Phosphorus-nitrogen compounds part 22. Syntheses, structural investigations, biological activities and DNA interactions of new mono and bis (4-fluorobenzyl) spirocyclophosphazenes

Article abstract of DOI:10.1016/j.poly.2011.08.035

The reactions of hexachlorocyclotriphosphazene, N₃P ₃Cl₆, with mono (1 and 2) and bis(4-fluorobenzyl) diamines (3-5), FPhCH₂NH(CH₂)_nNHR (RH or FPhCH ₂-), produce mono (1a and 2a)

Full text of DOI:10.1016/j.poly.2011.08.035

Polyhedron 30 (2011) 2896–2907
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Polyhedron
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Phosphorus–nitrogen compounds part 22. Syntheses, structural investigations,
biological activities and DNA interactions of new mono and bis (4-fluorobenzyl)
spirocyclophosphazenes
b
c
d
d
Aytug˘ Okumußs a, Zeynel Kılıç a, , Tuncer Hökelek , Hakan Dal , Leyla Açık , Yag˘mur Öner ,
⇑
L. Yasemin Koç e
a Department of Chemistry, Ankara University, 06100 Tandog˘an-Ankara, Turkey
b Department of Physics, Hacettepe University, 06800 Beytepe-Ankara, Turkey
c Department of Chemistry, Anadolu University, 26470 Yunus Emre Kampüsü-Eskißsehir, Turkey
d Department of Biology, Gazi University, 06500 Teknikokullar-Ankara, Turkey
e Department of Biology, Ankara University, 06100 Tandog˘an-Ankara, Turkey
a r t i c l e i n f o
a b s t r a c t
Article history:
The reactions of hexachlorocyclotriphosphazene, N3P3Cl6, with mono (1 and 2) and bis(4-fluorobenzyl)
diamines (3-5), FPhCH2NH(CH2)nNHR (R@H or FPhCH2–), produce mono (1a and 2a) and bis(4-fluoroben-
zyl) monospirocyclophosphazenes (3a–5a). The tetraaminomonospirocyclophosphazenes (1b–2d) are
obtained from the reactions of the partly substituted phosphazenes (1a and 2a) with excess pyrrolidine,
morpholine and 1,4-dioxa-8-azaspiro[4,5]decane (DASD), respectively. The tetrachlorobis(4-fluoroben-
zyl) monospirocyclophosphazenes (4a and 5a) with excess pyrrolidine, morpholine and DASD afford
the fully substituted bis(4-fluorobenzyl) monospirocyclophosphazenes (4b, 4d–5d) in boiling THF. In
addition, monochlorobis(4-fluorobenzyl) monospirocyclophosphazenes (4e and 4f) have also been iso-
lated from the reactions with excess morpholine and DASD in boiling THF. The structural investigations
of the compounds have been verified by elemental analyses, MS, FTIR, 1H, 13C, 19F (for 1d and 2d), 31P
NMR, HSQC and HMBC techniques. The crystal structures of 3a, 4a, 5a and 2b have been determined
by X-ray crystallography. The compounds 2a–5a, 1b–2d, 4b, 4d–5d, 4e and 4f have been screened for
antibacterial effects on bacteria and for antifungal activity against yeast strains. The compounds 1b
and 4b showed antimicrobial activity against three species of bacteria, Bacillus subtilis, Bacillus cereus
and Staphylococcus aureus, and two fungi, Candida albicans and Candida tropicalis. Minimum inhibitory
Received 30 April 2011
Accepted 24 August 2011
Available online 8 September 2011
Keywords:
Fluorobenzylspirocyclophosphazenes
Spectroscopy
Crystal structure
Antimicrobial activity
DNA cleavage
concentrations (MIC) were determined for 1b and 4b. The MIC values were found to be 5000
bacteria. The most effective compound, 4b has exhibited activity with a MIC of 312 M for C. albicans and
625 M for C. tropicalis. DNA-binding and the nature of the interaction with pBR322 plasmid DNA are
lM for each
l
l
studied. All of the compounds induce changes on the DNA mobility and intensity. Prevention of HindIII
digestion with the compounds indicates that the compounds bind with AT nucleotides in DNA.
Ó 2011 Elsevier Ltd. All rights reserved.
1. Introduction
cyclophosphazenes in particular [1,2]. Most of the phosphazene
derivatives have been prepared by chloride replacement reactions
The word phosphazene refers to a broad range of molecules,
containing phosphorus and nitrogen atoms attached by regularly
PN bonds. The PN units are joined together to form either short
and long chains or cyclophosphazenes. The hexachlorocyclotri-
phosphazene, N3P3Cl6, is the best known starting compound and
the most extensively studied in the field of phosphazene chemis-
try. In the last decade, there has been a considerable amount of
interest in the syntheses of spirocyclic phosphazenes in general
and in the determination of the stereogenic properties of chiral
on N3P3Cl6, due to the ease of introducing a wide variety of organic,
inorganic and organometallic groups onto the P centers [3–5]. On
the other hand, cyclophosphazenes are intensively used as building
blocks for polyorganophosphazenes, such as open-chain, cyclolin-
ear, cyclomatrix polymers and dendrimers [6–8]. The properties
of linear polyorganophosphazenes especially depend on the inor-
ganic PN skeleton as well as on the nature of the substituents
attached to the phosphorus atoms [9,10]. Moreover, they have
been prepared for use in alternative industrial applications in
different areas, for instance in rechargeable lithium batteries and
polymer electrolytes [11,12], high performance elastomers [13],
non-linear optics [14,15], biomedical membranes [16] and
⇑
Corresponding author. Tel.: +90 3122126720 1043; fax: +90 3122232395.
E-mail address: zkilic@science.ankara.edu.tr (Z. Kılıç).
0277-5387/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2011.08.035

A. Okumußs et al. / Polyhedron 30 (2011) 2896–2907
2897
biomedical materials including synthetic bones [17]. Recently, our
group has focused on the replacement reactions of the Cl atoms of
N3P3Cl6 by bulky aromatic diamines [18], NxOy-donor type (x,
y = 2–4) dibenzo-diaza-crown ethers (coronands) [19], diamino-
phenolates [20–22] and ferrocenyldiamines [23] to obtain novel
phosphazene derivatives with different architectures, namely
spiro-, ansa-, dispiro-, trispiro-, spiro-ansa-, spiro-ansa-spiro-, spiro-
bino-spiro- and spiro-crypta-skeletons. As far as we are aware,
there is no report on the reactions of difunctional reagents contain-
ing pendant 4-fluorobenzyl groups. Thus, this study primarily fo-
cuses on the substitution reactions of N3P3Cl6 with mono and
bis(4-fluorobenzyl) diamines with the aim of the preparation of
possible biologically active phosphazene derivatives.
We report here (i) the syntheses of new mono (1a, 2a, 1b–2d)
and bis(4-fluorobenzyl) monospirocyclo phosphazenes (3a–5a,
4b, 4d–4f, 5b–5d) (Scheme 1), (ii) the determination of the struc-
tures of all the compounds by elemental analyses, mass spectrom-
etry, Fourier transform (FTIR), one-dimensional (1D) 1H, 13C, 19F
(for 1d and 2d) and 31P NMR, two-dimensional (2D) heteronuclear
single quantum coherence (HSQC), and heteronuclear multiple-
bond correlation (HMBC) techniques; (iii) the solid-state structures
of 3a, 4a, 5a and 2b, established by X-ray diffraction techniques;
(iv) investigations of antibacterial and antifungal activities of
2a–5a, 1b–2d, 4b, 4d–5d, 4e and 4f and (v) the interactions be-
tween these compounds and pBR322 plasmid DNA examined by
agarose gel electrophoresis.
2. Experimental
2.1. General methods
The reactions have been monitored using thin-layer chromatog-
raphy (TLC) in different solvents, and the experiments were carried
out under an argon atmosphere. The melting points were mea-
sured on a Gallenkamp apparatus using a capillary tube. The IR
spectra were recorded on a Jasco FT/IR-430 spectrometer in KBr
discs and are reported in cmꢀ1 units. Mass spectra are recorded
on an AGILEND 1100 MSD spectrometer using the API-ES method.
Elemental analyses were carried out by the microanalytical service
1
of TÜBITAK-Turkey. H, 13C, 19F, 31P, HSQC and HMBC spectra were
_
recorded on a Bruker DPX FT NMR (400 MHz) spectrometer (SiMe4
as an internal standard for 1H, CFCl3 as an internal standard for 19
F
and 85% H3PO4 as an external standard for 31P NMR), operating at
400.13, 100.62, 376.46, and 161.97 MHz. The spectrometer was
equipped with a 5 mm PABBO BB inverse-gradient probe. Standard
Cl
Cl
P
N
P
N
P
Cl
Cl
Cl
Cl
R
R
Compound
1
2
N
(CH )
2 4
H
H
1
2
3
4
5
(CH )
2 3
R
THF
CH PhF
(CH )
1
2
2 4
CH2
-CH PhF =
F
2
(CH )
CH PhF
2
2 3
NHR
FPhCH
2
2
(CH )
CH PhF
2 2
2
R
R
1
1
N
NH
N
N
F
F
F
CH2
CH2
CH2
P
P
Compound
R
Compound
R
1
1
N
N
P
N
N
(CH )
(CH )
1a
2a
(CH )
(CH )
(CH )
3a
4a
5a
2 4
2 3
2 4
2 3
2 2
Cl
Cl
Cl
Cl
Cl
Cl
Cl
P
P
P
Cl
N
N
bis(4-fluorobenzyl)spiro-
mono(4-fluorobenzyl)spiro-
THF
THF
THF
R
1
R
1
R
1
N
N
N
NH
N
N
F
F
F
CH2
F
F
CH2
CH2
CH2
CH2
P
P
P
N
N
N
N
P
N
N
X
X
X
X
X
X
X
X
Y
X
X
X
P
P
P
P
P
N
X
N
X
N
R
1
R
R
Compound
Compound
X
Compound
Y
1
1
O
(CH )
1b
1c
(CH )
4b
4c
N
N
2 4
4e
4f
(CH )
N
2 3
Cl
2 3
O
O
O
(CH )
2 4
(CH )
2 3
N
N
O
O
O
(CH )
2 3
N
Cl
O
O
(CH )
2 4
1d
(CH )
2 3
4d
N
N
(CH )
2 3
(CH )
2 2
2b
2c
5b
5c
N
N
O
O
(CH )
2 3
N
N
(CH )
2 2
O
O
O
O
2d
5d
(CH )
2 3
(CH )
2 2
N
N
Scheme 1. The chloride replacement reaction pathway of N3P3Cl6 with mono and bis(4-fluorobenzyl) diamines, pyrrolidine, morpholine and DASD.

2898
A. Okumußs et al. / Polyhedron 30 (2011) 2896–2907
Bruker pulse programs [24] were used. Antimicrobial susceptibility
testing was performed by the disk diffusion method. The DNA
binding abilities were examined using agarose gel electrophoresis
[2,23].
2.2.5. 7,10-Bis(4-fluorobenzyl)-2,2,4,4-tetrachloro-1,3,5,7,10-
pentaaza-2k5,4k5,6k5-triphosphaspiro[4.5]dodeca-1,3,5-triene (5a)
The procedure was as for compound 1a, using 5 (1.02 g,
3.70 mmol), and triethylamine (1.03 mL) and N3P3Cl6 (1.29 g,
3.70 mmol) (26 h). The product was purified by column chroma-
tography using toluene and crystallized from toluene. Yield:
2.04 g (74%). M.p.: 146 °C. Anal. Calc. for C16H16N5F2P3Cl4: C,
34.87; H, 2.93; N, 12.71. Found: C, 35.19; H, 3.03; N, 12.79%.
APIES-MS (fragments are based on 35Cl, Ir%): m/z 550 ([M]+,
56.3). FTIR (KBr, cmꢀ1): 3072, 3020 (C–H arom.), 1059 (C–F),
1227, 1190 (P@N), 574, 512 (PCl).
2.2. Preparation of Compounds
The 4-fluorobenzyldiamines (1–5) were obtained by the reduc-
tion of the corresponding Schiff bases prepared from the reaction
of 4-fluorobenzyaldehyde with the appropriate diamines in meth-
anol according to the methods reported in the literature [25,26].
2.2.6. 7-(4-Fluorobenzyl)-2,2,4,4-tetrapyrrolidin-1-yl-1,3,5,7,12-
pentaaza-2k5,4k5,6k5-triphosphaspiro[5.6]trideca-1,3,5-triene (1b)
A solution of compound 1a (1.00 g, 2.12 mmol) and triethyl-
amine (1.18 mL) in dry THF (150 mL) was added slowly to a solu-
tion of pyrrolidine (2.10 mL, 26.00 mmol) with stirring, and then
the mixture was refluxed for 34 h. The oily product was purified
by column chromatography using toluene-THF (1:4) as eluent
and then crystallized from n-heptane. Yield: 0.94 g (73%). M.p.:
107 °C. Anal. Calc. for C27H47N9FP3: C, 53.20; H, 7.77; N, 20.68.
Found: C, 51.61; H, 7.41; N, 20.00%. APIES-MS (fragments are based
on 35Cl, Ir%): m/z 610 ([M]+, 100). FTIR (KBr, cmꢀ1): 3068, 3022
(C–H arom.), 1056 (C–F), 1236, 1198 (P@N).
2.2.1. 2,2,4,4-Tetrachloro-7-(4-fluorobenzyl)-1,3,5,7,12-pentaaza-
2k5,4k5,6k5-triphosphaspiro[5.6]trideca-1,3,5-triene (1a)
A solution of 1 (1.00 g, 5.10 mmol) in THF (150 mL) and trieth-
ylamine (1.42 mL) was added to a stirred solution of N3P3Cl6
(1.78 g, 5.10 mmol) in THF (50 mL) at room temperature. The mix-
ture was stirred for 25 h at ambient temperature, with argon being
passed over the reaction mixture. The precipitated amine hydro-
chloride was filtered off, and the solvent was evaporated at re-
duced pressure. The crude product was purified by column
chromatography with toluene. A white powder crystallized out
from toluene. Yield: 1.56 g (65%). M.p.: 122 °C. Anal. Calc. for
C
11H15N5FP3Cl4: C, 28.05; H, 3.18; N, 14.86. Found: C, 28.77; H,
3.34; N, 14.59%. APIES-MS (fragments are based on 35Cl, Ir%): m/z
469 ([M]+, 79.8). FTIR (KBr, cmꢀ1): 3068, 3022 (C–H arom.), 1055
(C–F), 1236, 1186 (P@N), 568, 518 (PCl).
2.2.7. 7-(4-Fluorobenzyl)-2,2,4,4-tetramorpholin-4-yl-1,3,5,7,12-
pentaaza-2k5,4k5,6k5-triphosphaspiro[5.6]trideca-1,3,5-triene (1c)
The procedure was similar to that of compound 1b, using 1a
(0.98 g, 2.07 mmol), morpholine (2.17 mL, 25.00 mmol) and trieth-
ylamine (1.16 mL) (35 h). The product was purified by column
chromatography using toluene-THF (1:4) and crystallized from n-
heptane. Yield: 0.98 g (70%). M.p.: 157 °C. Anal. Calc. for
2.2.2. 2,2,4,4-Tetrachloro-7-(4-fluorobenzyl)-1,3,5,7,11-pentaaza-
2k5,4k5,6k5-triphosphaspiro[5.5]undeca-1,3,5-triene (2a)
The procedure was as for compound 1a, using 2 (1.00 g,
5.49 mmol), and triethylamine (1.53 mL) and N3P3Cl6 (1.91 g,
5.49 mmol) (26 h). The product was purified by column chroma-
tography using toluene and crystallized from toluene. Yield:
1.75 g (70%). M.p.: 68 °C. Anal. Calc. for C10H13N5FP3Cl4: C, 26.29;
H, 2.87; N, 15.33. Found: C, 26.38; H, 2.91; N, 15.23%. APIES-MS
(fragments are based on 35Cl, Ir%): m/z 455 ([M]+, 0.2). FTIR (KBr,
cmꢀ1): 3070, 3048 (C–H arom.), 1051 (C–F), 1228, 1178 (P@N),
570, 510 (PCl).
C
27H47N9FP3O4: C, 53.33; H, 7.18; N, 16.46. Found: C, 51.93; H,
7.12; N, 16.31%. APIES-MS (fragments are based on 35Cl, Ir%): m/z
674 ([M]+, 100). FTIR (KBr, cmꢀ1): 3053, 3030 (C–H arom.), 1054
(C–F), 1230, 1194 (P@N).
2.2.8. 7-(4-Fluorobenzyl)-2,2,4,4-tetra-1,4-dioxa-8-azaspiro[4.5]dec-
8-yl-1,3,5,7,12-pentaaza-2k5,4k5,6k5-triphosphaspiro[5.6]trideca-
1,3,5-triene (1d)
The procedure was similar to that of compound 1b, using 1a
(1.00 g, 2.12 mmol), DASD (3.26 mL, 26.00 mmol) and triethyl-
amine (1.18 mL) (35 h). The product was purified by column chro-
matography using toluene-THF (1:4) and crystallized from n-
heptane. Yield: 1.38 g (72%). M.p.: 174 °C. Anal. Calc. for
2.2.3. 2,2,4,4-Tetrachloro-7,12-bis(4-fluorobenzyl)-1,3,5,7,12-
pentaaza-2k5,4k5,6k5-triphosphaspiro[5.6]trideca-1,3,5-triene (3a)
The procedure was as for compound 1a, using
3 (0.1 g,
C
39H63N9FP3O8: C, 52.20; H, 7.07; N, 14.03. Found: C, 52.75; H,
3.29 mmol), and triethylamine (0.55 mL) and N3P3Cl6 (0.11 g,
3.29 mmol) (26 h). The product was purified by column chroma-
tography using toluene and crystallized from toluene. Yield:
0.12 g (63%). M.p.: 177 °C. Anal. Calc. for C18H20N5F2P3Cl4: C,
37.33; H, 3.48; N, 12.09. Found: C, 37.53; H, 3.61; N, 12.18%.
APIES-MS (fragments are based on 35Cl, Ir%): m/z 577 ([M]+,
56.5). FTIR (KBr, cmꢀ1): 3072, 3043 (C–H arom.), 1051 (C–F),
1224, 1182 (P@N), 567, 514 (PCl).
6.67; N, 13.01%. APIES-MS (fragments are based on 35Cl, Ir%): m/z
898 ([M]+, 91.9). FTIR (KBr, cmꢀ1): 3064, 3033 (C–H arom.), 1052
(C–F), 1210, 1188 (P@N).
2.2.9. 7-(4-Fluorobenzyl)-2,2,4,4-tetrapyrrolidin-1-yl-1,3,5,7,11-
pentaaza-2k5,4k5,6k5-triphosphaspiro[5.5]undeca-1,3,5-triene (2b)
The procedure was similar to that of compound 1b, using 2a
(0.70 g, 1.53 mmol), pyrrolidine (1.52 mL, 18.00 mmol) and trieth-
ylamine (0.85 mL) (36 h). The product was purified by column
chromatography using toluene-THF (1:4) and crystallized from tol-
uene. Yield: 0.69 g (76%). M.p.: 106 °C. Anal. Calc. for C26H45N9FP3:
C, 52.43; H, 7.62; N, 21.16. Found: C, 52.25; H, 7.48; N, 21.03%.
APIES-MS (fragments are based on 35Cl, Ir%): m/z 596 ([M]+, 100).
FTIR (KBr, cmꢀ1): 3062, 3021 (C–H arom.), 1051 (C–F), 1230,
1182 (P@N).
2.2.4. 2,2,4,4-Tetrachloro-7,11-bis(4-fluorobenzyl)-1,3,5,7,11-
pentaaza-2k5,4k5,6k5-triphosphaspiro[5.5]undeca-1,3,5-triene (4a)
The procedure was as for compound 1a, using 4 (0.50 g,
1.72 mmol), and triethylamine (0.96 mL) and N3P3Cl6 (0.60 g,
1.72 mmol) (26 h). The product was purified by column chroma-
tography using toluene and crystallized from toluene. Yield:
0.66 g (68%). M.p.: 108 °C. Anal. Calc. for C17H18N5FP3Cl4: C,
36.13; H, 3.21; N, 12.39. Found: C, 36.45; H, 3.28; N, 12.33%.
APIES-MS (fragments are based on 35Cl, Ir%): m/z 563 ([M]+,
49.1). FTIR (KBr, cmꢀ1): 3064, 3030 (C–H arom.), 1052 (C–F),
1228, 1172 (P@N), 579, 517 (PCl).
2.2.10. 7-(4-Fluorobenzyl)-2,2,4,4 tetramorpholin-4-yl-1,3,5,7,11-
pentaaza-2k5,4k5,6k5-triphosphaspiro[5.5]undeca-1,3,5-triene (2c)
The procedure was similar to that of compound 1b, using 2a
(0.70 g, 1.53 mmol), morpholine (1.60 mL, 18.00 mmol) and

A. Okumußs et al. / Polyhedron 30 (2011) 2896–2907
2899
triethylamine (0.85 mL) (37 h). The product was purified by col-
umn chromatography using toluene-THF (1:4) and crystallized
from n-heptane. Yield: 0.65 g (65%). M.p.: 183 °C. Anal. Calc. for
triethylamine (1.00 mL) (33 h). The product was purified by col-
umn chromatography using toluene-THF (1:1) and crystallized
from n-heptane. Yield: 0.88 g (69%). M.p.: 166 °C. Anal. Calc. for
C
26H45N9FP3O4: C, 47.34; H, 6.86; N, 19.11. Found: C, 49.07; H,
C38H54N8F2P3O6Cl: C, 51.56; H, 6.15; N, 12.66. Found: C, 52.78; H,
6.73; N, 17.03%. APIES-MS (fragments are based on 35Cl, Ir%): m/z
660 ([M]+, 100). FTIR (KBr, cmꢀ1): 3059, 3035 (C–H arom.), 1050
(C–F), 1230, 1190 (P@N).
6.27; N, 12.16%. APIES-MS (fragments are based on 35Cl, Ir%): m/z
884 ([M]+, 2.0). FTIR (KBr, cmꢀ1): 3075, 3041 (C–H arom.), 1056
(C–F), 1219, 1194 (P@N), 577 (PCl).
2.2.11. 7-(4-Fluorobenzyl)-2,2,4,4-tetra-1,4-dioxa-8-azaspiro[4.5]dec-
8-yl-1,3,5,7,11-pentaaza-2k5,4k5,6k5-triphosphaspiro[5.5]undeca-
1,3,5-triene (2d)
The procedure was similar to that of compound 1b, using 2a
(0.60 g, 1.30 mmol), DASD (2.00 mL, 16.00 mmol) and triethyl-
amine (0.73 mL) (37 h). The product was purified by column
chromatography using toluene-THF (1:4) and crystallized from
n-heptane. Yield: 0.85 g (73%). M.p.: 223 °C. Anal. Calc. for
2.2.16. 7,10-Bis(4-fluorobenzyl)-2,2,4,4-tetrapyrrolidin-1-yl-
1,3,5,7,10-pentaaza-2k5,4k5,6k5-triphosphaspiro[4.5]dodeca-1,3,5-
triene (5b)
The procedure was similar to that of compound 1b, using 5a
(1.07 g, 1.94 mmol), pyrrolidine (1.93 mL, 23.00 mmol) and trieth-
ylamine (1.09 mL) (30 h). The product was purified by column
chromatography using toluene-THF (1:1) and crystallized from n-
heptane. Yield: 1.09 g (81%). M.p.: 207 °C. Anal. Calc. for
C
38H61N9FP3O8: C, 51.60; H, 6.96; N, 14.26. Found: C, 52.03; H,
6.87; N, 13.83%. APIES-MS (fragments are based on 35Cl, Ir%): m/z
884 ([M]+, 100). FTIR (KBr, cmꢀ1): 3064, 3037 (C–H arom.), 1052
(C–F), 1220, 1192 (P@N).
C
32H48N9F2P3: C, 55.88; H, 6.74; N, 18.33. Found: C, 55.36; H,
6.88; N, 18.04%. APIES-MS (fragments are based on 35Cl, Ir%): m/z
690 ([M]+, 100). FTIR (KBr, cmꢀ1): 3082, 3039 (C–H arom.), 1058
(C–F), 1212, 1186 (P@N).
2.2.12. 7,11-Bis(4-fluorobenzyl)-2,2,4,4-tetrapyrrolidin-1-yl-
1,3,5,7,11-pentaaza-2k5,4k5,6k5-triphosphaspiro[5.5]undeca-1,3,5-
triene (4b)
The procedure was similar to that of compound 1b, using 4a
(1.08 g, 1.91 mmol), pyrrolidine (1.89 mL, 23.00 mmol) and trieth-
ylamine (1.06 mL) (30 h). The product was purified by column
chromatography using toluene-THF (1:1) and crystallized from n-
heptane. Yield: 0.99 g (74%). M.p.: 87 °C. Anal. Calc. for
2.2.17. 7,10-Bis(4-fluorobenzyl)-2,2,4,4-tetramorpholin-4-yl-
1,3,5,7,10-pentaaza-2k5,4k5,6k5-triphosphaspiro[4.5]dodeca-1,3,5-
triene (5c)
The procedure was similar to that of compound 1b, using 5a
(1.14 g, 2.07 mmol), morpholine (2.17 mL, 25.00 mmol) and trieth-
ylamine (1.20 mL) (31 h). The product was purified by column
chromatography using toluene-THF (1:1) and crystallized from n-
heptane. Yield: 1.17 g (75%). M.p.: 260 °C. Anal. Calc. for
C
33H50N9F2P3: C, 56.35; H, 7.16; N, 17.92. Found: C, 56.13; H,
7.03; N, 17.72%. APIES-MS (fragments are based on 35Cl, Ir%): m/z
704 ([M]+, 100). FTIR (KBr, cmꢀ1): 3062, 3034 (C–H arom.), 1054
(C–F), 1218, 1182 (P@N).
C
32H48N9F2P3O4: C, 51.03; H, 6.42; N, 16.73. Found: C, 51.48; H,
6.06; N, 16.37%. APIES-MS (fragments are based on 35Cl, Ir%): m/z
754 ([MH]+, 100). FTIR (KBr, cmꢀ1): 3070, 3020 (C–H arom.),
1054 (C–F), 1224, 1190 (P@N).
2.2.13. 7,11-Bis(4-fluorobenzyl)-2,2,4,4-tetra-1,4-dioxa-8-
azaspiro[4.5]dec-8-yl-1,3,5,7,11-pentaaza-2k5,4k5,6k5-
triphosphaspiro[5.5]undeca-1,3,5-triene (4d)
2.2.18. 7,10-Bis(4-fluorobenzyl)-2,2,4,4-tetra-1,4-dioxa-8-
azaspiro[4.5]dec-8-yl-1,3,5,7,10-pentaaza-2k5,4k569k5-
triphosphaspiro[4.5]dodeca-1,3,5-triene (5d)
The procedure was similar to that of compound 1b, using 5a
(1.08 g, 1.96 mmol), DASD (3.00 mL, 24.00 mmol) and triethyl-
amine (1.10 mL) (31 h). The product was purified by column
chromatography using toluene-THF (3:1) and crystallized from
n-heptane. Yield: 1.17 g (75%). M.p.: 300 °C. Anal. Calc. for
A solution of compound 4a (1.06 g, 1.90 mmol) and triethyl-
amine (1.00 mL) in dry o-xylene (150 mL) was added slowly to a
solution of DASD (1.86 mL, 21.00 mmol) with stirring, and then
the mixture was refluxed for 32 h. The oily product was purified
by column chromatography using toluene-THF (1:1) as the eluent
and then was crystallized from n-heptane. Yield: 1.34 g (72%).
M.p.: 222 °C. Anal. Calc. for C45H66N9F2P3O8: C, 54.49; H, 6.71; N,
12.71. Found: C, 53.81; H, 6.44; N, 12.67%. APIES-MS (fragments
are based on 35Cl, Ir%): m/z 992 ([M]+, 100). FTIR (KBr, cmꢀ1):
3068, 3041 (C–H arom.), 1052 (C–F), 1219, 1195 (P@N).
C
44H64N9F2P3O8: C, 54.04; H, 6.60; N, 12.89. Found: C, 54.87; H,
6.39; N, 12.42%. APIES-MS (fragments are based on 35Cl, Ir%): m/z
978 ([M]+, 100). FTIR (KBr, cmꢀ1): 3073, 3046 (C–H arom.), 1051
(C–F), 1215, 1198 (P@N).
2.2.14. 7,11-Bis(4-fluorobenzyl)-2-chloro-2,4,4-trimorpholin-4-yl-
1,3,5,7,11-pentaaza-2k5,4k5,6k5-triphosphaspiro[5.5]undeca-1,3,5-
triene (4e)
2.3. X-ray crystallography
The procedure was similar to that of compound 1b, using 4a
(1.00 g, 1.78 mmol), morpholine (1.86 mL, 21.00 mmol) and trieth-
ylamine (1.00 mL) (32 h). The product was purified by column
chromatography using toluene-THF (1:1) and crystallized from n-
heptane. Yield: 0.88 g (69%). M.p.: 108 °C. Anal. Calc. for
Suitable crystals of compounds 3a, 4a, 5a and 2b were obtained
from toluene at room temperature. The crystallographic data are
given in Table 1, selected bond lengths and angles are listed in
Table 2 and hydrogen bond data are given in Table 3. Crystallo-
graphic data were recorded on a Bruker Kappa APEXII CCD area-
C
29H42N8F2P3O3Cl: C, 48.57; H, 5.90; N, 15.62. Found: C, 48.43; H,
6.14; N, 13.56%. APIES-MS (fragments are based on 35Cl, Ir%): m/z
716 ([M]+, 0.8). FTIR (KBr, cmꢀ1): 3056, 3034 (C–H arom.), 1056
(C–F), 1228, 1194 (P@N), 500 (PCl).
detector diffractometer using MoKa radiation (k = 0.71073 Å) at
T = 100(2) K. Absorption corrections by multi-scan [27] were
applied. The structures were solved by direct methods and refined
by full-matrix least squares against F2 using all data [28]. All non-H
atoms were refined anisotropically. In compounds 3a, 4a, 5a and
2.2.15. 7,11-Bis(4-fluorobenzyl)-2-chloro-2,4,4-tri-1,4-dioxa-8-
azaspiro[4.5]dec-8-yl-1,3,5,7,11-pentaaza-2k5,4k5,6k5-
triphosphaspiro[5.5]undeca-1,3,5-triene (4f)
The procedure was similar to that of compound 1b, using 4a
(1.00 g, 1.78 mmol), DASD (1.86 mL, 21.00 mmol) and
2b, the
H atom positions were calculated geometrically at
distances of 0.93 Å (CH) and 0.97 Å (CH2) from the parent C atoms;
a riding model was used during the refinement process and the
Uiso(H) values were constrained to 1.2 Ueq(carrier atom).

2900
A. Okumußs et al. / Polyhedron 30 (2011) 2896–2907
Table 1
Crystallographic data for 3a, 4a, 5a and 2b.
3a
4a
5a
2b
Empirical formula
Formula weight
Crystal system
Space group
a (Å)
C
18H20Cl4F2N5P3
C17H18Cl4F2N5P3
565.07
monoclinic
P 21/c
8.9912(2)
13.8214(3)
18.7501(4)
90.00
98.111(4)
90.00
C16H16Cl4 F2 N5P3
551.05
monoclinic
C 2/c
22.8721(7)
8.8214(3)
11.9577(4)
90.00
112.288(1)
90.00
C26H45FN9P3
595.62
579.12
triclinic
P1
triclinic
ꢀ
ꢀ
P1
9.4049(2)
11.4354(3)
12.0907(4)
106.658(3)
96.985(2)
105.415(3)
1173.08(6)
2
10.6000(2)
11.5826(2)
13.6823(3)
69.948(2)
75.185(3)
75.152(3)
1499.05(6)
2
b (Å)
c (Å)
a
(°)
b (°)
c
(°)
V (Å3)
2306.78(9)
4
2232.38(13)
4
Z
l
q
(MoK
a
) (cmꢀ1
)
)
0.744 (MoK
1.640
a
)
0.754 (MoK
a
)
0.777 (MoK
a)
0.238 (MoK
1.320
a)
(Calc.) (g cmꢀ3
1.627
1.640
Number of reflections total
Number of reflections unique
Rint
21028
5844
0.0230
56.76
19380
5596
0.0485
57.18
7903
2540
0.0201
55.12
25799
7405
0.0200
56.80
2hmax (°)
Tmin/Tmax
0.7940/0.8534
289
0.0261
0.7782/0.7943
280
0.0447
0.6973/0.9263
137
0.0238
0.9066/0.9429
352
0.0389
Number of parameters
R [F2 > 2
r
(F2)]
wR
0.0690
0.1153
0.0637
0.1026
Table 2
The selected bond lengths (Å) and angles (°) with the selected torsion angles (°) for 3a, 4a, 5a and 2b.
3a
4a
5a
2b
P1–N1
P1–N3
P1–N4
P1–N5
P2–N1
P2–N2
P3–N3
P3–N2
1.615(2)
1.619(1)
1.631(1)
1.629(1)
1.561(1)
1.588(1)
1.559(1)
1.587(2)
1.997(6)
2.013(5)
113.2(1)
115.3(1)
106.5(1)
105.5(1)
113.5(1)
102.6(1)
119.7(1)
120.2(1)
–1.0(1)
P1–N1
P1–N3
P1–N4
P1–N5
P2–N1
P2–N2
P3–N3
P3–N2
1.607(2)
1.631(2)
1.642(2)
1.629(2)
1.560(2)
1.591(2)
1.556(2)
1.588(2)
1.994(10)
2.022(8)
111.0(1)
109.1(1)
109.8(1)
110.4(1)
112.0(1)
104.2(1)
120.1(1)
119.5(1)
3.7(2)
P1–N1
1.616(0)
P1–N1
P1–N3
P1–N4
P1–N5
P2–N1
P2–N2
P3–N3
P3–N2
1.529(2)
1.592(2)
1.687(1)
1.663(1)
1.611(1)
1.592(2)
1.595(1)
1.600(2)
1.653(2)
1.657(2)
118.3(1)
107.8(1)
110.6(1)
109.2(1)
107.4(1)
102.4(1)
116.6(1)
115.2(1)
7.3(1)
P1–N10
1.617(0)
1.629(0)
1.629(0)
1.563(1)
1.584(0)
1.584(0)
1.563(1)
1.994(1)
2.013(1)
115.2(0)
109.8(0)
109.8(0)
115.2(0)
94.7(0)
P1–N3
P1–N30
P2–N1
P2–N2
P20–N2
P20–N10
P2–Cl2
P3–Cl4
P2–Cl2
P3–Cl4
P2–Cl1
P2–Cl2
P2–N7
P3–N9
N1–P1–N3
N1–P1–N4
N1–P1–N5
N3–P1–N4
N3–P1–N5
N4–P1–N5
N1–P2–N2
N3–P3–N2
N3–P1–N1–P2
N4–P1–N1–P2
N1–P1–N3
N1–P1–N4
N1–P1–N5
N3–P1–N4
N3–P1–N5
N4–P1–N5
N1–P2–N2
N3–P3–N2
N3–P1–N1–P2
N4–P1–N1–P2
N1–P1–N3
N10–P1–N3
N30–P1–N1
N30–P1–N10
N3–P1–N30
N1–P1–N10
N1–P2–N2
P2–N2–P20
N3–P1–N1–P2
N30–P1–N1–P2
N1–P1–N3
N1–P1–N4
N1–P1–N5
N3–P1–N4
N3–P1–N5
N4–P1–N5
N1–P2–N2
N3–P3–N2
N3–P1–N1–P2
N4–P1–N1–P2
111.4(0)
119.6(0)
118.3(0)
–131.4(0)
123.3(0)
120.6(9)
125.6(2)
131.7(9)
Table 3
Hydrogen-bond geometry (,°).
zyl)diamines (1 and 2) are higher than those of the bis(4-fluoroben-
zyl)diamines (3 and 4). The yield of 3 is very low. The reaction of
4-fluorobenzyaldehyde with ethylene diamine gave eventually only
the bis product, N,N0-bis(4-fluorobenzyl)ethane-1,2-diamine (5),
and the expected mono product, N-(4-fluorobenzyl)ethane-1,2-dia-
mine, could not be obtained. The tetrachloromono(4-fluorobenzyl)
monospirocyclophosphazene derivatives (1a and 2a) and tetra-
chlorobis(4-fluorobenzyl) monospirocyclophosphazenes (3a–5a)
have been synthesized from the reactions of N3P3Cl6, with the mono
(1 and 2) and bis(4-fluorobenzyl)diamines (3-5), respectively in dry
THF. The amount of 3a is very limited, which is why the reactions of
3a with amines could not be carried out. All the fully substituted
mono(4-fluorobenzyl) monospirocyclophosphazenes (1b–2d) and
bis(4-fluorobenzyl) monospirocyclophosphazenes (4b, 4d–5d) are
prepared from the reactions of 1a, 2a, 4a and 5a with excess pyrrol-
idine, morpholine and DASD in boiling THF (Scheme 1). The chloride
replacement reactions of N3P3Cl6 with the bifunctional ligands 1–5
appear to be regioselective because only spirocyclic compounds
are formed. On the other hand, the partly substituted phosphazenes
Compound
3a
D–Hꢁ ꢁ ꢁA
D–H
Hꢁ ꢁ ꢁA
Dꢁ ꢁ ꢁA
D–Hꢁ ꢁ ꢁA
C6–H6Aꢁ ꢁ ꢁN3
C17–H17Aꢁ ꢁ ꢁN1
C2–H2ꢁ ꢁ ꢁN3i
0.97
0.97
0.93
0.99
0.99
2.50
2.41
2.44
2.55
2.65
3.010 (2)
2.956 (2)
3.366 (3)
3.544 (2)
3.139 (2)
112.7(1)
115.2(1)
177.4(2)
177.7(1)
110.7(1)
4a
2b
C9–H92ꢁ ꢁ ꢁN6ii
C7–H71ꢁ ꢁ ꢁN1
i
ii
Symmetry codes: x ꢀ 1, y, z; ꢀx, ꢀy + 1, ꢀz.
3. Results and discussion
3.1. Synthesis
The starting compounds, mono and bis(4-fluorobenzyl)diamines
(1–5), were obtained from the reduction of the corresponding Schiff
bases prepared from 4-fluorobenzaldehyde with the appropriate
diamines in methanol. The reaction yields of the mono(4-fluoroben-

A. Okumußs et al. / Polyhedron 30 (2011) 2896–2907
2901
4e and 4f have been obtained by the reactions of 4a with excess mor-
pholine and DASD respectively, in boiling THF. All attempts for the
preparation of the expected fully substituted products 4c and 4d
failed in boiling THF, while compound 4d has been prepared in boil-
ing o-xylene. All the new phosphazenes have been purified by col-
umn chromatography.
The microanalyses, FTIR, APIES-MS and NMR data are in agree-
ment with the proposed structures of the compounds. In addition,
the mass spectra of all the compounds display the molecular [M+]
ion peaks.
bonded to the same P atoms show two groups of NCH2 and
NCH2CH2 signals with small separations (Table 5).
As expected, in CDCl3 solution all of the bis(4-fluorobenzyl)
monospirocyclophosphazenes have symmetric structures, accord-
ing to their 1H and 13C NMR spectral data. In the 13C NMR spectra
of all the compounds, the expected carbon signals are assigned. The
NCH2 signals of the compounds are determined using HSQC and
HMBC experiments, and these are observed at 46.21–46.34 ppm
for NCH2(pyrr), 43.79–44.80 ppm for NCH2 (morph), 42.53–
42.72 ppm for NCH2 (DASD), 47.83–51.67 ppm for ArCH2N,
44.23–47.05 ppm for NCH2 and 40.05–41.77 ppm for NHCH2. The
3JPC couplings give rise to triplets for the NCH2CH2(pyrr) carbons
of 1b, the NCH2CH2(pyrr) carbons of 5b, and the OCH2(morph) car-
bons of 5c (Supplementary material, Fig. S2). The triplets probably
depend on the second-order effects that were previously observed
3.2. NMR and FTIR spectroscopy
The 1H decoupled 31P NMR data of all the compounds indicate
that they have monospirocyclic structures. The spin systems are
interpreted as simple AB2 for 1c, 1d, 2b, 2c, 2d and 4d, AX2 for
1a–5a, 1b, 4b, 5b, 5c and 5d, and ABX for 4e and 4f. The coupling
constants 2JPP of the compounds are in the range 36.9–47.9 Hz. The
average value of 2JPP is 41.5 Hz. As expected, compounds 1a–5a, 1b,
4b, 5b, 5c and 5d give rise to one triplet and one doublet in the 1H
decoupled 31P NMR spectra. This finding is clearly in agreement
with the two different kinds of P atoms present in the cyclophos-
phazene skeleton. While, in 4e and 4f three different kinds of P
atoms are present, according to their 31P NMR data (Table 4).
The 1H and 13C NMR signals of all the phosphazenes are as-
signed on the basis of chemical shifts, multiplicities and chemical
constants. The assignments are made undoubtedly using HSQC
and HMBC experiments (Tables 5 and 6). As an example, the HSQC
and HMBC spectra of 1d are illustrated in the Supplementary mate-
rial (Figs. S1a and S1b). The benzylic ArCH2N protons of all the
compounds are observed at 3.84–4.37 ppm, and give rise to dou-
blets, indicating that these protons are equivalent to each other.
3
for some phosphazene compounds [2] and the JPC coupling con-
stants are estimated using the external transitions of the triplets
3
[29]. In addition, the JPC couplings of the ipso-C4 carbons and P
atoms are observed at 4.9–10.9 Hz, and the average value is
7.6 Hz. On the other hand, the 3JPC values of compounds containing
seven-membered spiro-rings (1a, 3a, 1b, 1c and 1d) are smaller
than those containing five- and six-membered spiro-rings. In addi-
tion, the assignments of the aromatic carbons are easily deter-
1
4
mined using the coupling constants of JFC
,
2JFC
,
3JFC and JFC. As
1
4
expected, the average values of JFC
,
2JFC
,
3JFC and JFC are 245.1,
21.4, 8.3 and 2.8 Hz, respectively.
The 19F NMR spectra of 1d and 2d are recorded as examples, and
the chemical shifts values are observed at ꢀ117.02 and
ꢀ116.56 ppm, respectively.
The characteristic C–F stretching vibrations are strongly coupled
with the C–H in-plane bending vibrations in the mono fluorinated
benzene and are observed at 1100–1000 cmꢀ1 [30]. The
mC–F values
3
are in agreement with the literature findings. All the phosphazene
derivatives show two medium intensity absorption bands at
3082–3053 and 3048–3020 cmꢀ1, attributed to the asymmetric
and symmetric stretching vibrations of the Ar–H protons. The phos-
phazene derivatives also display intense bands between 1236 and
1172 cmꢀ1, related to the mP@N bonds of the phosphazene ring
[31,32]. The characteristic mNH stretching vibrations of the
mono(4-fluorobenzyl) monospirocyclophosphazenes (1a, 2a,1b–
2d) are observed at 3398–3242 cmꢀ1. In addition, asymmetric and
The JPH coupling constants of the tetrachloro (1a–5a) and seven-
membered fully substituted spiro cyclic phosphazenes (1b, 1c
and 1d) are larger than those of the five and six-membered ones
(Table 5). On the other hand, the assignments of the aromatic
3
protons are also clearly made using the coupling constants of JFH
4
3
4
and JFH. As expected, the average values of JFH and JFH are 8.6
and 5.5 Hz, respectively. The protons (H3 and H5) and (H2 and
H6) are observed at ca. 7.38 and 7.02 ppm, respectively, as two
groups of multiplets for all the compounds except 1d, 4e and 4f.
In the 1H NMR spectra of the partly substituted bis-(4fluorobenzyl)
monospirocyclophosphazenes (4e and 4f), the two substituents
symmetric vibrations of
mPCl2 have arisen for the partly substituted
spirocyclophosphazenes (1a–5a) at 579–568 and 518–510 cmꢀ1
.
Table 4
31P NMR data in CDCl3 (d in ppm, J in Hz).
Compound
Spin system
dPN (spiro)
dPCl2
dPN2
dPNCl
2JPP
1a
2a
3a
4a
5a
1b
2b
4b
5b
1c
2c
5c
1d
2d
4d
5d
4e
AX2
AX2
AX2
AX2
AX2
AX2
AB2
AX2
AX2
AB2
AB2
AX2
AB2
AB2
AB2
AX2
ABX
PA: 14.40
PA: 10.38
PA: 16.33
PA: 12.70
PA: 18.00
PA: 22.25
PA: 20.56
PA: 23.59
PA: 27.75
PA: 22.54
PA: 19.97
PA: 28.14
PA: 21.95
PA: 19.55
PA: 22.44
PA: 27.87
PA: 19.55
PX: 21.10
PX: 22.17
PX: 20.94
PX: 22.60
ꢀ
ꢀ
2JAX: 45.7
2JAX: 41.3
2JAX: 45.3
2JAX: 38.4
2JAX: 42.9
2JAX: 42.1
2JAB: 36.9
2JAX: 39.2
2JAX: 43.0
2JAB: 43.9
2JAB: 38.3
2JAX: 42.5
2JAB: 38.0
2JAB: 40.9
2JAB: 39.9
2JAX: 43.1
2JAX: 41.4
2JAB: 39.4
2JBX: 47.9
2JAX: 43.0
2JAB: 38.7
2JBX: 41.3
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
PX: 24.20
ꢀ
ꢀ
ꢀ
PX: 18.50
PB: 18.71
PX: 17.84
PX: 18.64
PB: 21.72
PB: 21.06
PX: 22.17
PB: 21.48
PB: 20.76
PB: 20.27
PX:22.13
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
PX: 31.15
PB: 20.01
4f
ABX
PA: 19.31
PX: 30.83
ꢀ
PB: 20.00

2902
A. Okumußs et al. / Polyhedron 30 (2011) 2896–2907
Table 5
1H NMR data for the compounds [d are reported in ppm, J values in Hz, d: DASD, m: morpholine, p: pyrrolidine, s: singlet, d: doublet, t: triplet, q: quartet and m: multiplet].
H2, H6
H3, H5
N–CH2–CH2
NH–CH2–CH2 N–CH2
NH–CH2
Ar–CH2–N O–CH2
NH
H
H
2
3
F
CH2
6
5
H
H
1a
2a
3a
4a
5a
1b
2b
4b
7.00
7.30
1.50(m,2H)
1.78(m,2H)
1.53(m,4H)
1.76(m,2H)
ꢀ
1.65(m,2H)
3.20(m,3H)
3,10(m,1H) 4.30(d,2H)
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
2.50(m,1H)
3JHH = 8.5
3JFH = 8.6
7.05
3JHH = 8.5
4JFH = 5.5
7.38
3JPH = 13.1
ꢀ
3.31(m,2H)
3.05(m,2H) 3.97(d,2H)
2.87(m,1H)
3JHH = 8.6
3JFH = 8.7
7.05
3JHH = 8.6
4JFH = 5.4
7.34
3JPH = 9.2
ꢀ
3.27(d,4H)
ꢀ
ꢀ
ꢀ
4.37(d,4H)
ꢀ
3JHH = 8.6
3JFH = 9.8
7.07
3JHH = 8.6
4JFH = 5.2
7.41
3JPH = 15.6
3JPH = 13.5
ꢀ
3.05(m,4H)
3JPH = 14.2
3JHH = 8.1
4.05(d,4H)
ꢀ
3JHH = 8.4
3JFH = 8.6
7.10
3JHH = 8.4
4JFH = 5.5
7.40
3JPH = 9.4
ꢀ
3.12(d,4H)
4.10(d,4H)
ꢀ
3JHH = 8.2
3JFH = 8.6
6.90
3JHH = 8.2
4JFH = 5.5
7.40
3JPH = 10.3
3JPH = 9.6
1.40(m,2H)
p:1.65(m,8H)
1.74(m,8H)
1.61(m,2H)
p:1.75(m,16H)
1.50(m,2H)
3.08(m,2H)
p:3.08(m,16H)
2.95(m,2H) 4.30(d,2H)
2.48(m,1H)
2.38(m,1H)
ꢀ
3JHH = 8.4
3JFH = 8.7
6.97
3JHH = 8.4
4JFH = 5.6
7.38
3JPH = 11.1
ꢀ
ꢀ
3.10(m,2H)
p:3.18(m,16H)
2.91(m,2H) 3.91(d,2H)
3JHH = 8.6
3JFH = 8.7
7.00
3JHH = 8.6
4JFH = 5.6
7.40
3JPH = 13.4
3JPH = 6.8
1.64(m,2H)
p:1.73(m,16H)
3.00(m,4H)
3JPH = 13.9
ꢀ
4.10(d,4H)
3JHH = 8.5
3JFH = 8.7
3JHH = 8.5
4JFH = 5.6
3JPH = 6.7
2JHH = 8.2
p:3.15(m,16H)
2.95(d,4H)
5b
1c
7.00
7.43
p:1.74(m,16H)
ꢀ
ꢀ
4.01(d,4H)
ꢀ
ꢀ
3JHH = 8.4
3JFH = 8.7
6.99
3JHH = 8.4
4JFH = 5.6
7.42
3JPH = 10.0
3JPH = 6.6
p: 3.15(m,16H)
3.10 (m,2H)
m:3.15(m,16H)
1.38(m,2H)
1.52(m,2H)
3.05(m,2H) 4.25(d,2H) m:3.55(t,8H)
2.40(m,1H)
3JHH = 8.5
3JFH = 8.7
3JHH = 8.5
4JFH = 5.5
3JPH = 9.3
3.65(t,8H)
3JHH = 4.4
3JHH = 4.5
2c
5c
1d
7.01
7.36
1.65(m,2H)
ꢀ
ꢀ
3.20(m,2H)
2.94(m,2H) 3.87(d,2H) m:3.59(m,16H) 2.28(m,1H)
3JHH = 8.5
3JFH = 8.7
7.04
3JHH = 8.5
4JFH = 5.9
7.37
m:3.24(m,16H) 3JPH = 13.7
3JPH = 6.5
ꢀ
3.03(d,4H)
ꢀ
4.01(d,4H) m:3.64(m,16H)
3JPH = 6.6
ꢀ
3JHH = 8.6
3JFH = 8.7
7.00;
3JHH = 8.6
4JFH = 5.4
7.43; 7.26
3JPH = 10.2
m:3.17(m,16H)
3.11(m,2H)
d:3.17(m,8H)
3.21(m,8H)
1.52(m,2H)
1.57(m,2H)
2.85(m,2H) 4.26(d,2H) d:3.91(m,8H)
3JPH = 9.0
3.96(m,8H)
1.69(m,1H)
7.18
3JHH = 8.3; 8.4 d:1.66(m,8H)
3JHH = 8.3; 8.4 4JFH = 5.7; 5,8 1.69(m,8H)
3JFH = 8.7; 8.8
2d
4d
6.99
7.37
1.69(m,2H)
d:1.60(m,16H)
ꢀ
ꢀ
3.05(m,2H)
d:3.22(m,16H)
2.92(m,2H) 3.84(d,2H) d:3.93(m,8H)
1.79(m,1H)
3JHH = 8.5
3JFH = 8.7
6.97
3JHH = 8.5
4JFH = 5.6
7.35
3JPH = 11.5
3JHH = 5.8
ꢀ
3JPH = 6.8
3.96(m,8H)
1.61(m,2H)
d:1.53(m,16H)
2.95(m,4H)
3JPH = 13.8
3.96(d,4H) d:3.88(m,16H)
3JPH = 6.7
ꢀ
3JHH = 8.3
3JFH = 8.6
3JHH = 8.4
4JFH = 5.5
2JHH = 8.1
d:3.14(m,16H)
2.99(d,4H)
3JPH = 9.9
d:3.24(m,16H)
2.95(m,4H)
m:3.10(m,8H)
3.20(m,4H)
5d
4e
7.02
7.38
d:1.60(m,16H)
ꢀ
ꢀ
ꢀ
ꢀ
4.01(d,4H) d:3.88(m,16H)
3JPH = 6.0
ꢀ
ꢀ
3JHH = 8.2
3JFH = 8.3
7.01; 7.04
3JHH = 8.2
4JFH = 5.6
7.37;
1.70(m,2H)
3,96(d,2H) m:3.55(m,8H)
3JHH = 8.5; 8.4 7.44
3JFH = 8.7; 8.6 3JHH = 8.5; 8.4
4JFH = 5.4; 5.4
3JPH = 7.9
3,90(d,2H)
3JPH = 8.0
3.62(m,4H)
4f
7.02; 7.05
7.37; 7.42
1.59(m,2H)
ꢀ
2.83(m,4H)
d: 3.13(m,8H)
3.15(m,4H)
ꢀ
4.05(d,2H) d:3.84(m,8H)
ꢀ
3JHH = 8.5; 8.6 3JHH = 8.5; 8.6 d:1.60(m,8H)
3JFH = 8.7; 8.8 4JFH = 5.4; 5.5 1.66(m,4H)
3JPH = 8.6
4.15(d,2H)
3JPH = 8.8
3.83(m,4H)
3.3. X-ray structures of 3a, 4a, 5a and 2b
with the atom numbering schemes, are depicted in Figs. 1–4,
respectively. The phosphazene rings of 3a, 4a and 2b are in flat-
tened-boat conformations [Supplementary material, Fig. S3a;
The molecular and solid-state structure determinations of 3a, 4a,
5a and 2b confirm the assignments of their structures from spectro-
scopic data. The molecular structures of 3a, 4a, 5a and 2b, along
u
2 = ꢀ26.4(4)°, h2 = 108.4(4)°, Fig. S4a;
u
2 = ꢀ151.9(6)°, h2 =
60.7(5)°, and Fig. S5a; 2 = 6.2(1.3)°, h2 = 157.0(5)°] having total
u

A. Okumußs et al. / Polyhedron 30 (2011) 2896–2907
2903
Table 6
13C NMR (decoupled) spectral data for the compounds [d are reported in ppm, J values in Hz, d: DASD, m: morpholine and p: pyrrolidine].
C4
C3, C5
C2, C6
C1
N–CH2–
CH2
NH–CH2–
CH2
N–CH2
NH–CH2
Ar–CH2–N
O–CH2
O–C–O
2
6
3
5
1
4
F
CH2
1a
2a
3a
4a
5a
1b
134.12
129.33
115.41
162.13
27.36
26.00
31.10
45.92
40.50
40.35
–
50.77
ꢀ
–
–
–
–
–
ꢀ
–
–
–
–
–
3JPC = 6.0
132.20
3JFC = 7.9 2JFC = 21.5 1JFC = 245.2
2JPC = 7.1
45.55
2JPC = 6.1
49.75
129.57
114.91
161.85
–
3JPC = 8.9
134.06
3JFC = 8.0 2JFC = 21.4 1JFC = 246.0 3JPC = 4.5
2JPC = 3.4
45.12
2JPC = 3.0
50.20
129.14
3JFC = 7.9 2JFC = 21.4 1JFC = 245.2
130.01 115.46 162.39
3JFC = 8.1 2JFC = 21.3 1JFC = 245.9
129.94 115.56 162.42
3JFC = 8.1 2JFC = 21.5 1JFC = 245.8
115.46
162.15
26.27
25.16
–
–
3JPC = 4.9
132.52
2JPC = 6.7
45.77
2JPC = 6.8
50.14
–
–
3JPC = 8.2
132.33
2JPC = 3.7
47.83
–
44.23
–
3JPC = 9.1
136.70
2JPC = 14.6
45.54
2JPC = 6.0
51.01
129.27
114.52
161.61
27.90
32.05
40.05
3JPC = 5.0
3JFC = 7.9 2JFC = 21.2 1JFC = 243.4 p: 26.37
2JPC = 6.6
p: 46.25
46.34
2JPC = 5.5
26.26
3JPC = 9.2
3JPC = 9.8
2JPC = 2.0
46.77
2b
135.04
130.03
114.71
161.80
28.33
–
41.77
51.12
–
–
3JPC = 10.6 3JFC = 7.8 2JFC = 21.2 1JFC = 244.2 p: 26.26
p: 46.06
46.21
2JPC = 1.0
4JFC = 3.0
26.31
3JPC = 9.5
3JPC = 9.4
26.31
4b
5b
1c
135.40
129.51
114.68
161.81
–
45.98
p: 46.28
–
50.25
–
–
–
–
–
3JPC = 10.9 3JFC = 7.8 2JFC = 21.2 1JFC = 243.9 3JPC = 9.2
2JPC = 1.7
4JFC = 3.0
134.86
p: 23.97
p: 26.30
129.54
114.95
161.94
–
44.23
–
48.79
3JPC = 8.8
4JFC = 2.6
136.21
3JFC = 7.9 2JFC = 21.2 1JFC = 244.4 3JPC = 9.5
2JPC = 11.5
p: 46.23
46.47
2JPC = 5.7
129.54
114.97
161.89
29.67
30.31
40.21
51.67
m: 67.30
67.35
3JPC = 6.5
3JFC = 7.7 2JFC = 21.2 1JFC = 244.5
2JPC = 6.6
m: 44.70
44.80
2JPC = 5.2
3JPC = 7.8
3JPC = 7.9
m: 67.21
3JPC = 8.1
2c
5c
1d
134.15
129.74
115.09
162.00
28.17
–
46.93
41.70
51.19
–
–
3JPC = 8.7
3JFC = 7.9 2JFC = 21.3 1JFC = 244.9 3JPC = 4.6
m: 44.75
2JPC = 4.9
44.51
2JPC = 2.7 2JPC = 0.9
133.88
129.07
115.33
161.20
–
–
–
48.91
m: 67.26
3JPC = 8.7
3JPC = 8.6
3JFC = 7.9 2JFC = 21.5 1JFC = 246.2
2JPC = 12.0
m: 44.77
46.28
2JPC = 6.1
136.49
128.56
114.79
161.69
28.34
31.94
40.21
51.38
d: 64.08
64.13
107.54
107.77
3JPC = 7.1
3JFC = 7.7 2JFC = 21.2 1JFC = 243.2 d: 35.54
2JPC = 5.9
d: 42.56
;42.67
2JPC = 5.4
2d
134.49
129.93
114.86
161.89
28.25
32.50
47.05
41.75
51.56
d: 64.16
64.32
107.58
107.79
3JPC = 8.4
3JFC = 7.9 2JFC = 21.3 1JFC = 244.1 3JPC = 3.8
d: 35.56
2JPC = 6.6
d: 42.69
46.32
2JPC = 1.1
4d
5d
134.93
129.51
115.03
161.94
24.56
–
–
–
–
50.32
d: 64.24
d: 64.21
107.65
107.5
3JPC = 8.5
134.30
3JFC = 7.8 2JFC = 21.2 1JFC = 244.8 d: 35.70
d: 42.84
44.42
2JPC = 1.2
48.90
129.36
115.10
162.00
d: 29.70
3JPC = 9.5
3JFC = 7.9 2JFC = 21.3 1JFC = 244.4
2JPC = 11.5
d: 42.70
45.80;45.25
m:44.15
43.79
2JPC = 5.0
4e
4f
133.55
129.37
128.75
114.83
114.61
161.63
161.61
24.29
–
–
–
–
49.87;49.76 m: 66.01
–
133.70
2JPC = 2,3
2JPC = 2,4
66.58
3JPC = 8.2
4JFC = 2.6
3JFC = 7.9 2JFC = 21.5 1JFC = 249.9
3JFC = 7.8 2JFC = 21.6 1JFC = 241.7
3JPC = 11.9
3JPC = 12.3
2JPC = 5.3
2JPC = 2.6
45.77;46.21
d:42.53
42.72
134.39
130.30
129.70
114.94
115.08
162.03
24.95
50.10;50.32 d: 64.24
2JPC = 2.6
107.04
3JPC = 9.2
4JFC = 2.7
1JFC = 249.3 3JPC = 4.8
d:34.68
4JPC = 1.7
107.46
3JFC = 7.9 2JFC = 21.4
3JFC = 7.9 2JFC = 21.5
2JPC = 2.7
3JPC = 11.4
2JPC = 5.7
2JPC = 2.6
4JPC = 4.5
35.36
3JPC = 11.6
puckering amplitudes QT of 0.144(1) for 3a, 0.174(2) for 4a and
0.115(1) for 2b. The phosphazene ring of 5a is in a twisted
are in twisted forms [Supplementary material, Fig. S3b;
QT = 1.333(2) Å, 2 = 130.7(0.1)°, h2 = 50.5(0.1)°, Fig. S6b;
u
conformation [Supplementary material, Fig. S6a;
u
2 = 90.0(0)°,
u
2 = ꢀ110.7(0)°]. As mentioned before in Section 3.2, in CDCl3 solu-
h2 = 90.1(0)°] having total puckering amplitude QT of 0.123(0). In
4a and 2b, the six-membered rings (P1/N4/N5/C8-C10) are in chair
conformations [Supplementary material, Fig. S4b; QT = 0.657(5) Å,
tion 3a, 4a and 5a have symmetric structures, according to their 1H
and 13C NMR spectral data (Tables 5 and 6), but 3a and 4a are not
symmetric structures in the solid state.
u
2 = ꢀ167.5(8)°, h2 = 38.2(2)°, Fig. S5b; QT = 1.188(3) Å, u2
=
The average P–N bond lengths in the phosphazene rings of 3a,
4a, 5a and 2b are 1.588(1), 1.589(2), 1.588(1) and 1.597(1) Å,
which are shorter than the spiro-ring P–N bonds of 1.631(1),
143.9(2)°, h2 = 59.7(0.1)°] [33]. In 3a and 5a, the seven- and five-
membered rings [(P1/N5/N4/C13-C16) and (P1/N3/N30/C8/C80)]

2904
A. Okumußs et al. / Polyhedron 30 (2011) 2896–2907
Fig. 1. An ORTEP-3 [34] drawing of 3a with the atom numbering scheme.
Displacement ellipsoids are drawn at the 30% probability level. Hydrogen bonds
are shown as dashed lines.
Fig. 4. An ORTEP-3 [34] drawing of 2b with the atom numbering scheme.
Displacement ellipsoids are drawn at the 30% probability level. Hydrogen bonds
are shown as dashed lines.
ionic bonding is the dominant feature. Besides, these phosphazene
bonding alternatives, in fact, are both very important and they are
not mutually exclusive. The electron withdrawing groups bonding
to the P atoms increase the negative hyperconjugation of the P–N
bonds, and eventually contribute to the multiple-bond character.
Thereby, an explanation for the shortening of the P–N bonds with
electron withdrawing groups could be made qualitatively using
more efficient pN–
a⁄ overlapping for the rings of the phospha-
PR2
zene derivatives [36,37].
The endocyclic N1–P1–N3 (a) and P2–N2–P3 (d) angles of 3a, 4a
and 5a are narrowed, whilst the P1–N3–P3 (b) angles are highly ex-
panded with respect to the corresponding values in the ‘‘standard’’
Fig. 2. An ORTEP-3 [34] drawing of 4a with the atom numbering scheme.
Displacement ellipsoids are drawn at the 30% probability level.
compound, N3P3Cl6. In N3P3Cl6, the
121.4(3), 118.3(2) and 121.4(3)°, respectively [38]. On the other
hand, in compound 2b, the N3–P3–N2 ( ) angles [115.1(7) and
116.6(7)°] are narrowed, the b [123.1(8)°] and d [123.9(8)°] angles
are noticeably expanded, whereas the [118.3(7)°] angle is un-
a, b, c and d angles are 118.3(2),
c
a
changed. Generally, in phosphazenes the variations in the endocy-
clic and exocyclic angles may be explained by negative
hyperconjugation and substituent-dependent charges at the P
atoms. The charge separations between the N and P atoms in the
phosphazenes differ significantly depending on the electron-with-
drawing properties of the groups bonded to the P atoms [36]. Con-
sequently, the electronic properties and the steric interactions of
the substituents bonded to the P atoms of the phosphazenes can
play an important role for the endocyclic and exocyclic angles, as
their bond characters change [31].
In compound 2b, there are both intramolecular C–Hꢁ ꢁ ꢁN and
intermolecular C–Hꢁ ꢁ ꢁN hydrogen bonds (Table 3) (Fig. 4 and Sup-
plementary material, Fig. S7), whilst in 3a there are two intramo-
lecular hydrogen bonds between the benzylic-CH protons and
the nitrogen atoms of the phosphazene ring (Fig. 1). In addition,
in 4a intermolecular C–Hꢁ ꢁ ꢁN hydrogen bonds link the molecules
into infinite chains (Supplementary material, Fig. S8).
Fig. 3. An ORTEP-3 [34] drawing of 5a with the atom numbering scheme.
Displacement ellipsoids are drawn at the 30% probability level.
1.636(2), 1.629(1) and 1.675(1) Å, respectively. It is found that the
P–N single and double bonds of phosphazenes are generally spread
in the ranges 1.628–1.691 Å and 1.571–1.604 Å, respectively [35].
The results obtained in this study are in agreement with these val-
ues (Table 2). The P–N bond is, on the other hand, known to be the
most intriguing bond in chemistry. In recent years, the electronic
structures and the P–N bonds of phosphazene derivatives have
been reinvestigated using natural bond orbital (NBO) and topolog-
ical electron density analyses [36]. The ionic bonding and negative
hyperconjugation alternatives for phosphazenes are evaluated
with the NBO method. It is understood from the estimations that
3.4. Antibacterial activity
The bacterial and fungal species used in this study were Esche-
richia coli (ATCC 35218), E. coli (ATCC 25922), Staphylococcus aureus
(ATCC 6538), Pseudomonas aerouginosa (ATCC 27853), Enterococcus
faecalis ATCC 292112, Proteus vulgaris (NRRL B-123), B. cereus (NRLL
B-3008), B. subtilis (ATCC 29213), C. albicans (ATCC 10231) and C.
tropicalis (ATCC 13803). Only the compounds 1b and 4b exhibit

A. Okumußs et al. / Polyhedron 30 (2011) 2896–2907
2905
Table 7
Antimicrobial activities of the compounds 1b and 4b (Antibiotics; Amp = Ampicilin and C = Chloramfenicol, Antifungal; Keto = Ketoconozole).
Inhibition zone diameter (mm)
Agar well diffusion
Antibiotics
Amp
Antifungal
C
Test bacteria/compounds
1b
4b
Keto
S. aureus ATCC 25923
B. cereus NRRL-B-3711
B. subtilis ATCC 6633
C. albicans ATCC 10231
C. tropicalis ATCC 13803
15.00 0.00
16.66 0.57
12.33 0.57
–
–
9.66 0.57
12.66 0.57
11.33 0.57
19.00 0.00
25.00 0.00
35.0 0.0
10.0 1.0
10.0 1.0
NS
29.6 0.5
23.4 0.7
23.4 0.7
NS
NS
NS
NS
30.0 0.0
29.0 0.5
NS
NS
Table 8
MIC Values of the compounds 1b and 4b.
B. subtilis (
l
M)
B. cereus (
lM)
S. aureus (
lM)
C. albicans
C. tropicalis
1b
4b
5000
5000
5000
5000
5000
5000
–
–
312.5
lM
625 lM
Fig. 5. Electrophoretic results of the incubation of pBR322 plasmid DNA with varying concentrations of 2a–5a, 1b–2d, 4b, 4d–5d, 4e and 4f (Lane 1): pBR322 DNA, Lanes 2–6:
pBR322 DNA incubated with compounds 5.000, 2.500, 1.250, 625 and 312
respectively.
lM. The roman numerals I and II indicate form I and form II and form III pBR322 plasmid DNAs

2906
A. Okumußs et al. / Polyhedron 30 (2011) 2896–2907
Fig. 6. Electrophoretograms for the BamHI (A) and HindIII (B) digested mixtures of pBR322 plasmid DNA after treatment with 1b, 1c, 1d, 2a, 2b, 2c, 2d, 3a, 4a, 4b, 4d, 4e, 4f,
5a, 5b, 5c and 5d. Lane 1, untreated pBR322 plasmid DNA, line PB and PH apply to plasmid DNA restricted with enzymes BamHI and HindIII respectively.
antimicrobial activity against the bacterial and fungal species (Ta-
ble 7). In addition, 1b exhibits strong and moderate growth inhibi-
tion against B. cereus, S. aureus and B. subtilis. Compound 4b is the
only effective compound against the Cantida species. C. albicans
and C. tropicalis. MIC values are in the range 312.5–5000 lM
(Table 8).
restriction analysis of the compound-DNA adducts digested with
BamHI and HindIII enzymes was carried out. BamHI and HindIII en-
zymes bind at the sites DNA 50-G/GATCC-30 and 50-A/AGCTT-30 and
cleave these sequences respectively, and convert forms I and II
DNA to the linear form III DNA [39]. Only one concentration for
each compound was used for the restriction analysis. All of the
compounds prevent digestion with HindIII, whereas BamHI
enzymes cut all the compounds interacted with DNA (Fig. 6).
3.5. Interactions of DNA with the compounds
Interactions of 2a–5a, 1b–2d, 4b, 4d–5d, 4e and 4f with super-
coiled pBR322 plasmid DNA have been studied. The compounds
were incubated over a range of concentrations with supercoiled
pBR322 plasmid DNA in the dark at 37 °C for 24 h. The DNA cleav-
age by these compounds has been examined by observing the con-
version of supercoiled DNA to the open circular form II and linear
form III DNA. Fig. 5 depicts the electrophoretograms for the inter-
action of pBR322 plasmid DNA with the compounds 2a–5a, 1b–2d,
4b, 4d–5d, 4e and 4f at concentrations of the compounds ranging
4. Conclusions
The NN donor mono and bis(4-fluorobenzyl)diamines (1–5)
have regioselectively led to the formation of spirocyclic mono (1a
and 2a) and bis(4-fluorobenzyl) monospirocyclophosphazenes
(3a–5a) via chloride replacement reactions of N3P3Cl6. The fully
substituted mono(4-fluorobenzyl) (1b–2d) and bis(4-fluorobenzyl)
(4b,4d–5d) monospirocyclophosphazenes are obtained from the
reactions of compounds 1a–5a with pyrrolidine, morpholine and
DASD. Afterwards, the monochlorobis(4-fluorobenzyl) monospiro-
cyclophosphazenes 4e and 4f have also been isolated from the
reactions of excess morpholine and DASD in boiling THF. Com-
pounds 4e and 4f have one stereogenic P atom and they can be
thought of as good candidates for chiral investigations. The struc-
tures of the compounds have been ascertained unambiguously by
one and two dimensional NMR techniques and X-ray crystallogra-
phy. Especially, the assignments of the aromatic carbons are easily
corroborated using the couplings between the fluorine and carbon
atoms. The solid-state structures of 3a, 4a, 5a and 2b reveal intra
and intermolecular C–Hꢁ ꢁ ꢁN hydrogen bondings. Compounds 1b
and 4b exhibit potential antimicrobial activities with Gram-posi-
tive bacteria. In addition, compound 4b shows strong antifungal
activities against C. albicans and C. tropicalis. Furthermore, the
interactions of the compounds 2a–5a, 1b–2d, 4b, 4d–5d, 4e and
4f with pBR322 plasmid DNA have been evaluated. It is understood
that they are very effective in changing the mobility and the shape
of pBR322 plasmid DNA. Compounds 4a, 5a, 2a, 3a, 4e and 4f are
the most efficient DNA cleavers amongst the other tested com-
pounds. Moreover, restriction analyses indicate that phosphazene
derivatives bind to A/T of the DNA.
from 5000 to 312 lM. Lane 1 applies to the untreated pBR322 plas-
mid DNA (control DNA), showing the major supercoiled (form I)
and minor nicked (form II) forms [2,23]. Lanes 2–6 apply to
pBR322 plasmid DNA incubated with the compounds with
concentrations ranging from 5000 to 312 lM.
When the pBR322 plasmid DNA interacted with decreasing con-
centrations of 1b, 1d and 5a, the mobility of form I slightly de-
creased in all the concentrations tested. In the case of 4a, the
plasmid DNA interaction with the compound leads to a two strands
break of the DNA, and the linear form III is observed. On the other
hand, in the case of 4b, 1c and 2d, the mobility of form I DNA in-
creases and that of form II DNA decreases with a decreasing con-
centration of the compound. In addition, the linear form III DNA
is generated with 1c. Compounds 5c and 2c have no effect on the
mobility of form I or form II DNA. However, these two compounds
induce breaks in the DNA structure and form III is observed. Com-
pounds 2a, 3a, 4f and 4e change the intensities and the mobilities
of the form I DNA such that the two bands comigrate, especially at
higher concentrations, and a smear of DNA is observed. In the case
of 2b, 5b and 5d there is no effect on the mobility of form I and
form II DNA, however the linear form III bands are observed for
2b, 5b and 5d as a result of conformational changes in form I of
DNA emerging from covalent binding of the compounds with the
nucleotides in DNA.
Acknowledgements
The authors acknowledge the ‘‘Ankara University, Scientific Re-
searches Unit’’ Grant No. 09B4240006, and also thank the ‘‘Medic-
inal Plants and Medicine Research Center of Anadolu University,
Eskißsehir’’ for the use of the X-ray facility. We also thank the State
Planning Organization (Grant No: 1998K121480).
3.6. BamHI and HindIII digestion of compounds-pBR322 plasmid DNA
In order to find out whether the compounds bind guanine–
guanine (GG) and/or adenine–adenine (AA) nucleotides of DNA,

A. Okumußs et al. / Polyhedron 30 (2011) 2896–2907
2907
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Appendix A. Supplementary data
CCDC 823467, 823468, 823465, and 823466 contain the supple-
mentary crystallographic data for 3a, 4a, 5a, and 2b. These data can
be obtained free of charge via http://www.ccdc.cam.ac.uk/conts/
retrieving.html, or from the Cambridge Crystallographic Data Cen-
tre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336
033; or e-mail: deposit@ccdc.cam.ac.uk. Supplementary data asso-
ciated with this article can be found, in the online version, at
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