ‐glucopyranoses were synthesised from 1,6 : 3,4‐dianhydro‐β‐D ‐galactopyranose ( 8 ). Treatment of 8 with KHF₂ and KF gave 43% of 4‐deoxy‐4‐fluorolevoglucosan ( 9 ), which was transformed into the 3‐O‐protected derivatives 13 by silylation and 15 by silylation, acetylation, and desilylation. 4‐Deoxy‐4‐methyllevoglucosan ( 19 ) and 4‐deoxylevoglucosan ( 21 ) were prepared as reference compounds that can only form a bivalent H‐bond from HO? C(2) to O? C(5). They were synthesised from the ⁱPr₃Si‐protected derivative of 8 . Intramolecular bifurcated H‐bonds from HO? C(2) to F? C(4) and O? C(5) of the 4‐fluorinated levoglucosans in CDCl₃ solution are evidenced by the ¹H‐NMR scalar couplings ^h1J(F,OH) and ³J(H,OH). The OH???F H‐bond over an O???F distance of ca. 3.0 Å is thus formed in apolar solvents, at least when favoured by the simultaneous formation of an OH???O H‐bond.     

Bifurcated hydrogen-bonding effect on the shielding and coupling constants in trifluoroacetyl pyrroles as studied by 1H, 13C and 15N NMR spectroscopy and DFT calculations

According to the (1)H, (13)C and (15)N NMR spectroscopic data and DFT calculations, bifurcated N--H...N and N--H...O intramolecular hydrogen bond is shown to be present in 2-trifluoroacetyl-5-(2'-pyridyl)-pyrrole. This bifurcated hydrogen bond causes an increase in the absolute size of the (1)J(N,H) coupling constant by about 6 Hz, and the deshielding of the bridge proton by 2 ppm. DFT calculations show that the influence of the N--H...N and N--H...O intramolecular hydrogen bonds on the (1)J(N,H) coupling and proton shielding is almost additive, although the components of the bifurcated hydrogen bond slightly weaken each other. In 2-trifluoroacetyl-5-(2'-pyridyl)-pyrrole, the coupling constants involving the fluorine and the N--H covalent bond nuclei depend dramatically on the spatial position of the pyridine ring. The pyridine ring rotation operates as a quantum switch controlling the spin information transfer between the (19)F and (15)N nuclei, as well as the proton.     

Comparison of methyl rotation axis order parameters derived from model-free analyses of (2)H and (13)C longitudinal and transverse relaxation rates measured in the same protein sample.

Recombinant HIV-1 protease was obtained from bacteria grown on a 98% D(2)O medium containing 3-(13)C pyruvic acid as the sole source of (13)C and (1)H. The purified protein is highly deuterated at non-methyl carbons, but contains significant populations of (13)CHD(2) and (13)CH(2)D methyl isotopomers. This pattern of isotope labeling permitted measurements of (1)H and (13)C relaxation rates of (13)CHD(2) isotopomers and (2)H (D) relaxation rates of (13)CH(2)D isotopomers using a single sample. The order parameters S(axis)(2), which characterize the motions of the methyl rotation axes, were derived from model-free analyses of R(1) and R(2) data sets measured for (13)C and (2)H spins. Our primary goal was to compare the S(axis)(2) values derived from the two independent types of data sets to test our understanding of the relaxation mechanisms involved. However, S(axis)(2) values derived from the analyses depend strongly on the geometry of the methyl group, the sizes of the quadrupolar and dipolar couplings, and the effects of bond vibrations and librations on these couplings. Therefore uncertainties in these basic physical parameters complicate comparison of the order parameters. This problem was circumvented by using an experimental relationship, between the methyl quadrupolar, (13)C-(13)C and (13)C-(1)H dipolar couplings, derived from independent measurements of residual static couplings of weakly aligned proteins by Ottiger and Bax (J. Am. Chem. Soc. 1999, 121, 4690-4695) and Mittermaier and Kay (J. Am. Chem. Soc. 1999, 121, 10608-10613). This approach placed a tight experimental restraint on the values of the (2)H quadrupolar and (13)C-(1)H dipolar interactions and greatly facilitated the accurate comparison of the relative values of the order parameters. When applied to our data this approach yielded satisfactory agreement between the S(axis)(2) values derived from the (13)C and (2)H data sets.     

(13)C-(1)H and (13)C-(13)C NMR J-couplings in (13)C-labeled N-acetyl-neuraminic acid: correlations with molecular structure

N-acetyl-neuraminic acid (Neu5Ac, 2) was prepared enzymatically containing single sites of (13)C-enrichment at C1, C2, and C3. Aqueous solutions of the three (13)C isotopomers were studied by (1)H and (13)C NMR spectroscopy at p(2)H 2 and pH 8 to obtain J(CH) and J(CC) values involving the labeled carbons. Experimental studies were complemented by DFT calculations of the same set of J-couplings in protonated and ionized structural mimics of 2 to determine how well theoretical predictions match the experimental findings in saccharides bearing ionizable functionality. Results show that: (a) (2)J(C2,H3ax/eq) values in 2 depend on anomeric configuration, thus complementing (3)J(C1,H3ax/eq) behavior, (b) J(CH) and J(CC) values involving C2 depend on anomeric configuration, the C1-C2 bond torsion, and solution pH, and (c) long-range (4)J(C2,H7) is sensitive to glycerol side-chain conformation. Intraring J(HH) and most (2)J(CH), (3)J(CH), (2)J(CC), and (3)J(CC) involving C1-C3 of 2 appear largely unaffected by the ionization state of the carboxyl group. In vacuo and solvated DFT calculations of geminal and vicinal J(CH) and J(CC) values are similar and reproduce the experimental data well, but better agreement with experiment was observed for (1)J(C1,C2) in the solvated calculations. The present work provides new information for future treatments of trans-glycoside couplings involving Neu5Ac residues by (a) providing new standard values of intraring J(CC) for coupling pathways that mimic those for trans-glycoside J(CC), (b) identifying potential effects of solution pH on trans-glycoside couplings inferred through the behavior of related intraring couplings, and (c) providing specific guidelines for more reliable DFT predictions of J(CH) and J(CC) values in ionizable saccharides.     

Experimental and computational studies of nJ(77Se, 1H) selenium-proton couplings in selenoglycosides

Selenoglycosides are important starting materials in synthetic carbohydrate chemistry and play a role in biological interactions as well. Both aspects are influenced by the conformation around the glycosidic bond. Here, we present a combined experimental and computational approach to measure and evaluate (n)J((77)Se, (1)H) coupling constants for their use in conformational analysis. The measurements were carried out using a modified CPMG-HSQMBC pulse scheme which yields pure absorption antiphase multiplets to allow accurate determination of the (n)J(XH) values regardless of the size of the proton-proton couplings. Theoretical calculations were performed at the Second-Order Polarization Propagator Approach (SOPPA) level. Population-averaged values calculated for geminal and vicinal couplings are in a good agreement with experiment indicating an adequate theoretical level of the calculations. Experimental observations and computations alike have indicated that two-bond (77)Se-(1)H couplings, (2)J((77)Se, (1)H), in a H1-C1-Se-X moiety are very sensitive to the torsion angle around the C1-Se-bond and will, therefore, be useful for conformational studies.     

Measurement of long-range 1H-19F scalar coupling constants and their glycosidic torsion dependence in 5-fluoropyrimidine-substituted RNA

Long-range scalar 5J(H1',F) couplings were observed in 5-fluoropyrimidine-substituted RNA. We developed a novel S3E-19F-alpha,beta-edited NOESY experiment for quantitation of these long-range scalar 5J(H1',F) couplings, where the J-couplings can be extracted from inspection of intraresidual (H1',H6) NOE cross-peaks. Quantum chemical calculations were exploited to investigate the relation between scalar couplings and conformations around the glycosidic bond in oligonucleotides. The theoretical dependence of the observed 5J(H1',F) couplings on the torsion angle chi can be described by a generalized Karplus relationship. The corresponding density functional theory (DFT) analysis is outlined. Additional NMR experiments facilitating the resonance assignments of 5-fluoropyrimidine-substituted RNAs are described, and chemical shift changes due to altered shielding in the presence of fluorine-19 (19F) are presented.     

Insights into the mobility of methyl-bearing side chains in proteins from (3)J(CC) and (3)J(CN) couplings

Side-chain dynamics in proteins can be characterized by the NMR measurement of (13)C and (2)H relaxation rates. Evaluation of the corresponding spectral densities limits the slowest motions that can be studied quantitatively to the time scale on which the overall molecular tumbling takes place. A different measure for the degree of side-chain order about the C(alpha)-C(beta) bond (chi(1) angle) can be derived from (3)J(C)(')(-)(C)(gamma) and (3)J(N)(-)(C)(gamma) couplings. These couplings can be measured at high accuracy, in particular for Thr, Ile, and Val residues. In conjunction with the known backbone structures of ubiquitin and the third IgG-binding domain of protein G, and an extensive set of (13)C-(1)H side-chain dipolar coupling measurements in oriented media, these (3)J couplings were used to parametrize empirical Karplus relationships for (3)J(C)(')(-)(C)(gamma) and (3)J(N)(-)(C)(gamma). These Karplus curves agree well with results from DFT calculations, including an unusual phase shift, which causes the maximum (3)J(CC) and (3)J(CN) couplings to occur for dihedral angles slightly smaller than 180 degrees, particularly noticeable in Thr residues. The new Karplus curves permit determination of rotamer populations for the chi(1) torsion angles. Similar rotamer populations can be derived from side-chain dipolar couplings. Conversion of these rotamer populations into generalized order parameters, S(J)(2) and S(D)(2), provides a view of side-chain dynamics that is complementary to that obtained from (13)C and (2)H relaxation. On average, results agree well with literature values for (2)H-relaxation-derived S(rel)(2) values in ubiquitin and HIV protease, but also identify a fraction of residues for which S(J,D)(2) < S(rel)(2). This indicates that some of the rotameric averaging occurs on a time scale too slow to be observable in traditional relaxation measurements.     

H(C)P and H(P)C triple-resonance experiments at natural abundance employing long-range couplings

Modified two-dimensional (2D) triple-resonance H(C)P and H(P)C experiments based on INEPT/HMQC and double-INEPT schemes are applied to the study of organophosphorus compounds at natural abundances. The implementation of effective (1)H--(13)C gradient selection, additional purging pulsed field gradients, spinlock pulses, and improved phase cycling is demonstrated to allow weak correlation signals based on long-range couplings to be readily observed. Through the combination of two heteronuclear long-range coupling constants, (n)J(CH) and (n)J(PC) in H(C)P experiments or (n)J(PH) and (n)J(PC) in H(P)C experiments, protons can be correlated to a second heteronucleus through 4-7 chemical bonds. These experiments thus overcome the inherit limitations of classical (1)H-X HMBC experiments, which require a nonzero value of the heteronuclear coupling constant (n)J(XH). Ultra-broadband inversion composite pulses are successfully employed in the H(P)C INEPT/HMQC and H(P)C double-INEPT pulse sequences to increase the utility of the experiments and the quality of obtained spectra. This work extends and completes a set of 2D phase-sensitive triple-resonance experiments applicable at natural abundances, and also offers insight into the methodology of triple-resonance experiments and the application of pulsed field gradients. A one-dimensional triple-resonance experiment employing carbon detection is suggested for accurate determination of small (n)J(PC).     

A 1H NMR and theoretical investigation of the conformations of some monosubstituted cyclobutanes

The complete analysis of the complex (1)H NMR spectra of some monosubstituted cyclobutanes was achieved to give all the (1)H chemical shifts and (n)J(HH) (n = 2, 3 and 4) coupling constants in these molecules. The substituent chemical shifts of the substituents in the cyclobutane ring differ significantly from those in acyclic systems. For example, the OH and the NH(2) groups in cyclobutanol and cyclobutylamine produce a large shielding of the hydrogens of the opposite CH(2) group of the ring compared with little effect on the comparable methylene protons of butane. These effects and the other (1)H shifts in the cyclobutanes were modelled successfully in the CHARGE program. The RMS error (calculated vs observed shifts) for the 34 (1)H shifts recorded was 0.053 ppm. The conformational equilibrium in these compounds between the axial and the equatorial conformers was obtained by comparing the observed and the calculated (4)J(HH) couplings. These couplings in cyclobutanes, in contrast to the corresponding (3)J(HH) couplings, show a pronounced orientation dependence; (4)J(eq-eq) is ca 5 Hz and (4)J(ax-ax) ca 0 Hz. The couplings in the individual conformers were calculated at the B3LYP/EPR-III level. The conformer energy differences ΔG(ax-eq) vary from 1.1 kcal mol(-1) for OH to 0.2 kcal mol(-1) for the CH(2)OH substituent. The values of the conformer energy differences are compared with the previous IR data and the corresponding theoretical values from molecular mechanics (MM) and DFT theory. Generally, good agreement is observed although both the MM and the DFT calculations deviate significantly from the observed values for some substituents.     

Hydroxymethyl group conformation in saccharides: structural dependencies of (2)J(HH), (3)J(HH), and (1)J(CH) spin-spin coupling constants

Experimental and theoretical methods have been used to correlate (2)J(HH) and (3)J(HH) values within the exocyclic hydroxymethyl groups (CH(2)OH) of saccharides with specific molecular parameters, and new equations are proposed to assist in the structural interpretation of these couplings. (3)J(HH) depends mainly on the C-C torsion angle (omega) as expected, and new Karplus equations derived from J-couplings computed from density functional theory (DFT) in a model aldopyranosyl ring are in excellent agreement with experimental values and with couplings predicted from a previously reported general Karplus equation. These results confirm the reliability of DFT-calculated (1)H-(1)H couplings in saccharides. (2)J(HH) values depend on both the C-C (omega) and C-O (theta) torsions. Knowledge of the former, which may be derived from other parameters (e.g., (3)J(HH)), allows theta to be evaluated indirectly from (2)J(HH). This latter approach complements more direct determinations of theta from (3)J(HCOH) and potentially extends these more conventional analyses to O-substituted systems lacking the hydroxyl proton. (1)J(CH) values within hydroxymethyl fragments were also examined and found to depend on r(CH), which is modulated by specific bond orientation and stereoelectronic factors. These latter factors could be largely, but not completely, accounted for by C-C and C-O torsional variables, leading to only semiquantitative treatments of these couplings (details discussed in the Supporting Information). New equations pertaining to (2)J(HH) and (3)J(HH) have been applied to the analysis of hydroxymethyl group J-couplings in several mono- and oligosaccharides, yielding information on C5-C6 and/or C6-O6 rotamer populations.     

Correlated C-C and C-O bond conformations in saccharide hydroxymethyl groups: parametrization and application of redundant 1H-1H, 13C-1H, and 13C-13C NMR J-couplings

Methyl alpha- and beta-pyranosides of d-glucose and d-galactose 1-4 were prepared containing single sites of (13)C-enrichment at C4, C5, and C6 (12 compounds), and (1)H and (13)C[(1)H] NMR spectra were obtained to determine a complete set of J-couplings ((1)J, (2)J, and (3)J) involving the labeled carbon and nearby protons and carbons within the exocyclic hydroxymethyl group (CH(2)OH) of each compound. In parallel theoretical studies, the dependencies of (1)J, (2)J, and (3)J involving (1)H and (13)C on the C5-C6 (omega) and C6-O6 (theta;) torsion angles in aldohexopyranoside model compounds were computed using density functional theory (DFT) and a special basis set designed to reliably recover the Fermi contact contribution to the coupling. Complete hypersurfaces for (1)J(C5,C6), (2)J(C5,H6)(R), (2)J(C5,H6)(S), (2)J(C6,H5), (2)J(C4,C6), (3)J(C4,H6)(R), (3)J(C4,H6)(S), and (3)J(C6,H4), as well as (2)J(H6)(R)(,H6)(S), (3)J(H5,H6)(R), and (3)J(H5,H6)(S), were obtained and used to parametrize new equations correlating these couplings to omega and/or theta;. DFT-computed couplings were also tested for accuracy by measuring J-couplings in (13)C-labeled 4,6-O-ethylidene derivatives of d-glucose and d-galactose in which values of omega and theta; were constrained. Using a new computer program, Chymesa, designed to utilize multiple J-couplings sensitive to exocyclic CH(2)OH conformation, the ensemble of experimental couplings observed in 1-4 were analyzed to yield preferred rotamer populations about omega and theta;. Importantly, due to the sensitivity of some couplings, most notably (2)J(H6)(R)(,H6)(S), (2)J(C5,H6)(R), and (2)J(C5,H6)(S), to both omega and theta;, unique information on correlated conformation about both torsion angles was obtained. The latter treatment represents a means of evaluating correlated conformation in 1,6-linked oligosaccharides, since psi and theta; are redundant in these linkages. In the latter regard, multiple, redundant scalar couplings originating from both sides of the glycosidic linkage can be used collectively to evaluate conformational correlations between psi/theta; and C5-C6 bond rotamers.     

The indirect through-space F-F coupling in peri-difluoronaphthalene: is it anisotropic?

The (1)H, (19)F and (13)C spectra have been obtained of a sample of peri-difluoronaphthalene dissolved in the nematic liquid crystalline solvent ZLI 1695. The (13)C satellite spectra from the six, single-(13)C isotopomers at natural abundance in both the (1)H and (19)F spectra were identified and analysed to yield a set of residual total, anisotropic spin-spin couplings, T(ij). This was achieved by first obtaining residual (13)C-(19)F and (13)C-(1)H couplings from a proton-encoded, (13)C detected, local field 2D spectrum. The 45 values of T(HH), T(HF) and T(CH) were used to obtain the structure of the molecule, and then to estimate whether there is a significant contribution from the component along the magnetic field, J, of the anisotropic, electron-mediated, spin-spin coupling tensors for (13)C-(19)F and (19)F-(19)F pairs. It is found that there is strong evidence for a significant contribution of J to T(FF) but not for the (13)C-(19)F pairs.     

Determination of the geometry of acetoxyendiynes and acetoxyenynes by NMR heteronuclear 13C?1H scalar couplings and 13C NMR chemical shifts. Structural assignment of the oxylipin natural products peyssonenynes A and B

Solution NMR methods were used for the structural characterization of the acetoxyendiyne E/Z configuration of the marine natural products peyssonenynes A and B and their synthetic analogs derived from palmitic acid. The scarcity of protons in the proximity of the olefin precluded the determination of the double bond geometry using ¹H NMR methods that rely on proton–proton scalar couplings or experiments such as NOESY or ROESY. Long range ¹H? ¹³C heteronuclear scalar couplings, ⁿJ_CH, measured with the 2D excitation sculptured indirect detection experiment (EXSIDE) proved useful and highly reliable for the analysis of the enol acetate geometry. In addition, it was found that the chemical shift of some carbon atoms in the proximity of the olefin was also sensitive to the double bond configuration of these molecules providing an even simpler way to determine their geometry. This protocol showed its robustness by similar analysis of simpler silyl‐protected acetoxyenynes derived from fatty acids. These NMR experimental results and stereochemical predictions were rationalized by DFT calculations. Copyright © 2010 John Wiley & Sons, Ltd.     

Interpreting 2hJ(F,N), 1hJ(H,N) and 1J(F,H) in the hydrogen‐bonded FH–collidine complex

Ab initio EOM‐CCSD calculations were performed to determine ¹⁹F,¹H, ¹⁹F,¹⁵N and ¹H,¹⁵N spin–spin coupling constants in model complexes FH–NH₃ and FH–pyridine as a function of the F—H and F—N distances. The absolute value of ¹J(F,H) decreases and that of ^1hJ(H,N) increases rapidly along the proton‐transfer coordinate, even in the region of the proton‐shared F—H—N hydrogen bond. In contrast, ^2hJ(F,N) remains essentially constant in this region. These results are consistent with the recently reported experimental NMR spectra of FH–collidine which show that ^1hJ(H,N) increases and ¹J(F,H) decreases, while ^2hJ(F,N) remains constant as the temperature of the solution decreases. They suggest that the FH–collidine complex is stabilized by a proton‐shared hydrogen bond over the range of experimental temperatures investigated, being on the traditional side of quasi‐symmetric at high temperatures, and on the ion‐pair side at low temperatures. Copyright © 2002 John Wiley & Sons, Ltd.     

19F and 1H NMR spectra of halocarbons

19F NMR chemical shifts and coupling constants are reported for 215 compounds. For 77 of these compounds, 1H NMR spectral data are also given. Long-range couplings, including 8J(F,F) and 5J(F,H), are reported. The complexity of halocarbon spectra owing to the presence of rotational isomers, asymmetric centers, long-range couplings, and chlorine isotope effects are illustrated, and the methods used for analyzing such complex spectra are briefly discussed.