4',4',6',6'-Tetra-chloro-2-(6-methyl-pyridin-2-yl)-1H,2H-spiro-[naphtho-[1,2-e][1,3,2]oxaza-phosphinine-3,2'-[1,3,5,2,4,6]tri-aza-triphosphinine].

The title compound, C17H14Cl4N5OP3, is a spiro-phosphazene derivative with bulky naphthalene and pyridine rings. The phosphazene and the six-membered N/O rings are in flattened-boat and twisted-boat conformations, respectively. The naphthalene ring system and the pyridine ring are oriented at a dihedral angle of 18.06 (8)°. In the crystal, weak π-π stacking between the pyridine rings and between the pyridine rings and the naphthalene ring system [centroid-centroid distances = 3.594 (2) and 3.961 (2) Å, respectively] occur. Weak C-H⋯π inter-actions are also observed. These interactions link the molecules into a three-dimensional supramolecular network.

Related literature

Fn class="Chemical">or products from the reaction of N3P3Cl6 with bifunctional reagents, see: Beşli et al. (2006 ▶). For N/O donor type bifunctional reagents used for the reaction of hexa­chloro­cyclo­triphosphazene giving spiro derivatives, see: Beşli et al. (2007 ▶); Sournies et al. (1997 ▶); Deutsch & Shaw (1990 ▶); Işıklan et al. (2010 ▶); İlter et al. (2004 ▶, 2007 ▶); Tercan et al. (2004 ▶). For industrial applications of cyclo­phosphazenes, see: Omotowa et al. (2004 ▶); Barbera et al. (2005 ▶); Schneider et al. (1999 ▶); Ding et al. (2005 ▶); Allcock (2006 ▶); Xu et al. (2006 ▶); Allcock & Wood (2006 ▶); Li et al. (2004 ▶); Singh et al. (2006 ▶); Greish et al. (2005 ▶). For bond-length data, see: Allen et al. (1987 ▶). For the standard compound, N3P3Cl6, see: Bullen (1971 ▶). For ring-puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C17H14Cl4N5OP3

M = 539.04

Orthorhombic,

a = 21.7784 (5) Å

b = 7.8573 (3) Å

c = 25.1034 (5) Å

V = 4295.7 (2) Å3

Z = 8

Mo Kα radiation

μ = 0.80 mm−1

T = 100 K

0.38 × 0.28 × 0.08 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.752, T max = 0.939

22083 measured reflections

5297 independent reflections

3446 reflections with I > 2σ(I)

R int = 0.070

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.129

S = 1.01

5297 reflections

272 parameters

H-atom parameters constrained

Δρmax = 0.73 e Å−3

Δρmin = −0.77 e Å−3

Data collection: APEX2 (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: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶) and PLATON (Spek, 2009 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813012348/xu5701sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813012348/xu5701Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813012348/xu5701Isup3.cml

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

C17H14Cl4N5OP3	F(000) = 2176
Mr = 539.04	Dx = 1.667 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 2741 reflections
a = 21.7784 (5) Å	θ = 2.5–26.6°
b = 7.8573 (3) Å	µ = 0.80 mm−1
c = 25.1034 (5) Å	T = 100 K
V = 4295.7 (2) Å3	Plate, colorless
Z = 8	0.38 × 0.28 × 0.08 mm

Bruker Kappa APEXII CCD area-detector diffractometer	5297 independent reflections
Radiation source: fine-focus sealed tube	3446 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.070
φ and ω scans	θmax = 28.3°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −25→29
Tmin = 0.752, Tmax = 0.939	k = −10→6
22083 measured reflections	l = −31→33

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.129	H-atom parameters constrained
S = 1.01	w = 1/[σ2(Fo2) + (0.0611P)2 + 1.3984P] where P = (Fo2 + 2Fc2)/3
5297 reflections	(Δ/σ)max < 0.001
272 parameters	Δρmax = 0.73 e Å−3
0 restraints	Δρmin = −0.77 e Å−3

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
Cl1	0.23736 (4)	0.09286 (12)	0.33683 (4)	0.0310 (2)
Cl2	0.12400 (4)	−0.12370 (11)	0.36507 (4)	0.0315 (2)
Cl3	0.12654 (4)	0.54678 (12)	0.27056 (3)	0.0268 (2)
Cl4	0.00013 (4)	0.37802 (12)	0.28234 (3)	0.0277 (2)
P1	0.10765 (4)	0.37524 (10)	0.42559 (3)	0.01570 (18)
P2	0.14946 (4)	0.11972 (11)	0.35899 (3)	0.0203 (2)
P3	0.08161 (4)	0.38196 (11)	0.31822 (3)	0.01836 (19)
O1	0.15089 (10)	0.5220 (3)	0.44668 (8)	0.0188 (5)
N1	0.14830 (12)	0.2097 (3)	0.41488 (10)	0.0195 (6)
N2	0.11206 (13)	0.2007 (4)	0.31138 (11)	0.0243 (7)
N3	0.07526 (12)	0.4618 (3)	0.37531 (10)	0.0183 (6)
N4	0.06038 (12)	0.3449 (3)	0.47683 (10)	0.0161 (6)
N5	0.00488 (13)	0.1705 (3)	0.42067 (11)	0.0220 (6)
C1	0.15699 (15)	0.5167 (4)	0.59375 (12)	0.0170 (7)
C2	0.12413 (15)	0.4649 (4)	0.63968 (12)	0.0197 (7)
H2	0.0861	0.4068	0.6357	0.024*
C3	0.14637 (16)	0.4972 (4)	0.68968 (13)	0.0241 (8)
H3	0.1242	0.4585	0.7199	0.029*
C4	0.20163 (17)	0.5872 (5)	0.69686 (14)	0.0279 (8)
H4	0.2163	0.6104	0.7317	0.033*
C5	0.23409 (16)	0.6410 (4)	0.65326 (14)	0.0248 (8)
H5	0.2713	0.7021	0.6581	0.030*
C6	0.21268 (15)	0.6066 (4)	0.60098 (13)	0.0202 (7)
C7	0.24658 (15)	0.6603 (4)	0.55567 (13)	0.0213 (7)
H7	0.2839	0.7211	0.5606	0.026*
C8	0.22672 (15)	0.6265 (4)	0.50547 (13)	0.0203 (7)
H8	0.2499	0.6612	0.4753	0.024*
C9	0.17088 (14)	0.5387 (4)	0.49938 (12)	0.0167 (6)
C10	0.13573 (14)	0.4829 (4)	0.54063 (12)	0.0164 (6)
C11	0.07536 (14)	0.3917 (4)	0.53259 (11)	0.0147 (6)
H11A	0.0758	0.2865	0.5543	0.018*
H11B	0.0420	0.4651	0.5464	0.018*
C12	0.00836 (14)	0.2393 (4)	0.46936 (13)	0.0184 (7)
C13	−0.03482 (15)	0.2132 (4)	0.50891 (13)	0.0182 (7)
H13	−0.0292	0.2574	0.5438	0.022*
C14	−0.08672 (15)	0.1197 (4)	0.49558 (14)	0.0229 (7)
H14	−0.1179	0.1002	0.5213	0.027*
C15	−0.09263 (16)	0.0552 (4)	0.44471 (14)	0.0244 (8)
H15	−0.1287	−0.0045	0.4346	0.029*
C16	−0.04548 (17)	0.0783 (4)	0.40862 (14)	0.0263 (8)
C17	−0.0465 (2)	−0.0028 (6)	0.35445 (15)	0.0493 (12)
H17A	−0.0384	0.0838	0.3273	0.074*
H17B	−0.0869	−0.0539	0.3481	0.074*
H17C	−0.0149	−0.0913	0.3526	0.074*

	U11	U22	U33	U12	U13	U23
Cl1	0.0266 (5)	0.0330 (5)	0.0333 (5)	0.0062 (4)	0.0064 (4)	−0.0064 (4)
Cl2	0.0411 (6)	0.0177 (4)	0.0357 (5)	−0.0001 (4)	0.0043 (4)	−0.0053 (4)
Cl3	0.0293 (5)	0.0327 (5)	0.0184 (4)	−0.0093 (4)	0.0004 (3)	0.0037 (3)
Cl4	0.0211 (4)	0.0374 (5)	0.0245 (4)	−0.0040 (4)	−0.0045 (3)	0.0029 (4)
P1	0.0188 (4)	0.0146 (4)	0.0137 (4)	0.0009 (4)	0.0004 (3)	−0.0004 (3)
P2	0.0245 (5)	0.0173 (4)	0.0192 (4)	0.0029 (4)	0.0014 (3)	−0.0034 (3)
P3	0.0199 (4)	0.0200 (4)	0.0151 (4)	−0.0005 (4)	−0.0005 (3)	0.0000 (3)
O1	0.0211 (12)	0.0192 (12)	0.0161 (11)	−0.0042 (10)	0.0013 (9)	0.0005 (9)
N1	0.0233 (15)	0.0169 (14)	0.0182 (14)	0.0053 (12)	−0.0021 (11)	−0.0008 (11)
N2	0.0315 (17)	0.0241 (15)	0.0174 (14)	0.0053 (13)	−0.0010 (11)	−0.0054 (12)
N3	0.0222 (15)	0.0169 (14)	0.0159 (13)	0.0050 (12)	−0.0021 (11)	0.0026 (11)
N4	0.0170 (14)	0.0163 (14)	0.0152 (12)	−0.0027 (11)	0.0010 (10)	−0.0001 (10)
N5	0.0297 (16)	0.0186 (14)	0.0179 (13)	−0.0036 (13)	−0.0055 (11)	0.0005 (11)
C1	0.0191 (17)	0.0131 (16)	0.0189 (15)	0.0029 (13)	0.0002 (12)	0.0018 (12)
C2	0.0201 (17)	0.0192 (17)	0.0199 (16)	−0.0004 (14)	0.0011 (13)	0.0006 (13)
C3	0.030 (2)	0.0240 (18)	0.0185 (16)	0.0026 (15)	−0.0009 (13)	0.0006 (13)
C4	0.032 (2)	0.031 (2)	0.0212 (17)	0.0033 (16)	−0.0050 (14)	−0.0046 (14)
C5	0.0244 (18)	0.0215 (18)	0.0286 (18)	−0.0027 (16)	−0.0045 (14)	−0.0024 (14)
C6	0.0216 (17)	0.0159 (17)	0.0233 (16)	0.0003 (14)	−0.0043 (13)	0.0003 (13)
C7	0.0166 (17)	0.0177 (18)	0.0295 (18)	−0.0027 (13)	0.0016 (13)	−0.0011 (14)
C8	0.0221 (17)	0.0166 (16)	0.0223 (16)	−0.0005 (15)	0.0031 (13)	0.0002 (13)
C9	0.0198 (17)	0.0139 (16)	0.0164 (15)	0.0033 (13)	−0.0017 (12)	−0.0019 (12)
C10	0.0180 (16)	0.0122 (15)	0.0191 (15)	0.0029 (13)	0.0032 (12)	0.0007 (12)
C11	0.0161 (15)	0.0161 (15)	0.0118 (13)	0.0012 (13)	−0.0002 (11)	0.0025 (12)
C12	0.0187 (17)	0.0129 (16)	0.0235 (16)	0.0020 (14)	−0.0044 (13)	0.0027 (13)
C13	0.0205 (17)	0.0118 (15)	0.0225 (16)	0.0012 (14)	0.0006 (13)	0.0000 (13)
C14	0.0191 (17)	0.0146 (16)	0.0349 (19)	0.0023 (14)	0.0019 (14)	0.0056 (14)
C15	0.0239 (18)	0.0155 (16)	0.0337 (19)	−0.0032 (15)	−0.0093 (15)	0.0058 (14)
C16	0.035 (2)	0.0184 (18)	0.0251 (18)	−0.0069 (16)	−0.0101 (15)	0.0037 (14)
C17	0.069 (3)	0.054 (3)	0.025 (2)	−0.034 (2)	−0.003 (2)	−0.0021 (19)

Cl1—P2	2.0047 (12)	C6—C5	1.419 (4)
Cl2—P2	1.9972 (13)	C6—C7	1.420 (5)
Cl3—P3	2.0165 (12)	C7—C8	1.358 (4)
Cl4—P3	1.9902 (12)	C7—H7	0.9500
P1—O1	1.580 (2)	C8—H8	0.9500
P1—N1	1.596 (3)	C9—C8	1.407 (4)
P1—N3	1.598 (3)	C10—C1	1.436 (4)
P1—N4	1.665 (3)	C10—C9	1.360 (4)
P2—N1	1.571 (3)	C11—C10	1.511 (4)
P2—N2	1.580 (3)	C11—H11A	0.9900
P3—N2	1.581 (3)	C11—H11B	0.9900
P3—N3	1.571 (3)	C12—N5	1.339 (4)
O1—C9	1.399 (4)	C12—C13	1.383 (4)
N4—C11	1.483 (4)	C13—C14	1.389 (5)
N4—C12	1.416 (4)	C13—H13	0.9500
C1—C2	1.417 (4)	C14—C15	1.380 (5)
C1—C6	1.415 (4)	C14—H14	0.9500
C2—C3	1.369 (4)	C15—C16	1.381 (5)
C2—H2	0.9500	C15—H15	0.9500
C3—H3	0.9500	C16—N5	1.348 (4)
C4—C3	1.407 (5)	C16—C17	1.502 (5)
C4—H4	0.9500	C17—H17A	0.9800
C5—C4	1.370 (5)	C17—H17B	0.9800
C5—H5	0.9500	C17—H17C	0.9800
O1—P1—N1	108.71 (14)	C1—C6—C7	119.4 (3)
O1—P1—N3	102.53 (13)	C5—C6—C7	120.9 (3)
O1—P1—N4	102.37 (12)	C6—C7—H7	119.4
N1—P1—N3	117.31 (14)	C8—C7—C6	121.3 (3)
N1—P1—N4	110.87 (14)	C8—C7—H7	119.4
N3—P1—N4	113.47 (14)	C7—C8—C9	118.2 (3)
Cl2—P2—Cl1	100.69 (5)	C7—C8—H8	120.9
N1—P2—Cl1	108.08 (11)	C9—C8—H8	120.9
N1—P2—Cl2	110.98 (11)	O1—C9—C8	114.7 (3)
N1—P2—N2	119.09 (15)	C10—C9—O1	121.0 (3)
N2—P2—Cl1	108.95 (12)	C10—C9—C8	124.2 (3)
N2—P2—Cl2	107.47 (12)	C1—C10—C11	119.5 (3)
Cl4—P3—Cl3	100.03 (5)	C9—C10—C1	117.8 (3)
N2—P3—Cl3	108.10 (12)	C9—C10—C11	122.7 (3)
N2—P3—Cl4	108.11 (11)	N4—C11—C10	115.8 (2)
N3—P3—Cl3	109.12 (11)	N4—C11—H11A	108.3
N3—P3—Cl4	109.92 (11)	N4—C11—H11B	108.3
N3—P3—N2	119.75 (14)	C10—C11—H11A	108.3
C9—O1—P1	124.78 (19)	C10—C11—H11B	108.3
P2—N1—P1	121.72 (17)	H11A—C11—H11B	107.4
P2—N2—P3	119.79 (17)	N5—C12—N4	113.8 (3)
P3—N3—P1	120.78 (17)	N5—C12—C13	123.8 (3)
C11—N4—P1	123.9 (2)	C13—C12—N4	122.4 (3)
C12—N4—P1	118.4 (2)	C12—C13—C14	117.3 (3)
C12—N4—C11	116.5 (2)	C12—C13—H13	121.3
C12—N5—C16	117.9 (3)	C14—C13—H13	121.3
C6—C1—C2	118.2 (3)	C13—C14—H14	120.2
C6—C1—C10	119.2 (3)	C15—C14—C13	119.5 (3)
C2—C1—C10	122.6 (3)	C15—C14—H14	120.2
C1—C2—H2	119.5	C14—C15—C16	119.3 (3)
C3—C2—C1	120.9 (3)	C14—C15—H15	120.4
C3—C2—H2	119.5	C16—C15—H15	120.4
C2—C3—C4	120.9 (3)	N5—C16—C15	121.9 (3)
C2—C3—H3	119.6	N5—C16—C17	116.3 (3)
C4—C3—H3	119.6	C15—C16—C17	121.8 (3)
C3—C4—H4	120.2	C16—C17—H17A	109.5
C5—C4—C3	119.6 (3)	C16—C17—H17B	109.5
C5—C4—H4	120.2	C16—C17—H17C	109.5
C4—C5—C6	120.7 (3)	H17A—C17—H17B	109.5
C4—C5—H5	119.6	H17A—C17—H17C	109.5
C6—C5—H5	119.6	H17B—C17—H17C	109.5
C1—C6—C5	119.7 (3)
N1—P1—O1—C9	−81.1 (3)	C10—C1—C2—C3	179.0 (3)
N3—P1—O1—C9	154.0 (2)	C2—C1—C6—C5	0.4 (5)
N4—P1—O1—C9	36.2 (3)	C2—C1—C6—C7	−179.9 (3)
O1—P1—N1—P2	−123.90 (19)	C10—C1—C6—C5	179.9 (3)
N3—P1—N1—P2	−8.3 (3)	C10—C1—C6—C7	−0.4 (5)
N4—P1—N1—P2	124.32 (19)	C1—C2—C3—C4	1.8 (5)
O1—P1—N3—P3	121.15 (19)	C5—C4—C3—C2	−0.9 (5)
N1—P1—N3—P3	2.2 (3)	C6—C5—C4—C3	−0.2 (5)
N4—P1—N3—P3	−129.23 (18)	C1—C6—C5—C4	0.5 (5)
O1—P1—N4—C11	−22.8 (3)	C7—C6—C5—C4	−179.2 (3)
O1—P1—N4—C12	170.1 (2)	C1—C6—C7—C8	−0.3 (5)
N1—P1—N4—C11	93.0 (3)	C5—C6—C7—C8	179.4 (3)
N1—P1—N4—C12	−74.1 (3)	C6—C7—C8—C9	1.0 (5)
N3—P1—N4—C11	−132.5 (2)	O1—C9—C8—C7	174.6 (3)
N3—P1—N4—C12	60.4 (3)	C10—C9—C8—C7	−1.0 (5)
Cl1—P2—N1—P1	128.10 (17)	C9—C10—C1—C2	179.9 (3)
Cl2—P2—N1—P1	−122.37 (17)	C9—C10—C1—C6	0.4 (4)
N2—P2—N1—P1	3.2 (3)	C11—C10—C1—C2	1.3 (5)
Cl1—P2—N2—P3	−116.35 (18)	C11—C10—C1—C6	−178.2 (3)
Cl2—P2—N2—P3	135.37 (17)	C1—C10—C9—O1	−175.1 (3)
N1—P2—N2—P3	8.2 (3)	C1—C10—C9—C8	0.3 (5)
Cl3—P3—N2—P2	111.53 (18)	C11—C10—C9—O1	3.5 (5)
Cl4—P3—N2—P2	−141.03 (17)	C11—C10—C9—C8	178.9 (3)
N3—P3—N2—P2	−14.2 (3)	N4—C11—C10—C1	−173.4 (3)
Cl3—P3—N3—P1	−116.34 (17)	N4—C11—C10—C9	8.1 (4)
Cl4—P3—N3—P1	134.90 (16)	N4—C12—N5—C16	−175.2 (3)
N2—P3—N3—P1	8.9 (3)	C13—C12—N5—C16	4.0 (5)
P1—O1—C9—C8	154.1 (2)	N4—C12—C13—C14	174.3 (3)
P1—O1—C9—C10	−30.1 (4)	N5—C12—C13—C14	−4.7 (5)
P1—N4—C11—C10	4.4 (4)	C12—C13—C14—C15	1.1 (5)
C12—N4—C11—C10	171.6 (3)	C13—C14—C15—C16	2.9 (5)
P1—N4—C12—N5	2.2 (4)	C14—C15—C16—N5	−3.8 (5)
P1—N4—C12—C13	−177.0 (2)	C14—C15—C16—C17	174.1 (4)
C11—N4—C12—N5	−165.9 (3)	C15—C16—N5—C12	0.4 (5)
C11—N4—C12—C13	15.0 (4)	C17—C16—N5—C12	−177.6 (3)
C6—C1—C2—C3	−1.5 (5)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···Cg2i	0.95	2.97	3.746 (4)	140
C7—H7···Cg3i	0.95	2.82	3.507 (3)	130

Table 1

Selected bond lengths (Å)

P1—O1	1.580 (2)
P1—N1	1.596 (3)
P1—N3	1.598 (3)
P1—N4	1.665 (3)
P2—N1	1.571 (3)
P2—N2	1.580 (3)
P3—N2	1.581 (3)
P3—N3	1.571 (3)

Table 2

Hydrogen-bond geometry (Å, °)

Cg3 is the centroid of the C8-benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7⋯Cg3i	0.95	2.82	3.507 (3)	130

Symmetry code: (i) .