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1-Methyl-1-azonia-3,5-diaza-7-phospha-
tricyclo[3.3.1.1]decane 7-oxide triiodide
Alexander M. Kirillov,
a
Piotr Smolen
´ski,
a
M. Fa
´tima C.
Guedes da Silva
a,b
* and Armando J. L. Pombeiro
a
a
Centro de Quı
´mica Estrutural, Complexo Interdisciplinar, Instituto Superior Te
´cnico,
TU Lisbon, Avenida Rovisco Pais, 1049-001 Lisbon, Portugal, and
b
Universidade
Luso
´fona de Humanidades e Tecnologias, ULHT Lisbon, Avenida do Campo Grande
376, 1749-024 Lisbon, Portugal
Correspondence e-mail: fatima.guedes@ist.utl.pt
Received 7 January 2008; accepted 14 January 2008
Key indicators: single-crystal X-ray study; T= 150 K; mean (N–C) = 0.009 A
˚; some
non-H atoms missing; Rfactor = 0.042; wR factor = 0.103; data-to-parameter ratio =
16.2.
The title compound, C
7
H
15
N
3
OP
+
I
3
, is a derivative of the
well known water-soluble aminophosphine 1,3,5-triaza-7-
phosphaadamantane (PTA). The crystal structure is composed
of a cage-like 1-methyl-1-azonia-3,5-diaza-7-phospha-
tricyclo[3.3.1.1]decane 7-oxide cation and a triiodide anion.
The N-methylation of the PTA cage results in a slight
elongation of the corresponding C—N bonds, while the
oxidation of the P atom leads to a slight shortening of the
C—P bonds in comparison with those of PTA. In general, most
of the bonding parameters are comparable with those
reported for related compounds bearing the PTA core. Two
intermolecular C—HO hydrogen bonds between methyl-
ene groups and the P O group are responsible for the
linkage of neighbouring cations into linear one-dimensional
hydrogen-bonded chains.
Related literature
For a comprehensive review of PTA chemistry, see: Phillips et
al. (2004). For general background, see: Kirillov et al. (2007);
Smolen
´ski & Pombeiro (2008). For synthesis of PTA and its N-
methylated derivative, see: Daigle et al. (1974); Daigle (1998).
For related structures, see: Forward et al. (1996a,b); Otto et al.
(2005); Frost et al. (2006); Marsh et al. (2002).
Experimental
Crystal data
C
7
H
15
N
3
OP
+
I
3
M
r
= 568.89
Monoclinic, P21=n
a= 7.1570 (8) A
˚
b= 8.2257 (8) A
˚
c= 25.903 (3) A
˚
= 92.472 (7)
V= 1523.5 (3) A
˚
3
Z=4
Mo Kradiation
= 6.24 mm
1
T= 150 (2) K
0.13 0.10 0.10 mm
Data collection
Bruker SMART CCD area-detector
diffractometer
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
T
min
= 0.497, T
max
= 0.574
(expected range = 0.464–0.536)
11526 measured reflections
2789 independent reflections
2214 reflections with I>2(I)
R
int
= 0.040
Refinement
R[F
2
>2(F
2
)] = 0.042
wR(F
2
) = 0.102
S= 1.12
2789 reflections
172 parameters
H atoms treated by a mixture of
independent and constrained
refinement
max
= 2.44 e A
˚
3
min
=1.03 e A
˚
3
Table 1
Selected geometric parameters (A
˚,).
C1—N1 1.479 (8)
C1—P1 1.821 (8)
C2—N2 1.486 (8)
C2—P1 1.799 (7)
C3—N3 1.495 (9)
C3—P1 1.825 (8)
C4—N3 1.496 (9)
C12—N1 1.462 (9)
C12—N2 1.467 (10)
C23—N2 1.440 (9)
C23—N3 1.550 (9)
C31—N1 1.441 (9)
C31—N3 1.551 (9)
O1—P1 1.483 (5)
I1—I3 2.9067 (8)
I1—I2 2.9127 (7)
I3—I1—I2 172.41 (2)
Table 2
Hydrogen-bond geometry (A
˚,).
D—HAD—H HADAD—HA
C23—H23AO1
i
0.99 (10) 2.26 (11) 3.161 (9) 150 (9)
C31—H31AO1
i
0.97 (10) 2.23 (10) 3.160 (9) 161 (8)
Symmetry code: (i) xþ1;y;z.
Data collection: SMART (Bruker, 2004); cell refinement: SAINT
(Bruker, 2004); data reduction: SAINT; program(s) used to solve
structure: WinGX (Version 1.70.01; Farrugia, 1999); program(s) used
to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics:
Mercury (Macrae et al., 2006); software used to prepare material for
publication: SHELXL97.
This work was supported by the Foundation for Science and
Technology (FCT), Portugal, and its POCI 2010 programme
(FEDER funded).
Supplementary data and figures for this paper are available from the
IUCr electronic archives (Reference: KP2159).
organic compounds
o496 Kirillov et al. doi:10.1107/S1600536808001426 Acta Cryst. (2008). E64, o496–o497
Acta Crystallographica Section E
Structure Reports
Online
ISSN 1600-5368
References
Bruker (2004). APEX2,SMART and SAINT. Bruker AXS Inc., Madison,
Wisconsin, USA.
Daigle, D. J. (1998). Inorg. Synth. 32, 40–45.
Daigle, D. J., Pepperman, A. B. Jr & Vail, S. L. (1974). J. Heterocycl. Chem. 11,
407–408.
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.
Forward, J. M., Staples, R. J. & Fackler, J. P. Jr (1996a). Z. Kristallogr. 211, 129–
130.
Forward, J. M., Staples, R. J. & Fackler, J. P. Jr (1996b). Z. Kristallogr. 211, 131–
132.
Frost, B. J., Mebi, C. A. & Gingrich, P. W. (2006). Eur. J. Inorg. Chem. pp.
1182–1189.
Kirillov, A. M., Smolen
´ski, P., Guedes da Silva, M. F. C. & Pombeiro, A. J. L.
(2007). Eur. J. Inorg. Chem. pp. 2686–2692.
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor,
R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457.
Marsh, R. E., Kapon, M., Hu, S. & Herbstein, F. H. (2002). Acta Cryst. B58, 62–
77.
Otto, S., Ionescu, A. & Roodt, A. (2005). J. Organomet. Chem. 690, 4337–4342.
Phillips, A. D., Gonsalvi, L., Romerosa, A., Vizza, F. & Peruzzini, M. (2004).
Coord. Chem. Rev. 248, 955–993.
Sheldrick, G. M. (1996). SADABS. University of Gottingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Smolen
´ski, P. & Pombeiro, A. J. L. (2008). Dalton Trans. pp. 87–91.
organic compounds
Acta Cryst. (2008). E64, o496–o497 Kirillov et al. C
7
H
15
N
3
OP
+
I
3
o497
supporting information
sup-1
Acta Cryst. (2008). E64, o496–o497
supporting information
Acta Cryst. (2008). E64, o496–o497 [doi:10.1107/S1600536808001426]
1-Methyl-1-azonia-3,5-diaza-7-phosphatricyclo[3.3.1.1]decane 7-oxide
triiodide
Alexander M. Kirillov, Piotr Smoleński, M. Fátima C. Guedes da Silva and Armando J. L.
Pombeiro
S1. Comment
Within our ongoing research (Kirillov et al., 2007; Smoleński & Pombeiro, 2008) on the synthesis of transition metal
complexes with PTA or derived ligands, we have attempted the reaction of a copper(II) salt with N-methyl-1,3,5-triaza-7-
phospha-adamantane iodide, which resulted in the formation of the title compound, (I), as a by-product. Its crystal
structure is reported herein.
The molecular structure of (I) (Fig. 1) bears a cage-like cation [C7H15N3OP]+ and a tri-iodide anion, with the shortest
cation···anion separation of ca 4.0 Å. The N-methylation of the PTA cage results in a slight elongation of the C—N bonds
around N3 atom [avg. 1.53 (1) Å] in comparison with the C—N bonds around N1 and N2 atoms [avg. 1.46 (1) Å] (Table
1). The oxidation of P1 atom also slightly affects the C—P bonds [avg. 1.82 (1) Å] which are somewhat shorter than
those in PTA [avg. 1.86 (1) Å]. The tri-iodide anion with the I2—I1—I3 angle of 172.41 (2)° deviates from the linear
geometry. In general, most of the bonding parameters of (I) agree within values reported for the related compound,
[C7H15N3OP][BPh4] (Forward et al., 1996a,b), possessing similar cation, as well as for other N-alkylated (Otto et al.,
2005; Forward et al., 1996a,b) or P-oxidized (Frost et al., 2006; Marsh et al., 2002) PTA derivatives.
In (I), the neighbouring cationic units are combined into the linear one-dimensional H-bonded chains (Fig. 2) by means
of two intermolecular C—H···O hydrogen bonds [C23—H23A···O1i 1.00 (11) Å, 2.26 (11) Å, 3.161 (9) Å, 150 (9)°; C31
—-H31A···O1i 0.97 (10) Å, 2.23 (10) Å, 3.160 (9) Å, 161 (8)°; symmetry code: 1 + x, y, z], which link the methylene
groups (C23, C31) with the O1 atom of the P=O moiety.
S2. Experimental
The aqueous solutions (5 ml each) of Cu(NO3)2.2.5 H2O (116 mg, 0.50 mmol) and N-methyl-1,3,5-triaza-7-phospha-
adamantane iodide, [C7H15N3P]I (299 mg, 1.00 mmol) [for the synthesis of this compound, see: Daigle et al. (1974);
Daigle (1998)], were combined and left stirring in air at ambient temperature for 1 h. The resulting white suspension
containing mainly a CuI aminophosphine compound was filtered off. The colourless filtrate was left to evaporate in a
beaker in air for two weeks, leading to the formation of a small crop of red X-ray quality crystals of compound (I) as a
by-product (it is typically contaminated by a colourless crystalline material). FT–IR (KBr pellet), cm-1: 2967 w, 2939 w,
1449 m, 1384 s, 1304 m, 1279 w, 1246 w, 1195 s [ν(P=O)], 1108 w, 1091 w, 1066 w, 1019 m, 983 m, 934 m, 900 w, 876
w, 816 m, 792 w, 752 m, 544 w, 441 w, 408 w. FAB-MS+ (m-nitrobenzylicalcohol), m/z: 188 [C7H15N3OP]+.
S3. Refinement
All hydrogen atoms were located except from H4A, H4B and H4C which were inserted in calculated positions.
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Acta Cryst. (2008). E64, o496–o497
Figure 1
The molecular structure of the title compound with the atom labelling scheme. Displacement ellipsoids are drawn at the
50% probability level. H atoms are represented as grey sticks. C, grey; N, blue; P, orange; O, red; I, purple.
Figure 2
Fragment of the crystal packing diagram of (I) showing the generation of a one-dimensional linear chain from the
neighbouring cations via intermolecular C—H···O hydrogen bonds (dotted lines). Tri-iodide anions are omitted for
clarity. C, grey; N, blue; P, orange; O, red; H, pale grey.
supporting information
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Acta Cryst. (2008). E64, o496–o497
1-Methyl-1-azonia-3,5-diaza-7-phosphatricyclo[3.3.1.1]decane 7-oxide triiodide
Crystal data
C7H15N3OP+·I3−
Mr = 568.89
Monoclinic, P21/n
Hall symbol: -P2yn
a = 7.1570 (8) Å
b = 8.2257 (8) Å
c = 25.903 (3) Å
β = 92.472 (7)°
V = 1523.5 (3) Å3
Z = 4
F(000) = 1040
Dx = 2.480 Mg m−3
Mo Kα radiation, λ = 0.71069 Å
Cell parameters from 2835 reflections
θ = 2.6–27.9°
µ = 6.24 mm−1
T = 150 K
Plate, red
0.13 × 0.10 × 0.10 mm
Data collection
Bruker SMART CCD area-detector
diffractometer
Radiation source: fine-focus sealed tube
Graphite monochromator
φ and ω scans
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
Tmin = 0.497, Tmax = 0.574
11526 measured reflections
2789 independent reflections
2214 reflections with I > 2σ(I)
Rint = 0.040
θmax = 25.4°, θmin = 2.9°
h = −8→8
k = −9→9
l = −29→31
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.042
wR(F2) = 0.102
S = 1.12
2789 reflections
172 parameters
0 restraints
0 constraints
Primary atom site location: structure-invariant
direct methods
Secondary atom site location: difference Fourier
map
Hydrogen site location: inferred from
neighbouring sites
H atoms treated by a mixture of independent
and constrained refinement
w = 1/[σ2(Fo2) + (0.045P)2 + 6.2243P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.017
Δρmax = 2.44 e Å−3
Δρmin = −1.03 e Å−3
Special details
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full
covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and
torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry.
An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2,
conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used
only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2
are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
xyz U
iso*/Ueq
C1 0.5522 (9) 0.4541 (10) 0.1979 (3) 0.0186 (16)
C2 0.5510 (9) 0.1132 (8) 0.1974 (3) 0.0156 (15)
C3 0.5535 (10) 0.2823 (10) 0.1042 (3) 0.0188 (15)
C4 0.8586 (11) 0.2823 (11) 0.0631 (3) 0.0294 (18)
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Acta Cryst. (2008). E64, o496–o497
H4A 0.9942 0.2819 0.0701 0.044*
H4B 0.8230 0.3796 0.0432 0.044*
H4C 0.8222 0.1851 0.0432 0.044*
C12 0.8197 (10) 0.2815 (10) 0.2227 (3) 0.0192 (15)
C23 0.8255 (10) 0.1301 (8) 0.1442 (3) 0.0162 (15)
C31 0.8255 (10) 0.4347 (10) 0.1446 (3) 0.0192 (16)
N1 0.7565 (7) 0.4292 (7) 0.1960 (2) 0.0169 (13)
N2 0.7569 (7) 0.1334 (7) 0.1956 (2) 0.0141 (12)
N3 0.7614 (8) 0.2828 (7) 0.1131 (2) 0.0168 (12)
O1 0.2300 (7) 0.2825 (7) 0.1582 (2) 0.0268 (12)
P1 0.4367 (2) 0.2827 (2) 0.16547 (7) 0.0168 (4)
I1 0.42016 (7) 0.78153 (6) 0.088953 (18) 0.02270 (15)
I2 0.14227 (7) 0.78170 (6) 0.16786 (2) 0.02691 (16)
I3 0.73414 (8) 0.78543 (8) 0.02143 (2) 0.03606 (18)
H1A 0.517 (12) 0.452 (11) 0.232 (4) 0.043*
H1B 0.498 (12) 0.558 (11) 0.183 (3) 0.043*
H2A 0.501 (12) 0.108 (11) 0.232 (4) 0.043*
H2B 0.521 (12) 0.008 (12) 0.182 (3) 0.050*
H3A 0.512 (14) 0.190 (12) 0.084 (4) 0.060*
H3B 0.522 (14) 0.380 (13) 0.085 (4) 0.060*
H12A 0.948 (16) 0.286 (12) 0.225 (4) 0.060*
H12B 0.793 (14) 0.282 (11) 0.256 (4) 0.050*
H23A 0.964 (15) 0.135 (13) 0.147 (4) 0.060*
H23B 0.769 (13) 0.034 (13) 0.127 (4) 0.060*
H31A 0.959 (14) 0.414 (12) 0.147 (4) 0.060*
H31B 0.768 (13) 0.538 (13) 0.126 (4) 0.060*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
C1 0.010 (3) 0.026 (5) 0.020 (4) 0.005 (3) 0.001 (3) −0.003 (3)
C2 0.014 (3) 0.011 (4) 0.022 (4) −0.002 (3) 0.006 (3) 0.000 (3)
C3 0.013 (3) 0.021 (4) 0.023 (4) 0.002 (3) −0.003 (3) 0.000 (3)
C4 0.027 (4) 0.041 (5) 0.022 (4) −0.001 (4) 0.017 (3) −0.007 (4)
C12 0.016 (4) 0.021 (4) 0.020 (4) −0.001 (3) −0.006 (3) 0.000 (3)
C23 0.018 (4) 0.006 (4) 0.026 (4) 0.004 (3) 0.005 (3) 0.002 (3)
C31 0.012 (4) 0.027 (5) 0.019 (4) 0.001 (3) 0.002 (3) 0.001 (3)
N1 0.011 (3) 0.020 (3) 0.019 (3) −0.001 (2) −0.002 (2) 0.000 (3)
N2 0.009 (3) 0.017 (3) 0.017 (3) 0.001 (2) 0.002 (2) 0.002 (2)
N3 0.014 (3) 0.020 (3) 0.016 (3) −0.005 (3) 0.002 (2) −0.004 (3)
O1 0.009 (2) 0.029 (3) 0.042 (3) 0.000 (2) −0.002 (2) 0.002 (3)
P1 0.0075 (8) 0.0187 (9) 0.0244 (10) 0.0007 (7) 0.0003 (7) −0.0004 (8)
I1 0.0282 (3) 0.0183 (3) 0.0215 (3) 0.0009 (2) −0.00114 (19) −0.0002 (2)
I2 0.0230 (3) 0.0207 (3) 0.0376 (3) 0.0000 (2) 0.0081 (2) 0.0000 (2)
I3 0.0341 (3) 0.0527 (4) 0.0218 (3) 0.0017 (3) 0.0054 (2) −0.0023 (3)
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Acta Cryst. (2008). E64, o496–o497
Geometric parameters (Å, º)
C1—N1 1.479 (8) C12—N1 1.462 (9)
C1—P1 1.821 (8) C12—N2 1.467 (10)
C1—H1A 0.94 (9) C12—H12A 0.92 (11)
C1—H1B 1.01 (9) C12—H12B 0.90 (11)
C2—N2 1.486 (8) C23—N2 1.440 (9)
C2—P1 1.799 (7) C23—N3 1.550 (9)
C2—H2A 0.98 (9) C23—H23A 0.99 (10)
C2—H2B 0.97 (10) C23—H23B 0.99 (10)
C3—N3 1.495 (9) C31—N1 1.441 (9)
C3—P1 1.825 (8) C31—N3 1.551 (9)
C3—H3A 0.96 (10) C31—H31A 0.97 (10)
C3—H3B 0.96 (11) C31—H31B 1.06 (10)
C4—N3 1.496 (9) O1—P1 1.483 (5)
C4—H4A 0.9800 I1—I3 2.9067 (8)
C4—H4B 0.9800 I1—I2 2.9127 (7)
C4—H4C 0.9800
N1—C1—P1 107.9 (5) N2—C23—H23A 108 (6)
N1—C1—H1A 109 (5) N3—C23—H23A 106 (6)
P1—C1—H1A 107 (6) N2—C23—H23B 107 (6)
N1—C1—H1B 118 (5) N3—C23—H23B 107 (6)
P1—C1—H1B 109 (5) H23A—C23—H23B 117 (8)
H1A—C1—H1B 105 (7) N1—C31—N3 110.8 (6)
N2—C2—P1 109.3 (5) N1—C31—H31A 109 (6)
N2—C2—H2A 116 (5) N3—C31—H31A 99 (6)
P1—C2—H2A 106 (5) N1—C31—H31B 108 (5)
N2—C2—H2B 107 (5) N3—C31—H31B 108 (5)
P1—C2—H2B 114 (5) H31A—C31—H31B 122 (8)
H2A—C2—H2B 104 (7) C31—N1—C12 110.7 (6)
N3—C3—P1 110.8 (5) C31—N1—C1 114.0 (5)
N3—C3—H3A 112 (6) C12—N1—C1 112.6 (6)
P1—C3—H3A 109 (6) C23—N2—C12 110.4 (6)
N3—C3—H3B 106 (6) C23—N2—C2 113.9 (5)
P1—C3—H3B 110 (6) C12—N2—C2 111.2 (6)
H3A—C3—H3B 109 (8) C4—N3—C3 111.3 (6)
N3—C4—H4A 109.5 C4—N3—C31 108.6 (5)
N3—C4—H4B 109.5 C3—N3—C31 110.7 (6)
H4A—C4—H4B 109.5 C4—N3—C23 108.0 (6)
N3—C4—H4C 109.5 C3—N3—C23 110.4 (6)
H4A—C4—H4C 109.5 C31—N3—C23 107.8 (5)
H4B—C4—H4C 109.5 O1—P1—C2 119.2 (3)
N1—C12—N2 112.4 (5) O1—P1—C1 119.3 (3)
N1—C12—H12A 107 (6) C2—P1—C1 101.5 (3)
N2—C12—H12A 111 (6) O1—P1—C3 112.4 (3)
N1—C12—H12B 112 (6) C2—P1—C3 100.5 (4)
N2—C12—H12B 113 (6) C1—P1—C3 100.8 (4)
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Acta Cryst. (2008). E64, o496–o497
H12A—C12—H12B 100 (9) I3—I1—I2 172.41 (2)
N2—C23—N3 111.1 (5)
N3—C31—N1—C12 57.7 (7) N1—C31—N3—C4 −172.0 (6)
N3—C31—N1—C1 −70.5 (8) N1—C31—N3—C3 65.6 (7)
N2—C12—N1—C31 −59.3 (8) N1—C31—N3—C23 −55.2 (7)
N2—C12—N1—C1 69.6 (8) N2—C23—N3—C4 172.4 (6)
P1—C1—N1—C31 65.5 (7) N2—C23—N3—C3 −65.7 (7)
P1—C1—N1—C12 −61.6 (7) N2—C23—N3—C31 55.3 (7)
N3—C23—N2—C12 −57.4 (7) N2—C2—P1—O1 174.7 (4)
N3—C23—N2—C2 68.6 (7) N2—C2—P1—C1 −52.0 (5)
N1—C12—N2—C23 59.1 (7) N2—C2—P1—C3 51.4 (5)
N1—C12—N2—C2 −68.4 (7) N1—C1—P1—O1 −175.4 (4)
P1—C2—N2—C23 −64.0 (7) N1—C1—P1—C2 51.3 (6)
P1—C2—N2—C12 61.6 (6) N1—C1—P1—C3 −51.8 (6)
P1—C3—N3—C4 179.9 (5) N3—C3—P1—O1 179.9 (5)
P1—C3—N3—C31 −59.2 (7) N3—C3—P1—C2 −52.2 (6)
P1—C3—N3—C23 60.0 (7) N3—C3—P1—C1 51.8 (6)
Hydrogen-bond geometry (Å, º)
D—H···AD—H H···AD···AD—H···A
C23—H23A···O1i0.99 (10) 2.26 (11) 3.161 (9) 150 (9)
C31—H31A···O1i0.97 (10) 2.23 (10) 3.160 (9) 161 (8)
Symmetry code: (i) x+1, y, z.
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