Development of acetabular retroversion in LCPD hips-an observational radiographic study from early stage to healing.

BACKGROUND: Acetabular retroversion is observed frequently in healed Legg-Calvé-Perthes disease (LCPD). Currently, it is unknown at which stage and with what prevalence retroversion occurs because in non-ossified hips, retroversion cannot be measured with standard radiographic parameters. METHODS: In a retrospective, observational study; we examined pelvic radiographs in children with LCPD the time point of occurrence of acetabular retroversion and calculated predictive factors for retroversion. Between 2004 and 2017, we included 55 children with a mean age of 5.7 ± 2.4 years at diagnosis. The mean radiographic follow-up was 7.0 ± 4.4 years. We used two new radiographic parameters which allow assessment of acetabular version in non-ossified hips: the pelvic width index and the ilioischial angle. They are based on the fact that the pelvic morphology differs depending on the acetabular version. These parameters were compared among the four Waldenström stages and to the contralateral side. Logistic regression analysis was performed to determine predictive factors for acetabular retroversion. RESULTS: Both parameters differed significantly among the stages of Waldenström (p < 0.003 und 0.038, respectively). A more retroverted acetabulum was found in stage II and III (prevalence ranging from 54 to 56%) compared to stage I and IV (prevalence ranging from 23 to 39%). In hips of the contralateral side without LCPD, the prevalence of acetabular retroversion was 0% in all stages for both parameters. Predictive factors for retroversion were younger age at stage II and IV, collapse of the lateral pillar in stage II or a non-dysplastic hip. CONCLUSIONS: This is the first study evaluating acetabular version in children with LCPD from early stage to healing. In the developing hip, LCPD may result in acetabular retroversion and is most prevalent in the fragmentation (stage II) and early healing stage (stage III). Partial correction of acetabular retroversion can occur after healing. This has a potential clinical impact on the timing and type of surgical correction, especially in pelvic osteotomies for correction of acetabular version. LEVEL OF EVIDENCE: Level III, retrospective observational study.

Surgical hip dislocation with relative femoral neck lengthening and retinacular soft-tissue flap for sequela of Legg-Calve-Perthes disease.

OBJECTIVE: Correction of post-LCP (Legg-Calve-Perthes) morphology using surgical hip dislocation with retinacular flap and relative femoral neck lengthening for impingent correction reduces the risk of early arthritis and improves the survival of the native hip joint. INDICATIONS: Typical post-LCP deformity with external and internal hip impingement due to aspherical enlarged femoral head and shortened femoral neck with high riding trochanter major without advanced osteoarthritis (Tönnis classification ≤ 1) in the younger patient (age < 50 years). CONTRAINDICATIONS: Advanced global osteoarthritis (Tönnis classification ≥ 2). SURGICAL TECHNIQUE: By performing surgical hip dislocation, full access to the hip joint is gained which allows intra-articular corrections like cartilage and labral repair. Relative femoral neck lengthening involves osteotomy and distalization of the greater trochanter with reduction of the base of the femoral neck, while maintaining vascular perfusion of the femoral head by creation of a retinacular soft-tissue flap. POSTOPERATIVE MANAGEMENT: Immediate postoperative mobilization on a passive motion device to prevent capsular adhesions. Patients mobilized with partial weight bearing of 15 kg with the use of crutches for at least 8 weeks. RESULTS: In all, 81 hips with symptomatic deformity of the femoral head after healed LCP disease were treated with surgical hip dislocation and offset correction between 1997 and 2020. The mean age at operation was 23 years; mean follow-up was 9 years; 11 hips were converted to total hip arthroplasty and 1 patient died 1 year after the operation. The other 67 hips showed no or minor progression of arthrosis. Complications were 2 subluxations due to instability and 1 pseudarthrosis of the lesser trochanter; no hip developed avascular necrosis.

Less in-toeing after femoral derotation osteotomy in adult patients with increased femoral version and posterior hip impingement compared to patients with femoral retroversion.

In-toeing of the foot was associated with high femoral version (FV), while Out-toeing was associated with femoral-retroversion. Therefore, we report on (i) foot-progression-angle (FPA), (ii) prevalence of In-toeing and Out-toeing, and (iii) clinical outcome of patients treated with femoral-derotation-osteotomy (FDO). We performed a retrospective analysis involving 20 patients (20 hips) treated with unilateral FDO (2017-18). Of them, 14 patients had increased FV, 6 patients had femoral-retroversion. Follow-up time was mean 1 ± 1 years. All patients had minimal 1-year follow-up and the mean age was 29 ± 8 years. Patients with increased FV (FV > 35°) presented with positive posterior-impingement-test and mean FV was 49 ± 11° (Murphy method). Six patients with femoral-retroversion (FV < 10°) had positive anterior impingement test and mean FV of 5 ± 4°. Instrumented gait analysis was performed preoperatively and at follow-up using the Gaitrite system to measure FPA and was compared to a control group of 18 healthy asymptomatic volunteers (36 feet, mean age 29 ± 6 years). (i) Mean FPA increased significantly (P = 0.006) from preoperative 1.3 ± 7° to 4.5 ± 6° at follow-up for patients with increased FV and was not significantly different compared to the control group (4.0 ± 4.5°). (ii) In-toeing decreased from preoperatively (five patients) to follow-up (two patients) for patients with increased FV. Out-toeing decreased from preoperatively (two patients) to follow-up (no patient) for patients with femoral-retroversion. (iii) Subjective-hip-value of all patients increased significantly (P < 0.001) from preoperative 21 to 78 points at follow-up. WOMAC was 12 ± 8 points at follow-up. Patients with increased FV that underwent FDO walked with less In-toeing. FDO has the potential to reduce In-toeing and Out-toeing and to improve subjective satisfaction at follow-up.

Minimal Out-Toeing and Good Hip Scores of Severe SCFE Patients Treated With Modified Dunn Procedure and Contralateral Prophylactic Pinning at Minimal 5-year Follow up.

BACKGROUND: Slipped capital femoral epiphyses (SCFE) is associated with out-toeing of the foot and external rotation gait. But it is unknown if SCFE patients treated with the modified Dunn procedure have out-toeing at follow up.Therefore, we used instrumented gait analysis and questioned (1) do severe SCFE patients treated with a modified Dunn procedure have symmetrical foot progression angle (FPA) compared with contralateral side and compared with asymptomatic volunteers (2) what is the prevalence of out-toeing gait and what are the outcome socres at follow up. METHODS: Gait analysis of 22 patients (22 hips) treated with an unilateral modified Dunn procedure for severe SCFE (slip angle >60 degrees, 2002 to 2011) was retrospectively evaluated. Of 38 patients with minimal 5-year follow up, 2 hips (4%) had avascular necrosis of the femoral head and were excluded for gait analysis. Twenty-two patients were available for gait analysis at follow up (mean follow up of 9±2 y). Mean age at follow up was 22±3 years. Mean preoperative slip angle was 64±8 degrees (33% unstable slips) and decreased postoperatively (slip angle of 8±4 degrees). Gait analysis was performed with computer-based instrumented walkway system (GAITRite) to measure FPA with embedded pressure sensors. Patients were compared with control group of 18 healthy asymptomatic volunteers (36 feet, mean age 29±6 y). RESULTS: (1) Mean FPA of SCFE patients (3.6±6.4 degrees) at follow up was not significantly different compared with their contralateral side (5.6±5.5 degrees) and compared with FPA of controls (4.0±4.5 degrees). (2) Of the 22 SCFE patients, most of them (19 hips, 86%) had normal FPA (-5 to 15 degrees), 2 patients had in-toeing (FPA<-5 degrees) and 1 had out-toeing (FPA >15 degrees) and was not significantly different compared with control group. (3) Mean modified Harris hip score (mHHS) was 93±11 points, mean Hip Disability and Osteoarthritis Outcome Score (HOOS) score was 91±10 points. Three patients (14%) had mHHS <80 points and walked with normal FPA. The 2 patients with in-toeing and one patient with out-toeing had mHHS >95 points. CONCLUSIONS: Patients with severe SCFE treated with modified Dunn procedure had mostly symmetrical FPA and good hip scores at long term follow up. This is in contrast to previous studies. Although 1 patient had out-toeing and 2 patients had in-toeing at follow up, they had good hip scores. LEVEL OF EVIDENCE: Level III-retrospective comparative study.

Multiplanar reformation improves identification of the anterolateral ligament with MRI of the knee.

The anterolateral ligament (ALL) is subject of the current debate concerning rotational stability in case of anterior cruciate ligament (ACL) injuries. Today, reliable anatomical and biomechanical evidence for its existence and course is available. Some radiologic studies claim to be able to identify the ALL on standard coronal plane MRI sections. In the experience of the authors, however, ALL identification on standard MRI sequences frequently fails and is prone to errors. The reason for this mainly lies in the fact, that the entire ALL often cannot be identified on a single MRI image. This study aimed to establish an MRI evaluation protocol improving the visualization of the ALL, using multiplanar reformation (MPR) with the goal to be able to evaluate the ALL on one MRI image. A total of 47 knee MRIs performed due to atraumatic knee pain between 2018 and 2019 without any pathology were analyzed. Identification of the ALL was performed twice by an orthopedic surgeon and a radiologist on standard coronal plane and after MPR. For the latter axial and coronal alignment was obtained with the femoral condyles as a reference. Then the coronal plane was adjusted to the course of the ALL with the lateral epicondyle as proximal reference. Visualization of the ALL was rated as "complete" (continuous ligamentous structure with a tibial and femoral insertion visible on one coronal image), "partial" (only parts of the ALL like the tibial insertion were visible) and "not visible". The distances of its tibial insertion to the bony joint line, Gerdy's tubercle and the tip of the fibular head were measured. On standard coronal images the ALL was fully visible in 17/47, partially visible in 27/47, and not visible in 3/47 cases. With MPR the ALL was fully visible in 44/47 and not visible in 3/47 cases. The median distance of its tibial insertion to the bony joint line, Gerdy's tubercle and the tip of the fibular head were 9, 21 and 25 mm, respectively. The inter- (ICC: 0.612; 0.645; 0.757) and intraobserver (ICC: 0.632; 0.823; 0.857) reliability was good to excellent. Complete visualization of the ALL on a single MRI image is critical for its identification and evaluation. Applying multiplanar reformation achieved reliable full-length visualization of the ALL in 94% of cases. The described MPR technique can be applied easily and fast in clinical routine. It is a reliable tool to improve the assessment of the ALL.

The Acetabular Wall Index Is Associated with Long-term Conversion to THA after PAO.

BACKGROUND: Periacetabular osteotomy (PAO) has been shown to be a valuable option for delaying the onset of osteoarthritis in patients with hip dysplasia. Published studies at 30 years of follow-up found that postoperative anterior overcoverage and posterior undercoverage were associated with early conversion to THA. The anterior and posterior wall indices are practical tools for assessing AP coverage on standard AP radiographs of the pelvis pre-, intra-, and postoperatively. However, no study that we know of has evaluated the relationship between the postoperative anterior and posterior wall indices and survivorship free from arthroplasty. QUESTIONS/PURPOSES: In a study including patients after PAO for developmental dysplasia of the hip (DDH), we evaluated whether the acetabular wall index is associated with conversion to THA in the long-term after PAO. We asked: (1) Is an abnormal postoperative anterior wall index associated with conversion to THA after PAO? (2) Is an abnormal postoperative posterior wall index associated with conversion to THA after PAO? (3) Are there other factors associated with joint replacement after PAO? METHODS: This retrospective study involved pooling data of PAO for DDH from two previously published sources. The first series (1984-1987) comprised the very first 75 PAOs for symptomatic DDH performed at the inventor's institution. The second (1997-2000) comprised a series of PAOs for symptomatic DDH completed at the same institution 10 years later. No patient was lost to follow-up. Fifty hips (44 patients) were excluded for predefined reasons (previous surgery, substantial femoral pathomorphologies, poor-quality radiographs), leaving 115 hips (102 patients, mean age 29 ± 11 years, 28% male) for analysis with a mean follow-up of 22 ± 6 years. One observer not involved in patient treatment digitally measured the anterior and posterior wall indices on postoperative AP pelvic radiographs of all patients. All patients were contacted by mail or telephone to confirm any conversion to THA and the timing of that procedure relative to the index procedure. We performed univariate and multivariate Cox regression analyses using conversion to THA as our endpoint to determine whether the anterior and posterior wall indices are associated with prosthetic replacement in the long-term after PAO. Thirty-one percent (36 of 115) of hips were converted to THA within a mean of 15 ± 7 years until failure. The mean follow-up duration of the remaining patients was 22 ± 6 years. RESULTS: A deficient anterior wall index was associated with conversion THA in the long-term after PAO (adjusted hazard ratio 10 [95% CI 3.6 to 27.9]; p < 0.001). Although observed in the univariate analysis, we could not find a multivariate association between the posterior wall index and a higher conversion rate to THA. Grade 0 Tönnis osteoarthritis was associated with joint preservation (adjusted HR 0.2 [95% CI 0.07 to 0.47]; p = 0.005). Tönnis osteoarthritis Grades 2 and 3 were associated with conversion to THA (adjusted HR 2.3 [95% CI 0.9 to 5.7]; p = 0.08). CONCLUSION: A deficient anterior wall index is associated with a decreased survivorship of the native hip in the long-term after PAO. Intraoperatively, in addition to following established radiographical guidelines, the acetabular wall indices should be measured systematically to ascertain optimal acetabular fragment version to increase the likelihood of reconstructive survival after PAO for DDH. LEVEL OF EVIDENCE: Level III, therapeutic study.

Location of Intra- and Extra-articular Hip Impingement Is Different in Patients With Pincer-Type and Mixed-Type Femoroacetabular Impingement Due to Acetabular Retroversion or Protrusio Acetabuli on 3D CT-Based Impingement Simulation.

BACKGROUND: Diagnosis and surgical treatment of hips with different types of pincer femoroacetabular impingement (FAI), such as protrusio acetabuli and acetabular retroversion, remain controversial because actual 3-dimensional (3D) acetabular coverage and location of impingement cannot be studied via standard 2-dimensional imaging. It remains unclear whether pincer hips exhibit intra- or extra-articular FAI. PURPOSE: (1) To determine the 3D femoral head coverage in these subgroups of pincer FAI, (2) determine the impingement-free range of motion (ROM) through use of osseous models based on 3D-computed tomography (CT) scans, and (3) determine the osseous intra-and extra-articular 3D impingement zones by use of 3D impingement simulation. STUDY DESIGN: Cross-sectional study; Level of evidence, 3. METHODS: This is a retrospective, comparative, controlled study involving 70 hips in 50 patients. There were 24 patients (44 hips) with symptomatic pincer-type or mixed-type FAI and 26 patients (26 hips) with normal hips. Surface models based on 3D-CT scans were reconstructed and compared for hips with acetabular retroversion (30 hips), hips with protrusio acetabuli (14 hips), and normal asymptomatic hips (26 hips). Impingement-free ROM and location of impingement were determined for all hips through use of validated 3D collision detection software based on CT-based 3D models. No abnormal morphologic features of the anterior iliac inferior spine were detected. RESULTS: (1) Mean total femoral head coverage was significantly (P < .001) increased in hips with protrusio acetabuli (92% ± 7%) and acetabular retroversion (71% ± 5%) compared with normal hips (66% ± 6%). (2) Mean flexion was significantly (P < .001) decreased in hips with protrusio acetabuli (104°± 9°) and acetabular retroversion (116°± 6°) compared with normal hips (125°± 13°). Mean internal rotation in 90° of flexion was significantly (P < .001) decreased in hips with protrusio acetabuli (16°± 12°) compared with normal hips (35°± 13°). (3) The prevalence of extra-articular subspine impingement was significantly (P < .001) higher in hips with acetabular retroversion (87%) compared with hips with protrusio acetabuli (14%) and normal hips (0%) and was combined with intra-articular impingement. The location of anterior impingement differed significantly (P < .001) between hips with protrusio acetabuli and normal hips. CONCLUSION: Using CT-based 3D hip models, we found that hips with pincer-type and mixed-type FAI have significantly larger femoral head coverage and different osseous ROM and location of impingement compared with normal hips. Additionally, intra- and extra-articular subspine impingement was detected predominantly in hips with acetabular retroversion. Acetabular rim trimming during hip arthroscopy or open surgical hip dislocation should be performed with caution for these hips. Patient-specific analysis of location of impingement using 3D-CT could theoretically improve diagnosis and planning of surgical treatment.

Femoral osteotomies for the treatment of avascular necrosis of the femoral head.

OBJECTIVE: Unloading of the area of necrosis out of the weight-bearing region by shifting healthy bone in the main weight-bearing area, which may delay the progression of the necrosis and enable healing. INDICATIONS: Circumscribed osteonecrosis of the femoral head without advanced degenerative signs (Tönnis grade ≤ 1) in the relatively young patient (age < 50 years). CONTRAINDICATIONS: Radiographic joint degeneration (> Tönnis grade 1); extensive avascular necrosis (Kerboul angle > 240°); advanced lesions (≥ Association Research Circulation Osseous [ARCO] classification 3b). SURGICAL TECHNIQUE: By performing a surgical hip dislocation, full access to the hip joint is gained. A femoral varus osteotomy is used to turn the necrotic lesion of the femoral head out of the central weight-bearing area and more medially. Osteosynthesis is performed with an angular stable screw or a blade plate. Via a trapdoor procedure, direct debridement and autologous bone grafting from the trochanter major is possible. The cartilage flap is preserved whenever possible or supplanted by an autologous matrix-induced chondrogenesis (AMIC). POSTOPERATIVE MANAGEMENT: A passive motion device is installed during hospital stay beginning immediately after surgery to prevent capsular adhesions. After surgery, patients are mobilized with partial weight-bearing of 15 kg with the use of crutches for at least 8 weeks. Forced abduction and adduction as well as flexion of more than 90° are restricted to protect the trochanteric osteotomy. After radiographic confirmation of healing at the 8­week follow-up, stepwise return to full weight-bearing is allowed and abductor training is initiated. RESULTS: Nine patients (10 hips) with osteonecrosis of the femoral head were treated with surgical hip dislocation and varus osteotomy. Six hips were treated with autologous bone grafting, four hips with antegrade drilling. Chondral lesions were sutured in four cases, whereas two cases needed an AMIC treatment. The mean age at operation was 29 ± 9 years (20-49), and the mean follow-up time for all patients was 3 ± 2 years (1-7). Conversion to a total hip prosthesis was required for one hip with progressing arthrosis. The other nine hips showed no progression of necrosis and an improved clinical outcome. Complications were pseudarthrosis of the femoral osteotomy and pseudarthrosis of the greater trochanter.

[Torsional deformities of the femur in patients with femoroacetabular impingement : Dynamic 3D impingement simulation can be helpful for the planning of surgical hip dislocation and hip arthroscopy]. / Femorale Torsionsfehler bei Patienten mit femoroazetabulärem Impingement : Die dynamische 3D Impingementsimulation kann bei der Planung der chirurgischen Hüftluxation und der Hüftarthroskopie behilflich sein.

BACKGROUND: Torsional deformities of the femur include femoral retrotorsion and increased femoral torsion, which are possible causes for hip pain and osteoarthritis. For patients with femoroacetabular impingement (FAI), torsional deformities of the femur represent an additional cause of FAI in addition to cam and pincer-type FAI. OBJECTIVES: The aim of this article is to provide an overview of measurement techniques and normal values of femoral torsion. The clinical presentation, possible combinations and surgical therapy of patients with torsional deformities of the femur will be discussed. METHODS: For measurement of femoral torsion, CT or MRI represent the method of choice. The various definitions should be taken into account, because they can lead to differing values and misdiagnosis. This is the case especially for patients with high femoral torsion. Dynamic 3D impingement simulation using 3D-CT can help to differentiate between intra und extra-articular FAI. RESULTS AND DISCUSSION: Femoral retrotorsion (< 5°) can lead to anterior intra- and extraarticular (subspine) FAI, between the anterior iliac inferior spine (AIIS) and the proximal femur. Increased femoral torsion (> 35°) can lead to posterior intra- and extra-articular ischiofemoral FAI, between the lesser/greater trochanter and the ischial tuberosity. During clinical examination, a patient with femoral retrotorsion exhibits loss of internal rotation and a positive anterior impingement test. Hips with increased femoral torsion show high internal rotation if examined in prone position and have a positive FABER and posterior impingement test. During surgical therapy for patients with torsional deformities, intra and extra-articular causes for FAI in addition to cam and pincer-deformities should be considered. In addition to hip arthroscopy and surgical hip dislocation, also femoral rotational or derotational osteotomies should be evaluated during surgical planning of these patients.

[Femoroacetabular Impingement - Current Understanding]. / Femoroazetabuläres Impingement ­ aktuelles Verständnis.

Femoroacetabular impingement (FAI) is a painful and early contact between the proximal femur and the acetabular rim or the pelvis. The pathological bony abutment typically leads to a characteristic pattern of chondrolabral damage and is one of the main reasons for development of early osteoarthritis in the young hip joint. Classically, FAI was described as an intraarticular problem but the extraarticular impingement has recently gained in importance. This article provides an overview of the concept of FAI, the clinical presentation, the radiological assessment including its coxometric parameters and the treatment options currently available.

Trifluoromethanesulfenyl acetate, CF3S-OC(O)CH3, and trifluoromethanesulfenyl trifluoroacetate, CF3S-OC(O)CF3: unexpected conformational properties.

Structural and conformational properties of two sulfenyl derivatives, trifluoromethanesulfenyl acetate, CF3S-OC(O)CH3 (1), and trifluoromethanesulfenyl trifluoroacetate, CF3S-OC(O)CF3 (2), were determined by gas electron diffraction, vibrational spectroscopy, in particular with IR (matrix) spectroscopy, which includes photochemical studies, and by quantum chemical calculations. Both compounds exist in the gas phase as a mixture of two conformers, with the prevailing component possessing a gauche structure around the S-O bond. The minor form, 15(5)% in 1 and 11(5)% in 2 according to IR(matrix) spectra, possesses an unexpected trans structure around the S-O bond. The C=O bond of the acetyl group is oriented syn with respect to the S-O bond in both conformers. UV-visible broad band irradiation of 1 and 2 isolated in inert gas matrixes causes various changes to occur. Conformational randomization clearly takes place in 2 with simultaneous formation of CF3SCF3. For 1 the only reaction channel detected leads to the formation of CH3SCF3 with the consequent extrusion of CO2. Quantum chemical calculations (B3LYP/6-31G and MP2 with 6-31G and 6-311G(2df,pd) basis sets) confirm the existence of a stable trans conformer. The calculations reproduce the conformational properties for both compounds qualitatively correct with the exception of the B3LYP method for compound 2 which predicts the trans form to be prevailing, in contrast to the experiment.

Gas-phase structure, conformation, and sulfur 2p photoelectron spectroscopy of pentafluorosulfur fluorosulfonate, SF5OSO2F.

The structure of SF(5)OSO(2)F has been investigated using gas-phase electron diffraction and quantum-chemical calculations. It is found to exist primarily in the gauche form (SF(5) group gauche relative to the S-F bond of the SO(2)F group with phi(S-O-S-F = 71(7) degrees ). A small contribution of the trans conformer cannot be excluded. Photoelectron spectroscopy gives ionization energies for the sulfur 2p electrons that reflect the relative electronegativities of fluorine and oxygen. The widths of the peaks in the photoelectron spectra indicate that there is considerable vibrational excitation associated with the core ionization of the sulfur atoms.

Trifluoromethyl chlorosulfonate, CF3OSO2Cl: gas phase and crystal structure, conformation and vibrational analysis studied by experimental and theoretical methods.

The geometric structure and conformational properties of trifluoromethyl chlorosulfonate (chlorosulfuric acid trifluoromethyl ester), CF(3)OSO(2)Cl, have been determined by X-ray crystallography, gas electron diffraction (GED), and vibrational spectroscopy (IR(gas), IR(matrix), and Raman(liquid)). These experimental investigations were supplemented by quantum chemical calculations (B3LYP with 6-311G* and 6-311+G(3df) basis sets). All experimental methods result in a single conformer with gauche orientation of the CF(3) group relative to the S[bond]Cl. The dihedral angle delta(COSCl) is determined to be 91.7(3) degrees in the crystal and 94(3) degrees in the gas phase. This dihedral angle corresponds to a near-eclipsed orientation of the O[bond]C relative to one of the S[double bond]O bonds (delta(CO[bond]SO) = -23.0(3) degrees and -21(3) degrees in the crystal and gas phase, respectively).

Structure and conformations of N-(fluoroformyl)imidosulfurous dichloride, FC(O)N=SCl2.

The IR (gas) and Raman (liquid) spectra of FC(O)NSCl(2) demonstrate the presence of a conformational mixture in both phases. According to a gas electron diffraction study, the main conformer (94(8)%) possesses a syn-syn structure (C(O)F group synperiplanar with respect to the SCl(2) bisector and the C=O bond synperiplanar to the N=S bond). Quantum chemical calculations (HF, B3LYP and MP2 with 6-31G basis set, and MP2/6-311(2df)) predict a syn-anti structure for the second conformer. Analysis of the IR (gas) spectrum results in a contribution of 5(1)% of the minor form, corresponding to a Gibbs free energy difference DeltaG degrees = G degrees (syn-anti) - G degrees (syn-syn) = 1.75(15) kcal/mol. This value is reproduced very well by quantum chemical calculations, which include electron correlation effects (DeltaG degrees = 1.28-1.56 kcal/mol). The HF approximation overestimates this energy difference (DeltaG degrees = 3.24 kcal/mol).

Structure of a fluorinated azoxy compound: fluoro(trifluoromethyl)-diazene-2-oxide, CF3N(O)NF.

A gas-phase electron diffraction study of the azoxy compound which was synthesized by the reaction of CF3NO with N2F4 in a Pyrex glass vessel results in a trans CF3N(O)NF structure (F trans to CF3), although quantum chemical calculations (MP2 and B3LYP) predict a greater stability of the cis CF3NN(O)F isomer by about 12 kcal/mol. The CF3 group eclipses the N=N double bond. The following skeletal geometric parameters (r(a) values with 3sigma uncertainties) were obtained: N=N 1.287(15) A; N=O 1.231(6) A; N-F 1.380(6) A; N-C 1.498(6) A; N=N=O 131.2(13) degrees; N=N-F 103.5(13) degrees; N=N-C 114.0(12) degrees. The bond lengths in CF3N(O)NF are compared to those in azo, nitryl, and nitrosyl compounds with fluorine and/or CF3 substituents.