Complexes of heteroscorpionate trispyrazolylborate ligands. Part XI. Weak CH/π interactions in crystals of hydrotris(3-phenylpyrazolyl) boratothallium(I) and hydrobis(5-methyl-3-phenylpyrazolyl)(3,5-dimethylpyrazol- yl)boratothallium(I) studied by X-ray c

Article abstract of DOI:10.1016/j.molstruc.2003.12.002

Thallium(I) complexes of heteroscorpionate hydrobis(3-phenyl-5- methylpyrazolyl)(3,5-dimethylpyrazol-yl)borate and hydrotris(3-phenylpyrazol-1- yl)borate were studied crystallographically. Both ligands were coordinated in κ³ fashion via N₂

Full text of DOI:10.1016/j.molstruc.2003.12.002

Journal of Molecular Structure 690 (2004) 175–180
www.elsevier.com/locate/molstruc
Complexes of heteroscorpionate trispyrazolylborate ligands. Part XI.
Weak CH/p interactions in crystals of hydrotris(3-phenylpyrazolyl)
boratothallium(I) and hydrobis(5-methyl-3-phenylpyrazolyl)(3,5-
dimethylpyrazol-yl)boratothallium(I) studied by X-ray crystallography
Zbigniew Ciunika, Tomasz Rumanb, Marta Lukasiewicza, Stanislaw Wolowieca,b,
*
aFaculty of Chemistry, University of Wroclaw, 14 Joliot-Curie St., 50-383 Wroclaw, Poland
b
´ ´ ´ ´
Faculty of Chemistry, Rzeszow University of Technology, 6 Powstancow Warszawy Ave., 35-959 Rzeszow, Poland
Received 8 October 2003; revised 26 November 2003; accepted 2 December 2003
Abstract
Thallium(I) complexes of heteroscorpionate hydrobis(3-phenyl-5-methylpyrazolyl)(3,5-dimethylpyrazol-yl)borate and hydrotris(3-
phenylpyrazol-1-yl)borate were studied crystallographically. Both ligands were coordinated in k3 fashion via N2 atoms of pyrazol-1-yl
moieties. Both compounds crystallize as centrosymmetric dimers in which weak CH/p intra- and interdimer interactions are responsible for
arrangement in crystal structure.
q 2003 Elsevier B.V. All rights reserved.
Keywords: Trispyrazolylboratothallium complexes; Structures; CH/p interaction
1. Introduction
to readily crystallization, Tp0Tl(I) complexes are particu-
larly useful species used both for purification of Tp0
ligands and for their structural characterization [23–39].
Recently the subject of thallium(I) complexes with Cp
and structurally related Tp ligands was extensively
reviewed [40].
Tris(pyrazolyl)borates (Tp0) are convenient anionic
ligands (scorpionates) to construct metal ion complexes
of valuable properties [1]. The steric hindrance of those
tripodal ligands can be tuned by choice of the
appropriate alkyl and/or aryl substituents at 3–5 positions
of pyrazolyl moieties. Thus, the properties of transition
metal ion complexes of those ligands, of the general
formula Tp0M(XYZ) (where M—transition metal ion, X,
Y, Z—neutral or anionic exchangeable, monodentate
ligands) can be influenced by steric demands of Tp’s
resulting in additional, metal ion centered reactivity of
the complexes, including catalytic activity [2–14]. Our
systematic studies of transition metal ion complexes of
Tp0 ligands [15–22] are focused on construction of low-
symmetry Tp0 ligands of desired spatial anisotropy. Tp0
ligands can be characterized by boron-centered bite angle
or metal-ion centered bite angle in their complexes. Due
Here we report on the crystal and molecular
structure of heteroscorpionate hydrobis(3-phenyl-5-methyl-
pyrazolyl)(3,5-dimethylpyrazol-yl)boratothallium(I) and
homoscorpionate hydrotris(3-phenylpyrazol-1-yl)bora-
tothallium(I) complexes, for which the structural details
were unavailable till now.
2. Experimental
2.1. Syntheses
3-Phenylpyrazole and potassium hydrotris(3-phenylpyr-
azolyl)borate KTpPh were synthesized according to known
procedure [41]. Hydrotris(3-phenylpyrazolyl)boratothal-
lium(I) (TpPhTl(I)) was obtained according to slightly
modified published method [40], i.e. by addition of 120 mg
of KTpPh (0.25 mmol) dissolved in 25 cm3 tetrahydrofuran
*
´
Corresponding author. Address: Faculty of Chemistry, Rzeszow
´ ´
University of Technology, 6 Powstancow Warszawy Ave., 35-959
´
Rzeszow, Poland. Tel.: þ48-17-8651657; fax: þ48-17-8543655.
E-mail address: sw@prz.rzeszow.pl (S. Wolowiec).
0022-2860/$ - see front matter q 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.molstruc.2003.12.002

176
Z. Ciunik et al. / Journal of Molecular Structure 690 (2004) 175–180
into the stock water solution of thallium(I) nitrate (50 cm3,
0.1 M). The reaction mixture was stirred 2 h and the product
was extracted with 50 cm3 methylene dichloride. The
organic phase was washed twice with 100 cm3 water
followed by removal of methylene dichloride. The crude
product was dissolved in hot toluene and left for crystal-
lization from toluene/heptane at 4 8C (130 mg, 0.20 mmol,
80% yield). The same crystals were also obtained by
crystallization from chloroform. In both cases the crystals
were examined by X-ray diffraction method.
Table 1
Crystal data and structure refinement
Compound
1
2
Empirical formula
Formula weight
T (K)
˚
l (A)
Crystal system
C
27H22BN6Tl
C25H26BN6Tl
625.70
100(2)
0.71073
Monoclinic
C2=c
645.69
100(2)
0.71073
Triclinic
P1
Space group
˚
a (A)
˚
b (A)
10.609(2)
10.968(2)
12.098(2)
66.40(3)
87.58(3)
72.32(3)
1224.0(4)
2
20.139(2)
11.8827(10)
24.976(2)
90
˚
c (A)
Anal. Calcd. for C27H22N6BTl: C, 50.22; H, 3.43; N,
13.02. Found: C, 50.51; H, 3.60; N, 12.84. Sodium
hydrobis(3-phenyl-5-methylpyrazolyl)(3,5-dimethylpyra-
zol-yl)borate (Na[HB(3-Ph,5-Mepz)2(3,5-diMepz)]) has
been obtained as before [20]. The thallium complex
[HB(3-Ph,5-Mepz)2(3,5-diMepz)]Tl(I) has been syn-
thesized in the same way as TpPhTl(I). The crystals suitable
for crystallographic studies were grown from THF/heptane.
Anal. Calcd. for C25H26BN6Tl: C, 47.99; H, 4.19; N,
13.43. Found: C, 48.31; H, 4.31; N, 13.16. 1H NMR (CDCl3,
298 K): 7.9–11.5 (15H, overlapping multiplets, o-, m-, and
p- H of 5-Ph and 3-Ph); 5.93 (1H, s, 4-H(3,5-diMepz); 6.35
(2H, s, 4-H(3-Ph,5-Mepz); 4.72 (1H, B-H, broad s); 2.17
(6H, two overlapping s, 3- and 5-CH3(3,5-diMepz),
assigned by NOESY experiment); 2.03 (3H, 5-CH3(3-
Ph,5-Mepz)).
a (8)
b (8)
g (8)
111.080(15)
90
3
˚
V (A )
5576.9(9)
8
Z
Dc (Mg m23)
1.752
1.490
m (mm21
)
6.626
5.814
Fð000Þ
624
2432
Crystal size/mm
u range for data
collection (8)
0.12 £ 0.10 £ 0.10 0.12 £ 0.12 £ 0.10
3.43-28.86
3.50-28.44
h; k; l ranges
212 ! 14,
214 ! 14,
216 ! 15
226 ! 23,
215 ! 15,
233 ! 33
Reflections collected
Independent reflections ðRint
Data/parameters
8741
18808
Þ
5585 (0.0742)
5585/316
6529 (0.1344)
6529/302
Transmission coefficients
min./max.
0.5036/0.5571
0.5421/0.5940
2.2. X-ray crystallography
Goodness-of-fit ðF2Þ
1.059
1.087
Final R1=wR2 indices ðI . 2sIÞ 0.0406/0.1092
0.0767/0.2055
3.314/23.149
-3
Largest diff. peak/hole (e A )
Crystal data are given in Table 1, together with
refinement details. All measurements of crystals were
performed on a Kuma KM4CCD k-axis diffractometer
with graphite-monochromated Mo Ka radiation. Both
crystals were positioned at 65 mm from the KM4CCD
camera. 612 frames were measured at 0.758 intervals with a
counting time of 15 s. The data were corrected for Lorentz
and polarization effects. Absorption correction based on
least-squares fitted against to lFcl 2 lFol differences were
also applied [42]. Data reduction and analysis were carried
out with the Kuma Diffraction (Wroclaw) programs. The
structures were solved by direct methods (program
SHELXS97 [43]) and refined by the full-matrix least-squares
method on all F2 data using the SHELXL97 [44] programs.
Non-hydrogen atoms were refined with anisotropic thermal
parameters; hydrogen atoms were included from geometry
of molecules but were not refined.
˚
2.951/23.520
Tp0 ligands are coordinated in k3 fashion via N2 atoms of
pyrazol-1-yl moieties (Fig. 1). Selected bond distances and
angles are given in the caption of Fig. 1. The Tl–N
˚
bond lengths for both 1 and 2 (2.513(8)–2.620(4) A) and
N–Tl–N bond angles ranging from 69.39(14) to 79.56(13)8
fall into the region typical for all Tp0Tl complexes based on
3-Rpyrazolyl moieties (where R—aromatic substituent,
entries 1–6 in Table 2). Longer Tl–N distances were
observed in Tp0Tl complexes with large steric hindrance
around metal center (hydrotris(3-(9-triptycyl)pyrazolyl)bor-
˚
atothallium(I)—2.76 A [23] and hydrotris(7-t-butylindazol-
˚
2-yl)boratothallium(I)—2.66 A [24] and in those cases
where additional donor atoms were involved: (hydrotris(3-
(pyrrolidinylcarbonyl)pyrazol-1-yl)boratothallium(I)—
˚
2.71 A [25] and hydrotris(3-(2-pyridyl)pyrazolyl)bora-
(CF3
tothallium(I)—2.67 A [26] as well as in Tp )2 Tl complex
˚
(2.71 A), in the latter possibly due to electronic reason [27].
˚
3. Results and discussion
There are weak edge-to-face CH/p interactions present
in the lattice of both 1 and 2, which are responsible for
crystal organization. This kind of interaction has been
recognized as important factor responsible for crystal
organization in many solids [45]. The crystal packing of 1
with three edge-to-face contacts is presented at Fig. 2A.
Two scorpionate trispyrazolylboratethallium(I) com-
plexes have been studied structurally here: the homoscor-
pionate hydrotris(3-phenyl)pyrazolyl)boratothallium(I) (1)
and the heteroscorpionate hydrobis(3-phenyl-5-methylpyr-
azolyl)(3,5-dimethylpyrazolyl)borato thallium(I) (2). Both
complexes crystallized as centrosymmetric dimers, in which

Z. Ciunik et al. / Journal of Molecular Structure 690 (2004) 175–180
177
˚
Fig. 1. Molecular structures of 1 (left) and 2 (right) with crystallographic numbering. Selected bond lengths (A) and angles (8), 1: Tl(1)–N(1), 2.598(4); Tl(1)–
N(3), 2.596(4); Tl(1)–N(5), 2.620(4); N(3)–Tl(1)–N(1), 69.39(14); N(3)–Tl(1)–N(5), 79.56(13); N(1)–Tl(1)–N(5), 76.46(14), 2:Tl(1)–N(2), 2.513(8);
Tl(1)–N(4), 2.519(7); Tl(1)–N(6), 2.609(8); N(2)–Tl(1)–N(4), 75.2(3); N(2)–Tl(1)–N(6), 78.2(3); N(4)–Tl(1)–N(6), 75.9(2).
The 3-phenyl moieties within TpPhTl–TlTpPh dimers are
arranged in specific way; there are three (Ph)C–H
Ph(centroid) intermolecular, intradimer contacts of edge-
to-face type, with two Hmeta Ph and one Hortho Ph distances
as in bis-ligand TpB2 oM(II) (M ¼ Fe, Co, Ni, Cu, and Zn)
complexes [48].
The intradimer Tl· · ·Tl contact in 1 is equal to 3.85 A.
Such interaction has been found previously in hydrotris(3-
˚
˚
equal 3.03, 2.57, and 3.26 A, respectively, and additional
˚
( p-tolyl)pyrazolyl)boratothallium(I) (3.86 A) [28] and in
hydrotris(3-(2,4-dimethoxyphenyl)pyrazolyl)boratothal-
˚
lium(I) (3.99 A) [29] but it was absent in hydrotris(3,5-di-
( p-t-butyl)phenylpyrazolyl)boratothallium(I) [30] due to
interdimer (Ph)C–H Ph(centroid) contact with H Ph
˚
distance of 2.99 A (Table 3). These result in formation of
polymeric chains composed of TpPhTl TlTpPh dimers with
aromatic hydrophobic surface rendering the complex totally
insoluble in common organic solvents. Similar interactions
were observed in other cases. In dimeric Tpp-TolTl complex
the R-phenyl rings of two Tp0 ligands intermesh and their
Table 2
Geometry of the C–H· · ·Ph(centroid) hydrogen bonds for 1 and 2
˚
aromatic rings are stacked with a distance longer than 4.0 A
without interdimer contacts [28]. The dimeric Tp(2,4(OMe)
Ph)Tl shows both intra- and interdimer C–H· · ·Ph contacts,
C–H· · ·Ph
H· · ·Ph
/C–H· · ·Ph
2-
Compound 1
similarly as those in 1 [29]. Thus, there are three edge-to-
˚
face intradimer C(Ph)Hmeta Ph contacts with 3.01 A
C(8)–H(8)· · ·Ph1(i)
C(9)–H(9)· · ·Ph1(i)
C(15)–H(15)· · ·Ph2(i)
C(23)–H(23)· · ·Ph3(ii)
3.03
3.26
2.57
2.99
134
123
154
154
distance and three interdimer o-CH3 Ph contacts with
˚
˚
2.91 A distance (calculated for idealized 0.96 A C–H bond
length) in trigonal crystal.
Compound 2
C(23)–H(23A)· · ·Ph1(iii)
C(18)–H(18A)· · ·pz(iv)
Moreover, the intermolecular CH(fused benzene ring in
dihydrobis(indazol-1-yl)boratothallium(I))/p interaction
was found to be responsible for crystal packing [46],
and chiral supramolecular organization in crystals of
tris(indazol-1-yl)boratothallium(I) (TpBoTl) [47] as well
.
2.83
2.63
137
148
.
Symmetry transformations used to generate equivalent atoms:
(none) x; y; z; (i) 1 2 x; 2y;2z; (ii) 2 2 x; 2y; 2z; (iii) x; 1 þ y; z; (iv)
2x; 1 2 y; 2z:

178
Z. Ciunik et al. / Journal of Molecular Structure 690 (2004) 175–180
Fig. 2. Crystal packing diagram with CH/p contacts in the crystal structure of 1 (top) and 2 (bottom).
considerable steric hindrance from t Bu substituents. Neither
it was found in hydrotris(3-(2-methoxyphenyl)pyrazol-1-
yl)boratothallium(I) [31] due to additional involvement of
two methoxy group oxygens engaged in coordination.
Unlike in 1, two intradimer CH/p interactions occur
between 4-H(3-Phpz) and 3,5-dimethylpyrazolyl p acceptor
in 2. Two thallium metal ions point away from the center of
hindrance of Tp0 ligand depending on 3- and/or 5-
substituents. The boron-centered bite angle has been
introduced by us in order to compare the metal ion-
independent ligand steric demands [20]. Thus, this par-
ameter is attributed to ligand. The value of b for
heteroscorpionate [HB(3-Ph,5-Mepz)(3,5-diMepz)]2 varies
depending on coordination mode of the ligand and
coordination number of central metal ion and is equal:
90.08 (bidentate in Tp0Rh(CO)2, [49]) 86.98 (terdentate in
Tp0Tl, 2), 80.48 (terdentate in Tp’Co(NCS)(THF), [20]).
The comparison made for Tp’Tl(I) complexes, in which
Tp0 ligands are k3 coordinated via three N2 pyrazol-1-yl
˚
dimer (Tl· · ·Tl distance is 10.70 A). Additionally, there are
two CH/p (3-PH) interdimer interactions, which are
responsible for formation of 1D chains composed of dimers.
The thallium-centered ðaÞ and boron-centered ðbÞ bite
angles for Tp0Tl complexes (Table 3) reflect the steric

Z. Ciunik et al. / Journal of Molecular Structure 690 (2004) 175–180
179
Table 3
Values of thallium-centered ðaÞ; boron-centered ðbÞ bite angles and averaged Tl–N(pz) bond lengths in Tp’Th(I) complexes. The fourth column shows the Tl–
Tl distance in Tp0Tl TlTp0 dimers
a (8)a
b (8)a
˚
Tl–N (A)
˚
Tl–Tl (A)
Entry
Compound
1
2
3
4
5
Hydrotris(3-phenylpyrazolyl)boratothallium(I) (TpPhTl)h
Ferrocenyltris(3-phenylpyrazolyl)boratothallium(I) [50]
Hydrotris(3-( p-tolyl)pyrazolyl)boratothallium(I) (Tpp MePhTl) [28]
Hydrotris(3-(2-methoxyphenyl)pyrazolyl)boratothallium(I) [31]
Hydrotris(3-(2,4-dimethoxyphenyl)pyrazolyl)boratothallium(I)
(Tp2,4-diOMePhTl) [29]
167.1
167.1
161.0
151.4
164.2
84.0
85.8
79.1
77.1
80.6
2.61
2.56
2.59
2.59f
2.58
3.85
3.86
3.99
6
Hydrotris(3,5-di-(p-t-butyl)phenylpyrazolyl)boratothallium(I)
(Tp(p-t BuPh)Tl) [30]
166.9b
87.1b
2.60
2
7
Hydrotris(3-(2-pyridyl)pyrazolyl)boratothallium(I) [26]
164.2
243.5
190.8
162.5
172.4
217.8
172.4c
199.9d
172.4c
196.6d
136.0
150.1
164.1
73.3
120.2
97.4
2.67e
2.63
2.52
2.58
2.50
2.62
2.71
8
Hydrotrispyrazolylboratothallium(I) (TpTl) [32]
9
Hydrotris(3,5-dimethylpyrazolyl)boratothallium(I) (TpM2 eTl) [33]
Hydrotris(3-t-butylpyrazolyl)boratothallium(I) (Tpt BuTl) [34]
Hydrotris(3-t-butyl-5-methylpyrazolyl)boratothallium(I) (Tpt Bu,MeTl) [35]
Hydrobis(3-t-butylpyrazolyl)(pyrazolyl)boratothallium(I) [36]
Hydrotris(3,5-di-trifluoromethylpyrazolyl)boratothallium(I) [27]
10
11
12
13
81.8
88.2
107.7
76.2c
97.7d
81.2c
99.0d
73.8
14
Hydrotris(3-trifluoromethyl,5-(2-thienyl)pyrazolyl)boratothallium(I) [37]
2.62
15
16
17
Hydrotris(3-(9-triptycyl)pyrazolyl)boratothallium(I) (TpTriptycylTl) [23]
Hydrotris(7-t-butylindazol-2-yl)boratothallium(I) [24]
(Hydrotris(1,4-dihydroindeno(1,2-c)pyrazol-1-yl)borato)thallium(I)
(TpindenTl) [38]
2.76
2.66
2.53
75.6
89.8
18
19
Hydrotris(7(R)-t-butyl-4(R)-Me-4,5,6,7-tetrahydro-2-
indazolyl)hydroboratothallium(I) [39]
167.7
171.2
83.9
81.4
2.56
2.55
Hydrotris(7(R)-i-propyl-4(R)-Me-4,5,6,7-tetrahydro-2-
indazolyl)hydroboratothallium(I) [39]
20
21
Hydrotris(3-(pyrrolidinylcarbonyl)pyrazol-1-yl)boratothallium(I) [25]
Hydrobis(3-phenyl-5-methylpyrazolyl)(3,5-dimethylpyrazolyl)-
boratothallium(I)h
164.5
189.2
78.7
86.9
2.71 g
2.55
a, measured for the atom of 3-R substituent (non-hydrogen atom) closest to metal ion, unless otherwise stated; b, measured for o-C(Ph); c, measured to
˚
fluorine atom of CF3; d, measured to carbon atom of CF3; e, Tl-N(py); mean contact distance 3.18 A; f, two methoxy group oxygen atoms are in close contact
˚
with Tl(I) (3.20 A); g, three carbonyl oxygen atoms are at the mean distance of 3.00 A from Tl atom; h, this work.
˚
atoms indicates clearly that unsubstituted Tp and 3,5-diMe
substituted ligands possess the smallest steric hindrance,
whereas the 3-(9-triptycyl) substituent produces the most
sterically demanding homoscorpionate Tp0 ligand. Con-
sidering the boron-centered bite angle, the Tp0 ligands can
be put in the following order of increasing steric hindrance
of 3,5 substituents:
structural modifications of Tp3-R cause the severe twist of
coordinated pyrazolyl rings in respect to the B-Tl axis, or
more precisely the deviation of B–N1–N2–Tl dihedral
angle from 08. These effects demonstrate the flexibility of
Tp0 ligands in teracoordinate Tp0Tl complexes. As one can
anticipate, the bite angles for heteroscorpionate 2 (entry 21
in Table 3) are intermediate between TpPhTl and Tp2Me
although the measured b for 2 (86.98) is apparently larger
from the averaged value for those two (84.78).
In conclusion, the structural data are obtained from X-ray
analysis of crystals of TpPhTl(I) and [HB(3-Ph,5-
Mepz)2(3,5-diMepz)]Tl(I) obtained from various organic
solvents as dimers stabilized by numerous weak edge-to-
face C(Ph)H· · ·Ph interactions. These weak interactions are
responsible for arrangement of dimers rather than thallium-
thallium interaction.
Tp , TpBo , TpM2 e , Tpinden , Tpt Bu,Me , [HB(3-
Ph,5-Mepz)2(3,5-diMepz)]2 , Tp2( p-t BuPh) , TpPh
Tpt Bu , Tp2,4-diOMePh , TppMePh , TpTriptycyl
,
According to the values of b (see above) the steric
hindrance from 3-aryl substituents is comparable to that
from 3-t Bu one. Moreover, the presence of 5-R substituents
different from hydrogen atom results in increase of bite
angle which can be seen when one compare the values of b
for Tpt Bu (81.88) and Tpt Bu,Me (88.28) or TppMePh (79.18)
and Tp2( p-t BuPh) (87.18). Similarly, the replacement of
ferrocenyl residue for boron-attached hydrogen in TpPh
[50] resulted in increase of b from 84.0 to 85.88. These steric
effects can be assigned to the fact, that both of those
4. Supplementary data
Crystallographic data for the structures reported in
this paper have been deposited with the Cambridge

180
Z. Ciunik et al. / Journal of Molecular Structure 690 (2004) 175–180
[22] T. Ruman, Z. Ciunik, A. Goclan, M. Lukasiewicz, S. Wolowiec,
Polyhedron 20 (2001) 2965.
Crystallographic Data Centre, CCDC no. 208716 for
compound 1, and CCDC no. 208715 for 2. Copies of this
information may be obtained free of charge from the
Director, CCDC, 12 Union Road, Cambridge 1EZ. UK (fax:
þ44-1223-336033; e-mail: deposit@ccdc.cam.ac.uk or
http://www.ccdc.cam.ac.uk).
[23] T. Filebeen, T. Hascall, G. Parkin, Inorg. Chem. 36 (1997) 3787.
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Acknowledgements
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Authors thank to KBN (Poland) for the Grant number 3
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