The Hexaammine Copper(II) Fluoride Monohydrate

[Cu(NH3 )6 ][F(H2 O)F]: Synthesis and Crystal Structure

Patrick Woidya , Weizhe Menga and Florian Krausa
AG Fluorchemie, Department Chemie, Technische Universität München, Lichtenbergstraße 4,
85747 Garching, Germany
Reprint requests to PD Dr. Florian Kraus. Fax: +49-89-289-13762. E-mail: fluorchemie@tum.de

Z. Naturforsch. 2014, 69b, 1 – 7 / DOI: 10.5560/ZNB.2014-3291

Received October 18, 2013

We report the synthesis and crystal structure of the monohydrate of hexaammine copper(II) di-
fluoride, [Cu(NH3 )6 ]F2 · H2 O, which was synthesized from CuF2 · 2 H2 O in liquid ammonia. The
compound crystallizes in the chiral space group P32 21 (no. 154) as traffic-blue, plate-shaped crys-
tals with a = 6.738(1), c = 18.210(6) Å, V = 715.9(3) Å3 at 150 K with Z = 3. It contains the rare
[F(H2 O)F]2− anion bound by strong O–H···F hydrogen bonding.
Key words: Copper(II) Fluoride, Liquid Ammonia, Ammine Complexes, Hydrates, Crystal
Structure, Hydrogen Bonds

Introduction (for further crystallographic data see Table 1). The

color of the compound has been determined with the
W. Biltz and coworkers reported the reaction of
naked eye by comparison with RAL color cards. The
CuF2 · 2 H2 O with liquid ammonia. In their study,
asymmetric unit contains one copper atom residing on
CuF2 · 2 H2 O was extracted with ammonia to remove
the Wyckoff position 3a (.2.), one oxygen atom on the
the water at temperatures between 30 and 65 ◦ C to
Wyckoff position 3b (.2.) and three nitrogen atoms and
produce copper ammoniates [1]. With tensieudiomet-
one fluorine atom on the 6c (1) position (Table 2). The
ric measurements the authors established the exis-
copper atom Cu(1) is surrounded by three symmetry-
tence of a dark-blue pentaammoniate of copper flu-
inequivalent NH3 molecules with nitrogen atoms N(1),
oride, CuF2 · 5 NH3 , at −78 ◦ C and putatively of
N(2) and N(3). By application of the symmetry opera-
CuF2 · 3.33 NH3 at 18 ◦ C [1, 2]. To our knowledge,
tion (.2.), the coordination number of the copper atom
these are the only pure Cu(II) fluoride ammoniates re-
becomes six, and a coordination polyhedron best de-
ported, but their structures have not been determined
scribed as a slightly distorted tetragonal bipyramid is
yet. Biltz and coworkers have chosen the dihydrate of
obtained (Fig. 1).
CuF2 as starting material, since hydrates generally re-
The Cu(II)–N distances are 2.120(4) and 2.103(4) Å
act much better with liquid NH3 than the anhydrous
for the equatorial nitrogen atoms N(1)/N(1)#1 and
salts. This is due to their lower lattice energy and the
N(2)/N(2)#1, respectively (Table 3). The distance
very good solubility of water in ammonia [1]. Here
from the Cu atom to the axial nitrogen atoms
we show that CuF2 · 2 H2 O reacts with liquid ammo-
N(3) and N(3)#1 is 2.370(5) Å which is signifi-
nia at −78 ◦ C forming a traffic-blue solution. After
cantly longer than the equatorial Cu–N distances.
storage for two months at −40 ◦ C, single crystals of
Thus, the polyhedron reveals the expected Jahn–Teller
[Cu(NH3 )6 ][F(H2 O)F] (1) of the same color were ob-
distortion for a Cu(II) d 9 system [3]. These find-
tained which were characterized by low-temperature
ings fit to the values of the Cu–N distances re-
single-crystal X-ray diffraction.
ported in the literature: The equatorial Cu–N dis-
tances in [Cu(NH3 )6 ]Cl2 and [Cu(NH3 )6 ]Br2 are
Results and Discussion
2.07(7) and 2.15(8) Å, respectively, and for the ax-
[Cu(NH3 )6 ]F2 · H2 O crystallizes as traffic-blue ial Cu–N distances 2.62(11) and 2.45(28) Å are re-
(RAL 5017) single crystals in space group type P32 21 ported [4]. In a more recent study, [Cu(NH3 )6 ]Cl2

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2 P. Woidy et al. · [Cu(NH3 )6 ][F(H2 O)F]

Table 2. Wyckoff positions, atomic coordinates (×104 ) and

equivalent isotropic displacement parameters (Å2 × 103 )
of 1.
Atom Position x y z Ueq
Cu(1) 3a 4680(1) 4680(1) 0 30(1)
N(1) 6c 5813(7) 7966(7) 460(2) 31(1)
H(1A) 6c 4584 8070 612 46
H(1B) 6c 6599 9058 115 46
H(1C) 6c 6745 8181 849 46
N(2) 6c 1350(8) 3503(7) 403(2) 27(1)
H(2A) 6c 1093 2570 795 41
H(2B) 6c 314 2707 43 41
H(2C) 6c 1201 4718 542 41
N(3) 6c 6043(9) 3651(8) 1050(3) 46(1)
H(3A) 6c 5076 3378 1433 69
H(3B) 6c 7461 4814 1168 69
Fig. 1. A projection of the distorted tetragonal-bipyramidal H(3C) 6c 6118 2368 953 69
coordination sphere of Cu(1). Displacement ellipsoids are F(1) 6c 1251(5) 7694(5) 775(1) 35(1)
shown at the 70 % probability level at 150 K, H atoms as O(1) 3b 92(9) 0 1/6 36(2)
spheres with arbitrary radii. Symmetry transformation used H(4) 6c 550(110) −700 1360(30) 50(20)
to generate equivalent atoms: #1 x, y, −z.

Table 1. Selected crystallographic data for compound 1. ues for the chloride/bromide: 2.060(7) / 2.064(7) Å
[Cu(NH3 )4 (NH3 )2 ][F(H2 O)F] (equatorial) and 2.32(2)/2.34(2) Å (axial) [5]. A the-
Empirical formula H20 CuF2 N6 O oretical study on [Cu(NH3 )6 ]2+ in the gas phase
Color and habitus traffic-blue plate showed three different Cu–N distances with 2.171 and
Molecular mass, g mol−1 221.76 2.174 Å for the equatorial and 2.512 Å for the ax-
Crystal system trigonal
Space group P32 21 (no. 154) ial positions [6]. Therefore, the cationic unit of the
a, Å 6.7377(12) chloride/bromide and of the title compound is best de-
c, Å 18.210(6) scribed as [Cu(NH3 )4 (NH3 )2 ]2+ .
V , Å3 715.9(3) In the isotypic compound [Cd(NH3 )6 ][F(H2 O)F]
Z 3
the Cd(II)–N distances of the axial and equatorial
ρcalcd. , Mg m−3 1.54
λ , Å 0.71073 ligands are not different [7]. The Cd–N distances
T, K 150(2) are 2.336(2) Å for Cd(1)–N(1) to 2.406(2) Å for
F(000), e 351 Cd(1)–N(3), thus they are elongated compared to the
µ( MoKα ), mm−1 2.3 ones in 1. For [Cd(NH3 )6 ]Cl2 a similar Cd–N dis-
Crystal size, mm3 0.3 × 0.15 × 0.1
θ -range, deg 3.34 – 32.40
tance has been reported at 2.341(4) Å [5], and in
Refl. measured/independent/ 5432/509/471 [Cd(NH3 )6 ]C60 · 6 NH3 the Cd–N distances are in the
observed [I > 2 σ (I)] range from 2.321 to 2.407 Å [8].
Rint /Rσ 0.0703/0.0295 The fluorine atom F(1) in 1 shows no direct contact
h, k, l range −6 to 6, −6 to 6, −18 to 18
R(F) (I > 2 σ (I)/all data) 0.0301/0.0336
to the copper atom. The Cu–F distance is 4.018(3) Å
wR(F 2 ) (I > 2 σ (I)/all data) 0.0746/0.0765 compared to 1.9062(9) and 1.90(7) Å in pure CuF2 [9,
S (all data) 1.088 10]. In the isotypic Cd compound the Cd–F distance
Data/parameter/restraints 509/47/0 is very similar with 4.099(2) Å [7]. The fluoride an-
(∆/σ )max 0.000
ion is an acceptor of in total seven N–H···F hydrogen
Flack parameter 0.05(6)
∆ρmax/min , e Å−3 0.39/ − 0.28 bonds from four [Cu(NH3 )6 ]2+ units and from the H2 O
solvate molecule with oxygen atom O(1). The coordi-
nation sphere of F(1) is shown in Fig. 2, the coordina-
and [Cu(NH3 )6 ]Br2 were reinvestigated, and single- tion of the [Cu(NH3 )6 ]2+ cation by eight symmetry-
crystal X-ray diffraction on the chloride has shown equivalent F− anions in Fig. 3.
Cu–N distances of 2.068(7) (equatorial) and 2.24(2) Å An accepted and simple model for the assessment
(axial). EXAFS studies revealed the following val- of hydrogen bond strength is the shortening of the

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P. Woidy et al. · [Cu(NH3 )6 ][F(H2 O)F] 3

Table 3. Selected distances (Å) and angles (deg) of 1. Sym-

metry transformations for the generation of equivalent atoms:
#1 x, y, −z; #2 x −y, −y, −z +1/3; #3 x, y −1, z; #4 x −y +1,
−y + 1, −z + 1/3.
Atoms Atoms
Cu(1)–N(1) 2.120(4) N(1)–H(1A) 0.91
Cu(1)–N(2) 2.103(4) N(1)–H(1B) 0.91
Cu(1)–N(3) 2.370(5) N(1)–H(1C) 0.91
Cu(1)–F(1) 4.018(3) N(2)–H(2A) 0.91
Cu(1)–O(1) 4.355(2) N(2)–H(2B) 0.91
N(1)–Cu(1)–N(1)#1 90.8(2) N(2)–H(2C) 0.91
N(1)–Cu(1)–N(3) 89.8(2) N(3)–H(3A) 0.91
N(2)–Cu(1)–N(3) 96.0(2) N(3)–H(3B) 0.91
N(2)–Cu(1)–N(1)#1 177.1(2) N(3)–H(3C) 0.91
N(3)#1–Cu(1)–N(3) 174.6(3) O(1)–H(4) 0.88(6)
H(4)–O(1)–H(4)#2 104(5) F(1)#3–O(1)–F(1)#4 107.09(9)

Fig. 3. Projection of the [Cu(NH3 )6 ]2+ cation and its coordi-

nation to symmetry-equivalent F− anions via N–H···F hydro-
gen bonding (dashed in black). The bridging of two fluoride
ions by an H2 O molecule via O–H···F hydrogen bonds is also
indicated. Displacement ellipsoids are shown at 70 % proba-
bility level at 150 K, H atoms as spheres with arbitrary radii.
Atomic numbering and symmetry transformations are omit-
ted for clarity.

F–H···F [14 – 18] and N–H···N [19 – 22] hydrogen

bonding has been investigated much less, and N–H···F
Fig. 2. A projection of the coordination sphere of the flu- hydrogen bonding – outside the area of modified pro-
oride ion F(1). N–H···F and O–H···F hydrogen bonds are
dashed in black. Displacement ellipsoids are shown at the
teins – is very little explored [7, 23 – 33]. The N–H···F
70 % probability level at 150 K, H atoms as spheres with hydrogen bonds in 1 show donor···acceptor (D···A)
arbitrary radii. Symmetry transformations used to generate distances between 2.938(5) and 3.229(6) Å, and the
equivalent atoms: #5 x + 1, y, −z; #7 x, y − 1, −z; #9 x, y + 1, D···A distances for the N–H···O hydrogen bonds are
z; #10 x − 1, y, z; #11 x − y, −y + 1, −z + 1/3. 3.096(4) and 3.327(6) Å (Table 4). The deviation of
the D–H···A angles from 180◦ is in the range of 7.6 to
hydrogen···acceptor distance (H···A), compared to the 31.1◦ for N–H···F and 7.2 to 19.9◦ for the N–H···O hy-
sum of the van der Waals radii, and the deviation of drogen bonds. These data are summarized in Table 5,
the D−H···A angles (D = donor) from 180◦ . When the and a graphical presentation is given in Fig. 4. The iso-
shortening of the hydrogen bond is plotted as a func- typic Cd compound shows similar distances for the
tion of the deviation of the angle, the strongest hydro- hydrogen bonds, with D···A (N–H···F) distances be-
gen bonds are found in the upper left, and the weak- tween 2.900(2) and 3.135(3) Å, and D···A (N–H···O)
est ones in the lower right region of the plot [11]. distances between 3.056(2) and 3.262(3) Å. The devi-
Among all hydrogen bonds, the O–H···O, N–H···O, O– ation of the D–H···A angles from 180◦ is in the range
H···N, O–H···F and F–H···O contacts are the best ex- from 5.0 to 28.8◦ for N–H···F, and from 14.0 to 19.0◦
plored in organic and inorganic compounds [12, 13]. for the N–H···O hydrogen bonds [7].

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4 P. Woidy et al. · [Cu(NH3 )6 ][F(H2 O)F]

Table 4. Selected D–H, H···A, D···A hydrogen bond lengths

(Å) and <DHA angles (deg) of 1 (D = donor, A = acceptor).
Symmetry transformations for the generation of equivalent
atoms: #4 x − y + 1, −y + 1, −z + 1/3; #5 x + 1, y, −z; #6
x + 1, y + 1, z; #7 y − 1, x, −z; #8 x + 1, y, z.
Atoms D–H H···A D···A <DHA
N(1)–H(1A)···F(1) 0.91 2.15 3.041(6) 166.2
N(1)–H(1B)···F(1)#5 0.91 2.07 2.959(5) 167.5
N(1)–H(1C)···O(1) 0.91 2.46 3.327(6) 160.1
N(2)–H(2A)··· O(1)#7 0.91 2.19 3.096(4) 172.8
N(2)–H(2B)···F(1) 0.91 2.14 3.038(5) 170.3
N(2)–H(2C)··· F(1)#6 0.91 2.03 2.938(5) 172.4
N(3)–H(3A)···F(1)#4 0.91 2.24 3.107(5) 158.5 Fig. 4. A diagram showing the strengths of hydrogen bonds
N(3)–H(3B)···F(1)#8 0.91 2.42 3.229(6) 148.9 in 1. The percental shortening of the H···A distance compared
O(1)–H(4)···F(1)#8 0.88(6) 1.74(6) 2.621(5) 175(6) to the sum of the van der Waals radii is plotted as a function
of the deviation of the D–H···A angle from 180◦ (D = donor,
Table 5. Shortening of H···A distances (%) as compared to A = acceptor). The black square indicates O–H···F, black di-
the sum of their van der Waals radii [47] and deviation of amonds N–H···F and black balls N–H···O hydrogen bonding.
D–H···A angles from 180◦ (D = donor, A = acceptor). Sym- The margins of error are typically within 0.7 % and 3 deg.
metry transformations for the generation of equivalent atoms:
#4 x −y+1, −y+1, −z+1/3; #5 x +1, y, −z; #6 x +1, y+1,
z; #7 x, y − 1, −z; #8 x + 1, y, z. O···F distance of 1 is in good agreement with these val-
ues [34, 35].
Hydrogen bond Shortening Deviation from
Due to the short D···A distance of only 2.621(4) Å
(%) 180◦ (deg)
N(1)–H(1A)···F(1) 19.48 13.80
for O···F− in compound 1 and in view of the well
N(1)–H(1B)···F(1)#5 22.47 12.50 known N2 H7 + ([H3 N–H···NH3 ]+ ) cation [36], the
N(1)–H(1C)···O(1) 9.56 19.90 moiety can also be described as a bent, C2v -symmetric
N(2)–H(2A)···O(1)#7 19.49 7.20 [F···H–O–H···F]2− anion. This anion has been re-
N(2)–H(2B)···F(1) 19.85 9.70
N(2)–H(2C)···F(1)#6 23.97 7.60
ported previously by Bowman-James and cowork-
N(3)–H(3A)···F(1)#4 16.10 21.50 ers in the compound [H6 L(F)2 (H2 O)][SiF6 ]2 · 12 H2 O
N(3)–H(3B)···F(1)#8 9.36 31.10 (L = PEAcrypt) [37]. They reported a comparable
O(1)–H(4)···F(1)#8 34.83 5.00 D···A distance in the range of 2.709(1) to 2.717(1) Å,
which is approximately 0.2 Å longer compared to the
[F(H2 O)F]2− anion of compound 1. Molecular species
The strongest N–H···F hydrogen bond with 24 % of hydrated fluoride anions are known in the litera-
shortening and only 7.6◦ deviation from 180◦ ture, for example [F(H2 O)]− [38], [F(H2 O)4 ]− [39],
is N(2)–H(2C)···F(1)#6 with a D···A distance of [F(H2 O)4 ]−
4 [40], and [F4 (H2 O)10 ]
4− [41] were re-

only 2.938(5) Å, while the weakest one is N(3)– ported stabilized in various cryptand-like molecules.
H(3B)···F(1)#8 with only 9.4 % shortening and a de- For the anion [F2 (H2 O)6 ]2− comparable D···A dis-
viation of 31.1◦ from linearity. The two N–H···O hy- tances ranging from 2.655 to 2.912 Å were re-
drogen bonds show 19.5 and 9.6 % shortening and ported [42]. To the best of your knowledge, compound
7.2 and 19.9◦ angle deviation. Since fluorine and 1 and the isotypic [Cd(NH3 )6 ][F(H2 O)F] [7] are the
oxygen are more electronegative than nitrogen, they first examples of the [F(H2 O)F]2− anion outside the
should form stronger hydrogen bonds. In our case, stabilizing environment of a cryptand.
the O(1)–H(4)···F(1)#8 hydrogen bond is the strongest No clear discrimination of N–H···O and N–H···F
one with 34.8 % shortening, only 5◦ angle deviation hydrogen bond strength is possible from Fig. 4. How-
and with a D···A distance of only 2.621(4) Å. The ever, only N–H···F and O–H···F hydrogen bonds, but
educt, CuF2 · 2 H2 O, also features O–H···F hydro- no O–H···N hydrogen bonds are present in 1. This may
gen bonding, with O···F distances of 2.717(1) [10], be due to the fact that first, fluorine is the better accep-
and 2.715(6) Å [9]. Compounds like FeSiF6 · 6 H2 O, tor for hydrogen bonds forming the strongest hydrogen
ZnF2 · 4 H2 O, SrTiF6 · 2 H2 O, and Te(OH)6 · NaF have bonds, and second that NH3 has a higher tendency to
O···F distances ranging from 2.50 to 2.77 Å, and the bind to Cu(II) than H2 O, and therefore the lone pair of

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P. Woidy et al. · [Cu(NH3 )6 ][F(H2 O)F] 5

Table 6. Anisotropic displacement parameters (Å2 × 103 ) axial Cu–N distances of 2.370(5) Å. An analysis of the
for 1. U is defined as exp(−2π2(a∗2 h2U11 + b∗2 k2U22 + hydrogen bonding in 1 revealed the expected strong N–
c∗2 l 2U33 + 2b∗ c∗ klU 23 + 2a∗ c∗ hlU 13 + 2a∗ b∗ hkU 12 )). H···O, O–H···F and N–H···F hydrogen bonds, which
Atom U11 U22 U33 U23 U13 U12 lead to the formation of a three-dimensional network
Cu(1) 23(1) 23(1) 42(1) −1 1(1) 10(1) of interconnected [Cu(NH3 )6 ]2+ , H2 O and F− moi-
N(1) 28(3) 28(3) 37(3) 4(2) 0(2) 14(2) eties, with F− as a linker between [Cu(NH3 )6 ]2+ and
N(2) 22(3) 23(3) 35(3) 0(2) −1 11(2)
N(3) 34(3) 33(4) 67(4) −10 8(3) 12(3)
H2 O units via hydrogen bonding. To the best of your
F(1) 34(2) 34(2) 42(2) −3 −2 20(2) knowledge, the compound presents the first example of
O(1) 30(3) 45(4) 39(4) −5 −2 22(2) the [F(H2 O)F]2− anion outside the stabilizing environ-
ment of a cryptand.

Experimental Section
All experiments were carried out excluding humidity and
air in an atmosphere of dried and purified argon (West-
falen AG) using a high-vacuum glass line or a glove box
(MBraun). Liquid ammonia (Westfalen AG) was dried and
stored over sodium (VWR) in a special high-vacuum glass
line. All vessels used for reactions with liquid ammonia were
made of borosilicate glass and flame-dried before use.

Synthesis and crystallographic details of

[Cu(NH3 )6 ]F2 · H2 O (1)

CuF2 · 2 H2 O was synthesized from commercially avail-

able CuCl2 (VWR) by repeated reaction with aqueous HF
(40 %, VWR) and slow crystallization form the solution.
CuF2 · 2 H2 O (100 mg, 7.4 mmol) was then reacted with
15 mL of liquid ammonia at −78 ◦ C. The color of the so-
lution and of the solid remaining at the bottom of the reac-
tion vessel changed to light-green, green and finally traffic-
Fig. 5. Projection of the unit cell of 1 onto the ac plane (a) and blue within half an hour. After 2 months of storage at −38 ◦ C
hydrogen bonding network (dashed in black) of 1 (b). Dis- tiny traffic-blue crystals were observed. Due to the instabil-
placement ellipsoids are shown at 70 % probability level at ity of the crystals above −20 ◦ C, no elemental or spectro-
150 K, H atoms as spheres with arbitrary radii. Atomic num-
bering and symmetry transformations are omitted for clarity. scopic analyses were carried out. One of the crystals was se-
lected at low temperature (< −40 ◦ C) and mounted onto the
goniometer using the Mitegen system. The extinction con-
a nitrogen atom is not available to act as an acceptor ditions pointed to the chiral space groups P31 , P32 , P31 21
atom for hydrogen bonding. and P32 21 with similar Rint values. The mean |E 2 −1| result
A projection of the unit cell of 1 on the ac plane is was 0.736, indicating a non-centrosymmetric space group.
shown in Fig. 5a, and the connectivity of the moieties The structure was solved by Direct Methods using S HELXS-
by hydrogen bonding leading to a three-dimensional 97 [43] and refined against F 2 using SHELXL-97 [44] in
space group P32 21, giving the results reported in Table 1. Re-
network is displayed in Fig. 5b.
finements and twin refinements in the other space groups led
In summary we have shown that CuF2 · 2 H2 O re-
to similar R values. However, there were Flack values close to
acts with dry liquid ammonia forming traffic-blue crys- 1 and obvious correlations between the atoms. Searches for
tals of the composition [Cu(NH3 )4 (NH3 )2 ][F(H2 O)F] higher symmetry in these space groups using PLATON [45]
(1) the structure of which has been presented. 1 is the or KPLOT [46] always showed a two-fold axis and clearly in-
ammoniate of CuF2 with the highest ammonia con- dicated the space group P32 21 to be correct. All atoms were
tent known so far. The hexaammine copper(II) ion localized by Fourier cycling methods and refined anisotropi-
shows the expected Jahn–Teller distortion with equa- cally, hydrogen atoms were refined isotropically by the usage
torial Cu–N distances of 2.103(4) and 2.120(4) Å and of a riding model or freely where applicable. All fluorine,

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6 P. Woidy et al. · [Cu(NH3 )6 ][F(H2 O)F]

oxygen and nitrogen atoms could be clearly discriminated karlsruhe.de/request for deposited data.html) on quoting the
by their isotropic and anisotropic displacement parameters deposition number CSD-419094.
(Table 6). Because the presence of Cu(II) was indicated by
Acknowledgement
the crystal color, the F atom must reside on a Wyckoff po-
sition with multiplicity six as the Cu atom resides on the 3a F. K. would like to thank the Deutsche Forschungsge-
position. meinschaft for a Heisenberg fellowship. P. W. would like to
Further details of the crystal structure investigation thank the Deutsche Forschungsgemeinschaft for financial
may be obtained from Fachinformationszentrum Karlsruhe, support and the TUM Graduate School. We thank Prof. Dr.
76344 Eggenstein-Leopoldshafen, Germany (fax: +49-7247- B. G. Müller, Giessen, and Prof. R. Hoppe, Giessen, for the
808-666; e-mail: crysdata@fiz-karlsruhe.de, http://www.fiz- donation of many chemicals and equipment.

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