Journal of Molecular Structure 1051 (2013) 354–360

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Journal of Molecular Structure

j o u r n a l h o m e p a g e : w w w . e l s e v ie r . c o m / l o c a t e / m o l s t r u c

Molybdenum(V) complexes with formate: Geometric isomerism of the

[Mo2O4Cl2(Py)2(HCOO)] ion
⇑
Barbara Modec , Darko Dolenc
Department of Chemistry and Chemical Technology, University of Ljubljana, Aškercˇeva 5, 1000 Ljubljana, Slovenia

highlights graphical abstract

Formate binds to the fMo2O4g2þ core to form The PyH+ cis-[Mo2O4Cl2(Py)2(HCOO)] synthon.
dinuclear anionic complexes.
The [Mo2O4Cl2(Py)2(HCOO)] ion
exists as trans and cis geometric
isomers.
DFT calculations show the trans
isomer to be energetically more
favored.
H-bonds and CAH Cl interactions between
PyH+ and complex ions stabilize the cis
isomer.

article info abstract

Article history: Reactions of (PyH)5[MoOCl4(H2O)]3Cl2 with formate resulted in trans-{(Py)2H}[Mo2O4Cl2(Py)2(HCOO)] (1) and cis-
Received 21 May 2013 (PyH)[Mo2O4Cl2(Py)2(HCOO)] (2), whereas the bromide starting material (PyH)[MoOBr4], yielded
Received in revised form 23 July 2013
Accepted 8 August 2013 (PyH)3[Mo2O4Br4(HCOO)] 2CH3CN (3) and cis-(PyH)[Mo2O4Br2(Py)2(HCOO)] (4) (where Py stands for pyr-idine, PyH+
Available online 20 August 2013 for pyridinium cation and (Py)2H+ for a hydrogen-bonded PyH+ Py ion). In all, the dinuclear metal–metal bonded fMo2O4g2 þ
core may be recognized with its six coordination sites distributed among halides, pyridine ligands and formate. The latter is
Keywords: coordinated via both oxygen atoms, with each to a different metal ion. The [Mo 2O4Cl2(Py)2(HCOO)] ion exhibits geometric
Molybdenum(V) coordination chemistry isomerism: the pyridine ligands, on each metal ion one, are either trans or cis to each other. The trans isomer crystallized with
+ +
{Mo2O4}2+ compounds (Py)2H countercations, whereas the cis isomer as a PyH salt. In the crystal lattice of cis-(PyH)[Mo2O4Cl2 (Py)2(HCOO)]
Carboxylato ligand (2), as confirmed by the X-ray structure analysis, pyridinium cation forms a hydrogen bond with the doubly-bridging oxide of
Geometric isomerism the cis-[Mo2O4Cl2(Py)2(HCOO)] ion. The countercations of trans-{(Py)2H}[Mo2O4Cl2(Py)2(HCOO)] (1) cannot participate
DFT calculations
in hydrogen-bonding. The DFT calculations on the isomers of the [Mo 2O4Cl2(Py)2(HCOO)] ion show the trans isomer to be
by ca. 15 kJ/mol more stable than the cis isomer. The calculations on the hydrogen-bonded PyH+ [Mo2O4Cl2(Py)2(HCOO)]
ion-pairs show a reversed order of stability. Hydrogen-bonding and weak CAH Cl interactions between PyH+ cations and the
cis-[Mo2O4Cl2(Py)2(HCOO)] ion increase the stability of the cis compound.

2013 Elsevier B.V. All rights reserved.

1. Introduction in this oxidation state [1]. Its structure was undoubtedly confirmed
with the X-ray structure determination of Ba[Mo2O4(g2-C2O4)2 (H2O)2]
The dinuclear singly metal–metal bonded fMo2O4g2þ core (illustrated in 3H2O in 1965 [2]. Recent reports on the {Mo2O4}2+-
Scheme 1) pervades the chemistry of molybdenum containing compounds appear in very diverse contexts of molybdenum
coordination chemistry. Examples include discrete dinuclear species with
⇑ Corresponding author. Tel.: +386 (0)1 2419 108; fax: +386 (0)1 2419 220. E-mail
address: barbara.modec@fkkt.uni-lj.si (B. Modec).
ligands such as sulfite [3], tris(1-pyrazolyl)

0022-2860/$ - see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.molstruc.2013.08.009
 B. Modec, D. Dolenc / Journal of Molecular Structure 1051 (2013) 354–360
Scheme 1. The fMo2 O4 g2þ core: terminal oxides are cis to each other, the {Mo(l2-O)2Mo}
rhombus is not planar and the intermetal distance of 2.5–2.6 Å signifies a single metal–metal
bond [1].
methanesulfonate [4], imidazole [5], pyrazolate [6] or diketiminate [7] and
self-assemblies of two or more {Mo2O4}2+ cores [8–13]. The linkage of
dinuclear cores can be achieved also with the agency of multidentate oxygen-
and, rarely, nitrogen-donor ligands. Some of the ligands serving this role are
sulfite [3], biphosphonate [14], oxalate [15], molybdate(VI) [16] and pyrazine
[17]. Of the latter, only the oxalate and molybdate(VI) covalently linked the
{Mo2O4}2+ cores into infinite chain structures. The carboxylates present
themselves as another type of suitable ligands. Owing to the variety of the
coordination modes that the carboxylate function can employ, even the ligand
with one functional group can link two {Mo2O4}2+ cores. The latter was
demonstrated by the acetate in [Mo4O8(CH3COO)3(OH)(Py)4] with the
carboxylate serving either as a monodentate ligand or as bidentate bridging
ones to a pair of metal–metal bonded molybdenum atoms or to molybdenum
atoms from different {Mo2O4}2+ cores [18]. The number of coordi-nation
patterns increases with the number of carboxylate groups in the ligand.
Malonate dianion (mal2 ), a ligand with two carboxyl-ate groups, coordinated
in [Mo2O4Cl(g2-mal)(l2-Hmal)(Py)]2 (Hmal = hydrogen malonate) in a
chelating manner engaging the oxygens from different carboxylate groups
[19]. On the other hand, one of the malonate ions of [{Mo2O4(g2-mal)2}2(l4-
mal)]6 bonded via all four oxygen atoms and thereby linked two {Mo2O4}2+
cores into a tetranuclear anion [20]. Similarly, the hep-tanedioate (hda2 ) fully
exploited its coordination abilities and as such linked two dinuclear cores into
[(Mo2O4Cl4)2(l4-hda)]6 [21].
In continuation of our research on the carboxylato complexes of
molybdenum(V) the interaction of (PyH)5[MoOCl4(H2O)]3Cl2 or
(PyH)[MoOBr4] with formate was investigated. Herein we report on the
preparation and structural characterization of a series of products of these
reactions, trans-{(Py)2H}[Mo2O4Cl2(Py)2(HCOO)] (1), cis-
(PyH)[Mo2O4Cl2(Py)2(HCOO)] (2), (PyH)3[Mo2O4Br4 (HCOO)] 2CH3CN
(3) and cis-(PyH)[Mo2O4Br2(Py)2(HCOO)] (4). Surprisingly, a dinuclear
complex anion with the [Mo2O4Cl2(Py)2 (HCOO)] composition was isolated
as two geometric isomers, one with the trans and the other with the cis
disposition of pyridine ligands. Previously prepared complexes with the
[Mo2O4Cl2(Py)2 (RCOO)] (RCOO = acetate, pivalate, hydrogen succinate)
compo-sition are with no exception cis isomers [19,22]. This motivated us to
see if we could understand the preference for the cis isomeric form.
2. Experimental section
2.1. General procedures
Chemicals were obtained from Aldrich Chemical Co. They were used
without further purification. Acetonitrile solution of pyridinium formate was
prepared by dissolving the appropriate amounts of pyridine and formic acid in
a 1:1 M ratio. (PyH)5[MoOCl4(H2O)]3Cl2 and (PyH)[MoOBr4] were
prepared by published procedures [23]. Elemental analyses were performed
by the Chemistry Department service at the University of Ljubljana. The
infrared spectra were measured on solid samples as Nujol or poly(chlorotri-
fluoroethylene) mulls using a Perkin Elmer 2000 Series FT-IR spectrometer.
355
2.2. Preparation of trans-{(Py)2H}[Mo2O4Cl2(Py)2(HCOO)] (1)
Procedure A. (PyH)5[MoOCl4(H2O)]3Cl2 (400 mg, 0.93 mmol of Mo)
was dissolved in the mixture of pyridine (4 mL) and formic acid (0.211 g,
4.50 mmol). The solution of deep red color was left to stand in a closed vessel
at ambient conditions. Within two days, red crystals of 1 deposited from the
solution. Yield: 90 mg; 28%. Procedure B. A glass tube was charged with
(PyH)5[MoOCl4(H2O)]3Cl2 (400 mg, 0.93 mmol of Mo), formic acid (0.211
g, 4.50 mmol) and pyridine (4 mL). The tube was sealed and heated in an
electric oven maintained at 115 LC for 120 h. After cooling to room
temperature, the resulting red solution was con-centrated under vacuum to ca.
one third of the initial volume. Methanol (1 mL), acetonitrile (1 mL) and
diethyl ether (4 mL) were added to the residue. The resulting solution was left
to stand at ambient conditions in a closed flask. Within two days a copious
amount of red crystals of 1 deposited from the solution. Yield: 232 mg; 72%.
Found C, 36.52; H, 3.26; N, 7.93%. C21H22Cl2Mo2N4O6 requires C, 36.60;
H, 3.22; N, 8.13%. IR (cm 1): 1635m, 1603s, 1571m, 1558vs [masym(OCO)],
1447vvs, 1345vs [msym(OCO)], 1253w, 1239w, 1217s, 1205w, 1160m,
1147m, 1075vs, 1067s, 1044vs, 1039vs, 1017m, 1006s, 956vvs, 938vvs,
897m, 879m, 873m, 762vs, 752vvs, 735vvs, 720vs, 711vvs, 693vs, 683vvs,
650w, 640m, 630s, 572m, 506w, 479vs, 436m.
2.3. Preparation of cis-(PyH)[Mo2O4Cl2(Py)2(HCOO)] (2)
(PyH)5[MoOCl4(H2O)]3Cl2 (150 mg, 0.35 mmol of Mo) was dissolved in
acetonitrile (20 mL). Upon the addition of pyridinium formate (2.0 mmol, 4.0
mL of 0.5 M solution in acetonitrile) the solution changed color from green to
orange. The solution was concentrated under vacuum to ca. one half of the
initial volume and then left to stand at 8 LC. Within two days red crystals of 2
deposited from the solution. The crystals were filtered off and washed with
the hexanes. Yield: 56 mg; 52%. Found C, 31.07; H, 2.88; N, 6.61%.
C16H17Cl2Mo2N3O6 requires C, 31.50; H, 2.81; N, 6.89%. IR (cm 1): 1607s,
1557vvs [masym(OCO)], 1449vvs, 1346vvs [msym(OCO)], 1219s, 1199w,
1158m, 1070s, 1046s, 1017m, 1000w, 960vvs, 941vs, 881w, 755vs, 729vvs,
693vs, 681vs, 643m, 604m, 489m, 439m.
2.4. Preparation of (PyH)3[Mo2O4Br4(HCOO)] 2CH3CN (3) and
cis-(PyH)[Mo2O4Br2(Py)2(HCOO)] (4)
(PyH)[MoOBr4] (512 mg, 1.0 mmol) was dissolved in acetoni-trile (20
mL). Upon the addition of pyridinium formate (2.70 mmol, 5.4 ml of 0.5 M
solution in acetonitrile) the solution acquired a deep red color. The mixture
was divided into two aliquots. One was concentrated under vacuum to ca. one
half of the initial volume and then left to stand at ambient conditions. Orange
crystals of 3 deposited from the solution overnight. Yield: 95 mg; 40%.
Found C, 20.31; H, 2.15; N, 3.39%. C14H16Br4Mo2N2O6 (dried sample)
requires C, 20.51; H, 1.97; N, 3.42%. IR (cm 1): 1634m, 1608m, 1567vs
[masym(OCO)], 1531vs, 1505w, 1338vvs [msym(OCO)], 1248w, 1196s,
1164w, 1052m, 1002m, 957vvs, 943vs, 778m, 745vvs, 720w, 699vs, 673vvs,
604vs, 481s. The second aliquot was left to stand at ambient conditions for
two weeks. Red crystals of 4 were collected by filtration and washed with the
hexanes. Yield: 48 mg; 27%. Found C, 27.61; H, 2.88; N, 6.61%.
C16H17Br2Mo2 N3O6 requires C, 27.49; H, 2.45; N, 6.01%. IR (cm 1):
1660vs, 1632w, 1618w, 1606vs, 1548vs [ masym(OCO)], 1445vvs, 1346vvs
[msym(OCO)], 1277w, 1251m, 1214s, 1201m, 1162w, 1148m, 1067vvs,
1046s, 1014s, 998m, 956vvs, 935vvs, 874m, 790w, 766vs, 750vvs, 731vvs,
704vvs, 681vvs, 643m, 604vs, 502w, 481s.
356 B. Modec, D. Dolenc / Journal of Molecular Structure 1051 (2013) 354–360

2.5. X-ray structure determinations
Data were collected on Nonius Kappa CCD diffractometer using graphite
monochromated Mo Ka radiation (k = 0.71073 Å). Data reduction and
integration were performed with the software pack-age DENZO-SMN [24].
Specific absorption corrections were not applied since the averaging of the
symmetry-equivalent reflections largely compensated for any absorption
effects. The coordinates of the majority of non-hydrogen atoms were found
via direct meth-ods using the structure solution program SHELXS [25]. The
posi-tions of the remaining non-hydrogen atoms were located by use of a
combination of least-squares refinement and difference Fou-rier maps in the
SHELXL-97 program [25]. Hydrogen atoms were included in the structure
factor calculations at idealized positions. In 1, the cationic part consists of two
pyridines sharing a proton. The protonation site could not be located from the
electron density map. To maintain the charge balance, the proton was placed
on N(4). The structures of 1 and 4 were solved and successfully refined in
non-centrosymmetric space groups, P bc21 and P 212121, respec-tively. The
Flack parameter was 0.47(4) for 1, and 0.029(8) for 4 [26]. In the case of 1,
the value suggests that the crystal was a racemic twin. Figures depicting the
structures were prepared by ORTEP3 [27] and Mercury [28]. Cell parameters
and refinement results are summarized in Table 1.
2.6. Computational details
All calculations were performed with Jaguar package of pro-grams [29].
Geometry optimizations were carried out initially by
B3LYP, MPW1K and M06 [30] density functionals with 6-311+G basis set
and LACV3P + pseudopotential for molybdenum. By comparison of the
calculated geometries with the experimental ones for the trans-
[Mo2O4Cl2(Py)2(HCOO)]– ion, it was found that MPW1K functional
behaves the best and all subsequent calcula-tions were made at MPW1K/6-
311+G level of theory. The opti-mized molecular structures for the trans/cis
geometric isomers of the [Mo2O4Cl2(Py)2(HCOO)]– ion and the hydrogen-
bonded PyH+ [Mo2O4Cl2(Py)2(HCOO)]– ion-pairs at the MPW1K/6-311+G
level are shown in Supporting information. An overall agreement has been
found between the calculated and experimen-tal geometric parameters (Tables
2 and 3).
3. Results and discussion
3.1. Structural studies
trans-{(Py)2H}[Mo2O4Cl2(Py)2(HCOO)] (1) crystallizes in an
orthorhombic space group P bc21. Its crystal structure is built of dinuclear
complex anions with the trans-[Mo2O4Cl2(Py)2(HCOO)]– composition and
PyH+ Py as the cationic part, hereafter desig-nated in short as (Py)2H+. The
N(3) N(4) distance in the cation, 2.716(6) Å, is significantly shorter than the
sum of the van der Waals radii, 3.10 Å [31,32]. The ORTEP drawing of the
cation is shown in Fig. 1 and that of the anion in Fig. 2. The complex anion
consists of a central {Mo2O4}2+ core. The coordination environment of the
two metal ions is the same: a terminal oxide, two doubly-bridging oxides, a
pyridine ligand, a chloride and a formate oxygen define a highly distorted
octahedron. The origin of the distortion

Table 1
Crystallographic data for compounds 1–4.

Compound 1 Compound 2 Compound 3 Compound 4

C H Cl Mo N O C H Cl Mo N O C H Br Mo N O C H Br Mo N O
Empirical formula 21 22 2 2 4 6 16 17 2 2 3 6 20 25 4 2 5 6 16 17 2 2 3 6

Formula mass 689.21 610.11 942.97 699.03

Crystal system Orthorhombic Triclinic Monoclinic Orthorhombic
Space group P bc21 P1 P 21/m P 212121
T (K) 150(2) 150(2) 150(2) 150(2)
a (Å) 7.9138(1) 8.0427(2) 8.0655(1) 10.03160(10)
b (Å) 16.7747(3) 9.5438(3) 16.6510(3) 14.4172(2)
c (Å) 19.0363(4) 15.2704(5) 11.1006(2) 14.8396(2)
a (L) 90 102.5990(10) 90 90
b (L) 90 98.8810(10) 94.2535(7) 90
c (L) 90 96.4090(10) 90 90
V (Å3) 2527.10(8) 1117.28(6) 1486.69(4) 2146.22(5)
Z 4 2 2 4
k (Å) 0.71073 0.71073 0.71073 0.71073
qcalc (g cm–3) 1.811 1.814 2.106 2.163
l (mm–1) 1.248 1.397 6.261 4.929
Collected reflections 9854 9024 6713 13741
Unique reflections, Rint 4300, 0.041 5043, 0.0201 3510, 0.0210 4807, 0.043
Observed reflections 4129 4450 3211 4718
R1a (I > 2r(I)) 0.0289 0.0330 0.0303 0.0267
wR2b (all data) 0.0661 0.0889 0.0775 0.0721
a P P
R1 =
n
||Fo|–|Fc||/ |Fo|. .
b wR2 = w Fo2 Fc2 2 =w Fo2
2
o

1=2

P P
½ ð ½ ð Þ& Þ&
Table 2
Comparison of the experimentally determined and calculated bond lengths (Å) and angles (L) for the trans-[Mo2O4Cl2(Py)2(HCOO)]– ion.

X-ray MPW1K M06 B3LYP

MoAMo 2.5483(6) 2.564 2.601 2.613
Mo@O 1.685(3), 1.686(3) 1.679 1.698 1.709
MoAO(l2) 1.921(3)–1.937(3) 1.921–1.953 1.937–1.979 1.945–1.984
O(l2)AMoAO(l2) 95.83(13), 95.92(13) 95.60, 95.62 95.38 95.18, 95.21
MoAO(l2)AMo 82.48(12), 82.78(12) 82.88 83.22 83.36
MoAO(formate) 2.290(3), 2.305(3) 2.320 2.360, 2.361 2.363, 2.365
MoAN(Py) 2.238(4), 2.253(4) 2.276, 2.277 2.307, 2.309 2.327
MoACl 2.454(1), 2.461(1) 2.452 2.469, 2.470 2.494
 B. Modec, D. Dolenc / Journal of Molecular Structure 1051 (2013) 354–360 357

Table 3
Comparison of the experimentally determined and calculated bond lengths (Å) and angles (L)
for the hydrogen-bonded PyH+ cis-[Mo2O4Cl2(Py)2(HCOO)]– ion-pair.

X-ray MPW1K
MoAMo 2.5639(4) 2.577
Mo@O 1.683(2) 1.669, 1.670
MoAO(l2) 1.931(2)–1.949(2) 1.936–1.964
O(l2)AMoAO(l2) 95.79(9), 96.20(9) 95.98, 96.11
MoAO(l2)AMo 82.32(8), 82.93(8) 82.01, 83.30
MoAO(formate) 2.273(2), 2.289(2) 2.293, 2.308
MoAN(Py) 2.233(3), 2.242(3) 2.239, 2.241
MoACl 2.4419(8), 2.4517(9) 2.443
N(PyH+) O(l2) 2.658(4) 2.481
CAH Cl 3.494(4), 3.569(4) 3.490, 3.494

Fig. 3. A view along the Mo@O bonds of trans-[Mo2O4Cl2(Py)2(HCOO)]–, highlight-ing a

trans disposition of pyridine ligands.
Fig. 1. (Py)2H+ cation in 1.

Fig. 2. ORTEP drawing of trans-[Mo2O4Cl2(Py)2(HCOO)]–, an anion of 1, with the Fig. 4. ORTEP drawing of cis-[Mo2O4Cl2(Py)2(HCOO)]–, an anion of 2, with the displacement
displacement ellipsoids drawn at the 30% probability level. ellipsoids drawn at the 30% probability level.

lies mainly in the trans influence of the molybdenyl moiety [1]. The sites
trans to the Mo@O moieties are occupied with formate oxy-gens. The
formate has engaged in coordination both oxygen atoms, it binded with each
to a different metal atom. The formate thereby serves as a third bridging
ligand between the two molybdenum atoms. Its presence is reflected in the
value of the dihedral angle between the two Mo(l2-O)2 planes. In 1, the
dihedral angle is 160.4(2)L, a value which is by ca. 10L larger than in
{Mo2O4}2+ spe-cies without a third bridging ligand [23]. The formate-to-
molybde-num bond lengths do not differ significantly, i.e., 2.290(3) vs.
2.305(3) Å. The distribution of pyridine or chloride ligands on the two metal
atoms is trans (Fig. 3). The overall symmetry of the anion approximates that
of C2 point group. The cis isomer of the [Mo2O4Cl2(Py)2(HCOO)]– complex
ion crystallizes as a pyridinium
salt in triclinic space group P 1. The ORTEP drawing of the complex anion of
cis-(PyH)[Mo2O4Cl2(Py)2(HCOO)] (2) is shown in Fig. 4, whereas Fig. 5
gives its projection along the Mo@O bonds. With the distribution of pyridine
ligands being cis, the anion has a virtual symmetry C s. Relevant geometric
parameters of the anions in 1 and 2 are given in Table 4. As for trans-
[Mo2O4Cl2(Py)2(HCOO)]– ion, no pronounced asymmetry in the formate-to-
molybdenum bonding
pattern could be observed for cis-[Mo2O4Cl2(Py)2(HCOO)]– ion, i.e.,
2.273(2) vs. 2.289(2) Å. However, some of the structural parameters of the
cis-[Mo2O4Cl2(Py)2(HCOO)]– ion are significantly different from the ones
determined for the trans isomer. The metal–metal bond is longer for the cis
isomer, i.e., 2.5639(4) Å vs. 2.5483(6) Å. The strength of the latter bond is
influenced mostly by the nature of the ligands which apart from the oxides
complete the metal’s coordination sphere. With both isomers containing the
same ligands, a difference of this magnitude is rather surprising. The
distances between the bridging oxides and molybdenum atoms in the cis
isomer are also longer than in the trans isomer.
The structures of trans-{(Py)2H}[Mo2O4Cl2(Py)2(HCOO)] (1) and cis-
(PyH)[Mo2O4Cl2(Py)2(HCOO)] (2) differ also in the intermolecular
interactions. In 2, an interaction of the formate hydrogen with the molybdenyl
oxide from an adjacent anion is observed, C(1) O(2) [x + 1, y, z] = 3.301(4) Å
[32]. As a result, the cis-[Mo2O4Cl2(Py)2(HCOO)]– anions are linked into
chains which propagate along the a-axis (Fig. 6). Surprisingly, no such
interaction exists in the solid state structure of trans-{(Py)2H}
[Mo2O4Cl2(Py)2(HCOO)] (1). Another apparent difference is that pyridinium
cations of 2 are hydrogen-bond donors whereas the
358 B. Modec, D. Dolenc / Journal of Molecular Structure 1051 (2013) 354–360

Fig. 5. A view along the Mo@O bonds of cis-[Mo2O4Cl2(Py)2(HCOO)]–, highlighting a cis

disposition of pyridine ligands.

Table 4
Relevant geometric parameters (Å, L) of the geometric isomers of the [Mo2O4Cl2(Py)2
(HCOO)]– anion.
Compound 1 Compound 2
Isomer trans cis
MoAMo 2.5483(6) 2.5639(4)
Fold anglea 160.4(2) 161.2(1)
Mo@O 1.685(3), 1.686(3) 1.683(2), 1.683(2)
MoAO(l2) 1.921(3)–1.937(3) 1.931(2)–1.949(2)
O(l2)AMoAO(l2) 95.83(13), 95.92(13) 95.79(9), 96.20(9)
MoAO(l2)AMo 82.48(12), 82.78(12) 82.32(8), 82.93(8)
MoACl 2.454(1), 2.461(1) 2.4419(8), 2.4517(9)
MoAN(Py) 2.238(4), 2.253(4) 2.233(3), 2.242(3)
MoAO(formate) 2.290(3), 2.305(3) 2.273(2), 2.289(2)
a
Defined as a dihedral angle between the two Mo(l2-O)2 planes.

Fig. 6. (a) A linkage of cis-[Mo2O4Cl2(Py)2(HCOO)]– anions in 2 via CAH (formate)

cations of 1, i.e., the (Py)2H+ ions, are not. Consequently, the pyridinium
cations in 2 are H-bonded to the anionic chains. Weak intermolecular
interactions which include also the p p stacking interactions between the
coordinated pyridine rings link the chains into a three-dimensional structure
which possesses channels running parallel to the a-axis. The solid state
structures of 1 is governed solely by the weak intermolecular interactions
which produce the following connectivity patterns: (i) the trans-
[Mo2O4Cl2(Py)2(HCOO)]– anions are linked with 6 adjacent ones to form
layers which are coplanar with the bc plane, and (ii) each layer is covered on
both sides with the (Py)2H+ cations (Fig. 7). It is of interest to note that the
interaction of the formate hydrogen with the molybdenyl oxide was observed
also in the solid state structures of both bromide compounds,
(PyH)3[Mo2O4Br4(HCOO)] 2CH3CN (3) and cis-
(PyH)[Mo2O4Br2(Py)2(HCOO)] (4). This interac-tion is particularly strong in
4, C(1) O(2) [ x + 0.5, y + 1, z–0.5] = 3.150(5) Å [33]. Similarly to the
structure of 2, the anions of (PyH)3[Mo2O4Br4(HCOO)] 2CH3CN (3) or cis-
(PyH)[Mo2O4Br2 (Py)2(HCOO)] (4) are linked into infinite chains with
pyridinium cations attached with hydrogen bonds to the bridging oxides
(compounds 3 and 4) and to the formate oxygens (3) (Figs. S1 and S2).
O(molybdenyl) interactions. (b) Pyridinium cations are H-bonded to these chains. (c) Weak
intermolecular interactions link the chains with the appended cations into a three-dimensional
structure with channels running parallel to the a-axis.
two protonated pyridine molecules, an acetonitrile solvent mole-cule and a
half of the [Mo2O4Br4(HCOO)]3– complex atom. The anion is located with
some of its atoms on the mirror plane. cis-(PyH)[Mo2O4Br2(Py)2(HCOO)]
(4) crystallizes in an orthorhom-bic space group P 212121 with both the
pyridinium cations and the cis-[Mo2O4Br2(Py)2(HCOO)]– complex anions
occupying the gen-eral positions. Relevant geometric parameters of the
anions in 3 and 4 are given in Table 5, whereas their ORTEP drawings are
given in Figs. S3 and S4. The metal–metal bond lengths are 2.5728(5) Å for
[Mo2O4Br4(HCOO)]3 and 2.5662(5) Å for cis-[Mo2O4Br2(Py)2 (HCOO)] .
The anion of 3 displays the longest metal–metal bond length. The explanation
lies in the absence of pyridine ligands which are electron-donating. On the
other hand, in species with pyridine ligands, as exemplified by cis-
[Mo2O4Br2(Py)2(HCOO)]–, the metal–metal bond lengths are shorter. The
anion of 3 also displays the longest formate-to-molybdenum bond lengths of
all four compounds.

(PyH)3[Mo2O4Br4(HCOO)] 2CH3CN (3) crystallizes in a mono-clinic It is to be noted that the structures of the two compounds con-taining the
space group P 21/m with the asymmetric unit containing cis isomers, cis-(PyH)[Mo2O4Cl2(Py)2(HCOO)] (2) and
 B. Modec, D. Dolenc / Journal of Molecular Structure 1051 (2013) 354–360 359

Table 6
Total energies of the geometric isomers of the [Mo2O4Cl2(Py)2(HCOO)]– ion.

Method Etot (Hartree) Etot(cis)–Etot(trans)

(kJ/mol)
cis trans

B3LYP/LACV3P + 2042.864622 2042.870183 +14.6

M06/LACV3P + 2042.105075 2042.110534 +14.3
MPW1K/LACV3P + 2042.425918 2042.431756 +15.3

Fig. 8. The PyH+ cis-[Mo2O4Cl2(Py)2(HCOO)]– synthon in 2, viewed along the Mo@O bond
vectors.

with other carboxylates are cis isomers [19,22]. The prevalence of the cis
isomeric form over the trans could speak of its greater sta-bility. We have
employed theory to get insight into this question. The density functional
theory calculations were carried out on the trans/cis geometric isomers of the
[Mo2O4Cl2(Py)2(HCOO)]– ion. Contrary to our expectations, all the
calculation methods show the trans isomer to be energetically more favored
than the cis iso-mer (Table 6). With such a small difference, ca. 15 kJ/mol,
both iso-mers are likely to persist in the solution. A certain isomeric form in
the gas phase and a crystalline compound containing the same spe-cies can be
Fig. 7. (a) Section of a layer of trans-[Mo2O4Cl2(Py)2(HCOO)]– anions in 1, viewed along a- differentiated by the intermolecular interactions which occur not only among
axis. (b) A layer with both of its sides covered with (Py)2H+ cations, a view along c-axis. ions of opposite charges but also among ions of the same type. When the
differences in the stabilities of the two free isomers are small, the determining
factor for the crystalliza-tion of either isomer are the crystal packing forces.
Table 5 With the change of the countercation, the intermolecular interactions change
Relevant geometric parameters (Å, L) of the bromide compounds, (PyH)3 [Mo2O4Br4(HCOO)] as well. All cis isomers, including the title compounds 2 and 4, are pyridinium
2CH3CN (3) and cis-(PyH)[Mo2O4Br2(Py)2(HCOO)] (4). salts [19,22]. Pyridinium cation as a good hydrogen-bond donor forms in all
Compound 3 Compound 4 compounds a hydrogen-bonding interaction with a doubly-bridging oxide
(Fig. 8). The resulting N O contact is typically around 2.70 Å and the
MoAMo 2.5728(5) 2.5662(5)
Fold anglea 157.18(9) 161.6(2)
orientation of pyridinium cation such that its ortho hydrogens participate in
Mo@O 1.674(3), 1.685(3) 1.679(3), 1.682(3) weak interactions with coordinated halides. The CAH Cl contacts in 2 are
MoAO(l2) 1.945(2), 1.951(2) 1.928(3)–1.966(3) 3.494(4) and 3.569(4) Å, and the CAH Br contacts in 4 are 3.478(5) and
O(l2)AMoAO(l2) 95.11(14), 95.47(14) 95.87(12), 96.27(12) 3.989(7) Å. Contacts of approximately the same length were observed for
MoAO(l2)AMo 82.66(10) 81.98(11), 83.23(11) other cis compounds [19,22]. It appears that the formation of the ion-pair
MoABr 2.6030(5), 2.6064(5) 2.6048(6), 2.6113(6)
MoAN(Py) – 2.237(3), 2.243(3) between the pyridinium cation and the [Mo2O4Cl2(Py)2(HCOO)]– ion is
MoAO(formate) 2.306(3) 2.262(3), 2.276(3) possible only if the disposi-tion of pyridine ligands is cis, whereas in the trans
a
Defined as a dihedral angle between the two Mo(l2-O)2 planes.
isomer the pyridine ligand could present a steric hindrance and therefore
make such an interaction less likely to take place. In order to confirm the
latter, the DFT calculations on the hydrogen-bonded PyH+
cis-(PyH)[Mo2O4Br2(Py)2(HCOO)] (4), are not isotypical. A closer [Mo2O4Cl2(Py)2(HCOO)]– ion-pairs were also performed. The results show
inspection reveals that the complex anions of 2 and 4 differ in the mutual the ion-pair with the cis disposition of pyridine rings in the
[Mo2O4Cl2(Py)2(HCOO)]– ion to be by 24 kJ/mol more stable than the one
orientation of coordinated pyridine ligands.
with the trans disposition. According to the
3.2. DFT calculations and theoretical considerations

With the exception of trans-{(Py)2H}[Mo2O4Cl2(Py)2(HCOO)] (1) all

previously isolated compounds containing the analogous anions
360 B. Modec, D. Dolenc / Journal of Molecular Structure 1051 (2013) 354–360
calculations, the interaction of pyridinium cation with the bridging oxide of
the trans-[Mo2O4Cl2(Py)2(HCOO)]– ion no longer produces the ion-pair.
Namely, the PyH+ proton has migrated to the bridging oxide and the resulting
pair is Py trans-[Mo2O3(OH)Cl2(Py)2 (HCOO)] with one CAH Cl interaction
(see Supporting informa-tion). However, the solid state structure of a PyH+
salt of a complex with a single pyridine ligand, i.e., [Mo2O4Cl3(Py)(Piv)]2–
(Piv– = pivalate) shows that pyridine ligand does not prevent the H-bonding
interaction of the l2-oxide with PyH+ ion [22]. Namely, in the latter
compound both l2-oxides are engaged in H-bonding with the N O contacts of
about 2.68 Å. Nevertheless, trans-[Mo2O4Cl2(Py)2(HCOO)]– ion does not
crystallize with pyridinium cations: it crystallizes with the (Py)2H+
countercations which can-not form hydrogen bonds. Another question to be
addressed is in what way the reaction conditions employed in the preparation
of the only trans isomer, i.e., compound 1, differ from all others. It is to be
noted that our reaction mixtures contain PyH+ cations in excessive amounts.
When the reaction is run in pure pyridine, as in the preparation of trans-
{(Py)2H}[Mo2O4Cl2(Py)2(HCOO)] (1), the PyH+ ions interact with pyridine
molecules to form the (Py)2H+ cations. On the other hand, the acetate
compound, cis-(PyH)[Mo2O4Cl2(Py)2(CH3COO)] Py, whose composition is
highly reminiscent to that of 1 and which was also isolated from pure
pyridine, shows that this is not always the case [19]. This example also speaks
in favor of the fact that the presence of PyH+ cations in the compound
imposes a restriction on the disposition of pyridine rings in the anion. cis-
(PyH)[Mo2O4Cl2(Py)2 (CH3COO)] Py, as confirmed by its X-ray analysis, is
a proper PyH+ salt with the cation H-bonded to the doubly-bridging oxide of
the cis-[Mo2O4Cl2(Py)2(CH3COO)]– ion and pyridine molecule of crys-
tallization trapped into the crystal lattice via weak interactions only.
The metal–metal bond length in cis-(PyH)[Mo2O4Cl2(Py)2 (HCOO)] (2)
merits further comment. It is noticeably longer than in trans-
{(Py)2H}[Mo2O4Cl2(Py)2(HCOO)] (1). It is known that bonding between the
molybdenum(V) centers of the {Mo2O4}2+ core occurs through r overlap of
the dxy orbitals [2]. In addition, the theoretical calculations have shown a
significant contribution from the bridging oxides [8,34]. The involvement of a
bridging oxide in hydrogen-bonding, as in the case of cis-(PyH)[Mo2O4Cl2
(Py)2(HCOO)] (2), probably diminishes the strength of the overall MoAMo
bonding.
3.3. Infrared spectroscopy
The masym(OCO) and msym(OCO) bands of the coordinated for-mate
ions appear in the spectra of compounds 1–4 at ca. 1560 and 1340 cm–1,
respectively. Their positions are in agreement with the literature data [35].
The spectra of trans-{(Py)2H}[Mo2O4Cl2 (Py)2(HCOO)] (1) and cis-
(PyH)[Mo2O4Cl2(Py)2(HCOO)] (2) are not the same: many pyridine-
associated bands are either split or have different intensities.
4. Conclusions
Reactions of molybdenum(V) starting materials with formate afforded
discrete dinuclear [Mo2O4Br4(HCOO)]3– and [Mo2O4X2(Py)2 (HCOO)]– (X
= Cl, Br) anionic species. In all, the carboxylate served as a third bridging
ligand in the {Mo2O4}2+ core. The [Mo2O4Cl2(Py)2 (HCOO)]– ion exhibited
the trans/cis geometric isomerism. The theoretical calculations on both
geometric isomers in the gas phase have shown the trans isomer to be more
stable. Hydrogen bonding and CAH Cl interactions with pyridinium cations in
the solid state stabilize the cis isomer. The higher thermodynamic stability of
the
+ cis – pair is in agreement with
PyH -[Mo2O4Cl2(Py)2(HCOO)] ion- +
the cis arrangement observed for all PyH salts of the homologous
[Mo2O4Cl2(Py)2(RCOO)]– (RCOO– = acetate, pivalate, hydrogen succi-nate)
ions.
Acknowledgment
The work was supported by the Slovenian Ministry of Educa-tion, Science
and Sport (Grant P1-0134).
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in the online
version, at http://dx.doi.org/10.1016/j.molstruc.2013. 08.009.
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