Reaction of thiophosphoryl trichloride with N,N′-Diphenylthiourea

Article abstract of DOI:10.1135/cccc20070297

New heterocyclic thiophosphoric compounds containing the N-C-N sequence in the ring were prepared by the reaction of thiophosphoryl trichloride (PSCl ₃) with N,N′-diphenyl-thiourea. Depending on the reaction conditions, two types of heterocyclic compounds were obtained, namely 2-chloro-1,3-diphenyl-1,3,2λ⁵-diazaphosphetidine-2,4-dithione (1) and 2-chloro-1,3,5-triphenyl-1,3,5,2λ⁵-triazaphosphinane- 2,4,6-trithione (2). N,N′,N″-Triphenyl-guanidinium chloride (3) was identified in the reaction mixture as a by-product in all cases. The course of reactions was followed by ³¹P NMR spectroscopy and compound 3 was characterized by single-crystal X-ray diffraction.

Full text of DOI:10.1135/cccc20070297

Reaction of Thiophosphoryl Trichloride
297
REACTION OF THIOPHOSPHORYL TRICHLORIDE WITH
N,N′-DIPHENYLTHIOUREA
1
2,
3
Lenka DASTYCHOVÁ , Jiří PŘÍHODA * and Jan TARABA
Department of Inorganic Chemistry, Faculty of Science, Masaryk University,
1
Kotlářská 2, CZ- 61137 Brno, Czech Republic; e-mail: lenka.dastychova@email.cz,
2
3
prihoda@chemi.muni.cz, taraba@chemi.muni.cz
Received July 25, 2006
Accepted Jan uary 26, 2007
New h eterocyclic th ioph osph oric com poun ds con tain in g th e N–C–N sequen ce in th e rin g
were prepared by th e reaction of th ioph osph oryl trich loride (PSCl3) with N,N′-diph en yl-
th iourea. Depen din g on th e reaction con dition s, two types of h eterocyclic com poun ds were
obtain ed, n am ely 2-ch loro-1,3-diph en yl-1,3,2λ5-diazaph osph etidin e-2,4-dith ion e (1) an d
2-ch loro-1,3,5-triph en yl-1,3,5,2λ5-triazaph osph in an e-2,4,6-trith ion e (2). N,N′,N″-Triph en yl-
guan idin ium ch loride (3) was iden tified in th e reaction m ixture as a by-product in all cases.
Th e course of reaction s was followed by 31P NMR spectroscopy an d com poun d 3 was ch arac-
terized by sin gle-crystal X-ray diffraction .
Keywords: Th ioph osph oric com poun ds; Triph en ylguan idin ium ch loride; Diazaph osph etidin e;
Triazaph osph in an e; Ph osph ah eterocycles; Ph osph orus.
Th ioph osph oric acid ch lorides are often used for syn th eses of m an y
th ioph osph oric com poun ds in cludin g h eterocycles wh ere th e ph osph orus
atom is a m em ber of th e rin g1–4. Th e m ain reaction type is n ucleoph ilic
substitution of a h alogen atom . It is supposed th at th e ph osph orus atom in
PSCl3 is attacked, e.g., by n itrogen atom s of a n ucleoph ilic reagen t, an d
ch lorin e atom s are replaced.
Th e size an d com position of h eterocycles are usually stron gly in fluen ced
by reaction con dition s. Th e reaction between pyridin ium ph osph oroch lor-
idodith ioate (pyPS2Cl) an d urea, e.g., leads to th e form ation of th e cyclic
am m on ium 4,6-dioxo-2-th ioxo-1,3,5,2λ5-triazaph osph in an e-2-th iolate. Th is
com poun d can react first with aqueous solution of NH4HCO3 (ref.5) an d
th en eith er with H2O2 yieldin g am m on ium 2,4,6-trioxo-1,3,5,2λ5-triaza-
ph osph in an e-2-olate or m eth yl ch loroacetate yieldin g am m on ium 4,6-dioxo-
2-th ioxo-1,3,5,2λ5-triazaph osph in an e-2-olate. Th e reaction of pyPS2Cl with
N,N′-diph en ylth iourea yields, depen din g on reaction con dition s, two differ-
en t h eterocyclic com poun ds, pyridin ium 1,3-diph en yl-2,4-dith ioxo-1,3,2λ5-
Collect. Czech. Chem. Commun. 2007, Vol. 72, No. 3, pp. 297–306
© 2007 Institute of Organic Chemistry and Biochemistry
doi:10.1135/cccc20070297

298
Dastychová, Příhoda, Taraba:
diazaph osph etidin e-2-th iolate an d pyridin ium 1,3-diph en yl-2,4-dith ioxo-
1,3,2λ5,4λ5-diazadiph osph etidin e-2,4-dith iolate. Th e latter substan ce is
form ed in th e presen ce of trieth ylam in e as an HCl acceptor6.
Th e in vestigation of reaction s between PSCl3 an d N-n ucleoph iles leads to
m an y com poun ds th at can be used in ph arm aceutical in dustry, e.g. N,N′,N″-
trieth ylen eth ioph osph oram ide (th ioTEPA)7 serves as a polyfun ction al
alkylatin g agen t in th e treatm en t of can cer8. Th is article describes th e reac-
tion between PSCl3 an d N,N′-diph en ylth iourea, (Ph NH)2CS. Th e course of
th e reaction is m arkedly differen t from previously studied reaction , in
wh ich pyPS2Cl was used as a substrate6, wh en h eterocyclic com poun ds
con tain ig exocyclic PS2 group were form ed togeth er with pyridin ium ch lo-
ride as a by-product. In th e case of th e reaction PSCl3 with (Ph NH)2CS, we
obtain ed com poun ds 1 an d 2 togeth er with un expectedly form ed N,N′,N″-
triph en ylguan idin ium ch loride (3; Sch em e 1).
Ph
N
S
P
P
C
S
+
2 HCl
Cl
N
1
Ph
Ph
PSCl3
+
n (PhNH)2CS
(n = 1, 2)
S
N C
S
N Ph
+
2 HCl + PhNH2
Cl
N C
Ph
S
2
SCHEME 1
RESULTS AND DISCUSSION
Synthesis
Th e reaction s between PSCl3 an d (Ph NH)2CS were carried out in aceton itrile
solution at various reaction con dition s with th e aim to prepare th e desired
com poun ds 1 an d 2. Th e reaction con dition s are described in Table I. Th e
m olar ratio of startin g com poun ds PSCl3 an d (Ph NH)2CS was kept at 1:2 in
th e absen ce of pyridin e (reaction m ixture A) or at 1:1 in th e presen ce of
pyridin e (reaction m ixture B) th at played th e role of HCl acceptor. Th e
course of reaction s was followed by 31P NMR spectroscopy over th e period
of several weeks. Ch em ical sh ifts are sh own in Table I.
It follows from 31P NMR m easurem en ts th at a m ixture of reaction prod-
ucts is m ostly form ed in th e course of th e reaction . Th is situation is docu-
m en ted by th e NMR spectrum wh ich correspon ds to th e reaction m ixture A
Collect. Czech. Chem. Commun. 2007, Vol. 72, No. 3, pp. 297–306

Reaction of Thiophosphoryl Trichloride
299
at 20 °C after 18-h reaction (Table I). However, th e com position of th e re-
action m ixture is tim e depen den t an d th at is wh y it was n ot possible to
iden tify all in term ediates (δ 85.4, 93.9 ppm ). With in 14 days, th ese in ter-
m ediates were gradually con verted to on ly on e reaction product with
ch em ical sh ift δ 83.7 ppm . Th is reson an ce sign al (Table I) was assign ed to
com poun d 1. Th e sam e product can be prepared also by refluxin g th e reac-
tion m ixture A at 82 °C for 2 h .
Wh en startin g com poun ds were allowed to react in th e presen ce of pyri-
din e at am bien t tem perature for 14 days (reaction m ixture B), com poun d 2
(with ch em ical sh ift 108.7 ppm , see Table I) was form ed besides com poun d
1. Sin gle reaction product 2 can be obtain ed after refluxin g th e reaction
m ixture B for 3 h (Table I). After solven t evaporation , both substan ces form
yellow oily liquids. Attem pts to grow crystals were even after coolin g solu-
tion s of 1 or 2 to –90 °C un successful. Th e procedure yielded on ly am or-
ph ous, glassy substan ces. As follows from Table I, it is n ecessary to use
differen t approach es for preparation of com poun ds 1 an d 2.
Formation of Compound 3
A wh ite crystallin e substan ce precipitated in th e course of reaction in both
cases. IR spectra of th ese solids were iden tical an d th erefore th is com poun d
was furth er den oted as 3. In th e presen ce of pyridin e, com poun d 3 precipi-
tated togeth er with pyridin ium ch loride, wh ich was proved by IR spectros-
copy. Th e precipitation of 3 was accelerated wh en aceton itrile was partially
evaporated.
TABLE I
Reaction of PSCl3 an d (Ph NH)2CS
Reaction
m ixture
Molar ratio
Reaction tem perature
° C
Reaction
tim e
δ(31P), ppm
PSCl3:(Ph NH)2CS:(pya)
A
1:2
20
18 h
83.7; 85.4;
93.9; 108.7
14 d
2 h
83.7
1:2
82
20
82
83.7
B
1:1:2
14 d
3 h
83.7; 108.7
108.7
a
py = pyridin e.
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300
Identification of Compounds 1 and 2
Dastychová, Příhoda, Taraba:
Both reaction products were in vestigated by m ass spectrom etry. Th e m ass
of com poun d 1 was foun d at m/z = 324 (exact m ass is 323.971150), th e m o-
lecular peak of 2 at m/z = 460 (exact m ass is 458.985419). Th e foun d m asses
of fragm en ts also support th e form ation of com poun ds 1 an d 2.
We also tried to substitute ch lorin e atom of com poun ds 1 an d 2 by th eir
reaction with eth ylam in e, tert-butylam in e or an ilin e with th e aim to pre-
pare crystallin e com poun ds th at could be better iden tified, e.g., by X-ray
diffraction . Un fortun ately, th ese reaction s led to decom position of 1 or 2
(in th e case of eth ylam in e or tert-butylam in e) or n o reaction was observed
(an ilin e).
Identification of Compound 3
Mass spectrom etry m easurem en t determ in ed m/z = 287 for com poun d 3.
Th e m asses of fragm en ts an d th eir com parison with th e library of m ass
spectra9 led to th e con clusion th at th is substan ce can be N,N′,N″-triph en yl-
guan idin e (exact m ass 287.142249). However, X-ray diffraction studies of 3
(see below) proved th at com poun d 3 is in fact N,N′,N″-triph en ylguan idin -
ium ch loride.
Th e form ation of com poun d 3 in th e reaction m ixture can be explain ed
by two routes:
a) It is kn own th at N,N′-diph en ylth iourea decom poses in acid m edia in to
an ilin e an d ph en yl isoth iocyan ate10. Th e decom position products, an ilin e
an d ph en ylisoth iocyan ate, th en react with HCl to form N,N′,N″-triph en yl-
guan idin ium ch loride an d CS2.
b) An ilin e, wh ich is form ed durin g th e form ation of th e six-m em bered
cycle (see Sch em e 1), reacts in acid m edia with N,N′-diph en ylth iourea form -
in g N,N′,N“-triph en ylguan idin ium ch loride.
Crystal Structure of N,N′,N“-Triphenylguanidinium Chloride (3)
Th e crystal structure of 3 h as n ot been publish ed so far. Com poun d 3 crys-
tallizes in th e m on oclin ic space group P21/c. All details of crystallograph ic
determ in ation s are given in Tables II an d III an d th e m olecular structure of
3 is drawn in Fig. 1. Th e asym m etric un it of com poun d 3 con tain s on e for-
m ula un it th e cation an d an ion of wh ich are in gen eral position s. Crystal-
lograph ic data for N,N′,N″-triph en ylguan idin ium n itrate11 or pure N,N′,N″-
Collect. Czech. Chem. Commun. 2007, Vol. 72, No. 3, pp. 297–306

Reaction of Thiophosphoryl Trichloride
301
triph en ylguan idin e (as m on om er or trim er)12,13 were reported (see th e com -
parison in Table III).
Th e an gles aroun d th e cen tral carbon atom of th e N,N′,N″-triph en yl-
guan idin ium cation (alm ost 360°) in dicate plan arity of th e CN3 un it
wh ereas th e m ean deviation of th e C(19) carbon atom from th e plan e
N(1)–N(2)–N(3) is on ly 0.0019 Å. Th e len gth s of C(19)–N bon ds are be-
tween 1.333 an d 1.340 Å wh ich is com parable with th e len gth s of an alo-
TABLE II
Basic crystallograph ic data an d structure refin em en t for com poun d 3
Em pirical form ula
C19H18Cl1N3
323.8
Form ula weigh t
Tem perature, K
183(2)
Crystal system
m on oclin ic
P21/c
Space group
Un it cell dim en sion s
a, b, c, Å
14.0019(4), 15.8702(5), 7.7796(2)
90, 101.5160(10), 90
1693.93(8)
α, β, γ, °
Cell volum e, Å3
Calculated den sity, Mg/m 3
Form ula un its per un it cell
X-ray
1.270
4
MoKα
Wavelen gth , Å
0.71069
Absorption coefficien t, m m –1
Crystal size, m m –1
0.228
0.40 × 0.30 × 0.20
1.96 to 27.01
θ ran ge for data collection , °
Reflection s collected/un ique
Com pleten ess to θ = 25.00, %
Absorption correction
Max. an d m in . tran sm ission
Refin em en t m eth od
Goodn ess-of-fit on F2
Fin al R in dices [I > 2σ(I)]
R in dices (all data)
Largest diff. peak an d h ole, eA–3
15894/3670 [R(in t) = 0.0211]
99.9
Sem i-em pirical from equivalen ts
0.8620 an d 0.7555
Full-m atrix least-squares on F2
1.070
R1 = 0.0299, wR2 = 0.0757
R1 = 0.0432, wR2 = 0.0791
0.159 an d –0.217
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302
Dastychová, Příhoda, Taraba:
TABLE III
Com parison of selected geom etric param eters of com poun d 3 with structure data of sim ilar
com poun ds. Space groups in paren th eses
– 11
12
13
Bon d, Å
An gle, °
3
TPGH+NO3
TPG
TPG3
(P21/c)
(P-421/c)
(Pna21)
(P21/c)
N(1)–C(18)
N(1)–C(19)
N(2)–C(15)
N(2)–C(19)
N(3)–C(16)
N(3)–C(19)
1.425
1.340
1.426
1.334
1.429
1.333
1.427
1.355
1.440
1.335
1.442
1.354
1.430
1.362
1.429
1.335
1.414
1.321
1.453
1.390
1.415
1.264
1.452
1.409
N(1)–C(19)–N(2)
N(3)–C(19)–N(1)
N(3)–C(19)–N(2)
C(18)–N(1)–C(19)
C(15)–N(2)–C(19)
C(16)–N(3)–C(19)
120.9
117.2
121.9
127.9
124.8
124.7
115.1
118.7
126.2
124.5
124.5
124.1
113.8
117.9
128.4
126.0
125.7
120.2
128.8
113.8
117.3
117.6
125.3
116.9
a
TPG = N,N′,N″-triph en ylguan idin e.
FIG. 1
Th e m olecular structure of 3 (th erm al ellipsoids are drawn at th e 50% probability level)
Collect. Czech. Chem. Commun. 2007, Vol. 72, No. 3, pp. 297–306

Reaction of Thiophosphoryl Trichloride
303
gous bon ds in N,N′,N″-triph en ylguan idin e, its trim er, n itrate11–13, an d oth er
guan idin e derivatives14,15. It follows from th e data in Table III th at th e
greatest differen ces in C(arom )–N bon d len gth s are in th e trim er.
Two types of h ydrogen bon ds are presen t in th e crystal structure of
com poun d 3. Th e ch lorin e atom is surroun ded with two NH groups wh ich
belon g to two differen t cation s (Table IV). Th e an gle aroun d th e ch lorin e
atom is 127.1° an d in dicates lin ear ben t orien tation of th e Cl-H2 un it. Th e
crystal packin g overview of th e com poun d 3 is sh own in Fig. 2.
TABLE IV
Hydrogen bon d param eters (in Å an d °) for com poun d 3
D–H···A
d(D–H)
d(H···A)
d(D···A)
<(DHA)
N(3)–H(3N)···Cli
N(2)–H(2N)···Cli
0.843(16)
0.843(16)
2.257(17)
2.257(17
3.0963(11)
3.0963(11)
173.8(14)
173.8(14)
Sym m etry tran sform ation s used to gen erate equivalen t atom s: (i) –x + 1, y – 1/2, –z + 1/2.
FIG. 2
Weak bon din g in teraction s in com poun d 3 (th erm al ellipsoids are drawn at th e 50% probabil-
ity level)
Collect. Czech. Chem. Commun. 2007, Vol. 72, No. 3, pp. 297–306

304
Dastychová, Příhoda, Taraba:
EXPERIMENTAL
Materials
(Ph NH)2CS (Fluka) was dissolved in boilin g eth an ol an d precipitated by addin g h ot water16
.
PSCl3 was prepared from PCl3 an d sulfur in th e presen ce of AlCl3 (ref.17). Purification of ace-
ton itrile an d pyridin e was carried out accordin g to th e kn own procedures16
.
Gen eral Procedure
All reaction s an d subsequen t m an ipulation s were carried out in th e atm osph ere of dry n itro-
gen .
Apparatus an d Meth ods
1H, 13C an d 31P NMR spectra were recorded on a 500 MHz NMR spectrom eter Bruker DRX
Avan ce. Ch em ical sh ifts are given in ppm (δ-scale) relative to 85% H3PO4 as an extern al
stan dard. Mass spectrom etric an alyses were perform ed on a m ultifun ction al quadrupole
spectrom eter TRIO 1000 Series II, Fin n igan MAT, Fison s In strum en ts. Th e ion ization en ergy
was 35 eV (for com poun ds 1 an d 2) an d 70 eV (for com poun d 3). Th e sam ples were in serted
in to th e spectrom eter by th e Direct In sert Probe. FT-IR spectra were m easured on an Equin ox
55/S/NIR FTIR Bruker spectrom eter. Com poun d 3 was an alyzed in Nujol. Crystal structure
determ in ation was perform ed with a th ree-circle diffractom eter Siem en s Sm art-CCD by th e
ω-scan m eth od usin g a graph ite m on och rom atized MoKα radiation (λ = 0.71069 Å). Th e
structure was solved by direct m eth ods. Non -h ydrogen atom s were refin ed an isotropically
wh ile h ydrogen atom s were in serted in calculated position s an d isotropically refin ed as-
18
sum in g a “ride-on ” m odel. Th e SHELX97
program package was used for th e structure de-
19
term in ation ; drawin gs were m ade with XP program of Bruker SHELXTL NT, Version 5.1
.
CCDC 284389 (for com poon d 3) con tain s th e supplem en tary crystallograph ic data for th is
paper. Th ese data can be obtain ed free of ch arge via www.ccdc.cam .ac.uk/con ts/retrievin g.h tm l
(or from th e Cam bridge Crystallograph ic Data Cen tre, 12, Un ion Road, Cam bridge, CB2 1EZ,
UK; fax: +44 1223 336033; or deposit@ccdc.cam .ac.uk).
2-Ch loro-1,3-diph en yl-1,3,2λ5-diazaph osph etidin e-2,4-dith ion e (1)
A solution of 1 g PSCl3 (5.90 m m ol) in 15 cm 3 CH3CN was added to a suspen sion of 2.7 g
(11.83 m m ol) (Ph NH)2CS in 30 cm 3 CH3CN an d th e reaction m ixture was refluxed at 82 °C
for 2 h . Th e reaction m ixture turn ed pale yellow an d first portion of a wh ite solid 3 precipi-
tated. Th e solution was th en con cen trated un der vacuum an d furth er portion of precipitated
com poun d 3 was filtered off. Th e solven t was th en com pletely evaporated. Com poun d 1
was isolated as a viscous yellow liquid always sligh tly con tam in ated with 3. Yield 1.67 g
(87% based on PSCl3). 1H NMR (CH3CN): 7.25–7.40 m , 10 H (ArH). 13C NMR (CH3CN):
126.46 s (Ar); 128.44 s (Ar); 130.58 s (Ar); 131.33 s (Ar); 150.9 s (CS). 31P NMR (CH3CN):
83.7 s. EI MS, m/z (%): 324 (1) C13H10ClN2PS2, 180 (3) C7H5N2PS, 167 (3) C7H6NPS, 154 (2)
C6H5NPS, 151 (3) C7H7N2S, 135 (44) C7H5NS, 118 (19) C7H6N2, 103 (3) CN2PS, 93 (100)
C6H7N, 77 (44) C6H5, 63 (8) PS. IR: 3399 (sh ), 3313 (sh ), 3174 (sh ), 3079 (sh ) νCH, 3051 (sh )
ν
CH, 3035 (sh ) νCH, 3005 (sh ) νCH, 2944 (sh ), 2888 (sh ), 2768 (sh ), 2702 (sh ), 2556 (vw),
2457 (vw), 2162 (s), 2089 (vs), 1666 (s) δCH, 1629 (s) νCC, 1585 (sh ) νCC, 1582 (vs) νCC, 1492
Collect. Czech. Chem. Commun. 2007, Vol. 72, No. 3, pp. 297–306

Reaction of Thiophosphoryl Trichloride
305
(s) δCH, 1441 (w) δCH, 1352 (w) δCH, 1071 (w) δCH, 752 (vs) PS, 704 (sh ), 691 (s) PS, 577 (m )
PS, 504 (w) νPCl, 489 (w) νPCl, 443 (w).
2-Ch loro-1,3,5-triph en yl-1,3,5,2λ5-triazaph osph in an e-2,4,6-trith ion e (2)
A m ixture of 0.7 g (4.13 m m ol) PSCl3, 0.95 g (4.13 m m ol) (Ph NH)2CS, 2.0 g (8.26 m m ol)
pyridin e, an d 25 cm 3 CH3CN was refluxed for 3 h . Th en CH3CN was partially evaporated
an d th e precipitated solid, a m ixture of com poun d 3 an d pyHCl, was filtered off. Th e sol-
ven t was th en com pletely rem oved. Com poun d 2 was isolated as a viscous yellow liquid.
Yield 1.88 g (98% based on PSCl3). 1H NMR (CH3CN): 7.2–7.5 m , 15 H (ArH). 13C NMR
(CH3CN): 120.2 s (Ar); 124.3 s (Ar); 126.3 s (Ar); 128.3 s (Ar); 128.5 s (Ar); 129.1 s (Ar); 136.8 s
(Ar); 139.5 s (Ar); 236.7 s (CS). 31P NMR (CH3CN): 108.7 s. EI MS, m/z (%): 460 (1)
C
20H15ClN3PS3, 383 (5) C14H10ClN3PS3, 324 (1) C13H10ClN2PS2, 271 (2) C8H6N3PS3, 167 (2)
C7H6NPS, 154 (6) C6H5NPS, 135 (100) C7H5NS, 118 (31) C7H6N2, 103 (6) CN2PS, 93 (55)
C6H7N, 77 (90) C6H5, 63 (27) PS. IR: 2377–2867 (s), 2347 (m ), 2291 (m ), 1992 (s) δCH, 1572
(m ) νCC, 1560 (sh ) νCC, 1486 (vs) νCC, 1197 (w) δCH, 1054 (m ) δCH, 1002 (m ), 964 (m ) δCH
682 (vs) PS, 608 (m ) PS, 596 (m ) PS, 507 (w) νPCl, 437 (w).
,
N,N′,N″-Triph en ylguan idin ium Ch loride (3)
Com poun d 3 was form ed in th e case of both described reaction s between PSCl3 an d
(Ph NH)2CS as a by-product. M.p. 252–255 °C (decom p.). 1H NMR (CDCl3): 7.05–7.19 m ,
15 H (ArH); 10.08 bs, 3 H (NH). 13C (APT) NMR (CDCl3): 124.26 s (Ar); 127.42 s (Ar); 129.83 s
(Ar); 134.84 s, 3 C (Carom -N); 153.12 s, 1 C (CN3). EI MS, m/z (%): 287 (47) C19H17N3, 194
(100) C13H10N2, 168 (4) C12H10N, 118 (7) C7H6N2, 104 (8) C7H6N, 93 (95) C6H7N, 77 (46)
C6H5. IR: 3277 (m ), 3209 (m ), 3156 (m ), 3105 (m ), 3047 (m ), 3028 (m ) νNH, 2987 (sh ) νNH
,
1644 (m ) νC=N, 1603 (w) νCC, 1598 (m ) νCC, 1579 (m ) νCC, 1540 (m ) νCN, 1495 (m ) νCC, 1445
(m ) νCC, 1323 (m ) νCC, 1313 (sh ) νCC, 1292 (w) δCH, 1256 (m ) δCH, 756 (m ) γCH, 749 (sh )
γCH, 731 (m ) γr, 696 (w) δCC + νCC, 689 (m ).
The crystal structure determination was performed at the Faculty of Chemistry, Bielefeld University,
Germany. We thank Prof. W. Plass for X-ray measurements.
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