A crystallographically isolated dimeric hydrolyzed chloro­phosphazene dianion

Panzner, M.J.; Youngs, W.J.; Tessier, C.A.

doi:10.1107/S1600536808042116

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 1| January 2009| Page m105

doi:10.1107/S1600536808042116

Open

access

A crystallographically isolated dimeric hydrolyzed chlorophosphazene dianion

Matthew J. Panzner,^a Wiley J. Youngs ^a and Claire A. Tessier ^a ^*

^aThe University of Akron, Chemistry Department, Akron, OH 44325-3601, USA
^*Correspondence e-mail: tessier@uakron.edu

(Received 17 November 2008; accepted 10 December 2008; online 20 December 2008)

Single crystals of the title compound bis[bis(1-ethyl-3-methyl-imidazol-2-ylidene)silver(I)] 1,5,5,7,11,11-hexachloro-2,8-dioxa-4,6,10,12,13,14-hexaaza-1λ⁵,3,5λ⁵,7λ⁵,9,11λ⁵-hexaphosphatricyclo[7.3.1.1^3,7]tetradeca-1(13),4,7(14),10-tetraene-6,12-diide 3,9-dioxide, [Ag(C₆H₁₀N₂)₂](Cl₆N₆O₄P₆)_0.5, were isolated from the reaction of the silver N-heteocyclic carbene complex [Ag(C₆H₁₀N₂)₂]Cl and hexachlorocyclotriphosphazene [NPCl₂]₃in the presence of water. The asymmetric unit contains one silver carbene cation with the carbene ligands bound to the Ag(I) in an almost linear arrangement and one half of a hydrolyzed phosphazene dianion. The second cation and additional half of the anion are generated by an inversion center.

Related literature

For background on phosphazene hydrolysis products, see: Allcock (2003 ); Allcock et al. (1975 ); Gabler & Haw (1990 ); Murray et al. (1994 ); van de Grampel (1992 ). For related structures, see: Bartlett et al. (2006 ); Brandt et al. (1991 ); Bullen (1971 ); Meetsma et al. (1990 ).

Experimental

Crystal data

[Ag(C₆H₁₀N₂)₂](Cl₆N₆O₄P₆)_0.5
M_r = 601.48
Triclinic, $[P \overline 1]$
a = 9.3224 (15) Å
b = 10.6190 (18) Å
c = 12.257 (2) Å
α = 78.916 (3)°
β = 71.558 (3)°
γ = 76.107 (3)°
V = 1108.4 (3) Å³
Z = 2
Mo Kα radiation
μ = 1.51 mm⁻¹
T = 100 (2) K
0.30 × 0.08 × 0.04 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.660, T_max = 0.942
8912 measured reflections
4459 independent reflections
3484 reflections with I > \2s(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.123
S = 1.04
4459 reflections
257 parameters
H-atom parameters constrained
Δρ_max = 2.25 e Å⁻³
Δρ_min = −1.02 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Ag—C1	2.065 (5)
Ag—C7	2.070 (5)
Cl1—P2	2.0118 (16)
Cl2—P2	2.0171 (17)
Cl3—P3	2.0217 (16)
P1—O1	1.468 (3)
P1—N5	1.610 (4)
P1—N6	1.615 (4)
P1—O2	1.657 (3)
P2—N6	1.555 (4)
P2—N7	1.578 (4)
P3—N5ⁱ	1.554 (4)
P3—O2	1.578 (3)
P3—N7ⁱ	1.594 (4)

C1—Ag—C7	178.72 (19)
Symmetry code: (i) -x+1, -y+1, -z+1.

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808042116/br2087sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808042116/br2087Isup2.hkl

checkCIF report

Comment top

Hexachlorocyclotriphosphazene [NPCl₂]₃ is used as a starting material for the synthesis of poly(dichlorophosphazene). This conversion can be achived by a ring opening melt polymerization process at high temperature, generally greater than 473 °K. It has long been contested that trace amounts of water not only accelerate the rate of polymerization but are necessray to generate active species needed to simply promote polymer formation (Allcock, 2003; Allcock et al., 1975). Isolation of hydrolyzed species gives insight into the still unclear role that water plays in this polymerization reaction (Gabler et al., 1990). As part of our broader studies on the irreproducibility in the synthesis of poly(dichlorophosphazene) we report the first crystal structure of a dimeric hydrolyzed chlorophosphazene dianion.

The asymmetric unit consists of one silver N-heteocyclic carbene cation [AgC₁₂H₂₀N₄]⁺ and half of a hydrolyzed phosphazene dianion [Cl₆N₆O₄P₆]^2-. The second cation and other half of the dianion are generated by a crystallographic inversion center at x,y,z (1/2,1/2,1/2) located between one of the bridging oxygen atoms of the dimeric dianion and its symmetry generated equivalent. Each of the Ag(I) atoms is bound to two identical N-heterocyclic carbene ligands in a linear fashion. Two partially hydrolyzed phosphazene rings are joined by bridging oxygen atoms from a phosphorus atom of one ring to the other to form the dimeric dianion. The P—O—P bonds of the bridging oxygen atoms are inequivalent . The P—N bond distances of the individual rings deviate from the reported values of hexachlorocyclotriphosphazene, all six being virtually equivalent (Bartlett et al., 2006; Bullen, 1971). Two of the P—N bonds on each of the rings show significant double bond character while the remaining P—N bonds are lengthened to give more single bond character.

Related literature top

For background on phosphazene hydrolysis products, see: Allcock (2003); Allcock et al. (1975); Gabler et al. (1990); Murray et al. (1994); van de Grampel (1992). For related structures, see: Bartlett et al. (2006); Brandt et al. (1991); Bullen (1971); Meetsma et al. (1990).

Experimental top

The title compound, bis[bis(1-ethyl-3-methylimidazol-2-ylidene)silver(I)] 1,5,5,7,11,11-hexachloro-2,8-dioxa-4,6,10,12,13,14-hexaaza-1λ⁵,3,5λ⁵,7λ⁵,9,11λ⁵-hexaphosphatricyclo[7.3.1.1^3,7]tetradeca-1(13),4,7(14),10-tetraene-6,12-diide 3,9-dioxide, [Ag(C₆H₁₀N₂)₂](Cl₆N₆O₄P₆)_0.5, was isolated from the reaction of silver N-heteocyclic carbene complex [AgC₁₂H₂₀N₄]⁺.Cl^- (generated in situ) and hexachlorocyclotriphosphazene, [NPCl₂]₃. A small amount of crystals were obtained after removing volatiles from the reaction.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SMART (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. Structure of the title compound, first crystallographically characterized dimeric oxygen-bridged chlorophosphazene dianion. A numbering scheme of the non-H atoms is shown and thermal ellipsoids shown at 50% probability.

bis[bis(1-ethyl-3-methylimidazol-2-ylidene)silver(I)] 1,5,5,7,11,11-hexachloro-2,8-dioxa-4,6,10,12,13,14-hexaaza- 1λ⁵,3,5λ⁵,7λ⁵,9,11λ⁵-hexaphosphatricyclo[7.3.1.1^3,7]tetradeca- 1(13),4,7(14),10-tetraene-6,12-diide 3,9-dioxide top

Crystal data top

[Ag(C₆H₁₀N₂)₂](Cl₆N₆O₄P₆)_0.5	Z = 2
M_r = 601.48	F(000) = 600
Triclinic, P1	D_x = 1.802 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.3224 (15) Å	Cell parameters from 2618 reflections
b = 10.6190 (18) Å	θ = 2.5–26.8°
c = 12.257 (2) Å	µ = 1.51 mm⁻¹
α = 78.916 (3)°	T = 100 K
β = 71.558 (3)°	Plate, colourless
γ = 76.107 (3)°	0.30 × 0.08 × 0.04 mm
V = 1108.4 (3) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	4459 independent reflections
Radiation source: fine-focus sealed tube	3484 reflections with I > \2s(I)
Graphite monochromator	R_int = 0.031
ϕ and ω scans	θ_max = 26.3°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −11→11
T_min = 0.660, T_max = 0.942	k = −13→13
8912 measured reflections	l = −15→15

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.123	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0737P)²] where P = (F_o² + 2F_c²)/3
4459 reflections	(Δ/σ)_max < 0.001
257 parameters	Δρ_max = 2.25 e Å⁻³
0 restraints	Δρ_min = −1.02 e Å⁻³

Crystal data top

[Ag(C₆H₁₀N₂)₂](Cl₆N₆O₄P₆)_0.5	γ = 76.107 (3)°
M_r = 601.48	V = 1108.4 (3) Å³
Triclinic, P1	Z = 2
a = 9.3224 (15) Å	Mo Kα radiation
b = 10.6190 (18) Å	µ = 1.51 mm⁻¹
c = 12.257 (2) Å	T = 100 K
α = 78.916 (3)°	0.30 × 0.08 × 0.04 mm
β = 71.558 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	4459 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	3484 reflections with I > \2s(I)
T_min = 0.660, T_max = 0.942	R_int = 0.031
8912 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.123	H-atom parameters constrained
S = 1.04	Δρ_max = 2.25 e Å⁻³
4459 reflections	Δρ_min = −1.02 e Å⁻³
257 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
Ag	0.92396 (4)	0.82923 (3)	0.02673 (3)	0.02921 (14)
Cl1	0.20816 (15)	0.96514 (11)	0.50044 (11)	0.0364 (3)
Cl2	0.06691 (14)	0.72027 (14)	0.58126 (11)	0.0402 (3)
Cl3	0.32100 (13)	0.28263 (12)	0.39490 (11)	0.0312 (3)
P1	0.50886 (13)	0.63373 (11)	0.34302 (10)	0.0220 (3)
P2	0.27569 (13)	0.76965 (11)	0.50900 (10)	0.0218 (3)
P3	0.46494 (13)	0.36960 (11)	0.43519 (10)	0.0196 (3)
O1	0.5964 (4)	0.6691 (3)	0.2226 (3)	0.0298 (8)
O2	0.4577 (3)	0.4948 (3)	0.3425 (3)	0.0243 (7)
N1	0.6862 (5)	1.0763 (4)	0.0964 (4)	0.0346 (10)
N2	0.6984 (5)	1.0504 (4)	−0.0734 (4)	0.0330 (10)
N3	1.1582 (4)	0.6223 (4)	0.1266 (3)	0.0298 (9)
N4	1.1637 (4)	0.5782 (4)	−0.0374 (3)	0.0277 (9)
N5	0.6039 (4)	0.5991 (3)	0.4376 (3)	0.0219 (8)
N6	0.3458 (4)	0.7321 (4)	0.3838 (3)	0.0259 (9)
N7	0.3694 (4)	0.7221 (3)	0.6012 (3)	0.0207 (8)
C1	0.7588 (5)	0.9961 (4)	0.0151 (4)	0.0287 (11)
C2	0.5818 (6)	1.1759 (5)	0.0603 (6)	0.0454 (15)
H2	0.5168	1.2441	0.1033	0.055*
C3	0.5876 (6)	1.1600 (5)	−0.0462 (5)	0.0414 (14)
H3	0.5274	1.2135	−0.0937	0.050*
C4	0.7138 (7)	1.0544 (6)	0.2095 (5)	0.0455 (14)
H4A	0.8242	1.0172	0.2013	0.055*
H4B	0.6891	1.1391	0.2404	0.055*
C5	0.6220 (9)	0.9672 (7)	0.2893 (6)	0.0638 (19)
H5A	0.5127	1.0074	0.3028	0.096*
H5B	0.6483	0.9494	0.3629	0.096*
H5C	0.6423	0.8850	0.2569	0.096*
C6	0.7431 (8)	0.9969 (6)	−0.1845 (5)	0.0513 (16)
H6A	0.8545	0.9887	−0.2195	0.077*
H6B	0.6889	1.0558	−0.2370	0.077*
H6C	0.7155	0.9106	−0.1707	0.077*
C7	1.0921 (5)	0.6642 (5)	0.0399 (4)	0.0263 (10)
C8	1.2702 (6)	0.5110 (5)	0.1032 (5)	0.0398 (13)
H8	1.3328	0.4632	0.1511	0.048*
C9	1.2735 (6)	0.4839 (5)	0.0001 (4)	0.0375 (13)
H9	1.3389	0.4132	−0.0394	0.045*
C10	1.1113 (6)	0.6846 (5)	0.2325 (4)	0.0369 (12)
H10A	1.2010	0.6708	0.2631	0.044*
H10B	1.0781	0.7800	0.2135	0.044*
C11	0.9870 (8)	0.6337 (8)	0.3212 (6)	0.074 (2)
H11A	0.9042	0.6342	0.2878	0.111*
H11B	0.9471	0.6884	0.3843	0.111*
H11C	1.0255	0.5439	0.3516	0.111*
C12	1.1316 (6)	0.5854 (5)	−0.1481 (4)	0.0313 (11)
H12A	1.0230	0.6247	−0.1405	0.047*
H12B	1.1532	0.4971	−0.1697	0.047*
H12C	1.1970	0.6390	−0.2081	0.047*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ag	0.0342 (2)	0.0232 (2)	0.0293 (2)	0.00745 (15)	−0.01754 (17)	−0.00302 (15)
Cl1	0.0483 (7)	0.0219 (6)	0.0319 (7)	0.0102 (5)	−0.0150 (6)	−0.0023 (5)
Cl2	0.0273 (6)	0.0564 (9)	0.0366 (7)	−0.0102 (6)	−0.0147 (5)	0.0073 (6)
Cl3	0.0295 (6)	0.0343 (7)	0.0365 (7)	−0.0071 (5)	−0.0155 (5)	−0.0084 (5)
P1	0.0282 (6)	0.0178 (6)	0.0176 (6)	0.0025 (5)	−0.0096 (5)	0.0003 (4)
P2	0.0234 (6)	0.0208 (6)	0.0185 (6)	0.0026 (5)	−0.0095 (5)	0.0015 (5)
P3	0.0223 (6)	0.0175 (6)	0.0200 (6)	−0.0007 (4)	−0.0114 (5)	0.0005 (4)
O1	0.0401 (19)	0.0250 (17)	0.0163 (17)	0.0015 (14)	−0.0058 (14)	0.0028 (13)
O2	0.0313 (17)	0.0224 (16)	0.0219 (17)	0.0008 (13)	−0.0180 (14)	0.0010 (13)
N1	0.037 (2)	0.025 (2)	0.039 (3)	0.0035 (18)	−0.015 (2)	−0.0027 (19)
N2	0.036 (2)	0.025 (2)	0.035 (2)	−0.0018 (18)	−0.0168 (19)	0.0090 (18)
N3	0.030 (2)	0.033 (2)	0.027 (2)	0.0016 (17)	−0.0141 (18)	−0.0029 (18)
N4	0.029 (2)	0.027 (2)	0.022 (2)	0.0010 (17)	−0.0080 (17)	0.0022 (16)
N5	0.0208 (18)	0.022 (2)	0.022 (2)	0.0016 (15)	−0.0099 (15)	−0.0025 (15)
N6	0.032 (2)	0.024 (2)	0.0180 (19)	0.0097 (16)	−0.0143 (16)	0.0007 (15)
N7	0.0247 (19)	0.0208 (19)	0.0169 (19)	−0.0001 (15)	−0.0103 (15)	−0.0007 (15)
C1	0.034 (3)	0.023 (2)	0.033 (3)	−0.003 (2)	−0.019 (2)	0.000 (2)
C2	0.039 (3)	0.027 (3)	0.058 (4)	0.005 (2)	−0.010 (3)	0.002 (3)
C3	0.033 (3)	0.032 (3)	0.048 (4)	0.000 (2)	−0.015 (3)	0.018 (3)
C4	0.053 (4)	0.041 (3)	0.045 (3)	−0.003 (3)	−0.015 (3)	−0.018 (3)
C5	0.088 (5)	0.062 (4)	0.055 (4)	−0.026 (4)	−0.032 (4)	−0.004 (3)
C6	0.076 (4)	0.048 (4)	0.033 (3)	−0.007 (3)	−0.030 (3)	0.006 (3)
C7	0.025 (2)	0.027 (3)	0.025 (2)	−0.0039 (19)	−0.010 (2)	0.0021 (19)
C8	0.034 (3)	0.040 (3)	0.044 (3)	0.010 (2)	−0.024 (3)	−0.001 (3)
C9	0.035 (3)	0.036 (3)	0.031 (3)	0.013 (2)	−0.011 (2)	−0.003 (2)
C10	0.037 (3)	0.045 (3)	0.031 (3)	−0.002 (2)	−0.017 (2)	−0.008 (2)
C11	0.086 (5)	0.110 (6)	0.034 (4)	−0.055 (5)	0.013 (3)	−0.029 (4)
C12	0.032 (3)	0.040 (3)	0.016 (2)	−0.004 (2)	−0.003 (2)	0.000 (2)

Geometric parameters (Å, º) top

Ag—C1	2.065 (5)	N5—P3ⁱ	1.554 (4)
Ag—C7	2.070 (5)	N7—P3ⁱ	1.594 (4)
Cl1—P2	2.0118 (16)	C2—C3	1.331 (8)
Cl2—P2	2.0171 (17)	C2—H2	0.9500
Cl3—P3	2.0217 (16)	C3—H3	0.9500
P1—O1	1.468 (3)	C4—C5	1.432 (9)
P1—N5	1.610 (4)	C4—H4A	0.9900
P1—N6	1.615 (4)	C4—H4B	0.9900
P1—O2	1.657 (3)	C5—H5A	0.9800
P2—N6	1.555 (4)	C5—H5B	0.9800
P2—N7	1.578 (4)	C5—H5C	0.9800
P3—N5ⁱ	1.554 (4)	C6—H6A	0.9800
P3—O2	1.578 (3)	C6—H6B	0.9800
P3—N7ⁱ	1.594 (4)	C6—H6C	0.9800
N1—C1	1.341 (6)	C8—C9	1.338 (8)
N1—C2	1.365 (6)	C8—H8	0.9500
N1—C4	1.454 (7)	C9—H9	0.9500
N2—C1	1.348 (6)	C10—C11	1.448 (8)
N2—C3	1.374 (6)	C10—H10A	0.9900
N2—C6	1.475 (7)	C10—H10B	0.9900
N3—C7	1.345 (6)	C11—H11A	0.9800
N3—C8	1.385 (6)	C11—H11B	0.9800
N3—C10	1.465 (6)	C11—H11C	0.9800
N4—C7	1.347 (6)	C12—H12A	0.9800
N4—C9	1.374 (6)	C12—H12B	0.9800
N4—C12	1.464 (6)	C12—H12C	0.9800

C1—Ag—C7	178.72 (19)	C5—C4—H4A	109.4
O1—P1—N5	116.2 (2)	N1—C4—H4A	109.4
O1—P1—N6	113.33 (19)	C5—C4—H4B	109.4
N5—P1—N6	112.96 (19)	N1—C4—H4B	109.4
O1—P1—O2	104.90 (18)	H4A—C4—H4B	108.0
N5—P1—O2	104.43 (17)	C4—C5—H5A	109.5
N6—P1—O2	103.29 (19)	C4—C5—H5B	109.5
N6—P2—N7	120.75 (19)	H5A—C5—H5B	109.5
N6—P2—Cl1	108.88 (15)	C4—C5—H5C	109.5
N7—P2—Cl1	108.31 (15)	H5A—C5—H5C	109.5
N6—P2—Cl2	110.61 (17)	H5B—C5—H5C	109.5
N7—P2—Cl2	107.54 (15)	N2—C6—H6A	109.5
Cl1—P2—Cl2	98.43 (7)	N2—C6—H6B	109.5
N5ⁱ—P3—O2	113.38 (18)	H6A—C6—H6B	109.5
N5ⁱ—P3—N7ⁱ	119.10 (19)	N2—C6—H6C	109.5
O2—P3—N7ⁱ	109.28 (18)	H6A—C6—H6C	109.5
N5ⁱ—P3—Cl3	109.53 (15)	H6B—C6—H6C	109.5
O2—P3—Cl3	97.59 (12)	N3—C7—N4	104.7 (4)
N7ⁱ—P3—Cl3	105.49 (14)	N3—C7—Ag	127.0 (3)
P3—O2—P1	126.57 (19)	N4—C7—Ag	128.2 (3)
C1—N1—C2	111.3 (5)	C9—C8—N3	106.8 (4)
C1—N1—C4	123.2 (4)	C9—C8—H8	126.6
C2—N1—C4	125.5 (5)	N3—C8—H8	126.6
C1—N2—C3	111.5 (4)	C8—C9—N4	106.6 (4)
C1—N2—C6	124.2 (4)	C8—C9—H9	126.7
C3—N2—C6	124.3 (4)	N4—C9—H9	126.7
C7—N3—C8	110.6 (4)	C11—C10—N3	112.4 (5)
C7—N3—C10	123.6 (4)	C11—C10—H10A	109.1
C8—N3—C10	125.7 (4)	N3—C10—H10A	109.1
C7—N4—C9	111.2 (4)	C11—C10—H10B	109.1
C7—N4—C12	124.6 (4)	N3—C10—H10B	109.1
C9—N4—C12	124.2 (4)	H10A—C10—H10B	107.9
P3ⁱ—N5—P1	124.3 (2)	C10—C11—H11A	109.5
P2—N6—P1	123.1 (2)	C10—C11—H11B	109.5
P2—N7—P3ⁱ	118.6 (2)	H11A—C11—H11B	109.5
N1—C1—N2	103.8 (4)	C10—C11—H11C	109.5
N1—C1—Ag	127.0 (4)	H11A—C11—H11C	109.5
N2—C1—Ag	129.2 (4)	H11B—C11—H11C	109.5
C3—C2—N1	107.4 (5)	N4—C12—H12A	109.5
C3—C2—H2	126.3	N4—C12—H12B	109.5
N1—C2—H2	126.3	H12A—C12—H12B	109.5
C2—C3—N2	105.9 (4)	N4—C12—H12C	109.5
C2—C3—H3	127.0	H12A—C12—H12C	109.5
N2—C3—H3	127.0	H12B—C12—H12C	109.5
C5—C4—N1	111.3 (5)

N5ⁱ—P3—O2—P1	47.2 (3)	C7—Ag—C1—N1	−47 (9)
N7ⁱ—P3—O2—P1	−88.3 (3)	C7—Ag—C1—N2	133 (8)
Cl3—P3—O2—P1	162.3 (2)	C1—N1—C2—C3	−0.3 (7)
O1—P1—O2—P3	136.3 (2)	C4—N1—C2—C3	−178.1 (5)
N5—P1—O2—P3	13.5 (3)	N1—C2—C3—N2	−0.7 (6)
N6—P1—O2—P3	−104.8 (3)	C1—N2—C3—C2	1.5 (6)
O1—P1—N5—P3ⁱ	146.1 (3)	C6—N2—C3—C2	−179.9 (5)
N6—P1—N5—P3ⁱ	12.6 (4)	C1—N1—C4—C5	−84.8 (7)
O2—P1—N5—P3ⁱ	−98.9 (3)	C2—N1—C4—C5	92.9 (7)
N7—P2—N6—P1	5.5 (4)	C8—N3—C7—N4	0.0 (6)
Cl1—P2—N6—P1	131.7 (2)	C10—N3—C7—N4	−177.7 (4)
Cl2—P2—N6—P1	−121.2 (3)	C8—N3—C7—Ag	−177.6 (4)
O1—P1—N6—P2	−144.9 (3)	C10—N3—C7—Ag	4.7 (7)
N5—P1—N6—P2	−10.1 (4)	C9—N4—C7—N3	−0.2 (6)
O2—P1—N6—P2	102.2 (3)	C12—N4—C7—N3	−179.0 (4)
N6—P2—N7—P3ⁱ	−2.2 (4)	C9—N4—C7—Ag	177.5 (4)
Cl1—P2—N7—P3ⁱ	−128.6 (2)	C12—N4—C7—Ag	−1.4 (7)
Cl2—P2—N7—P3ⁱ	125.9 (2)	C1—Ag—C7—N3	40 (9)
C2—N1—C1—N2	1.2 (6)	C1—Ag—C7—N4	−137 (8)
C4—N1—C1—N2	179.1 (5)	C7—N3—C8—C9	0.1 (6)
C2—N1—C1—Ag	−178.8 (4)	C10—N3—C8—C9	177.7 (5)
C4—N1—C1—Ag	−0.9 (7)	N3—C8—C9—N4	−0.2 (6)
C3—N2—C1—N1	−1.6 (6)	C7—N4—C9—C8	0.2 (6)
C6—N2—C1—N1	179.8 (5)	C12—N4—C9—C8	179.0 (5)
C3—N2—C1—Ag	178.3 (4)	C7—N3—C10—C11	87.5 (7)
C6—N2—C1—Ag	−0.2 (8)	C8—N3—C10—C11	−89.9 (7)

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	[Ag(C₆H₁₀N₂)₂](Cl₆N₆O₄P₆)_0.5
M_r	601.48
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	9.3224 (15), 10.6190 (18), 12.257 (2)
α, β, γ (°)	78.916 (3), 71.558 (3), 76.107 (3)
V (Å³)	1108.4 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.51
Crystal size (mm)	0.30 × 0.08 × 0.04

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.660, 0.942
No. of measured, independent and observed [I > \2s(I)] reflections	8912, 4459, 3484
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.623

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.123, 1.04
No. of reflections	4459
No. of parameters	257
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	2.25, −1.02

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Ag—C1	2.065 (5)	P1—N6	1.615 (4)
Ag—C7	2.070 (5)	P1—O2	1.657 (3)
Cl1—P2	2.0118 (16)	P2—N6	1.555 (4)
Cl2—P2	2.0171 (17)	P2—N7	1.578 (4)
Cl3—P3	2.0217 (16)	P3—N5ⁱ	1.554 (4)
P1—O1	1.468 (3)	P3—O2	1.578 (3)
P1—N5	1.610 (4)	P3—N7ⁱ	1.594 (4)

C1—Ag—C7	178.72 (19)

Symmetry code: (i) −x+1, −y+1, −z+1.

Acknowledgements

We thank the National Science Foundation (USA) for support of this work under grants CHE-0316944 and CHE-0616601 and grant CHE-0116041 for the funds used to support the X-ray facilities at the University of Akron.

References

Allcock, H. R. (2003). Chemistry and Applications of Polyphosphazenes, pp. 137–187. New Jersey: Wiley-Interscience. Google Scholar
Allcock, H. R., Gardener, J. E. & Smeltz, K. M. (1975). Macromolecules, 8, 36–42. CrossRef CAS Web of Science Google Scholar
Bartlett, S. W., Coles, S. J., Davies, D. B., Hursthouse, M. B., İbişogˇlu, H., Kiliç, A., Shaw, R. A. & Ün, İ. (2006). Acta Cryst. B62, 321–329. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Brandt, K., van de Grampel, J. C., Meetsma, A. & Jekel, A. P. (1991). Recl Trav. Chim. Pays Bas, 110, 27–28. CrossRef CAS Google Scholar
Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bullen, G. J. (1971). J. Chem. Soc. A, 1450–1453. CrossRef Google Scholar
Gabler, D. G. & Haw, J. F. (1990). Inorg. Chem. 29, 4018–4021. CrossRef CAS Web of Science Google Scholar
Meetsma, A., van der Lee, A., Jekel, A. P., van de Grampel, J. C. & Brandt, K. (1990). Acta Cryst. C46, 909–911. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Murray, M., Penkett, C. J., Rillie, I. M. & Singh, G. (1994). Phosphorus, Sulfur, Silicon. 93–94, 313–316. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Grampel, J. C. van de (1992). Coord. Chem. Rev. 112, 247-271. Google Scholar