X-ray diffraction studies of three 1-phenylethynylgermatranes with two phenyl groups in atrane skeleton

Article abstract of DOI:10.1016/j.molstruc.2004.12.025

Single crystal structures of treo-N(CH₂CH₂O) ₂(CHPhCHPhO)GeCCPh (1), erythro-N(CH₂CH₂O) ₂(CHPhCHPhO)GeCCPh (2) and N(CH₂CH₂O) ₂(CH₂CPh₂O)GeCCPh (3) were determined by X-ray diffraction studies. These compounds show transannular N→Ge interactions; the strength of this interaction depends on the Ph groups position in atrane skeleton (1, d(N→Ge)=2.210(4) ?; 2, d(N→Ge)=2.166(4) ?; 3, d(N→Ge)=2.138(3) ?). The structures of these compounds are discussed along with performed DFT calculations data. General trends for molecular structures of the group 14 elements (Si, Ge) metallatranes containing carbon substituents in atrane framework are reviewed.

Full text of DOI:10.1016/j.molstruc.2004.12.025

Journal of Molecular Structure 740 (2005) 1–8
www.elsevier.com/locate/molstruc
X-ray diffraction studies of three 1-phenylethynylgermatranes
with two phenyl groups in atrane skeleton
a,
a
a
a
*
Sergey S. Karlov , Anastasia A. Selina , Eleonora S. Chernyshova , Maxim V. Zabalov ,
Andrei V. Churakovb, Judith A.K. Howardc, Victor A. Tafeenkoa, Galina S. Zaitsevaa
aChemistry Department, Moscow State University, B-234 Leninskie Gory, 119899 Moscow, Russian Federation
bN.S. Kurnakov Institute of General and Inorganic Chemistry RAS, Leninskii pr. 31, 119991 Moscow, Russian Federation
cDepartment of Chemistry, University of Durham, South Road, Durham DH1 3LE, UK
Received 28 October 2004; revised 14 December 2004; accepted 16 December 2004
Abstract
Single crystal structures of treo-N(CH2CH2O)2(CHPhCHPhO)GeCbCPh (1), erythro-N(CH2CH2O)2(CHPhCHPhO)GeCbCPh (2) and
N(CH2CH2O)2(CH2CPh2O)GeCbCPh (3) were determined by X-ray diffraction studies. These compounds show transannular N/Ge
˚
interactions; the strength of this interaction depends on the Ph groups position in atrane skeleton (1, d(N/Ge)Z2.210(4) A; 2, d(N/Ge)Z
˚
˚
2.166(4) A; 3, d(N/Ge)Z2.138(3) A). The structures of these compounds are discussed along with performed DFT calculations data.
General trends for molecular structures of the group 14 elements (Si, Ge) metallatranes containing carbon substituents in atrane framework
are reviewed.
q 2004 Elsevier B.V. All rights reserved.
Keywords: Metallatranes; Germatranes; Hypervalent interactions; X-ray diffraction studies; DFT calculations
1. Introduction
compounds [6–8].
The chemistry of metal derivatives of aminoalcohols
such as triethanolamine—metallatranes (A)—has attracted
considerable attention [1]. The particular interest has been
shown in silatranes and germatranes due to a broad
spectrum of their biological activity, which fosters the
importance of these species for applications in medical
science and pharmacology [4,5]. On the other side, these
compounds are important from the theoretical point of view,
the nature of intramolecular N/M interaction being the
subject of interest [1–3]. Up to date several relationships
between the nature of substituent at metal atom [both axial
(Z) and three equatorial (YaO, N–R, S, CH2)] and the
strength of N/M bond have been found for metallatranes
(A). In general, stronger electron withdrawing substituent
resulted in contraction of N/M distance in these
It should be noted that the structural chemistry of
metallatranes with various substituents attached to carbon
atoms of atrane cage has been studied to a very limited
extent; accordingly, the influence of these substituents with
different electronic and steric properties on the transannular
bond strength is still unclear. Among atrane cage
substituted metallatranes 3,7,10-trimethyl-substituted com-
pounds [2–4,9] and so-called ‘tribenzometallatranes’
[derivatives of tris(2-hydroxyphenyl)amine (or 2,20,200-
nitrilotriphenol)] [10–13] are the most known to date.
There are only few reports concerning metallatranes
* Corresponding author. Tel.: C70 9593 93887; fax: C70 9593 28846.
E-mail address: sergej@org.chem.msu.su (S.S. Karlov).
0022-2860/$ - see front matter q 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.molstruc.2004.12.025

2
S.S. Karlov et al. / Journal of Molecular Structure 740 (2005) 1–8
bearing other groups attached to carbon atoms of atrane
fragment. The work of Herrmann and co-workers dealing
with silatranes, which contain terpene moieties in one arm
of triethanolamine ligand should be particularly mentioned
[14]. Very recently we have reported on molecular
structure of four germatranes contained phenyl group in
position 3 or 4 of atrane cage [15]. Although, one phenyl
group does not influence significantly N/Ge distance in
three studied compounds, however, in the case of
1-trimethylsiloxy-3-phenylgermatrane the elongation of
N/Ge distance in comparison with that in unsubstituted
analogue was found. Here and after the terms ‘substituted’
and ‘unsubstituted’ mean metallatranes with or without any
substituents at carbon atoms of atrane cage (positions 3, 4,
6, 7, 10, 11), respectively. At the same time, one could
expect that the presence of two phenyl groups at 3- or
4-position of atrane skeleton may considerably influence
the nature of N/Ge bond and affect the structure and
properties of these molecules. To the best of our knowl-
edge, no diphenylsubstituted main group atranes had been
reported in literature when we began this study. However,
it is worth to note, that Kim and Do very recently reported
the preparation of (R,R,R)–Cp*Ti(OCHPhCH2)3N, they
also found the distinction in catalytic behavior (styrene
polymerization) of this compound in comparison with that
for monomethyl-, dimethyl-, and trimethylsubstituted
cyclopentadienyltitanatranes [16]. Nugent et al. also
prepared the number of transition metals atranes with
(R,R,R)–N(CH2CHPhOH)3 as a ligand, but no X-ray
structures were reported [17–19].
with those for four recently studied germatranes 4–6: 4,
N(CH2CH2O)3GeCbCPh [22]; 4$CHCl3, N(CH2CH2O)3
GeCbCPh$CHCl3 [28]; 5, N(CH2CHMeO)3GeCbCPh [9];
6 N(CH2CH2O)2(CH2CHPhO)GeCbCPh [15] was particu-
larly important.
2. Experimental
2.1. Materials and procedures
All manipulations were performed under an argon
atmosphere using standard Schlenk techniques. Solvents
were dried by standard methods and distilled prior to use.
Starting materials PhCbCGe(OEt)3 [29] and trialkanola-
mines [30] were prepared according to the literature. 1H and
13C NMR spectra were recorded on a Varian VXR 400
spectrometer (in CDCl3); chemical shifts (in the 1H and 13
C
NMR spectra) are given in ppm relative to internal Me4Si.
The IR spectra were recorded on Zeiss UR-20. Elemental
analyses were carried out by the Microanalytical Laboratory
of the Chemistry Department of the Moscow State
University.
2.1.1. Preparation of treo-
N(CH2CH2O)2(CHPhCHPhO)GeCbCPh (1), erythro-
N(CH2CH2O)2(CHPhCHPhO)GeCbCPh (2) and
N(CH2CH2O)2(CH2CPh2O)GeCbCPh (3)
The germatranes were synthesized by stirring of
equivalent amounts of PhCbCGe(OEt)3 and the appropriate
trialkanolamine using benzene as the solvent. After 24 h the
reaction mixture was filtered to give the product as a white
solid, which was then washed with n-hexane and dried in
vacuo. Crystals suitable for structural analysis were
obtained by slow evaporation of the n-hexane/chloroform
solution.
Here we describe the molecular structures of three
diphenylsubstituted 1-phenylacetylenyl germatranes (1, 2,
3) as well as their synthesis and spectral characterization.
These complexes were synthesized as a part of our research
program dedicated to the investigation of main group
elements derivatives of alkanolamines (metallatranes and
metallocanes) and triethylenetetramines (azametallatranes)
[9,15,20–27].
Our motivation was: (1) to study the possible influence of
two phenyl groups in different positions of atrane frame-
work on structure of germatranes in solid state; (2) to
compare our data with those previously found for other
substituted group 14 elements atranes (X-ray data) and with
DFT calculation results. The comparison of presented data
treo-N(CH2CH2O)2(CHPhCHPhO)GeCbCPh (1). Anal.
Calcd for C26H25GeNO3: C 66.16, H 5.34, N 2.97. Found C
66.11, H 5.22, N 3.02. 1H NMR d 7.52–7.50, 7.32–7.10 (2m,
15H, Ph-rings protons), 5.21 (d, 1H, OCHPh), 3.73 (d, 1H,
NCHPh), 4.13–4.02, 3.84–3.78, 3.36–3.29, 3.00–2.96,

S.S. Karlov et al. / Journal of Molecular Structure 740 (2005) 1–8
3
2.79–2.71, 2.34–2.30 (6m, 8H (AA0XX0)2 system, 2NCH2-
CH2O). 13C NMR d 140.30, 132.52, 131.51, 130.15, 129.33,
128.84, 128.19, 128.13, 127.81, 127.77, 127.16, 123.03 (Ph-
rings carbons), 99.41 (PhCb), 90.87 (bC–Ge), 71.61
(OCHPh), 68.61 (NCHPh), 56.64, 56.55 (2OCH2), 48.22,
47.79 (2NCH2). IR (Nujol): n(CbC) 2179 cmK1. Yield
81%. M.p.O250 8C.
Ph-rings protons), 3.82–3.77, 3.70–3.65 (2m, 4H, OCH2),
3.61 (s, 2H, NCH2CPh2); 2.76–2.65 (m, 4H, 2NCH2). 13C
NMR d 146.58, 132.55, 128.45, 128.19, 127.86, 127.08,
125.67, 123.23 (Ph-rings carbons), 99.15 (PhCb),
91.41 (bCGe), 75.56 (OCPh2), 61.05 (NCH2CPh2), 56.93
(2OCH2), 53.18 (2NCH2). IR (Nujol): n(CbC) 2173 cmK1
Yield 76%. M.p. 244–245 8C.
.
According to 1H and 13C NMR spectra, each of
compounds 1 and 2 represents one diastereomeric pair.
erythro-N(CH2CH2O)2(CHPhCHPhO)GeCbCPh (2).
Anal. Calcd for C26H25GeNO3: C 66.16, H 5.34, N 2.97.
1
Found C 65.86, H 5.31, N 2.99. H NMR d 7.57–7.53,
7.34–7.13, 7.01–6.98 (3m, 15H, Ph-rings protons), 5.41 (d,
1H, OCHPh), 4.33 (d, 1H, NCHPh), 4.08–3.96, 3.80–3.75,
3.26–3.19, 2.95–2.90, 2.81–2.73, 2.54–2.49 (6m, 8H
(AA0XX0)2 system, 2NCH2CH2O). 13C NMR d 139.43,
132.47, 131.94, 131.23, 129.21, 128.33, 128.21, 127.78
(broad signal, two carbon atoms), 127.48, 127.31, 122.94
(Ph-rings carbons), 99.39 (PhCb), 91.00 (bCGe), 74.33
(OCHPh), 66.77 (NCHPh), 57.47, 56.73 (2OCH2), 50.62
2.2. X-ray crystallographic study
Crystal data, data collection, and refinement parameters
for compounds 1, 2 and 3 are listed in Table 1. The
structures were solved by direct methods [31] and refined by
full matrix least-squares on F2 [32]. All non-hydrogen
atoms were refined with anisotropic thermal parameters. In
the structure of 1, all hydrogen atoms were placed in
calculated positions and refined using a riding model. As for
compounds 2 and 3, all hydrogen atoms were found from
diff. Fourier synthesis and refined isotropically. Crystal-
lographic data (excluding structure factors) for the struc-
tures reported in this paper have been deposited with
(broad signal, 2NCH2). IR (Nujol): n(CbC) 2175 cmK1
Yield 80%. M.p. 238–239 8C.
N(CH2CH2O)2(CH2CPh2O)GeCbCPh (3). Anal. Calcd
.
for C26H25GeNO3: C 66.16, H 5.34, N 2.97. Found 66.10, H
1
5.20, N 3.00. H NMR d 7.61–7.56, 7.34–7.17 (2m, 15H,
Table 1
Crystal and structure refinement data for 1, 2 and 3
1
2
3
Empirical formula
Formula weight
Color, habit
C26H25Ge1N1O3
472.06
C26H25Ge1N1O3
472.06
C26H25Ge1N1O3
472.06
Colorless block
0.20!0.20!0.04
Triclinic
Colorless block
0.30!0.25!0.10
Monoclinic
P21/c
Colorless plate
0.30!0.10!0.02
Monoclinic
P21/c
Crystal size (mm)
Crystal system
Space group
P-1
Cell dimensions
˚
a (A)
˚
b (A)
10.385(2)
10.748(2)
11.034(2)
81.504(4)
82.899(4)
64.701(4)
1098.7(4)
2
13.439(2)
8.060(2)
21.390(2)
90
11.108(1)
22.560(2)
18.259(2)
90
˚
c (A)
a (8)
b (8)
g (8)
106.98(2)
90
106.835(2)
90
3
˚
V (A )
2215.9(7)
4
4379.5(7)
8
Z
Dcalc (g cmK3
)
1.427
1.415
1.432
m(Mo Ka) (mmK1
F(000)
)
1.422
1.410
1.427
488
976
1952
Diffractometer
˚
Radiation, l (A)
Bruker SMART
Nonius CAD4
Bruker SMART
Graphite monochromatized Mo Ka(0.71073)
293
Temperature (K)
q range (8)
Index ranges
120
120
1.87–27.00
K10%h%13
K13%k%13
K14%h%14
5429
1.58–24.98
K15%h%15
0%k%9
0%l%25
3889
1.47–27.00
K14%l%8
K28%k%14
K23%l%23
28,181
Refl. collected
Unique refl., Rint
Data/restr./param.
Goof on F2
4565 (0.0526)
4565/0/281
0.976
3889(0.0634)
3889/0/380
0.947
9561(0.0602)
9561/0/760
0.819
R1 [IO2s(I)]
0.0716
0.0598
0.0404
wR2 (all data)
Extinction coeff.
˚
Largest diff. peak/hole (e A
0.1268
0.1082
0.1238
0.0039(8)
0.942/K0.815
–
0.00061(13)
1.641/K0.550
K3
)
0.351/K0.401

4
S.S. Karlov et al. / Journal of Molecular Structure 740 (2005) 1–8
the Cambridge Crystallographic Data Centre as supplemen-
tary publication no. CCDC-240915 (1), CCDC-240916 (2)
and CCDC-240917 (3). Copies of the data can be obtained
free of charge on application to CCDC, 12 Union Road,
Cambridge CB2 1EZ, UK [Fax: C44 1223 336 033; e-mail:
deposit@ccdc.cam.ac.uk].
polyhedron of the germanium atoms in studied germatranes
represents as usually a distorted trigonal bipyramid with N
and C atoms in the apical positions and the three oxygen
atoms in equatorial sites. The germanium atom is displaced
from the equatorial plane defined by three oxygen atoms by
˚
0.21 (for 1), 0.20 (for 2) and 0.18, 0.19 A (for 3) towards
phenylacetylenyl substituent. The N–Ge–C fragment is
almost linear (177.1(2)–179.6(2)8) in all these compounds.
All five-membered rings of the germatrane skeleton in 1–3
adopt an ‘envelope’-like conformation, the carbon atoms
lying in the a-positions to the N atom occupy ‘flap’ sites.
The latter contrasts with geometry previously found for the
structures of 3,7,10-trimethylsubstituted atranes [9,40–45].
As stated above, the strength of the N/M intramole-
cular interaction in metallatranes is the most intriguing
aspect of their structure. The N/M bond length is well-
known to become shorter with increasing of electron
withdrawing potential of the apical substituent [1,7]. The
effect of atrane cage substituent on N/M bond strength is
still unexplored. However, as it was found for silatranes
contained the same apical group Z (X-ray data), a formal
replacement of one to three hydrogen atoms in positions 3,
7, and 10 of atrane skeleton by one to three electron donor
alkyl groups (Me or Et) leads to minor alterations in N/Si
transannular bond length. For example, the value of N/Si
transannular bond in N(CH2CHMeO)3Si-p-tolyl
2.3. Calculations
All calculations were performed using the program
‘PRIRODA’ developed by Laikov, which implements an
economical computational procedure [33]. In this work, the
non-empirical generalized gradient approximation (GGA)
for the exchange-correlation functional of Perdew et al.
(PBE) was employed [34,35]. The all electron large orbital
basis sets of contracted Gaussian-type functions of the size
(8s3p2d):[4s3p2d] for H (14s8p3d2f):[8s4p3d2f] for C
(14s8p3d2f):[8s4p3d2f] for N (14s8p3d2f):[8s4p3d2f] for
O, and (25s19p14d3f):[18s14p9d3f] for Ge were used for
DFT-PBE. Full geometry optimization was performed by
DFT-PBE for a number of structures followed by
vibrational frequency calculation using analytical first and
second derivatives. Each structure has been characterized by
the vibrational analysis. The present theoretical method has
been used and has given very useful results in the
germanium chemistry [36–39].
˚
(2.236(3) A) is greater than that in N(CH2CH2O)3Si-p-
˚
tolyl (2.169(2) A) [40]. Of special note is the existence of
three different modifications of N(CH2CH2O)3Si–Ph, where
values of N/Si bond length are 2.193(5), 2.156(4) and
3. Results and discussions
˚
2.132(4) A [46–48], while the analogous distance in
˚
N(CH2CHMeO)3Si–Ph is 2.175(6) A [41]. The same values
The molecular structures of 1, 2, and 3 are shown in
Figs. 1–3. Important bond lengths and angles are summar-
ized in Tables 2 and 3, respectively. The coordination
˚
of N/Si bond length (2.120 A) were found for pair
Fig. 1. Molecular structure of 1. Displacement ellipsoids are shown at 50% probability level.

S.S. Karlov et al. / Journal of Molecular Structure 740 (2005) 1–8
5
Fig. 2. Molecular structure of 2. Displacement ellipsoids are shown at 50% probability level.
Fig. 3. Molecular structure of 3 (one independent molecule). Displacement ellipsoids are shown at 50% probability level.

6
S.S. Karlov et al. / Journal of Molecular Structure 740 (2005) 1–8
˚
unsubstituted analogue—2.18(3) A [55]). Analogously to
Table 2
˚
Selected bond lengths (A) for 1–3
above, N/Si bond length in silatran-3-ones ([N(CH2
˚
CH2O)2(CH2COO)Si–Z, {ZZCH2Cl, 2.085 A [56], unsub-
1
2
3
˚
˚
stituted derivative, 2.120 A [40], ZZ(CH2)3Cl, 2.149 A
N–Ge
2.210(4)
1.927(5)
1.791(4)
1.793(4)
1.791(4)
1.429(6)
1.429(6)
1.427(6)
1.555(7)
1.525(7)
1.519(7)
1.477(7)
1.496(7)
1.468(7)
2.166(4)
1.898(6)
1.785(3)
1.780(3)
1.774(4)
1.426(6)
1.420(7)
1.416(8)
1.555(8)
1.517(9)
1.52(1)
2.138(3)
1.918(4)
1.783(3)
1.796(3)
1.794(3)
1.430(5)
1.417(5)
1.413(5)
1.545(6)
1.527(6)
1.519(6)
1.467(5)
1.487(5)
1.479(5)
2.140(3)
1.924(4)
1.786(3)
1.794(3)
1.788(3)
1.429(5)
1.434(5)
1.423(5)
1.543(6)
1.524(6)
1.506(6)
1.475(5)
1.492(5)
1.476(5)
˚
[57], unsubstituted derivative, 2.18(3) A [55], ZZCH3,
2.134 A [58], unsubstituted derivative, 2.1604(3) A [59]}
and in silatran-3,7-dione (N(CH2CH2O)(CH2COO)2Si–Z,
Cax–Ge
Osub–Ge
O–Ge
˚
˚
˚
{ZZCH3, 2.146 A [60], unsubstituted derivative,
(O–C)sub
O–C
˚
2.1604(3) A [59]} is similar to that for unsubstituted
compounds.
(C–C)sub
C–C
However, there are at least two factors which lead to
considerable elongation of N/Si bond in substituted
silatranes: (a) the presence of one bulky substituent in
position 4 or three Me groups in positions 4, 6, 11 of
(N–C)sub
N–C
1.486(7)
1.476(7)
1.468(7)
˚
silatrane skeleton {[N(CHMeCH2O)3Si–CH3—2.325 A
˚
[61], unsubstituted analogue—2.1604(3) A [59]; N(CH2
˚
CH2O)2[CH(i-Pr)CH2O]Si–C6H5—2.265 A [62], 1-phenyl-
˚
3,4-terpene-substituted silatrane—2.241(1) A [14], unsub-
N(CH2CHMeO)3Si–CH2Cl and N(CH2CH2O)3Si–CH2Cl
[40] while some alterations have been noticed for N(CH2-
stituted analogue—three modifications, see above
[46–48])} or (b) the presence in atrane cage of one to
three benzene rings (benzosilatranes, N(CH2CHMeO)2(o-
˚
CH2O)(CH2CHMeO)2Si–CH2Cl (2.128 A) [49] and N(CH2-
˚
CH2O)2(CHEtCH2O)Si–CH2Cl (2.102 A) [50]. Of interest,
the presence of electron withdrawing group (COOH) in
position 4 of atrane skeleton does not substantially change
transannular N/Si distance in N(CH2CH2O)2[CH(COOH)
˚
C6H4–O)Si–CH2Cl—2.177 A [63], N(o–C6H4–O)3Si–
˚
CH2Cl—2.256 A [64], unsubstituted analogue—2.120 A
˚
˚
[40]; N(CH2CHMeO)2(o-C6H4–O)Si–C6H5—2.193 A
˚
[65]; N(o-C6H4–O)3Si–C6H5—2.344(5) A [11], unsubsti-
˚
CHMeO]Si–CH2Cl (2.136(3) A) [51] as well as in N(CH2
˚
CH2O)2[CH(COOH)CHMeO]Si–CHaCH2 (2.169(3) A
˚
[52], unsubstituted analogue—2.150 A [53]) and in N(CH2
tuted analogue—three modifications, see above [46–48]).
To our opinion, one of the significant reasons for these
changes is steric crowding in these systems, such as special
steric requirements of 1,2-phenylene group.
CH2O)2[CH(COOH)CHMeO]Si–(CH2)3Cl (2.198(3),
˚
2.244(3) A [51], N(CH2CH2O)2[CH(COOH)CH2O]Si–
˚
(CH2)3Cl (2.178, 2.206 A, two independent molecules [54],
According to the previously reported data on X-ray study
of substituted and unsubstituted germatranes contained the
same apical group Z (Table 4), a formal replacement of
three hydrogen atoms in positions 3, 7, and 10 of atrane
skeleton by three electron donor methyl groups leads to
minor lengthening of N/Ge bond in all cases except one.
The substitution of one hydrogen atom in position 3- or 4-
by one Ph or Et group does not drastically change N/Ge
transannular bond length in germatranes. However, it should
be noted the sufficient contraction of this bond in derivative
of nitrilotriacetic acid in comparison with that in unsub-
stituted analogue (Table 4). Thus, according to data known
to date the found alterations of N/M bond length in
substituted silatranes and germatranes have rather steric
than electronic nature or might be caused by crystal field
effects as well as dipole–dipole interactions in the solid state
[6,74,75].
Table 3
Selected angles (8) for 1, 2 and 3
1
2
3
N–Ge–Cax
ax–Ge–Osub
179.6(2)
97.3(2)
177.4(2)
96.8(2)
177.1(2)
97.6(2)
176.0(2)
97.7(2)
C
Cax–Ge–O
97.2(2)
98.0(2)
96.6(2)
97.5(2)
95.4(2)
94.6(2)
93.8(2)
92.3(2)
N–Ge–Osub
N–Ge–O
82.4(2)
83.5(2)
83.8(1)
83.9(1)
84.5(2)
84.1(2)
85.1(1)
85.2(1)
83.2(2)
83.0(2)
83.4(1)
83.8(1)
O–Ge–Osub
120.3(2)
118.8(2)
117.0(2)
116.8(4)
114.3(4)
114.0(4)
103.5(3)
104.2(3)
101.7(3)
120.9(3)
118.9(3)
118.5(3)
107.6(4)
109.1(4)
108.5(4)
106.8(4)
110.4(4)
109.3(4)
119.6(2)
118.4(2)
118.3(2)
116.8(5)
112.8(5)
112.2(5)
104.2(3)
105.5(3)
103.9(4)
122.0(3)
119.2(4)
119.1(4)
109.6(5)
108.4(6)
107.1(5)
107.6(5)
110.4(6)
110.1(5)
123.4(1)
118.1(1)
115.3(1)
114.7(3)
113.2(3)
112.9(3)
105.9(2)
105.6(2)
103.3(2)
121.0(2)
119.1(3)
117.2(3)
109.9(3)
107.7(4)
106.8(3)
109.9(3)
110.1(4)
109.9(3)
124.6(1)
119.9(1)
112.6(1)
114.2(3)
113.3(3)
112.8(3)
105.9(2)
105.9(3)
103.5(2)
119.8(2)
118.1(3)
116.9(2)
109.5(3)
108.2(3)
107.1(3)
107.6(3)
109.7(3)
109.7(4)
O–Ge–O
C–N–Csub
C–N–C
Csub–N–Ge
C–N–Ge
Values of N/Ge bond length in 1–3 as well as these
values for previously studied compounds 4–6 lie within the
˚
range of 2.138(3)–2.210(4) A. The shortest contact has been
(C–O)sub–Ge
C–O–Ge
found in compound 3 with two electron withdrawing phenyl
groups in position 3 of atrane fragment. However, the
analysis of values of N/Ge bond length for other
structures (Table 2, 4—2.178(6), 4 CHCl3—2.160(2),
˚
5—2.199(4), 6—2.166(6) A) does not prove the conclusion
about the contraction of N/Ge bond in germatranes with
electron withdrawing group at carbon atoms of atrane cage.
(N–C–C)sub
N–C–C
(C–C–O)sub
C–C–O

S.S. Karlov et al. / Journal of Molecular Structure 740 (2005) 1–8
7
Table 4
Values of N–Ge bond length in substituted germatranes and unsubstituted analogues
˚
N–Ge (A)
˚
N–Ge (A) in unsubstituted analogue,
Substituted germatrane
Z–Ge(OCH2CH2)3N
C13H8(SnMe3)–Ge(OCHMeCH2)3N
C13H8(H)–Ge(OCHMeCH2)3N
2.247(9) [43]
2.194(5), 2.191(5) [43]b
2.206(6) [66]
2.166(2) [27]
2.23(1) [21]
C6H5–C(Br)aC(Br)–Ge(OCHMeCH2)3N
C6H5–C(Cl)aC(I)–Ge(OCHMeCH2)3N
C6H5–CbC–Ge(OCHMeCH2)3N (5)
C6H5–CbC–Ge(OCH2CH2)2[OCH(C6H5)CH2]N (6)
Me3SiO–Ge(OCH2CH2)2[OCH(C6H5)CH2]N
F–Ge(OCH2CH2)2[OCH(C6H5)CH2]N
HO–Ge(OCH2CH2)2[OCH2CH(C6H5)]N
HO–Ge(OCH2CH2)2[OCH2CHEt]N
C6H5–Ge(OCH2CH2)2[OC(O)CH2]N
HO–Ge[OC(O)CH2]3N$H2O
2.196(7) [8]
2.216(8) [44]
2.213(5) [44]
4, 2.178(6) [21]a
4, 2.178(6) [21]a
2.128(5) [67]
2.104(2) [68]
2.146(9) [69]
2.146(9) [69]
2.212(5) [72]
2.146(9) [69]
2.199(4) [8]
2.166(6) [14]
2.170(4) [14]
2.108(2) [14]
2.187(2) [14]
2.166(6), 2.185(6) [70]b
2.203(3) [71]
2.084(3) [73]
a
˚
The value of N–Ge bond length in adduct 4$CHCl3 is 2.160(2) A [27].
Two independent molecules.
b
Analogously, the absent of correlation between N/Ge
bond length contraction and elongation of C–Ge bond
length in the same compounds (Table 2, 4—1.920(8),
effects and dipole–dipole interactions in the solid state being
the main reason of N/Ge bond length alterations.
In conclusion, to all appearance steric effects caused by
replacement of hydrogen atoms in atrane cage by phenyl
groups are the basic reason for N/Ge transannular bond
alteration.
˚
4$CHCl3—1.924(2), 5—1.919(6), 6—1.914(7) A) testifies
also against the conclusion referred above. The other
important geometrical parameters do not change signifi-
cantly in the range of compounds 1–6.
We also have carried out DFT calculations on germa-
tranes 1–6 up to the PBE level of theory. The most
important calculated geometrical parameters of these
compounds are listed in Table 5. There is a good agreement
between the geometry parameters of studied substances for
the solid phase (X-ray data) and for the free molecules
(calculated data). However, calculated values of the N/Ge
distances for these compounds are somewhat longer
Acknowledgements
A.V.C. is grateful for the grant of The President of
Russian Federation for young scientists (MK-3697.2004.3)
and to the Royal Society of Chemistry for the RSC Journal
Grants for International Authors.
˚
(w0.2 A) than those found in the solid state. An explanation
for these discrepancies is the weakness of the transannular
bond in compounds 1–6, which are exposed to crystal field
effects and dipole–dipole interactions in the solid state [6,
References
˚
[1] J.G. Verkade, Coord. Chem. Rev. 137 (1994) 233.
[2] S.S. Karlov, G.S. Zaitseva, Chem. Heterocycl. Compd. 37 (2001)
1325.
74,75]. Of interest, the noticeable difference (w0.04 A) has
been also found between calculated values of Ge–O bond
length and those determined in the solid state. The latter
values are smaller. It should be also noted the invariability
of calculated values of C–Ge bond length for compounds 1–
6. The contraction of N/Ge bond length for single
molecule (calculated data) is observed in the following
range: 4O5O2O6O1O3. It does not correspond to the
same range found for solid state: 1O5O4O2Z6O4
CHCl3O3. The latter observation testifies crystal field
[3] S.N. Tandura, M.G. Voronkov, N.V. Alekseev, Top. Curr. Chem. 131
(1986) 99.
[4] V. Pestunovich, S. Kirpichenko, M. Voronkov, in: Z. Rappoport,
Y. Apeloig (Eds.), The Chemistry of Organic Silicon Compounds,
Vol. 2, Part 1, Wiley, New York, 1998, p. 1447.
[5] E. Lukevics, S. Germane, L. Ignatovich, Appl. Organomet. Chem. 6
(1992) 543.
[6] S. Belyakov, L. Ignatovich, E. Lukevics, J. Organomet. Chem. 577
(1999) 205.
[7] M.W. Schmidt, T.L. Windus, M.S. Gordon, J. Am. Chem. Soc. 117
(1995) 7480.
Table 5
˚
The key bond distances (in A) (calculated data) in 1–6
[8] M.S. Gordon, M.T. Carroll, J.H. Jensen, L. Davis, L.W. Burggraf,
R.M. Guidry, Organometallics 10 (1991) 2657.
[9] A.A. Selina, S.S. Karlov, E.V. Gauchenova, A.V. Churakov,
L.G. Kuz’mina, J.A.K. Howard, J. Lorberth, G.S. Zaitseva, Heteroat.
Chem. 15 (2004) 43.
1
2
3
4
5
6
N–Ge
2.317
1.913
1.832
1.828
1.832
2.302
1.914
1.835
1.832
1.830
2.292
1.916
1.838
1.829
1.828
2.366
1.912
1.829
1.830
1.829
2.338
1.915
1.830
1.830
1.830
2.308
1.914
1.837
1.830
1.830
Cax–Ge
[10] C.L. Frye, G.A. Vincent, G.L. Hauschildt, J. Am. Chem. Soc. 88
(1966) 2727.
O
sub–Ge
O–Ge
[11] F.P. Boer, J.W. Turley, J.J. Flynn, J. Am. Chem. Soc. 90 (1968) 5102.
´
[12] C. Soulie, P. Bassoul, J. Simon, New J. Chem. 17 (1993) 787.

8
S.S. Karlov et al. / Journal of Molecular Structure 740 (2005) 1–8
[13] T. Wang, Y. Luo, G. Wu, Huaxue Shiji 13 (1991) 347 (Chem. Abstr.
116:174238).
[43] Yu.E.
Ovchinnikov,
Yu.T.
Struchkov, V.P.
Baryshok,
M.G. Voronkov, Zh. Struct. Khim. 35 (1994) 199.
[14] G. Wagner, R. Herrmann, B. Pedersen, W. Scherer, Z. Naturforsch.
56b (2001) 25.
[44] A.V. Churakov, L.G. Kuz’mina, S.S. Karlov, P.L. Shutov,
G.S. Zaitseva, Koord. Khim. 25 (1999) 870.
[15] E.V. Gauchenova, S.S. Karlov, A.A. Selina, E.S. Chernyshova,
A.V. Churakov, J.A.K. Howard, N.A. Troitsky, S.N. Tandura,
J. Lorberth, G.S. Zaitseva, J. Organomet. Chem. 676 (2003) 8.
[16] Y. Kim, Y. Do, J. Organomet. Chem. 655 (2002) 186.
[17] W.A. Nugent, R.L. Harlow, J. Am. Chem. Soc. 116 (1994) 6142.
[18] M. Bonchio, G. Licini, G. Modena, S. Moro, O. Bortolini, P. Traldi,
W.A. Nugent, Chem. Commun. (1997) 869.
[45] A.A. Selina, A.E. Zhachkina, S.S. Karlov, A.V. Churakov,
G.S. Zaitseva, Heteroat. Chem. 15 (2004) 169.
[46] J.W. Turley, F.P. Boer, J. Am. Chem. Soc. 90 (1968) 4026.
´ ´
[47] L. Parkanyi, K. Simon, J. Nagy, Acta Crystallogr. B30 (1974) 2328.
´
´
[48] L. Parkanyi, J. Nagy, K. Simon, J. Organomet. Chem. 101 (1975) 11.
[49] M.G. Voronkov, M.P. Demidov, V.E. Shklover, V.P. Borishok,
V.M. D’yakov, Yu.L. Frolov, Zh. Strukt. Khim. 21 (2) (1980) 100.
[50] Y. Yang, C. Yin, G. Chen, C He, Gaodeng Xuexiao Huaxue Xuebao
11 (1990) 102.
[19] F. Di Furia, G. Licini, G. Modena, R. Motterle, W.A. Nugent, J. Org.
Chem. 61 (1996) 5175.
[20] G.S. Zaitseva, L.I. Livantsova, M. Nasim, S.S. Karlov,
A.V. Churakov, J.A.K. Howard, E.V. Avtomonov, J. Lorberth,
Chem. Ber. 130 (1997) 739.
[51] Z.-R. Lu, R.-X. Zhuo, L.-R. Shen, X.-D. Zhang, L.-F. Shen,
J. Organomet. Chem. 489 (1995) C38.
[52] R.-X. Zhuo, Z.-R. Lu, J. Liao, L.-F. Shen, J. Organomet. Chem. 446
(1993) 107.
[21] S.S. Karlov, P.L. Shutov, N.G. Akhmedov, M.A. Seip, J. Lorberth,
G.S. Zaitseva, J. Organomet. Chem. 598 (2000) 387.
[22] S.S. Karlov, P.L. Shutov, A.V. Churakov, J. Lorberth, G.S. Zaitseva,
J. Organomet. Chem. 627 (2001) 1.
[53] S. Wang, C. Hu, K’o Hsueh T’ung Pao 26 (1981) 603.
[54] Z.-R. Lu, R.-X. Zhuo, L.-R. Shen, B.-S. Luo, Main Group Met. Chem.
17 (1994) 377.
[23] P.L. Shutov, S.S. Karlov, K. Harms, D.A. Tyurin, A.V. Churakov,
J. Lorberth, G.S. Zaitseva, Inorg. Chem. 41 (2002) 6147.
[24] P.L. Shutov, S.S. Karlov, K. Harms, A.V. Churakov, J.A.K. Howard,
J. Lorberth, G.S. Zaitseva, Eur. J. Inorg. Chem. (2002) 2784.
[25] P.L. Shutov, D.A. Sorokin, S.S. Karlov, K. Harms, Yu.F. Oprunenko,
A.V. Churakov, M.Yu. Antipin, G.S. Zaitseva, J. Lorberth, Organo-
metallics 22 (2003) 516.
[55] A.A. Kemme, Ya. Ya Bleidelis, V.M. D’yakov, M.G. Voronkov, Izv.
Akad. Nauk SSSR, Ser. Khim. (1976) 2400.
[56] J. Dai, J. Zhang, Y. Wu, G. Wu, Jiegou Huaxue 2 (1983) 207.
[57] J. Dai, J. Zhang, Y. Wu, Jiegou Huaxue 2 (1983) 107.
[58] V. Fulop, A. Kalman, P. Hencsei, G. Csonka, I. Kovacs, Acta
Crystallogr. C47 (1988) 720.
[59] K.A. Lyssenko, A.A. Korlyukov, M.Yu. Antipin, S.P. Knyazev,
V.N. Kirin, N.V. Alexeev, E.A. Chernyshev, Mendeleev Commun.
(2000) 88.
[26] P.L. Shutov, S.S. Karlov, K. Harms, O.Kh. Poleshchuk, J. Lorberth,
G.S. Zaitseva, Eur. J. Inorg. Chem. (2003) 1507.
[27] P.L. Shutov, S.S. Karlov, K. Harms, A.V. Churakov, J. Lorberth,
G.S. Zaitseva, Eur. J. Inorg. Chem. (2004) 2123.
[60] A. Kemme, J. Bleidelis, A.F. Lapsina, M. Fleisher, G. Zelchans,
E. Lukevics, Latv. PSR Zinat. Akad. Vestis Khim. Ser. (1985) 242.
[61] S.J. Stachel, J.W. Ziller, D.L. Van Vranken, Tetrahedron Lett. 40
(1999) 5811.
[28] G.S. Zaitseva, S.S. Karlov, A.V. Churakov, J.A.K. Howard,
E.V. Avtomonov, J. Lorberth, Z. Anorg. Allg. Chem. 623 (1997)
1144.
[29] I.V. Efimova, B.E. Kalganov, M.A. Kazankova, I.F. Lutsenko, Zh.
Obshch. Khim. 54 (1984) 459.
[62] M. Tasaka, M. Hirotsu, M. Kojima, S. Utsuno, Y. Yoshikawa, Inorg.
Chem. 35 (1996) 6981.
[30] S.S. Karlov, A.A. Selina, A.V. Churakov, E.S. Chernyshova, G.S.
Zaitseva, Russ. Chem. Bull. submitted.
[63] B. Chen, G. Wu, Y. Luo, Jiegou Huaxue 5 (1986) 193.
[64] B. Chen, G. Wu, Y. Luo, Jiegou Huaxue 6 (1987) 165.
[65] B. Chen, G. Wu, Y. Luo, Jiegou Huaxue 6 (1987) 58.
[66] G.S. Zaitseva, S.S. Karlov, B.A. Siggelkow, E.V. Avtomonov,
A.V. Churakov, J.A.K. Howard, J. Lorberth, Z. Naturforsch. 53b
(1998) 1247.
[31] G.M. Sheldrick, Acta Crystallogr. A46 (1990) 467.
[32] G.M. Sheldrick, SHELXL-97. Program for the Refinement of Crystal
¨
Structures, University of Gottingen, Germany, 1997.
[33] D.N. Laikov, Chem. Phys. Lett. 281 (1997) 151.
[34] M. Ernzerhof, G.E. Scuseria, J. Chem. Phys. 110 (1999) 5029.
[35] J.P. Perdew, K Burke, M. Ernzerhof, Phys. Rev. Lett. 77 (1996) 3865.
[36] A.A. Selina, S.S. Karlov, K. Harms, D.A. Tyurin, Yu.F. Oprunenko,
J. Lorberth, G.S. Zaitseva, Z. Naturforsch. 58b (2003) 613 (references
cited herein).
[67] E. Lukevics, S. Belyakov, L. Ignatovich, N. Shilina, Bull. Soc. Chim.
Fr. 132 (1995) 545.
[68] R. Eujen, E. Petrauskas, A. Roth, D.J. Brauer, J. Organomet. Chem.
613 (2000) 86.
[69] S.N. Gurkova, A.I. Gusev, N.V. Alexeev, T.K. Gar, N.Yu. Khromova,
Zh. Strukt. Khim. 26 (6) (1985) 154.
[37] S.S. Karlov, E.Kh. Yakubova, E.V. Gauchenova, A.A. Selina,
A.V. Churakov, J.A.K. Howard, D.A. Tyurin, J. Lorberth,
G.S. Zaitseva, Z. Naturforsch. 58b (2003) 1165.
[70] Yu.E.
Ovchinnikov,
Yu.T.
Struchkov, V.P.
Baryshok,
Yu.A. Ovchinnikova, M.G. Voronkov, Doklady RAN 330 (1993) 464.
[71] N.V. Alexeev, S.N. Gurkova, S.N. Tandura, V.M. Nosova,
A.I. Gusev, T.K. Gar, R.I. Segel’man, N.Yu. Khromova, Zh. Strukt.
Khim. 22 (6) (1981) 135.
[38] A.V. Churakov, L.G. Kuz’mina, S.S. Karlov, E.V. Gauchenova,
D.A. Tyurin, G.S. Zaitseva, Russ. J. Inorg. Chem. 48 (2003) 1008.
[39] P.L. Shutov, S.S. Karlov, K. Harms, D.A. Tyurin, M.V. Zabalov,
A.V. Churakov, J.A.K. Howard, J. Lorberth, G.S. Zaitseva, J. Mol.
Struct. 689 (2004) 261.
[72] E. Lukevics, L. Ignatovich, S. Belyakov, J. Organomet. Chem. 588
(1999) 222.
`
[40] L. Parkanyi, P. Hencsei, L. Bihatsi, I. Kovacs, A. Szollosy,
´
´
´
´
´
¨
[73] A.B. Il’uhin, L.M. Shkol’nikova, I.I. Sejfulina, T.P. Batalova,
N.M. Dyatlova, Koord. Khim. 17 (1991) 795.
Polyhedron 4 (1985) 243.
¨
´ ´ ´
[41] L. Parkanyi, V. Fu¨lop, P. Hencsei, I. Kovacs, J. Organomet. Chem.
[74] K.R. Leopold, M. Canagaratna, J.A. Phillips, Acc. Chem. Res. 30
(1997) 57.
418 (1991) 173.
[42] G.S. Zaitseva, S.S. Karlov, G.V. Pen’kovoy, A.V. Churakov,
J.A.K. Howard, B.A. Siggelkow, E.V. Avtomonov, J. Lorberth, Z.
Anorg. Allg. Chem. 625 (1999) 655.
[75] J.M. Anglada, C. Bo, J.M. Bofill, R. Crehuet, J.M. Poblet,
Organometallics 18 (1999) 5584.