Secondary interactions in gold(I) complexes with thione ligands, 4. Three further salts of the bis(imidazolidine-2-thione)gold(I) cation [1, 2]

Article abstract of DOI:10.1515/znb-2006-1112

Three structures of the form bis(imidazolidine-2-thione)gold(I) disulfonylamide [disulfonylamide = benzene-1,2-di(sulfonyl)amide (1), di(4-chlorobenzenesulfonyl)amide (2), di(4-iodobenzenesulfonyl)amide (3)] were determined. Compound 3 crystallizes with four independent formula units. The cations in 1 and 3 show an antiperiplanar conformation about the S?S axis, whereas the corresponding torsion angle in 2 is 72°. The packing in 1 consists of linked ribbons in which the NH groups of neighbouring cations are bridged by O-S-O groups of the anions. Compound 2 exhibits a complex layer structure in which several multi-centre hydrogen bonds are observed. The structural subunits of compound 3 involve an alternating anion-cation chain for two of the cations and inversion-symmetric anion-cation dimers for the other two cations. Short C-H?Au contacts (shortest H?Au 2.63 A? in 2) contribute to the packing of compounds 2 and 3.

Full text of DOI:10.1515/znb-2006-1112

Secondary Interactions in Gold(I) Complexes with Thione Ligands, 4.
Three Further Salts of the Bis(imidazolidine-2-thione)gold(I) Cation [1, 2]
Steffi Friedrichs and Peter G. Jones
Institut fu¨r Anorganische und Analytische Chemie, Technische Universita¨t Braunschweig,
Postfach 3329, D-38023 Braunschweig, Germany
Reprint requests to Prof. Dr. P. G. Jones. E-mail: p.jones@tu-bs.de
Z. Naturforsch. 61b, 1391 – 1400 (2006); received August 29, 2006
Dedicated to Dr. Jose´-Antonio Abad on the occasion of his retirement
Three structures of the form bis(imidazolidine-2-thione)gold(I) disulfonylamide [disulfonyl-
amide = benzene-1,2-di(sulfonyl)amide (1), di(4-chlorobenzenesulfonyl)amide (2), di(4-iodobenz-
enesulfonyl)amide (3)] were determined. Compound 3 crystallizes with four independent formula
units. The cations in 1 and 3 show an antiperiplanar conformation about the S···S axis, whereas the
corresponding torsion angle in 2 is 72◦. The packing in 1 consists of linked ribbons in which the NH
groups of neighbouring cations are bridged by O–S–O groups of the anions. Compound 2 exhibits a
complex layer structure in which several multi-centre hydrogen bonds are observed. The structural
subunits of compound 3 involve an alternating anion-cation chain for two of the cations and inversion-
symmetric anion-cation dimers for the other two cations. Short C–H···Au contacts (shortest H···Au
˚
2.63 A in 2) contribute to the packing of compounds 2 and 3.
Key words: Thiones, Disulfonylamides, Gold, Hydrogen Bonds
Introduction
Our previous studies of secondary interactions in
gold(I) complexes of heterocyclic ligands bearing a
thione group have involved chloride [3], camphor-
sulfonate [4] and di(methanesulfonyl)amide (DMS)
[1] salts of the complex cations [L2Au]+ with
L = imidazolidine-2-thione (“ethylenethiourea”, etu),
1-methyl-imidazolidine-2-thione and thiazolidine-2-
thione. The earlier publications may be consulted
for a summary of results. Ideally, one would like
to obtain structures for all possible combinations of
thione ligands and counteranions. In practice, many
potential candidates either cannot be prepared in a
pure state, refuse to form single crystals or present
severely disordered structures. For this reason, we
reverse our previous practice of varying the cation
for a constant anion and present here three further
salts of the cation bis(imidazolidine-2-thione)gold(I),
[(etu)2Au]+X−, with various disulfonylamide anions,
namely X = benzene-1,2-di(sulfonyl)amide (1), di(4-
chlorobenzenesulfonyl)amide (2), and di(4-iodobenz-
enesulfonyl)amide (3) (Scheme 1). Reference will be
made to the previously determined structures of the
same cation, namely the chloride, chloride hydrate [3],
DMS [1] and camphorsulfonate [4] salts.
Scheme 1.
Discussion
General aspects
All three compounds crystallize solvent-free (Ta-
ble 1). Compound 1 (Fig. 1) is non-centrosymmetric
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S. Friedrichs – P. G. Jones · Secondary Interactions in Gold(I) Complexes with Thione Ligands, 4
Table 1. Crystallographic data
collection, solution and refine-
ment details for 1, 2 and 3.
Compound
Formula
1
2
3
C12H16AuN5O4S4
619.50
orthorhombic
Pna21
C18H20AuCl2N5O4S4 C18H20AuI2N5O4S4
Mr [g mol−1
]
766.50
monoclinic
P21/n
949.40
triclinic
P1
Crystal system
Space group
¯
˚
a [A]
18.889(3)
7.3727(10)
13.430(2)
90
90
90
1870.3
4
7.7821(8)
23.813(2)
13.3609(14)
90
97.799(8)
90
15.541(3)
17.735(3)
20.053(4)
88.74(2)
70.66(2)
89.97(2)
5213.8
8
˚
b [A]
˚
c [A]
α [deg]
β [deg]
γ [deg]
3
˚
V [A ]
2453.0
4
Z
F(000)
1192
1488
3552
Crystal habit
colourless plate
colourless prism
0.36×0.28×0.24
2.075
50
6.59
colourless tablet
0.28×0.20×0.12
2.419
50
8.37
Crystal size [mm3]
0.45×0.24×0.03
Dx [g cm−3
]
2.200
56.6
8.34
163
2θmax [deg]
µ [mm−1
]
Temperature [K]
173
173
Absorption correction
multiple scans (SADABS) ψ scans
ψ scans
0.97/0.48
18370
Tmin/Tmax
0.99/0.37
12150
0.67/0.58
5596
Measured reflections
Independent reflections 4552
4314
18235
Rint
0.083
199
236
0.024
4
320
0.059
2118
1261
0.69
0.048
0.078
1.13/−1.02
Restraints
Parameters
S
0.96
0.90
R1[F2 ≥ 2σ(F2)]
0.042
0.091
1.7/−2.1
0.024
0.049
0.96/−0.49
wR2(F2, all refl.) −3
˚
∆ρmin/∆ρmax [e A
]
Table 2. Bond lengths, bond angles and torsion angles
˚
(A, deg) for compound 1.
Au-S(1)
2.282(2) Au-S(2)
2.283(2)
1.732(7)
1.590(6)
1.441(5)
1.439(5)
1.776(6)
S(1)-C(11)
N(1)-S(4)
S(3)-O(2)
S(3)-C(31)
S(4)-O(4)
1.721(7) S(2)-C(21)
1.586(6) N(1)-S(3)
1.438(5) S(3)-O(1)
1.771(6) S(4)-O(3)
1.445(5) S(4)-C(32)
S(1)-Au-S(2)
C(21)-S(2)-Au
175.86(10) C(11)-S(1)-Au
103.7(2) S(4)-N(1)-S(3)
105.9(2)
114.5(4)
Fig. 1. Bis(imidazolidine-2-thione)gold(I) benzene-1,2-di- C(11)-S(1)···S(2)-C(21) 175.8(4)
Au-S(1)-C(11)-N(11) 8.7(8)
Au-S(2)-C(21)-N(21) −3.9(7)
(sulfonyl)amide, 1, asymmetric unit with numbering scheme.
S(4)-N(1)-S(3)-O(2)
S(3)-N(1)-S(4)-O(3)
−97.7(4) S(4)-N(1)-S(3)-O(1) 133.6(4)
−138.7(4) S(3)-N(1)-S(4)-O(4) 91.5(4)
Thermal ellipsoids are shown with 50% probability. Hydro-
gen radii are arbitrary. The dashed line represents a classical
hydrogen bond.
close to linearity, with values of 172– 178◦, Au–S
but racemically twinned; compound 3 crystallizes with
four independent formula units in the asymmetric unit
(Fig. 3 shows one formula unit). Accordingly, these
two structures are less precisely determined than that
of compound 2 (Fig. 2). Summaries of bond lengths,
bond angles and torsion angles are presented in Tables
2 – 4.
˚
bond lengths in the range 2.27– 2.30 A, or the angles
at sulfur, 101– 108◦. Individual values may be taken
from Tables 2 – 4 or the Supplementary Material.
The benzene-1,2-di(sulfonyl)amide anion in 1 dis-
plays the usual structural features [5], except that the
˚
sulfur atom S4 lies as much as 0.23 A out of the plane
All [(etu)2Au]+ cations display bond lengths and of the six-membered ring (to the opposite side from the
˚
angles broadly as expected, e. g. S–Au–S bond angles nitrogen atom, which lies 0.10 A out of the plane). The
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1393
Table 3. Bond lengths, bond angles and
torsion angles (A, deg) for compound 2.
Au–S(2)
2.2704(12)
1.724(5)
1.598(4)
1.435(4)
1.766(5)
1.445(3)
Au–S(1)
2.2808(11)
1.719(5)
1.613(4)
1.443(3)
1.441(3)
1.773(4)
˚
S(1)–C(11)
N(1)–S(4)
S(3)–O(1)
S(3)–C(31)
S(4)–O(3)
S(2)–C(21)
N(1)–S(3)
S(3)–O(2)
S(4)–O(4)
S(4)–C(41)
S(2)–Au–S(1)
C(21)–S(2)–Au
171.96(5)
107.97(15)
C(11)–S(1)–Au
S(4)–N(1)–S(3)
103.86(15)
123.7(2)
C(11)–S(1)··· S(2)–C(21)
Au–S(2)–C(21)–N(21)
S(4)–N(1)–S(3)–O(1)
S(3)–N(1)–S(4)–O(4)
O(2)–S(3)–C(31)–C(32)
72.5(2)
Au–S(1)–C(11)–N(11)
C(31)–S(3)··· S(4)–C(41)
S(4)–N(1)–S(3)–O(2)
S(3)–N(1)–S(4)–O(3)
O(4)–S(4)–C(41)–C(42)
−20.0(4)
−20.7(5)
−166.9(3)
43.7(3)
5.2(2)
−38.0(3)
170.7(2)
12.2(4)
22.1(4)
Fig. 3. Bis(imidazolidine-2-thione)gold(I) di(4-iodobenzene-
sulfonyl)amide, 3, one of four formula units with numbering
scheme. Thermal ellipsoids are shown with 30% probability.
Hydrogen radii are arbitrary. The arbitrarily defined “first”
cation is numbered with Au1, S1, S2, C1x, C2x, N1x, N2x,
the second as Au2–C43, etc. The first anion is numbered with
S11, S12, N1, O1-4, C10x, C20x, I1 and I2, the second as
S13–I4, etc. Correspondingly, this Fig. shows the fourth for-
mula unit.
Fig. 2. Bis(imidazolidine-2-thione)gold(I) di(4-chlorobenz-
enesulfonyl)amide, 2, asymmetric unit with numbering
scheme. Thermal ellipsoids are shown with 50% probabil-
ity. Hydrogen radii are arbitrary. The dashed line represents
a classical hydrogen bond.
N–S–N–O torsion angles thus differ pairwise (two ab-
solute values of ca. 135◦, two of ca. 95◦; by convention
the odd-numbered oxygen atoms display the larger ab-
solute torsion angles). For a more extensive discussion
of the standard geometry, see Ref. [5].
The di(4-halo-benzenesulfonyl)amide anions of
compounds 2 and 3, like their parent disulfonylamines,
may in principle display either a folded conformation
with local mirror symmetry (“hairpin” form) or an ex-
tended conformation with local twofold symmetry. Ir-
respective of the local symmetry, two of the N–S–
N–O torsion angles are approximately 180◦, leading
to a W-shaped O–S–N–S–O sequence; these antiperi-
planar oxygen atoms are assigned the odd numbers,
and 3.58, 3.63, 3.71, 3.62 for the four anions of 3, cor-
responding interplanar angles 9.2(2)◦; 12.9(3), 14.1(3),
19.0(3), 12.8(4)◦, and absolute C–S···S–C torsion an-
gles 5.2(2)◦; 1.9(5), 6.2(5), 3.7(5), 4.5(5)◦. The valid-
ity of the local symmetry can be expressed by ∆τSN
,
the average difference between related pairs of abso-
lute torsion angles about the S–N bonds, which is 5.9◦
for 2 and 1.3, 6.3, 4.6, 5.4◦ for 3. The parent amines
display the extended conformation for the chloro
[7] and iodo [8] derivatives, although both forms
are known, as separate polymorphs, for the bromo
compound [6].
Our previous publications [1, 3, 4] established that
whereas the even-numbered oxygens are involved in the most relevant structural degree of freedom in
synclinal S=O bonds. Each C(x1)–C(x2) ring bond the bis(thione)gold(I) cations is the torsion angle C–
is synperiplanar to the adjacent S=O(sc) bond. For S···S–C. For the [(etu)2Au] cation, the chloride hy-
a more complete description of the standard geome- drate displays the unfavourable cis (synperiplanar)
try, see Refs. [6, 7]. Here, all anions in 2 and 3 are conformation, with a torsion angle of −20◦, because
˚
folded, with intercentroid distances (A) of 3.66 for 2 of hydrogen bonding from both cis NH groups of
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S. Friedrichs – P. G. Jones · Secondary Interactions in Gold(I) Complexes with Thione Ligands, 4
Table 4. Bond lengths, bond angles and
torsion angles (A, deg) for compound 3.
Au(1)–S(1)
Au(1)–S(2)
S(1)–C(11)
S(2)–C(21)
Au(2)–S(4)
Au(2)–S(3)
S(3)–C(31)
S(4)–C(41)
Au(3)–S(5)
Au(3)–S(6)
S(5)–C(51)
S(6)–C(61)
Au(4)–S(7)
Au(4)–S(8)
S(7)–C(71)
S(8)–C(81)
S(11)–O(2)
S(11)–O(1)
S(11)–N(1)
S(11)–C(101)
S(12)–O(3)
S(12)–O(4)
S(12)–N(1)
S(12)–C(201)
S(13)–O(5)
S(13)–O(6)
S(13)–N(2)
S(13)–C(301)
S(14)–O(8)
S(14)–O(7)
S(14)–N(2)
2.297(4)
2.297(4)
1.696(10) S(16)–O(11)
1.714(10) S(16)–O(12)
2.276(4)
2.296(4)
1.714(10) S(17)–O(14)
1.737(10) S(17)–O(13)
2.284(4)
2.289(4)
1.702(10) S(18)–O(16)
1.708(10) S(18)–O(15)
2.290(4)
2.298(4)
1.721(10)
1.728(10)
1.427(8)
1.442(8)
1.597(10) C(21)–S(2)–Au(1)
1.760(11) S(4)–Au(2)–S(3)
1.440(10) C(31)–S(3)–Au(2)
S(15)–N(3)
S(15)–C(501)
1.602(11)
1.768(11)
1.415(9)
1.426(8)
1.601(10)
1.794(11)
1.433(9)
1.437(8)
1.587(11)
1.772(11)
1.427(9)
1.430(9)
1.593(10)
1.739(12)
˚
S(16)–N(3)
S(16)–C(601)
S(17)–N(4)
S(17)–C(701)
S(18)–N(4)
S(18)–C(801)
S(1)–Au(1)–S(2)
C(11)–S(1)–Au(1)
176.42(15)
105.3(4)
104.9(4)
177.21(12)
101.3(4)
104.9(4)
175.58(14)
101.8(4)
102.6(4)
178.39(13)
105.7(4)
105.7(4)
123.1(6)
124.0(7)
125.3(6)
123.7(7)
1.440(8)
C(41)–S(4)–Au(2)
1.616(10) S(5)–Au(3)–S(6)
1.753(11) C(51)–S(5)–Au(3)
1.418(10) C(61)–S(6)–Au(3)
1.448(8)
1.620(10) C(71)–S(7)–Au(4)
1.776(11) C(81)–S(8)–Au(4)
1.444(8)
1.463(8)
1.560(11) S(16)–N(3)–S(15)
1.766(11) S(17)–N(4)–S(18)
1.443(8)
S(7)–Au(4)–S(8)
S(11)–N(1)–S(12)
S(14)–N(2)–S(13)
S(14)–C(401)
S(15)–O(9)
S(15)–O(10)
1.443(8)
C(31)–S(3)··· S(4)–C(41)
C(51)–S(5)··· S(6)–C(61)
C(71)–S(7)··· S(8)–C(81)
Au(1)–S(1)–C(11)–N(11)
Au(1)–S(2)–C(21)–N(21)
Au(2)–S(3)–C(31)–N(31)
Au(2)–S(4)–C(41)–N(41)
Au(3)–S(5)–C(51)–N(51)
Au(3)–S(6)–C(61)–N(61)
Au(4)–S(7)–C(71)–N(71)
Au(4)–S(8)–C(81)–N(81)
−163.4(6) C(11)–S(1)··· S(2)–C(21)
166.3(7)
−177.4(6)
170.6(6)
41.1(8)
173.0(6)
43.3(8)
−168.4(6)
−39.4(8)
47.9(8)
170.2(6)
O(7)–S(14)–N(2)–S(13)
−163.4(7) O(5)–S(13)–N(2)–S(14)
0.9(13) O(6)–S(13)–N(2)–S(14)
−9.8(14) O(11)–S(16)–N(3)–S(15)
−10.2(12) O(12)–S(16)–N(3)–S(15)
4.8(13)
O(9)–S(15)–N(3)–S(16)
−26.6(13) O(10)–S(15)–N(3)–S(16)
1.1(13)
2.4(15)
O(14)–S(17)–N(4)–S(18)
O(13)–S(17)–N(4)–S(18)
175.4(6)
−41.8(8)
−170.1(7)
−5.0(9)
−6.3(14) O(16)–S(18)–N(4)–S(17)
C(101)–S(11)··· S(12)–C(201) −1.9(5)
C(301)–S(13)··· S(14)–C(401) −6.2(5)
C(501)–S(15)··· S(16)–C(601) 3.7(5)
C(701)–S(17)··· S(18)–C(801) 4.5(5)
O(15)–S(18)–N(4)–S(17)
O(2)–S(11)–C(101)–C(102)
O(4)–S(12)–C(201)–C(202)
O(6)–S(13)–C(301)–C(302)
−16.5(10)
−14.4(9)
−6.6(9)
O(2)–S(11)–N(1)–S(12)
O(1)–S(11)–N(1)–S(12)
O(3)–S(12)–N(1)–S(11)
O(4)–S(12)–N(1)–S(11)
O(8)–S(14)–N(2)–S(13)
−44.1(8) O(8)–S(14)–C(401)–C(402)
−172.6(6) O(10)–S(15)–C(501)–C(502) −15.0(9)
173.4(6)
42.3(8)
O(12)–S(16)–C(601)–C(602) −12.9(10)
O(14)–S(17)–C(701)–C(702) 3.1(10)
−50.0(8) O(16)–S(18)–C(801)–C(802) 16.4(11)
the same cation to the water molecule. This value re- widened torsion angles of 111◦ in two independent
laxes to −79◦ in the anhydrous chloride, where the cations, whereas the DMS salt [1] shows a nearly ideal
NH groups hydrogen bond to the chloride [3]. The trans (antiperiplanar) conformation (−174◦), which,
other derivatives show no such “intracationic” hydro- other things being equal, might be expected to be the
gen bonding; the camphorsulfonate [4] shows further most stable form. The complex cations in 1 and 3 show
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˚
D–H···A
d(D–H)
0.88
0.88
0.88
0.88
0.88
1.08
1.08
1.08
d(H···A)
2.12
2.13
2.08
2.07
2.72
2.37
2.38
2.46
d(D···A)
2.909(8)
2.935(8)
2.920(8)
2.913(8)
3.263(9)
3.178(9)
3.170(9)
3.267(9)
∠(DHA)
149
151
160
160
121
130
129
131
Table 5. Hydrogen bonds (A, deg) for
compound 1.
(a)
(b)
(c)
(d)
N(11)–H(11)··· O(3)
N(12)–H(12)··· O(4)#1
N(21)–H(21)··· O(1)#2
N(22)–H(22)··· O(2)#3
N(11)–H(11)··· N(1)
C(35)–H(35)··· O(2)#4
C(36)–H(36)··· O(4)#5
C(22)–H(22A)··· O(3)#6
Symmetry transformations used to gener-
#1
#3
1
1
ate equivalent atoms:
x + /2,−y + /2,z;
#2
1
1 1
−x+1,−y,z+ /2;
−x+ /2,y+ /2,z+
#5
1
(e)
(f )
(g)
#4
1
1
1
/2;
−x + /2,y + /2,z − /2;
−x +
1
1
1
/2,y− /2,z− /2.
similar antiperiplanar conformations [torsion angles
−176◦ (1) and 166, −163, 170, −163◦ (3)], whereas
the corresponding value in 2 is 72◦.
A second degree of freedom is the planarity of the
heterocyclic rings. This too varies from compound to
compound, but in the previously determined structures
the rings are in general approximately planar, with
˚
mean deviations < 0.1 A and absolute torsion angles
≤ 20◦; this is also the case for the compounds 1 – 3. Fi-
nally, the gold atoms are usually approximately copla-
nar with the rings (absolute Au–S–C–N torsion angles
close to zero); values here are −4, 9◦ for 1, −21, −20◦
for 2 and 1, −10, −10, 5, −27, 1, 2, −6◦ for 3. In
our previous publications we have noted that these de-
grees of flexibility, especially of the C–S···S–C tor-
sion angle, make the cations less suitable for “crystal
engineering” concepts, but the detailed analysis of the
packing (see below) reveals instructive ways in which
the cations adapt to their crystal environment.
1
Fig. 4. Compound 1, ribbon structure in the region y ≈ /4
viewed parallel to the y axis. Dashed lines represent classical
hydrogen bonds. For labels see Table 5.
None of the compounds 1 – 3 display short “au-
rophilic contacts” [9]; there are no Au···Au distances
˚
< 5 A.
Crystal packing: compound 1
Compound 1 has four classical hydrogen bond
donors (the four NH groups) and five potential accep-
tors (the anion N and four O atoms). Four two-centre
hydrogen bonds (Table 5) are formed, whereby the ac-
ceptor N1 is not involved except as a possible weak
component of an asymmetric three-centre interaction
together with H11···O3. These bonds combine in a
straightforward manner to form ribbons parallel to the
x axis (Fig. 4), in which the NH groups of neighbour-
ing cations are bridged by O–S–O groups of the an-
ions. Bonds a and b (for labels see Table 5) form a
chain of graph set C22(8) [10], as do bonds c and d.
These oppositely directed chains combine to form the
complete ribbon, whereby the S–Au–S moieties act as
crosslinks to form rings of graph set R44(24). Within
1
Fig. 5. Compound 1, anion layer at x ≈ /4 viewed parallel to
the x axis. Dashed lines represent classical hydrogen bonds.
For labels see Table 5.
˚
3.27 and 3.33 A, respectively. Within any given rib-
bon, each anion only uses two oxygen acceptors; the
other two then link to the next ribbons either above or
below in the y direction and thus lead to the overall
three-dimensional packing.
There are three structurally significant C–H···O in-
these rings, atom O1 approaches atoms Au and S1 to teractions (although their angles are narrow). Two of
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S. Friedrichs – P. G. Jones · Secondary Interactions in Gold(I) Complexes with Thione Ligands, 4
˚
D–H···A
d(D–H)
0.83(2)
0.84(2)
0.84(2)
0.81(2)
0.81(2)
0.82(2)
0.82(2)
0.82(2)
1.08
d(H···A)
2.21(2)
2.51(3)
2.67(4)
2.29(4)
2.59(4)
2.31(3)
2.64(4)
2.69(4)
2.63
d(D···A)
3.029(5)
3.250(5)
3.338(5)
2.944(5)
3.253(6)
3.055(5)
3.295(6)
3.249(5)
3.680(4)
3.799(4)
3.980(5)
3.790(5)
3.761(5)
∠(DHA)
174(5)
147(4)
137(4)
138(5)
139(5)
151(5)
138(5)
127(4)
163
Table 6. Hydrogen bonds (A, deg) for
compound 2.
(a)
(b)
(c)
(d)
(e)
(f )
(g)
(h)
(i)
N(12)–H(12)··· N(1)
N(11)–H(11)··· O(3)#1
N(11)–H(11)··· O(1)#2
N(21)–H(21)··· O(3)#1
N(21)–H(21)··· O(1)#2
N(22)–H(22)··· O(4)#3
N(22)–H(22)··· O(2)#3
N(22)–H(22)··· N(1)#3
C(13)–H(13B)··· Au#4
C(22)–H(22A)··· Au#1
C(22)–H(22A)··· S(1)#1
C(46)–H(46)··· S(1)
C(33)–H(33)··· S(2)#5
Symmetry transformations used to generate
#1
1
1
1
equivalent atoms:
x + /2,−y + /2,z + /2;
#3
1
#2
#4
1
1
x − /2,−y + /2,z + /2;
x,y,z + 1;
1 − x,1 − y,
#5
1
1
1
x − /2,−y + /2,z − /2;
1−z.
(j)
(k)
(l)
1.08
1.08
1.08
1.08
3.00
2.93
2.74
2.82
131
164
164
146
(m)
these, e and f, combine to form anion layers [1] par-
allel to the yz plane (Fig. 5), in which rings of graph
set R44(21) may be recognised. In Fig. 4, bond f acts
across the centre of the rings (but is not explicitly in-
cluded), whereas bond e links adjacent ribbons in the
xz plane. Bond g links cations and anions of neighbour-
ing layers.
Because the S–Au–S axes of the cations are ster-
ically exposed, many short contacts of the form C–
H···Au and C–H···S are observed. In previous struc-
tures and elsewhere in this paper, we have attributed
hydrogen bonding properties to such interactions. In
compound 1, they are mostly very long (H···Au ca.
1
Fig. 6. Compound 2, layer structure at y ≈ /4 viewed parallel
to the y axis. Only the ipso C atoms of the anion rings are
shown. Thick dashed lines represent short classical hydrogen
bonds; thin dashed lines (for clarity only one of each type is
shown) represent weaker interactions (see text). For labels
see Table 6.
˚
3.3 A) and probably do not influence the packing sig-
nificantly. A complete list can be found in the Supple-
mentary Material.
once each.
The layers also involve one very short (H···Au
Crystal packing: compound 2
˚
2.63 A) C–H···Au (i) and a three-centre C–H···(S,Au)
interaction (j,k). Again, each is included in Fig. 6 only
once.
Compound 2 fulfils the same preconditions as com-
pound 1 for hydrogen bonding; the cation is the same
and the anion also has five potential hydrogen bond
acceptors. Indeed, a layer structure is again formed
(Fig. 6), but in this case the layers are not linked as
in 1. However, the nature of the hydrogen bonding is
completely different. Most surprisingly, there is only
one simple two-centre classical hydrogen bond (entry
a in Table 6, also shown in Fig. 2) and this involves
Because of the extensively multi-centre hydrogen
bonding, graph set analysis is less meaningful. One
easily recognisable feature is the R22(4) ring formed by
H bonds b-e, right of centre in the unit cell (Fig. 6).
The gold atom is positioned above this ring and makes
˚
a short contact of 3.375(3) A to O3.
Because the chlorophenyl rings are omitted from
the anion nitrogen atom as acceptor. The other N–H Fig. 6 for clarity, some features involving these
donors are involved in asymmetric three-centre (H11, rings need extra explanation. These and other con-
H21) or four-centre (H22) hydrogen bonds to the anion tacts can be recognised in the side view of adja-
O and N atoms; it is noteworthy that atoms O1 and O2 cent layers (Fig. 7). There are two C–H···S interac-
accept none of the shortest components of the multi- tions (l,m) and the contacts Au···Cl2 (1 − x,1 − y,
˚
centre H bonds, but only two or one weaker branches, 1−z) 3.414(2) A (n) and S2···Cl1 (1−x,1−y,1−z)
˚
respectively. In Fig. 6, only the shortest branches of 3.480(2) A (o), all within the layers. Between the lay-
˚
each H bond system are included throughout the Fig- ers, only a single contact, Cl1···Cl2 3.655(2) A (p), is
ure; for clarity, the longer branches are shown only observed via the x axis translation. With C–Cl···Cl an-
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S. Friedrichs – P. G. Jones · Secondary Interactions in Gold(I) Complexes with Thione Ligands, 4
1397
˚
D–H···A
d(D–H)
0.83(2)
0.83(2)
0.83(2)
0.82(2)
0.83(2)
0.88
d(H···A)
2.05(4)
2.10(6)
2.15(4)
2.14(5)
2.27(6)
2.12
d(D···A)
2.859(12)
2.843(12)
2.940(14)
2.903(12)
3.003(13)
2.827(14)
2.859(13)
2.955(12)
3.020(12)
2.932(13)
2.819(13)
2.827(12)
2.820(12)
2.831(12)
3.818(9)
<(DHA)
165(12)
149(11)
160(11)
155(11)
147(10)
136
Table 7. Hydrogen bonds (A, deg) for
compound 3.
(a)
(b)
(c)
(d)
(e)
(f )
(g)
(h)
(i)
(j)
(k)
(l)
(m)
(n)
(o)
N(12)–H(12)···O(9)#2
N(21)–H(21)···O(7)
N(22)–H(22)···N(4)
N(31)–H(31)···O(13)
N(32)–H(32)···N(2)
N(41)–H(41)···O(3)
N(42)–H(42)···N(1)#3
N(51)–H(51)···O(6)#4
N(52)–H(52)···O(14)#3
N(61)–H(61)···O(11)#5
N(62)–H(62)···N(3)#4
N(72)–H(72)···O(1)#3
N(81)–H(81)···O(16)#3
N(82)–H(82)···O(8)#4
N(11)–H(11)···I(1)#1
N(11)–H(11)···I(2)#1
N(71)–H(71)···I(5)
Symmetry transformations used to gen-
#1
erate equivalent atoms:
x,y − 1,z;
#2
#4
#6
#3
−x+1,−y,−z+1;
−x+1,−y+1,−z;
#5
−x + 1,−y + 1,−z + 1;
−x+1,−y+2,−z+1.
x,y + 1,z;
0.83(2)
0.88
2.04(3)
2.29
170(12)
133
0.82(2)
0.83(2)
0.83(2)
0.82(2)
0.83(2)
0.82(2)
0.88
0.88
0.88
1.08
1.08
2.22(4)
2.33(9)
2.06(5)
2.09(7)
2.09(6)
2.25(9)
3.06
3.41
3.01
2.78
2.81
163(11)
129(10)
153(11)
149(12)
147(10)
128(10)
145
124
156
137
158
3.972(10)
3.830(10)
3.639(12)
3.831(13)
3.641(14)
3.760(13)
(p)
(q)
(r)
(s)
(t)
C(43)–H(43A)··· Au(2)#3
C(63)–H(63A)··· Au(3)#6
C(33)–H(33A)··· Au(1)
C(53)–H(53A)··· Au(4)
1.08
1.08
2.66
2.72
152
161
Fig. 8. Compound 3, chain formation parallel to the z axis.
Dashed lines represent classical hydrogen bonds. For italic
labels see Table 7. Numbering of cations and anions refers to
the Au and N atoms, respectively. Hydrogen atoms are omit-
ted; p-iodophenyl rings are represented by the ipso carbon
atoms.
NH donors and ten of the 16 potential oxygen accep-
tors (six ap and four sc); all four anion nitrogen atoms
act as acceptors. All the classical H bonds are two-
centre systems.
As is usual in complex three-dimensional packing
systems, it is easier to split the structure into more eas-
ily assimilable parts. In this way, it can be seen that the
anions play a mediating role between two substructures
involving all anions together with cations 1 and 4 or 2
and 3, respectively.
Fig. 7. Compound 2, three adjacent layers viewed edge on.
Dashed lines represent various secondary interactions. For
labels see Table 6 and text.
gles of 74.0 and 115.1(2)◦, this may be classified as a
“type I” interaction [11], which are not considered to
arise from specific attractive forces.
Crystal packing: compound 3
Replacing the p-chloro substituent in 2 by p-iodo
The cations 1 and 4 (based on the gold numbering)
has a dramatic effect. Compound 3 crystallizes with interact with the anions to form the first substructure,
four independent formula units and the packing is an alternating cation-anion chain parallel to the z axis
correspondingly complicated. Involvement in classical (Fig. 8). Within the chain, the hydrogen bonds m,c,b,n
hydrogen bonds is restricted to 14 of the 16 potential (Table 7) combine to yield the graph set C44(16). The
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1398
S. Friedrichs – P. G. Jones · Secondary Interactions in Gold(I) Complexes with Thione Ligands, 4
Fig. 10. Compound 3, connection of dimers (seen edge on)
via H bonds (thick dashed lines). For italic labels see Ta-
ble 7. Numbering of dimers refers to the Au atoms. Hydro-
gen atoms are omitted; p-iodophenyl rings are represented by
the ipso carbon atoms.
Fig. 9. Compound 3, cyclic dimer formation via H bonds
(dashed lines). For italic labels see Table 7. Numbering of
cations and anions refers to the Au and N atoms, respec-
tively. Hydrogen atoms are omitted; p-iodophenyl rings are
represented by the ipso carbon atoms.
bridging anions are not topologically equivalent, be-
cause anion 4 (based on the nitrogen numbering) is
an N,O and anion 2 an O,O acceptor. The hydrogen
bonds a and l branch off the main chain to anions 1
and 3, which play a terminating role in this substruc-
ture (but connect to the second substructure).
Fig. 11. Compound 3, cation-anion association via Au···I
and S···I contacts and NH···I hydrogen bonds. Distances
˚
are in A.
Cation 2 combines with anion 1 (as an N,O accep-
tor) to form an inversion-symmetric, cyclic dimer of
graph set R44(16) via H bonds f and g; the H bond d is
formed exocyclically to anion 4. An exactly analogous
topology is shown by the dimer of cation 3 and an-
ion 3, with anion 2 exocyclic (H bonds j,k,h). These
dimers, shown in Fig. 9, constitute the second sub-
structure. The anions exert a pincer effect on the two
cations that they connect; the short C–H···Au interac-
tions q and r (not shown in Fig. 9) probably reinforce
this effect across the dimers. The remaining two clas-
sical bonds e and i connect the dimers to each other
(Fig. 10), whereas the remaining two C–H···Au in-
teractions s and t connect the two substructures (not
shown).
∆y = +1 causes the narrow S–Au–S unit of cation 1
of the translated chain to lie between the ring iodines
of anion 2, the ends of the “hairpin”. This associ-
ation is illustrated in more detail in Fig. 11, which
shows the H bond o together with the S···Au and
S···I contacts. Although these are somewhat longer
than the sum of the van der Waals radii, the overall
effect of the contacts may well be to stabilize the sys-
tem. A similar effect applies to cation 4 and anion 3
via ∆y = −1; this may be additionally recognised in
Fig. 3, in which however the contacts are not explicitly
drawn.
In view of the structure-determining nature of the
classical hydrogen bonds, we do not analyse a series
of C–H···S and C–H···I interactions; for details, the
Supplementary Material should be consulted.
Two NH donors (H11, H71) remain that do not take
part in classical hydrogen bonds. These form short
contacts, which may reasonably be regarded as hy-
drogen bonds (o, p), to iodine atoms. A closer in-
spection of the chains of Fig. 8 reveals the structural
Conclusions
Despite the apparently closely similar nature of the
role of these contacts. The translation of the chain by three compounds investigated, especially compounds 2
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S. Friedrichs – P. G. Jones · Secondary Interactions in Gold(I) Complexes with Thione Ligands, 4
1399
and 3, their hydrogen bonding patterns are completely Bis(imidazolidine-2-thione)gold(I) di(4-iodobenzenesulfon-
yl)amide (3)
different. Although the packing of compound 1 is con-
ceptually simple (all NH groups act as donors and all
anion O atoms as acceptors in two-centre H bonds),
compound 2, for no obvious reason, instead exhibits
several multi-centre H bond systems, and compound
3 crystallizes with four independent formula units. In
both these compounds the anion nitrogen atoms func-
tion as H bond acceptors, while several potential oxy-
gen acceptors are not utilised. This again demonstrates
the resistance of the whole series of compounds to
structure prediction or analogies based on chemical
similarity; in other words to the concept of “crystal en-
gineering”.
◦
1
Yield: 0.24 g (25%). – Dec. > 183 C. – H NMR (d6–
DMSO): δ = 3.75 (8H, s; CH2), 7.38 (4H, d, J(Ho–Hm) =
3
8.3 Hz; Ho), 7.73 (4H, d; Hm), 9.31 (4H, bs; NH). – MS
(NBA): FAB (neg.) m/z = 421 (6%, [A−I]−), 547 (100%,
[A−H]−), 548 (100%, [A]−); FAB (pos.) = 299 (20%,
[K−(C3H6NS2)]+), 401 (100%, [K]+), 402 (12%, [K+H]+),
699 (7%, [2K−(C3H6NS2)–H]+). – C18H20AuI2N5O4S4
(949.44): calcd. C 22.77, H 2.13, N 7.38; found C 22.93,
H 2.15, N 7.22.
X-ray structure determinations
The crystals were mounted in inert oil on glass fibres. Data
were measured using Mo Kα radiation (λ = 0.71073 A) on
˚
Experimental Section
Siemens P4 (2, 3) or Bruker SMART 1000 CCD diffractome-
ters (1), fitted with low temperature attachments. Structures
were refined anisotropically on F2 [12]. Crystal data and re-
finement details are presented in Table 1, selected molecular
dimensions in Tables 2 – 4, and hydrogen bond dimensions
in Tables 5 – 7.
Physical measurements
These were recorded as described in [3].
Preparations
The compounds [(etu)2Au]+ X− were prepared from the
corresponding chloride as follows: 1 mmol [(etu)2Au]+ Cl−
was dissolved in 50 mL of ethanol and treated with a solution
of the silver disulfonylamide AgX (1 mmol; kindly provided
by Prof. A. Blaschette) in acetonitrile (5 mL). The cloudy
reaction mixture was stirred for 1.5 h at r. t. in the dark. After
filtering off the◦precipitated AgCl, the colourless filtrate was
stored at −18 C for 12 h to yield crystals of the required
products 1 – 3.
Hydrogen atom treatment: For 2, associated with its good
crystal quality, hydrogen atoms bonded to nitrogen atoms
were located in Fourier syntheses and refined freely, but with
N–H distances restrained to be equal using the SADI instruc-
tion [12]. For 1 and 3, the moderate crystal quality led to
problems in locating the hydrogen atoms of the NH groups
(these H atoms cannot be geometrically positioned with cer-
tainty because their parent nitrogen atoms cannot be assumed
to have a planar substituent geometry). Some H atoms were
located directly, some were placed geometrically assuming a
planar geometry and then allowed to refine; those that were
not stable were fixed at idealised planar geometry. The relia-
bility of the H atom positions can be judged by their sensible
hydrogen bonding interactions (see Discussion). Other hy-
drogen atoms were placed in calculated positions and refined
using a riding model.
Bis(imidazolidine-2-thione)gold(I) benzene-1,2-di(sulfonyl)
amide (1)
Yield: 0.50 g (81%). – Dec. > 187 ◦C. – 1H NMR
(d6–DMSO): δ = 3.75 (H, s; CH2), 7.72 (4H, m; HAr),
9.31 (4H, bs; NH). – MS (gly): FAB (neg.; A = anion)
m/z = 218 (13%, [A]−); FAB (pos.; K = cation) m/z =
401 (100%, [K]+). – C12H18AuN5O4S4 (619.54): calcd.
C 23.33, H 2.61, N 11.31, S 20.70; found C 23.60, H 2.74,
N 11.40, S 20.60.
Special features of refinement: Compound 1 was refined
as a racemic twin, with components 0.55 : 0.45(1). For com-
pounds 1 and 3, an extensive system of restraints (to displace-
ment parameters, local ring symmetries and equivalence of
independent molecules) was employed to improve refine-
ment stability.
Bis(imidazolidine-2-thione)gold(I) di(4-chlorobenzenesulf-
onyl)amide (2)
For the calculation of hydrogen bonding parameters, C–H
◦
1
˚
bond lengths were normalised to 1.08 A [13]. Contacts with
Yield: 0.33 g (43%). – Dec. > 176 C. – H NMR (d6–
DMSO): δ = 3.76 (8H, s; CH2), 7.44 (4H, d, 3J(Hm–Ho) =
8.7 Hz; Hm), 7.64 (4H, d; Ho), 9.31 (4H, bs; NH). – MS
(NBA): FAB (neg.) m/z = 364 (100%, [A]−); FAB (pos.)
uncorrected angles < 130◦ at hydrogen have generally been
omitted.
Complete crystallographic data (excluding structure fac-
m/z = 299 (25%, [K−C3H6N2S)]+), 401 (100%, [K]+), tors) have been deposited at the Cambridge Crystallographic
699 (5%, [2K–(C3H6N2S)–H]+). – C18H20AuCl2N5O4S4 Data Centre under the numbers CCDC 681656 (1), 681657
(766.54): calcd. C 28.20, H 2.64, N 9.14, Cl 9.25; found (2) and 681658 (3). Copies may be obtained free of charge
C 28.17, H 2.71, N 9.13, Cl 9.21.
via www.ccdc.cam.ac.uk/data request/cif.
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1400
S. Friedrichs – P. G. Jones · Secondary Interactions in Gold(I) Complexes with Thione Ligands, 4
[1] Part 3: S. Friedrichs, P. G. Jones, Z. Naturforsch. 59b,
1429 (2004).
[2] This publication also represents Part CLXXVI of the
series “Polysulfonylamines”. Part CLXXV: O. Moers,
A . Blaschette, V. Latorre, P. G. Jones, Z. Naturforsch.
61b, 923 (2006).
[7] D. Henschel, T. Hamann, O. Moers, P. G. Jones,
A. Blaschette, Z. Naturforsch. 60b, 645 (2005).
[8] E.-M. Zerbe, P. G. Jones, A. Blaschette, unpublished
results.
[9] H. Schmidbaur, Gold Bull. 23, 11 (1990).
[10] J. Bernstein, R. E. Davis, L. Shimoni, N.-L. Chang,
Angew. Chem. 107, 1689 (1995); Angew. Chem. Int.
Ed. Engl. 34, 1555 (1995).
[3] S. Friedrichs, P. G. Jones, Z. Naturforsch. 59b, 49
(2004).
[4] S. Friedrichs, P. G. Jones, Z. Naturforsch. 59b, 793
(2004).
[5] O. Moers, S. Friedrichs, A. Blaschette. P. G. Jones,
Z. Anorg. Allg. Chem. 628, 589 (2002).
[6] V. Lozano, O. Moers, P. G. Jones, A. Blaschette,
Z. Naturforsch. 59b, 661 (2004).
[11] V. R. Pedireddi, D. S. Reddy, B. S. Goud, D. C. Craig,
A. D. Rae, G. R. Desiraju, J. Chem. Soc., Perkin Trans.
2, 2353 (1994).
[12] G. M. Sheldrick, SHELXL-97, Program for the Refine-
ment of Crystal Structures, University of Go¨ttingen,
Go¨ttingen (Germany) (1997).
[13] T. Steiner, Acta Cryst. B54, 456 (1998).
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