Ethyl 5-amino-1-(4-chloro­phenyl-5,5-dimethyl-2-oxo-1,3,2-dioxaphosphinan-2-yl)-3-(6-chloro-3-pyridylmethyl­amino)-1H-pyrazole-4-carboxyl­ate

In the title compound, C₂₃H₂₆Cl₂N₅O₅P, the P atom adopts a distorted tetra­hedral coordination. The terminal ethyl carboxyl­ate group is almost coplanar with the plane of the pyrazole ring. Intra­molecular N—H...O hydrogen bonds influence the overall conformation of the mol­ecule. C—H...π Inter­actions contribute to the crystal packing.

Key indicators

• Single-crystal X-ray study
• T = 292 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.050
• wR factor = 0.140
• Data-to-parameter ratio = 13.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C22
PLAT480_ALERT_4_C Long H...A H-Bond Reported H3B    ..  O3      ..       2.63 Ang.

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

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

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S1. Comment

Neonicotinoide insecticides as nicotinic acetylcholine receptor inhibitors have attracted increasing attention because of their safety, low toxicity, wide range of activities and high potency (Shiokawa et al., 1986). It has been found that most biologically active nicotinic compounds contain the 3-aminomethylpyridine moiety (Yamamoto et al., 1994). Pyrazole and phosphorus heterocyclic compounds appear to be very important due to their wide biological activities (Tomcufcik et al., 1985; Hirashima et al., 1986). We report here the crystal and molecular structure of the title compound, (I) (Fig. 1), which was synthesized by attachement of a 1,3,2-dioxaphosphinane and an 3-aminomethylpyridine moiety to pyrazole. The distorted tetrahedron of the P atom can be attributed to the presence of the dioxaphosphinane ring whose sterical and electronic properties influence the coordination. The values of the double P1═O3 and single P1—N1 bonds and the angles O—P—O' and O—P—N illustrate the irregularities (Table 1). The dioxaphosphinane ring adopts a distorted chair conformation, with the parameters Q = 0.5186 (28) Å, θ = 151.45 (26)° and ϕ = 11.2 (6)° (Cremer & Pople, 1975). Atoms C11, O1, C7 and O2 of the dioxaphosphinane ring are not coplanar, the average deviation is 0.0245 (3) Å. The P—O single and double bonds are shorter (Table 1) than the analogous chemical bonds observed previously [1.586 (2), 1.572 (2) and 1.468 (2) Å; Liu et al., 2005]; on the other hand, the P1—N1 bond [1.677 (2) Å] is longer than the literature value [1.605 (3) Å; Liu et al., 2005]. The terminal ethyl carboxylate group is almost coplanar with the plane of the pyrazole ring (Table 1). The C16—C17 bond distance [1.481 (4) Å] can be attributed to a disorder of the terminal ethyl group.

Intramolecular N—H···O hydrogen bonds form six-membered rings (Table 2) and contribute to the stability of the overall conformation. The intermolecular C20—H···O3 interaction joins molecules into a chain along the b axis (Table 2 and Fig. 2). Methyl atom C17 and methylene atom C18 are involved in C—H···π interactions: C17···Cg1 = 3.669 (3) Å, H17A···Cg1 = 2.81 Å and C17—H17A···Cg1 = 148.97°; C18···Cg2 = 3.521 (3) Å, H18A···Cg2 = 2.63 Å and C18—H18A···Cg2 = 153.61° [Cg1 is the centroid of the pyrazole ring of the molecule at (1 − x, 1 − y, −z) and Cg2 is the centroid of the pyrazole ring of symmetry-related molecule at (−x, 2 − y, −z)]. The interaction of methyl and methylene groups with the aromatic π systems, described by Desiraju (2002), contribute to the crystal packing of (I).

S2. Experimental

A solution of 5-amino-3-(6-chloro-3-pyridylmethylamino)-4-(ethoxycarbonyl)pyrazole (4 mmol) in anhydrous CH₃CN (20 ml) and NaOH powder (5 mmol) were added to a three-necked flask. After vigorously stirring for 5 min, a solution of 2-chloro-4-chlorophenyl-5,5-dimethyl-1,3,2-dioxaphosphinane 2-oxide (4.5 mmol) was added dropwise while cooling in an ice-bath. After the addition was complete, the mixture was stirred at room temperature until the reaction was complete (monitored by thin-layer chromatography). The work-up involved stripping of the solvent followed by an addition of water and extraction of the product mixture into chloroform, after phase separation, drying over Na₂SO₄, filtration and evaporation, the crude product was purified by flash colum chromatography on silica gel using petroleum ether/ethyl acetate (2:1 v/v) as eluent, giving a white solid (yield: 35%, m.p. 453 K). A colourless crystal grown from absolute ethanol was selected for X-ray structure analysis.

S3. Refinement

H atoms were treated as riding, with C—H distances in the range 0.93–0.98 Å and N—H distances of 0.86 Å, and U_iso (H) = 1.2 or 1.5U_eq(parent atom).

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); 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

	Fig. 1. A view of the molecule of (I), showing the atom-numbering scheme and 50% probability displacement ellipsoids. H atoms have been omitted for clarity.
	Fig. 2. The crystal packing of (I), showing a chain running along b formed by C—H···O interactions.

Ethyl 5-amino-1-(4-chlorophenyl-5,5-dimethyl-2-oxo-1,3,2-dioxaphosphinan-2-yl)- 3-(6-chloro-3-pyridylmethylamino)-1H-pyrazole-4-carboxylate

Crystal data

C23H26Cl2N5O5P	Z = 2
Mr = 554.36	F(000) = 576
Triclinic, P1	Dx = 1.415 Mg m^−3
Hall symbol: -P1	Mo Kα radiation, λ = 0.71073 Å
a = 8.1968 (11) Å	Cell parameters from 2290 reflections
b = 10.2180 (14) Å	θ = 2.7–27.3°
c = 16.581 (2) Å	µ = 0.36 mm^−1
α = 86.447 (2)°	T = 292 K
β = 85.668 (3)°	Prism, colourless
γ = 70.083 (2)°	0.40 × 0.30 × 0.20 mm
V = 1301.0 (3) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	4540 independent reflections
Radiation source: fine-focus sealed tube	3469 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.058
ϕ and ω scans	θmax = 25.0°, θmin = 1.2°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −9→9
Tmin = 0.871, Tmax = 0.932	k = −12→11
6926 measured reflections	l = −18→19

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.050	H-atom parameters constrained
wR(F^2) = 0.140	w = 1/[σ^2(Fo^2) + (0.0711P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
4540 reflections	Δρmax = 0.44 e Å^−3
333 parameters	Δρmin = −0.45 e Å^−3
1 restraint	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.044 (3)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.2703 (4)	0.6301 (3)	0.51541 (16)	0.0572 (8)
C2	0.2893 (4)	0.7489 (3)	0.47930 (18)	0.0615 (8)
H2	0.3513	0.7956	0.5034	0.074*
C3	0.2148 (4)	0.7981 (3)	0.40659 (17)	0.0539 (7)
H3	0.2282	0.8781	0.3815	0.065*
C4	0.1202 (3)	0.7304 (3)	0.37024 (14)	0.0409 (6)
C5	0.1107 (4)	0.6082 (3)	0.40636 (16)	0.0494 (7)
H5	0.0530	0.5588	0.3816	0.059*
C6	0.1855 (4)	0.5576 (3)	0.47887 (17)	0.0586 (8)
H6	0.1782	0.4748	0.5027	0.070*
C7	0.0316 (3)	0.7929 (3)	0.29437 (14)	0.0392 (6)
H7	0.0995	0.8445	0.2645	0.047*
C8	−0.1582 (3)	0.8911 (3)	0.30511 (16)	0.0452 (7)
C9	−0.1661 (5)	1.0188 (3)	0.3510 (2)	0.0724 (10)
H9A	−0.1302	0.9903	0.4050	0.109*
H9B	−0.2830	1.0834	0.3532	0.109*
H9C	−0.0900	1.0628	0.3235	0.109*
C10	−0.2770 (4)	0.8194 (3)	0.34920 (17)	0.0615 (8)
H10A	−0.2697	0.7382	0.3209	0.092*
H10B	−0.3947	0.8825	0.3511	0.092*
H10C	−0.2413	0.7924	0.4033	0.092*
C11	−0.2201 (4)	0.9466 (3)	0.22128 (16)	0.0480 (7)
H11A	−0.3392	1.0095	0.2266	0.058*
H11B	−0.1492	0.9991	0.1969	0.058*
C12	0.1906 (3)	0.6589 (2)	0.03163 (14)	0.0363 (6)
C13	0.2881 (3)	0.7361 (3)	−0.00493 (14)	0.0381 (6)
C14	0.2380 (3)	0.8602 (3)	0.03968 (15)	0.0378 (6)
C15	0.4009 (3)	0.7086 (3)	−0.07720 (16)	0.0434 (6)
C16	0.5173 (4)	0.5514 (3)	−0.18462 (16)	0.0574 (8)
H16A	0.6359	0.5459	−0.1777	0.069*
H16B	0.4703	0.6214	−0.2268	0.069*
C17	0.5131 (4)	0.4145 (3)	−0.20690 (18)	0.0634 (8)
H17A	0.5589	0.3463	−0.1645	0.095*
H17B	0.5824	0.3869	−0.2563	0.095*
H17C	0.3954	0.4215	−0.2144	0.095*
C18	0.1983 (4)	1.1043 (3)	0.05332 (17)	0.0516 (7)
H18A	0.0792	1.1229	0.0398	0.062*
H18B	0.2396	1.1727	0.0234	0.062*
C19	0.1990 (3)	1.1253 (3)	0.14211 (17)	0.0439 (7)
C20	0.0862 (4)	1.2448 (3)	0.1756 (2)	0.0622 (8)
H20	0.0057	1.3096	0.1438	0.075*
C21	0.0916 (5)	1.2690 (3)	0.2552 (2)	0.0736 (10)
H21	0.0165	1.3496	0.2784	0.088*
C22	0.2125 (4)	1.1693 (3)	0.29985 (19)	0.0624 (8)
C23	0.3122 (4)	1.0322 (3)	0.19330 (17)	0.0488 (7)
H23	0.3876	0.9499	0.1720	0.059*
Cl1	0.35738 (13)	0.56981 (11)	0.60849 (5)	0.0890 (4)
Cl2	0.22464 (18)	1.19385 (12)	0.40208 (6)	0.1122 (4)
N1	0.0909 (3)	0.7350 (2)	0.09358 (11)	0.0374 (5)
N2	0.1212 (3)	0.8629 (2)	0.09908 (12)	0.0412 (5)
N3	0.1845 (3)	0.5341 (2)	0.01454 (13)	0.0485 (6)
H3A	0.1161	0.4992	0.0430	0.058*
H3B	0.2491	0.4889	−0.0249	0.058*
N4	0.3021 (3)	0.9675 (3)	0.02604 (15)	0.0493 (6)
N5	0.3205 (3)	1.0525 (2)	0.27129 (15)	0.0569 (7)
O1	−0.2109 (2)	0.83466 (18)	0.16781 (11)	0.0467 (5)
O2	0.0350 (2)	0.67659 (16)	0.24527 (9)	0.0410 (4)
O3	−0.0861 (2)	0.57817 (19)	0.13796 (10)	0.0490 (5)
O4	0.4757 (3)	0.7850 (2)	−0.10750 (12)	0.0635 (6)
O5	0.4131 (2)	0.5878 (2)	−0.10948 (10)	0.0508 (5)
P1	−0.05044 (9)	0.69940 (7)	0.16237 (4)	0.0377 (2)
H4	0.356 (4)	0.964 (3)	−0.0164 (11)	0.075 (11)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0558 (19)	0.071 (2)	0.0314 (15)	−0.0031 (16)	−0.0060 (13)	−0.0043 (14)
C2	0.065 (2)	0.070 (2)	0.0478 (18)	−0.0168 (17)	−0.0121 (15)	−0.0158 (16)
C3	0.065 (2)	0.0519 (17)	0.0470 (17)	−0.0209 (15)	−0.0075 (14)	−0.0023 (14)
C4	0.0447 (15)	0.0440 (15)	0.0303 (13)	−0.0103 (12)	0.0004 (11)	−0.0043 (11)
C5	0.0550 (18)	0.0551 (18)	0.0401 (15)	−0.0214 (15)	−0.0044 (13)	0.0015 (13)
C6	0.065 (2)	0.0604 (19)	0.0466 (17)	−0.0180 (16)	−0.0014 (15)	0.0089 (15)
C7	0.0472 (16)	0.0383 (14)	0.0318 (13)	−0.0146 (12)	0.0008 (11)	−0.0035 (11)
C8	0.0491 (16)	0.0415 (15)	0.0402 (15)	−0.0094 (13)	0.0037 (12)	−0.0076 (12)
C9	0.082 (2)	0.0547 (19)	0.069 (2)	−0.0041 (17)	−0.0088 (18)	−0.0224 (17)
C10	0.0497 (18)	0.074 (2)	0.0508 (18)	−0.0111 (16)	0.0085 (14)	0.0033 (16)
C11	0.0458 (16)	0.0406 (15)	0.0521 (17)	−0.0077 (13)	−0.0006 (13)	−0.0019 (13)
C12	0.0431 (15)	0.0379 (14)	0.0280 (13)	−0.0129 (12)	−0.0071 (11)	0.0001 (11)
C13	0.0408 (15)	0.0417 (14)	0.0334 (13)	−0.0158 (12)	−0.0049 (11)	0.0008 (11)
C14	0.0425 (15)	0.0411 (14)	0.0339 (13)	−0.0195 (12)	−0.0084 (11)	0.0054 (11)
C15	0.0411 (15)	0.0492 (16)	0.0393 (15)	−0.0148 (13)	−0.0045 (12)	0.0034 (13)
C16	0.0550 (19)	0.075 (2)	0.0370 (15)	−0.0174 (16)	0.0106 (13)	−0.0057 (15)
C17	0.0572 (19)	0.074 (2)	0.0498 (18)	−0.0093 (16)	0.0018 (15)	−0.0150 (16)
C18	0.0644 (19)	0.0405 (16)	0.0548 (18)	−0.0236 (14)	−0.0156 (15)	0.0114 (14)
C19	0.0445 (16)	0.0331 (14)	0.0583 (17)	−0.0184 (12)	−0.0084 (13)	0.0051 (13)
C20	0.061 (2)	0.0395 (17)	0.079 (2)	−0.0066 (15)	−0.0118 (17)	0.0018 (16)
C21	0.079 (2)	0.0462 (19)	0.085 (3)	−0.0054 (17)	0.003 (2)	−0.0189 (18)
C22	0.078 (2)	0.0548 (19)	0.059 (2)	−0.0270 (18)	−0.0011 (17)	−0.0119 (16)
C23	0.0473 (17)	0.0424 (16)	0.0550 (18)	−0.0128 (13)	−0.0032 (14)	−0.0033 (14)
Cl1	0.0913 (7)	0.1104 (8)	0.0439 (5)	−0.0035 (6)	−0.0225 (5)	0.0024 (5)
Cl2	0.1633 (12)	0.1059 (9)	0.0656 (7)	−0.0384 (8)	−0.0066 (7)	−0.0304 (6)
N1	0.0460 (13)	0.0365 (11)	0.0338 (11)	−0.0190 (10)	−0.0019 (10)	−0.0031 (9)
N2	0.0519 (13)	0.0395 (12)	0.0380 (12)	−0.0231 (11)	−0.0031 (10)	−0.0017 (10)
N3	0.0635 (15)	0.0462 (13)	0.0412 (13)	−0.0262 (12)	0.0089 (11)	−0.0118 (10)
N4	0.0599 (16)	0.0492 (14)	0.0457 (15)	−0.0287 (13)	0.0014 (12)	0.0012 (12)
N5	0.0626 (17)	0.0538 (16)	0.0536 (16)	−0.0170 (13)	−0.0111 (13)	−0.0027 (12)
O1	0.0427 (11)	0.0506 (11)	0.0430 (10)	−0.0100 (9)	−0.0051 (8)	−0.0043 (9)
O2	0.0513 (11)	0.0371 (10)	0.0305 (9)	−0.0092 (8)	−0.0020 (8)	−0.0048 (7)
O3	0.0602 (12)	0.0508 (11)	0.0451 (11)	−0.0309 (10)	0.0021 (9)	−0.0070 (9)
O4	0.0677 (14)	0.0669 (14)	0.0607 (13)	−0.0338 (12)	0.0180 (11)	−0.0007 (11)
O5	0.0567 (12)	0.0587 (12)	0.0383 (10)	−0.0223 (10)	0.0092 (9)	−0.0087 (9)
P1	0.0429 (4)	0.0398 (4)	0.0324 (4)	−0.0168 (3)	−0.0008 (3)	−0.0015 (3)

Geometric parameters (Å, º)

C1—C6	1.367 (4)	C14—N4	1.369 (3)
C1—C2	1.372 (4)	C15—O4	1.213 (3)
C1—Cl1	1.738 (3)	C15—O5	1.344 (3)
C2—C3	1.380 (4)	C16—O5	1.449 (3)
C2—H2	0.9300	C16—C17	1.481 (4)
C3—C4	1.390 (3)	C16—H16A	0.9700
C3—H3	0.9300	C16—H16B	0.9700
C4—C5	1.375 (3)	C17—H17A	0.9600
C4—C7	1.497 (3)	C17—H17B	0.9600
C5—C6	1.381 (4)	C17—H17C	0.9600
C5—H5	0.9300	C18—N4	1.446 (4)
C6—H6	0.9300	C18—C19	1.502 (4)
C7—O2	1.473 (3)	C18—H18A	0.9700
C7—C8	1.541 (4)	C18—H18B	0.9700
C7—H7	0.9800	C19—C20	1.376 (4)
C8—C11	1.525 (4)	C19—C23	1.379 (4)
C8—C10	1.527 (4)	C20—C21	1.364 (4)
C8—C9	1.531 (4)	C20—H20	0.9300
C9—H9A	0.9600	C21—C22	1.377 (4)
C9—H9B	0.9600	C21—H21	0.9300
C9—H9C	0.9600	C22—N5	1.311 (4)
C10—H10A	0.9600	C22—Cl2	1.744 (3)
C10—H10B	0.9600	C23—N5	1.333 (3)
C10—H10C	0.9600	C23—H23	0.9300
C11—O1	1.468 (3)	N1—N2	1.420 (3)
C11—H11A	0.9700	N1—P1	1.677 (2)
C11—H11B	0.9700	N3—H3A	0.8600
C12—N3	1.341 (3)	N3—H3B	0.8600
C12—N1	1.367 (3)	N4—H4	0.799 (10)
C12—C13	1.388 (3)	O1—P1	1.5516 (19)
C13—C14	1.428 (3)	O2—P1	1.5584 (17)
C13—C15	1.438 (4)	O3—P1	1.4529 (18)
C14—N2	1.316 (3)
C6—C1—C2	121.0 (3)	O4—C15—O5	122.7 (2)
C6—C1—Cl1	119.5 (3)	O4—C15—C13	124.9 (3)
C2—C1—Cl1	119.5 (2)	O5—C15—C13	112.4 (2)
C1—C2—C3	118.9 (3)	O5—C16—C17	107.5 (2)
C1—C2—H2	120.5	O5—C16—H16A	110.2
C3—C2—H2	120.5	C17—C16—H16A	110.2
C2—C3—C4	121.2 (3)	O5—C16—H16B	110.2
C2—C3—H3	119.4	C17—C16—H16B	110.2
C4—C3—H3	119.4	H16A—C16—H16B	108.5
C5—C4—C3	118.1 (2)	C16—C17—H17A	109.5
C5—C4—C7	122.5 (2)	C16—C17—H17B	109.5
C3—C4—C7	119.3 (2)	H17A—C17—H17B	109.5
C4—C5—C6	121.1 (3)	C16—C17—H17C	109.5
C4—C5—H5	119.5	H17A—C17—H17C	109.5
C6—C5—H5	119.5	H17B—C17—H17C	109.5
C1—C6—C5	119.5 (3)	N4—C18—C19	115.6 (2)
C1—C6—H6	120.2	N4—C18—H18A	108.4
C5—C6—H6	120.2	C19—C18—H18A	108.4
O2—C7—C4	107.08 (19)	N4—C18—H18B	108.4
O2—C7—C8	108.20 (19)	C19—C18—H18B	108.4
C4—C7—C8	116.4 (2)	H18A—C18—H18B	107.4
O2—C7—H7	108.3	C20—C19—C23	116.6 (3)
C4—C7—H7	108.3	C20—C19—C18	119.7 (3)
C8—C7—H7	108.3	C23—C19—C18	123.6 (3)
C11—C8—C10	111.0 (2)	C21—C20—C19	120.5 (3)
C11—C8—C9	105.7 (2)	C21—C20—H20	119.8
C10—C8—C9	109.7 (2)	C19—C20—H20	119.8
C11—C8—C7	107.7 (2)	C20—C21—C22	117.5 (3)
C10—C8—C7	112.6 (2)	C20—C21—H21	121.3
C9—C8—C7	109.9 (2)	C22—C21—H21	121.3
C8—C9—H9A	109.5	N5—C22—C21	124.4 (3)
C8—C9—H9B	109.5	N5—C22—Cl2	116.0 (3)
H9A—C9—H9B	109.5	C21—C22—Cl2	119.6 (3)
C8—C9—H9C	109.5	N5—C23—C19	124.3 (3)
H9A—C9—H9C	109.5	N5—C23—H23	117.8
H9B—C9—H9C	109.5	C19—C23—H23	117.8
C8—C10—H10A	109.5	C12—N1—N2	111.48 (18)
C8—C10—H10B	109.5	C12—N1—P1	130.92 (16)
H10A—C10—H10B	109.5	N2—N1—P1	117.57 (15)
C8—C10—H10C	109.5	C14—N2—N1	103.74 (19)
H10A—C10—H10C	109.5	C12—N3—H3A	120.0
H10B—C10—H10C	109.5	C12—N3—H3B	120.0
O1—C11—C8	112.4 (2)	H3A—N3—H3B	120.0
O1—C11—H11A	109.1	C14—N4—C18	119.0 (2)
C8—C11—H11A	109.1	C14—N4—H4	113 (2)
O1—C11—H11B	109.1	C18—N4—H4	117 (2)
C8—C11—H11B	109.1	C22—N5—C23	116.6 (3)
H11A—C11—H11B	107.9	C11—O1—P1	121.95 (15)
N3—C12—N1	122.4 (2)	C7—O2—P1	122.63 (14)
N3—C12—C13	130.8 (2)	C15—O5—C16	117.6 (2)
N1—C12—C13	106.8 (2)	O3—P1—O1	114.92 (10)
C12—C13—C14	104.9 (2)	O3—P1—O2	113.32 (10)
C12—C13—C15	128.9 (2)	O1—P1—O2	106.83 (9)
C14—C13—C15	125.9 (2)	O3—P1—N1	108.80 (10)
N2—C14—N4	120.9 (2)	O1—P1—N1	105.96 (10)
N2—C14—C13	113.0 (2)	O2—P1—N1	106.44 (10)
N4—C14—C13	126.0 (2)
C6—C1—C2—C3	2.7 (5)	C18—C19—C20—C21	−176.4 (3)
Cl1—C1—C2—C3	−178.0 (2)	C19—C20—C21—C22	−0.4 (5)
C1—C2—C3—C4	0.7 (4)	C20—C21—C22—N5	−1.0 (5)
C2—C3—C4—C5	−3.6 (4)	C20—C21—C22—Cl2	−179.6 (2)
C2—C3—C4—C7	175.8 (3)	C20—C19—C23—N5	−1.4 (4)
C3—C4—C5—C6	3.2 (4)	C18—C19—C23—N5	176.4 (2)
C7—C4—C5—C6	−176.2 (2)	N3—C12—N1—N2	180.0 (2)
C2—C1—C6—C5	−3.1 (5)	C13—C12—N1—N2	−0.2 (3)
Cl1—C1—C6—C5	177.6 (2)	N3—C12—N1—P1	2.0 (4)
C4—C5—C6—C1	0.0 (4)	C13—C12—N1—P1	−178.17 (18)
C5—C4—C7—O2	−33.6 (3)	N4—C14—N2—N1	−179.3 (2)
C3—C4—C7—O2	146.9 (2)	C13—C14—N2—N1	−0.4 (3)
C5—C4—C7—C8	87.5 (3)	C12—N1—N2—C14	0.4 (3)
C3—C4—C7—C8	−91.9 (3)	P1—N1—N2—C14	178.64 (16)
O2—C7—C8—C11	−61.5 (2)	N2—C14—N4—C18	−24.5 (4)
C4—C7—C8—C11	177.9 (2)	C13—C14—N4—C18	156.8 (2)
O2—C7—C8—C10	61.2 (3)	C19—C18—N4—C14	78.2 (3)
C4—C7—C8—C10	−59.4 (3)	C21—C22—N5—C23	1.1 (5)
O2—C7—C8—C9	−176.2 (2)	Cl2—C22—N5—C23	179.77 (19)
C4—C7—C8—C9	63.3 (3)	C19—C23—N5—C22	0.2 (4)
C10—C8—C11—O1	−64.3 (3)	C8—C11—O1—P1	−44.3 (3)
C9—C8—C11—O1	176.8 (2)	C4—C7—O2—P1	178.01 (15)
C7—C8—C11—O1	59.4 (3)	C8—C7—O2—P1	51.8 (2)
N3—C12—C13—C14	179.7 (2)	O4—C15—O5—C16	−1.5 (4)
N1—C12—C13—C14	−0.1 (3)	C13—C15—O5—C16	177.4 (2)
N3—C12—C13—C15	6.2 (4)	C17—C16—O5—C15	179.0 (2)
N1—C12—C13—C15	−173.6 (2)	C11—O1—P1—O3	153.86 (18)
C12—C13—C14—N2	0.3 (3)	C11—O1—P1—O2	27.2 (2)
C15—C13—C14—N2	174.1 (2)	C11—O1—P1—N1	−85.97 (19)
C12—C13—C14—N4	179.2 (2)	C7—O2—P1—O3	−159.76 (17)
C15—C13—C14—N4	−7.0 (4)	C7—O2—P1—O1	−32.19 (19)
C12—C13—C15—O4	176.3 (3)	C7—O2—P1—N1	80.69 (18)
C14—C13—C15—O4	4.0 (4)	C12—N1—P1—O3	−12.2 (3)
C12—C13—C15—O5	−2.6 (4)	N2—N1—P1—O3	169.96 (15)
C14—C13—C15—O5	−174.9 (2)	C12—N1—P1—O1	−136.2 (2)
N4—C18—C19—C20	−171.1 (2)	N2—N1—P1—O1	45.88 (18)
N4—C18—C19—C23	11.1 (4)	C12—N1—P1—O2	110.3 (2)
C23—C19—C20—C21	1.5 (4)	N2—N1—P1—O2	−67.60 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C23—H23···N4	0.93	2.55	2.904 (4)	103
C20—H20···O3^i	0.93	2.58	3.253 (3)	129
N3—H3A···O3	0.86	2.17	2.839 (3)	134
N3—H3B···O5	0.86	2.29	2.832 (3)	121
N3—H3B···O3^ii	0.86	2.63	3.108 (3)	116
N4—H4···O4	0.80 (1)	2.34 (3)	2.938 (3)	132 (3)

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