Diethyl {2-[(4-chloro­phen­oxy)meth­yl]-9-(methyl­sulfanyl)-7H-pyrazolo[4,3-d][1,2,4]-triazolo[1,5-d]pyrimidin-7-yl}(phen­yl)methyl­phospho­nate

Xiao, L.-X.; Shi, D.-Q.

doi:10.1107/S1600536807035532

Diethyl {2-[(4-chlorophenoxy)methyl]-9-(methylsulfanyl)-7H-pyrazolo[4,3-d][1,2,4]-triazolo[1,5-d]pyrimidin-7-yl}(phenyl)methylphosphonate

In the title compound, C₂₅H₂₆ClN₆O₄PS, the fused pyrazolotriazolopyrimidine ring system is almost planar. It makes dihedral angles of 78.1 (1) and 17.1 (1)°, respectively, with the attached phenyl ring and 4-chlorophenoxymethyl fragment. The P atom has a distorted tetrahedral configuration. Intra- and intermolecular C—H

O and C—H

N hydrogen bonds, together with strong π–π stacking interactions (interplanar distances 3.312–3.567 Å), stabilize the structure.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807035532/cf2126sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807035532/cf2126Isup2.hkl Contains datablock I

CCDC reference: 657849

checkCIF report

Key indicators

Single-crystal X-ray study
T = 294 K
Mean (C-C) = 0.005 Å
R factor = 0.059
wR factor = 0.150
Data-to-parameter ratio = 15.9

checkCIF/PLATON results

No syntax errors found



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

Alert level C
RINTA01_ALERT_3_C  The value of Rint is greater than 0.10
            Rint given   0.108
PLAT020_ALERT_3_C The value of Rint is greater than 0.10 .........       0.11
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.84 Ratio
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         O1
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C16
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          5

Alert level G
PLAT793_ALERT_1_G Check the Absolute Configuration of C15    = ...          R

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

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

Comment top

Pyrazolotriazolopyrimidine derivatives have been reported to retain high affinity for adenosine receptors (Gatta et al., 1993). A series of pyrazolo[4,3-e]-1,2,4-triazolo[1,5-c]-pyrimidines has been synthesized with the aim of finding potent and selective adenosine A2A antagonists (Baraldi et al., 1996, 1998). Organic phosphorus compounds play an important role in pesticidal science because of their significant biological properties. The title compound, (I), has been prepared as part of our work in the search for novel biologically active heterocyclic compounds. We report here the crystal structure of (I). In the molecule of (I) (Fig. 1), the pyrazolotriazolopyrimidine ring system is almost planar, with a maximum deviation of 0.023 (2) Å, for N2, forming a fully delocalized system. The dihedral angles between the pyrimidine and the triazole and pyrazole rings are 1.31 (1) and 1.1 (1)°, respectively. In the pyrazolotriazolopyrimidine ring system, the the C—N bonds are significantly shorter than a normal single C—N bond (1.47 Å; Sasada, 1984) and close to the value for a C=N bond (1.28 Å; Wang et al., 1998). This indicates significant electron delocalization in the pyrazolotriazolopyrimidine system. The O2—P1—O4, O2—P1—O3 and O2—P1—C15 bond angles are larger than the O4—P1—O3, O4—P1—C15 and O3—P1—C15 bond angles, indicating a distorted tetrahedral configuration for the phosphorus atom.

Intra- and intermolecular C—H···O and C—H···N hydrogen bonds contribute strongly to the stability of the crystal structure (Fig. 2 and Table 1). Strong π—π stacking interactions also occur between C1—C6 and N1—N3/C8/C9, N5/N6/C10/C11/C13, N3/N4/C9—C12 rings of neighboring molecules. Centroid-centroid distances are 3.990 (2), 3.909 (2) and 3.509 (2) Å, dihedral angles are 7.76, 7.35 and 8.26°, and shortest interplanar distances are 3.312, 3.567 and 3.439 Å, respectively.

Related literature top

Many derivatives of pyrazolotriazolopyrimidines have been prepared, and their biological and pharmaceutical activities have been studied by Gatta et al. (1993) and Baraldi et al. (1996, 1998). For bond-length comparisons, see Sasada (1984) and Wang et al. (1998).

Experimental top

A solution of ethyl N-4-cyano-1-((diethoxyphosphoryl)(phenyl)methyl)- 3-(methylthio)-1H-pyrazol-5-ylformimidate (0.87 g, 2 mmol) and 2-(4-chlorophenoxy)acetohydrazide (0.41 g, 2 mmol) in ethylene glycol monomethyl ether (20 ml) was refluxed for 4 h, cooled briefly and evaporated. The residue was purified by chromatography on a silica gel column by eluting with petroleum ether/acetone (6:1, v/v) to give the title compound (yield 61%). Colorless crystals of (I) suitable for X-ray structure analysis were grown from petroleum ether and acetone (6:1, v/v).

Structure description top

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Figures top

	Fig. 1. View of the molecular structure of (I), showing the atom labelling scheme and displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. A partial view of the crystal packing of (I), showing the formation of C—H···O and C—H···N hydrogen bonds and π—π stacking interactions, as dashed lines. H atoms not involved in hydrogen bonding have been omitted.

Diethyl {2-[(4-chlorophenoxy)methyl]-9-(methylsulfanyl)-7H-pyrazolo[4,3-d][1,2,4]triazolo[1,5-d]pyrimidin-7-yl}(phenyl)methylphosphonate top

Crystal data top

C₂₅H₂₆ClN₆O₄PS	F(000) = 1192
M_r = 573.00	D_x = 1.360 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.8732 (12) Å	Cell parameters from 4496 reflections
b = 13.5760 (11) Å	θ = 2.2–21.0°
c = 16.2034 (14) Å	µ = 0.31 mm⁻¹
β = 113.515 (2)°	T = 294 K
V = 2798.4 (4) Å³	Plate, colorless
Z = 4	0.20 × 0.20 × 0.10 mm

Data collection top

Bruker SMART CCD diffractometer	5485 independent reflections
Radiation source: fine-focus sealed tube	3386 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.108
φ and ω scans	θ_max = 26.0°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −17→17
T_min = 0.941, T_max = 0.970	k = −15→16
26250 measured reflections	l = −19→19

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.150	H-atom parameters constrained
S = 0.94	w = 1/[σ²(F_o²) + (0.0775P)²] where P = (F_o² + 2F_c²)/3
5485 reflections	(Δ/σ)_max < 0.001
346 parameters	Δρ_max = 0.51 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₂₅H₂₆ClN₆O₄PS	V = 2798.4 (4) Å³
M_r = 573.00	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.8732 (12) Å	µ = 0.31 mm⁻¹
b = 13.5760 (11) Å	T = 294 K
c = 16.2034 (14) Å	0.20 × 0.20 × 0.10 mm
β = 113.515 (2)°

Data collection top

Bruker SMART CCD diffractometer	5485 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	3386 reflections with I > 2σ(I)
T_min = 0.941, T_max = 0.970	R_int = 0.108
26250 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.059	0 restraints
wR(F²) = 0.150	H-atom parameters constrained
S = 0.94	Δρ_max = 0.51 e Å⁻³
5485 reflections	Δρ_min = −0.27 e Å⁻³
346 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
C1	−0.1149 (2)	0.5777 (2)	0.75100 (19)	0.0508 (7)
C2	−0.0868 (2)	0.5265 (2)	0.6910 (2)	0.0557 (8)
H2	−0.0980	0.4589	0.6843	0.067*
C3	−0.0417 (2)	0.57556 (19)	0.64043 (19)	0.0508 (7)
H3	−0.0210	0.5412	0.6006	0.061*
C4	−0.0279 (2)	0.6763 (2)	0.64991 (18)	0.0451 (7)
C5	−0.0550 (2)	0.72648 (19)	0.71144 (19)	0.0518 (7)
H5	−0.0433	0.7940	0.7189	0.062*
C6	−0.0990 (2)	0.6773 (2)	0.7617 (2)	0.0522 (7)
H6	−0.1180	0.7113	0.8028	0.063*
C7	0.0502 (2)	0.68771 (19)	0.5432 (2)	0.0487 (7)
H7A	−0.0041	0.6472	0.5000	0.058*
H7B	0.1097	0.6460	0.5769	0.058*
C8	0.08293 (19)	0.76692 (19)	0.49599 (18)	0.0408 (6)
C9	0.15006 (18)	0.83186 (18)	0.41392 (17)	0.0383 (6)
C10	0.19804 (18)	0.86846 (17)	0.35807 (17)	0.0372 (6)
C11	0.19344 (18)	0.96985 (18)	0.34508 (17)	0.0379 (6)
C12	0.1020 (2)	1.00255 (18)	0.42829 (19)	0.0456 (7)
H12	0.0675	1.0450	0.4526	0.055*
C13	0.2525 (2)	0.83244 (19)	0.30701 (18)	0.0441 (7)
C14	0.3413 (3)	0.7131 (3)	0.2211 (3)	0.0995 (14)
H14A	0.2925	0.7369	0.1639	0.149*
H14B	0.3643	0.6482	0.2140	0.149*
H14C	0.4008	0.7565	0.2441	0.149*
C15	0.2671 (2)	1.08765 (18)	0.26658 (18)	0.0421 (6)
H15	0.2141	1.1318	0.2722	0.051*
C16	0.3721 (2)	1.1259 (2)	0.33355 (19)	0.0453 (7)
C17	0.4588 (3)	1.0674 (2)	0.3706 (2)	0.0709 (10)
H17	0.4548	1.0014	0.3543	0.085*
C18	0.5531 (3)	1.1053 (3)	0.4323 (3)	0.0866 (12)
H18	0.6115	1.0645	0.4573	0.104*
C19	0.5600 (3)	1.2017 (3)	0.4563 (2)	0.0765 (10)
H19	0.6231	1.2273	0.4973	0.092*
C20	0.4743 (3)	1.2605 (3)	0.4199 (3)	0.0808 (11)
H20	0.4788	1.3266	0.4362	0.097*
C21	0.3804 (2)	1.2231 (2)	0.3590 (2)	0.0699 (10)
H21	0.3220	1.2640	0.3350	0.084*
C22	0.3442 (4)	0.9654 (3)	0.0871 (3)	0.0991 (14)
H22A	0.2788	0.9305	0.0742	0.119*
H22B	0.4015	0.9218	0.1218	0.119*
C23	0.3527 (4)	0.9898 (3)	0.0029 (3)	0.1031 (14)
H23A	0.2944	1.0306	−0.0328	0.155*
H23B	0.3520	0.9303	−0.0294	0.155*
H23C	0.4172	1.0246	0.0154	0.155*
C24	0.2595 (3)	1.2565 (3)	0.0636 (2)	0.0849 (11)
H24A	0.1950	1.2935	0.0339	0.102*
H24B	0.2643	1.2079	0.0214	0.102*
C25	0.3491 (4)	1.3229 (4)	0.0895 (3)	0.1304 (18)
H25A	0.3501	1.3646	0.1377	0.196*
H25B	0.3434	1.3628	0.0388	0.196*
H25C	0.4129	1.2853	0.1091	0.196*
Cl1	−0.17098 (9)	0.51602 (7)	0.81553 (7)	0.0888 (4)
N1	0.13835 (16)	0.74467 (15)	0.44512 (15)	0.0419 (5)
N2	0.05817 (17)	0.86038 (15)	0.49857 (15)	0.0461 (6)
N3	0.10306 (16)	0.90381 (14)	0.44590 (14)	0.0401 (5)
N4	0.14721 (16)	1.03871 (15)	0.37903 (15)	0.0430 (5)
N5	0.24196 (17)	0.99000 (14)	0.28979 (15)	0.0423 (5)
N6	0.28024 (17)	0.90563 (15)	0.26614 (16)	0.0482 (6)
O1	0.01191 (16)	0.73385 (14)	0.60181 (14)	0.0632 (6)
O2	0.14870 (16)	1.04858 (16)	0.08870 (14)	0.0684 (6)
O3	0.25682 (18)	1.20711 (13)	0.14157 (14)	0.0650 (6)
O4	0.34735 (17)	1.05220 (16)	0.13979 (15)	0.0686 (6)
P1	0.24715 (6)	1.09311 (5)	0.14878 (5)	0.0484 (2)
S1	0.27892 (8)	0.70881 (5)	0.29756 (6)	0.0705 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0521 (17)	0.0527 (19)	0.0503 (18)	−0.0048 (14)	0.0232 (15)	0.0076 (15)
C2	0.072 (2)	0.0378 (16)	0.061 (2)	−0.0079 (14)	0.0303 (18)	0.0005 (15)
C3	0.0659 (18)	0.0376 (16)	0.0561 (19)	−0.0010 (14)	0.0318 (16)	−0.0004 (14)
C4	0.0496 (16)	0.0401 (16)	0.0487 (18)	0.0053 (13)	0.0228 (14)	0.0107 (13)
C5	0.0699 (19)	0.0324 (15)	0.059 (2)	0.0051 (14)	0.0320 (17)	0.0057 (14)
C6	0.0608 (18)	0.0460 (18)	0.0562 (19)	0.0099 (14)	0.0300 (16)	0.0065 (14)
C7	0.0570 (17)	0.0395 (16)	0.0583 (19)	0.0033 (13)	0.0324 (16)	0.0073 (14)
C8	0.0436 (15)	0.0338 (15)	0.0470 (17)	0.0005 (12)	0.0202 (14)	0.0035 (12)
C9	0.0370 (14)	0.0326 (14)	0.0433 (16)	0.0013 (11)	0.0138 (13)	−0.0004 (12)
C10	0.0395 (14)	0.0273 (14)	0.0450 (16)	−0.0008 (11)	0.0173 (13)	−0.0014 (12)
C11	0.0382 (14)	0.0340 (14)	0.0405 (16)	−0.0038 (11)	0.0146 (13)	0.0010 (12)
C12	0.0528 (16)	0.0316 (15)	0.0586 (19)	0.0044 (12)	0.0286 (15)	0.0002 (13)
C13	0.0521 (16)	0.0343 (15)	0.0495 (17)	−0.0034 (13)	0.0241 (14)	−0.0005 (13)
C14	0.145 (4)	0.067 (2)	0.135 (4)	0.019 (2)	0.108 (3)	0.003 (2)
C15	0.0487 (15)	0.0297 (14)	0.0545 (18)	−0.0009 (12)	0.0275 (14)	0.0027 (13)
C16	0.0493 (16)	0.0399 (16)	0.0519 (18)	−0.0064 (13)	0.0258 (15)	0.0022 (14)
C17	0.065 (2)	0.0445 (19)	0.089 (3)	0.0003 (16)	0.015 (2)	0.0056 (18)
C18	0.060 (2)	0.069 (3)	0.102 (3)	0.0019 (19)	0.003 (2)	0.010 (2)
C19	0.062 (2)	0.081 (3)	0.074 (3)	−0.017 (2)	0.013 (2)	−0.008 (2)
C20	0.065 (2)	0.060 (2)	0.108 (3)	−0.0165 (19)	0.025 (2)	−0.030 (2)
C21	0.058 (2)	0.050 (2)	0.098 (3)	−0.0006 (16)	0.026 (2)	−0.0136 (19)
C22	0.149 (4)	0.060 (2)	0.138 (4)	0.013 (2)	0.109 (3)	0.000 (2)
C23	0.131 (4)	0.100 (3)	0.089 (3)	0.027 (3)	0.055 (3)	−0.007 (2)
C24	0.128 (3)	0.061 (2)	0.073 (3)	−0.011 (2)	0.048 (2)	0.0154 (19)
C25	0.153 (4)	0.118 (4)	0.149 (5)	−0.041 (3)	0.090 (4)	0.015 (3)
Cl1	0.1260 (8)	0.0782 (7)	0.0883 (7)	−0.0364 (6)	0.0703 (7)	−0.0041 (5)
N1	0.0457 (12)	0.0331 (12)	0.0509 (14)	0.0003 (10)	0.0234 (11)	0.0048 (10)
N2	0.0529 (13)	0.0383 (14)	0.0559 (15)	−0.0023 (11)	0.0311 (12)	0.0022 (11)
N3	0.0461 (12)	0.0306 (12)	0.0495 (14)	0.0009 (10)	0.0252 (11)	0.0011 (10)
N4	0.0484 (13)	0.0332 (12)	0.0528 (15)	0.0003 (10)	0.0260 (12)	0.0005 (11)
N5	0.0503 (13)	0.0312 (12)	0.0526 (15)	−0.0011 (10)	0.0281 (12)	0.0025 (10)
N6	0.0592 (14)	0.0358 (13)	0.0593 (16)	0.0009 (11)	0.0338 (13)	−0.0003 (11)
O1	0.0972 (16)	0.0402 (12)	0.0766 (15)	−0.0045 (11)	0.0603 (14)	0.0021 (10)
O2	0.0690 (14)	0.0707 (15)	0.0536 (13)	−0.0144 (12)	0.0119 (12)	0.0025 (11)
O3	0.1016 (16)	0.0395 (12)	0.0639 (14)	−0.0030 (11)	0.0434 (13)	0.0087 (10)
O4	0.0833 (15)	0.0649 (14)	0.0787 (16)	0.0024 (11)	0.0547 (13)	−0.0039 (12)
P1	0.0607 (5)	0.0382 (4)	0.0514 (5)	−0.0034 (4)	0.0277 (4)	0.0035 (4)
S1	0.1130 (7)	0.0354 (4)	0.0902 (7)	0.0041 (4)	0.0692 (6)	−0.0014 (4)

Geometric parameters (Å, º) top

C1—C6	1.370 (4)	C15—N5	1.458 (3)
C1—C2	1.372 (4)	C15—C16	1.519 (4)
C1—Cl1	1.745 (3)	C15—P1	1.818 (3)
C2—C3	1.384 (4)	C15—H15	0.980
C2—H2	0.930	C16—C17	1.364 (4)
C3—C4	1.381 (4)	C16—C21	1.373 (4)
C3—H3	0.930	C17—C18	1.389 (4)
C4—O1	1.366 (3)	C17—H17	0.930
C4—C5	1.377 (4)	C18—C19	1.358 (5)
C5—C6	1.371 (4)	C18—H18	0.930
C5—H5	0.930	C19—C20	1.356 (5)
C6—H6	0.930	C19—H19	0.930
C7—O1	1.407 (3)	C20—C21	1.380 (4)
C7—C8	1.492 (3)	C20—H20	0.930
C7—H7A	0.970	C21—H21	0.930
C7—H7B	0.970	C22—O4	1.446 (4)
C8—N2	1.320 (3)	C22—C23	1.453 (5)
C8—N1	1.367 (3)	C22—H22A	0.970
C9—N1	1.322 (3)	C22—H22B	0.970
C9—N3	1.385 (3)	C23—H23A	0.960
C9—C10	1.411 (3)	C23—H23B	0.960
C10—C11	1.390 (3)	C23—H23C	0.960
C10—C13	1.412 (3)	C24—O3	1.444 (4)
C11—N5	1.346 (3)	C24—C25	1.456 (5)
C11—N4	1.367 (3)	C24—H24A	0.970
C12—N4	1.293 (3)	C24—H24B	0.970
C12—N3	1.369 (3)	C25—H25A	0.960
C12—H12	0.930	C25—H25B	0.960
C13—N6	1.333 (3)	C25—H25C	0.960
C13—S1	1.738 (3)	N2—N3	1.374 (3)
C14—S1	1.772 (3)	N5—N6	1.380 (3)
C14—H14A	0.960	O2—P1	1.455 (2)
C14—H14B	0.960	O3—P1	1.5619 (19)
C14—H14C	0.960	O4—P1	1.557 (2)

C6—C1—C2	120.8 (3)	C16—C17—H17	119.6
C6—C1—Cl1	119.0 (2)	C18—C17—H17	119.6
C2—C1—Cl1	120.2 (2)	C19—C18—C17	120.1 (3)
C1—C2—C3	120.0 (3)	C19—C18—H18	120.0
C1—C2—H2	120.0	C17—C18—H18	120.0
C3—C2—H2	120.0	C20—C19—C18	119.6 (3)
C4—C3—C2	119.1 (3)	C20—C19—H19	120.2
C4—C3—H3	120.5	C18—C19—H19	120.2
C2—C3—H3	120.5	C19—C20—C21	120.5 (3)
O1—C4—C5	114.8 (2)	C19—C20—H20	119.8
O1—C4—C3	124.9 (2)	C21—C20—H20	119.8
C5—C4—C3	120.3 (2)	C16—C21—C20	120.7 (3)
C6—C5—C4	120.3 (3)	C16—C21—H21	119.6
C6—C5—H5	119.9	C20—C21—H21	119.6
C4—C5—H5	119.9	O4—C22—C23	111.9 (3)
C1—C6—C5	119.5 (3)	O4—C22—H22A	109.2
C1—C6—H6	120.2	C23—C22—H22A	109.2
C5—C6—H6	120.2	O4—C22—H22B	109.2
O1—C7—C8	107.4 (2)	C23—C22—H22B	109.2
O1—C7—H7A	110.2	H22A—C22—H22B	107.9
C8—C7—H7A	110.2	C22—C23—H23A	109.5
O1—C7—H7B	110.2	C22—C23—H23B	109.5
C8—C7—H7B	110.2	H23A—C23—H23B	109.5
H7A—C7—H7B	108.5	C22—C23—H23C	109.5
N2—C8—N1	116.6 (2)	H23A—C23—H23C	109.5
N2—C8—C7	122.7 (2)	H23B—C23—H23C	109.5
N1—C8—C7	120.6 (2)	O3—C24—C25	110.6 (3)
N1—C9—N3	109.9 (2)	O3—C24—H24A	109.5
N1—C9—C10	136.2 (2)	C25—C24—H24A	109.5
N3—C9—C10	113.9 (2)	O3—C24—H24B	109.5
C11—C10—C9	116.2 (2)	C25—C24—H24B	109.5
C11—C10—C13	104.9 (2)	H24A—C24—H24B	108.1
C9—C10—C13	138.9 (2)	C24—C25—H25A	109.5
N5—C11—N4	124.6 (2)	C24—C25—H25B	109.5
N5—C11—C10	107.3 (2)	H25A—C25—H25B	109.5
N4—C11—C10	128.1 (2)	C24—C25—H25C	109.5
N4—C12—N3	122.2 (2)	H25A—C25—H25C	109.5
N4—C12—H12	118.9	H25B—C25—H25C	109.5
N3—C12—H12	118.9	C9—N1—C8	102.5 (2)
N6—C13—C10	111.2 (2)	C8—N2—N3	101.81 (19)
N6—C13—S1	124.3 (2)	C12—N3—N2	125.4 (2)
C10—C13—S1	124.5 (2)	C12—N3—C9	125.5 (2)
S1—C14—H14A	109.5	N2—N3—C9	109.12 (19)
S1—C14—H14B	109.5	C12—N4—C11	114.2 (2)
H14A—C14—H14B	109.5	C11—N5—N6	111.5 (2)
S1—C14—H14C	109.5	C11—N5—C15	126.2 (2)
H14A—C14—H14C	109.5	N6—N5—C15	121.7 (2)
H14B—C14—H14C	109.5	C13—N6—N5	105.2 (2)
N5—C15—C16	112.8 (2)	C4—O1—C7	118.6 (2)
N5—C15—P1	110.86 (17)	C24—O3—P1	123.9 (2)
C16—C15—P1	115.91 (17)	C22—O4—P1	121.9 (2)
N5—C15—H15	105.4	O2—P1—O4	115.10 (13)
C16—C15—H15	105.4	O2—P1—O3	116.57 (13)
P1—C15—H15	105.4	O4—P1—O3	103.89 (12)
C17—C16—C21	118.3 (3)	O2—P1—C15	113.24 (12)
C17—C16—C15	122.8 (3)	O4—P1—C15	108.43 (12)
C21—C16—C15	119.0 (3)	O3—P1—C15	97.89 (11)
C16—C17—C18	120.8 (3)	C13—S1—C14	102.04 (15)

C6—C1—C2—C3	0.0 (5)	N4—C12—N3—N2	179.0 (2)
Cl1—C1—C2—C3	−179.5 (2)	N4—C12—N3—C9	−0.6 (4)
C1—C2—C3—C4	−1.5 (4)	C8—N2—N3—C12	−178.5 (2)
C2—C3—C4—O1	−177.5 (3)	C8—N2—N3—C9	1.2 (3)
C2—C3—C4—C5	2.5 (4)	N1—C9—N3—C12	178.7 (2)
O1—C4—C5—C6	177.8 (3)	C10—C9—N3—C12	−0.9 (4)
C3—C4—C5—C6	−2.1 (4)	N1—C9—N3—N2	−0.9 (3)
C2—C1—C6—C5	0.4 (4)	C10—C9—N3—N2	179.5 (2)
Cl1—C1—C6—C5	179.9 (2)	N3—C12—N4—C11	1.4 (4)
C4—C5—C6—C1	0.7 (4)	N5—C11—N4—C12	177.7 (3)
O1—C7—C8—N2	−12.1 (4)	C10—C11—N4—C12	−0.7 (4)
O1—C7—C8—N1	169.8 (2)	N4—C11—N5—N6	−179.5 (2)
N1—C9—C10—C11	−178.0 (3)	C10—C11—N5—N6	−0.8 (3)
N3—C9—C10—C11	1.4 (3)	N4—C11—N5—C15	9.3 (4)
N1—C9—C10—C13	2.6 (6)	C10—C11—N5—C15	−172.0 (2)
N3—C9—C10—C13	−178.0 (3)	C16—C15—N5—C11	86.7 (3)
C9—C10—C11—N5	−179.4 (2)	P1—C15—N5—C11	−141.5 (2)
C13—C10—C11—N5	0.2 (3)	C16—C15—N5—N6	−83.7 (3)
C9—C10—C11—N4	−0.7 (4)	P1—C15—N5—N6	48.2 (3)
C13—C10—C11—N4	178.9 (2)	C10—C13—N6—N5	−0.9 (3)
C11—C10—C13—N6	0.4 (3)	S1—C13—N6—N5	178.5 (2)
C9—C10—C13—N6	179.9 (3)	C11—N5—N6—C13	1.1 (3)
C11—C10—C13—S1	−178.9 (2)	C15—N5—N6—C13	172.7 (2)
C9—C10—C13—S1	0.5 (5)	C5—C4—O1—C7	174.5 (3)
N5—C15—C16—C17	40.2 (4)	C3—C4—O1—C7	−5.6 (4)
P1—C15—C16—C17	−89.0 (3)	C8—C7—O1—C4	176.9 (2)
N5—C15—C16—C21	−138.9 (3)	C25—C24—O3—P1	−128.6 (3)
P1—C15—C16—C21	91.8 (3)	C23—C22—O4—P1	106.1 (3)
C21—C16—C17—C18	−0.1 (5)	C22—O4—P1—O2	−10.1 (3)
C15—C16—C17—C18	−179.3 (3)	C22—O4—P1—O3	−138.8 (3)
C16—C17—C18—C19	−0.4 (6)	C22—O4—P1—C15	117.8 (3)
C17—C18—C19—C20	0.4 (6)	C24—O3—P1—O2	−66.4 (3)
C18—C19—C20—C21	0.1 (6)	C24—O3—P1—O4	61.3 (3)
C17—C16—C21—C20	0.6 (5)	C24—O3—P1—C15	172.6 (3)
C15—C16—C21—C20	179.8 (3)	N5—C15—P1—O2	45.4 (2)
C19—C20—C21—C16	−0.5 (6)	C16—C15—P1—O2	175.57 (18)
N3—C9—N1—C8	0.2 (3)	N5—C15—P1—O4	−83.64 (19)
C10—C9—N1—C8	179.7 (3)	C16—C15—P1—O4	46.5 (2)
N2—C8—N1—C9	0.6 (3)	N5—C15—P1—O3	168.81 (17)
C7—C8—N1—C9	178.8 (2)	C16—C15—P1—O3	−61.0 (2)
N1—C8—N2—N3	−1.2 (3)	N6—C13—S1—C14	−2.3 (3)
C7—C8—N2—N3	−179.3 (2)	C10—C13—S1—C14	177.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C22—H22A···O2	0.97	2.49	2.948 (4)	109
C17—H17···N6	0.93	2.61	3.238 (4)	125
C15—H15···N4	0.98	2.60	2.991 (3)	104
C7—H7A···O2ⁱ	0.97	2.36	3.324 (4)	171
C12—H12···N2ⁱⁱ	0.93	2.53	3.450 (3)	169

Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) −x, −y+2, −z+1.

Experimental details

Crystal data
Chemical formula	C₂₅H₂₆ClN₆O₄PS
M_r	573.00
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	294
a, b, c (Å)	13.8732 (12), 13.5760 (11), 16.2034 (14)
β (°)	113.515 (2)
V (Å³)	2798.4 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.31
Crystal size (mm)	0.20 × 0.20 × 0.10

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 2001)
T_min, T_max	0.941, 0.970
No. of measured, independent and observed [I > 2σ(I)] reflections	26250, 5485, 3386
R_int	0.108
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.150, 0.94
No. of reflections	5485
No. of parameters	346
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.51, −0.27

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.