Solvatothermal chemistry of organically-templated vanadium fluorides and oxyfluorides

Article abstract of DOI:10.1016/j.ica.2009.09.053

The solvatothermal reactions of V₂O₅, the appropriate organoamine and HF in the temperature range 100-180 °C yielded a series of vanadium fluorides and oxyfluorides. The compounds [NH₄][H₃N(CH₂)₂NH₃][VF₆] (1) and [H₃N(CH₂)₂NH₃][VF₅(H₂O)] (2) contain mononuclear V(III) anions, while [H₃N(CH₂)₂NH₂(CH₂)₂NH₃]₂ [VF₅(H₂O)]₂[VOF₄(H₂O)] (3) exhibits both V(IV) and V(III) mononuclear anions. Both compound 4, [H₃NCH₂(C₆H₄)CH₂NH₃][VOF₄]·H₂O (4·H₂O) and compound 5, [HN(C₂H₄)₃NH][V₂O₂F₆ (H₂O)₂] (5) contain binuclear anions constructed from edge-sharing V(IV) octahedra. In contrast, [H₃N(CH₂)₂NH₂(CH₂)₂NH₃]₂[V₄O₄F₁₄(H₂O)₂], (6) exhibits a tetranuclear unit of edge- and corner-sharing V(IV) octahedra. Compound 7, [H₃N(CH₂)₂NH₂][VF₅], contains chains of corner-sharing {V^IVF₆} octahedra, while [H₂N(C₂H₄)₂NH₂]₃[V₄F₁₇O]·1.5H₂O (8·1.5H₂O) is two-dimensional with a layer of V(III) and V(IV) octahedra in an edge- and corner-sharing arrangement. In the case of [H₃N(CH₂)₂NH₃][V₂O₆] (9), there was no fluoride incorporation, and the {V₂ O₆}_n^{2 n -} anion is a one-dimensional chain of corner-sharing V(V) tetrahedra.

Full text of DOI:10.1016/j.ica.2009.09.053

Inorganica Chimica Acta 363 (2010) 1102–1113
Contents lists available at ScienceDirect
Inorganica Chimica Acta
journal homepage: www.elsevier.com/locate/ica
Solvatothermal chemistry of organically-templated vanadium fluorides
and oxyfluorides
Paul DeBurgomaster a, Wayne Ouellette a, Hongxue Liu b, Charles J. O’Connor b,
Gordon T. Yee c, Jon Zubieta a,
*
a Department of Chemistry, Syracuse University, Syracuse, NY 13244, USA
b Advanced Materials Research Institute, College of Sciences, University of New Orleans, New Orleans, LA 70148, USA
c Virginia Tech Chemistry Department, 107 Davidson Hall, Blacksburg, VA 24061-0001, USA
a r t i c l e i n f o
a b s t r a c t
Article history:
The solvatothermal reactions of V2O5, the appropriate organoamine and HF in the temperature range
100–180 °C yielded a series of vanadium fluorides and oxyfluorides. The compounds [NH4][H3N(CH2)2-
NH3][VF6] (1) and [H3N(CH2)2NH3][VF5(H2O)] (2) contain mononuclear V(III) anions, while [H3N
(CH2)2NH2(CH2)2NH3]2 [VF5(H2O)]2[VOF4(H2O)] (3) exhibits both V(IV) and V(III) mononuclear anions.
Both compound 4, [H3NCH2(C6H4)CH2NH3][VOF4]ꢀH2O (4ꢀH2O) and compound 5, [HN(C2H4)3NH][V2O2F6
(H2O)2] (5) contain binuclear anions constructed from edge-sharing V(IV) octahedra. In contrast,
[H3N(CH2)2NH2(CH2)2NH3]2[V4O4F14(H2O)2], (6) exhibits a tetranuclear unit of edge- and corner-sharing
V(IV) octahedra. Compound 7, [H3N(CH2)2NH2][VF5], contains chains of corner-sharing {VIVF6} octahedra,
while [H2N(C2H4)2NH2]3[V4F17O]ꢀ1.5H2O (8ꢀ1.5H2O) is two-dimensional with a layer of V(III) and V(IV)
octahedra in an edge- and corner-sharing arrangement. In the case of [H3N(CH2)2NH3][V2O6] (9), there
Received 23 June 2009
Accepted 13 September 2009
Available online 14 October 2009
Dedicated to Prof. Jonathan R. Dilworth
Keywords:
Vanadium fluorides
Vanadium oxyfluorides
Solvatothermal synthesis
2nꢁ
was no fluoride incorporation, and the fV2O6gn anion is a one-dimensional chain of corner-sharing
V(V) tetrahedra.
Ó 2009 Elsevier B.V. All rights reserved.
1. Introduction
erating an expansive structural chemistry, fluoride incorporation
also provides enhanced thermal stability of the oxide phases.
Hydrothermal reaction conditions afford a practical method for
the preparation of organic–inorganic hybrid materials, where the
inorganic substructure is modified by the introduction of organic
components as charge-compensating units and/or as conventional
ligands [1–9]. Under such conditions, it is also noted that at the
acidic pH range employed for metal oxide-based hybrids, fluoride
was essential to effect mineralization and to induce crystallization,
although fluoride was not present in the products [10]. However,
judicious modification of reaction conditions allows incorporation
of fluoride to produce oxyfluorinated materials, a phenomenon ini-
tially observed for the aluminum and gallium phosphates and
demonstrated to provide even more varied coordination types
[11,12]. More recently, fluoride incorporation into oxovanadium
and oxomolybdenum organophosphonates has been shown to re-
sult in considerable structural complexity and novelty [13–20].
For example the family of oxyfluorovanadates of the general type
{Cu2(bisterpy)}4+/VxOyFznꢁ/{O3P(CH2)nPO3}4ꢁ exhibits a range of V/
P/O/F building blocks such as embedded clusters, chains and net-
works and even three-dimensional frameworks. In addition to gen-
Metal oxyfluorides have also attracted considerable interest for
properties such as magnetism [21], catalysis [22] and non-linear
optical behavior [23]. Systematic studies of the vanadium oxyfluo-
rides by Lightfoot have revealed an extensive structural chemistry,
including oligomeric, chain and ladder building blocks [24–28].
However, as noted by this author and others [29–31], the complex-
ity of the hydrothermal reaction domain often results in unusual,
unprecedented and inconceivable structures, and it is certain that
many metal oxyfluoride structures remain to be discovered. Cer-
tainly, variations in temperature, pH, reactant stoichiometry, the
presence or absence of organic cations, and even the fill volume
can influence the product outcome.
In the course of our own investigations of the hydrothermal
chemistry of vanadium oxides in the presence of HF, we have
encountered numerous examples of vanadium oxyfluoride phases.
Herein, we report the structural chemistry of a number of vana-
dium fluoride and oxyfluoride materials: the mononuclear [NH4]
[H3N(CH2)2NH3][VF6] (1), [H3N(CH2)2NH3][VF5(H2O)] (2) and
[H3N(CH2)2NH2(CH2)2NH3]2[VF5(H2O)]2[VOF4(H2O)] (3), the binu-
clear [H3NCH2(C6H4)CH2NH3][VOF4]ꢀH2O (4ꢀH2O) and [H2NC6H12
-
NH2] [V2O2F6(H2O)2] (5), the tetranuclear [H3N(CH2)2NH2
(CH2)2NH3]2 [V4O4F14(H2O)2] (6), the one-dimensional [H3N(CH2)2-
NH2][VF5] (7) and the two-dimensional phase [H2NC4H8NH2]3
* Corresponding author. Tel.: +1 315 443 2547; fax: +1 315 443 4070.
E-mail address: jazubiet@syr.edu (J. Zubieta).
0020-1693/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2009.09.053

P. DeBurgomaster et al. / Inorganica Chimica Acta 363 (2010) 1102–1113
1103
[V3IIIVIVF17O]ꢀ1.5H2O (8ꢀ1.5H2O). The structure of the one-dimen-
sional vanadium oxide [H3N(CH2)2NH3][V2O6] (9) is also reported.
The magnetic properties of selected phases are discussed.
1508(m), 1055(m), 966(m), 843(w), 533(m). Anal. calc. for
C2H14F6N3V: C, 9.88; H, 5.76; N, 17.3. Found: C, 9.68; H, 5.53; N,
17.1%.
2. Experimental
2.1.2. Synthesis of [H3N(CH2)2NH3][VIIIF5(H2O)] (2)
A
solution of V2O5 (0.159 g, 0.87 mmol), ethylenediamine
2.1. General considerations
(0.240 mL, 4.05 mmol), H2O (2.50 mL, 138.73 mmol), ethanol
(2.50 mL, 42.80 mmol), and HF (1.20 mL, 34.80 mmol) in the mole
ratio 1.00:4.66:159.43:49.19:40.00 was stirred briefly before heat-
ing to 180 °C for 5 days (initial and final pH value of 1.5 and 1.5,
respectively). Light green needles of 2 were isolated in 10% yield.
IR (KBr pellet, cmꢁ1): 3421(s), 3248(s), 2931(w), 1618 (m),
1508(m), 1055(m), 966(w), 844(w), 533(w). Anal. calc. for
C2H12F5N2OV: C, 10.6; H, 5.31; N, 12.4. Found: C, 10.9; H, 5.45;
N, 12.2%.
All chemicals were used as obtained without further purifica-
tion: vanadium(V) oxide, ethylene diamine, piperazine, diethylene
triamine, triethylene diamine, para-xylylene diamine, piperazine,
ethylene glycol, ethanol, and hydrofluoric acid (48–51%) were pur-
chased from Aldrich. All syntheses were carried out in 23 mL
poly(tetrafluoroethylene) lined stainless steel containers under
autogeneous pressure. The reactants were stirred briefly and initial
pH was measured before heating. Water was distilled above
3.0 M
X in-house using a Barnstead Model 525 Biopure Distilled
2.1.3. Synthesis of [H3N(CH2)2NH2(CH2)2NH3]2[VIIIF5(H2O)]2
[VIVOF4(H2O)] (3)
Water Center. The reactions initial and final pH was measured
using Hydrion pH sticks.
A mixture of V2O5 (0.160 g, 0.88 mmol), diethylenetriamine
(0.192 mL,1.78 mmol), H2O (2.00 mL, 110.99 mmol), ethylene gly-
col (5.00 mL, 89.68 mmol) and HF (0.400 mL, 11.60 mmol) in the
mole ratio 1.00:2.02:126.13:101.91:13.81 was stirred briefly be-
fore heating to 150 °C for 48 h. Initial and final pH values of 3.0
and 3.0, respectively, were recorded. Green crystals of 3 suitable
for X-ray diffraction were isolated in 60% yield. IR (KBr pellet,
cmꢁ1): 3239(s), 2944(m), 1610(m), 1509(m), 1453(w), 1050(m),
2.1.1. Synthesis of [NH4][H3N(CH2)2NH3][VIIIF6] (1)
A solution of V2O5 (0.161 g, 0.885 mmol), ethylenediamine
(0.240 mL, 3.59 mmol), ethanol (5 mL, 185.59 mmol), and HF
(0.200 mL, 5.80 mmol) in the mole ratio 1.00:4.05:209.70:6.55
was heated to 150 °C for 4 days (initial and final pH value of 5.0
and 5.0, respectively). Green blocks of 1 were isolated in 5% yield.
IR (KBr pellet, cmꢁ1): 3421(s), 3247(m), 2931(w), 1560(m),
Table 1
Summary of crystallographic data for the structures of [NH4][H3N(CH2)2NH3][VF6] (1), [H3N(CH2)2NH3][VF5(H2O)] (2), [H3N(CH2)2NH2(CH2)2NH3]2[VF5(H2O)]2[VOF4(H2O)] (3),
[H3NCH2(C6H4)CH2NH3][VOF4]ꢀH2O (4ꢀH2O), [HN(C2H4)3NH][V2O2F6(H2O)2] (5), [H3N(CH2)2NH2(CH2)2NH3]2[V4O4F14(H2O)2] (6), [H3N(CH2)2NH2][VF5] (7), [H2N(C2H4)2NH2]3-
[V4F17O]ꢀ1.5H2O (8ꢀ1.5H2O) and [H3N(CH2)2NH3][V2O6] (9).
1
2
3
4
5
Empirical formula
Formula weight
Crystal system
Space group
a (Å)
C2H14F6N3V
245.10
monoclinic
P21/c
11.676(2)
10.125(2)
14.507(3)
90.
C2H12F5N2OV
226.08
monoclinic
C2/c
12.2147(10)
12.9834(11)
10.4855(9)
90.
C8H38F14N6O4V3
701.26
monoclinic
P21/c
9.4050(5)
20.6986(11)
13.1142(7)
90.
C8H16F4N2O2V
299.17
monoclinic
P21/c
11.3790(6)
12.1694(6)
8.8454(5)
90.
C3H9F3NO2V
199.05
monoclinic
P21/c
7.0857(8)
7.2338(8)
12.9537(14)
90.
b (Å)
c (Å)
a
(°)
b (°)
90.93(3)
90.
1714.7(6)
8
1.899
1.213
106.007(2)
90.
1598.4(2)
8
1.879
1.281
100.5020(10)
90.
2510.2(2)
4
1.856
1.225
111.9130(10)
90.
1136.38(10)
4
1.749
0.919
99.127(2)
90.
655.56(13)
4
2.017
1.513
c
(°)
V (Å3)
Z
Dcalc (g cmꢁ3
)
l
(mmꢁ1
)
T (K)
90(2)
90(2)
90(2)
90(2)
90(2)
Wavelength (Å)
R1
wR2
0.71073
0.0916
0.1807
6
0.71073
0.0558
0.1018
0.71073
0.0694
0.1326
0.71073
0.0589
0.1337
0.71073
0.0398
0.1064
9
7
8
Empirical formula
Formula weight
Crystal system
Space group
a (Å)
C4H18F7N3O3V2
C2H9F5N2V
207.04
orthorhombic
Pnma
10.5231(9)
5.7185(5)
10.1319(8)
90
C12H39F17N6O2.50V4
837.25
monoclinic
P2/c
16.8083(10)
13.5767(8)
12.7430(7)
90
CH5NO3V
130.00
monoclinic
P21/c
5.5430(5)
12.6715(12)
5.7127(5)
90
391.09
monoclinic
P21/n
11.7636(8)
10.2859(7)
11.8956(8)
90
b (Å)
c (Å)
a
(°)
b (°)
90
90
90
90
609.70(9)
4
2.255
107.9370(10)
90
2766.6(3)
4
2.010
1.454
97.890(2)
90
397.45(6)
4
2.173
2.347
c
(°)
V (Å3)
1287.06(15)
4
2.018
Z
Dcalc (g cmꢁ3
)
l
(mmꢁ1
)
1.546
1.656
T (K)
90(2)
90(2)
90(2)
90(2)
Wavelength (Å)
R1
wR2
0.71073
0.0287
0.0667
0.71073
0.0414
0.1025
0.71073
0.0682
0.1377
0.71073
0.0269
0.0664

1104
P. DeBurgomaster et al. / Inorganica Chimica Acta 363 (2010) 1102–1113
Table 2 (continued)
Table 2
Selected bond lengths (Å) and angles (°) for the compounds of this study.
Compound 7
V(1)–F(1)#4
V(1)–F(1)
V(1)–F(2)
V(1)–F(4)
1.760(2)
1.760(2)
1.915(3)
1.916(2)
2.1317(5)
2.1317(5)
3.42
F(2)–V(1)–F(4)
165.03(11)
171.46(8)
171.46(8)
180.0
Compound 1
F(1)–V(1)–F(3)#5
F(1)#1–V(1)–F(3)
V(1)–F(3)–V(1)#6
V(1)–F(6)
V(1)–F(5)
V(1)–F(4)
V(1)–F(2)
V(1)–F(1)
PV(1)–F(3)
1.821(4)
1.899(4)
1.947(3)
1.951(4)
1.962(4)
1.963(4)
3.15
1.829(4)
1.884(4)
1.946(4)
1.951(4)
1.976(4)
1.982(3)
3.12
F(4)–V(1)–F(2)
F(6)–V(1)–F(1)
F(5)–V(1)–F(3)
F(8)–V(2)–F(10)
F(9)–V(2)–F(11)
F(7)–V(2)–F(12)
176.11(15)
178.20(18)
173.48(17)
170.70(17)
173.32(16)
179.29(17)
V(1)–F(3)#5
PV(1)–F(3)
sij
Compound 8
sij
V(1)–O(1)
V(1)–F(4)
V(1)–F(1)
V(1)–F(3)
V(1)–F(6)
V(1)–F(5)
1.704(3)
1.900(3)
1.911(3)
1.9575(7)
2.028(2)
2.142(2)
3.87
1.857(3)
1.895(2)
1.925(2)
1.954(2)
1.964(2)
2.010(2)
3.06
1.862(2)
1.871(2)
1.911(2)
1.990(2)
1.998(2)
2.019(2)
3.02
1.906(2)
1.913(3)
1.916(2)
1.924(3)
1.963(2)
1.9876(11)
3.04
F(4)–V(1)–F(1)
F(3)–V(1)–F(6)
F(2)–V(1)–F(5)
F(7)–V(2)–F(8)
F(5)–V(2)–F(14)
F(9)–V(2)–F(6)
F(13)–V(3)–F(10)
F(11)–V(3)–F(12)#7
F(9)–V(3)–F(12)
F(16)–V(4)–F(19)
F(17)–V(4)–F(14)
F(18)–V(4)–F(15)
V(1)#2–F(3)–V(1)
V(2)–F(5)–V(1)
V(2)-F(6)–V(1)
V(2)–F(9)–V(3)
V(3)#1–F(12)–V(3)
V(2)–F(14)–V(4)
V(4)#3–F(15)–V(4)
165.85(12)
167.01(8)
169.55(12)
170.17(12)
169.59(11)
173.25(10)
172.77(11)
173.06(10)
175.84(11)
178.27(11)
175.38(11)
176.45(11)
178.6(2)
101.32(10)
102.43(10)
148.32(14)
102.15(10)
156.93(15)
152.4(2)
V(2)–F(7)
V(2)–F(8)
V(2)–F(9)
V(2)–F(10)
V(2)–F(11)
V(2)–F(12)
P
sij
P
sij
V(2)–F(7)
V(2)–F(8)
V(2)–F(5)
V(2)–F(14)
V(2)–F(9)
V(2)–F(6)
Compound 2
V(1)–F(4)
V(1)–F(3)
V(1)–F(1)
V(1)–F(2)
V(1)–F(5)
V(1)–O(90)
1.839(2)
1.9181(19)
1.9219(19)
1.942(2)
1.9679(19)
2.068(2)
3.11
F(3)–V(1)–F(1)
F(4)–V(1)–F(2)
F(5)–V(1)–O(90)
174.08(9)
176.31(10)
177.83(10)
P
sij
V(3)–F(11)
V(3)–F(13)
V(3)–F(10)
V(3)–F(9)
P
sij
Compound 3
V(1)–F(4)
V(1)–F(5)
V(1)–F(1)
V(1)–F(3)
V(1)–F(2)
V(1)–O(90)
1.761(3)
1.832(2)
1.890(2)
1.942(2)
1.960(2)
2.145(3)
3.37
1.757(3)
1.853(3)
1.924(2)
1.926(2)
2.017(2)
2.038(3)
3.37
1.619(3)
1.913(2)
1.940(2)
1.947(2)
2.051(3)
2.070(2)
3.92
F(1)–V(1)–F(3)
F(4)–V(1)–F(2)
F(5)–V(1)–O(90)
F(6)–V(2)–F(8)
F(9)–V(2)–F(7)
F(10)–V(2)–O(91)
F(13)–V(3)–F(11)
F(14)–V(3)–O(92)
O(1)–V(3)–F(12)
172.06(10)
171.14(12)
173.96(12)
172.40(11)
175.97(11)
172.19(13)
163.80(12)
168.84(11)
176.03(13)
V(3)–F(12)#7
V(3)–F(12)
P
sij
V(4)–F(16)
V(4)–F(19)
V(4)–F(17)
V(4)–F(18)
V(4)–F(14)
V(4)–F(15)
P
sij
V(2)–F(9)
V(2)–F(6)
V(2)–F(8)
V(2)–F(10)
V(2)–F(7)
V(2)–O(91)
P
sij
Compound 9
V(1)–O(3)
1.6452(16)
1.6457(15)
1.8057(15)
1.8079(15)
4.68
O(3)–V(1)–O(1)
O(3)–V(1)–O(2)#8
O(1)–V(1)–O(2)#8
O(3)–V(1)–O(2)
O(1)–V(1)–O(2)
O(2)#1–V(1)–O(2)
V(1)#2–O(2)–V(1)
109.41(8)
110.66(7)
107.33(8)
110.11(7)
111.36(7)
107.93(5)
132.52(9)
P
V(1)–O(1)
sij
V(3)–O(1)
V(3)–F(13)
V(3)–F(14)
V(3)–F(11)
V(3)–O(92)
V(3)–F(12)
V(1)–O(2)#8
V(1)–O(2)
P
sij
P
Symmetry transformations used to generate equivalent atoms: #1 ꢁx,ꢁy,ꢁz + 2; #2
ꢁx,ꢁy,ꢁz + 1; #3 ꢁx + 1,ꢁy + 2,ꢁz; #4 x,ꢁy + 1/2,z; #5 ꢁx + 1,y + 1/2,ꢁz + 1; #6
ꢁx + 1,ꢁy,ꢁz + 1; #7 ꢁx + 1,y,ꢁz + 3/2; #8 x,ꢁy + 3/2,z + 1/2; #9 x,ꢁy + 3/2,zꢁ1/2.
sij
Compound 4
V(1)–O(1)
V(1)–F(4)
V(1)–F(3)
V(1)–F(1)
V(1)–F(2)#1
V(1)–F(2)
1.598(2)
F(4)–V(1)–F(1)
F(3)–V(1)–F(2)#1
O(1)–V(1)–F(2)
165.01(8)
157.62(8)
173.27(10)
1.9275(19)
1.9440(19)
1.9475(19)
1.9765(18)
2.2139(18)
3.84
966(m), 520(m), 489(m). Anal. calc. for C8H38F14N6O4V3: C, 13.7; H,
5.42; N, 12.0. Found: C, 13.4; H, 5.21; N, 12.3%.
P
sij
2.1.4. Synthesis of [H3NCH2(C6H4)CH2NH3][VIVOF4]ꢀ1H2O (4)
A solution of V2O5 (0.161 g, 0.89 mmol), para-xylylenediamine
(0.244 g, 1.79 mmol), H2O (2.00 mL, 110.99 mmol), ethylene glycol
(5.00 mL, 89.68 mmol), and HF (0.300 mL, 8.70 mmol) in the mole
ratio 1.00:2.01:124.71:100.76:9.78 was heated at 135 °C for 48 h
(initial and final pH values of 3.5 and 3.0, respectively). Blue plates
of 4 were isolated in 40% yield. IR (KBr pellet, cmꢁ1): 3239(s),
2944(m), 1611(m), 1509(m), 1453(w), 1050(m), 966(m), 843(w),
520(m), 489(m). Anal. calc. for C8H16F4N2O2V: C, 32.1; H, 5.35; N,
9.36. Found: C, 32.4; H, 5.21; N, 9.25%.
Compound 5
V(1)–O(1)
V(1)–F(1)
V(1)–F(3)
V(1)–F(2)
1.617(2)
F(1)–V(1)–F(3)
163.85(7)
101.06(10)
161.75(8)
171.01(9)
1.9209(17)
1.9347(16)
1.9601(16)
2.034(2)
2.1422(16)
4.23
O(1)–V(1)–O(90)
F(2)–V(1)–O(90)
O(1)–V(1)–F(2)#1
V(1)–O(90)
V(1)–F(2)#2
P
sij
Compound 6
V(1)–O(1)
V(1)–F(3)
V(1)–F(2)
V(1)–F(1)
V(1)–O(90)
V(1)–F(4)
1.6202(13)
1.9089(12)
1.9229(12)
1.9304(12)
2.0370(15)
2.1230(11)
3.94
1.6080(14)
1.9309(11)
1.9429(11)
1.9473(11)
1.9579(11)
2.1825(11)
3.84
F(3)–V(1)–F(2)
O(1)–V(1)–F(1)
F(1)–V(1)–O(90)
O(1)–V(1)–F(4)
F(5)–V(2)–F(7)#3
O(2)–V(2)–F(7)
V(2)–F(4)–V(1)
V(2)#1–F(7)–V(2)
165.95(5)
100.65(6)
165.91(6)
171.63(6)
155.58(5)
173.22(6)
142.16(6)
106.82(5)
2.1.5. Synthesis of [HN(C2H4)3NH][VIV2O2F6(H2O)2] (5)
A solution of V2O5 (0.162 g, 0.89 mmol), diaminobicyclooctane
(DABCO) (0.197 g, 1.76 mmol), H2O (2.0 mL, 110.99 mmol), ethyl-
ene glycol (5.0 mL, 89.68 mmol) and HF (0.400 mL, 11.60 mmol)
with the mole ratio 1.00:1.98:124.71:100.76:13.03 was stirred
briefly before heating to 150 °C for 48 h (initial and final pH values
of 2.0 and 2.0, respectively). Blue crystals of 5 were isolated in 25%
yield. IR (KBr pellet, cmꢁ1): 3239(s), 2944(m), 1611(m), 1509(s),
P
sij
V(2)–O(2)
V(2)–F(5)
V(2)–F(4)
V(2)–F(7)#3
V(2)–F(6)
V(2)–F(7)
P
sij

P. DeBurgomaster et al. / Inorganica Chimica Acta 363 (2010) 1102–1113
1105
1050(m), 966(s), 843(w), 520(s), 489(s). Anal. calc. for C3H9F3NO2V:
C, 18.1; H, 4.52; N, 7.04. Found: C, 18.3; H, 4.46; N, 7.11%.
isolated in 60% yield. IR (KBr pellet, cmꢁ1): 3239(s), 2944(m),
1611(m), 1508(m), 1050(m), 966(s), 843(w), 521(s), 489(s). Anal.
calc. for C2H9F5N2V: C, 11.6; H, 4.34; N, 13.5. Found: C, 11.8; H,
4.22; N, 13.3%.
2.1.6. Synthesis of [H3N(CH2)2NH2(CH2)2NH3]2[VIV4O4F14(H2O)2] (6)
A solution of V2O5 (0.160 g, 0.88 mmol), diethylenetriamine
(0.192 mL, 1.78 mmol), H2O (2.00 g, 110.99 mmol), ethylene glycol
(5.00 mL, 89.68 mmol) and HF (0.400 mL, 11.60 mmol) in the mole
ratio 1.00:2.02:126.13:101.91:13.81 was stirred briefly before
heating to 100 °C for 48 h (initial and final pH values of 3.0 and
3.0, respectively). Blue crystals of 6 suitable for X-ray diffraction
were isolated in 15% yield. IR (KBr pellet, cmꢁ1): 3239(s),
2944(m), 1611(m), 1509(m), 1453(w), 1050(m), 966(m), 520(m),
489(m). Anal. calc. for C4H18F7N3O3V2: C, 12.3; H, 4.60; N, 10.7.
Found: C, 12.5; H, 4.48; N, 10.4%.
2.1.8. Synthesis of [H2NC4H8NH2]3[V4F17O]ꢀ1.5 H2O (8)
A mixture of V2O5 (0.181 g, 1.00 mmol), piperazine (0.283 g,
3.28 mmol), H2O (2.00 mL, 110.99 mmol), ethylene glycol (5.00
mL, 89.68 mmol) and HF (0.800 mL, 23.20 mmol) in the mole ratio
1.00:3.28:110.99:89.68:23.20 was stirred briefly before heating to
150 °C for 48 h (initial and final pH values of 2.0 and 1.5, respec-
tively). Brown blocks of 8 suitable for X-ray diffraction were iso-
lated in 80% yield. IR (KBr pellet, cmꢁ1): 3239(s), 2944(m),
1611(m), 1509(s), 1050(m), 966(s), 843(w), 520(s), 489(s). Anal.
calc. for C12H39F17N6O2.5V4: C, 17.3; H, 4.68; N, 10.1. Found: C,
17.6; H, 4.78; N, 9.84%.
2.1.7. Synthesis of [H3N(CH2)2NH2][VIVF5] (7)
A solution of V2O5 (0.158 g, .87 mmol), ethylenediamine (0.240
mL, 4.05 mmol), H2O (2.50 mL, 138.73 mmol), ethanol (2.5 mL,
42.80 mmol) and HF (0.200 mL, 5.8 mmol) in the mole ratio
1.00:4.50:159.46:49.20:6.67 was heated to 120 °C for 60 h (initial
and final pH values of 5.0 and 4.5, respectively). Blue rods of 7 were
2.1.9. Synthesis of [H3N(CH2)2NH3][VV2O6] (9)
A
solution of V2O5 (0.163 g, .90 mmol), ethylenediamine
(0.240 mL, 4.05 mmol), H2O (5.0 mL, 277.47 mmol), and HF
(0.100 mL, 2.90 mmol) in the mole ratio 1.00:4.50:308.30:3.22
Fig. 1. (a) Polyhedral and ball and stick representation of the hydrogen-bonding interactions between the {VF6}3ꢁ anions and the {H3NC2H4NH3}2+ and NH4+ cations of 1. (b)
Hydrogen-bonding interactions between the {VF5(H2O)}2ꢁ octahedra and the {H3NC2H4NH3}2+ cations of 2. Colour scheme: vanadium, orange polyhedra; carbon, black
spheres; nitrogen, blue spheres; hydrogen, pink spheres; fluorine, green spheres; oxygen, red spheres; coordinated water, red spheres with black outline. This colour scheme
is used throughout the figures. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

1106
P. DeBurgomaster et al. / Inorganica Chimica Acta 363 (2010) 1102–1113
Fig. 2. Polyhedral representation of the {VF4O(H2O)}2ꢁ and {VF5(H2O)}2ꢁ anions and ball and stick representation of the {H3N(CH2)2NH2(CH2)2NH3}3+ cations of 3.
was stirred briefly before heating to 100 °C for 48 h (initial and
final pH values of 6 and 5.5, respectively). Brown blocks of 9
were isolated in 5% yield. IR (KBr pellet, cmꢁ1): 3421(s),
3248(m), 2931(w), 1509(m), 1498(m), 1054(m), 966(w),
844(w), 533(m).
2.2. X-ray crystallography
X-ray measurements were performed on a Bruker-AXS SMART-
CCD diffractometer at low temperature (90 K) using graphite-mono-
chromated Mo Ka radiation (kMo K = 0.71073 Å) [32]. The data were
a
Table 3
Selected structural characteristics of vanadium fluorides and oxyfluorides.
Chemical formula
Dimensionality
Structural unit
Ox. state
Reference
Na3VOF5
Na2VOF5
Cs2VOF4(H2O)
Cs2VF6
[NH4]3[VO2F4]
Na3VF6
K2VF5(H2O)
RbVF4(H2O)2
[C6N4H22][VOF4(H2O)]2ꢀH2O
[NH4][H3N(CH2)2NH3][VF6] (1)
[H3N(CH2)2NH3][VF5(H2O)] (2)
[H3N(CH2)2NH2(CH2)2NH3]2[VF5(H2O)]2[VF4O(H2O)] (3)
(NMe4)3V2F9
molecular
molecular
molecular
molecular
molecular
molecular
molecular
molecular
molecular
molecular
molecular
molecular
molecular
molecular
molecular
molecular
molecular
molecular
molecular
molecular
molecular
molecular
molecular
molecular
molecular
molecular
molecular
molecular
Molecular cluster
Molecular cluster
1-D
monomer
monomer
trans-monomer
monomer
cis-monomer
monomer
monomer
trans-monomer
monomer
monomer
monomer
monomer
binuclear, face-sharing octahedra
binuclear, face-sharing octahedra
binuclear, face-sharing octahedra
binuclear, edge-sharing octahedra (axial H2O)
binuclear, edge-sharing octahedra (F bridge)
binuclear, edge-sharing octahedra (F bridge)
binuclear, edge-sharing octahedra (F bridge)
binuclear, edge-sharing octahedra (F bridge)
binuclear, corner-sharing octahedra (F bridge)
binuclear, corner-sharing octahedra (F bridge)
trinuclear, corner-sharing octahedra (F bridge)
tetranuclear, corner-sharing octahedra
IV
V
IV
IV
V
III
III
III
IV
III
III
III/IV
III
IV
V
IV
IV
IV
IV
IV
V
V
V
V
IV
IV
III/IV
IV
IV/V
IV/V
III
III/IV
III
[51]
[52]
[46]
[43]
[53]
[54]
[45]
[55]
[27]
this work
this work
this work
[56]
[57]
[56]
[47]
[27]
[27]
this work
this work
[58]
[58]
[58]
[59]
[27]
[27]
[26]
this work
[60]
[42]
[25]
[26]
[26]
this work
this work
Cs3V2O2F7
[NH4]3[V2O4F5]
[NMe4]2[V2O2F6(H2O)2]
[C6N2H14][V2O2F6(H2O)2]
[C6N4H22][V2O2F8]
[H3NCH2(C6H4)CH2NH3][VF4O]ꢀH2O (4)
[HN(C2H4)3NH][V2F6O2(H2O)2] (5)
[NMe4]Cs[V2O2F8(H2O)]
K2[NMe4][V2O2F9]
Na[NMe4]2[V3O3F12
Ba3V2O4F8
]
[C6N4H21]2[V4O4F14]ꢀ3H2O
tetranuclear, edge- and corner-sharing octahedra
tetranuclear, edge- and corner-sharing octahedra
tetranuclear, edge- and corner-sharing octahedra
tetranuclear, edge- and corner-sharing octahedra (F bridges)
polyanion [H6V12O30F2]6ꢁ
[C6N3H20][V4O4F14]0.5ꢀH2O
[C4N2H12]4[V4O3F17]ꢀ4H2O
[H3N(CH2)2NH2(CH2)2NH3]2[V4F14O4(H2O)]2 (6)
Na6[H6V12O30F2]ꢀ22H2O
[H3N(C2H4)nNH3]4[V14O36F4]
polyanion [V14O36F4]8ꢁ
chain of corner-sharing octahedra (F bridges)
chain of edge- and corner-sharing octahedra
chain of corner-sharing octahedra
chain of corner-sharing octahedra (F bridges)
layer of edge- and corner-sharing octahedra (F bridges)
[C4H12N2]3[V7F27
]
[C4N2H12]4[V5O3F20]ꢀ2H2O
1-D
1-D
1-D
2-D
[C4N2H12][VF5]ꢀH2O
[H3N(CH2)2NH2][VF5] (7)
[H2NC4H8NH2]3[V4F17O]ꢀ1.5 H2O (8)
IV
III/IV

P. DeBurgomaster et al. / Inorganica Chimica Acta 363 (2010) 1102–1113
1107
Table 4
of magnetization as a function of temperature were performed
from 5 to 300 K and in a 5000 G field. The samples were prepared
by packing ꢂ15 mg between cotton plugs in a gelatin capsule,
cooled in zero applied field, and measured upon warming. Diamag-
netic corrections were applied on the basis of Pascal’s constants.
The data were corrected for the diamagnetism of the sample
holder. For compounds 5 and 6, magnetic data were recorded on
50.6 and 56.2 mg samples, respectively, in the 2–300 K tempera-
ture range using a Quantum Design MPMS-XL-7 SQUID spectrom-
eter. Calibrating and operating procedures have been reported
previously [36]. The temperature dependent data were obtained
at a magnetic field of H = 1000 Oe after zero field cooling.
Summary of Curie–Weiss parameters for the magnetic susceptibilities of compounds
4–7.
Compound
Vanadium sites
g
h (K)
4
5
6
7
2 ꢃ V(IV)
2 ꢃ V(IV)
4 ꢃ V(IV)
V(IV)
1.99
2.10
2.03
2.06
ꢂ0.0
ꢁ1.9
ꢂ0.0
ꢁ8.9
corrected for Lorentz and polarization effects and absorption using
SADABS [33]. The structures were solved by direct methods. All
non-hydrogen atoms were refined anisotropically. After all of the
non-hydrogen atoms were located, the model was refined against
F2, initially using isotropic and later anisotropic thermal displace-
ment parameters. Hydrogen atoms were introduced in calculated
positions and refined isotropically. Neutral atom scattering coeffi-
cients and anomalous dispersion corrections were taken from the
International Tables, Vol. C. All calculations were performed using
SHELXTL crystallographic software packages [34,35]. The crystallo-
graphic details for the X-ray crystallographic studies of compounds
1–9 are summarized in Table 1. Selected bond lengths and angles for
the compounds of this study are given in Table 2.
3. Results and discussion
The vanadium fluorides and oxyfluorides of this study were pre-
pared by conventional hydrothermal methods [37–40], which pro-
vide suitable conditions for solubilizing and crystallizing organic/
inorganic hybrid materials [41]. The reaction mixtures consisted
of a vanadate source, an organoammonium cation and HF with
reaction times of 48–120 h at temperatures of 100–180 °C. While
HF is generally introduced into hydrothermal reactions as a miner-
alizer to promote solubility and crystal growth and not as a compo-
nent of the final product, fluorinated and oxyfluorinated products
have been reported for hybrid materials of both vanadium and
molybdenum oxides [13–20,42]. In these studies, it was observed
2.3. Magnetic susceptibilities
Magnetically susceptibility measurements were performed on a
7 T Quantum Design MPMS SQUID magnetometer. Measurements
Fig. 3. Polyhedral view of the {V2F8O2}4ꢁ dimer of 4 and its hydrogen-bonding interactions with the {H3NCH2(C6H4)CH2NH3}2+ cations.

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P. DeBurgomaster et al. / Inorganica Chimica Acta 363 (2010) 1102–1113
Fig. 4. Mixed polyhedral and ball and stick representation of the {V2F6O2(H2O)2}2ꢁ anion and {HN(C2H4)3NH}2+ cations of 5.
6ꢁ
Fig. 5. A polyhedral representation of the fV4F14O4ðH2OÞg2 cluster of 6 and its hydrogen-bonding interactions with the {H3N(CH2)2NH2(CH2)2NH3}3+ cations.
that fluoride incorporation depended on the HF/V molar ratio, with
increased molar ratios favoring fluoride uptake into the product.
It is also noteworthy that although V(V) starting materials were
used exclusively, the products contained reduced vanadium. Thus,
compounds 4, 5, 6, and 7 contain only V(IV) and compounds 1 and
2 are V(III) materials while compounds 3 and 8 are mixed valence
V(III)/V(IV) species. Reduction of vanadium in the presence of
nitrogenous compounds under hydrothermal conditions is not
unusual. However, reduction from V(V) to V(III) generally occurs
only in the presence of HF and most commonly with excess fluo-
ride and concomitant fluoride incorporation.
The structural characteristics of the compounds of this study
and related vanadium fluorides and oxyfluorides are summarized
in Table 3. The structures of compounds 1–6 consist of discrete
molecular cations and anions. As shown in Fig. 1a, the structure
of 1 consists of distorted octahedral V(IV) sites with V–F distances
in the range 1.821(4)–1.982(3) Å, hydrogen-bonded to the
ethylenediammonium cations. The metrical parameters for the

P. DeBurgomaster et al. / Inorganica Chimica Acta 363 (2010) 1102–1113
1109
2nꢁ
Fig. 6. Polyhedral view of the fVF5gn chain of 7.
{VF6}2- anion are similar to those previously reported for Na3VF6
[54].
[NMe4]2[V2O2F6(H2O)2] [47] and [H3N(CH2)2NH2(CH2)2NH2(CH2)2-
NH3] [V2O2F6(H2O)2] [27]. Curiously, in both cases, the aqua
ligand adopts an axial orientation rather than the equatorial
position of 5.
As shown in Fig. 5, the structure of 6 contains discrete
[H3N(CH2)2NH2(CH2)2NH3]3+ cations and [V4O4F14(H2O)2]6ꢁ an-
ions. The structure of the anion consists of a chain of corner- and
edge-sharing V(IV) octahedra. The central pair of octahedra are
fused along a common edge through bridging fluorides. Each cen-
tral vanadium site in turn corner-shares with a terminal vanadium
The structure of the anion of [H3N(CH2)2NH3][VF5(H2O)] (2) is
shown in Fig. 1b. The vanadium is in the +3 oxidation, as confirmed
by valence sum calculations [44]. The V–F bond distances in the
VF4 plane are in the range 1.839(2)–1.942(2) Å, while that trans
to the aqua ligand is 1.968(2)Å, indicative of a weak trans influence.
There is hydrogen-bonding between the fluorine ligands and the
ethylenediammonium cations. The structure of the anion is com-
parable to those previously reported for K2[VF5(H2O)] [45] and
[H3N(CH2)2NH2(CH2)2NH2(CH2)2NH3] [VF5(H2O)]2 [27].
octahedra through
a bridging fluoride. The central {V2O2F8}
As shown in Fig. 2, the structure of 3 consists of discrete
[H3N(CH2)2NH2(CH2)NH3]3+ cations and both {VF5(H2O)}2ꢁ and
{VOF4(H2O)}2ꢁ anions with hydrogen-bonding interactions be-
tween the fluoride ligands and the cations. The {VF5(H2O)}2ꢁ anion
is structurally comparable to that discussed for compound 2. The
{VOF4(H2O)}2ꢁ anion exhibits a cis-disposition of the oxo-group
and the aqua ligand, with V–O distances of 1.619(3) and
2.051(3) Å, respectively. The V–F distances are in the range
1.913(2)–1.947(2) Å for the fluorides cis to the oxo-group, while
the V–F distance trans to this group is 2.070(3)Å, a significant
lengthening attributed to the trans-influence of the multiply
bonded oxo-group. Valence bond calculations are in agreement
with the assignment of the +4 oxidation state to the vanadium.
Curiously, this results in mixed valence character for compound
3, as a result of incorporation of two different anionic components.
It is also noteworthy that the {VOF4(H2O)}2ꢁ anions of
K2[VF8(H2O)] [46] and [H3NCH2CH2NH3][VOF4(H2O)] [28] exhibit
trans-oxo-aqua ligation, while [H3N(CH2)2NH2(CH2)2NH2(CH2)2-
NH3][VOF4(H2O)]2ꢀH2O exhibits both cis- and trans-isomers [27].
As shown in Fig. 3, the structure of 4ꢀH2O contains discrete
[H3NCH2(C6H4)CH2NH3]2+ cations, {V2O2F8}4ꢁ anions and water
molecules of crystallization. Once again, hydrogen-bonding be-
tween the fluoride ligands and the cations is significant. The
{V2O2F8}4ꢁ anion consists of edge-sharing {VOF5} octahedra, linked
through two bridging fluorides. The vanadium oxo-bonds are thus
exo- to the bridge and in the equatorial plane {VO2F4} with the
bridging fluoride groups. The trans influence of the terminal oxo-
group is evident in the V–F bond distance of 2.214(2) Å for the
trans fluoride, compared to an average of 1.949(3) Å for the cisoid
V–F bonds. The structure of the anion of 4 is similar to that previ-
ously reported for [H3N(CH2)2NH2(CH2)2NH2(CH2)2NH3][V2O2F8]
[27].
binuclear unit is similar to that of compound 4 with oxo-groups
trans to the bridging fluorides. The peripheral vanadium octahedra
exhibits cis oxo and aqua ligands, with the aqua ligand trans to
6ꢁ
the bridging fluoride. Tetranuclear anions of the type [V4O4F14
have been reported for [(H3NCH2CH2)3N][V4O4F14
[H3N(CH2)C2NH2(CH2)2NH3][V4O4F14 [27]. However, these are
]
]
and
]
cyclic tetramers, characterized by {V4F4} rings, in one case with
two edge-sharing {V2O2F8} binuclear units fused through corner-
sharing and in the second by a single {V2O2F8} unit corner-sharing
to two {VOF8} octahedra.
1nꢁ
The one-dimensional fVF5gn chain of [H3N(CH2)2NH2][VF5]
(7) is shown in Fig. 6. The chain consists of vanadium(III) {VF6}
octahedra sharing cis vertices to produce a zig-zag profile. The V–
F distances are 1.838(3) and 2.132(5) Å for the terminal and bridg-
ing fluorides, respectively. The chain axes align with the crystallo-
graphic b-axis, and the cations occupy the channels between
chains. A curious feature of 7 is the presence of a monoprotonated
(Hen)+ cation. This observation is confirmed by charge-balance
considerations and by the magnetic studies (vide infra) which
establish that 7 is a V(IV) species. The final Fourier difference maps
also clearly show three hydrogen atoms associated with one en ter-
minus and two with the other.
The two-dimensional structure of the mixed valence
6nꢁ
fVIIIVIVF17Og
anion of 8 is shown in Fig. 7a–c. The structure con-
3
n
sists of edge- and corner-sharing {VF6} and {VF5O) octahedra in an
arrangement that generates {V18F18} rings. The building blocks of
the layer are edge-sharing and corner-sharing binuclear units. The
structure may be described as zig-zag chains of alternate corner-
and edge-sharing octahedral units parallel to the crystallographic
c-axis, connected through {V2F10} binuclear units along the a-axis.
The V–F distances exhibit an unusual range. The V-terminal fluorine
distances are observed at 1.857(3)–1.924(3) Å, while V-bridging
fluoride distances are in the range 1.954(3)–2.142(3) Å.
The structure of the DABCO derivative 5, shown in Fig. 4, con-
sists of discrete H2DABCO2+ cations and [V2O2F6(H2O)2]2ꢁ anions.
The binuclear anion is constructed from {VIVO2F4} octahedra shar-
ing an edge through two bridging fluorides. The vanadium-oxo and
vanadium-aqua distances are 1.617(2)–2.034(2) Å, respectively.
The vanadium-fluoride distances trans to the oxo-ligand are
2.142(2)Å, compared to an average of 1.939(3) Å for the axial set
of fluorides. The equatorial plane {V2O2F2(H2O)2} contains the
oxo-group, the aqua ligands and the bridging fluorides. Two other
examples with the [V2O2F6(H2O)2]2ꢁ anion have been reported
Compound 9 did not incorporate fluoride and consists of dis-
crete [H3N(CH2)2NH3]2+ cations and VOn3ꢁ chains. As shown in
n
Fig. 8, the chains consist of corner-sharing V(V) tetrahedra. This
is a well-known structure type, first reported for potassium meta-
vanadate [48]. It has also been reported in organic–inorganic hy-
brid materials, such as [Ni(en)3][V2O6] [49,50].
The magnetic susceptibilities of compounds 4–8 were studied
in the 2–300 K temperature range. Compounds 4–7 exhibit
temperature dependent magnetic susceptibilities consistent with

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P. DeBurgomaster et al. / Inorganica Chimica Acta 363 (2010) 1102–1113
Fig. 7. (a) A view of the layer stacking and interlamellar occupancy of the cations in 8. (b) A polyhedral representation of the V4F17O2nꢁ layer of 8. (c) The stacking of layers for
n
8. The blue polyhedra represent the layer beneath the orange polyhedra. The cations occupy interlamellar positions above and below the cavities in the layers.
pffiffiffiffiffiffiffiffiffiffiffi
Curie–Weiss behavior, as shown in Table 4 and Fig. 9. However, the
mixed valence 8 showed more complicated magnetic properties. At
300 K, the effective magnetic moment
with three V(III) sites and one V(IV) site per formula unit. The
8
v
0T is 5.11
l
B, consistent

P. DeBurgomaster et al. / Inorganica Chimica Acta 363 (2010) 1102–1113
1111
nꢁ
Fig. 8. A polyhedral view of the fVO3gn chain and its hydrogen-bonding interactions with the {H3NC2H4NH3}2+ cations of 9.
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
400
350
300
250
200
150
100
50
0
0
50
100
150
200
250
300
temperature (K)
Fig. 9. The temperature dependence of the inverse susceptibility 1/v (red triangles) and of the susceptibility–temperature product vT (blue diamonds) for 5 in the 2–300 K
temperature range. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
v0
v0
¼
v0
ð2Þ
moment decreases with lowering temperature, indicating the exis-
tence of dominant antiferromagnetic interactions. The magnetic
data were analyzed using the model considering three V(III)
(S = 1) dimers and one V(IV) (S = ½) dimer, following Eq. (1) below.
The corresponding exchange Hamiltonian is H ¼ ꢁ2J1ðS1S2þ
S3S4 þ S5S6Þ ꢁ 2J2S7S8 Fig. 10.
1 ꢁ ð2zJ0=Ng2l2B
Þ
The best fit gives g = 1.97, J1/k = ꢁ18.63 K, J2/k = 19.10 K, zJ0/
k = ꢁ0.45 K and
v
TI = ꢁ3.94Eꢁ4 emu/mol.
4. Conclusions
v
¼
¼
v0
þ
vTI
A series of vanadium fluorides and oxyfluorides has been pre-
pared by the solvatothermal reactions of V2O5, an appropriate
organoamine and HF in ethanol/water or ethylene glycol/water
solvents. Both the identity of the organoammonium component
of the product and variations in reaction conditions influence the
product identity. For example, with ethylenediammonium cation
ꢀ
ꢁ
Ng2l2B 6e2J1=k1 þ 30e6J1=kT
2e2J2=kT
þ
þ
vTI
ð1Þ
kT
1 þ 3e2J1=kT þ 5e6J1=kT 1 þ 3e2J2=kT
The calculated susceptibility was also corrected for exchange inter-
action zJ0 between all spins as shown in Eq. (2).

1112
P. DeBurgomaster et al. / Inorganica Chimica Acta 363 (2010) 1102–1113
Fig. 10. The temperature dependence of the magnetic susceptibility
v (red circles) and of the effective magnetic moment leff (blue diamonds) for 8 in the 2–300 K
temperature range. The line through the circles is the fit to Eq. (1). (For interpretation of the references to colour in this figure legend, the reader is referred to the web version
of this article.)
[H2en]2+, [H2en][VF6] (1) is isolated at 150 °C and pH 5.0, while
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