Ferrocene derivatives (I). Synthesis and X-ray structure determination of N-o-methylphenylferrocenesulfonamide

Article abstract of DOI:10.1016/S0022-328X(01)00899-3

N-o-Methylphenylferrocenesulfonamide was synthesized from the reaction of ferrocenesulfonyl chloride with o-toluidine. The structure was determined by single-crystal diffraction. Crystal data: monoclinic, P2₁/c, with unit cell dimensions of a=10.436(2), b=12.377(3), c=12.6431(3) ?, and β=107.42(1)°, V=1558.1(6) ?³, Z=4. The most stable structure of the complex in theory was obtained by the Hartree-Fock SCF of GAUSSIAN 98W, and the two results have been compared.

Full text of DOI:10.1016/S0022-328X(01)00899-3

Journal of Organometallic Chemistry 637–639 (2001) 738–741
www.elsevier.com/locate/jorganchem
Note
Ferrocene derivatives (I). Synthesis and X-ray structure
determination of N-o-methylphenylferrocenesulfonamide
Ming Li, Yinjuan Bai, Jun Lu, Bingqin Yang, Kake Zhu, Huairang Ma *
Department of Chemistry, Northwest Uni6ersity, Xi’an 710069, People’s Republic of China
Received 20 December 2000; received in revised form 30 March 2001; accepted 4 April 2001
Abstract
N-o-Methylphenylferrocenesulfonamide was synthesized from the reaction of ferrocenesulfonyl chloride with o-toluidine. The
structure was determined by single-crystal diffraction. Crystal data: monoclinic, P21/c, with unit cell dimensions of a=10.436(2),
3
,
,
b=12.377(3), c=12.6431(3) A, and i=107.42(1)°, V=1558.1(6) A , Z=4. The most stable structure of the complex in theory
was obtained by the Hartree–Fock SCF of GAUSSIAN 98W, and the two results have been compared. © 2001 Elsevier Science
B.V. All rights reserved.
Keywords: Ferrocene; Ferrocenesulfonyl chloride; Ferrocenesulfonamide; X-ray structure
1. Introduction
ferrocenesulfonamides have been synthesized. In this
paper, we report the synthesis and X-ray structure
determination of N-o-methylphenylferrocenesulfon-
amide (Fig. 1) and compare the optimized spatial struc-
ture by GAUSSIAN 98W with the results obtained.
The search for biologically active ferrocene deriva-
tives has attracted considerable attention [1,2]. On the
other hand, sulfonamides have the qualities of antibio-
sis and anti-inflammation. The highly efficient sulfonyl-
urea-type herbicides have been developed [3,4]. By the
analyses of structures and biological activities, it has
been found that sulfonilamide group forms the key
part. It is thus clearly known that the ferrocenesulfon-
amides have high biological activity. The synthesis of
ferrocenesulfonamide (FcSO2NH2) was first reported by
Pauson et al. in 1958 [5]. In the subsequent years,
syntheses of N-monosubstituted and N,N-disubstituted
ferrocenesulfonamides have been reported [6]. In 1998,
Besenyei et al. reported the derivatives of N-ferrocene-
sulfonyl carbamic acid and the X-ray structure determi-
nation of the related compounds [7].
We have prepared and characterized a number of
ferrocene derivatives with strong biological activity
[8,9]. In order to continue our research project, some
* Corresponding author. Fax: +86-29-8303511.
E-mail address: lujunyue@hotmail.com (H. Ma).
Fig. 1. Molecular diagram for N-o-methylphenyl-ferrocenesulfon-
amide by X-ray determination.
0022-328X/01/$ - see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S0022-328X(01)00899-3

M. Li et al. / Journal of Organometallic Chemistry 637–639 (2001) 738–741
739
Table 1
,
Selected bond lengths (A) and bond angles (°) for the complex by X-ray determination
Bond lengths
FeꢀC(7)
FeꢀC(10)
SꢀN
C(6)ꢀC(7)
C(8)ꢀC(9)
2.066(4)
2.004(3)
1.641(2)
1.412(5)
1.421(6)
FeꢀC(8)
SꢀO(1)
SꢀC(10)
C(6)ꢀC(10)
C(9)ꢀC(10)
2.055(3)
1.434(2)
1.744(3)
1.427(4)
1.423(4)
FeꢀC(9)
SꢀO(2)
NꢀC(11)
C(7)ꢀC(8)
2.028(3)
1.429(2)
1.744(3)
1.414(6)
Bond angles
C(1)ꢀFeꢀC(2)
C(4)ꢀFeꢀC(5)
C(7)ꢀFeꢀC(8)
C(6)ꢀFeꢀC(10)
O(1)ꢀSꢀC(10)
NꢀSꢀC(10)
37.9(3)
39.9(2)
40.1(2)
C(2)ꢀFeꢀC(3)
C(1)ꢀFeꢀC(5)
C(8)ꢀFeꢀC(9)
O(1)ꢀSꢀO(2)
O(2)ꢀSꢀN
SꢀNꢀC(11)
C(8)ꢀC(9)ꢀC(10)
38.6(3)
38.8(2)
40.7(2)
119.6(1)
107.6(1)
1119.0(2)
107.1(3)
C(3)ꢀFeꢀC(4)
C(6)ꢀFeꢀC(7)
C(9)ꢀFeꢀC(10)
O(1)ꢀSꢀN
O(2)ꢀSꢀC(10)
C(6)ꢀC(7)ꢀC(8)
C(9)ꢀC(10)ꢀC(6)
40.4(3)
40.1(1)
41.3(1)
106.0(1)
108.9(1)
108.8(3)
108.6(3)
41.2(1)
108.1(1)
105.8(1)
108.3(3)
107.2(3)
C(7)ꢀC(8)ꢀC(9)
C(10)ꢀC(6)ꢀC(7)
tuted Cp ring rang from 107.1 to 108.8°. Each value is
in good agreement with the interior angle of the regular
pentagon. The average OꢀSꢀC (108.5°) and the OꢀSꢀO
(119.6°) angles are in agreement with the respective
values in ferrocenesulfonamide (107.9 and 119.4°). The
average OꢀSꢀN (106.8°) is a little less than the corre-
sponding value in FcSO2NH2 (107.9°) [7].
2. Results and discussion
In Table 1, the FeꢀC distances range from 2.004(3) to
,
,
2.066(4) A with the mean values of 2.040 A for the
,
substituted Cp ring, and 2.018 A for the unsubstituted
ring, respectively, in good agreement with the average
FeꢀC bond length in ferrocene (2.031 A). The FeꢀC
,
Like ferrocenesulfonamide, the sulfur atom was
placed in a distorted tetrahedron, with the bonds
distances for the substituted Cp ring follow a particular
order: FeꢀC (7)\FeꢀC (8)\FeꢀC (6)\FeꢀC (9)\
FeꢀC (10). Such results show that an interaction be-
tween the sulfonyl group and iron atom may exist,
causing a light distortion in the structure. This conclu-
sion is also supported by the following facts: the first
angle of 1.77° is between the substituted and unsubsti-
tuted Cp plan; the second of 41.92° is between the
unsubstituded cp plan and phenyl plan; and the third
angle of 40.89° is between the substituted Cp plan and
phenyl plan. The distance between the two Cp ring is
,
around sulfur atom (1.429–1.743 A) and the angles
(106.0–119.6°).
We used the GAUSSIAN 98W [10] to calculate the
most stable structure of the complex in the theory with
the method of Hartree–Fock SCF and the basis set of
LanL2MB [11,12] to obtain the values of bond lengths,
and bond angles (Table 2). The results of the calcula-
tion and determination are compared in the Table 3.
From the table, we find there is a little difference in the
FeꢀC, SꢀO, SꢀN bonds between the two results. The
electrons on the outer space contribute to this sequence.
If we consider all electrons to be self-consistent and the
workload too hard to carry, then we can reduce the
contribution of the electrons on the inner shields for
bond formation and regard these inner electrons as a
‘nucleus’. In addition, we consider only the contribu-
tion of those valence electrons that give such a differ-
ence. The differences between OꢀSꢀN, CꢀNꢀS, OꢀSꢀO
angles formed are based on the same reasons. However,
the calculated values of CꢀC, CꢀN bond length and the
CꢀCꢀC bond angles of Cp ring, are in good agreement
with the corresponding values obtained.
,
,
3.301 A (3.32 A in ferrocene).
The CꢀC distances in the substituted Cp ring rang
,
,
from 1.412(5)–1.426(4) A, the mean values is 1.419 A
,
(1.402 A in ferrocene). The average CꢀC distances in
,
the unsubstituted Cp ring is a little shorter, i.e. 1.351 A.
The aminosulphonyl substitution on the Cp ring influ-
ences the elongation of bonds in C(9)ꢀC(10) and
C(10)ꢀC(6), with the distances of these two bonds being
,
1.423(4) and 1.427(4) A, respectively, the longest ever in
the Cp moiety.
,
,
The average SꢀO (1.434 A) and the SꢀC (1.744 A)
bond distances are in good agreement with the respec-
tive values observed for FcSO2NH2 (1.434 and 1.734 A)
[7]. However, the SꢀN bond (1.641 A) is certainly
longer than the corresponding value in ferrocenesulfon-
,
,
,
amide (1.608 A).
3. Experimental
The adjacent CꢀFeꢀC angles of the ferrocene moiety
are nearly equal, e.g. C(1)ꢀFeꢀC(2) (37.9°), and
C(1)ꢀFeꢀC(5) (38.8°), C(9)ꢀFeꢀC(10) (41.3°) and
C(6)ꢀFeꢀC(10) (41.2°). The CꢀCꢀC angles of the substi-
1H-NMR spectra were recorded on a Varian IN-
OVA-400 MHz spectrometer with TMS as an internal
standard. IR spectra were obtained by using neat capil-

740
M. Li et al. / Journal of Organometallic Chemistry 637–639 (2001) 738–741
Table 2
,
Selected bond lengths (A) and bond angles (°) for the complex by GAUSSIAN 98W
Bond lengths
FeꢀC(7)
FeꢀC(10)
SꢀN
C(6)ꢀC(7)
C(8)ꢀC(9)
2.1846
2.1396
1.8952
1.4069
1.4071
FeꢀC(8)
SꢀO(1)
SꢀC(10)
C(6)ꢀC(10)
C(9)ꢀC(10)
2.1839
2.605
1.8666
1.4181
1.4178
FeꢀC(9)
SꢀO(2)
NꢀC(11)
C(7)ꢀC(8)
2.1847
2.7015
1.4668
1.4211
Bond angles
C(1)ꢀFeꢀC(2)
C(4)ꢀFeꢀC(5)
C(7)ꢀFeꢀC(8)
C(6)ꢀFeꢀC(10)
O(1)ꢀSꢀC(10)
NꢀSꢀC(10)
38.0482
38.0313
37.9685
38.278
92.7099
98.0019
108.3145
107.2647
C(2)ꢀFeꢀC(3)
C(1)ꢀFeꢀC(5)
C(8)ꢀFeꢀC(9)
O(1)ꢀSꢀO(2)
O(2)ꢀSꢀN
SꢀNꢀC(11)
C(8)ꢀC(9)ꢀC(10)
38.0464
38.2457
37.5778
111.6943
128.5386
111.5734
107.2664
C(3)ꢀFeꢀC(4)
C(6)ꢀFeꢀC(7)
C(9)ꢀFeꢀC(10)
O(1)ꢀSꢀN
O(2)ꢀSꢀC(10)
C(6)ꢀC(7)ꢀC(8)
C(9)ꢀC(10)ꢀC(6)
38.2425
37.5766
38.2596
118.1074
91.6558
108.3142
108.769
C(7)ꢀC(8)ꢀC(9)
C(10)ꢀC(6)ꢀC(7)
lary cells on a Bruker Equinox-55 instrument. Elemen-
tal analysis was performed using a PE-2400 analyzer.
Hartree–Fock SCF and the basis set of LanL2MB, and
obtained the values of bond lengths and bond angles.
Selected bond lengths and bond angles are given in
Table 2.
3.1. Synthesis of FcSO2NHC6H4-o-CH3
The ferrocenesulfonamide is prepared according to
the procedure outlined in the literature [7]. Under nitro-
gen atmosphere, 2.84 g of FcSO2Cl (10 mmol) was
added to 80 ml of dry Et2O, and then 2.14 g of
o-toluidine (20 mmol) was introduced dropwise. The
reaction mixture was stirred for 3 h in an ice bath, and
stirred for another 3 h with refluxing. The solvent was
removed in vacuum. The residue was extracted with
water and ether, and the organic layer was separated
and dried by MgSO4. The solvent was removed; recrys-
tallization from Et2O gave red crystals. Yield: 59.3%;
4. Conclusion
The single crystal structure of N-o-methylphenyl-
ferrocenesulfonamide was determined and the stable
structure in the theory was calculated by GAUSSIAN
98W. The two results were compared and found to be
essentially in good agreement. The related structural
data of the complex and ferrocenesulfonamide were
also very close.
1
m.p. (dec.): 158–159 °C. H-NMR (CDCl3): l 7.33 (m,
1H), 7.16 (m, 3H), 6.27 (s, 1H), 4.47 (s, 2H), 4.37 (s,
SH), 4.31 (s, 2H), 2.09 (s, 3H). IR (KBr, cm−1): 3266.2
(s), 1608.3 (m), 1577.4 (s), 1488.8 (s), 1391.2 (m), 1329.7
(s), 1136.5 (s), 481.9 (s). Anal. Found: C, 57.79; H, 4.65;
N, 4.05. Calc. for C17H17FeNO2S, (MW 355.23): C,
57.70; H, 4.79; N, 3.95%.
Table 3
Comparison of the calculation and determination of results
Mean value
FeꢀC (sub. Cp ring) bond length (A)
FeꢀC (unsub. Cp ring) bond length (A)
CꢀC (sub. Cp ring) bond length (A)
CꢀC (unsub. Cp ring) bond length (A)
CꢀC (phenyl ring) bond length (A)
SꢀO bond length (A)
SꢀN bond length (A)
SꢀC bond length (A)
NꢀC bond length (A)
C(16)ꢀC(17) bond length (A)
CꢀCꢀC (sub. Cp ring) bond angle (°)
CꢀCꢀC (unsub. Cp ring) bond angle (°)
CꢀCꢀC (phenyl ring) bond length (°)
OꢀSꢀO bond angle (°)
OꢀSꢀN bond angle (°)
FeꢀCꢀS bond angle (°)
CꢀNꢀS bond angle (°)
Calc.
Found
,
2.167
2.018
2.040
1.419
1.351
1.388
1.432
1.641
1.744
1.443
l.505
108.0
108.0
120.0
119.6
106.8
128.8
119.0
,
2.175
1.414
1.414
1.390
2.653
1.895
1.866
1.467
1.528
3.2. X-ray structure determination of the product
,
,
The size of the single crystal chosen for the determi-
nation was 0.20×0.20×0.30 mm. The determination
of the unit cell and data collections was performed on
Rigaka AFC7R diffractometer (Mo–Ka radiation. u=
,
,
,
,
,
,
0.71069 A, graphite monochromated). Selected bond
,
lengths and bond angles are given in Table 1.
108.0
108.0
120.0
116.7
123.3
127.9
111.6
3.3. Theoretical optimized structure of the complex
with GAUSSIAN 98W
We used the GAUSSIAN 98W to calculate the most
stable structure in the theory with the method of

M. Li et al. / Journal of Organometallic Chemistry 637–639 (2001) 738–741
741
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Crystallographic data for structural analysis have
been deposited with the Cambridge Crystallographic
Data Centre, CCDC no. 161498. Copies of this infor-
mation may be obtained free of charge from The
Director, CCDC, 12 Union Road, Cambridge CB2
1EZ, UK (Fax: +44-1223-336033; e-mail: deposit@
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Acknowledgements
We thank the Shaanxi Natural Science Foundation
(97H-06) for financial support. We are also indebted to
Dr Min-Zhi Deng and Zhen-Yi Wen for the acquisition
of the X-ray structure determination and data
calculation.
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