The syntheses and structures of Ph4EN3 (E = P, As, Sb), an example for the transition from ionic to covalent azides within the same main group

Article abstract of DOI:10.1002/zaac.200500289

The compounds Ph₄EN₃ (E = P, As, Sb) were prepared from the corresponding halides by ion exchange in aqueous solution. [Ph ₄P]N₃ crystallizes in the triclinic space group P1, while [Ph₄As]N₃·H₂O and Ph₄SbN ₃ crystallize in the monoclinic space group P2₁/n. In contrast to ionic [Ph₄P]⁺[N₃]- and [Ph ₄As]⁺[N₃]^-, the antimony atom in Ph₄SbN₃ is pentacoordinated and contains a covalently bound azide ligand. This family of compounds serves as an example for the transition from ionic to covalent azides with increasing size of the central atom within the same group of the periodic table.

Full text of DOI:10.1002/zaac.200500289

The Syntheses and Structures of Ph4EN3 (E ؍ P, As, Sb), an Example for the
Transition from Ionic to Covalent Azides within the Same Main Group
Ralf Haiges*, Thorsten Schroer, Muhammed Yousufuddin, and Karl O. Christe*
Los Angeles/USA, University of Southern California, Loker Research Institute and Department of Chemistry
Received June 27th, 2005.
Dedicated to Professor Herbert W. Roesky on the Occasion of his 70th Birthday
Abstract. The compounds Ph4EN3 (E ϭ P, As, Sb) were prepared
as an example for the transition from ionic to covalent azides with
increasing size of the central atom within the same group of the
periodic table.
from the corresponding halides by ion exchange in aqueous solu-
¯
tion. [Ph4P]N3 crystallizes in the triclinic space group P1, while
[Ph4As]N3·H2O and Ph4SbN3 crystallize in the monoclinic space
group P21/n. In contrast to ionic [Ph4P]ϩ[N3]Ϫ and [Ph4As]ϩ[N3]Ϫ,
the antimony atom in Ph4SbN3 is pentacoordinated and contains
a covalently bound azide ligand. This family of compounds serves
Keywords: Azides; Phosphorus; Arsenic; Antimony; Crystal struc-
tures; Ion exchange
Introduction
polyazido anions by large counter-ions (e.g. [EPh4]ϩ, E ϭ
P, As). Therefore, ionic azides with large counter-ions, such
There has been much recent interest in polyazido chemistry
[1Ϫ13]. The azido group is highly energetic and adds about
70 kcal·molϪ1 to the energy content of a molecule. Poly-
azides are, therefore, highly endothermic compounds,
whose energy content increases with an increasing number
of azido ligands. The relatively stable azide anion possesses
two double bonds, but covalent azides are polarized
towards structures containing a single and a triple bond,
which greatly facilitates the elimination of dinitrogen and
enhances their sensitivity. The synthesis of molecules with
a high number of azido groups is a useful but challenging
way to synthesize high energy-density materials (HEDM).
Neutral covalent polyazides are extremely shock-sensitive
compounds. The danger can be reduced, at least in part, by
anion formation due to reaction of the neutral compound
with ionic azides [Eq. (1)].
Ϫ
as [Ph4P]ϩN3 and [Ph4As]ϩN3Ϫ, are frequently used re-
agents in polyazide chemistry.
Phosphonium-, arsonium- and stibonium azides are
generally prepared by metathesis between the correspond-
ing chloride and an excess of sodium azide [Eq. (2), E ϭ P,
As, Sb] [14].
Ph4ECl ϩ NaN3 Ǟ Ph4EN3 ϩ NaCl
(2)
Another method is the reaction of the bromide or iodide
compound with silver azide, respectively, [Eq. (3), X ϭ
Br, I] [2, 15, 16].
Ph4EX ϩ AgN3 Ǟ Ph4EN3 ϩ AgX
(3)
However, azides obtained from reaction (2) may contain
impurities of chloride which often cannot be removed.
Furthermore, reaction (3) involves the handling of shock
sensitive silver azide and is not a convenient general
method. It was therefore desirable to find a convenient
method for converting halide salts into the corresponding
azide salts in high yield and purity. In addition, only the
structure of the arsenic compound in the series Ph4EN3
(E ϭ P, As, Sb) has previously been determined by X-ray
diffraction techniques [14]. Furthermore, the detailed X-ray
data files deposited under the given number with the FIZ,
M(N3)x ϩ AϩN3 Ǟ Aϩ[M(N3)xϩ1
Ϫ
]
(1)
Ϫ
The resulting Aϩ[M(N3)xϩ1
]
salts are stabilized by their
Ϫ
crystal lattice enthalpies and the increased formal negative
charges of the anions. These negative charges reside largely
on the terminal Nγ atoms, reducing the Nβ-Nγ triple-bond
character and the ease of N2 elimination. In addition, the
detonation velocity is greatly reduced or propagation of de-
composition is completely eliminated by separation of the
Ϫ
Karlsruhe, are for N(C2H5)4ϩN3 and not for [Ph4As]N3.
Results and Discussion
Tetraphenylphosphonium, tetraphenylarsonium, and tetra-
phenylstibonium azide were prepared in quantitative yields
from the corresponding chlorides, bromides or iodides,
respectively, by ion exchange in aqueous solution [Eq. (4),
X ϭ halogen].
* Dr. R. Haiges, Dr. T. Schroer, M. Yousufuddin,
Prof. Dr. K. O. Christe
Loker Research Institute and Department of Chemistry
University of Southern California
Los Angeles, CA 90089-1661 /USA
Fax: (ϩ1) 213-740-6679
E-mail: haiges@usc.edu, kchriste@usc.edu
Resin-NR3ϩN3 ϩ Ph4EX Ǟ Ph4EN3 ϩ Resin-NR3ϩXϪ
Ϫ
(4)
Z. Anorg. Allg. Chem. 2005, 631, 2691Ϫ2655
DOI: 10.1002/zaac.200500289
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R. Haiges, Th. Schroer, M. Yousufuddin, K. O. Christe
Table 1 Structure refinement data for [Ph4P]N3, [Ph4As]N3·H2O,
and Ph4SbN3
Table 3 Atomic coordinates (x104) and isotropic displacement
factors Ueq /A x10 for [P(C6H5)4]N3. Ueq is defined as one third
of the trace of the orthogonalized Uij tensor
2
3
˚
empirical formula C24H20N3P
C24H22AsN3O
441.35
133(2)
monoclinic
P21/n
10.778(3)
16.040(5)
12.853(4)
90
90.545(4)
90
2222.1(11)
4
1.319
904
C24H20N3Sb
472.18
143(2)
monoclinic
P21/n
12.3975(14)
10.5524(12)
16.3295(19)
90
107.132(2)
90
2041.5(4)
4
1.536
944
formula weight
Temperature, K
crystal system
space group
381.40
110(2)
triclinic
x
y
z
Ueq
P(1)
640(1)
4126(3)
4802(3)
5480(3)
Ϫ1261(3)
Ϫ1630(3)
Ϫ3105(4)
Ϫ4201(4)
Ϫ3839(3)
Ϫ2382(3)
1068(3)
140(3)
3440(1)
8761(3)
9757(3)
10767(3)
4106(3)
5518(3)
6017(3)
5116(4)
3709(4)
3192(3)
2382(3)
2392(3)
1617(3)
833(3)
2672(1)
3343(3)
2866(2)
2394(2)
2983(3)
2813(3)
3037(3)
3432(3)
3620(3)
3404(3)
1547(3)
832(3)
23(1)
48(1)
30(1)
38(1)
24(1)
32(1)
39(1)
41(1)
41(1)
32(1)
22(1)
27(1)
34(1)
35(1)
34(1)
30(1)
22(1)
29(1)
34(1)
33(1)
31(1)
29(1)
22(1)
27(1)
30(1)
32(1)
30(1)
26(1)
¯
P1
N(1)
N(2)
N(3)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
˚
a, A
9.671(2)
10.208(2)
11.237(2)
72.397(4)
69.412(3)
80.509(4)
987.6(4)
2
˚
b, A
˚
c, A
Ͱ, °
β, °
γ, °
3
˚
V, A
Z
ρcalc g/cm3
F(000)
1.283
400
C(8)
C(9)
554(3)
Ϫ75(3)
Ϫ285(3)
409(3)
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
C(19)
C(20)
C(21)
C(22)
C(23)
C(24)
1892(3)
2821(3)
2417(3)
975(3)
Ϫ189(3)
140(3)
1591(4)
2752(3)
2443(3)
1855(3)
2054(3)
2930(3)
3604(3)
3418(3)
2546(3)
Index ranges
Ϫ10 Յ h Յ 10,
Ϫ11 Յ k Յ 7,
Ϫ12 Յ l Յ 12
0.153
Ϫ13 Յ h Յ 13,
Ϫ16 Յ k Յ 16,
Ϫ20 Յ l Յ 12
1.548
Ϫ12 Յ h Յ 16,
Ϫ12 Յ k Յ 13,
Ϫ21 Յ l Յ 20
1.365
834(3)
1592(3)
2455(3)
1892(3)
1046(3)
732(3)
1291(3)
2155(3)
4834(3)
5628(3)
6743(3)
7078(3)
6301(3)
5183(3)
1324(3)
4184(3)
5313(3)
6417(3)
6414(3)
5297(3)
4192(3)
1887(3)
2629(3)
2013(3)
656(3)
µ, mmϪ1
crystal size, mm
λ, A
0.12 x 0.16 x 0.08 0.22 x 0.15 x 0.04 0.67 x 0.12 x 0.02
˚
0.71073
0.71073
0.71073
no. of rflns. collect. 4309
no. of indep. rflns. 2807
13294
4958
0.0411
285
12097
4576
0.0432
253
Rint
0.0414
254
no. of params.
R1, wR2 [I>2σ(I)] 0.0438, 0.0730
R1, wR2 (all data) 0.0780, 0.0793
0.0482, 0.1308
0.0584, 0.1354
1.492/Ϫ0.402
0.0351, 0.0687
0.0523, 0.0733
0.866/Ϫ0.560
Ϫ92(3)
518(3)
Ϫ3
˚
(∆/ρ)min/max, e A
0.248/Ϫ0.263
Table 4 Atomic coordinates (x104) and isotropic displacement
factors Ueq (A x10 for Sb(C6H5)4N3. Ueq is defined as one third
of the trace of the orthogonalized Uij tensor
˚
Table 2 Selected bond length /A and angles /° for [Ph4P]N3 and
Ph4SbN3
2
3
˚
[Ph4P]N3
Ph4SbN3
x
y
z
Ueq
N1-N2
N2-N3
M-C1
1.179(3)
1.193(3)
1.800(3)
1.801(3)
1.803(3)
1.801(3)
Ϫ
1.198(4)
1.150(4)
2.102(3)
2.121(3)
2.153(3)
2.102(3)
2.373(3)
Sb(1)
N(1)
N(2)
N(3)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(9)
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
C(19)
C(20)
C(21)
C(22)
C(23)
C(24)
7705(1)
8393(2)
8675(2)
8948(3)
9206(3)
9915(3)
10892(3)
11135(3)
10426(3)
9458(3)
6290(3)
6360(3)
5396(3)
4369(3)
4301(3)
5263(3)
7118(3)
7152(3)
6693(3)
6208(3)
6177(3)
6619(3)
7688(3)
8552(3)
8479(3)
7554(3)
6693(3)
6755(3)
3056(1)
2525(3)
3278(3)
3976(3)
2143(3)
2752(3)
2150(4)
938(4)
329(3)
934(3)
1950(3)
971(3)
314(3)
248(1)
Ϫ920(2)
Ϫ1366(2)
Ϫ1808(2)
961(2)
1670(2)
2150(2)
1941(2)
1253(2)
749(2)
Ϫ416(2)
Ϫ963(2)
Ϫ1392(2)
Ϫ1290(2)
Ϫ748(2)
Ϫ298(2)
1341(2)
1910(2)
2577(2)
2712(2)
2167(2)
1485(2)
Ϫ172(2)
204(2)
25(1)
35(1)
33(1)
56(1)
28(1)
36(1)
44(1)
38(1)
32(1)
29(1)
29(1)
32(1)
39(1)
43(1)
45(1)
36(1)
27(1)
34(1)
40(1)
46(1)
41(1)
34(1)
29(1)
39(1)
41(1)
45(1)
50(1)
41(1)
M-C7
M-C13
M-C19
M-N1
N1-N2-N3
C1-M-C7
179.4(3)
109.27(13)
110.93(13)
110.15(13)
110.18(12)
107.07(13)
109.16(13)
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
178.2(4)
119.49(12)
94.81(11)
115.26(12)
95.40(12)
115.26(12)
97.15(12)
82.47(11)
84.13(11)
176.54(10)
86.14(11)
124.8(2)
C1-M-C13
C1-M-C19
C7-M-C13
C7-M-C19
C13-M-C19
N1-M-C1
N1-M-C7
N1-M-C13
N1-M-C19
M-N1-N2
639(4)
1601(4)
2256(3)
3429(3)
2428(3)
2539(4)
3659(4)
4677(4)
4561(3)
4941(3)
5769(3)
7019(3)
7454(4)
6629(4)
5373(3)
Ϫ42(2)
Ϫ664(3)
Ϫ1053(2)
Ϫ814(2)
The ion-exchange resin was prepared from Amberjet 4200
quaternary ammonium chloride resin by exchange with
azide ions and proper washing. The corresponding azides
were isolated as colorless solids, and were characterized by
their crystal structure and vibrational spectroscopy.
˚
ing ions of 4.973 A is considerably longer than the sum of
van der Waals radii (1.55 ϩ 1.80 ϭ 3.35 A) [21]. The azide
anion is symmetric and linear.
˚
Tetraphenylphosphonium azide crystallizes in the tri-
clinic space group P1. The crystallographic data, bond
¯
distances, and atomic coordinates are listed in Tables 1-3.
As expected for tetraphenylphosphonium compounds
[17Ϫ20], and shown in Figure 1, the cations and anions are
well separated. The closest P···N contact between neighbor-
Tetraphenylarsonium azide monohydrate crystallizes in
the monoclinic space group P21/n. The crystallographic
data are listed in Table 1. Although the refined structure
(Fig. 2) had a low R factor of 4.8 %, the anion part was
2692
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Z. Anorg. Allg. Chem. 2005, 631, 2691Ϫ2695

Syntheses and Structures of Ph4EN3 (E ϭ P, As, Sb)
Fig. 3 ORTEP drawing of Sb(C6H5)4N3. Thermal ellipsoids are
shown at the 50 % probability level
Fig. 1 ORTEP drawing of [P(C6H5)4]N3. Thermal ellipsoids are
shown at the 50 % probability level
Fig. 4 IR (top) and Raman (bottom) spectra of [P(C6H5)4]N3
lecular structure (Fig. 3) is that of a trigonal bipyramid with
the azido and one phenyl-group occupying the axial posi-
tions. The angle N-Sb-C13 of 176.54(10)° is nearly linear.
The atoms Sb, C1, C7, and C19 are approximately
coplanar. These findings are in excellent agreement with in-
frared and electrical conductance studies on Ph4SbN3 [15]
and previously reported structures of other tetraphenyl-
stibonium compounds [22Ϫ27].
Fig. 2 ORTEP drawing of the disordered [As(C6H5)4]N3·H2O
structure. Thermal ellipsoids are shown at the 50 % probability
level, and the water molecule has been omitted
disordered. The structure clearly showes an isolated
[Ph4As]ϩ cation with the expected tetrahedral structure
around the arsenic atom. This structure is not discussed in
The observed vibrational frequencies of [Ph4P]N3,
[Ph4As]N3, and Ph4SbN3 and their tentative assignment are
listed in the Experimental Part. The vibrational spectra of
[Ph4P]N3 (Fig. 4) and [Ph4As]N3·H2O confirm their ionic
nature in the solid state, while that of Ph4SbN3 (Fig. 5) lends
further support for its covalent structure. The IR spectra of
the compounds show the two characteristic azide bands: the
very intense antisymmetric stretching mode at about
2000 cmϪ1 and the weak symmetric stretching mode at
Ϫ
further detail because that for anhydrous [Ph4As]ϩN3 has
already been reported previously [14].
Tetraphenylstibonium azide also crystallizes in the mono-
clinic space group P21/n with 4 molecules per unit cell. The
crystallographic data, bond distances, and atomic coordi-
nates are listed in Tables 1, 2, and 4, respectively. The mo-
Z. Anorg. Allg. Chem. 2005, 631, 2691Ϫ2695
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R. Haiges, Th. Schroer, M. Yousufuddin, K. O. Christe
it was washed with de-ionized water, until the eluents were neutral
(pH 7). After that, the resin was washed with 150 ml of 10 % NaN3
solution and then with de-ionized water, until the eluents gave no
precipitate with AgNO3.
Preparations of (C6H5)4EN3 (E ؍ P, As, Sb)
20 mmol of (C6H5)4EX (X ϭ Cl, Br, I) were dissolved in 100 ml of
de-ionized water and 50 ml ethanol. This solution was passed
through the azide loaded Amberjet 4200 resin column and then
washed with de-ionized water, until the eluents gave no precipitate
with AgNO3. The eluents were combined, and the water was
pumped off, leaving behind colorless solids. Single crystals were
obtained from ethanol/water solutions by slow evaporation of the
solvent with a stream of nitrogen.
[(C6H5)4P]N3: yield: 98 %.
IR (20 °C, KBr) ν˜ ϭ 3447w (OH, H2O); 3282mw (νas ϩ νs N3Ϫ); 3081w,
3048mw, 3018w, 2992w (νC-H), 2036m, 1998vs (νasN3Ϫ); 1585m, 1481m,
1439s, 1434s, 1342w (ring); 1314mw (νsN3Ϫ); 1184mw, 1158mw, 1107s,
1025w (ring); 997m, 859w, 764m, 750m, 722s, 693s, 668w, 634w (C-H); 616w
(δN3Ϫ); 528vs, 460w (C-H) cmϪ1. Raman (20 °C, 50 mW) ν˜ ϭ 3067 (4.9)
(νC-H); 1586 (4.4), 1575 (1.1), 1482 (0.1), 1436 (0.2) (ring); 1314 (2.0)
(νsN3Ϫ); 1241 (0.3), 1187 (0.6), 1163 (0.5), 1108 (0.9), 1098 (1.7), 1028 (2.5)
(ring); 1001 (6.6), 727 (0.3), 679 (1.4), 614 (1.1), 283 (1.0), 266 (1.2), 257 (2.2)
Fig. 5 IR (top) and Raman (bottom) spectra of Sb(C6H5)4N3
about 1300 cmϪ1. The absence of the antisymmetric stretch-
ing mode in the Raman spectra of [Ph4P]N3 and [Ph4As]N3
demonstrates the presence of ionic azides. As expected for
a compound with a covalently bonded azido ligand, the
antisymmetric N3 stretching mode is observed in the Raman
spectrum of Ph4SbN3. The infrared spectrum of [Ph4P]N3
is in excellent agreement with a previous report by Mueller,
Duebgen and Dehnicke [28].
In summary, the crystal structures and vibrational spec-
tra of the series Ph4EN3 (E ϭ P, As, Sb) demonstrate the
ionic characters of the phosphorus and arsenic compounds
and the covalent nature of the antimony analogue. It
exemplifies that, with increasing size and coordination
number of the central atom, the energy gained by the
formation of an additional covalent bond outweighs the
Coulomb energy gained by the formation of an ionic com-
pound with lower coordination number.
(C-H); 208 (1.1), 198 (1.4), 107 (10.0) cmϪ1
.
[(C6H5)4As]N3: yield: 95 %.
IR (20 °C, KBr) ν˜ ϭ 3442ms (OH, H2O); 3076w, 3049w, 3015w (νC-H);
2037s, 2000vs (νasN3Ϫ); 1635w, 1580w, 1482m, 1440s, 1339vw (ring); 1311w
(νsN3Ϫ); 1183w, 1162vw, 1083s, 1025w (ring); 997s, 757s, 693s (C-H); 616w
(δN3Ϫ); 481s, 469s, 454w (δC6H5) cmϪ1. Raman (20 °C, 50 mW) ν˜ ϭ 3063
(6.2) (νC-H); 1579 (3.7), 1481 (0.3), 1436 (0.3) (ring); 1314 (2.4) (νsN3Ϫ);
1242 (0.5), 1182 (0.8), 1172 (0.4), 1161 (0.6), 1082 (1.1), 1024 (2.7) (ring);
1002 (9.1), 681 (0.6), 670 (2.6), 612 (1.1), 362 (0.4), 351 (0.4), 265 (1.5), 261
(1.5), 242 (3.5) (C-H); 193 (1.7), 184 (2.3), 98 (10.0) cmϪ1
.
(C6H5)4SbN3: yield: 94 %.
IR (20 °C, KBr) ν˜ ϭ 3442mw (OH, H2O); 3340w; 3062w, 3056w, 3040w
(νC-H); 2038vs (νasN3Ϫ); 1636w, 1576mw, 1479m, 1457vw, 1434ms, 1430ms,
1419vw, 1334w, 1325m (ring); 1307w (νsN3Ϫ); 1262w, 1183w, 1162w, 1068m,
1066m, 1062m, 1020m (ring); 996mw, 745ms, 698ms, 692s, 655w, 634w (C-
H); 613w, 605w (δN3); 464ms, 456ms, 445m (δC6H5) cmϪ1. Raman (20 °C,
50 mW) ν˜ ϭ 3070 (3.6), 3063 (3.1), 3056 (6.1), 3048 (6.9), 3041 (5.9) (νC-H);
2040 (0.6), 2034 (0.5), 2027 (0.2) (νasN3); 1576 (2.8), 1570 (1.4), 1478 (0.5),
1438 (0.3), 1434 (0.3) (ring); 1333 (0.8) (ring); 1325 (1.5) (νsN3); 1266 (0.3),
1186 (1.0), 1166 (0.4), 1161 (0.5), 1156 (0.6), 1067 (0.5), 1021 (2.8) (ring);
1002 (8.4), 997 (5.1), 985 (0.4) (C-H); 736 (0.1) 730 (0.1), 655 (3.5) (C-H);
635 (0.2) (δN3); 613 (0.8), 467 (0.3), 448 (0.3), 295 (0.4), 261 (1.5), 251 (1.2),
239 (1.4), 225 (4.3), 215 (2.9) (C-H); 193 (1.4), 180 (1.8), 168 (2.1), 95
Experimental Part
Materials and Apparatus
Infrared spectra were recorded in the range 4000Ϫ400 cmϪ1 on a
Midac FT-IR model 1720 at a resolution of 1 cmϪ1 using KBr
pellets. The pellets were prepared in the dry argon atmosphere of
a glove box using an Econo press (Barnes Engineering Co.). Raman
spectra were recorded in the range 3600Ϫ80 cmϪ1 on a Bruker
Equinox 55 FT-RA spectrophotometer using a Nd-YAG laser at
1064 nm with power levels of less than 100 mW. Pyrex melting
point tubes that were baked out at 300 °C for 48 h at 10 mTorr
vacuum were used as sample containers. AgNO3, NaN3, NaOH,
[(C6H5)4P]Cl, [(C6H5)4As]Cl·H2O, (C6H5)4SbCl, and Amberjet
4200(Cl) (all Aldrich) were used without further purification.
(10.0) cmϪ1
.
Crystal structure determination
The single crystal X-ray diffraction data of [(C6H5)4P]N3,
[Ph4As]N3·H2O, and (C6H5)4SbN3 were collected on a Bruker
3-circle platform diffractometer equipped with a SMART CCD
(APEX) detector with the χ-axis fixed at 54.74° and using Mo Kα
radiation (Graphite monochromator) from a fine-focus tube. This
diffractometer was equipped with an LT-3 apparatus for low-tem-
perature data collection using controlled liquid nitrogen boil off. A
few reasonably well-formed single crystals were selected in a glove-
box with a microscope. The crystals were coated with epoxy grease
and then mounted on a magnetic goniometer head. Cell constants
were determined from 90 ten-second frames. A complete hemi-
sphere of data was scanned on omega (0.3°) with a run time of 30-
second per frame at a detector resolution of 512 x 512 pixels using
Preparation of azide loaded ion-exchange resin
50 g (185 meq) Amberjet 4200(Cl) quaternary ammonium resin was
loaded into a 5 cm o.d. glass column which was equipped with a
grease-free Teflon valve. The resin was washed with 10 % NaOH
solution, until the eluents gave no precipitate with AgNO3. Then
2694
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Z. Anorg. Allg. Chem. 2005, 631, 2691Ϫ2695

Syntheses and Structures of Ph4EN3 (E ϭ P, As, Sb)
the SMART software package [29]. A total of 1271 frames were
collected in three sets and a final set of 50 frames, identical to the
first 50 frames, was also collected to determine any crystal decay.
The frames were then processed on a PC, running Windows 2000
software, by using the SAINT software package [30] to give the hkl
files corrected for Lp/decay. The absorption correction was per-
formed using the SADABS program [31]. The structures were
solved by the direct method using the SHELX-90 program and
refined by the least squares method on F2, SHELXL-97 incorpor-
ated in SHELXTL Suite 6.12 for Windows NT/2000 [32]. All non-
hydrogen atoms were refined anisotropically. For the anisotropic
displacement parameters, the Ueq is defined as one third of the
trace of the orthogonalized Uij tensor. ORTEP drawings were pre-
pared using the ORTEP-3 for Windows V1.076 program [33].
Further details of the crystal structure investigations reported in
this paper may be obtained from the Cambridge Crystallographic
Data Centre (CCDC), 12 Union Road, Cambridge CB2 1EZ (UK)
(fax: ϩ44 (1223)336-033 or email: deposit@ccdc.cam.ac.uk) by
quoting the depository numbers CCDC 263415 ( (C6H5)4SbN3),
CCDC 269384 ([(C6H5)4As]N3·H2O), and CCDC 263416
([(C6H5)4P]N3).
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Acknowledgement. This work was funded by the Air Force Office
of Scientific Research and the National Science Foundation. We
thank Prof. G. Olah, and Dr. M. Berman for their steady support,
and Dr. R. Wagner and Mr. CJ Bigler Jones for their help and
stimulating discussions.
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2695