2-(2H-Benzotriazol-2-yl)-4-methyl­phenyl diphenyl­phosphinate

Liu, Y.-C.; Lin, C.-H.; Ko, B.-T.

doi:10.1107/S1600536809029870

organic compounds

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ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page o2058

doi:10.1107/S1600536809029870

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2-(2H-Benzotriazol-2-yl)-4-methylphenyl diphenylphosphinate

Yi-Chang Liu,^a Chia-Her Lin ^a and Bao-Tsan Ko ^a ^*

^aDepartment of Chemistry, Chung Yuan Christian University, Chung-Li 320, Taiwan
^*Correspondence e-mail: btko@cycu.edu.tw

(Received 21 July 2009; accepted 28 July 2009; online 31 July 2009)

In the title molecule, C₂₅H₂₀N₃O₂P, the dihedral angle between the mean planes of the benzotriazol ring system and the N-bonded benzene ring is 45.8 (2)°. All but one of the angles at the P atom show slight distortions from an ideal tetrahedral geometry.

Related literature

For background to the use of 2-(2H-benzotriazol-2H-yl)phenol (BTP-H) derivatives, see: Li et al. (2009 ); Tsai et al. (2009 ). For related structures, see: Al-Farhan (1992 ); Cheng et al. (2007 ).

Experimental

Crystal data

C₂₅H₂₀N₃O₂P
M_r = 425.41
Orthorhombic, P c a 2₁
a = 12.7691 (7) Å
b = 9.4064 (5) Å
c = 18.6362 (10) Å
V = 2238.4 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.15 mm⁻¹
T = 296 K
0.30 × 0.20 × 0.15 mm

Data collection

Bruker SMART-1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.963, T_max = 0.974
11920 measured reflections
3684 independent reflections
3343 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.086
S = 1.05
3684 reflections
280 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.20 e Å⁻³
Absolute structure: Flack (1983 ), 1412 Friedel pairs
Flack parameter: 0.01 (7)

Table 1
Selected bond angles (°)

O2—P—O1	115.53 (10)
O2—P—C14	113.48 (8)
O1—P—C14	100.15 (8)
O2—P—C20	112.37 (9)
O1—P—C20	105.04 (8)
C14—P—C20	109.30 (8)

Data collection: SMART (Bruker, 1999 ); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809029870/lh2871sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809029870/lh2871Isup2.hkl

checkCIF report

Comment top

2-(2H-benzotriazol-2H-yl)phenol (BTP-H) derivatives are widely used as ultraviolet (UV) absorbers for the protection of commercially important synthetic plastics and fibers against the UV light in industry. In terms of coordination chemistry, the benzotriazol-phenolate group can provide N, O-bidentate chelation to stabilize the transition metal or main group metal complexes. For instance, our group has successfully synthesized and structural characterized the Pd complex (II) with 4-methyl-2-(2H-benzotriazol-2-yl)-phenolate ligands (Tsai et al., 2009). Recently, we also reported the synthesis and crystal structure of an Al(III) complex with the 4-methyl-2-(2H-benzotriazol-2-yl)-phenolate ligand (Li et al., 2009). Most recently, Cheng et al. (2007) reported some palladium complexes of monodentate phosphinite ligands and these complexes in the presence of Pd(OAc)₂ have been demonstrated effectively to catalyze Suzuki–Miyaura cross-coupling reactions. Therefore, our group is interested in the synthesis and preparation of the phosphinite functionalized benzotriazol-phenolate ligands derived from BTP-H. Here, we report the synthesis and crystal structure of the title compound, (I), a potential ligand for the preparation of metal complexes.

The molecule of (I) is composed of a benzotriazol-phenolate moiety and a diphenylphosphine oxide functionalized group (Fig. 1). The dihedral angle between the planes of the benzotriazole moiety and the benzene ring of the phenoxy group is 45.8 (2)°. The P atom is bonded one O atom of the phosphine oxide, one phenoxy O atom and two C atoms from two phenyl groups, forming a slightly distorted tetrahedral environment. The P-O and P=O bond distances bond distances are similar to those found in the crystal structure of triphenyphosphine oxide (Al-Farhan, 1992).

Related literature top

For background to the use of 2-(2H-benzotriazol-2H-yl)phenol (BTP-H) derivatives in industry as ultraviolet (UV) absorbers for the protection of synthetic plastics and fibers, see: Li et al. (2009); Tsai et al. (2009). For related structures, see: Al-Farhan (1992); Cheng et al. (2007).

Experimental top

The title compound I was synthesized by the following procedure (Fig. 2): To a rapidly stirred solution of 4-methyl-2-(2H-benzotriazol-2-yl)phenol (2.48 g, 10.0 mmol) in toluene (20 ml), Ph₂PCl (1.8 ml, 10.0 mmol) and NEt₃ (20.0 mmol, 2.02 g) was slowly added. The mixed solution was stirred at 363 K for 18 h. Subsequently, the HNEt₃Cl salt was filtered and the resulting solution was dried under reduced pressure. The resulting oily product was re-dissolved in MeOH (20 ml) and H₂O₂ (1 ml) was added. The final solution was stirred at room temperature for another 1 h and the volatile components were removed in vacuo. The residue was extracted with ethyl acetate (50 ml) and the extract was dried under vacuum to give oily, white solids. Colorless crystals were obtained on cooling the saturated Et₂O solution at 253 K overnight. ¹H NMR (CDCl₃, p.p.m.): δ 7.10–7.97 (17H, m, ArH), 2.35 (3H, s, CH₃).

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of I with the atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The synthetic procedure of the title compound.

2-(2H-Benzotriazol-2-yl)-4-methylphenyl diphenylphosphinate top

Crystal data top

C₂₅H₂₀N₃O₂P	F(000) = 888
M_r = 425.41	D_x = 1.262 Mg m⁻³
Orthorhombic, Pca2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 6495 reflections
a = 12.7691 (7) Å	θ = 2.7–26.0°
b = 9.4064 (5) Å	µ = 0.15 mm⁻¹
c = 18.6362 (10) Å	T = 296 K
V = 2238.4 (2) Å³	Block, colourless
Z = 4	0.30 × 0.20 × 0.15 mm

Data collection top

Bruker SMART-1000 CCD diffractometer	3684 independent reflections
Radiation source: fine-focus sealed tube	3343 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
ω scans	θ_max = 26.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −15→14
T_min = 0.963, T_max = 0.974	k = −11→11
11920 measured reflections	l = −19→22

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)] = 0.032	H-atom parameters constrained
wR(F²) = 0.086	w = 1/[σ²(F_o²) + (0.058P)²] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
3684 reflections	Δρ_max = 0.14 e Å⁻³
280 parameters	Δρ_min = −0.20 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1412 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.01 (7)

Crystal data top

C₂₅H₂₀N₃O₂P	V = 2238.4 (2) Å³
M_r = 425.41	Z = 4
Orthorhombic, Pca2₁	Mo Kα radiation
a = 12.7691 (7) Å	µ = 0.15 mm⁻¹
b = 9.4064 (5) Å	T = 296 K
c = 18.6362 (10) Å	0.30 × 0.20 × 0.15 mm

Data collection top

Bruker SMART-1000 CCD diffractometer	3684 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3343 reflections with I > 2σ(I)
T_min = 0.963, T_max = 0.974	R_int = 0.034
11920 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	H-atom parameters constrained
wR(F²) = 0.086	Δρ_max = 0.14 e Å⁻³
S = 1.05	Δρ_min = −0.20 e Å⁻³
3684 reflections	Absolute structure: Flack (1983), 1412 Friedel pairs
280 parameters	Absolute structure parameter: 0.01 (7)
1 restraint

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
P	−0.78562 (3)	−0.27388 (4)	−0.41236 (3)	0.04851 (13)
O1	−0.74629 (11)	−0.25123 (13)	−0.49386 (7)	0.0523 (3)
O2	−0.89556 (10)	−0.23744 (14)	−0.39862 (10)	0.0724 (4)
N1	−0.54417 (13)	−0.30745 (18)	−0.54995 (9)	0.0573 (4)
N2	−0.58778 (12)	−0.21611 (16)	−0.59589 (8)	0.0510 (3)
N3	−0.56809 (15)	−0.23649 (17)	−0.66558 (9)	0.0617 (4)
C1	−0.73324 (14)	−0.11822 (19)	−0.52534 (11)	0.0498 (4)
C2	−0.65289 (15)	−0.10047 (19)	−0.57421 (10)	0.0536 (4)
C3	−0.63716 (18)	0.0309 (2)	−0.60682 (12)	0.0641 (5)
H3B	−0.5823	0.0422	−0.6391	0.077*
C4	−0.7020 (2)	0.1451 (2)	−0.59187 (13)	0.0675 (6)
C5	−0.78319 (19)	0.1244 (2)	−0.54483 (14)	0.0710 (6)
H5A	−0.8283	0.1996	−0.5351	0.085*
C6	−0.80000 (17)	−0.0052 (2)	−0.51143 (12)	0.0652 (5)
H6A	−0.8558	−0.0163	−0.4798	0.078*
C7	−0.49173 (14)	−0.3965 (2)	−0.59453 (10)	0.0543 (4)
C8	−0.4308 (2)	−0.5185 (3)	−0.57796 (13)	0.0768 (6)
H8A	−0.4209	−0.5492	−0.5310	0.092*
C9	−0.3876 (2)	−0.5879 (3)	−0.63507 (16)	0.0861 (7)
H9A	−0.3471	−0.6683	−0.6265	0.103*
C10	−0.4020 (2)	−0.5427 (3)	−0.70636 (15)	0.0862 (7)
H10A	−0.3709	−0.5943	−0.7432	0.103*
C11	−0.45980 (19)	−0.4263 (3)	−0.72317 (13)	0.0762 (6)
H11A	−0.4683	−0.3963	−0.7704	0.091*
C12	−0.50631 (15)	−0.3531 (2)	−0.66534 (11)	0.0561 (4)
C13	−0.6860 (3)	0.2874 (3)	−0.6283 (2)	0.0984 (9)
H13A	−0.7377	0.3535	−0.6114	0.148*
H13B	−0.6929	0.2760	−0.6793	0.148*
H13C	−0.6173	0.3227	−0.6173	0.148*
C14	−0.75764 (14)	−0.45832 (18)	−0.40115 (10)	0.0511 (4)
C15	−0.66460 (14)	−0.5202 (2)	−0.42229 (12)	0.0612 (5)
H15A	−0.6144	−0.4658	−0.4459	0.073*
C16	−0.64533 (18)	−0.6626 (2)	−0.40869 (16)	0.0746 (6)
H16A	−0.5822	−0.7036	−0.4226	0.089*
C17	−0.7204 (3)	−0.7429 (2)	−0.37445 (17)	0.0840 (8)
H17A	−0.7086	−0.8391	−0.3663	0.101*
C18	−0.8118 (3)	−0.6822 (3)	−0.35251 (19)	0.0982 (9)
H18A	−0.8609	−0.7367	−0.3281	0.118*
C19	−0.83227 (19)	−0.5408 (3)	−0.36614 (16)	0.0811 (7)
H19A	−0.8956	−0.5008	−0.3520	0.097*
C20	−0.69692 (13)	−0.17140 (17)	−0.35845 (9)	0.0460 (4)
C21	−0.73139 (19)	−0.1249 (2)	−0.29154 (12)	0.0636 (6)
H21A	−0.7985	−0.1470	−0.2757	0.076*
C22	−0.6643 (2)	−0.0451 (3)	−0.24858 (12)	0.0791 (7)
H22A	−0.6865	−0.0153	−0.2035	0.095*
C23	−0.5668 (2)	−0.0102 (2)	−0.27184 (15)	0.0770 (6)
H23A	−0.5234	0.0449	−0.2430	0.092*
C24	−0.53189 (18)	−0.0559 (2)	−0.33777 (13)	0.0677 (5)
H24A	−0.4653	−0.0310	−0.3535	0.081*
C25	−0.59558 (14)	−0.1389 (2)	−0.38062 (11)	0.0562 (4)
H25A	−0.5708	−0.1731	−0.4243	0.067*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P	0.0399 (2)	0.0488 (2)	0.0569 (3)	−0.00062 (15)	0.0029 (2)	−0.0003 (2)
O1	0.0566 (7)	0.0499 (6)	0.0504 (7)	0.0003 (5)	−0.0023 (6)	0.0000 (5)
O2	0.0446 (7)	0.0726 (9)	0.0998 (14)	0.0035 (6)	0.0074 (7)	0.0013 (8)
N1	0.0617 (9)	0.0667 (10)	0.0436 (8)	0.0101 (8)	−0.0017 (7)	0.0031 (7)
N2	0.0576 (9)	0.0532 (8)	0.0424 (8)	0.0008 (6)	−0.0003 (6)	0.0025 (6)
N3	0.0772 (11)	0.0662 (10)	0.0416 (9)	0.0011 (8)	0.0019 (8)	0.0047 (7)
C1	0.0529 (10)	0.0484 (10)	0.0481 (10)	0.0013 (7)	−0.0086 (8)	−0.0012 (8)
C2	0.0621 (10)	0.0524 (10)	0.0462 (10)	0.0023 (8)	−0.0080 (8)	0.0007 (8)
C3	0.0749 (13)	0.0586 (12)	0.0588 (12)	−0.0026 (9)	−0.0006 (9)	0.0065 (9)
C4	0.0864 (14)	0.0510 (11)	0.0650 (14)	0.0023 (9)	−0.0146 (11)	0.0061 (10)
C5	0.0842 (14)	0.0547 (11)	0.0742 (15)	0.0183 (10)	−0.0125 (12)	−0.0007 (10)
C6	0.0687 (12)	0.0643 (12)	0.0625 (13)	0.0107 (9)	−0.0018 (10)	0.0021 (10)
C7	0.0533 (10)	0.0600 (10)	0.0498 (10)	0.0030 (8)	−0.0007 (8)	−0.0018 (8)
C8	0.0810 (13)	0.0845 (15)	0.0650 (13)	0.0261 (12)	0.0004 (12)	0.0052 (12)
C9	0.0862 (16)	0.0871 (16)	0.0849 (18)	0.0310 (13)	0.0016 (14)	−0.0089 (14)
C10	0.0905 (17)	0.0927 (17)	0.0752 (17)	0.0148 (14)	0.0108 (13)	−0.0277 (14)
C11	0.0877 (16)	0.0905 (17)	0.0504 (12)	0.0048 (13)	0.0065 (11)	−0.0092 (11)
C12	0.0598 (10)	0.0610 (11)	0.0476 (10)	−0.0026 (8)	0.0029 (8)	−0.0012 (8)
C13	0.124 (2)	0.0571 (13)	0.114 (2)	0.0010 (14)	0.0021 (19)	0.0205 (14)
C14	0.0516 (8)	0.0477 (8)	0.0540 (11)	−0.0075 (7)	−0.0029 (8)	−0.0012 (8)
C15	0.0549 (10)	0.0556 (10)	0.0731 (14)	0.0019 (7)	0.0007 (9)	0.0058 (10)
C16	0.0793 (13)	0.0602 (11)	0.0842 (15)	0.0131 (10)	−0.0135 (13)	−0.0024 (12)
C17	0.110 (2)	0.0502 (12)	0.0916 (19)	−0.0074 (12)	−0.0226 (15)	0.0083 (12)
C18	0.112 (2)	0.0664 (14)	0.116 (3)	−0.0274 (15)	0.0132 (18)	0.0180 (15)
C19	0.0705 (13)	0.0671 (14)	0.106 (2)	−0.0147 (10)	0.0195 (13)	0.0097 (13)
C20	0.0529 (9)	0.0382 (8)	0.0467 (9)	0.0036 (7)	0.0034 (7)	−0.0001 (7)
C21	0.0804 (16)	0.0569 (12)	0.0534 (13)	0.0099 (10)	0.0133 (10)	0.0009 (9)
C22	0.122 (2)	0.0656 (14)	0.0500 (12)	0.0125 (14)	−0.0011 (13)	−0.0161 (11)
C23	0.0982 (17)	0.0576 (12)	0.0752 (15)	−0.0024 (11)	−0.0260 (14)	−0.0107 (11)
C24	0.0624 (12)	0.0676 (13)	0.0733 (14)	−0.0109 (9)	−0.0138 (10)	−0.0027 (11)
C25	0.0527 (9)	0.0622 (11)	0.0536 (10)	−0.0032 (8)	0.0018 (8)	−0.0064 (8)

Geometric parameters (Å, º) top

P—O2	1.4675 (14)	C11—C12	1.410 (3)
P—O1	1.6138 (15)	C11—H11A	0.9300
P—C14	1.7835 (18)	C13—H13A	0.9600
P—C20	1.7948 (18)	C13—H13B	0.9600
O1—C1	1.392 (2)	C13—H13C	0.9600
N1—N2	1.335 (2)	C14—C15	1.380 (3)
N1—C7	1.357 (2)	C14—C19	1.391 (3)
N2—N3	1.337 (2)	C15—C16	1.385 (3)
N2—C2	1.427 (2)	C15—H15A	0.9300
N3—C12	1.351 (3)	C16—C17	1.377 (4)
C1—C2	1.382 (3)	C16—H16A	0.9300
C1—C6	1.387 (3)	C17—C18	1.362 (4)
C2—C3	1.392 (3)	C17—H17A	0.9300
C3—C4	1.385 (3)	C18—C19	1.379 (4)
C3—H3B	0.9300	C18—H18A	0.9300
C4—C5	1.371 (4)	C19—H19A	0.9300
C4—C13	1.515 (3)	C20—C25	1.392 (3)
C5—C6	1.385 (3)	C20—C21	1.393 (3)
C5—H5A	0.9300	C21—C22	1.392 (4)
C6—H6A	0.9300	C21—H21A	0.9300
C7—C12	1.394 (3)	C22—C23	1.359 (4)
C7—C8	1.420 (3)	C22—H22A	0.9300
C8—C9	1.365 (4)	C23—C24	1.376 (4)
C8—H8A	0.9300	C23—H23A	0.9300
C9—C10	1.407 (4)	C24—C25	1.381 (3)
C9—H9A	0.9300	C24—H24A	0.9300
C10—C11	1.357 (4)	C25—H25A	0.9300
C10—H10A	0.9300

O2—P—O1	115.53 (10)	N3—C12—C7	108.62 (16)
O2—P—C14	113.48 (8)	N3—C12—C11	129.8 (2)
O1—P—C14	100.15 (8)	C7—C12—C11	121.60 (19)
O2—P—C20	112.37 (9)	C4—C13—H13A	109.5
O1—P—C20	105.04 (8)	C4—C13—H13B	109.5
C14—P—C20	109.30 (8)	H13A—C13—H13B	109.5
C1—O1—P	123.55 (12)	C4—C13—H13C	109.5
N2—N1—C7	102.17 (15)	H13A—C13—H13C	109.5
N1—N2—N3	116.91 (16)	H13B—C13—H13C	109.5
N1—N2—C2	123.51 (16)	C15—C14—C19	119.22 (18)
N3—N2—C2	119.59 (15)	C15—C14—P	123.30 (13)
N2—N3—C12	102.88 (15)	C19—C14—P	117.40 (16)
C2—C1—C6	119.13 (19)	C14—C15—C16	120.55 (19)
C2—C1—O1	118.37 (16)	C14—C15—H15A	119.7
C6—C1—O1	122.45 (18)	C16—C15—H15A	119.7
C1—C2—C3	120.14 (18)	C17—C16—C15	119.5 (2)
C1—C2—N2	121.79 (16)	C17—C16—H16A	120.3
C3—C2—N2	117.97 (18)	C15—C16—H16A	120.3
C4—C3—C2	121.0 (2)	C18—C17—C16	120.3 (2)
C4—C3—H3B	119.5	C18—C17—H17A	119.8
C2—C3—H3B	119.5	C16—C17—H17A	119.8
C5—C4—C3	118.1 (2)	C17—C18—C19	120.8 (2)
C5—C4—C13	120.9 (2)	C17—C18—H18A	119.6
C3—C4—C13	121.0 (3)	C19—C18—H18A	119.6
C4—C5—C6	122.0 (2)	C18—C19—C14	119.6 (2)
C4—C5—H5A	119.0	C18—C19—H19A	120.2
C6—C5—H5A	119.0	C14—C19—H19A	120.2
C5—C6—C1	119.7 (2)	C25—C20—C21	119.38 (18)
C5—C6—H6A	120.2	C25—C20—P	122.57 (13)
C1—C6—H6A	120.2	C21—C20—P	118.05 (15)
N1—C7—C12	109.42 (16)	C22—C21—C20	119.3 (2)
N1—C7—C8	129.50 (19)	C22—C21—H21A	120.3
C12—C7—C8	121.07 (18)	C20—C21—H21A	120.3
C9—C8—C7	116.0 (2)	C23—C22—C21	120.7 (2)
C9—C8—H8A	122.0	C23—C22—H22A	119.7
C7—C8—H8A	122.0	C21—C22—H22A	119.7
C8—C9—C10	122.6 (2)	C22—C23—C24	120.4 (2)
C8—C9—H9A	118.7	C22—C23—H23A	119.8
C10—C9—H9A	118.7	C24—C23—H23A	119.8
C11—C10—C9	122.2 (2)	C23—C24—C25	120.1 (2)
C11—C10—H10A	118.9	C23—C24—H24A	119.9
C9—C10—H10A	118.9	C25—C24—H24A	119.9
C10—C11—C12	116.5 (2)	C24—C25—C20	119.98 (19)
C10—C11—H11A	121.7	C24—C25—H25A	120.0
C12—C11—H11A	121.7	C20—C25—H25A	120.0

O2—P—O1—C1	69.76 (16)	N1—C7—C12—N3	0.0 (2)
C14—P—O1—C1	−167.96 (14)	C8—C7—C12—N3	179.2 (2)
C20—P—O1—C1	−54.64 (15)	N1—C7—C12—C11	179.55 (19)
C7—N1—N2—N3	−0.5 (2)	C8—C7—C12—C11	−1.2 (3)
C7—N1—N2—C2	179.47 (16)	C10—C11—C12—N3	−179.2 (2)
N1—N2—N3—C12	0.5 (2)	C10—C11—C12—C7	1.3 (3)
C2—N2—N3—C12	−179.50 (16)	O2—P—C14—C15	169.14 (18)
P—O1—C1—C2	145.53 (15)	O1—P—C14—C15	45.41 (19)
P—O1—C1—C6	−36.9 (2)	C20—P—C14—C15	−64.59 (19)
C6—C1—C2—C3	2.4 (3)	O2—P—C14—C19	−14.0 (2)
O1—C1—C2—C3	−179.93 (17)	O1—P—C14—C19	−137.76 (18)
C6—C1—C2—N2	−174.01 (18)	C20—P—C14—C19	112.24 (19)
O1—C1—C2—N2	3.7 (3)	C19—C14—C15—C16	−0.2 (3)
N1—N2—C2—C1	−47.2 (3)	P—C14—C15—C16	176.57 (17)
N3—N2—C2—C1	132.8 (2)	C14—C15—C16—C17	0.7 (4)
N1—N2—C2—C3	136.33 (19)	C15—C16—C17—C18	−1.6 (4)
N3—N2—C2—C3	−43.7 (2)	C16—C17—C18—C19	2.1 (5)
C1—C2—C3—C4	−0.9 (3)	C17—C18—C19—C14	−1.6 (5)
N2—C2—C3—C4	175.64 (18)	C15—C14—C19—C18	0.6 (4)
C2—C3—C4—C5	−1.0 (3)	P—C14—C19—C18	−176.3 (2)
C2—C3—C4—C13	−179.0 (2)	O2—P—C20—C25	−151.46 (15)
C3—C4—C5—C6	1.4 (4)	O1—P—C20—C25	−25.08 (17)
C13—C4—C5—C6	179.3 (3)	C14—P—C20—C25	81.63 (17)
C4—C5—C6—C1	0.1 (4)	O2—P—C20—C21	29.44 (18)
C2—C1—C6—C5	−2.0 (3)	O1—P—C20—C21	155.82 (14)
O1—C1—C6—C5	−179.60 (18)	C14—P—C20—C21	−97.47 (16)
N2—N1—C7—C12	0.33 (19)	C25—C20—C21—C22	1.0 (3)
N2—N1—C7—C8	−178.8 (2)	P—C20—C21—C22	−179.91 (17)
N1—C7—C8—C9	179.6 (2)	C20—C21—C22—C23	1.2 (3)
C12—C7—C8—C9	0.6 (3)	C21—C22—C23—C24	−1.4 (4)
C7—C8—C9—C10	0.0 (4)	C22—C23—C24—C25	−0.6 (4)
C8—C9—C10—C11	0.2 (5)	C23—C24—C25—C20	2.7 (3)
C9—C10—C11—C12	−0.8 (4)	C21—C20—C25—C24	−2.9 (3)
N2—N3—C12—C7	−0.3 (2)	P—C20—C25—C24	178.04 (16)
N2—N3—C12—C11	−179.8 (2)

Experimental details

Crystal data
Chemical formula	C₂₅H₂₀N₃O₂P
M_r	425.41
Crystal system, space group	Orthorhombic, Pca2₁
Temperature (K)	296
a, b, c (Å)	12.7691 (7), 9.4064 (5), 18.6362 (10)
V (Å³)	2238.4 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.15
Crystal size (mm)	0.30 × 0.20 × 0.15

Data collection
Diffractometer	Bruker SMART1000 CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.963, 0.974
No. of measured, independent and observed [I > 2σ(I)] reflections	11920, 3684, 3343
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.086, 1.05
No. of reflections	3684
No. of parameters	280
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.20
Absolute structure	Flack (1983), 1412 Friedel pairs
Absolute structure parameter	0.01 (7)

Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond angles (º) top

O2—P—O1	115.53 (10)	O2—P—C20	112.37 (9)
O2—P—C14	113.48 (8)	O1—P—C20	105.04 (8)
O1—P—C14	100.15 (8)	C14—P—C20	109.30 (8)

Acknowledgements

We gratefully acknowledge the financial support in part from the National Science Council, Taiwan (NSC97–2113-M-033–005-MY2) and in part from the project of the specific research fields in the Chung Yuan Christian University, Taiwan (No. CYCU-97-CR—CH).

References

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