Crystal and molecular structure of the trans-hyponitrite compound Ph 3Sn(μ-ONNO)SnPh3

Article abstract of DOI:10.1002/zaac.201000444

The trans-hyponitrite compound Ph₃Sn(μ-ONNO)SnPh₃ (1) was revisited by NMR spectroscopy and the crystal and molecular structure was elucidated by X-ray diffraction. Compound 1 crystallizes from benzene in the triclinic space group Pβar{1}$ with a = 10.9674(2), b = 18.2786(2), c = 18.4592(2) A?; α = 115.979(1), β = 102.851(1), γ = 99.032(1)°; V = 3103.60(9) A?³; Z = 4, ρ = 1.627 g·cm^-3, T = 173(2) K. Copyright

Full text of DOI:10.1002/zaac.201000444

SHORT COMMUNICATION
DOI: 10.1002/zaac.201000444
Crystal and Molecular Structure of the trans-Hyponitrite Compound
Ph3Sn(μ-ONNO)SnPh3
Tobias Mayer,[a] Wolfgang Beck,[a] and Hans-Christian Böttcher*[a]
Dedicated to Professor Peter Klüfers on the Occasion of His 60th Birthday
Keywords: Hyponitrites; Tin; Structure elucidation; Density functional calculations; NMR spectroscopy
¯
Abstract. The trans-hyponitrite compound Ph3Sn(μ-ONNO)SnPh3 (1) from benzene in the triclinic space group P1 with a = 10.9674(2), b =
was revisited by NMR spectroscopy and the crystal and molecular 18.2786(2), c = 18.4592(2) Å; α = 115.979(1), β = 102.851(1), γ =
structure was elucidated by X-ray diffraction. Compound 1 crystallizes 99.032(1)°; V = 3103.60(9) Å3; Z = 4, ρ = 1.627 g·cm–3, T = 173(2) K.
structure of an organic hyponitrite was reported, namely for
Introduction
trans-di-tert-butyl hyponitrite, Me3C(μ-ONNO)CMe3.[14]
The chemistry of the hyponitrous acid, HONNOH (cis and
Herein we describe the crystal and molecular structure of the
trans configuration respectively), is in principle well known,[1]
title compound Ph3Sn(μ-ONNO)SnPh3 (1), which was not yet
whereas the coordination behavior of its corresponding anion
described to date.
2–
N2O2
towards transition metal ions is still scarcely
explored.[2,3] During the last years complexes containing hypo-
nitrito ligands got more and more in the focus of investigations
in the field of bioinorganic chemistry because they could serve
as possible model compounds of active intermediates in enzy-
matic nitric oxide reductase (NOR) processes.[4–7] Currently,
there is an active interest in studies on functional NOR model
compounds, e.g.[8] In this light we have recently reported the
synthesis and the X-ray crystal structure of the dinuclear com-
Results and Discussion
As described earlier,[12] the compound Ph3Sn(μ-
ONNO)SnPh3 (1) was prepared by the reaction of Ph3SnCl
with silver hyponitrite in toluene by stirring at room tempera-
ture overnight. Beside the known spectroscopic data,[12] com-
pound 1 was additionally characterized by NMR spectroscopy
(1H, 13C, and 119Sn) as well as by mass spectrometry. Thus,
the 1H NMR spectrum of 1 in [D8]toluene shows the expected
signals for the phenyl protons in the range of 7.70–7.53 ppm.
The 119Sn{1H} NMR spectrum in [D8]toluene exhibits a singlet
signal at –87.9 ppm, in agreement with a compound in which
tin exhibits a coordination number of four. The mass spectrum
(DEI+) shows no peak, which corresponds to the molecular
ion, but a peak that indicates the fragment M+–N2O at m/z =
716. This observation confirmed the described thermal decom-
position behavior leading to hexaphenyl-distannoxane and ni-
trous oxide.[12]
pound
[Ru2(CO)4(μ-PtBu)2(μ-dppm)(μ-η2-ONNOMe)]
(dppm = Ph2PCH2PPh2), which represents the first complex
bearing a deprotonated monoester of the hyponitrous acid as
the bridging ligand.[9] The latter species derived from the unu-
sual trans-hyponitrite complex [Ru2(CO)4(μ-H)(μ-PtBu)2(μ-
dppm)(μ-η2-ONNO)].[10] We could show that some other
closely related complexes with analogous structural motifs
exist.[11] In the field of compounds of main group elements
containing hyponitrite groups only two species were reported
in the literature. In 1968, Beck and co-workers described two
compounds with the formula Ph3E(μ-ONNO)EPh3 (E = Sn,
Pb), which were characterized by IR spectroscopy and elemen-
tal analysis and for which – from IR data and dipole moment
measurements – the trans structure was proposed.[12] The sec-
ond compound in this area was represented by bis(trimethyl-
silyl) hyponitrite, Me3Si(μ-ONNO)SiMe3 reported by Wiberg
and co-workers.[13] In 1982, for the first time the X-ray crystal
Suitable crystals for an X-ray diffraction study of 1 were
obtained by slow diffusion of iso-hexane into a toluene solu-
tion of the compound at room temperature. The crystal struc-
ture determination revealed that crystals of 1 belong to the
¯
triclinic space group P1 with four crystallographically inde-
pendent molecules in the asymmetric unit. The molecular
structure of 1 as a selected ORTEP view of one molecule is
shown in Figure 1. The molecule consists of two Ph3Sn units
bridged by a trans-hyponitrite group. The molecule of 1 is
closely related to that of the known organic trans-hyponitrite
Me3C(μ-ONNO)CMe3 (2).[14] Therefore, a comparison of
some important bond lengths and angles of 1 and 2 should be
* PD Dr. H.-C. Böttcher
E-Mail: hans.boettcher@cup.uni-muenchen.de
[a] Department Chemie
Ludwig-Maximilians-Universität
Butenandtstr. 5–13
81377 München, Germany
Z. Anorg. Allg. Chem. 2011, 637, 345–347
© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
345

T. Mayer, W. Beck, H.-C. Böttcher
SHORT COMMUNICATION
and SnMe4 (119Sn). Mass spectra were measured with a Jeol Mstation
JMS 700 in the DEI+ mode. Infrared spectra were recorded as solid
with a JASCO FT/IR-460 plus spectrometer.
given here. In both molecules the hyponitrite group is found
in the more stable trans configuration. Thus, the following
bonding characteristics were found for 2: d(N–N) = 1.252(6),
d(N–O) = 1.380(6) Å, and angles N–N–O = 106.5(3), N–O–
C = 109.3(3)°[14] (the corresponding data for 1 see Table 1).
Synthesis of Ph3Sn(μ-ONNO)SnPh3 (1): Ph3SnCl (262 mg,
0.68 mmol) was dissolved in toluene (10 mL). Ag2N2O2 (110 mg,
0.4 mmol) was added and the resulting slurry was vigorously stirred
for 20 h under exclusion of light. After filtration from the precipitated
silver chloride, the solvent was removed under reduced pressure. Crys-
tallization from toluene/iso-hexane yielded a colorless powder. Crys-
tals suitable for X-ray diffraction were obtained by slow diffusion of
iso-hexane into a toluene solution of 1. Yield 37 %. Mp 128 °C (dec.).
C36H30N2O2Sn2 (760.03): calcd. C 56.89, H 3.98, N 3.69 %; found: C
57.01, H 4.13, N 3.57 %. IR: ν = 1006 (NO) cm–1. 1H NMR
˜
([D8]toluene): δ = 7.7–7.53 (m, 30 H, C6H5). 13C{1H} NMR
([D8]toluene): δ = 138.4, 136.8, 136.6, 129.8 (C6H5). 119Sn{1H} NMR
([D8]toluene): δ = –87.9. MS (DEI+): m/z = 715.9 (M+–N2O).
Computational Details: The DFT calculations were performed using
the Gaussian03 software package.[16] The structure and the energy of
the model compound were optimized at the B3LYP level[17] with basis
sets: Sn: pseudopotential and basis set SDD. C, H, N, and O: basis set
G-31G, as implemented in the Gaussian program. A vibrational analy-
sis was performed to confirm that the structure has no imaginary fre-
quency.
Figure 1. Molecular structure of 1 with atom labelling scheme and
ellipsoids drawn at the 50 % probability level.
Crystal Structure Determination and Refinement: A crystal of 1
suitable for X-ray crystal structure determination was selected by
means of a polarization microscope, mounted on the tip of a class fiber,
and investigated on a Oxford XCalibur diffractometer using Mo-Kα
radiation (λ = 0.71073 Å). The structure was solved by direct methods
(SHELXS-97)[18] and refined by full-matrix least-squares calculations
on F2 (SHELXL-97).[19] Anisotropic displacement parameters were re-
fined for all non-hydrogen atoms. Details of crystal data, data collec-
tion, structure solution, and refinement parameters of 1 are summarized
in Table 2.
Table 1. Bond lengths /Å and angles /° for Ph3Sn(μ-ONNO)SnPh3 (1)
in comparison with the computed ones by DFT calculations.
X-ray
DFT
Sn–O
2.062(2)–2.069(2)
1.365(3)–1.372(3)
1.231(5)–1.240(5)
115.6(2)–117.0(2)
110.8(3)–111.6(3)
2.071
1.442
1.252
107.39
109.08
N–O
N–N
N–O–Sn
N–N–O
Table 2. Experimental details of the crystal structure determination of
compound 1.
As seen in Table 1, the by the DFT method calculated struc-
tural parameters of Ph3Sn(μ-ONNO)SnPh3 (1) agree well with
the observed ones from the X-ray diffraction study. Moreover,
the calculations afforded that the molecule with the hyponitrite
group in cis configuration is 17.0 kJ·mol–1 lower in energy
than the corresponding trans isomer.
1
M
760.03
–100
T /°C
Space group
a /Å
b /Å
c /Å
α /°
¯
P1
10.9674(2)
18.2786(2)
18.4592(2)
115.979(1)
102.851(1)
99.032(1)
3103.60(9)
4
Conclusions
β /°
γ /°
The trans-hyponitrite Ph3Sn(μ-ONNO)SnPh3 (1) was revis-
ited by NMR spectroscopy and its crystal and molecular struc-
V /Å3
Z
ture was determined by a single-crystal X-ray diffraction study. Density /g·cm–3
1.627
μ /mm–1
1.644
The thereby found bonding characteristics of 1 correspond well
2 θmax /°
with computed ones by DFT calculations.
reflections, collected
55
25877
reflections, independent
refined parameters
wR2 (all data)
R1
14206
757
Experimental Section
General: All synthetic work was carried out under argon using standard
0.0788
0.0329
Schlenk techniques. Toluene and Ph3SnCl were purchased from Sigma-
Aldrich. Ag2N2O2 was synthesized according to the known
procedure.[15] NMR spectra were recorded with a Jeol Eclipse 400 in- Full details of the structure determination (except structure factors)
strument operating at 400 (1H), 100 (13C) and at 149 MHz (119Sn), re- have been deposited with the Cambridge Data Centre as CCDC-
spectively. Chemical shifts are given in ppm relative to TMS (1H, 13C) 802678. Copies of this information may be obtained free of charge on
346
www.zaac.wiley-vch.de
© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2011, 345–347

The Trans-Hyponitrite Compound Ph3Sn(μ-ONNO)SnPh3
[12] W. Beck, H. Engelmann, H. S. Smedal, Z. Anorg. Allg. Chem.
1968, 357, 134.
[13] N. Wiberg, H. Bayer, G. Ziegleder, Z. Anorg. Allg. Chem. 1979,
459, 201.
quoting the depository number from The Director, CCDC, 12 Union
Road, Cambridge CB2 1EZ, UK (Fax: +44-1223-336033; E-Mail:
deposit@ccdc.cam.ac.uk or www: http://www.ccdc.cam.ac.uk).
[14] C. A. Ogle, K. A. Van der Kooi, G. D. Mendenhall, V. Lorpray-
oon, B. C. Cornilson, J. Am. Chem. Soc. 1982, 104, 5114.
[15] N. Arulsamy, D. S. Bohle, J. A. Imonigie, E. S. Sagan, Inorg.
Chem. 1999, 38, 2716.
Acknowledgement
The authors are grateful to the Department of Chemistry of the Ludwig
Maximilian University Munich for supporting these investigations. T.
M. thanks Prof. Dr. P. Klüfers for financial support. Furthermore we
thank P. Mayer for collecting the X-ray crystal data.
[16] Gaussian 03, Revision D.01, M. J. Frisch, G. W. Trucks, H. B.
Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. A.
Montgomery Jr., T. Vreven, K. N. Kudin, J. C. Burant, J. M. Mil-
lam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi,
G. Scalmani, N. Rega, G. A. Petersson, H. Nakatsuji, M. Hada,
M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nak-
ajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox,
H. P. Hratchian, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo,
R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R.
Cammi, C. Pomelli, J. W. Ochterski, P. Y. Ayala, K. Morokuma,
G. A. Voth, P. Salvador, J. J. Dannenberg, V. G. Zakrzewski, S.
Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K. Malick,
A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. Ortiz, Q.
Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B. Stefanov, G.
Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J.
Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M.
Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong,
C. Gonzalez, J. A. Pople, Gaussian 03, revision D.01; Gaussian,
Inc.: Wallingford CT, 2004.
References
[1] A. F. Holleman, E. Wiberg, Lehrbuch der Anorganischen Chemie,
Walter de Gruyter Verlag, Berlin, New York, 2007, 736–737.
[2] N. Arulsamy, D. S. Bohle, J. A. Imonigie, R. C. Moore, Polyhe-
dron 2007, 26, 4737.
[3] N. Xu, A. L. O. Campbell, D. R. Powell, J. Khandogin, G. B.
Richter-Addo, J. Am. Chem. Soc. 2009, 131, 2460 and references
cited therein.
[4] R. Silaghi-Dumitrescu, D. M. Kurtz Jr., L. G. Ljungdahl, W. N.
Lanzilotta, Biochemistry 2005, 44, 6492.
[5] P. Moënne-Loccoz, Nat. Prod. Rep. 2007, 24, 610.
[6] C. Varotsis, T. Ohta, T. Kitagawa, T. Soulimane, E. Pinakoulaki,
Angew. Chem. 2007, 119, 2260; Angew. Chem. Int. Ed. 2007, 46,
2210.
[17] a) A. D. Becke, J. Chem. Phys. 1993, 98, 5648; b) B. Miehlich,
A. Savin, H. Stoll, H. Preuss, Chem. Phys. Lett. 1989, 157, 200;
c) C. Lee, W. Yang, G. Parr, Phys. Rev. B 1988, 37, 785.
[18] G. M. Sheldrick, SHELXS, Program for Crystal Structure Solu-
tion, University of Göttingen, Germany, 1997.
[7] E. Pinakoulaki, C. Varotsis, J. Inorg. Biochem. 2008, 102, 1277.
[8] Y. Yang, A. Dey, R. A. Decréau, Eur. J. Inorg. Chem. 2010, 4870.
[9] H.-C. Böttcher, P. Mayer, Inorg. Chim. Acta 2010, 363, 799.
[10] H.-C. Böttcher, M. Graf, K. Mereiter, K. Kirchner, Organometal-
lics 2004, 23, 1269.
[19] G. M. Sheldrick, Acta Crystallogr., Sect. A 2008, 64, 112.
[11] P. Mayer, H.-C. Böttcher, manuscript in preparation.
Received: December 21, 2010
Published Online: February 20, 2011
Z. Anorg. Allg. Chem. 2011, 345–347
© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
347