S. V. Voitekhovich, B. Kersting et al.
FULL PAPER
was continued for 1 h. The resulting green precipitate of 4 was col-
lected by filtration, washed several times with cold ethanol and
diethyl ether and dried in vacuo to give 89 mg (0.089 mmol, 79%)
of 4 as a light green, air-stable, microcrystalline powder; m.p.
dination features of the anion 2–. Our previous investigations[30]
have shown the B3LYP/6-31G(d) level to provide data of calculated
geometries of tetrazoles in good agreement with experimental find-
ings. Nevertheless, in order to describe anions accurately use of a
basis set that includes diffuse functions is required. Therefore, in
284 °C (decomp.). IR (KBr): ν = 2996 (sh), 2956 (m), 2900 (m),
˜
2868 (m), 1463 (s), 1427 (sh), 1395 (w), 1378 (w), 1362 (m), 1329 the present work we have used the 6-31+G(d) basis set for geometry
(m), 1292 (sh), 1267 (w), 1232 (m), 1200 (w), 1165 (w), 1152 (w), optimization, NPA and MESP calculations of the isolated anion 2–.
1122 (s), 1108 (sh), 1095 (s), 1057 (m), 1043 (m), 999 (w), 981 (w),
We have used smaller basis sets for geometry optimization and total
928 (w), 913 (w), 881 (w), 827 (m), 818 (w), 807 (w), 754 (w), 742 energy calculation of complex [Ni2L(μ-SCN4Me)]+. Nickel atoms
(sh), 720 (w), 631 (sh), 624 (m), 600 (w), 567 (w), 540 (w), 493 (w), were described by the standard LANL2DZ double-ξ basis set, ap-
479 (w), 438 (w), 417 (w) cm–1. UV/Vis/NIR (MeCN): λmax (ε) = plying an effective core potential as suggested by Hay and Wadt.[31]
199 (55104), 248 (25755), 277sh (15823), 305sh (13044), 330 (9447),
All atoms of 2– were described by a 6-31G* basis set, and STO-3G
396sh (1724), 641 (29), 927sh (27), 1097 (69) (103 m–1 cm–1) nm. basis sets were used for the remaining atoms. The geometry of 2–
C40H67ClN10Ni2O4S3 (1001.06): calcd. C 47.99, H 6.75, N 13.99;
found C 47.96, H 6.57, N 13.08. ESI-MS+ (MeCN): m/z = 899.34
[C40H67N10Ni2S3+].
and its location relative to the macrocyclic hexaminedithiophenol-
ate ligand was fully optimized, while the Cartesian coordinates of
all atoms of [Ni2L]2+ were fixed as those as in crystals of 5·2MeCN.
In our calculations quintet configuration was considered for the
complex [Ni2L(μ-SCN4Me)]+.
[Ni2L(μ-SCN4Me)]BPh4 (5): Complex 4 (100 mg, 0.100 mmol) was
dissolved in methanol (50 mL), and a solution of NaBPh4 (342 mg,
1.00 mmol) in methanol (5 mL) was added. The mixture was stirred
at ambient temperature for 1 h. The green product was filtered,
washed with cold ethanol, cold diethyl ether and dried in vacuo to
give 105 mg (0.086 mmol, 86%) of 5 as a green, air-stable, micro-
Determination of the Temperature Dependence of the Magnetic
Susceptibility: Measurements of powdered polycrystalline
5·2MeCN were carried out with a Quantum Design MPMS-XL7
SQUID magnetometer from 2 to 330 K and vice versa at an applied
external field of 0.5 and 1.0 T, respectively, both in field cooling as
well as in zero-field cooling mode. All obtained data were processed
by using Bill’s julX program[32] and were corrected for underlying
diamagnetism by using Pascal’s constants and for the contribution
of the sample holder by subtraction of the previously determined
holder average. With respect to the limit of error, all data gave the
identical values mentioned above.
crystalline powder; m.p. 260 °C (decomp.). IR (KBr): ν = 3056 (m),
˜
3038 (m), 3000 (m), 2955 (s), 2902 (m), 2864 (s), 1580 (m), 1480
(s), 1462 (s), 1427 (m), 1394 (w), 1378 (m), 1362 (m), 1329 (s), 1309
(sh), 1292 (w), 1266 (m), 1231 (m), 1199 (w), 1165 (m), 1154 (m),
1134 (w), 1122 (w), 1109 (w), 1074 (m), 1056 (m), 1041 (m), 1000
(w), 981 (w), 928 (m), 914 (m), 891 (w), 881 (w), 845 (w), 826 (m),
819 (m), 809 (m), 754 (m), 732 (m), 707 (s), 667 (w), 628 (m), 612
(m), 567 (w), 536 (w), 473 (w), 414 (w) cm–1. UV/Vis/NIR (MeCN):
λmax (ε) = 194 (168363), 246sh (35290), 276sh (16012), 305sh
(12198), 332 (9093), 396sh (1808), 471sh (143), 638 (28), 919sh (25),
1094 (68 m–1 cm–1) nm. C64H87BN10Ni2S3 (1220.84): calcd. C 62.96,
H 7.18, N 11.47; found C 62.39, H 6.84, N 11.10. ESI-MS+
(MeCN): m/z = 899.34 [C40H67N10Ni2S3+].
Acknowledgments
We are grateful to Prof. Dr. E. Hey-Hawkins for providing facilities
for X-ray crystallographic measurements and Prof. Dr. J. Sieler for
their performance. This work was supported by the DAAD (Leon-
hard-Euler Program) and the University of Leipzig. S. V. V. grate-
fully acknowledges the Erasmus Mundus program “Advanced
Spectroscopy in Chemistry” for a research fellowship. R. S. grate-
fully acknowledges the University of Leipzig (Graduate School
BuildMoNa) for financial support.
Crystal Structure Determination: Single-crystals of 5·2MeCN were
obtained by slow concentration of an acetonitrile/ethanol (1:1)
solution of 5 at ambient temperature. Data collection was per-
formed at 130(2) K with a Siemens Smart CCD area detector dif-
fractometer by using monochromated Mo-Kα radiation (0.71073 Å)
and ω-scan rotation mode. Data reduction was carried out with
SAINT[24] and corrected for absorption by using SADABS.[25] The
structure was solved by direct methods (SHELXS-97)[26] and re-
fined by full-matrix least squares on the basis of all data against F2
using SHELXL-97.[27] PLATON[28] was used to search for higher
symmetry. All non-hydrogen atoms were refined anisotropically. H
atoms were placed at calculated positions and refined as riding
atoms with isotropic displacement parameters. Crystal data for
5·2MeCN: C68H93N12Ni2S3B, MR = 1302.95, orthorhombic, space
group Pbca (No. 61), a = 17.7371(3) Å, b = 17.5649(3) Å, c =
41.8483(9) Å, V = 13037.9(4) Å3, Z = 8, ρcalcd. = 1.328 gcm–3, T =
130(2) K, μ(Mo-Kα) 0.725 mm–1 (λ = 0.71073 Å), 155004 reflec-
tions measured, 9351 unique, 7012 with IϾ2σ(I), refinement con-
verged to R = 0.0552, wR = 0.0937 [IϾ2σ(I)], GoF = 1.061, –19 Յ
h Յ 19, –19 Յ k Յ 19, –46 Յ l Յ 46, 2.54° Յ θ Յ 23.26°, 772
parameters and 0 restraints, min/max residual electron density
+0.663/–0.506 e/Å3. CCDC-782779 contains the supplementary
crystallographic data for 5·2MeCN. These data can be obtained
free of charge from The Cambridge Crystallographic Data Centre
via www.ccdc.cam.ac.uk/data_request/cif.
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