Solvothermal Reactions in and with Nitriles

Article abstract of DOI:10.1002/ejic.201501019

Solvothermal reactions and in situ reductions in nitriles yield a variety of new metal complexes and organometallic compounds including ligands of dimers, trimers, and tetramers of the organic solvent upon (oxidative) C-C and/or C-N bond formation and destruction.

Full text of DOI:10.1002/ejic.201501019

FULL PAPER
DOI:10.1002/ejic.201501019
Solvothermal Reactions in and with Nitriles
Günther Thiele,[a] Bettina Wagner,[a] and Stefanie Dehnen*[a]
Keywords: Nitriles / Solvothermal reactions / Oligomerization / Cobalt / Lead / Nickel
Solvothermal reactions and in situ reductions in nitriles yield
a variety of new metal complexes and organometallic com-
pounds including ligands of dimers, trimers, and tetramers of
the organic solvent upon (oxidative) C–C and/or C–N bond
formation and destruction.
contrast, amines have been used extensively,[16] but they
have mostly led to transition metal cation sequestration to
form [M(amine)x]q+ cations or adducts of the latter with the
binary metalate substructures.[15,17] In order to explore the
influence of another solvent on the course of the reactions
and their product range in the supercritical treatment of
chalcogenidometalates, we have used acetonitrile in such
solvothermal reactions. During these studies, we found that
the phases lead to unexpected reactions with the solvent,
on which we report herein.
Introduction
Acetonitrile is a solvent that is extensively used both in
common organic chemistry and inorganic chemistry, be-
cause of its favorable solvation properties. Also, it has been
investigated as a synthon for hydrogenation and cyclization
processes. Various catalysts have been explored, ranging
from homogeneous Os[1] or Ru[2] compounds to hetero-
geneous Au[3] or Pd[4] systems. Cyclizations of acetonitrile,
with mesoporous carbon nitride[5] or SmI2[6] as catalysts, to
yield pyrimidine have been reported. In contrast, utilization
of acetonitrile or more complex organic nitriles in solvo-
thermal reactions, that is, under elevated temperature and
pressure, has remained rare. In most cases, such reactions
included the respective nitriles as ligands[7,8] or reactants
towards carboxylic acids,[9] oxadiazole,[10] hydrazines,[11] az-
ides, or ammonia.[12] A dimerization into imidazole or a
corresponding tetramerization has not been reported to
date.
Our current interests include the extraction of ternary
phases of the general type AxTyChz [A = alkali metal, T =
main group (heavy) metal, Ch = S, Se, Te] in the presence
of transition metal salts, under solvothermal conditions, to
use these for the generation and further reactions of
multinary, isolated, or extended metalate anions and to
check their reactivity under diverse reaction conditions[13]
and in the presence of various solvents. In contrast to the
syntheses and reactions of binary and multinary gallates,
indates, germanates, and stannates,[14] syntheses of heavy
main group metalates cannot be performed in water or
alcohols. The latter appear to be too reactive and lead to
decomposition of the initially produced ternary phases into
undefined powders along with polychalcogenides.[15] In
Results and Discussion
In a typical solvothermal synthesis, we apply 500 mg of
a ternary phase like “KPbTe”, 1 equiv. of a (transition)
metal salt per main group metal atom, and 2 mL of the
chosen solvent. All is combined under an inert gas in a glass
vial in a Teflon vessel, which is then placed in a stainless
steel autoclave. The latter is tightly closed, heated for one
week at 150 °C, and then cooled down to room temperature
within one day. Such reaction conditions, which had been
identified to be suitable for the generation of ternary met-
alate species such as K2Hg2Se3 or K4[PbSe4]·en·NH3 (en =
ethane-1,2-diamine) in amines as solvents, were now trans-
ferred to nitriles.[18]
In a reaction of “KPbTe” with water-free NiCl2, we did
not obtain a quaternary phase, as initially planned, but iso-
lated small amounts of the acetonitrile tetramer as a ligand
to Ni2+ cations in a dinuclear complex, [(C8H12N4)NiCl(μ-
Cl)]2 (1; Figure 1).
In 1, each tetrameric ligand coordinates to a Ni ion via
one of the pyrimidine N atoms and one NH group of the
anionic CH3C(NH)=N substituent, in addition to a ter-
minal Cl– ligand. Another Cl– ligand per subunit acts as a
μ-bridge to form a dinuclear complex of five-coordinate Ni
atoms. The unusual coordination geometry,[19] as well as
catalytic[20] and magnetic[21] properties of similar dinuclear
and five-coordinate Ni complexes have been discussed.
However, very small yields (ca. 5%) have so far prevented
[a] Fachbereich Chemie and Wissenschaftliches Zentrum
für Materialwissenschaften, Philipps-Universität Marburg
Hans-Meerwein-Strasse 4, 35032 Marburg, Germany
E-mail: dehnen@chemie.uni-marburg.de
https://www.uni-marburg.de/fb15/ag-dehnen
Supporting information and ORCID(s) from the author(s) for
this article are available on the WWW under http://dx.doi.org/
10.1002/ejic.201501019.
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Figure 1. Molecular structure of the dinuclear complex in 1. Ellip-
soids are drawn at 50% probability. Selected bond lengths [Å] and
angles [°]: Ni–N 1.955(2)–2.052(2), Ni–Cl 2.2984(8), Ni–μ-Cl
2.4032(7)–2.4266(8); N–Ni–N 91.34(9), Ni–μ-Cl–Ni 97.31(2), Cl–
Ni–μ-Cl 92.69(3).
Figure 2. Molecular structure of the complex cation in 2. Ellipsoids
are drawn at 50% probability. Selected bond lengths [Å] and angles
[°]: Ni–N 1.832(4)–1.875(4); C(2,3)–N(1,3) 1.278(5), 1.270(5);
C(6,7)–N(4,6) 1.309(5), 1.306(5); C(2,3)–N(2) 1.361(5), 1.370(5);
C(6,7)–N(5) 1.338(5), 1.349(5); N–Ni–N 88.9(2)–90.4(2), C–N(2)–
C 126.5(3), C–N(5)–C 119.3(4). The proton at N2 was observed
further investigation into these directions in the case of 1. crystallographically.
The oligomerization reaction is atom-balanced, as illus-
trated in Scheme 1.
of the two ligands in 2 appears uncommon. Yet, quantum
chemical calculations (see Supporting Information), single-
crystal structure refinement, intermolecular N–H···Cl
hydrogen bonding that appears only at N2 [N2(H)···Cl:
3.230(2) Å], and the charge balance (also in comparison
with the other compounds, vide infra) confirm the finding.
Scheme 1. Illustration of the tetramerization of acetonitrile in the
presence of “KPbTe” during the formation of compound 1. CCN
moieties from originally separate CH3CN molecules are repre-
sented by different colors in the product.
To determine the necessity of all involved components,
we performed a series of reactions, thereby successively re-
acting all of the involved (semi-)metal species separately un-
der different conditions in acetonitrile.
First, the necessity of the presence of “KPbTe” was ex-
plored by performing the corresponding solvothermal reac-
tions of only NiCl2 in CH3CN, which almost quantitatively
yielded single crystals of (NH4)[NiCl3] (see Supporting In-
formation). This compound, with perovskite-like structure,
Scheme 2. Illustration of the formation of the C4N3H10 ligand from
acetonitrile in the presence of NiCl2·6H2O and LiOH during the
formation of compound 2. The different CCN moieties from origi-
nally separate CH3CN molecules are represented by different colors
in the product. Before formation of the complex in 2, the ligand
underwent partial deprotonation. The identity of the organic by-
product could not be elucidated so far as it precipitates as an insol-
uble residue, indicating the formation of a polymer.
The role of the chloride counterion in the aforemen-
was obtained previously under much more drastic condi- tioned reactions was investigated by substitution of NiSO4
tions (400 °C, 1 kbar).[22] Presumably, the Ni complex has as starting material for NiCl2. Again, LiOH is required for
catalyzed the decomposition of acetonitrile to form the am- the formation of a crystalline product, which was found to
monium counterion.
be [Ni(C4H9N3)2](OAc)2 (3; Figure 3), in approximately
The potential influence of residual traces of (Lewis 70% yield.
acidic) SOCl2 within NiCl2 (from preceding drying pro-
In contrast to the mixed protonation of the ligands in 2,
cedures) on the latter reaction to give (NH4)[NiCl3] was both ligands within 3 are charge-neutral, which is in agree-
checked by using undried NiCl2·6H2O instead. However, ment with the overall charge compensation of the NiII com-
this did not lead to the formation of either crystalline or plex by two acetate anions. Since no acetate was present in
otherwise identifiable products. We therefore added 1 equiv. the original reaction mixture, the counterion was formed
of LiOH to the dried NiCl2. Under these (Lewis basic) con- during the reaction, possibly according to the reaction
ditions, another product, [Ni(C4H8N3)(C4H9N3)]Cl (2; Fig- mechanism proposed in Scheme 3.
ure 2) was obtained in approximately 15% yield.
To elucidate the transfer of such reactions to different
Here, a dimerization of the solvent took place with in- nitriles, we utilized benzonitrile as solvent under otherwise
clusion of another N atom – again gained upon cleavage of unchanged reaction conditions, which resulted in the for-
acetonitrile, but not yielding (NH4)+ under the basic condi- mation of [Ni(C14H12N3)2]·2C7H5N (4) in approximately
tions (Scheme 2). Additionally, (partial) deprotonation was 40% yield. As depicted in Figure 4, both ligands in 4 are
observed, producing the monoanionic ligand HN=C(CH3)– deprotonated at the bridging N atom. Thus, no further
N=C(CH3)=NH, similar to a corresponding reaction in- counterion is found, and only two further molecules of ben-
volving CrIII at 200 °C.[23] Again, an oligomerization of zonitrile are present as solvent of crystallization within the
acetonitrile has taken place. The asymmetric protonation crystal structure.
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Figure 3. Molecular structure of the complex in 3 and of the acetate
counterion in their relative orientation within the crystal. Ellipsoids
are drawn at 50% probability. Disorder of the acetate anion is not
shown for clarity. Selected bond lengths [Å] and angles [°]: Ni–N
1.849(3)–1.854(4), C–Nterm 1.282(5)–1.291(5), C–Nbridge 1.365(5)–
1.376(5); N–Ni–N 89.7(2)–90.3(2), C–N–C 125.9(4).
Figure 4. Molecular structure of the complex in 4. Ellipsoids are
drawn at 50% probability. Selected bond lengths [Å] and angles [°]:
Ni–N 1.841(3)–1.845(3), C–Nt 1.315(5)–1.316(5), C–Nb 1.344(5);
N–Ni–N 89.27(15), 90.73(15), C–N–C 119.4(3).
Scheme 4. Illustration of the formation of triphenyltriazine from
benzonitrile in the presence of CoCl2.
To gain further insight into the potential role of Pb2+
ions during the original synthesis of 1, we performed a sim-
ilar reaction with only PbCl2 instead of NiCl2 that yielded
the acetonitrile dimer imidazole, which coordinated to Pb2+
ions in the crystalline product of this reaction, [Pb(C4H8N2)2-
(μ-Cl)2]n (5; Figure 5) in approximately 40% yield. In 5, the
Pb atoms adopt a distorted octahedral coordination envi-
ronment through coordination by two imidazole molecules
and four chloride ions each. The octahedra are edge-bridg-
Scheme 3. Suggested reaction mechanism for the formation of the
ligands in 2 and 3, as well as the acetate counterions in 3. Enhance-
ment of electrophilic positions by coordination to the Lewis acidic
NiII ion is not shown for clarity.
In accordance with the discussed oligomerizations of ing via two chloride ions, thereby forming a coordination
nitriles, the utilization of different transition metal chlorides polymer along the crystallographic c axis.
within solvothermal reactions yield the same or similar
The formation of 5 suggests that the Pb atoms can trig-
nitrile “trimers”: Upon reaction of benzonitrile with CoCl2 ger C–N bond formation that comes along with the ob-
in the presence of LiOH, free triphenyltriazine[24] is ob- served oligomerization. Hence, Ni atoms are only welcome
tained in approximately 65% yield and high crystallinity central atoms and Lewis acids for the formation of rela-
(see Scheme 4), whereas acetonitrile with VCl3 in the pres- tively stable coordination compounds and may not be nec-
ence of pyridine/LiOH as base yields trace amounts of essary for the observed organic reactions themselves – at
[V(O)(C2N3H3)2(py)]Cl2·CH3CN (see Supporting Infor- least not in the presence of Pb2+ ions, and at least not for
mation). The reaction towards the latter two compounds dimerizations of the nitrile, which have also been observed
probably proceeds according to the above-mentioned in the presence of a Mo cluster.[25]
mechanisms. However, neither the (de-)protonation of the
To finally elucidate the impact of different chalcogenide
ligand nor the formal oxidation state of the vanadyl species anions on the reaction to form 1, we investigated the treat-
is completely understood yet, and small yields only have so ment of NiCl2 in acetonitrile in the presence of A2Ch (A =
far hampered further investigations. Therefore, the reac- Li, Na, K; Ch = S, Se, Te) under the same solvothermal
tions and the products will be discussed in a future publica- reaction conditions. However, no crystalline product could
tion.
be obtained so far.
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Under the given conditions, an oxidative C–C coupling
reaction took place that led to the functionalization of one
of the Cp rings with formation of a cyclopentadiene
(C5H5R) derivative. Since H2 generation was not observed
during the reaction, we assume that the role of the
“KPbTe” phase again was only to provide Lewis acidic
(Pb2+) and Lewis basic (Te2–) species.
Conclusions
Solvothermal treatment of Lewis acidic metal ions Co2+
,
Ni2+, and Pb2+ in nitriles, as both solvents and synthons,
yielded heterocyclic compounds in the presence of LiOH or
Te2–. Such oligomers and derivatives can be obtained either
as pure and isolable molecular compounds or as ligands to
new coordination compounds, as reported herein. The im-
pact of different species during the tetramerization of aceto-
nitrile was investigated by a series of reactions in which the
reaction conditions were varied; the results suggest the ne-
cessity of both a Lewis acidic metal ion and a Lewis basic
species for the corresponding transformation. A mechanism
for nitrile trimerization was proposed and supported by the
crystallographic determination of hitherto absent acetate
counterions.
Additionally, in the absence of an additional Lewis base,
a simple method for preparing the perovskite-type com-
pound (NH4)[NiCl3] with high crystallinity and yields, as
well as the synthesis of a nitrile-functionalized cobaltocene
complex under reductive reaction conditions has been pre-
sented, indicating the high and highly diverse synthetic po-
tential of the described reaction mixtures under solvother-
mal reaction conditions.
Figure 5. Fragment of one of the coordination polymer strands in
5. Ellipsoids are drawn at 50% probability. Imidazole molecules
that are connected via H-bridges are shown as wires. Selected bond
lengths [Å] and angles [°]: Pb–N 2.470(6), Pb–Cl 2.892(2), N–Pb–
N 81.1(3), N–Pb–Cl 89.85(15)–94.78(15), Cl–Pb–Cl 173.91(7).
Another approach for generating metalates that we are
currently developing is the in situ reduction of binary metal
chalcogenides or metal/chalcogen mixtures, such as
“PbTe·Te”, with elemental alkali metals in amines at room
temperature.[26]
Transferring the corresponding reaction strategy to
acetonitrile served to explore the utilization of another sol-
vent while at the same time changing from oxidizing (as in
the synthesis of 1) to reductive reaction conditions. Since
alkali metals cause immediate decomposition of the solvent
here, we used NiCp2 and CoCp2 as more gentle reduction
agents. Upon reflux of the chalcogenides with the latter for
two days, [CpCo(C7H7N)] (6; Figure 6) was obtained in ap-
proximately 35% yield.
Experimental Section
General: All synthesis steps were performed with strict exclusion of
air and moisture. Acetonitrile was dried with CaH2 and freshly
distilled before use. “KPbTe” and “PbTe·Te” was generated by fu-
sion of the elements in a 1:1:1 and 1:2 ratio in a quartz ampoule
using an oxygen/butane burner. NiCl2 was generated from
NiCl2·6H2O in excess SOCl2 reflux for 5 h, subsequent filtration
and under dynamic vacuum for 12 h at p Ͻ 1ϫ10–6 bar. All other
salts were dried under dynamic vacuum for 12 h at p Ͻ 1ϫ10–6 bar
and subsequent storage in an Ar operating glovebox. Standard pro-
cedure for solvothermal treatment places all reagents in a glass
within a Teflon vessel, which is then placed in a stainless steel auto-
clave. The latter is tightly closed, heated for one week at 150 °C,
and then cooled down to room temperature within one day. Single
crystals suitable for X-ray structure analysis can be picked man-
ually from the reaction mixture.
Synthesis of [(C8H12N4)2Ni2Cl4] (1): “KPbTe” (0.5 g, 1.37 mmol,
1 equiv.), NiCl2 (175 mg, 1.38 mmol, 1.1 equiv.), and acetonitrile
(2 mL) were treated according to the solvothermal method, afford-
ing orange-green blocks in approximately 5% yield.
Synthesis of [Ni(C4N3H8)(C4N3H9)]Cl (2): NiCl2 (500 mg,
3.85 mmol), LiOH (150 mg, 6.27 mmol), and acetonitrile (2 mL)
were treated according to the solvothermal method, affording yel-
low blocks in approximately 15% yield.
Figure 6. Molecular structure of 6. Ellipsoids are drawn at 50%
probability. Selected bond lengths [Å]: Co–C 1.970(4)–2.098(4), C–
N 1.155(5).
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Synthesis of [Ni(C4N3H9)2](O2C2H3)2 (3): NiSO4 (500 mg, V = 1295.7(4) Å3, final R1(I Ͼ 2σ) = 0.033, wR2(all) = 0.079, GooF
1.99 mmol), LiOH (150 mg, 6.27 mmol), and acetonitrile (2 mL) = 1.046. C12H12CoN (6): P21/c, a = 12.6373(13) Å, b = 7.4477(7) Å,
were treated according to the solvothermal method, affording
orange plates in approximately 70% yield.
c = 11.0658(10) Å, β = 106.189(8)°, V = 1000.20(17) Å3, final R1(I
Ͼ 2σ) = 0.041, wR2(all) = 0.0957, GooF = 0.846.
Synthesis of [Ni(C14N3H12)2]·2C7H5N (4): NiCl2 (500 mg,
3.85 mmol), LiOH (150 mg, 6.27 mmol), and benzonitrile (2 mL)
were treated according to the solvothermal method, affording
orange blocks in approximately 40% yield.
Acknowledgments
Financial support from the Deutsche Forschungsgemeinschaft
(SPP 1415) and the Friedrich-Ebert-Stiftung (FES) is gratefully
acknowledged. We thank Thomas Krüger, Marcus Müller, Ste-
phanie Göbeler-Scheuer, and Lukas Trombach for preparative sup-
port in preliminary studies.
Synthesis of [(C4H8N2)2PbCl2] (5): PbCl2 (500 mg, 1.80 mmol) and
acetonitrile (2 mL) were treated according to the solvothermal
method, affording colorless blocks in approximately 40% yield.
Synthesis of [(C5H5)(C7H7N)Co] (6): “PbTe·Te” (500 mg,
1.08 mmol, 1 equiv.), CoCp2 (410 mg, 2.17 mmol, 2 equiv.), and
acetonitrile (100 mL) were heated at reflux for 5 h. The resulting
reaction mixture was filtered and slowly concentrated until only a
small residue of approximately 5 mL of solvent was still present.
Compound 6 crystallizes as brown sticks in approximately 35%
yield.
[1] M. L. Buil, V. Cadierno, M. A. Esteruelas, J. Gimeno, G. Her-
rero, S. Izquierdo, E. Oñate, Organometallics 2012, 31, 6861.
[2] R. García-Álvarez, M. Zablocka, P. Crochet, C. Duhayon, J.-
P. Majoral, V. Cadierno, Green Chem. 2013, 15, 2447.
[3] Y.-M. Liu, L. He, M. M. Wang, Y. Cao, H.-Y. He, K.-N. Fan,
ChemSusChem 2012, 5, 1392.
Synthesis of (NH4)[NiCl3]: NiCl2 (500 mg, 3.85 mmol) and aceto-
nitrile (2 mL) were treated according to the solvothermal method,
affording yellow sticks in approximately 85% yield.
[4] K.-i. Shimizu, T. Kubo, A. Satsuma, T. Kamachi, K. Yoshiz-
awa, ACS Catal. 2012, 2, 2467.
Synthesis of Triphenyltriazine: CoCl2 (500 mg, 3.85 mmol), LiOH
(150 mg, 6.27 mmol), and benzonitrile (2 mL) were treated accord-
ing to the solvothermal method, affording colorless planks in ap-
proximately 65% yield.
[5] F. Goettmann, A. Fischer, M. Antonietti, A. Thomas, New J.
Chem. 2007, 31, 1455.
[6] F. Xu, J.-H. Sun, H.-B. Yan, Q. Shen, Synth. Commun. 2000,
30, 1017.
[7] C. D. Molek, J. A. Halfen, J. C. Loe, R. W. McGaff, Chem.
Commun. 2001, 24, 2644.
Synthesis of [V(O)(C2N3H3)2(py)]Cl2·CH3CN: VCl3 (500 mg,
3.18 mmol), LiOH (150 mg, 6.27 mmol), acetonitrile (2 mL), and
pyridine (5 μL) were treated according to the solvothermal method,
affording a few large violet blocks.
[8] M. R. Razali, A. Urbatsch, G. B. Deacon, S. R. Batten, Polyhe-
dron 2013, 64, 352.
[9] K. M. L. Rai, M. S. Babu, K. Byrappa, Asian J. Chem. 2012,
24, 1395.
X-ray Diffraction Experiments
[10] Y. Djebli, S. Mosbah, S. Boufas, L. Bencharif, T. Roisnel, Acta
Crystallogr., Sect. E 2010, 66, m410.
[11] L. Cheng, W.-X. Zhang, B.-H. Ye, J.-B. Lin, X.-M. Chen, Inorg.
Chem. 2007, 46, 1135.
[12] X.-M. Chen, M.-L. Tong, Acc. Chem. Res. 2007, 40, 162.
[13] Z. Hassanzadeh Fard, R. Clérac, S. Dehnen, Chem. Eur. J.
2010, 16, 2050.
[14] a) J. Heine, S. Santner, S. Dehnen, Inorg. Chem. 2013, 52, 4424;
b) J. Heine, S. Dehnen, Z. Anorg. Allg. Chem. 2012, 638, 2425.
[15] G. Thiele, L. Vondung, C. Donsbach, S. Pulz, S. Dehnen, Z.
Anorg. Allg. Chem. 2014, 640, 2684.
[16] a) W. S. Sheldrick, M. Wachhold, Angew. Chem. Int. Ed. Engl.
1997, 36, 206; Angew. Chem. 1997, 109, 214; b) G. Thiele, T.
Krüger, S. Dehnen, Angew. Chem. Int. Ed. 2014, 53, 4699; An-
gew. Chem. 2014, 126, 4787.
[17] G. Thiele, S. Santner, C. Donsbach, M. Assmann, M. Müller,
S. Dehnen, Z. Kristallogr. 2014, 229, 489.
[18] a) G. Thiele, S. Lippert, F. Fahrnbauer, P. Bron, O. Oeckler, A.
Rahimi-Iman, M. Koch, B. Roling, S. Dehnen, Chem. Mater.
2015, 27, 4114; b) G. Thiele, T. Krüger, S. Dehnen, Angew.
Chem. Int. Ed. 2014, 53, 4699; Angew. Chem. 2014, 126, 4787.
[19] G. J. Long, E. O. Schlemper, Inorg. Chem. 1974, 13, 279.
[20] a) A. O. Eseola, M. Zhang, J.-F. Xiang, W. Zuo, Y. Li, J. A. O.
Woods, W.-H. Sun, Inorg. Chim. Acta 2010, 363, 1970; b) R.
Gao, L. Xiao, X. Hao, W.-H. Sun, F. Wang, Dalton Trans.
2008, 5645.
Data for the X-ray structure analysis: T = 293 K (for 1, 2, 5) or
100 K (for 3, 4, 6), graphite monochromator, imaging plate detector
Stoe IPDS (for 1, 2, 5), IPDS2 (for 4, 6) or Bruker Quest (for
3). All structures were solved by direct methods in WinGX[27] and
OLEX2[28] by full-matrix least-squares refinement against F2 in
SHELXL-2013.[29] Absorption corrections were performed numeri-
cally including shape optimization with STOE X-AREA (1, 2, 4–
6) or semi-empirically with Bruker SADABS (multi-scan).
Tables S1 and S2 summarize the crystallographic data of all crystal-
line compounds.
CCDC-1422320 (for 1), -1422321 (for 2), -1422322 (for 3), -1422323
(for 4), -1422324 (for 5), -1422325 (for 6), -1422340 {for
(NH4)[NiCl3]}, -1422341 (for triphenyltriazine), and -1422342 {for
[V(O)(C2N3H3)2(py)]Cl2·CH3CN} contain the supplementary crys-
tallographic data for this paper. These data can be obtained free
of charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
Crystal Structure and Refinement Details: [(C8H12N4)2Ni2Cl4] (1):
P21/c, a = 8.3432(11) Å, b = 10.6886(16) Å, c = 13.128(2) Å, β =
101.468(11)°, V = 1147.3(3) Å3, final R1(I Ͼ 2σ) = 0.036, wR2(all)
= 0.096, GooF = 1.068. [Ni(C4N3H8)(C4N3H9)]Cl (2): P21/n, a =
8.8236(12) Å, b = 13.881(3) Å, c = 10.2611(16) Å, β = 91.900(12)°,
V = 1256.1(4) Å3, final R1(I Ͼ 2σ) = 0.048, wR2(all) = 0.084, GooF
= 0.943. [Ni(C4H9N3)2](OAc)2 (3): Ibam, a = 13.9820(11) Å, b =
17.640(2) Å, c = 6.5883(4) Å, V = 1625.0(3) Å3, final R1(I Ͼ 2σ) =
0.0412, wR2(all) = 0.1053, GooF = 1.194. [Ni(C14H12N3)2]·2C7H5N
[21] G. A. v. Albada, J. J. A. Kolnaar, W. J. J. Smeets, A. L. Spek, J.
Reedijk, Eur. J. Inorg. Chem. 1998, 1337.
[22] H. T. Witteveen, J. A. R. v. Veen, J. Phys. Chem. Solids 1974,
35, 337.
[23] L. J. Batchelor, M. Sander, F. Tuna, M. Helliwell, F. Moro,
J. v. Slageren, E. Burzurí, O. Montero, M. Evangelisti, F. Luis,
E. J. L. McInnes, Dalton Trans. 2011, 40, 5278.
[24] A. Damiani, E. Giglio, A. Ripamonti, Acta Crystallogr. 1965,
19, 161.
¯
(4): P1, a = 8.5822(4) Å, b = 9.4684(5) Å, c = 11.4969(7) Å, α =
101.834(3), β = 98.293(4)°, γ = 108.930(3)°, V = 842.21(8) Å3, final
R1(I Ͼ 2σ) = 0.0747, wR2(all) = 0.2236, GooF = 1.067. (C4H8N2)2-
PbCl2 (5): C2/c, a = 13.246(2) Å, b = 12.119(2) Å, c = 8.1684(13) Å,
Eur. J. Inorg. Chem. 2015, 5329–5334
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FULL PAPER
[25]
[28] O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard,
H. Puschmann, J. Appl. Crystallogr. 2009, 42, 339.
[29] G. M. Sheldrick, SHELXL13, Program for the Refinement of
Crystal Structures, University of Göttingen, 2014.
Received: September 7, 2015
J. Huang, M. Shang, J. Huang, S. Lu, J. Lu, Jiegou Huaxue
1984, 3, 129.
[26] G. Thiele, L. Vondung, S. Dehnen, Z. Anorg. Allg. Chem. 2015,
641, 247.
[27] L. J. Farrugia, J. Appl. Crystallogr. 2012, 45, 849.
Published Online: October 22, 2015
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© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim