1,1′,4,5-Tetra­hydro­tri­spiro­[1,3,2-di­aza­phosphole-2,2′-[1,3,5,2,4,6]tri­aza­triphosphinine-4′,6′′-dibenzo[d,f][1,3,2]dioxaphosphepine-6′,6′′′-dibenzo[d,f][1,3,2]dioxaphosphepine] acetone monosolvate

Fontenot, K.R.; Easson, M.W.; Fronczek, F.R.; Condon, B.D.

doi:10.1107/S1600536813023830

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 9| September 2013| Pages o1491-o1492

doi:10.1107/S1600536813023830

Open

access

1,1′,4,5-Tetrahydrotrispiro[1,3,2-diazaphosphole-2,2′-[1,3,5,2,4,6]triazatriphosphinine-4′,6′′-dibenzo[d,f][1,3,2]dioxaphosphepine-6′,6′′′-dibenzo[d,f][1,3,2]dioxaphosphepine] acetone monosolvate

Krystal R. Fontenot,^a Michael W. Easson,^a ^* Frank R. Fronczek ^b and Brian D. Condon ^a

^aUnited States Department of Agriculture Cotton Chemistry and Utilization, 1100 Robert E. Lee Blvd, New Orleans, LA 70124, USA, and ^bDepartment of Chemistry, Louisiana State University, Baton Rouge, LA 70803, USA
^*Correspondence e-mail: michael.easson@ars.usda.gov

(Received 14 August 2013; accepted 23 August 2013; online 31 August 2013)

The title compound, C₂₆H₂₂N₅O₄P₃·C₃H₆O, has been achieved in a two-step synthesis that does not require chromatography. This molecule contains a seven-membered spirocyclic ring at two P-atom positions and a five-membered ring containing new P—N bonds at the other P-atom position. Endocyclic torsion angles about the central biphenyl C—C bonds are −41.5 (3) and −44.4 (3)°, and P—N bonds of the central P₃N₃ ring are within the range 1.5665 (17)–1.6171 (17) Å, while the P—O distances are in the range 1.5940 (14)–1.6041 (14) Å. One N—H group makes an intermolecular N—H⋯N hydrogen bond, forming centrosymmetric dimers, while the other N—H group makes an N—H⋯O hydrogen bond to the acetone solvent molecule. The crystal was a two-component non-merohedral twin with ratio 0.811/0.189.

Related literature

For phosphazene-based flame retardants, see: Bakos et al. (1982 ); Drews & Barker (1985 ). For related structures, bond angles and lengths, see: Allcock (1972 ); Ciftci et al. (2013 ). For the geometry of phosphazene rings, see: Olthof (1969 ); Barclay et al. (2002 ). For the synthesis, see: Allen (1991 ); Carriedo et al. (1996 ). For related structures, see: Chandrasekhar et al. (2007 ; 2011 ; 2012 ); Harmjanz et al. (2004 ). For graph-set analysis, see: Etter (1990 ). For ring asymmetry parameters, see: Duax et al. (1976 ).

Experimental

Crystal data

C₂₆H₂₂N₅O₄P₃·C₃H₆O
M_r = 619.47
Monoclinic, P 2₁ /c
a = 9.4901 (9) Å
b = 22.9466 (19) Å
c = 13.1776 (13) Å
β = 97.978 (6)°
V = 2841.9 (5) Å³
Z = 4
Cu Kα radiation
μ = 2.34 mm⁻¹
T = 100 K
0.19 × 0.12 × 0.03 mm

Data collection

Bruker Kappa APEXII DUO CCD diffractometer
Absorption correction: multi-scan (TWINABS; Sheldrick, 2004 ) T_min = 0.664, T_max = 0.933
33208 measured reflections
5065 independent reflections
4276 reflections with I > 2σ(I)
R_int = 0.051

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.102
S = 1.08
5065 reflections
387 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4N⋯O5	0.82 (3)	2.22 (3)	2.991 (2)	158 (2)
N5—H5N⋯N3ⁱ	0.83 (3)	2.53 (3)	3.285 (2)	151 (2)
Symmetry code: (i) -x+2, -y+1, -z+1.

Data collection: APEX2 (Bruker, 2011 ); cell refinement: SAINT (Bruker, 2011); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536813023830/jj2173sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813023830/jj2173Isup2.hkl

checkCIF report

Comment top

The non-halogenated title compound contains two key elements phosphorus and nitrogen, which are incorporated into the backbone moiety of the molecule to achieve flame retardant properties (Bakos et al., 1982). Studies have shown that an increase in the number of phosphorus (P), nitrogen (N), or P—N bonds leads to improved flame retardancy (Drews & Barker, 1985). The substitution of two biphenol groups and ethylenediamine onto phosphazene was achieved through nucleophilic substitution in high yield. This compound was applied to cotton fabric and has shown promising preliminary results as a potential flame retardant.

The proposed efficacy and novelty of this flame retardant is based on the design of phosphorus (P3) surrounded by four nitrogen (N2, N3, N4, N5) atoms, thereby increasing the number of P—N bonds in the molecule. Incorporation of the 2,2'-biphenol moiety at P1 and P2 promotes a seven membered spirocyclic structure with endocyclic torsion angles about the central biphenol C—C bonds being nearly equal, -44.4 (3)° for C1/C6/C7/C12 and -41.5 (3)° for C13/C18/C19/C24. Both seven-membered rings have twist conformations with the P atom on the local twofold axis; however the deviation from C₂ local symmetry is substantial for both. The asymmetry parameter (Duax et al., 1976) is 14.83 (13)° for the ring containing P1 and 18.44 (14)° for that containing P2.

The utilization of ethylenediamine at the P3 position forms a five-membered ring with new P—N bonds, which lies roughly perpendicular (dihedral angle 81.42 (4)°) to the phosphazene ring. The conformation of the 5-membered ring is closest to an envelope with C25 at the flap position. C25 lies 0.554 (2) Å out of the plane of the other four atoms, and the C_s asymmetry parameter is 3.44 (17)°. The N—P—N bonds have angles of 94.47 (9)° to 113.64 (9)°, which is lower than typical angles of ~118° (Allcock, 1972). The narrowing of the angle may be due to van der Waals repulsions from the four N atoms surrounding P3 (Allcock, 1972). It has been reported that N—P—N bonds with two bulky phenyl groups on P have a narrowed angle of 115° due to mutual repulsions form the bulky phenyl group (Allcock, 1972). The phosphazene ring itself is slightly nonplanar, having a boat distortion, with P2 lying 0.1982 (4) Å and N3 lying 0.161 (2) Å on the same side of the plane defined by P1, P3, N1, and N2. The phosphazene ring has P—N bond lengths ranging from 1.5665 (17) to 1.6171 (17) Å. These values are typical for phosphazene rings (Barclay et al. 2002; Olthof, 1969). This molecule has similar bond angles and bond lengths, when substituted with the same or comparable spiro molecules, as found in the literature (Allcock, 1972, Ciftci et al., 2013). Overall, the molecule has approximate C₂ symmetry, as seen in Fig. 1.

Both NH groups donate intermolecular hydrogen bonds, as shown in Fig. 2. The N5—H···N3 (at 2 - x, 1 - y, 1 - z) bond leads to centrosymmetric hydrogen-bonded dimers, with graph set R²₂(8) (Etter, 1990), while N4 donates a hydrogen bond to acetone O. The acetone molecule forms two C—H···O hydrogen bonds with the phosphazene molecule, one as a donor and the other as an acceptor (Table 1).

Related literature top

For phosphazene-based flame retardants, see: Bakos et al. (1982); Drews & Barker, (1985). For related structures, bond angles and lengths, see: Allcock (1972); Ciftci et al. (2013). For the geometry of phosphazene rings, see: Olthof (1969); Barclay et al. (2002). For the synthesis, see: Allen (1991); Carriedo et al. (1996). For related structures, see: Chandrasekhar et al. (2007; 2011; 2012); Harmjanz et al. (2004). For graph-set analysis, see: Etter (1990). For ring asymmetry parameters, see: Duax et al. (1976).

Experimental top

All reagent grade chemicals were purchased from Sigma Aldrich and were used without further purification. ESI Mass Spectra were recorded on an Agilent Technologies 6520 Accurate Mass Q-TOF LC/MS. NMR spectra were recorded using a Varian 400MHZ spectrometer. ¹H and ¹³C are given in δ relative to TMS and ³¹P is given δ relative to external 85% aqueous H₃PO₄.

2,2-Dichloro-4,4,6,6-bis[spiro(2,2'-dioxy-1'1"-biphenyl)] Cyclotriphosphazene (1) was synthesized as previously reported in the literature (Allen, 1991; Carriedo et al. 1996).

A 3-neck round bottom flask was equipped with an argon inlet, an addition funnel, and a stopper. (1) was allowed to stir in CH₂C1₂ until completely dissolved. A solution of ethylenediamine in CH₂C1₂ was added drop-wise to the round bottom flask at 0°C and allowed to warm to room temperature. The reaction was allowed to stir for 24 h. Thin Layer Chromatography (TLC) was used to follow the reaction using Hexanes/ CH₂C1₂ (50:50) and DCM/MeOH (90:10). Purification was achieved by gently extracting the organic layer with warm distilled water. The organic layer was dried by anhydrous sodium sulfate and concentrated. The product (2) obtained was a white solid with a yield of 84%. The compound was tested by ESI-MS and ¹H, ¹³C, ³¹P –NMR using Acetone-d₆. Crystals of (2) were grown in an NMR tube from acetone.

Computing details top

Data collection: APEX2 (Bruker, 2011); cell refinement: SAINT (Bruker, 2011); data reduction: SAINT (Bruker, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with atomic numbering scheme and 50% ellipsoids. The solvent molecule is not shown.
	Fig. 2. Hydrogen bonding, illustrating the centrosymmetic dimer about 1, 1/2, 1/2 and the two acetone acceptors. H atoms on C are not shown.

1,1',4,5-Tetrahydrotrispiro[1,3,2-diazaphosphole-2,2'-[1,3,5,2,4,6]triazatriphosphinine-4',6''-dibenzo[d,f][1,3,2]dioxaphosphepine-6',6'''-dibenzo[d,f][1,3,2]dioxaphosphepine] acetone monosolvate top

Crystal data top

C₂₆H₂₂N₅O₄P₃·C₃H₆O	F(000) = 1288
M_r = 619.47	D_x = 1.448 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2ybc	Cell parameters from 3314 reflections
a = 9.4901 (9) Å	θ = 3.9–67.8°
b = 22.9466 (19) Å	µ = 2.34 mm⁻¹
c = 13.1776 (13) Å	T = 100 K
β = 97.978 (6)°	Plate, colorless
V = 2841.9 (5) Å³	0.19 × 0.12 × 0.03 mm
Z = 4

Data collection top

Bruker Kappa APEXII DUO CCD diffractometer	5065 independent reflections
Radiation source: IµS microfocus	4276 reflections with I > 2σ(I)
QUAZAR multilayer optics monochromator	R_int = 0.051
ϕ and ω scans	θ_max = 68.7°, θ_min = 3.9°
Absorption correction: multi-scan (TWINABS; Sheldrick, 2004)	h = −11→11
T_min = 0.664, T_max = 0.933	k = 0→27
33208 measured reflections	l = 0→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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.102	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0595P)² + 0.7869P] where P = (F_o² + 2F_c²)/3
5065 reflections	(Δ/σ)_max = 0.001
387 parameters	Δρ_max = 0.40 e Å⁻³
0 restraints	Δρ_min = −0.39 e Å⁻³

Crystal data top

C₂₆H₂₂N₅O₄P₃·C₃H₆O	V = 2841.9 (5) Å³
M_r = 619.47	Z = 4
Monoclinic, P2₁/c	Cu Kα radiation
a = 9.4901 (9) Å	µ = 2.34 mm⁻¹
b = 22.9466 (19) Å	T = 100 K
c = 13.1776 (13) Å	0.19 × 0.12 × 0.03 mm
β = 97.978 (6)°

Data collection top

Bruker Kappa APEXII DUO CCD diffractometer	5065 independent reflections
Absorption correction: multi-scan (TWINABS; Sheldrick, 2004)	4276 reflections with I > 2σ(I)
T_min = 0.664, T_max = 0.933	R_int = 0.051
33208 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.102	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.40 e Å⁻³
5065 reflections	Δρ_min = −0.39 e Å⁻³
387 parameters

Special details top

Experimental. The sample was a multiple crystal ("twin") with two components. The second domain was rotated from first domain by 2.6 degrees about reciprocal axis -0.141 1.000 0.976 and real axis -0.085 0.341 1.000

The twin law to convert hkl from first to this domain (SHELXL TWIN matrix): 1.002 - 0.016 0.017, 0.096 0.999 0.015, -0.032 - 0.001 0.996

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, using a TWIN4 hkl file prepared by TWINABS (Sheldrick, 2004).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
P1	0.86867 (5)	0.57153 (2)	0.27605 (4)	0.01501 (13)
P2	0.70274 (5)	0.47853 (2)	0.30698 (4)	0.01500 (13)
P3	0.79507 (5)	0.55177 (2)	0.47261 (4)	0.01498 (13)
O1	1.02561 (15)	0.56625 (6)	0.24629 (11)	0.0169 (3)
O2	0.80895 (14)	0.62781 (6)	0.21219 (11)	0.0171 (3)
O3	0.77860 (14)	0.41639 (6)	0.30107 (11)	0.0165 (3)
O4	0.54174 (14)	0.46339 (6)	0.26346 (11)	0.0174 (3)
N1	0.77084 (18)	0.51945 (7)	0.22950 (13)	0.0173 (4)
N2	0.69897 (18)	0.49976 (7)	0.41955 (13)	0.0178 (4)
N3	0.89141 (18)	0.58162 (7)	0.39485 (13)	0.0172 (4)
N4	0.70206 (19)	0.59910 (8)	0.52986 (14)	0.0190 (4)
H4N	0.659 (3)	0.6247 (11)	0.4945 (19)	0.023*
N5	0.89724 (19)	0.53234 (8)	0.57900 (13)	0.0182 (4)
H5N	0.921 (3)	0.4976 (11)	0.5831 (19)	0.022*
C1	1.0620 (2)	0.58150 (9)	0.14985 (16)	0.0175 (4)
C2	1.1120 (2)	0.53795 (9)	0.09149 (16)	0.0195 (4)
H2	1.1120	0.4985	0.1134	0.023*
C3	1.1619 (2)	0.55245 (9)	0.00081 (17)	0.0231 (5)
H3	1.1962	0.5228	−0.0399	0.028*
C4	1.1620 (2)	0.61020 (10)	−0.03067 (16)	0.0233 (5)
H4	1.1973	0.6201	−0.0925	0.028*
C5	1.1105 (2)	0.65351 (9)	0.02810 (16)	0.0205 (4)
H5	1.1096	0.6928	0.0054	0.025*
C6	1.0600 (2)	0.64004 (9)	0.12034 (15)	0.0170 (4)
C7	1.0101 (2)	0.68643 (8)	0.18533 (15)	0.0174 (4)
C8	1.0836 (2)	0.73950 (9)	0.20275 (16)	0.0203 (4)
H8	1.1679	0.7460	0.1730	0.024*
C9	1.0346 (2)	0.78235 (9)	0.26264 (16)	0.0225 (5)
H9	1.0854	0.8180	0.2735	0.027*
C10	0.9119 (2)	0.77390 (9)	0.30718 (16)	0.0218 (4)
H10	0.8794	0.8035	0.3486	0.026*
C11	0.8369 (2)	0.72215 (9)	0.29101 (16)	0.0205 (4)
H11	0.7523	0.7159	0.3206	0.025*
C12	0.8877 (2)	0.67975 (8)	0.23097 (16)	0.0175 (4)
C13	0.7274 (2)	0.37086 (8)	0.35739 (16)	0.0170 (4)
C14	0.8068 (2)	0.35465 (9)	0.44930 (16)	0.0207 (4)
H14	0.8913	0.3751	0.4752	0.025*
C15	0.7602 (3)	0.30792 (9)	0.50272 (17)	0.0265 (5)
H15	0.8124	0.2964	0.5663	0.032*
C16	0.6377 (2)	0.27796 (9)	0.46347 (18)	0.0265 (5)
H16	0.6068	0.2458	0.5000	0.032*
C17	0.5602 (2)	0.29493 (9)	0.37092 (18)	0.0234 (5)
H17	0.4765	0.2741	0.3446	0.028*
C18	0.6038 (2)	0.34235 (8)	0.31581 (16)	0.0182 (4)
C19	0.5226 (2)	0.36114 (9)	0.21647 (16)	0.0182 (4)
C20	0.4629 (2)	0.32016 (9)	0.14425 (18)	0.0246 (5)
H20	0.4762	0.2798	0.1586	0.029*
C21	0.3846 (2)	0.33719 (11)	0.05215 (19)	0.0296 (5)
H21	0.3440	0.3086	0.0047	0.036*
C22	0.3657 (2)	0.39597 (11)	0.02949 (18)	0.0291 (5)
H22	0.3130	0.4077	−0.0338	0.035*
C23	0.4239 (2)	0.43759 (10)	0.09950 (17)	0.0237 (5)
H23	0.4115	0.4779	0.0845	0.028*
C24	0.5001 (2)	0.41980 (9)	0.19118 (16)	0.0178 (4)
C25	0.7808 (2)	0.61684 (9)	0.62821 (16)	0.0233 (5)
H25A	0.7156	0.6317	0.6748	0.028*
H25B	0.8514	0.6475	0.6188	0.028*
C26	0.8542 (2)	0.56094 (9)	0.67000 (16)	0.0213 (4)
H26A	0.9382	0.5698	0.7211	0.026*
H26B	0.7880	0.5360	0.7024	0.026*
O5	0.53486 (16)	0.66469 (7)	0.35745 (12)	0.0258 (3)
C27	0.4623 (2)	0.62727 (9)	0.30959 (17)	0.0220 (5)
C28	0.3829 (2)	0.58239 (9)	0.36180 (18)	0.0255 (5)
H28A	0.4119	0.5846	0.4360	0.038*
H28B	0.4045	0.5435	0.3373	0.038*
H28C	0.2805	0.5897	0.3462	0.038*
C29	0.4499 (3)	0.62433 (11)	0.19530 (18)	0.0307 (5)
H29A	0.4922	0.6594	0.1695	0.046*
H29B	0.3493	0.6219	0.1661	0.046*
H29C	0.5002	0.5898	0.1754	0.046*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.0158 (3)	0.0150 (2)	0.0145 (3)	−0.00015 (19)	0.00280 (19)	0.00056 (18)
P2	0.0159 (3)	0.0140 (2)	0.0153 (3)	−0.00058 (19)	0.00309 (19)	−0.00092 (18)
P3	0.0156 (3)	0.0156 (2)	0.0139 (3)	0.00053 (19)	0.00267 (19)	−0.00072 (18)
O1	0.0168 (7)	0.0184 (7)	0.0161 (7)	0.0007 (5)	0.0041 (6)	0.0038 (5)
O2	0.0156 (7)	0.0159 (7)	0.0194 (7)	−0.0013 (5)	0.0007 (6)	0.0012 (5)
O3	0.0165 (7)	0.0152 (6)	0.0183 (7)	−0.0007 (5)	0.0041 (5)	−0.0009 (5)
O4	0.0157 (7)	0.0159 (6)	0.0206 (8)	0.0000 (5)	0.0024 (6)	−0.0040 (6)
N1	0.0196 (9)	0.0177 (8)	0.0151 (9)	−0.0020 (7)	0.0042 (7)	−0.0015 (6)
N2	0.0195 (9)	0.0173 (8)	0.0173 (9)	−0.0020 (7)	0.0051 (7)	0.0005 (7)
N3	0.0181 (9)	0.0174 (8)	0.0158 (9)	−0.0023 (7)	0.0016 (7)	−0.0005 (7)
N4	0.0203 (9)	0.0193 (8)	0.0176 (9)	0.0041 (7)	0.0030 (7)	−0.0017 (7)
N5	0.0204 (9)	0.0187 (8)	0.0154 (9)	0.0028 (7)	0.0019 (7)	0.0007 (7)
C1	0.0141 (10)	0.0234 (10)	0.0151 (10)	−0.0017 (8)	0.0029 (8)	0.0003 (8)
C2	0.0189 (10)	0.0177 (9)	0.0215 (11)	−0.0003 (8)	0.0013 (8)	−0.0007 (8)
C3	0.0216 (11)	0.0263 (11)	0.0212 (11)	0.0020 (9)	0.0025 (9)	−0.0039 (9)
C4	0.0239 (11)	0.0307 (11)	0.0160 (11)	−0.0022 (9)	0.0051 (9)	0.0007 (9)
C5	0.0215 (11)	0.0203 (10)	0.0198 (11)	−0.0004 (8)	0.0031 (8)	0.0031 (8)
C6	0.0151 (10)	0.0193 (10)	0.0167 (10)	−0.0017 (8)	0.0025 (8)	−0.0015 (8)
C7	0.0191 (10)	0.0181 (9)	0.0148 (10)	0.0008 (8)	0.0016 (8)	0.0033 (8)
C8	0.0225 (11)	0.0207 (10)	0.0184 (11)	−0.0024 (8)	0.0054 (8)	0.0034 (8)
C9	0.0307 (12)	0.0159 (9)	0.0209 (11)	−0.0046 (9)	0.0031 (9)	0.0009 (8)
C10	0.0286 (11)	0.0171 (10)	0.0201 (11)	0.0019 (9)	0.0051 (9)	−0.0019 (8)
C11	0.0199 (10)	0.0204 (10)	0.0212 (11)	0.0029 (8)	0.0036 (8)	0.0038 (8)
C12	0.0198 (10)	0.0132 (9)	0.0186 (10)	−0.0013 (8)	−0.0004 (8)	0.0023 (7)
C13	0.0207 (10)	0.0139 (9)	0.0182 (10)	0.0005 (8)	0.0091 (8)	−0.0011 (8)
C14	0.0228 (11)	0.0184 (9)	0.0213 (11)	0.0052 (8)	0.0044 (9)	−0.0030 (8)
C15	0.0379 (13)	0.0220 (10)	0.0208 (11)	0.0116 (10)	0.0087 (10)	0.0028 (9)
C16	0.0331 (13)	0.0194 (10)	0.0308 (13)	0.0044 (9)	0.0181 (10)	0.0044 (9)
C17	0.0236 (11)	0.0172 (10)	0.0316 (13)	0.0004 (8)	0.0113 (9)	−0.0014 (9)
C18	0.0185 (10)	0.0152 (9)	0.0227 (11)	0.0021 (8)	0.0092 (8)	−0.0027 (8)
C19	0.0148 (10)	0.0212 (10)	0.0202 (11)	−0.0021 (8)	0.0073 (8)	−0.0031 (8)
C20	0.0216 (11)	0.0228 (11)	0.0307 (13)	−0.0033 (9)	0.0086 (9)	−0.0087 (9)
C21	0.0229 (11)	0.0378 (13)	0.0276 (13)	−0.0032 (10)	0.0015 (9)	−0.0167 (10)
C22	0.0231 (12)	0.0412 (13)	0.0218 (12)	0.0024 (10)	−0.0015 (9)	−0.0063 (10)
C23	0.0209 (11)	0.0257 (11)	0.0241 (12)	0.0025 (9)	0.0019 (9)	−0.0006 (9)
C24	0.0138 (10)	0.0202 (10)	0.0196 (11)	−0.0008 (8)	0.0038 (8)	−0.0046 (8)
C25	0.0234 (11)	0.0275 (11)	0.0188 (11)	0.0003 (9)	0.0023 (9)	−0.0057 (9)
C26	0.0213 (11)	0.0268 (10)	0.0159 (11)	−0.0005 (9)	0.0029 (8)	−0.0013 (8)
O5	0.0236 (8)	0.0247 (8)	0.0291 (9)	−0.0022 (6)	0.0034 (7)	−0.0016 (6)
C27	0.0162 (10)	0.0234 (10)	0.0268 (12)	0.0065 (9)	0.0039 (9)	−0.0008 (9)
C28	0.0210 (11)	0.0245 (11)	0.0319 (13)	0.0012 (9)	0.0069 (9)	−0.0014 (9)
C29	0.0257 (12)	0.0403 (13)	0.0255 (13)	−0.0010 (10)	0.0017 (10)	0.0027 (10)

Geometric parameters (Å, º) top

P1—N3	1.5675 (17)	C10—H10	0.9500
P1—N1	1.5837 (17)	C11—C12	1.382 (3)
P1—O1	1.5965 (14)	C11—H11	0.9500
P1—O2	1.6016 (14)	C13—C14	1.385 (3)
P2—N2	1.5665 (17)	C13—C18	1.388 (3)
P2—N1	1.5890 (17)	C14—C15	1.388 (3)
P2—O4	1.5940 (14)	C14—H14	0.9500
P2—O3	1.6041 (14)	C15—C16	1.387 (3)
P3—N2	1.6024 (17)	C15—H15	0.9500
P3—N3	1.6171 (17)	C16—C17	1.390 (3)
P3—N4	1.6471 (17)	C16—H16	0.9500
P3—N5	1.6514 (18)	C17—C18	1.402 (3)
O1—C1	1.407 (2)	C17—H17	0.9500
O2—C12	1.410 (2)	C18—C19	1.488 (3)
O3—C13	1.407 (2)	C19—C24	1.396 (3)
O4—C24	1.400 (2)	C19—C20	1.401 (3)
N4—C25	1.461 (3)	C20—C21	1.388 (3)
N4—H4N	0.82 (3)	C20—H20	0.9500
N5—C26	1.473 (3)	C21—C22	1.388 (4)
N5—H5N	0.83 (3)	C21—H21	0.9500
C1—C2	1.384 (3)	C22—C23	1.388 (3)
C1—C6	1.398 (3)	C22—H22	0.9500
C2—C3	1.386 (3)	C23—C24	1.381 (3)
C2—H2	0.9500	C23—H23	0.9500
C3—C4	1.389 (3)	C25—C26	1.526 (3)
C3—H3	0.9500	C25—H25A	0.9900
C4—C5	1.390 (3)	C25—H25B	0.9900
C4—H4	0.9500	C26—H26A	0.9900
C5—C6	1.402 (3)	C26—H26B	0.9900
C5—H5	0.9500	O5—C27	1.220 (3)
C6—C7	1.484 (3)	C27—C29	1.496 (3)
C7—C12	1.389 (3)	C27—C28	1.498 (3)
C7—C8	1.406 (3)	C28—H28A	0.9800
C8—C9	1.381 (3)	C28—H28B	0.9800
C8—H8	0.9500	C28—H28C	0.9800
C9—C10	1.388 (3)	C29—H29A	0.9800
C9—H9	0.9500	C29—H29B	0.9800
C10—C11	1.386 (3)	C29—H29C	0.9800

N3—P1—N1	119.36 (9)	C11—C12—O2	118.47 (18)
N3—P1—O1	104.64 (8)	C7—C12—O2	118.17 (17)
N1—P1—O1	111.37 (8)	C14—C13—C18	123.09 (19)
N3—P1—O2	113.28 (8)	C14—C13—O3	118.37 (18)
N1—P1—O2	105.03 (8)	C18—C13—O3	118.46 (18)
O1—P1—O2	101.90 (7)	C13—C14—C15	118.6 (2)
N2—P2—N1	119.30 (9)	C13—C14—H14	120.7
N2—P2—O4	105.18 (8)	C15—C14—H14	120.7
N1—P2—O4	110.65 (8)	C16—C15—C14	120.2 (2)
N2—P2—O3	113.07 (9)	C16—C15—H15	119.9
N1—P2—O3	105.59 (8)	C14—C15—H15	119.9
O4—P2—O3	101.71 (7)	C15—C16—C17	120.2 (2)
N2—P3—N3	112.12 (9)	C15—C16—H16	119.9
N2—P3—N4	112.47 (9)	C17—C16—H16	119.9
N3—P3—N4	113.39 (9)	C16—C17—C18	120.9 (2)
N2—P3—N5	113.64 (9)	C16—C17—H17	119.6
N3—P3—N5	109.59 (9)	C18—C17—H17	119.6
N4—P3—N5	94.47 (9)	C13—C18—C17	117.1 (2)
C1—O1—P1	123.88 (13)	C13—C18—C19	121.14 (18)
C12—O2—P1	116.68 (12)	C17—C18—C19	121.76 (19)
C13—O3—P2	116.39 (12)	C24—C19—C20	116.8 (2)
C24—O4—P2	124.52 (12)	C24—C19—C18	122.21 (18)
P1—N1—P2	117.77 (11)	C20—C19—C18	120.98 (19)
P2—N2—P3	123.95 (11)	C21—C20—C19	121.5 (2)
P1—N3—P3	123.96 (11)	C21—C20—H20	119.3
C25—N4—P3	110.45 (14)	C19—C20—H20	119.3
C25—N4—H4N	117.0 (17)	C22—C21—C20	119.9 (2)
P3—N4—H4N	117.8 (18)	C22—C21—H21	120.0
C26—N5—P3	111.99 (14)	C20—C21—H21	120.0
C26—N5—H5N	118.6 (17)	C21—C22—C23	119.9 (2)
P3—N5—H5N	115.9 (17)	C21—C22—H22	120.1
C2—C1—C6	122.12 (19)	C23—C22—H22	120.1
C2—C1—O1	117.93 (18)	C24—C23—C22	119.3 (2)
C6—C1—O1	119.65 (18)	C24—C23—H23	120.3
C1—C2—C3	119.36 (19)	C22—C23—H23	120.3
C1—C2—H2	120.3	C23—C24—C19	122.56 (19)
C3—C2—H2	120.3	C23—C24—O4	116.64 (18)
C2—C3—C4	120.1 (2)	C19—C24—O4	120.46 (18)
C2—C3—H3	120.0	N4—C25—C26	103.74 (17)
C4—C3—H3	120.0	N4—C25—H25A	111.0
C3—C4—C5	120.1 (2)	C26—C25—H25A	111.0
C3—C4—H4	120.0	N4—C25—H25B	111.0
C5—C4—H4	120.0	C26—C25—H25B	111.0
C4—C5—C6	120.97 (19)	H25A—C25—H25B	109.0
C4—C5—H5	119.5	N5—C26—C25	104.18 (17)
C6—C5—H5	119.5	N5—C26—H26A	110.9
C1—C6—C5	117.38 (19)	C25—C26—H26A	110.9
C1—C6—C7	121.47 (18)	N5—C26—H26B	110.9
C5—C6—C7	121.13 (18)	C25—C26—H26B	110.9
C12—C7—C8	116.76 (18)	H26A—C26—H26B	108.9
C12—C7—C6	121.56 (18)	O5—C27—C29	120.8 (2)
C8—C7—C6	121.68 (18)	O5—C27—C28	122.0 (2)
C9—C8—C7	120.7 (2)	C29—C27—C28	117.21 (19)
C9—C8—H8	119.6	C27—C28—H28A	109.5
C7—C8—H8	119.6	C27—C28—H28B	109.5
C8—C9—C10	120.73 (19)	H28A—C28—H28B	109.5
C8—C9—H9	119.6	C27—C28—H28C	109.5
C10—C9—H9	119.6	H28A—C28—H28C	109.5
C11—C10—C9	119.85 (19)	H28B—C28—H28C	109.5
C11—C10—H10	120.1	C27—C29—H29A	109.5
C9—C10—H10	120.1	C27—C29—H29B	109.5
C12—C11—C10	118.6 (2)	H29A—C29—H29B	109.5
C12—C11—H11	120.7	C27—C29—H29C	109.5
C10—C11—H11	120.7	H29A—C29—H29C	109.5
C11—C12—C7	123.33 (18)	H29B—C29—H29C	109.5

N3—P1—O1—C1	−151.76 (15)	C5—C6—C7—C12	137.4 (2)
N1—P1—O1—C1	77.97 (16)	C1—C6—C7—C8	136.4 (2)
O2—P1—O1—C1	−33.56 (16)	C5—C6—C7—C8	−41.9 (3)
N3—P1—O2—C12	54.75 (16)	C12—C7—C8—C9	0.0 (3)
N1—P1—O2—C12	−173.32 (14)	C6—C7—C8—C9	179.33 (19)
O1—P1—O2—C12	−57.08 (15)	C7—C8—C9—C10	0.2 (3)
N2—P2—O3—C13	52.84 (16)	C8—C9—C10—C11	−0.4 (3)
N1—P2—O3—C13	−175.00 (13)	C9—C10—C11—C12	0.5 (3)
O4—P2—O3—C13	−59.42 (15)	C10—C11—C12—C7	−0.3 (3)
N2—P2—O4—C24	−148.34 (15)	C10—C11—C12—O2	−178.18 (18)
N1—P2—O4—C24	81.56 (17)	C8—C7—C12—C11	0.1 (3)
O3—P2—O4—C24	−30.24 (17)	C6—C7—C12—C11	−179.23 (19)
N3—P1—N1—P2	−1.48 (16)	C8—C7—C12—O2	177.90 (17)
O1—P1—N1—P2	120.63 (11)	C6—C7—C12—O2	−1.4 (3)
O2—P1—N1—P2	−129.84 (11)	P1—O2—C12—C11	−103.17 (18)
N2—P2—N1—P1	16.39 (16)	P1—O2—C12—C7	78.9 (2)
O4—P2—N1—P1	138.55 (10)	P2—O3—C13—C14	−103.07 (18)
O3—P2—N1—P1	−112.16 (11)	P2—O3—C13—C18	80.20 (19)
N1—P2—N2—P3	−17.32 (17)	C18—C13—C14—C15	−0.4 (3)
O4—P2—N2—P3	−142.15 (12)	O3—C13—C14—C15	−176.97 (17)
O3—P2—N2—P3	107.71 (12)	C13—C14—C15—C16	0.8 (3)
N3—P3—N2—P2	2.48 (16)	C14—C15—C16—C17	−0.6 (3)
N4—P3—N2—P2	131.67 (12)	C15—C16—C17—C18	−0.1 (3)
N5—P3—N2—P2	−122.48 (13)	C14—C13—C18—C17	−0.3 (3)
N1—P1—N3—P3	−14.21 (17)	O3—C13—C18—C17	176.31 (17)
O1—P1—N3—P3	−139.60 (11)	C14—C13—C18—C19	−179.62 (18)
O2—P1—N3—P3	110.26 (12)	O3—C13—C18—C19	−3.0 (3)
N2—P3—N3—P1	13.44 (16)	C16—C17—C18—C13	0.5 (3)
N4—P3—N3—P1	−115.26 (13)	C16—C17—C18—C19	179.83 (19)
N5—P3—N3—P1	140.61 (12)	C13—C18—C19—C24	−41.5 (3)
N2—P3—N4—C25	138.76 (14)	C17—C18—C19—C24	139.2 (2)
N3—P3—N4—C25	−92.72 (16)	C13—C18—C19—C20	139.6 (2)
N5—P3—N4—C25	20.88 (16)	C17—C18—C19—C20	−39.7 (3)
N2—P3—N5—C26	−112.97 (15)	C24—C19—C20—C21	−0.2 (3)
N3—P3—N5—C26	120.73 (15)	C18—C19—C20—C21	178.7 (2)
N4—P3—N5—C26	3.95 (16)	C19—C20—C21—C22	0.8 (3)
P1—O1—C1—C2	−117.03 (18)	C20—C21—C22—C23	−0.7 (4)
P1—O1—C1—C6	69.1 (2)	C21—C22—C23—C24	−0.1 (3)
C6—C1—C2—C3	0.1 (3)	C22—C23—C24—C19	0.7 (3)
O1—C1—C2—C3	−173.67 (18)	C22—C23—C24—O4	−172.71 (19)
C1—C2—C3—C4	0.2 (3)	C20—C19—C24—C23	−0.5 (3)
C2—C3—C4—C5	−0.7 (3)	C18—C19—C24—C23	−179.51 (19)
C3—C4—C5—C6	1.0 (3)	C20—C19—C24—O4	172.62 (18)
C2—C1—C6—C5	0.2 (3)	C18—C19—C24—O4	−6.3 (3)
O1—C1—C6—C5	173.83 (17)	P2—O4—C24—C23	−118.86 (18)
C2—C1—C6—C7	−178.11 (19)	P2—O4—C24—C19	67.6 (2)
O1—C1—C6—C7	−4.5 (3)	P3—N4—C25—C26	−37.8 (2)
C4—C5—C6—C1	−0.7 (3)	P3—N5—C26—C25	−25.7 (2)
C4—C5—C6—C7	177.58 (19)	N4—C25—C26—N5	38.3 (2)
C1—C6—C7—C12	−44.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4N···O5	0.82 (3)	2.22 (3)	2.991 (2)	158 (2)
N5—H5N···N3ⁱ	0.83 (3)	2.53 (3)	3.285 (2)	151 (2)

Symmetry code: (i) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4N···O5	0.82 (3)	2.22 (3)	2.991 (2)	158 (2)
N5—H5N···N3ⁱ	0.83 (3)	2.53 (3)	3.285 (2)	151 (2)

Symmetry code: (i) −x+2, −y+1, −z+1.

Acknowledgements

We would like to thank Dr Casey Grimm for the MS analysis. Upgrade of the diffractometer was made possible by grant No. LEQSF(2011–12)-ENH-TR-01, administered by the Louisiana Board of Regents.

References

Allcock, H. R. (1972). In Phosphorus-Nitrogen Compounds. New York: Academic Press, Inc. Google Scholar
Allen, C. W. (1991). Chem. Rev. 91, 119–135. CrossRef CAS Web of Science Google Scholar
Bakos, D., Kosik, M., Antos, K., Karolyova, M. & Vyskocil, I. (1982). Fire Mater. 6, 10–11. CAS Google Scholar
Barclay, T. M., Hicks, R. G., Ichimura, A. S. & Patenaude, G. W. (2002). Can. J. Chem. 80, 1501–1506. Web of Science CSD CrossRef CAS Google Scholar
Bruker (2011). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Carriedo, G. A., Fernandez-Catuxo, L., Alonso, F. J. G., Gomez-Elipe, P. & Gonzalez, P. A. (1996). Macromolecules, 29, 5320–5325. CrossRef CAS Web of Science Google Scholar
Chandrasekhar, V., Pandey, M. D., Das, B., Mahanti, B., Gopal, K. & Azhakar, R. (2011). Tetrahedron, 67, 6917–6926. Web of Science CSD CrossRef CAS Google Scholar
Chandrasekhar, V., Senapati, T., Dey, A., Das, S., Kalisz, M. & Clérac, R. (2012). Inorg. Chem. 51, 2031–2038. Web of Science CSD CrossRef CAS PubMed Google Scholar
Chandrasekhar, V., Thilagar, P., Krishnan, V., Bickley, J. F. & Steiner, A. (2007). Cryst. Growth Des. 7, 668–675. Web of Science CSD CrossRef CAS Google Scholar
Ciftci, G. Y., Ecik, E. T., Yildirim, T., Bilgin, K., Senkuytu, E., Yuksel, F., Uludag, Y. & Kilic, A. (2013). Tetrahedron, 69, 1454–1461. CAS Google Scholar
Drews, M. J. & Barker, R. H. (1985). Cellulose Chemistry and its applications, edited by T. P Nevell & S. H. Zeronian, pp. 423–454. John Wiley & Sons, Inc. Google Scholar
Duax, W. L., Weeks, C. M. & Rohrer, D. C. (1976). Topics in Stereochemistry, Vol. 9, edited by E. L. Eliel & N. Allinger, New York: New York: John Wiley, pp. 271–383. Google Scholar
Etter, M. C. (1990). Acc. Chem. Res. 23, 120–126. CrossRef CAS Web of Science Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Harmjanz, M., Piglosiewicz, I. M., Scott, B. L. & Burns, C. J. (2004). Inorg. Chem. 43, 642–650. Web of Science CSD CrossRef PubMed CAS Google Scholar
Olthof, R. (1969). Acta Cryst. B25, 2040–2045. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Sheldrick, G. (2004). TWINABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 9| September 2013| Pages o1491-o1492

doi:10.1107/S1600536813023830

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

1,1′,4,5-Tetra­hydro­tri­spiro­[1,3,2-di­aza­phosphole-2,2′-[1,3,5,2,4,6]tri­aza­triphosphinine-4′,6′′-dibenzo[d,f][1,3,2]dioxaphosphepine-6′,6′′′-dibenzo[d,f][1,3,2]dioxaphosphepine] acetone monosolvate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

1,1′,4,5-Tetrahydrotrispiro[1,3,2-diazaphosphole-2,2′-[1,3,5,2,4,6]triazatriphosphinine-4′,6′′-dibenzo[d,f][1,3,2]dioxaphosphepine-6′,6′′′-dibenzo[d,f][1,3,2]dioxaphosphepine] acetone monosolvate