1-Methyl-1-azonia-3,5-diaza-7-phospha-tricyclo-[3.3.1.1]decane 7-oxide triiodide.

The title compound, C(7)H(15)N(3)OP(+)·I(3) (-), is a derivative of the well known water-soluble amino-phosphine 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-methyl-ation 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 inter-molecular C-H⋯O 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 ▶); Smoleński & 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

C7H15N3OP+·I3 −

M = 568.89

Monoclinic,

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

Mo Kα radiation

μ = 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 > 2σ(I)

R int = 0.040

Refinement

R[F 2 > 2σ(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

Δρmax = 2.44 e Å−3

Δρmin = −1.03 e Å−3

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.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808001426/kp2159sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808001426/kp2159Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C7H15N3OP+·I3–	F000 = 1040
Mr = 568.89	Dx = 2.480 Mg m−3
Monoclinic, P21/n	Mo Kα radiation λ = 0.71069 Å
Hall symbol: -P2yn	Cell parameters from 2835 reflections
a = 7.1570 (8) Å	θ = 2.6–27.9º
b = 8.2257 (8) Å	µ = 6.24 mm−1
c = 25.903 (3) Å	T = 150 (2) K
β = 92.472 (7)º	Plate, red
V = 1523.5 (3) Å3	0.13 × 0.10 × 0.10 mm
Z = 4

Bruker SMART CCD area-detector diffractometer	2789 independent reflections
Radiation source: fine-focus sealed tube	2214 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.040
T = 150(2) K	θmax = 25.4º
φ and ω scans	θmin = 2.9º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)	h = −8→8
Tmin = 0.497, Tmax = 0.574	k = −9→9
11526 measured reflections	l = −29→31

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.042	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.102	w = 1/[σ2(Fo2) + (0.045P)2 + 6.2243P] where P = (Fo2 + 2Fc2)/3
S = 1.12	(Δ/σ)max = 0.017
2789 reflections	Δρmax = 2.44 e Å−3
172 parameters	Δρmin = −1.03 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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.

	x	y	z	Uiso*/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)
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*

	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)

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)
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)

D—H···A	D—H	H···A	D···A	D—H···A
C23—H23A···O1i	0.99 (10)	2.26 (11)	3.161 (9)	150 (9)
C31—H31A···O1i	0.97 (10)	2.23 (10)	3.160 (9)	161 (8)

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 (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C23—H23A⋯O1i	0.99 (10)	2.26 (11)	3.161 (9)	150 (9)
C31—H31A⋯O1i	0.97 (10)	2.23 (10)	3.160 (9)	161 (8)

Symmetry code: (i) .