Copper(II), Nickel(II), Cobalt(II), and Chromium(III) Complexes Based
on 6,6 -Bis{[methyl(oxido)imino]methyl}-2,2 -bipyridine
Elena G. Petkovaa , Rostislav D. Lampekaa, Marian V. Gorichkob, Gennadiy Palamarchukc,
Viktoriya V. Dyakonenkoc, Roman I. Zubatyukc, and Oleg V. Shishkinc
aDepartment of Inorganic Chemistry, Kiev University, Volodimirska St. 64, 01033 Kiev, Ukraine
bDepartment of Organic Chemistry, Kiev University, Volodimirska St. 64, 01033 Kiev, Ukraine
cSTC “Institute for Single Crystals”, National Academy of Science of Ukraine, 60 Lenina Ave.,
Kharkiv 61001, Ukraine
Reprint requests to Dr. R. D. Lampeka. Fax: +380-44-4907185. E-mail: [email protected]
Z. Naturforsch. 2008, 63b, 841 – 847; received March 5, 2008
The bipyridine-based ligand 6,6 -bis{[methyl(oxido)imino]methyl}-2,2 -bipyridine (L) reacts with
copper(II) chloride in methanol to produce a tetrachlorocuprate(II) salt [CuL][CuCl4 ] (1). Reac-
tions of equimolar quantities of Ni(NO3 )2 · 6H2 O and Co(NO3 )2 · 6H2 O with L in methanol produce
compounds [ML(NO3 )2 ] (M = Ni (2), M = Co (3)). Reaction of Cr(NO3 )3 · 6H2 O with L affords
[Cr(L)(H2 O)2 ](NO3 )3 · 0.5H2 O (4). The structures of compounds 1 – 4 were determined by X-ray
diffraction. In all four complexes L exhibits the tetradentae chelating mode of coordination.
Key words: Bipyridine-bis-nitrone Complexes, Copper(II), Nickel(II), Cobalt(II), Chromium(III)
Introduction phiphilic peptide, and a three-α -helix bundle protein
was synthesized using an iron(II) tris-bipyridine com-
Substituted bipyridine derivatives have found nu- plex as a template [5]. Furthermore, the four diastere-
merous applications in design and construction of ar- omeric forms obtained for the Fe(II) complex of three
tificial proteins and in modeling active sites of met- unsymmetrical bidentate ligands are in accordance
alloenzymes. The utility of modified bipyridine lig- with the metastable states of this template-assembled
ands can be illustrated, for example, by the syn- protein [6]. The analogous approach was employed in
theses of (S)-2-amino-3-(2,2-bipyridin-4-yl)- and (S)- work [7] in which 5-carboxy-2,2-bipyridine was cou-
2-amino-3-(2,2-bipyridin-5-yl)propanoic acids [1] as pled to the N-terminus of a 15-residue peptide that
well as (S)-2-amino-3-(2,2’-bipyridine-6-yl)propanoic underwent trimerization in the presence of transition
acid [2, 3] which, when incorporated into the rationally metal cations.
designed peptide sequences, form on addition of metal To model the features of active sites of natural
ions the synthetic metalloproteins. A few unnatural phosphodiesterases the copper(II) complexes of the
6,6 -bis(acylamino)-2,2-bipyridine-based amino acids ammonium-substituted ligands 6,6 -(Me2(H)N+ -
were synthesized and incorporated in different pep- CH2 C≡C)2 bipy and 6,6 -(Me3 N+ -CH2 C≡C)2 bipy
tides as metal binding β -turn mimics [4]. Their ability have been prepared and investigated [8].
to nucleate the formation of the β -sheet structure by Ferrocenyl ligands bearing one or two bipy subunits
coordination to copper(II) was investigated by spec- can be used for electrochemical recognition of cer-
troscopic methods. In order to predict the geometry tain metal cations [9]. As a rule, coordination of the
around the Cu(II) atom in peptides containing these (mono)bipy substituted ferrocenes leads to a gradual
β -turn mimics three model compounds were prepared, positive shift in the Fc/Fc+ redox potential (one-wave-
viz. 6,6 -bis(phenylacetamide)-2,2-bipyridine as well behavior) due to electrostatic repulsion between the
as its deprotonated (neutral) and 2+ charged (proto- bound cation and the positive charge on the oxidized
nated) Cu(II) complexes, and their structures were es- ferrocenyl subunit. Oxidation of the ferrocene center is
tablished by X-ray crystallography [4]. accompanied by a destabilization of the resultant com-
2,2-Bipyridine-4,4-dicarboxylic acid was cova- plex. Bis(bipy)-substituted ferrocenes form much more
lently attached to the N-terminus of a 15-residue am- stable complexes with the stoichiometry 1 : 1 and ex-
0932–0776 / 08 / 0700–0841 $ 06.00
c 2008 Verlag der Zeitschrift für Naturforschung, Tübingen · http://znaturforsch.com
842 E. G. Petkova et al. · 6,6 -Bis{[methyl(oxido)imino]methyl}-2,2 -bipyridine
Scheme 1.
hibit a sandwich effect that gives rise to a two-wave be-
havior – the growth of a new redox wave at the expense
of the original wave for the free ligand [9].
The cited papers are only a small selection from
many others that demonstrate the importance of further
development of bipyridine-like ligands.
The coordination chemistry of nitrones attracts a
growing interest. Nitrone complexes are shown to be
intermediates in metal catalyzed nucleophilic additions
and cycloadditions with electron-rich alkenes. As part
of our continuing study on coordinative properties of
heterocyclic nitrones [10 – 12], we describe here the
synthesis of a 2,2 -bipyridine ligand containing two
nitrone groups in 6,6 -positions, adjacent to the ring
N atoms.
Fig. 1a. Molecular unit of [CuL][CuCl4 ] (1). Selected
bond lengths and angles: Cu(1)–O(2) 1.920(2), Cu(1)–O(1)
1.932(2), Cu(1)–N(1) 1.941(3), Cu(1)–N(2) 1.953(3) Å;
N(1)–Cu(1)–N(2) 82.5(3), O(1)–Cu(1)–N(2) 94.0(3), O(2)–
Cu(1)–N(1) 95.3(3), O(2)–Cu(1)–O(1) 88.4(3)◦ .
The preparation and crystal structures of its com-
plexes [Cu(L)][CuCl4] (1), [Ni(L)(NO3)2 ] (2), [Co(L)-
(NO3 )2 ] (3), and [Cr(L)(H2O)2 ](NO3 )3 · 0.5H2 O (4)
are also reported in this paper.
Results and Discussion
Fig. 1b. Fragment of the one-dimensional chain of cations
The ligand L was obtained by condensation of 2,2 - and anions in [CuL][CuCl4 ] (1).
dipyridyl-6,6-dicarbaldehyde with N-methylhydrox-
ylamine (see Experimental Section). The starting di- ride through an “empty” CH3 OH/CH2 Cl2 layer. The
carbaldehyde was synthesized from 2-amino-6-meth- complexes 2 (brown), 3 (deep red) and 4 (red) were
ylpyridine in three steps, which include formation of produced from methanol solutions containing equimo-
2-bromo-6-methylpyridine, subsequent bis-aryl cou- lar amounts of L and of the corresponding nitrate. The
pling on a Pd/C catalyst and finally oxidation of the method employed for obtaining crystals of 1 has en-
methyl groups to aldehydes. The sequence of reactions abled us also to grow crystals of compounds 2, 3 and 4
is shown in Scheme 1. in the solvent system CH3 OH/CH2 Cl2 .
The coordination ability of ligand L was tested The X-ray diffraction study of 1 reveals the struc-
on Cu(II), Ni(II), Co(II) and Cr(III) ions. Reaction ture shown in Fig. 1a. The unit cell consists of
of L with copper(II) chloride in methanol in both [Cu(L)]2+ cations and tetrachlorocuprate(II) anions.
1 : 1 and 1 : 2 molar ratio leads to a rapid precipitation In the CuCl2−4 anion the copper atom adopts a co-
of the tetrachlorocuprate(II) salt [Cu(L)][CuCl4 ] (1). ordination geometry intermediate between tetrahedral
Green crystals of 1 suitable for X-ray analysis were and square-planar: the sum of the four cis angles is
grown by slow diffusion of a dichloromethane solu- 389.7◦ compared to the ideal sums of 438◦ for tetra-
tion of L and a methanol solution of copper(II) chlo- hedral and 360◦ for planar geometry. The trans angles
E. G. Petkova et al. · 6,6 -Bis{[methyl(oxido)imino]methyl}-2,2 -bipyridine 843
are 135.4(3) and 140.1(4)◦, and the Cu–Cl distances
are in the range from 2.223(3) to 2.284(3) Å. The lig-
and L coordinates to the copper(II) ion tetradentately
via the two nitrogen atoms of the pyridine rings and
the two oxygen atoms of the nitrone groups. The co-
ordination polyhedron of copper is square-planar de-
spite of a deviation of the N(3)–O(1) nitrone group
from the plane of the pyridine ring (torsion angle
N(2)–C(6)–C(7)–N(3) −8.2(5)◦). The nitrone frag-
ments O(1)–N(3)–C(8)–C(7) and O(2)–N(4)–C(14)–
C(13) are planar within 0.005 and 0.009 Å, re-
spectively. The coordination sphere of the copper
atom is completed by long axial bonds Cu(1)–Cl(1)
2.284(1) Å and Cu(1)–Cl(3) 2.275(1) Å. These inter-
actions link the [Cu(L)]2+ cations and the CuCl4 2−
anions into infinite chains running parallel to the
Fig. 2a. Molecular unit of [NiL(NO3 )2 ] (2). Selected
(0 1 0) crystallographic axis (Fig. 1b). The chlorine
bond lengths and angles: Ni(1)–N(1) 1.995(3), Ni(1)–
atoms Cl(1) and Cl(3 ) occupy the two semicoordi- O(1) 2.000(3), Ni(1)–O(2) 2.126(3) Å; N(1A)–Ni(1)–
nate sites in the coordination environment of Cu(1). N(1) 81.8(5), N(1)–Ni(1)–O(1) 92.8(4), O(1)–Ni(1)–O(1A)
Therefore the coordination around the Cu(1) atoms 92.9(4), O(1)–Ni(1)–O(2) 86.8(3)◦ .
can be considered as 4 + 2, and the CuCl4 2− ions
can be assumed as bridging ligands. The bridging
angles Cu(1)–Cl(1)–Cu(2) and Cu(1)–Cl(3)–Cu(2)
are 119.4◦ and 134.7◦, respectively. The majority of
the known tetrachlorocuprate(II) compounds are salts
of organic cations, usually protonated N-heterocycles
and alkylamines [13 – 22]. Together with a number of
complexes where the CuCl4 2− anions are involved in
coordination to other copper(II) ions [13, 23, 24], there Fig. 2b. Fragment of one-dimensional chain of [NiL(NO3 )2 ]
is also one example of a Cu(I) complex, whose charge (2) formed by interactions of the nitrate anions.
is compensated by a CuCl4 2− anion [25].
Neighboring chains in the crystal of complex 1 Waals radii 3.51 Å)]. Taking into account the value
are bound together by sets of C–H · · · Cl and stack- of the Cu(1)–Cl(2) · · · C(7 ) angle (104.3◦) this inter-
ing interactions. It should be noted that each chlo- action should rather be described as a repulsive inter-
rine atom forms three contacts. Based on the geo- action [27].
metrical parameters some of them may be considered Additional attraction between neighboring chains is
as weak hydrogen bonds, namely Cl(3) · · · H–C(5 ) provided by the stacking of pyridine rings. The dis-
2.63 Å (angle Cl · · · H–C 148◦) and Cl(4) · · · H–C(11) tance of 3.301 Å between the parallel planes indicates
2.66 Å (Cl · · · H–C 168◦ ). Other interactions corre- the presence of strong stacking interactions between
spond to strong electrostatic attraction: Cl(1) · · · H– the π systems of the aromatic rings.
C(14 ) 2.93 Å, Cl(1) · · · H–C(13) 2.81 Å, Cl(1) · · · H– The crystal structure of 2 is shown in Figs. 2a, 2b.
C(10 ) 2.74 Å, Cl(3) · · · H–C(4 ) 2.76 Å, Cl(3) · · · H– The nickel(II) atom occupies a special position at a
C(7 ) 2.80 Å, Cl(4) · · · H–C(14 ) 2.80 Å, Cl(4) · · · H– crystallographic center of symmetry and has a dis-
C(8) 2.73 Å (sum of van der Waals radii [26] 2.96 Å). torted octahedral environment. The ligand L is dis-
A significantly different environment is observed in the posed in the equatorial plane of the octahedron and
case of the Cl(2) atom which is involved in one weak coordinates to the nickel atom via the nitrogen atoms
hydrogen bond [Cl(2) · · · H–C(3 ) 2.62 Å (Cl · · · H– of the two pyridine rings (Ni(1)–N(1) 1.995(3) Å) and
C is 172◦ )], one electrostatic attraction [Cl(2) · · · H– the oxygen atoms of the two nitrone groups (Ni(1)–
C(9 ) 2.95 Å] and an interaction with one of the pyri- O(1) 2.000(3) Å). The axial positions of the octahedron
dine rings [Cl(2) · · · C(7 ) 3.394 Å (sum of van der are occupied by oxygen atoms of two nitrate anions
844 E. G. Petkova et al. · 6,6 -Bis{[methyl(oxido)imino]methyl}-2,2 -bipyridine
Fig. 3. Molecular unit of [Cr(L)(H2 O)2 ]-
(NO3 )3 · 0.5H2 O (4): Cr(1)–O(4) 1.945(2),
Cr(1)–O(3) 1.958(2), Cr(1)–O(1) 1.997(3),
Cr(1)–O(2) 2.006(1), Cr(1)–N(3) 2.010(3),
Cr(1)–N(2) 2.030(4) Å; O(3)–Cr(1)–N(2)
92.9(1), O(4)–Cr(1)–N(3) 93.3(1), N(3)–Cr(1)–
N(2) 81.3(2)◦ .
(Ni(1)–O(2) 2.126(3) Å). The N(1)–Ni(1)–N(1A) bite 2.47 Å. Other oxygen atoms are also involved in attrac-
angle shows a significant deviation from the ideal octa- tive interactions: O(2) · · · H–C(4) 2.71 Å, O(2) · · · H–
hedron (81.8(5)◦) because of the geometric constraints C(6) 2.69 Å, and O(4) · · · H–C(2) 2.57 Å. It should be
imposed by the bipyridine moiety. The bite angle in noted that the oxygen atom of the nitrone group also
the six-membered N,O-chelate ring, N(1)–Ni(1)–O(1), has such an interaction (O(1) · · · H–C(7) 2.56 Å).
is 92.8(4)◦. Both chelating units show some devia- In the X-ray diffraction study of 3 it has been
tion from planarity. So, the torsion angle between the demonstrated that this compound is isostructural
two pyridine rings is −10.6(1)◦. The nitrone fragment with 2. This concerns both the molecular structure and
O(1)–N(2)–C(7)–C(6) is planar within 0.002 Å, and the crystal packing.
the torsion angle with the adjacent pyridine ring N(1)– The X-ray diffraction study of 4 has shown that the
C(5)–C(6)–N(2) is equal to 6.8(2)◦. The angle between presence of water drastically changes the structure of
the O · · · O and N · · · N lines is 6.3◦ . the complex (Fig. 3). The asymmetric part of the unit
The crystal packing of compound 2 is very similar cell contains a [Cr(L)]3+ cation, three [NO3 ]− anions
to that of 1, but no coordination polymers are present. and 2.5 water molecules. The ligand L coordinates to
The molecules of 2 form infinite chains with contacts the chromium(III) ion in the same way as to the other
between nitrate anions (Fig. 2b). The two nitrate anions metal cations in compounds 1 – 3. The chromium atom
form parallel planes in such way that the N–O bonds adopts an octahedral coordination. The nitrone ligand
are placed in a head-to-tail manner providing electro- is situated in the equatorial plane and the two wa-
static attraction between the negatively charged oxy- ter molecules occupy the axial positions. The coor-
gen and positively charged nitrogen atoms. The N · · · O dinative bonds are within the range 1.945 – 2.030 Å.
distance of 3.059 Å is longer than the sum of the cor- It should be noted that all Cr–O bonds (1.945 –
responding van der Waals radii (2.79 Å). Neighboring 2.006 Å) are slightly shorter than the Cr–N bonds
chains of 2 are bound together in a way similar to that (2.010 – 2.030 Å). The nitrone fragments O(3)–N(1)–
of 1. There are sets of C–H · · · O interactions with par- C(2)–C(1) and O(4)–N(4)–C(14)–C(13) are planar
ticipation of the oxygen atoms of nitrate anions and within 0.005 and 0.003 Å, respectively, and slightly
stacking interactions between bipyridyl ligands (the twisted with respect to the pyridine rings (the torsion
distance between the average planes is 3.283 Å). The angles N(1)–C(2)–C(3)–N(2) and N(3)–C(12)–C(13)–
O(3) atom forms one weak hydrogen bond O(3) · · · H– N(4) are −7.5(7) and 2.9(7)◦, respectively). The cen-
C(3) [2.39 Å, O · · · H–C 121◦] and has three ad- tral bipyridine part is also not planar. The torsion an-
ditional attractive contacts: O(3) · · · H–C(4) 2.60 Å, gle N(2)–C(3)–C(2)–N(1) is −8.9(2)◦. Despite of the
O(3) · · · H(7A)–C(7) 2.51 Å, and O(3) · · · H(7B)–C(7) slight non-planarity of the ligand the coordination of
E. G. Petkova et al. · 6,6 -Bis{[methyl(oxido)imino]methyl}-2,2 -bipyridine 845
the chromium atom in the equatorial plane is planar. 1H NMR (400.45 MHz, [D6 ]DMSO): δ = 3.90 (s, 3 H),
The angle between the O · · · O and N · · · N lines is 8.06 (t, 3 J4−3 = 3 J4−5 = 7.2 Hz, 1 H), 8.09 (s, 1 H), 8.32
only 1.8◦ . (d, 3 J3−4 = 7.2 Hz, 1 H), 9.05 (d, 3 J5−4 = 7.2 Hz, 1 H). –
13 C{1 H} NMR (100.70 MHz, [D ]DMSO): δ = 55.0, 121.1,
The nitrate anions do not form coordinative bonds 6
122.9, 135.4, 138.3, 149.8, 155.3. – C14 H14 N4 O2 (270.3):
to the chromium atom. However, they play an impor-
calcd. C 62.21, H 5.22, N 20.73; found C 62.16, H 5.28,
tant role in the organization of the crystal structure. The
N 20.68.
components form layers parallel to the (101) crystallo-
graphic plane. Within one layer the units are linked by
H bonds between water molecules and nitrate anions: Synthesis of [Cu(L)][CuCl4 ] (1)
O(7) · · · H–O(2) 2.01 Å (O · · · H–O 139◦), O(9) · · · H– To a hot solution of L (0.07 g, 0.29 mmol) in methanol
O(2) 1.71 Å (O · · · H–O 144◦ ), O(8) · · · H–O(1) 1.96 Å (10 mL) was added CuCl2 · 2H2 O (0.1 g, 0.59 mmol)
(O · · · H–O 153◦), O(9) · · · H–O(1) 2.38 Å (O · · · H– dissolved in methanol (10 mL). An immediate color
O 148◦ ), O(8) · · · H–O(1) 1.96 Å (O · · · H–O 153◦), change to deep green was observed followed by precip-
and O(13) · · · H–O(1) 2.53 Å (O · · · H–O 121◦). The itation of a microcrystalline solid. The product was fil-
neighboring layers are bound by attractive C–H · · · O tered off and washed several times with the solvent mix-
interactions between the complex cations and nitrate ture CH3 OH/CH2 Cl2 [1 : 1]. Yield 0.114 g (76.1 %). –
anions: C(5)–H · · · O(10) 2.52 Å, C(11)–H · · · O(8) C14 H14 Cl4 Cu2 N4 O2 (539.2): calcd. C 31.19, H 2.62,
2.48 Å, C(11)–H · · · O(13) 2.61 Å, C(13)–H · · · O(14) N 10.39; found C 31.06, H 2.69, N 10.27.
2.36 Å, and C(14)–H · · · O(11) 2.55 Å. One of the ni-
trate anions is oriented almost parallel to the plane of Synthesis of [Ni(L)(NO3 )2 ] (2)
the N(2)–C(3)–C(7) pyridine ring. This orientation, to- To a hot solution of L (0.068 g, 0.28 mmol) was added
gether with the distance between the planes (3.13 Å), a solution of Ni(NO3 )2 · 6H2 O (0.083 g, 0.29 mmol) in
indicates the presence of stacking interactions between methanol (10 mL). The resulting brown solution was allowed
the π systems of the anion and the heterocycle. to boil for a while and left to stand in a beaker for 4 d. Af-
ter evaporation of methanol the brown precipitate was fil-
Experimental Section tered off and washed with several portions of the solvent
mixture CH3 OH/CH2 Cl2 [1 : 1]. Yield 0.096 g (79.3 %). –
Commercially available reagents N-methylhydroxyl- C14 H14 N6 NiO8 (453.0): calcd. C 37.12, H 3.12, N 18.55;
amine hydrochloride and 2-amino-6-methyl-pyridine were found C 37.05, H 3.18, N 18.47.
used without further purification. The ligand L was pre-
pared by reaction of N-methylhydroxylamine with 2,2 -di-
pyridyl-6,6 -dicarbaldehyde in a molar ratio 2 : 1. 6,6 -Di- Synthesis of [Co(L)(NO3 )2 ] (3)
methyl-2,2 -bipyridine [28] and 2,2 -dipyridyl-6,6 -dicarb- The procedure used to prepare 2 was followed except
aldehyde [29] were synthesized according to literature proce- that Co(NO3 )2 · 6H2 O was used as the metal salt. Com-
dures. The yield of 6,6 -dimethyl-2,2 -bipyridine can be in- pound 3 was obtained as a deep red solid in 76.4 % yield. –
creased when applying ethylene glycol as solvent under con- C14 H14 CoN6 O8 (453.2): calcd. C 37.10, H 3.11, N 18.54;
ditions described in [28]. The 1 H and 13 C NMR spectra were found C 37.02, H 3.24, N 18.45.
recorded on a “Mercury 400” Varian (400 MHz) spectrome-
ter. Synthesis of [Cr(L)(H2 O)2 ](NO3 )3 · 0.5H2 O (4)
Synthesis of bis-C-(2,2 -bipyridine-6,6 -diyl)-N-methylnitr- The same procedure as described for 2 and 3 was fol-
one (L) lowed except that Cr(NO3 )3 · 6H2 O was employed as the
metal salt. Compound 4 was obtained as a red solid in 70 %
N-Methylhydroxylamine hydrochloride (2.35 g, 28.1 yield. – C28 H38 Cr2 N14 O27 (1106.7): calcd. C 30.39, H 3.46,
mmol) and 2,2 -dipyridyl-6,6 -dicarbaldehyde (2.6 g, N 17.72; found C 30.19, H 3.52, N 17.63.
12.3 mmol) were added to a well stirred suspension
of sodium carbonate (7.8 g, 73.6 mmol) in 100 mL of
Crystal structure determination
dichloromethane. The mixture was refluxed for 3 h, then
filtered, and the precipitate washed twice with hot CH2 Cl2 . For determination of the structures of compounds 1 – 4,
The combined filtrates were evaporated under reduced pres- X-ray diffraction studies were performed. Intensities of re-
sure to dryness. Yield of crude product 2.18 g (73.4 %), after flections were measured on an automatic Xcalibur 3 diffrac-
recrystallization from dichloromethane 1.64 g (55.2 %). – tometer (graphite-monochromated MoKα radiation, CCD
846 E. G. Petkova et al. · 6,6 -Bis{[methyl(oxido)imino]methyl}-2,2 -bipyridine
1 2 3 4 Table 1. Crystal struc-
Formula C14 H14 Cl4 Cu2 N4 O2 C14 H14 N6 NiO8 C14 H14 CoN6 O8 C28 H38 Cr2 N14 O27 ture data for [CuL][Cu
Mr 539.19 453.02 453.24 1106.72 Cl4 ] (1), [ML(NO3 )2 ]
Crystal system monoclinic monoclinic monoclinic triclinic (M = Ni (2), M =
Space group P21 /n C2/c C2/c P1̄ Co (3)), [Cr(L)(H2 O)2 ]
a, Å 7.199(2) 4.279(3), 14.570(2) 8.125(2) (NO3 )3 · H2 O (4).
b, Å 8.114(2) 13.426(3), 13.503(2) 9.587(3)
c, Å 14.2591(3) 8.839(3), 8.7663(3) 8.7663(3)
α , deg 90 90 90 99.46(3)
β , deg 91.34(3) 103.57(3) 104.14(3) 102.52(3)
γ , deg 90 90 90 98.04(2)
V , Å3 1858.5(3) 1647.2(8) 1672.4(4) 1126.7(6)
Z 4 4 4 1
Dcalc , g cm−3 1.927 1.827 1.800 1.631
µ (MoKα ), mm−1 2.881 1.243 1.090 0.591
F(000), e 1072 928 924 568
2θmax , deg. 60 60 60 50
Refls. measured 10972 7798 5709 10825
Refls. unique 3669 2282 1942 2308
Rint 0.047 0.017 0.044 0.059
Param. refined 235 133 133 291
R1 [F ≥ 4σ (F)] 0.039 0.021 0.038 0.059
wR2 0.081 0.055 0.088 0.111
GoF (F 2 ) 0.855 1.084 1.002 0.995
∆ ρfin (max/min), e Å−3 0.49/−0.46 0.45/−0.39 0.49/−0.63 0.39/−0.40
detector ω scans). The essential experimental conditions and matrix least-squares refinement was carried out against F 2 in
crystal data are given in Table 1. All structures were solved anisotropic approximation.
by Direct Methods using the S HELX97 package [30, 31]. Po- CCDC 660705 (1), 660707 (2), 660706 (3), and 660708
sitions of the hydrogen atoms were located from electron (4) contain the supplementary crystallographic data for
density difference maps and refined by a “riding” model with this paper. These data can be obtained free of charge
Uiso = nUeq of the carrier non-hydrogen atom (n = 1.5 for from The Cambridge Crystallographic Data Centre via http:
methyl groups and n = 1.2 for other hydrogen atoms). Full- //www.ccdc.cam.ac.uk/data request/cif.
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