Synthesis and characterization of novel derivatives of N-(ferrocenesulfonyl)carbamic acid. X-ray structure determination of ferrocenesulfonamide and N-(ferrocenesulfonyl)-N′-butylurea

Article abstract of DOI:10.1016/S0022-328X(98)00579-8

Ferrocenesulfonamide, 1, was converted to novel N-(ferrocenesulfonyl)ureas and N-(ferrocenesulfonyl)carbamates via reacting 1 with the corresponding organic isocyanates or chloroformic acid esters. The molecular structures of 1 and N-(ferrocenesulfonyl)-N′-butylurea were determined by single-crystal X-ray diffraction. Crystal data: 1: monoclinic, P2₁/c, with unit cell dimensions a = 12.563(1), b = 9.977(2), c = 8.557(1) A, and β = 98.71(1)°, V = 1060.2(3) A³, Z = 4; 3e: orthorombic, Pbca, a = 9.278(1), b = 15.892(4), c = 22.043(3) A, and V = 3250.2(10) A³, Z = 8. In both 1 and 3e, the Fe-C distances of the substituted Cp ring follow a special sequence, the Fe-C(S) bonds being shorter than the Fe-C bonds with the neighboring or remote C atoms.

Full text of DOI:10.1016/S0022-328X(98)00579-8

Journal of Organometallic Chemistry 563 (1998) 81–86
Synthesis and characterization of novel derivatives of
N-(ferrocenesulfonyl)carbamic acid. X-ray structure determination of
ferrocenesulfonamide and N-(ferrocenesulfonyl)-N%-butylurea
Ga´bor Besenyei *, La´szlo´ Pa´rka´nyi, Sa´ndor Ne´meth, La´szlo´ I. Sima´ndi
Central Research Institute for Chemistry, Hungarian Academy of Sciences, PO Box 17, H-1525 Budapest, Hungary
Received 29 December 1997
Abstract
Ferrocenesulfonamide, 1, was converted to novel N-(ferrocenesulfonyl)ureas and N-(ferrocenesulfonyl)carbamates via reacting
1 with the corresponding organic isocyanates or chloroformic acid esters. The molecular structures of 1 and N-(ferrocenesulfonyl)-
N%-butylurea were determined by single-crystal X-ray diffraction. Crystal data: 1: monoclinic, P21/c, with unit cell dimensions
3
˚
˚
a=12.563(1), b=9.977(2), c=8.557(1) A, and i=98.71(1)°, V=1060.2(3) A , Z=4; 3e: orthorombic, Pbca, a=9.278(1),
3
˚
˚
b=15.892(4), c=22.043(3) A, and V=3250.2(10) A , Z=8. In both 1 and 3e, the Fe–C distances of the substituted Cp ring
follow a special sequence, the Fe–C(S) bonds being shorter than the Fe–C bonds with the neighboring or remote C atoms.
© 1998 Elsevier Science S.A. All rights reserved.
Keywords: Ferrocene; Sulfonylureas; Sulfonylcarbamates; X-ray structure
1. Introduction
decomposition of ferrocenesulfonyl azides [7]. No infor-
mation is, however, available on the synthetic possibili-
ties related to ferrocenesulfonamides, although the
corresponding benzene, thiophene and pyridine sulfon-
amides have widespread application in pharmaceutical
and agricultural chemistry. Sulfanilamide-based drugs
and N-arylsulfonyl-N%-alkylureas have been used over
several decades in human therapeutics. Discovery of the
excellent herbicidal activity of certain N-arylsulfonyl-
N%-heteroarylureas in the mid 1970’s initiated extensive
research and led to the development of more than a
dozen highly efficient sulfonylurea type herbicides [8].
In an attempt to help explore the possible synthetic
potential of ferrocene-based sulfonamide derivatives,
we have prepared and characterized a number of fer-
rocenesulfonylureas and ferrocenesulfonylcarbamates.
In this paper we report the synthesis and spectroscopic
properties of these compounds together with the crystal
and molecular structure of ferrocenesulfonamide and
N-ferrocenesulfonyl-N%-butylurea.
Metallocenes continue to be a major research area in
organometallic chemistry, as demonstrated by the high
output of communications devoted to synthetic, struc-
tural and mechanistic studies, concentrating largely on
ferrocene derivatives. One of the most extensively stud-
ied subjects is the synthesis of ferrocene-based phos-
phine ligands and their application in catalytic
reactions [1]. In this context the interaction of sub-
stituents on the Cp rings with the metallic center in the
same molecule is of considerable interest, as demon-
strated by recent X-ray studies [2]. Search for biologi-
cally active ferrocene derivatives has also attracted
considerable attention [3].
Ferrocenesulfonic acids and their derivatives are use-
ful starting materials in various organometallic synthe-
ses [4–6]. Abramovich et al. have studied the thermal
* Corresponding author. Fax: +36 1 3257554.
0022-328X/98/$19.00 © 1998 Elsevier Science S.A. All rights reserved.
PII S0022-328X(98)00579-8

82
G. Besenyei et al. / Journal of Organometallic Chemistry 563 (1998) 81–86
To our knowledge, there are only two communica-
tions devoted to the crystallographic characterization of
ferrocenesulfonic acid derivatives. Beside an early study
[10] on the structure of 1,1%-ferrocenedisulfonyl chloride
(recomputed in 1964) [11], the Cambridge Crystallo-
graphic Data Centre File contains only the related
structure of ferrocenesulfonyl azide [7]. We now de-
scribe the crystal and molecular structure of ferrocene-
sulfonamide, 1, and N-ferrocenesulfonyl-N%-butylurea,
3e.
The Fe–C distances in 1 range from 2.010(1) to
˚
˚
2.055(2) A with mean values of 2.039 A for the substi-
Fig. 1. Molecular diagram for ferrocenesulfonamide (1) with the
numbering of atoms. Thermal ellipsoids represent 40% probabilities.
˚
tuted, and 2.042 A for the unsubstituted Cp ring,
The
centroids
of
the
Cp
rings
are
defined
as
respectively, in good agreement with the average Fe–C
X(1)[C(1),C(2),C(3),C(4),C(5)] and X(2)[C(6),C(7),C(8),C(9),C(10)].
X(1)–Fe–X(2)=179.3 °, C(1)–X(1)–X(2)–C(9)=5.8°.
˚
bond length in ferrocene (2.031 A) [12]. The mean C–C
˚
bond length in the unsubstituted ring is 1.413 A (1.402
˚
A in ferrocene [12]) and the C–C–C angles vary only
2. Results and discussion
by a few tenths of a degree (107.8–108.4°) around the
theoretical value of 108°. The presence of the aminosul-
fonyl substituent in the other Cp ring leads to deforma-
tion reflected by the larger interval of the C–C–C
angles (106.8–108.7°) and also to some elongation of
the C(1)–C(2) and C(1)–C(5) bonds but exerts only a
Ferrocene is susceptible to electrophilic substitution
and the presence of an electron-withdrawing substituent
generally does not prevent the molecule from a second
electrophilic reaction in the unsubstituted Cp ring. Al-
though chlorothioformic acid esters have been reported
to form ferrocenethiocarboxylic acid S-esters in reac-
tions mediated by AlCl3 [9], we did not observe C-acy-
lation under non-catalytic conditions.
˚
negligible effect on the mean C–C distance (1.420 A).
˚
The average S–O (1.434 A) and the N–S bond
˚
distances (1.608 A) are in good agreement with the
In the 1H-NMR spectra of compounds 3a–k the four
protons of the substituted cyclopentadienyl ring form
an AA%BB% system, while the hydrogen atoms of the
other Cp moiety appear as a sharp singlet. The protons
attached to the sulfonamide nitrogen atoms show up
between 7.1 and 7.6 ppm as broadened resonances. The
position of the other N-bound H-atom depends on the
nature of the R substituent. It is located around 6.4–
6.5 ppm for R=alkyl groups and poorly resolved
couplings to the 6icinal hydrogen atoms can be ob-
served. The same protons in the N%-arylureas appear in
the region of 8.4–8.7 ppm reflecting an upfield shift
caused by the aromatic ring.
respective values observed for p-toluenesulfonamide
˚
˚
[13] (1.431 and 1.610 A). The C(1)–S bond (1.743 A),
however, is appreciably shorter than the corresponding
˚
value in p-toluenesulfonamide (1.788 A).
The bonds around the sulfur atom are disposed in a
distorted tetrahedral arrangement with angles very sim-
ilar to those observed in p-toluenesulfonamide. The
sulfur atom lies in the plane determined by the carbon
atoms of the cyclopentadienyl ring to which it is at-
tached (S€ (C1)=360°).
In the crystal structure of 1 (Fig. 1), the hydrophobic
parts of the molecules form a layer stabilized by van
Fig. 2. Molecular diagram for 3e with the numbering of atoms. Thermal ellipsoids represent 40% probabilities. The disordered atoms are drawn
as spheres and the hydrogen atoms linked to them are omitted for clarity. The centroids of the Cp rings are defined as
X(1)[C(1),C(2),C(3),C(4),C(5)] and X(2)[C(6),C(7),C(8),C(9),C(10)]. X(1)–Fe–X(2)=178.4 °, C(1)–X(1)–X(2)–C(8)=6.6°.

G. Besenyei et al. / Journal of Organometallic Chemistry 563 (1998) 81–86
83
Table 1
Selected spectroscopic data of compounds 3a–k
Com-
1H-NMR
IR (KBr, cm−1
)
pound
NH
N%H
Aliphatic protons
Cp, substituteda Cp, freeb
3a
3b
3c
3d
3e
7.46 (br)
7.24 (br)
7.57
8.42
—
4.72; 4.46
4.70; 4.48
4.71; 4.48
4.67; 4.45
4.64; 4.43
4.44
4.44
4.45
4.43
4.42
3327, 1679, 1600, 1547, 1351,
1126
3327, 1703, 1605, 1553, 1492,
1349, 1126, 1118
3350, 1696, 1566, 1347, 1337,
1167, 1128
3331, 1656, 1549, 1349, 1195,
1141
8.46
—
8.62
—
7.10
6.45(br)
6.50(br)
2.83 (3H, d, 4.8 Hz)
7.60
3.22 (2H, d/t, 5.7 Hz, 7.1
Hz), 1.49 (2H, m); 1.34 (2H,
m), 0.95 (3H, t, 7.3 Hz)
3341, 1659, 1550, 1344, 1196,
1141
3f
7.32 (br)
6.41 (br, d, 7.9 3.62 (1H, m), 1.91 (2H), 1.70 4.66; 4.44
4.42
3333, 1649, 1550, 1343, 1196,
1142
Hz)
(2H), 1.59 (2H), 1.35 (2H)
and 1.20 (2H) (all multiplets)
2.90 (6H, s)
3g
3h
7.47 (br)
7.28 (br)c
—
—
4.88; 4.44
4.83; 4.47
4.41
4.43
3266, 1684, 1431, 1361, 1331,
1201, 1124
4.14 (2H, q, 7.1 Hz), 1.24
(3H, t, 7.1 Hz)
3300–2800(br), 1704(br)e,
1478, 1432, 1381, 1362, 1312,
1203, 1142
d
3i
—
—
5.10 (2H, s)
4.79; 4.43
—
4.41
—
3240(br), 1756, 1744e, 1436,
1348, 1227, 1132
3j
Not recorded
7.48
—
—
3240, 1760, 1450, 1345, 1220,
1150
3400–2850, 1710(sh), 1700,
1595, 1445(br), 1330, 1130
3k
12.60
2.43 (6H, s), 6.71 (1H, s)f
4.92; 4.43
4.44
e
a AA%BB% multiplets, 2-2 H; b 5 H, s; c at 70°C: 7.08 ppm; d covered by aromatic protons; wCO=1750 cm−1 in 7 mg ml−1 CCl4 solution;
f pyrimidine CH.
s, singlet; d, doublet; t, triplet; q, quartet; m, multiplet; br, broad.
The bond lengths of the sulfur atom with O(1), O(2)
and C(1) are about the same in 1 and 3e. The wide
interval of angles around S (103.4–120.4°) reflects a
distorted tetrahedral arrangement of the atoms in-
der Waals interactions, while the aminosulfonyl moi-
eties constitute another plane in which the NH2 group
of molecule A and the sulfonyl group of molecule B are
connected by hydrogen bonds (respective distances and
angles are shown in Table 5). One of the hydrogen
atoms [H(1)N] is obviously involved in a bifurcated
H-bond system (S€ (H1N)=356.1°) [14]. H(2)N main-
tains only a week interaction with O(2).
˚
volved. The N(1)–S bond is longer by 0.05 A in 3e than
that in 1. This feature may be attributed to the strong
electron-withdrawing effect of the carbonyl group,
which reduces the ability of N(1) to donate electrons to
the sulfonyl group, thereby decreasing the N(1)–S bond
In 3e, the average Fe–C distances in the substituted
˚
˚
˚
(2.035 A) and in the unsubstituted Cp ring (2.038 A)
are practically equal. These numbers hide the fact,
however, that the individual Fe–C bonds in the unsub-
stituted Cp moiety are far more uniform (2.031–2.047
order. The length of the N(1)–S bond (1.656 A) in 3e is
comparable with the corresponding bond lengths in
tolbutamide [N-p-toluenesulfonyl-N%-n-butylurea] [16]
˚
(1.653 A) and chlorpropamide [N-p-chlorobenzenesul-
˚
˚
A) than they are in its sulfonylated counterpart (1.998–
2.057 A). The mean C–C distance is but slightly longer
in the substituted (1.410 A) than in the unsubstituted
ring (1.400 A) due to the presence of the electron-with-
fonyl-N%-n-propylurea] [17] (1.644 A). The difference
˚
between the N(2)–C(11) and N(1)–C(11) bonds is in
line with the larger electron density localized on N(2)
˚
˚
˚
compared with that on N(1). The value of 1.223 A is
drawing substituent. The crystal structure 3e (Fig. 2)
does not seem to follow the reported trend (valid also
for 1) that the longest C–C bonds in Cp rings involve
the substituted carbon atom [15]. However, this differ-
ence may only be apparent as the estimated S.D. of the
C–C bonds in 3e are twice as great as those observed
for 1.
typical for CꢀO double bonds.
The crystal structure of 3e is stabilized by both van
der Waals interactions and hydrogen bonds. The prox-
imity of N(2) and O(3%) as well as N(2) and one of the
sulfonyl oxygen atoms of a neighboring molecule (see
Table 5) indicates that hydrogen bond formation is
feasible. The sum of angles about HN(2) is 358.0°,

84
G. Besenyei et al. / Journal of Organometallic Chemistry 563 (1998) 81–86
Table 3
which satisfies the requirement for bifurcated hydrogen
bonds [14]. The proton attached to the sulfonyl nitro-
gen interacts only with a carbonyl oxygen. Similar
stabilizing interactions have been observed in the struc-
ture of the p-tosyl analogue [16], while the structural
analysis of chlorpropamide [17] revealed the presence of
only two types of hydrogen bonds.
Although many structural properties of ferrocene-
1,1%-disulfonyl chloride [11], ferrocenesulfonyl azide [7]
as well as 1 and 3e can be regarded as typical to
ferrocene derivatives, they also display some unex-
pected features. These ‘‘irregularities’’ involve the sul-
fonyl group and its neighborhood.
˚
Selected bond distances (A) and angles (°) for compound 1
˚
Bond length (A)
Fe–C(1)
Fe–C(2)
Fe–C(6)
Fe–C(10)
Fe–C(9)
N–S
2.010(1) Fe–C(7)
2.038(2) Fe–C(8)
2.041(2) Fe–C(5)
2.044(2) Fe–C(3)
2.050(2) Fe–C(4)
1.608(1) S–O(2)
2.034(2)
2.040(2)
2.041(2)
2.049(2)
2.055(2)
1.428(1)
1.743(1)
1.431(2)
1.406(3)
1.401(3)
1.419(3)
1.404(3)
S–O(1)
1.440(1) S–C(1)
C(1)–C(2)
C(2)–C(3)
C(4)–C(5)
C(6)–C(10)
C(8)–C(9)
1.428(2) C(1)–C(5)
1.420(3) C(3)–C(4)
1.417(2) C(6)–C(7)
1.418(3) C(7)–C(8)
1.421(3) C(9)–C(10)
The S–C bonds of both sulfonyl groups in ferrocene-
1,1%-disulfonyl chloride are bent by 5.5° toward the Cp
Bond angle (°)
O(2)–S–N
O2–S–C(1)
N–S–C(1)
C(2)–C(1)–S
O(1)–S–N
O(2)–S–O(1)
C(4)–C(3)–C(2)
C(4)–C(5)–C(1)
C(6)–C(7)–C(8)
106.8(1)
O(1)–S–C(1)
C(2)–C(1)–C(5)
C(5)–C(1)–S
C(3)–C(4)–C(5)
C(3)–C(2)–C(1)
C(7)–C(6)–C(10)
C(7)–C(8)–C(9)
C(9)–C(10)–C(6)
C(10)–C(9)–C(8)
107.1(1)
108.1(1)
107.9(1)
126.1(1)
107.0(1)
119.4(1)
108.9(2)
107.0(2)
107.8(2)
108.5(1)
125.4(1)
108.7(2)
106.8(2)
108.4(2)
107.9(2)
108.1(2)
107.8(2)
Table 2
Experimental data for the X-ray diffraction studies on compounds 1
and 3e
1
3e
Empirical formula
Formula weight
Crystal system
C10H11FeNO2S
265.11
Monoclinic
P21/c
C15H20FeN2O3S
364.24
Orthorhombic
Pbca
Space group
ring to which they are not attached. This phenomenon
was ascribed to the interaction of neighboring
molecules in the crystal lattice.
McManus et al. [7] noticed that in the solid state
structure of ferrocenesulfonyl azide the Fe atom is
‘‘slightly offset toward the sulfonyl azide group’’ and
postulated a weak bonding interaction ‘‘between a
metal d orbital and either of the oxygens or an empty
sulfur d orbital’’.
Unit cell dimensions
˚
a (A)
12.563(1)
9.977(2)
8.557(1)
98.71(1)
1060.2(3)
4
9.278(1)
15.892(4)
22.043(3)
—
3250.2(10)
8
˚
b (A)
˚
c (A)
i (°)
3
˚
Volume (A )
Z
Dcalc. (mg/m3)
1.661
1.489
Absorption coefficient, v 1.595
(mm−1
F(000)
1.069
)
544
1520
In both 1 and 3e, the Fe–C distances follow a
particular order, namely Fe–C(4)$Fe–C(3)\Fe–
C(5)$Fe–C(2)\Fe–C(1). Such sequence of bond
lengths indicate that an interaction between the sulfonyl
group and the iron atom may exist which causes a
slight distortion of the structure, as has been supposed
for ferrocenesulfonyl azide [7]. Taking into account that
the Fe–O(1) and Fe–O(2) distances (1: 3.739 and 3.713
Crystal color
Yellow
Block
Orange
Block
Crystal description
Crystal size (mm)
Index ranges
0.40×0.30×0.15 0.20×0.25×0.35
−225h522; − −75h511; −
75k517; 05l5 205k58;−125l
15
528
q range (°)
Reflections collected
Independent reflections
2.62–39.74
7508
2.56–27.05
3663
˚
˚
6459 [Rint
0.0128]
=
3564 [Rint
0.0292]
=
A; 3e: 3.601 and 3.846 A) are by far longer than the
˚
˚
Fe–S distances (1: 3.344 A; 3e: 3.298 A), a dy–dy
interaction between the iron and sulfur atoms seems to
be more likely. In our view, the observed displacement
of sulfur atoms in ferrocenedisulfonyl chloride may also
be attributed to a weak sulfur to iron bonding of this
type.
Bonding interactions of the iron center with electron
deficient substituents on the Cp ring {CR2+ [18,19],
BBr2 ([2]a)} are well documented. Similar forces seem
to affect the geometry of the sulfonated ferrocenes
discussed here and in the communications cited al-
though the strength of the Fe–S interaction is influ-
enced by the substituents attached to the sulfonyl
group.
Absorption correction
Empirical (C-
scans)
Empirical (C-
scans)
Min./max. transmission
factors
0.826/1.000
0.900/1.000
Refinement method
Full-matrix least- Full-matrix least-
squares on F2
5153/0/138
squares on F2
3492/46/223
Data/restraints/parame-
ters
Goodness-of-fit on F2
1.021
0.829
Final R indices [I\2|(I)] R1=0.0368,
wR2=0.0946
R1=0.0448,
wR2=0.1088
R1=0.1090,
wR2=0.1426
0.654 and −0.286
R indices (all data)
R1=0.1043,
wR2=0.1243
0.503 and
−0.575
Largest difference peak
−3
˚
and hole (e A
)

G. Besenyei et al. / Journal of Organometallic Chemistry 563 (1998) 81–86
85
Table 4
Selected bond distances (A) and angles (°) for compound 3e
acid derivatives. Experiments with organic isocyanates
R1NCO (2a–f), N,N-dimethylcarbamoyl chloride (2g)
and chloroformic acid derivatives ClC(O)OR2 (2h–j)
were carried out with the exclusion of moisture.
˚
˚
Bond length (A)
Fe–C(1)
Fe–C(8)
Fe–C(5)
Fe–C(9)
Fe–C(3)
S–O(1)
S–N(1)
O(3)–C(11)
N(2)–C(11)
C(1)–C(2)
C(2)–C(3)
C(4)–C(5)
C(6)–C(7)
C(8)–C(9)
C(12)–C(13)
C(13)–C(14)x
C(14)x–C(15)x
1.998(3)
2.035(4)
2.039(3)
2.038(4)
2.046(4)
1.423(2)
1.656(3)
1.223(4)
1.328(4)
1.410(4)
1.404(5)
1.419(5)
1.412(6)
1.396(6)
1.480(7)
1.504(5)
1.510(5)
Fe–C(7)
Fe–C(2)
Fe–C(6)
Fe–C(10)
Fe–C(4)
2.031(4)
2.035(3)
2.039(4)
2.047(4)
2.057(4)
1.424(3)
1.737(4)
1.393(4)
1.443(5)
1.429(5)
1.390(6)
1.400(6)
1.405(6)
1.386(6)
1.498(5)
1.513(5)
3.1. Synthesis of FcSO2NHC(O)NHR1 (3a–f); [3a,
R1=phenyl; 3b, R1=p-Cl-phenyl; 3c,
R1=m-CF3-phenyl; 3d, R1=methyl; 3e, R1=butyl;
3f, R1=cyclohexyl]
S–O(2)
S–C(1)
N(1)–C(11)
N(2)–C(12)
C(1)–C(5)
C(3)–C(4)
C(6)–C(10)
C(7)–C(8)
C(9)–C(10)
C(13)–C(14)
C(14)–C(15)
A total of 10 mmol of FcSO2NH2 and 10 mmol of
dried K2CO3 were added to 60 ml dry acetone, and 13
mmol of each aryl isocyanate 2a–c was introduced
dropwise. The reaction mixture was stirred for 4 h at
ambient temperature, while the original brownish color
turned yellow. The slurry was poured into 100 ml of
water, the white precipitate of (R1NH)2C(O) was re-
moved by filtration, and the filtrate was acidified to
pH=4 by adding 1M HCl solution. The yellow
product was collected on a filter, washed with water
and dried. Recrystallization from ethyl acetate gave
pure ureas in 60–70% yield.
Bond angle (°)
O(1)–S–N(1)
O(1)–S–C(1)
N(1)–S–C(1)
C(11)–N(2)–C(12) 121.3(3)
C(2)–C(1)–S
C(2)–C(3)–C(4)
C(4)–C(5)–C(1)
C(6)–C(7)–C(8)
C(8)–C(9)–C(10)
O(3)–C(11)–N(2)
N(2)–C(11)–N(1)
103.4(2)
110.3(2)
104.5(2)
O(1)–S–O(2)
O(2)–S–N(1)
O(2)–S–C(1)
120.4(2)
109.0(2)
108.1(2)
121.5(2)
108.8(3)
124.2(3)
108.3(3)
106.9(3)
107.3(4)
107.7(4)
108.6(4)
121.1(3)
C(11)–N(1)–S
C(2)–C(1)–C(5)
C(5)–C(1)–S
C(3)–C(4)–C(5)
C(3)–C(2)–C(1)
C(10)–C(6)–C(7)
C(9)–C(8)–C(7)
C(6)–C(10)–C(9)
O(3)–C(11)–N(1)
3d–f were prepared in an analogous way at reflux
temperature.
127.0(3)
109.6(3)
106.4(3)
107.9(4)
108.5(4)
124.3(3)
114.6(3)
Elemental analysis: 3a Calc. for C17H16FeN2O3S: C
53.14, H 4.20, N 7.29, S 8.34, found: C 53.29, H 4.25,N
7.22, S 8.08; 3b Calc. for C17H15ClFeN2O3S: C 48.77, H
3.61, N 6.69, S 7.66, found: C 48.89, H 3.68, N 6.80, S
7.55; 3c Calc. for C18H15F3FeN2O3S: C 47.81, H 3.34,
N 6.19, S 7.09, found: C 47.60, H 3.43, N 6.09, S 6.95;
3d Calc. for C12H14FeN2O3S: C 44.74, H 4.38, N 8.70,
S 9.95, found: C 44.64, H 4.15, N 8.78, S 9.93; 3e Calc.
for C15H20FeN2O3S: C 49.46, H 5.53, N 7.69, S 8.80,
found: C 49.28, H 5.46, N 7.74, S 8.64; 3f Calc. for
C17H22FeN2O3S: C 52.32, H 5.68, N 7.18, S 8.22,
found: C 52.17, H 5.76, N 7.30, S 8.18%.
C(12)–C(13)–C14 113.7(5)
C(13)–C(14x)
–C(15x)
109(2)
N(2)–C(12)–C(13) 114.1(4)
C(13)–C(14)–C(15) 115.9(7)
C(12)–C(13)–C(14x) 114.4(7)
In summary, we have found FcSO2NH2 to be a
convenient starting material for the synthesis of various
derivatives of ferrocenesulfonylcarbamic acids. Both
ferrocenesulfonamide and N-ferrocenylsulfonyl-N%-
butylurea exhibit the structural features of arylsulfonic
acid derivatives and, unless other factors interfere, fer-
rocenesulfonamide may be potential starting material
for biologically active compounds. Further studies are
needed to determine if the structural features of fer-
rocenesulfonic acid derivatives discussed in this work
are common also to other sulfonated metallocenes.
MS data: 3d (FAB): 323 (M+H)+, 322 (M+); 3e
[EI, 70 eV)]: 364 (M+) (22), 291 (24), 265 (100).
3.2. Synthesis of FcSO2NHC(O)N(CH3)2 (3g) and
FcSO2NHC(O)OR2 (3h–j) [3h, R2=ethyl; 3i,
R2=benzyl; 3j, R2=phenyl]
Compounds 3g–j were synthesized using N,N-
dimethylcarbamoyl chloride (2g) or chloroformic acid
esters ClC(O)OR2 (2h–j), as described above, but the
reactions were conducted at r.t. for 48 h.
3.3. FcSO2NHC(O)NH(4,6-dimethylpyrimidin-2-yl)
(3k)
3. Experimental section
Ferrocenesulfonic acid (FcSO3H) was prepared ac-
cording to a literature procedure [6] and isolated as its
p-toluidine salt. The latter was converted to ferrocene-
sulfonyl chloride [6] which, in turn, gave ferrocenesul-
fonamide, 1, upon treatment with NH3 in benzene. 1
served as starting material in the syntheses of carbamic
Compound 3k was prepared by refluxing 5 mmol of
3j and 5 mmol of 2-amino-4,6-dimethylpyrimidine in 30
ml of dry acetonitrile for 3 h. After all the phenylcarba-
mate had been converted, the reaction mixture was
concentrated to half volume and the product was
filtered. Recrystallization yielded 50% of 3k.

86
G. Besenyei et al. / Journal of Organometallic Chemistry 563 (1998) 81–86
Table 5
atoms. Neutral atomic scattering factors and anoma-
lous scattering factors were taken from the Interna-
tional Tables for X-ray Crystallography vol. C.
Experimental data for the X-ray diffraction studies, as
well as selected bond lengths and angles are collected in
Tables 2–5.
Hydrogen bonds in compounds 1 and 3e
D–H···A
D–H
(A)
H···A
(A)
D···A
(A)
D–H···A
(°)
˚
˚
˚
Compound 1
N–H(1)N···O(1)a
N–H(1)N···O(2)b
N–H(2)N···O(2)b
0.880
0.880
0.919
2.208
2.534
2.438
3.063
2.855
2.855
164.0
102.4
107.7
4. Supplementary material available
Compound 3e
N(1)–HN(1)···O(3)c 0.943
N(2)–HN(2)···O(2)c,d 0.922
N(2)–HN(2)···O(3)c,d 0.922
1.903
2.353
2.322
2.808
3.136
3.075
160.3
142.6
138.8
Tables of atomic coordinates, anisotropic thermal
parameters, bond lengths and angles, and hydrogen
atom parameters for 1 and 3e and figures depicting the
unit cells of 1 and 3e are available on request from the
authors.
a −x,−y,−z+1;
b x,−0.5−y,(−0.5+z)+1;
c (−0.5+x)+
1,y,(0.5−z)+1; d bifurcated.
Elemental analysis: 3g Calc. for C13H16FeN2O3S: C
46.44, H 4.80, N 8.33, S 9.54, found: C 46.60, H 4.77,
N 8.40, S 9.41; 3h Calc. for C13H15FeNO4S: C 46.31, H
4.48, N 4.15, S 9.51, found: C 46.11, H 4.43, N 4.21, S
9.12; 3i Calc. for C18H17FeNO4S: C 54.15, H 4.29, N
3.51, S 8.03, found: C 53.79, H 4.19, N 3.59, S 7.79; 3k
Calc. for C17H18FeN4O3S: C 49.29, H 4.38, N 13.52, S
7.74, found: C 49.28, H 4.40, N 13.60, S 7.80%.
MS data: 3g (FAB): 337 (M+H)+, 336 (M+); 3h
(EI): 337 (M+) (13), 291 (100), 265 (23), 227 (16), 184
(18); 3i (FAB): 400 (M+H)+, 399 (M+); 3k (FAB):
415 (M+H)+, 291.
Acknowledgements
We thank the Hungarian Research Fund (OTKA)
for financial support (grants T-16213 and B-033).
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