4,4,6,6-Tetra­chloro-2-[(2,4-dimethyl­phen­yl)sulfan­yl]-N-[4-(2,2,4,4-tetra­chloro-1,3,5,7,11-penta­aza-2λ5,4λ5,6λ5-triphosphaspiro­[5.5]undeca-1,3,5-trien-7-yl)but­yl]-1,3,5,2λ5,4λ5,6λ5-triaza­triphosphinin-2-amine

Coles, S.J.; Davies, D.B.; Hursthouse, M.B.; İbişoğlu, H.; Kılıç, A.; Shaw, R.A.

doi:10.1107/S1600536807038962

4,4,6,6-Tetrachloro-2-[(2,4-dimethylphenyl)sulfanyl]-N-[4-(2,2,4,4-tetrachloro-1,3,5,7,11-pentaaza-2λ⁵,4λ⁵,6λ⁵-triphosphaspiro[5.5]undeca-1,3,5-trien-7-yl)butyl]-1,3,5,2λ⁵,4λ⁵,6λ⁵-triazatriphosphinin-2-amine

S. J. Coles, D. B. Davies, M. B. Hursthouse, H. İbişoğlu, A. Kılıç and R. A. Shaw

Reaction of the spermidine-bridged cyclophosphazene compound (N₃P₃Cl₅)spd(N₃P₃Cl₄) (spd = spermidine residue) with 2,4-dimethylthiophenol results in substitution of the P—Cl bond at the bridgehead >P(NHR)Cl group to give the title compound, C₁₅H₂₅C_l8N₉P₆S. An N—H

N hydrogen bond helps to establish the packing.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807038962/hb2491sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807038962/hb2491Isup2.hkl Contains datablock I

CCDC reference: 660246

checkCIF report

Key indicators

Single-crystal X-ray study
T = 120 K
Mean (C-C) = 0.006 Å
Disorder in main residue
R factor = 0.043
wR factor = 0.107
Data-to-parameter ratio = 20.7

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT222_ALERT_3_A Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       7.10 Ratio

Author Response: see _publ_section_exptl_refinement


Alert level B
PLAT220_ALERT_2_B Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.53 Ratio

Alert level C
ABSTM02_ALERT_3_C  The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
            Tmin and Tmax reported:      0.539     0.835
            Tmin(prime) and Tmax expected:      0.604     0.829
            RR(prime) =      0.887
            Please check that your absorption correction is appropriate.
PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large .............       0.88
PLAT301_ALERT_3_C Main Residue  Disorder .........................       3.00 Perc.
PLAT318_ALERT_2_C Check Hybridisation of  N6     in Main Residue .          ?
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          6
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety         C7
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety         C8
PLAT420_ALERT_2_C D-H Without Acceptor       N6     -   H6N    ...          ?
PLAT431_ALERT_2_C Short Inter HL..A Contact  Cl3    ..  S1      ..       3.51 Ang.
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......      39.50 Deg.
              C14' -C13  -C14     1.555   1.555   1.555
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......      40.80 Deg.
              C14  -C15  -C14'    1.555   1.555   1.555

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.48
           From the CIF: _reflns_number_total               7560
           Count of symmetry unique reflns         4349
           Completeness (_total/calc)            173.83%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      3211
           Fraction of Friedel pairs measured     0.738
           Are heavy atom types Z>Si present        yes

   1 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
  11 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   6 ALERT type 2 Indicator that the structure model may be wrong or deficient
   5 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check


checkCIF publication errors

Alert level A
PUBL024_ALERT_1_A The number of authors is greater than 5.
              Please specify the role of each of the co-authors
              for your paper.

Author Response: This work is the product of a large ongoing international collaboration and involves intellectual input from three different institutions.

 Coles: Corresponding author responsible for manuscript preparation and
 crystal structure refinement, etc.
 Davies & Shaw: Co-coordinators of the international collaboration and
 intellectual founders/maintainers of the project.
 Hursthouse: Director of the x-ray crystallography laboratory.
 Ibisoglu: Research student responsible for synthesis.
 Kilic: Director of synthesis laboratory.



   1 ALERT level A = Data missing that is essential or data in wrong format
   0 ALERT level G = General alerts. Data that may be required is missing

Comment top

The reaction of biogenic spermidine with cyclophosphazene, N₃P₃Cl₆, in aprotic solvents gives a spermidine-bridged cyclophosphazene compound, (N₃P₃Cl₅)spd(N₃P₃Cl₄), (spd = trifunctional spermidine residue), (Labarre et al., 1984; Guerch et al., 1984; Kılıç et al., 1991) and in protic solvents such as CHCl₃ proceeds cleanly to yield a spiro-cis-ansa spermidine derivative, 2,2,6-trichloro-1,3,5,7,11,16-hexaaza-4,6-diphosphatricyclohexadeca-2,4,6-triene (Guerch & Labarre, 1989; Cameron et al.,1989). We have investigated previously the reactions of the spiro-cis-ansa compound with primary and secondary amines, mono- and difunctional alcohols (e.g. PhNH₂, PrⁿNH₂, HNC₄H₈, HNMe₂, MeOH, and HOCH₂(CF₂)₂CH₂OH) (Beşli et al., 2004; İbişoğlu, 2007).

In this work reaction of the spermidine-bridged cyclophosphazene with 2,4-dimethylthiophenol gave a novel cyclophosphazene-thiolate derivative, (I), (Fig. 1), in which the bridgehead P—Cl bond was replaced with a thiolate group. Thus the SR reagent has attacked the PCl(NHR) group, rather than the more electrophilic PCl₂ moiety, which is an attack not on the phosphorus centre, but on the hydrogen, giving the product via a proton abstraction/chloride elimination reaction.

In the cyclophosphazene rings of (I) the P—N bond lengths are in the range 1.554 (3)–1.632 (3) Å but separate into two distinct groups for each ring; the lengths of the four P—N bonds involving the >PCl₂ moiety in both rings are in a narrow range [1.554 (3)–1.585 (3) Å] with averages of ca. 1.57(±0.01) Å compared to the two P—N bond lengths involving the >P(N)(X) moiety [X =SPh or NH(bridge)], which are in the range 1.610 (3)–1.632 (3)Å and average ca. 1.62(±0.01) Å. The increase in bond length involving the >P(N)(X) moiety depend on electron release from either the SPh or the NH(bridge) atoms to the phosphazene rings. The donation of electrons from the >P(N)(X) moiety to the phosphazene ring is also manifested by the decrease in endocyclic N—P(N)(X)—N bond angles for the two rings [X = SPh, 114.6 (2)°; X = NH(bridge), 110.7 (2)°] compared to those found for the N—P(Cl₂)-N, 119.9(±0.3)°.

The effect of the electron-donating substituents is also reflected in differences in the P···P distances across the ring, even for rings that are nominally planar. It is found that the P···P distances involving the P(N)(X) moiety are 2.781 (6)/2.791 (6) Å (X = SPh) and 2.816 (5)/2.828 (6) Å (X = NH(bridge) are significantly greater than those involving the >PCl₂ moiety, 2.71–2.72 Å.

An N—H···N hydrogen bond (Table 1) helps to establish the packing.

Related literature top

For background chemistry, see: Labarre et al. (1984); Beşli et al. (2004); Guerch et al. (1984); Kılıç et al. (1991); Cameron et al. (1989); İbişoğlu (2007); Guerch & Labarre (1989).

Experimental top

A solution of (N₃P₃Cl₅)spd(N₃P₃Cl₄) (Labarre et al., 1984, Kılıç et al. 1991) (1 g, 1.367 mmol) in 10 ml dry THF was added dropwise to a stirred solution of triethylamine (1.38 g, 13.63 mmol) in 8 ml dry THF at 195 K. Then, 2,4-dimethylthiophenol (1.88 g, 13,6 mmol) in 10 ml dry THF was added and the reaction mixture was stirred under an atmosphere of argon at room temperature for 5 days. Triethylamine hydrochloride was filtered off and the solvent removed under reduced pressure at 303 K. One product,4,4,6,6-tetrachloro-2-[(2,4-dimethylphenyl)thio]-N-[4-(2,2,4,4-tetrachloro-1,3,5,7,11-pentaaza-2λ⁵,4λ⁵,6λ⁵-triphosphaspiro[5.5]undeca-1,3,5-trien-7-yl)butyl]-1,3,5,2λ⁵,4λ⁵,6λ⁵-triazatriphosphinin-2-amine, I, was detected by TLC using dichloromethane as mobile phase [R_f = 0.49] and was separated by column chromatography on silica gel using CHCl₃ as eluant. Colourless rods of (I) were re-crystallized from dichloromethane-n-hexane (1:1 v/v) (m.p. 405–406 K, 0.74 g, yield 65%).

Elemental analysis calcd (%) for C₁₅H₂₅Cl₈N₉P₆S;C, 21.63; H, 3.03; N, 15.13%; found: C, 21.36; H, 3.31; N, 15.22%; MS (M+H)⁺,833M⁺; 832.¹H NMR at 298 K in CDCl₃: δ 2.3 (s, 3H, CH₃); δ 2.5 (s, 3H, CH₃); δ 7.45 (q, 1H, CH-6); δ 7.07 (s, 1H, CH-3); δ 6.97 (d, 1H, CH-5); δ 3.3–2.8 p.p.m. (m, 8H)(4x N—CH₂); δ 1.6–1.8 (m, 6H)(3x C—CH₂); δ 3,0 (2H, 2x NH). The proton decoupled ³¹P NMR spectrum at 298 K in CDCl₃ has two different spin A₂X spin systems: >P(Nspiro) cyclophosphazene ring; (δP(Nspiro)(P₁), 10.7 p.p.m. (triplet); δPCl₂(P₂), 22.2 p.p.m. (doublet), ²J(P1P2) 40.3 Hz: >P(SC₈H₉) cyclophosphazene ring; δP(NHSC₈H₉)(P₃), 30.7 p.p.m. (triplet); δPCl₂ (P4), 20.3 p.p.m. (doublet), ²J(P3P4) 19.3 Hz.

Structure description top

An N—H···N hydrogen bond (Table 1) helps to establish the packing.

For background chemistry, see: Labarre et al. (1984); Beşli et al. (2004); Guerch et al. (1984); Kılıç et al. (1991); Cameron et al. (1989); İbişoğlu (2007); Guerch & Labarre (1989).

Computing details top

Data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); cell refinement: DENZO and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: publCIF (Westrip, 2007).

Figures top

Fig. 1. View of (I) (50% probability displacement ellipsoids; H atoms omitted for clarity).

4,4,6,6-Tetrachloro-2-[(2,4-dimethylphenyl)sulfanyl]-N-[4-(2,2,4,4-τetrachloro-1,3,5,7,11-pentaaza-2λ⁵,4λ⁵,6λ⁵-τriphosphaspiro[5.5]undeca-1,3,5-trien-7-yl)butyl]-\1,3,5,2λ⁵,4λ⁵,6λ⁵-triazatriphosphinin-2-amine top

Crystal data top

C₁₅H₂₅Cl₈N₉P₆S	F(000) = 1680
M_r = 832.92	D_x = 1.636 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 18434 reflections
a = 8.5829 (17) Å	θ = 2.9–27.5°
b = 15.587 (3) Å	µ = 1.04 mm⁻¹
c = 25.277 (5) Å	T = 120 K
V = 3381.6 (12) Å³	Rod, colourless
Z = 4	0.48 × 0.20 × 0.18 mm

Data collection top

Nonius KappaCCD diffractometer	6007 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.082
Absorption correction: multi-scan (SORTAV; Blessing, 1997)	θ_max = 27.5°, θ_min = 3.1°
T_min = 0.539, T_max = 0.835	h = −11→11
20485 measured reflections	k = −20→20
7560 independent reflections	l = −31→32

Refinement top

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)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.107	w = 1/[σ²(F_o²) + (0.0538P)²] where P = (F_o² + 2F_c²)/3
S = 0.99	(Δ/σ)_max = 0.010
7560 reflections	Δρ_max = 0.36 e Å⁻³
366 parameters	Δρ_min = −0.38 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 3211 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.10 (7)

Crystal data top

C₁₅H₂₅Cl₈N₉P₆S	V = 3381.6 (12) Å³
M_r = 832.92	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 8.5829 (17) Å	µ = 1.04 mm⁻¹
b = 15.587 (3) Å	T = 120 K
c = 25.277 (5) Å	0.48 × 0.20 × 0.18 mm

Data collection top

Nonius KappaCCD diffractometer	7560 independent reflections
Absorption correction: multi-scan (SORTAV; Blessing, 1997)	6007 reflections with I > 2σ(I)
T_min = 0.539, T_max = 0.835	R_int = 0.082
20485 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.107	Δρ_max = 0.36 e Å⁻³
S = 0.99	Δρ_min = −0.38 e Å⁻³
7560 reflections	Absolute structure: Flack (1983), 3211 Friedel pairs
366 parameters	Absolute structure parameter: 0.10 (7)
0 restraints

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.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.7799 (5)	0.2378 (2)	0.17416 (15)	0.0340 (9)
C2	0.6726 (5)	0.2176 (3)	0.13485 (16)	0.0385 (10)
C3	0.7270 (6)	0.2077 (3)	0.08372 (18)	0.0504 (12)
H3	0.6553	0.1926	0.0566	0.061*
C4	0.8822 (7)	0.2192 (3)	0.0706 (2)	0.0563 (14)
C5	0.9872 (6)	0.2373 (3)	0.1105 (2)	0.0579 (14)
H5	1.0947	0.2436	0.1024	0.069*
C6	0.9363 (5)	0.2464 (3)	0.1628 (2)	0.0468 (11)
H6	1.0088	0.2584	0.1903	0.056*
C7	0.5021 (6)	0.2092 (3)	0.1452 (2)	0.0607 (14)
H7A	0.4483	0.1949	0.1122	0.091*
H7B	0.4618	0.2636	0.1590	0.091*
H7C	0.4844	0.1637	0.1713	0.091*
C8	0.9353 (9)	0.2165 (3)	0.0138 (2)	0.095 (3)
H8A	1.0482	0.2254	0.0122	0.142*
H8B	0.8826	0.2619	−0.0063	0.142*
H8C	0.9094	0.1606	−0.0016	0.142*
C9	0.5008 (4)	0.1678 (3)	0.33785 (15)	0.0372 (9)
H9A	0.4487	0.1147	0.3502	0.045*
H9B	0.4545	0.1838	0.3034	0.045*
C10	0.4714 (4)	0.2383 (3)	0.37703 (14)	0.0333 (9)
H10A	0.3609	0.2560	0.3744	0.040*
H10B	0.5363	0.2884	0.3673	0.040*
C11	0.5061 (4)	0.2141 (2)	0.43411 (14)	0.0271 (8)
H11A	0.4547	0.1589	0.4425	0.032*
H11B	0.6198	0.2063	0.4385	0.032*
C12	0.4492 (4)	0.2824 (2)	0.47241 (14)	0.0270 (8)
H12A	0.4948	0.3384	0.4623	0.032*
H12B	0.3345	0.2874	0.4695	0.032*
C13	0.4204 (4)	0.1851 (2)	0.54963 (15)	0.0310 (8)
H13A	0.3142	0.1804	0.5346	0.037*
H13B	0.4809	0.1358	0.5360	0.037*
C14'	0.4070 (17)	0.1747 (8)	0.6071 (5)	0.034 (4)	0.341 (13)
H14A	0.3043	0.1973	0.6182	0.041*	0.341 (13)
H14B	0.4080	0.1125	0.6151	0.041*	0.341 (13)
C14	0.5145 (9)	0.1547 (4)	0.5968 (2)	0.033 (2)	0.659 (13)
H14C	0.4664	0.1016	0.6108	0.039*	0.659 (13)
H14D	0.6209	0.1400	0.5846	0.039*	0.659 (13)
C15	0.5264 (5)	0.2159 (3)	0.63906 (18)	0.0445 (10)
H15A	0.6221	0.1805	0.6376	0.053*
H15B	0.4908	0.2169	0.6763	0.053*
N1	0.9248 (3)	0.11118 (19)	0.28052 (12)	0.0283 (7)
N2	0.9007 (4)	−0.0284 (2)	0.21604 (15)	0.0443 (9)
N3	0.6461 (3)	0.0696 (2)	0.23679 (12)	0.0312 (7)
N4	0.6684 (4)	0.1507 (2)	0.33068 (12)	0.0295 (7)
N5	0.4910 (3)	0.26331 (18)	0.52811 (11)	0.0277 (7)
N6	0.5661 (4)	0.3034 (2)	0.62336 (12)	0.0308 (7)
H6N	0.6196	0.3349	0.6458	0.037*
N7	0.6552 (3)	0.40436 (18)	0.54310 (13)	0.0315 (7)
N8	0.4825 (4)	0.54976 (18)	0.53518 (15)	0.0393 (8)
N9	0.3597 (3)	0.40272 (18)	0.57517 (13)	0.0291 (7)
P1	0.74388 (10)	0.13582 (6)	0.27261 (4)	0.0250 (2)
P2	1.00284 (12)	0.03262 (6)	0.25224 (4)	0.0326 (2)
P3	0.72065 (12)	−0.01195 (6)	0.21149 (4)	0.0334 (2)
P4	0.51752 (10)	0.34622 (5)	0.56690 (4)	0.0243 (2)
P5	0.64364 (10)	0.50149 (6)	0.52941 (4)	0.0304 (2)
P6	0.33674 (10)	0.49668 (6)	0.55497 (4)	0.0271 (2)
S1	0.72088 (12)	0.25711 (6)	0.24069 (4)	0.0352 (2)
Cl1	1.11015 (15)	−0.03697 (8)	0.30779 (5)	0.0569 (3)
Cl2	1.18636 (13)	0.07085 (8)	0.20992 (6)	0.0611 (3)
Cl3	0.61143 (17)	−0.11661 (8)	0.23825 (5)	0.0639 (4)
Cl4	0.66310 (15)	−0.01667 (7)	0.13493 (4)	0.0517 (3)
Cl5	0.80436 (11)	0.56671 (7)	0.56962 (5)	0.0464 (3)
Cl6	0.71814 (13)	0.52044 (7)	0.45493 (4)	0.0490 (3)
Cl7	0.17627 (11)	0.49868 (6)	0.49709 (4)	0.0395 (2)
Cl8	0.22764 (12)	0.56464 (6)	0.61084 (4)	0.0415 (2)
H4N	0.722 (4)	0.129 (2)	0.3513 (16)	0.020 (10)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.051 (2)	0.0225 (19)	0.028 (2)	0.0072 (16)	0.0079 (18)	0.0050 (16)
C2	0.055 (3)	0.032 (2)	0.029 (2)	0.0059 (18)	0.0015 (19)	0.0086 (17)
C3	0.090 (4)	0.032 (2)	0.029 (2)	0.008 (2)	−0.001 (2)	0.0071 (18)
C4	0.103 (4)	0.021 (2)	0.045 (3)	−0.003 (2)	0.029 (3)	0.009 (2)
C5	0.068 (3)	0.034 (3)	0.071 (4)	−0.005 (2)	0.037 (3)	0.005 (2)
C6	0.053 (3)	0.030 (2)	0.057 (3)	−0.0063 (19)	0.007 (2)	0.003 (2)
C7	0.054 (3)	0.076 (4)	0.051 (3)	0.015 (3)	−0.010 (3)	0.004 (3)
C8	0.188 (7)	0.038 (3)	0.058 (4)	0.003 (4)	0.064 (5)	0.004 (3)
C9	0.027 (2)	0.059 (3)	0.026 (2)	−0.0028 (18)	0.0038 (16)	−0.0086 (19)
C10	0.032 (2)	0.042 (2)	0.025 (2)	0.0060 (16)	0.0009 (15)	−0.0065 (17)
C11	0.0256 (17)	0.0287 (19)	0.027 (2)	−0.0005 (14)	0.0036 (15)	0.0010 (16)
C12	0.0308 (18)	0.029 (2)	0.0209 (19)	0.0035 (14)	−0.0021 (14)	0.0002 (15)
C13	0.036 (2)	0.0249 (19)	0.032 (2)	−0.0008 (15)	0.0017 (16)	0.0012 (16)
C14'	0.044 (10)	0.034 (7)	0.025 (6)	−0.002 (5)	0.008 (5)	−0.003 (5)
C14	0.039 (5)	0.031 (3)	0.028 (3)	0.001 (3)	0.008 (3)	0.004 (3)
C15	0.066 (3)	0.034 (2)	0.034 (2)	−0.006 (2)	−0.011 (2)	0.0093 (19)
N1	0.0297 (15)	0.0263 (16)	0.0288 (17)	0.0001 (12)	−0.0021 (13)	−0.0043 (14)
N2	0.050 (2)	0.038 (2)	0.045 (2)	0.0053 (15)	−0.0034 (17)	−0.0168 (17)
N3	0.0316 (15)	0.0353 (18)	0.0270 (17)	−0.0037 (13)	0.0000 (13)	−0.0064 (14)
N4	0.0309 (17)	0.040 (2)	0.0173 (17)	0.0083 (14)	−0.0009 (13)	−0.0024 (14)
N5	0.0423 (17)	0.0206 (15)	0.0203 (16)	0.0012 (13)	0.0018 (13)	0.0011 (12)
N6	0.0408 (18)	0.0281 (17)	0.0237 (17)	−0.0022 (13)	−0.0059 (14)	−0.0020 (13)
N7	0.0306 (16)	0.0215 (15)	0.043 (2)	0.0029 (12)	0.0067 (14)	0.0004 (14)
N8	0.0343 (17)	0.0204 (16)	0.063 (2)	0.0056 (13)	0.0067 (16)	0.0076 (16)
N9	0.0302 (15)	0.0226 (16)	0.0347 (19)	0.0032 (12)	0.0022 (13)	0.0042 (14)
P1	0.0293 (5)	0.0253 (5)	0.0203 (5)	−0.0001 (3)	0.0018 (3)	−0.0038 (4)
P2	0.0363 (5)	0.0306 (5)	0.0308 (5)	0.0054 (4)	0.0038 (4)	−0.0049 (4)
P3	0.0471 (6)	0.0279 (5)	0.0253 (5)	−0.0067 (4)	0.0005 (4)	−0.0061 (4)
P4	0.0282 (4)	0.0207 (4)	0.0238 (5)	0.0015 (3)	0.0015 (4)	−0.0011 (4)
P5	0.0289 (5)	0.0238 (5)	0.0386 (6)	−0.0009 (4)	0.0064 (4)	0.0009 (4)
P6	0.0277 (4)	0.0225 (5)	0.0310 (5)	0.0028 (4)	0.0011 (4)	−0.0005 (4)
S1	0.0508 (5)	0.0262 (5)	0.0285 (5)	0.0066 (4)	0.0029 (4)	−0.0005 (4)
Cl1	0.0682 (8)	0.0498 (7)	0.0527 (7)	0.0245 (6)	−0.0079 (6)	0.0022 (6)
Cl2	0.0467 (6)	0.0669 (8)	0.0695 (9)	0.0057 (6)	0.0270 (6)	−0.0005 (7)
Cl3	0.0988 (10)	0.0427 (7)	0.0501 (8)	−0.0335 (6)	0.0029 (7)	−0.0012 (6)
Cl4	0.0788 (8)	0.0493 (7)	0.0268 (5)	0.0018 (6)	−0.0056 (5)	−0.0129 (5)
Cl5	0.0415 (5)	0.0398 (6)	0.0578 (7)	−0.0148 (4)	0.0028 (5)	−0.0044 (5)
Cl6	0.0599 (6)	0.0455 (6)	0.0416 (6)	0.0046 (5)	0.0146 (5)	0.0103 (5)
Cl7	0.0442 (5)	0.0385 (6)	0.0358 (5)	0.0040 (4)	−0.0094 (4)	0.0021 (5)
Cl8	0.0455 (6)	0.0374 (5)	0.0415 (6)	0.0103 (4)	0.0030 (4)	−0.0115 (5)

Geometric parameters (Å, º) top

C1—C2	1.391 (6)	C14'—C15	1.456 (13)
C1—C6	1.379 (6)	C14'—H14A	0.9900
C1—S1	1.782 (4)	C14'—H14B	0.9900
C2—C3	1.383 (6)	C14—C15	1.436 (7)
C2—C7	1.493 (7)	C14—H14C	0.9900
C3—C4	1.385 (8)	C14—H14D	0.9900
C3—H3	0.9500	C15—N6	1.460 (5)
C4—C5	1.381 (8)	C15—H15A	0.9900
C4—C8	1.508 (7)	C15—H15B	0.9900
C5—C6	1.401 (7)	N1—P2	1.568 (3)
C5—H5	0.9500	N1—P1	1.612 (3)
C6—H6	0.9500	N2—P3	1.571 (4)
C7—H7A	0.9800	N2—P2	1.585 (4)
C7—H7B	0.9800	N3—P3	1.561 (3)
C7—H7C	0.9800	N3—P1	1.609 (3)
C8—H8A	0.9800	N4—P1	1.621 (3)
C8—H8B	0.9800	N4—H4N	0.78 (4)
C8—H8C	0.9800	N5—P4	1.638 (3)
C9—N4	1.475 (5)	N6—P4	1.630 (3)
C9—C10	1.501 (5)	N6—H6N	0.8800
C9—H9A	0.9900	N7—P5	1.556 (3)
C9—H9B	0.9900	N7—P4	1.606 (3)
C10—C11	1.521 (5)	N8—P5	1.581 (3)
C10—H10A	0.9900	N8—P6	1.581 (3)
C10—H10B	0.9900	N9—P6	1.564 (3)
C11—C12	1.520 (5)	N9—P4	1.629 (3)
C11—H11A	0.9900	P1—S1	2.0651 (13)
C11—H11B	0.9900	P2—Cl2	1.9950 (15)
C12—N5	1.483 (4)	P2—Cl1	1.9991 (16)
C12—H12A	0.9900	P3—Cl4	1.9986 (15)
C12—H12B	0.9900	P3—Cl3	1.9995 (15)
C13—N5	1.466 (5)	P5—Cl5	1.9924 (14)
C13—C14'	1.466 (12)	P5—Cl6	2.0100 (15)
C13—C14	1.516 (7)	P6—Cl8	1.9984 (13)
C13—H13A	0.9900	P6—Cl7	2.0097 (13)
C13—H13B	0.9900

C2—C1—C6	121.2 (4)	H14A—C14'—H14B	107.3
C2—C1—S1	121.6 (3)	C15—C14—C13	114.6 (5)
C6—C1—S1	117.1 (4)	C15—C14—H14C	108.6
C3—C2—C1	118.1 (4)	C13—C14—H14C	108.6
C3—C2—C7	119.0 (5)	C15—C14—H14D	108.6
C1—C2—C7	122.9 (4)	C13—C14—H14D	108.6
C2—C3—C4	122.3 (5)	H14C—C14—H14D	107.6
C2—C3—H3	118.9	C14—C15—N6	115.7 (4)
C4—C3—H3	118.9	C14—C15—C14'	40.8 (5)
C5—C4—C3	118.6 (5)	N6—C15—C14'	115.2 (6)
C5—C4—C8	120.3 (6)	C14—C15—H15A	70.0
C3—C4—C8	121.0 (6)	N6—C15—H15A	108.5
C4—C5—C6	120.5 (5)	C14'—C15—H15A	108.5
C4—C5—H5	119.8	C14—C15—H15B	134.0
C6—C5—H5	119.8	N6—C15—H15B	108.5
C1—C6—C5	119.3 (5)	C14'—C15—H15B	108.5
C1—C6—H6	120.3	H15A—C15—H15B	107.5
C5—C6—H6	120.3	P2—N1—P1	122.7 (2)
C2—C7—H7A	109.5	P3—N2—P2	119.2 (2)
C2—C7—H7B	109.5	P3—N3—P1	122.6 (2)
H7A—C7—H7B	109.5	C9—N4—P1	121.8 (3)
C2—C7—H7C	109.5	C9—N4—H4N	125 (3)
H7A—C7—H7C	109.5	P1—N4—H4N	108 (3)
H7B—C7—H7C	109.5	C13—N5—C12	114.8 (3)
C4—C8—H8A	109.5	C13—N5—P4	119.4 (2)
C4—C8—H8B	109.5	C12—N5—P4	116.3 (2)
H8A—C8—H8B	109.5	C15—N6—P4	124.2 (3)
C4—C8—H8C	109.5	C15—N6—H6N	117.9
H8A—C8—H8C	109.5	P4—N6—H6N	117.9
H8B—C8—H8C	109.5	P5—N7—P4	125.84 (18)
N4—C9—C10	112.1 (3)	P5—N8—P6	118.17 (19)
N4—C9—H9A	109.2	P6—N9—P4	124.70 (19)
C10—C9—H9A	109.2	N3—P1—N1	114.83 (16)
N4—C9—H9B	109.2	N3—P1—N4	113.10 (17)
C10—C9—H9B	109.2	N1—P1—N4	107.87 (18)
H9A—C9—H9B	107.9	N3—P1—S1	108.49 (13)
C9—C10—C11	114.3 (3)	N1—P1—S1	111.01 (12)
C9—C10—H10A	108.7	N4—P1—S1	100.64 (13)
C11—C10—H10A	108.7	N1—P2—N2	119.74 (18)
C9—C10—H10B	108.7	N1—P2—Cl2	110.37 (13)
C11—C10—H10B	108.7	N2—P2—Cl2	107.86 (16)
H10A—C10—H10B	107.6	N1—P2—Cl1	107.48 (13)
C12—C11—C10	111.6 (3)	N2—P2—Cl1	109.54 (15)
C12—C11—H11A	109.3	Cl2—P2—Cl1	100.08 (7)
C10—C11—H11A	109.3	N3—P3—N2	120.47 (18)
C12—C11—H11B	109.3	N3—P3—Cl4	108.99 (13)
C10—C11—H11B	109.3	N2—P3—Cl4	107.95 (15)
H11A—C11—H11B	108.0	N3—P3—Cl3	109.50 (13)
N5—C12—C11	112.7 (3)	N2—P3—Cl3	107.62 (16)
N5—C12—H12A	109.0	Cl4—P3—Cl3	100.47 (7)
C11—C12—H12A	109.0	N7—P4—N9	110.77 (15)
N5—C12—H12B	109.0	N7—P4—N6	111.80 (17)
C11—C12—H12B	109.0	N9—P4—N6	108.77 (17)
H12A—C12—H12B	107.8	N7—P4—N5	108.85 (16)
N5—C13—C14'	119.5 (6)	N9—P4—N5	112.82 (16)
N5—C13—C14	109.3 (4)	N6—P4—N5	103.67 (15)
C14'—C13—C14	39.5 (5)	N7—P5—N8	119.88 (16)
N5—C13—H13A	107.4	N7—P5—Cl5	109.82 (13)
C14'—C13—H13A	107.4	N8—P5—Cl5	108.40 (14)
C14—C13—H13A	140.0	N7—P5—Cl6	109.32 (13)
N5—C13—H13B	107.4	N8—P5—Cl6	107.14 (15)
C14'—C13—H13B	107.4	Cl5—P5—Cl6	100.52 (6)
C14—C13—H13B	76.0	N9—P6—N8	119.59 (15)
H13A—C13—H13B	107.0	N9—P6—Cl8	108.95 (13)
C15—C14'—C13	116.5 (9)	N8—P6—Cl8	108.47 (14)
C15—C14'—H14A	108.2	N9—P6—Cl7	109.80 (13)
C13—C14'—H14A	108.2	N8—P6—Cl7	107.69 (15)
C15—C14'—H14B	108.2	Cl8—P6—Cl7	100.67 (6)
C13—C14'—H14B	108.2	C1—S1—P1	100.74 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4N···N9ⁱ	0.77 (4)	2.26 (4)	3.009 (4)	164 (3)

Symmetry code: (i) x+1/2, −y+1/2, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₅H₂₅Cl₈N₉P₆S
M_r	832.92
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	120
a, b, c (Å)	8.5829 (17), 15.587 (3), 25.277 (5)
V (Å³)	3381.6 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.04
Crystal size (mm)	0.48 × 0.20 × 0.18

Data collection
Diffractometer	Nonius KappaCCD
Absorption correction	Multi-scan (SORTAV; Blessing, 1997)
T_min, T_max	0.539, 0.835
No. of measured, independent and observed [I > 2σ(I)] reflections	20485, 7560, 6007
R_int	0.082
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.107, 0.99
No. of reflections	7560
No. of parameters	366
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.38
Absolute structure	Flack (1983), 3211 Friedel pairs
Absolute structure parameter	0.10 (7)

Computer programs: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), DENZO and COLLECT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), publCIF (Westrip, 2007).