Diethyl [4-(2,2′:6′,2′′-terpyridine-4′-yl)phen­yl]phospho­nate

Chyba, J.; Necas, M.; Pinkas, J.

doi:10.1107/S1600536813031541

organic compounds

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ISSN: 2056-9890

Volume 69| Part 12| December 2013| Page o1824

doi:10.1107/S1600536813031541

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Diethyl [4-(2,2′:6′,2′′-terpyridine-4′-yl)phenyl]phosphonate

Jan Chyba,^a,^b Marek Necas ^a,^b and Jiri Pinkas ^a,^b ^*

^aDepartment of Chemistry, Faculty of Science, Masaryk University, Kotlarska 2, CZ-61137 Brno, Czech Republic, and ^bCentral European Institute of Technology (CEITEC), Masaryk University, 625 00 Brno, Czech Republic
^*Correspondence e-mail: jpinkas@chemi.muni.cz

(Received 4 November 2013; accepted 19 November 2013; online 27 November 2013)

The title compound, C₂₅H₂₄N₃O₃P, was obtained by catalytic phosphonation of 4′-(4-bromphenyl)-2,2′:6′,2′′-terpyridine. The terpyridine moiety is nearly planar, the dihedral angles between the central and the outer rings being 4.06 (9) and 5.39 (9)°. The N atoms in the two pyridine rings are oriented nearly antiperiplanar to that of the central ring. The benzene ring is rotated out of the plane of the central ring of the terpyridine unit by 34.65 (6)°.

CCDC reference: 972723

Related literature

Terpyridines (Heller & Schubert, 2003 ) are frequently employed as tridentate chelating ligands for transition and rare earth metals forming very stable square planar mono- (Eryazici et al., 2008 ) or octahedral bis-complexes (Constable, 2007 , 2008 ). For related symmetrical 4′-substituted terpyridine derivatives, see: Hofmeier & Schubert (2004 ); Andres & Schubert (2004 ).

Experimental

Crystal data

C₂₅H₂₄N₃O₃P
M_r = 445.44
Monoclinic, P 2₁ /c
a = 12.5290 (4) Å
b = 13.0264 (4) Å
c = 14.5681 (5) Å
β = 111.674 (3)°
V = 2209.53 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.16 mm⁻¹
T = 120 K
0.40 × 0.40 × 0.30 mm

Data collection

Oxford Diffraction Xcalibur (Sapphire2) diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis RED and CrysAlis CCD. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.957, T_max = 1.000
23115 measured reflections
3886 independent reflections
2809 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.075
S = 1.02
3886 reflections
291 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis RED and CrysAlis CCD. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis RED and CrysAlis CCD. Oxford Diffraction Ltd, Yarnton, England.]$ ); data reduction: CrysAlis RED; 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: SHELXL97.

Supporting information

CCDC reference: 972723

Crystal structure: contains datablock I. DOI: 10.1107/S1600536813031541/nc2320sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813031541/nc2320Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813031541/nc2320Isup3.cml

checkCIF report

Comment top

The title compound was prepared as a precursor for our study of molecular aluminophosphate building blocks possessing metal-coordinating groups. The molecule presents the usual conformation of nitrogen atoms in the two pyridine rings as nearly antiperiplanar oriented to that of the central ring of the terpyridine moiety (Fig. 1). The P=O bond adopts an essentially syn conformation with the plane of the attached ring. The torsion angle O3–P1–C44–C43 is 6.93 (14)°. Thus, the ethyl groups are conveniently located below and above the plane of the ring. All four aromatic rings are planar, with r.m.s. deviations not exceeding 0.0066 Å.

Related literature top

Terpyridines (Heller & Schubert, 2003) are frequently employed as tridentate chelating ligands for transition and rare earth metals forming very stable square planar mono- (Eryazici et al., 2008) or octahedral bis-complexes (Constable, 2007, 2008). For related symmetrical 4'-substituted terpyridine derivatives, see: Hofmeier & Schubert (2004); Andres & Schubert (2004).

Experimental top

To a mixture of diethylphosphite (C₂H₅O)₂P(O)H (1.1 cm³, 8.5 mmol, Fluka), triethylamine (1.3 cm³, 9.4 mmol) and tetrakis(triphenylphosphine)palladium (0.337 g, 0.292 mmol), a solution of 4'-(4-bromophenyl)-2,2':6',2''-terpyridine (2.268 g, 5.841 mmol) in toluene (10 cm³) was added at 50 °C. The reaction mixture was stirred for 3.5 h at 90 °C and a white solid triethylammonium bromide precipitated. After cooling, the solid was filtered off and all volatile components were removed from the filtrate under vacuum. The final product was isolated by liquid chromatography (stationary phase: silicagel, mobile phase: petrolether, ethylacetate, triethylamine – 1:1:0.04). Yield 46.7% (1.215 g). M>.p. 122 °C. Single crystals suitable for X-ray diffraction analysis were obtained by a slow evaporation of a CHCl₃ solution.

NMR spectra were obtained on a Bruker AVANCE DRX 300 MHz spectrometer.

¹H NMR (300.13 MHz, CDCl₃): δ (p.p.m.) = 1.34 (t, 6H); 4.15 (m, 4H); 7.34 (m, 2H); 7.86 (m, 2H); 7.94 (AA'XX', m, 2H); 8.12 (AA'XX', m, 2H); 8.65 (m, 2H); 8.71 (m, 2H); 8.73 (s, 2H). ¹³C{¹H} NMR (75.48 MHz, CD₂Cl₂): δ (p.p.m.) = 16.8 (d, ³J_PC = 6.0 Hz); 62.7 (d, ²J_PC = 5.5 Hz); 119.1; 121.6; 124.4; 127.7 (d, ²J_PC = 15.4 Hz); 129.9 (d, ¹J_PC = 188.2 Hz); 132.8 (d, ³J_PC = 9.8 Hz); 137.2; 142.8 (d, ⁴J_PC = 3.2 Hz); 149.2; 149.6; 156.2; 156.6. ³¹P{¹H} NMR (121.50 MHz, CD₂Cl₂): δ (p.p.m.) = 18.8 (s).

Mass spectra were recorded on a quadrupole mass spectrometer TRIO 1000 series II, Finnigan MAT, Fisons Instruments, with resolution of 1 m/z in the range 0–1000 m/z. Mass spectrum (EI) m/z 445 (M⁺).

IR spectra were measured on a IFS 28 Bruker spectrometer on samples prepared as KBr pellets (1.5 mg in 100 mg of KBr). IR (KBr pellet, cm^-1): ν 3051 w, 2988 m, 2941 w, 2895 w, 1583 s, 1567 m, 1535 m, 1468 m, 1382 m, 1245 vs, 1163 m, 1132 m, 1058 s, 1024 vs, 972 vs, 958 s, 839 w, 794 s, 774 m, 747 m, 669 m, 622 w, 575 s, 533 m.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis RED (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 2009); 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: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. : ORTEP of the asymmetric unit with atoms represented as 50% probability ellipsoids.

Diethyl [4-(2,2':6',2''-terpyridine-4'-yl)phenyl]phosphonate top

Crystal data top

C₂₅H₂₄N₃O₃P	F(000) = 936
M_r = 445.44	D_x = 1.339 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25622 reflections
a = 12.5290 (4) Å	θ = 2.9–27.1°
b = 13.0264 (4) Å	µ = 0.16 mm⁻¹
c = 14.5681 (5) Å	T = 120 K
β = 111.674 (3)°	Prism, colourless
V = 2209.53 (12) Å³	0.40 × 0.40 × 0.30 mm
Z = 4

Data collection top

Oxford Diffraction Xcalibur (Sapphire2) diffractometer	3886 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2809 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
Detector resolution: 8.4353 pixels mm^-1	θ_max = 25.0°, θ_min = 2.9°
ω scan	h = −14→14
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	k = −15→15
T_min = 0.957, T_max = 1.000	l = −17→17
23115 measured reflections

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.075	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0428P)²] where P = (F_o² + 2F_c²)/3
3886 reflections	(Δ/σ)_max = 0.001
291 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.36 e Å⁻³

Crystal data top

C₂₅H₂₄N₃O₃P	V = 2209.53 (12) Å³
M_r = 445.44	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.5290 (4) Å	µ = 0.16 mm⁻¹
b = 13.0264 (4) Å	T = 120 K
c = 14.5681 (5) Å	0.40 × 0.40 × 0.30 mm
β = 111.674 (3)°

Data collection top

Oxford Diffraction Xcalibur (Sapphire2) diffractometer	3886 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	2809 reflections with I > 2σ(I)
T_min = 0.957, T_max = 1.000	R_int = 0.027
23115 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.075	H-atom parameters constrained
S = 1.02	Δρ_max = 0.26 e Å⁻³
3886 reflections	Δρ_min = −0.36 e Å⁻³
291 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
P1	0.50120 (4)	0.72076 (3)	−0.00200 (3)	0.02069 (12)
O1	0.46530 (9)	0.83650 (7)	−0.02492 (7)	0.0275 (3)
O2	0.39364 (8)	0.67611 (7)	0.01687 (7)	0.0228 (3)
O3	0.53164 (9)	0.66516 (8)	−0.07662 (7)	0.0272 (3)
C11	0.89136 (13)	0.75905 (11)	0.39920 (11)	0.0200 (3)
C12	0.98093 (13)	0.68836 (11)	0.43599 (11)	0.0209 (4)
H12	0.9839	0.6300	0.3979	0.025*
C13	1.06611 (13)	0.70391 (11)	0.52914 (11)	0.0207 (4)
N14	1.06504 (10)	0.78575 (9)	0.58592 (9)	0.0217 (3)
C15	0.97864 (13)	0.85442 (11)	0.54983 (11)	0.0190 (3)
C16	0.89195 (13)	0.84309 (11)	0.45779 (10)	0.0185 (3)
H16	0.8328	0.8931	0.4348	0.022*
C21	1.16156 (13)	0.62884 (11)	0.57298 (11)	0.0213 (4)
N22	1.15825 (11)	0.54273 (10)	0.52078 (9)	0.0263 (3)
C23	1.24131 (14)	0.47314 (12)	0.56195 (12)	0.0291 (4)
H23	1.2398	0.4117	0.5263	0.035*
C24	1.32901 (14)	0.48532 (12)	0.65303 (12)	0.0291 (4)
H24	1.3855	0.4335	0.6791	0.035*
C25	1.33247 (14)	0.57469 (13)	0.70507 (12)	0.0303 (4)
H25	1.3919	0.5859	0.7675	0.036*
C26	1.24803 (13)	0.64732 (12)	0.66465 (11)	0.0252 (4)
H26	1.2487	0.7095	0.6990	0.030*
C31	0.97814 (13)	0.94306 (11)	0.61461 (11)	0.0194 (4)
N32	0.89127 (10)	1.01071 (10)	0.57719 (9)	0.0257 (3)
C33	0.88630 (14)	1.08950 (12)	0.63477 (12)	0.0286 (4)
H33	0.8261	1.1381	0.6087	0.034*
C34	0.96454 (14)	1.10380 (12)	0.73049 (12)	0.0281 (4)
H34	0.9577	1.1602	0.7693	0.034*
C35	1.05227 (15)	1.03371 (12)	0.76736 (12)	0.0310 (4)
H35	1.1073	1.0410	0.8326	0.037*
C36	1.05986 (14)	0.95269 (11)	0.70898 (11)	0.0251 (4)
H36	1.1204	0.9042	0.7333	0.030*
C41	0.79611 (13)	0.74623 (10)	0.30129 (10)	0.0195 (3)
C42	0.81495 (13)	0.70342 (11)	0.22064 (11)	0.0237 (4)
H42	0.8895	0.6798	0.2285	0.028*
C43	0.72622 (13)	0.69490 (11)	0.12923 (11)	0.0236 (4)
H43	0.7408	0.6657	0.0753	0.028*
C44	0.61595 (13)	0.72881 (10)	0.11592 (11)	0.0189 (3)
C45	0.59641 (13)	0.76988 (11)	0.19754 (11)	0.0199 (3)
H45	0.5215	0.7921	0.1902	0.024*
C46	0.68515 (13)	0.77839 (10)	0.28863 (11)	0.0192 (3)
H46	0.6704	0.8064	0.3430	0.023*
C51	0.36229 (14)	0.86636 (12)	−0.10752 (12)	0.0311 (4)
H51A	0.2930	0.8506	−0.0927	0.037*
H51B	0.3574	0.8284	−0.1678	0.037*
C52	0.36991 (14)	0.97985 (11)	−0.12287 (12)	0.0276 (4)
H52A	0.3027	1.0020	−0.1796	0.041*
H52B	0.4399	0.9948	−0.1355	0.041*
H52C	0.3720	1.0167	−0.0636	0.041*
C61	0.39903 (14)	0.56972 (11)	0.05077 (12)	0.0241 (4)
H61A	0.4794	0.5449	0.0748	0.029*
H61B	0.3522	0.5251	−0.0044	0.029*
C62	0.35357 (15)	0.56613 (12)	0.13283 (11)	0.0318 (4)
H62A	0.3562	0.4953	0.1563	0.048*
H62B	0.2740	0.5907	0.1083	0.048*
H62C	0.4008	0.6100	0.1874	0.048*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.0205 (2)	0.0200 (2)	0.0200 (2)	−0.00170 (18)	0.00562 (18)	0.00025 (18)
O1	0.0267 (7)	0.0211 (6)	0.0264 (6)	−0.0013 (5)	0.0002 (5)	0.0043 (5)
O2	0.0203 (6)	0.0203 (5)	0.0264 (6)	−0.0003 (5)	0.0069 (5)	0.0015 (5)
O3	0.0278 (7)	0.0316 (6)	0.0216 (6)	−0.0048 (5)	0.0086 (5)	−0.0032 (5)
C11	0.0192 (9)	0.0223 (8)	0.0202 (9)	−0.0005 (7)	0.0093 (7)	0.0025 (7)
C12	0.0212 (9)	0.0224 (8)	0.0189 (9)	−0.0014 (7)	0.0072 (8)	−0.0026 (7)
C13	0.0201 (9)	0.0222 (8)	0.0202 (9)	−0.0031 (7)	0.0079 (8)	0.0019 (7)
N14	0.0218 (8)	0.0241 (7)	0.0189 (7)	−0.0020 (6)	0.0072 (6)	0.0017 (6)
C15	0.0164 (9)	0.0224 (8)	0.0184 (8)	−0.0025 (7)	0.0069 (7)	0.0034 (7)
C16	0.0163 (9)	0.0208 (8)	0.0182 (8)	0.0013 (6)	0.0062 (7)	0.0032 (6)
C21	0.0192 (9)	0.0248 (8)	0.0197 (9)	−0.0030 (7)	0.0071 (8)	0.0022 (7)
N22	0.0253 (8)	0.0261 (7)	0.0269 (8)	0.0017 (6)	0.0087 (7)	0.0025 (6)
C23	0.0293 (11)	0.0248 (9)	0.0349 (10)	0.0012 (8)	0.0139 (9)	0.0029 (7)
C24	0.0203 (10)	0.0293 (9)	0.0350 (10)	0.0028 (7)	0.0070 (8)	0.0124 (8)
C25	0.0211 (10)	0.0368 (10)	0.0271 (10)	−0.0033 (8)	0.0021 (8)	0.0060 (8)
C26	0.0226 (10)	0.0262 (9)	0.0236 (9)	−0.0025 (7)	0.0048 (8)	0.0001 (7)
C31	0.0166 (9)	0.0228 (9)	0.0194 (9)	−0.0028 (7)	0.0073 (8)	0.0028 (7)
N32	0.0215 (8)	0.0285 (7)	0.0246 (8)	−0.0009 (6)	0.0057 (6)	−0.0042 (6)
C33	0.0219 (10)	0.0310 (9)	0.0323 (10)	−0.0005 (8)	0.0093 (8)	−0.0069 (8)
C34	0.0291 (10)	0.0322 (9)	0.0263 (10)	−0.0074 (8)	0.0141 (9)	−0.0106 (7)
C35	0.0308 (11)	0.0379 (10)	0.0195 (9)	−0.0040 (8)	0.0038 (8)	−0.0041 (8)
C36	0.0243 (10)	0.0276 (9)	0.0191 (9)	0.0010 (7)	0.0028 (8)	0.0013 (7)
C41	0.0199 (9)	0.0171 (8)	0.0198 (9)	−0.0010 (6)	0.0054 (8)	0.0011 (6)
C42	0.0167 (9)	0.0273 (9)	0.0261 (10)	0.0034 (7)	0.0066 (8)	−0.0026 (7)
C43	0.0246 (10)	0.0257 (9)	0.0215 (9)	−0.0001 (7)	0.0098 (8)	−0.0044 (7)
C44	0.0197 (9)	0.0152 (7)	0.0216 (9)	−0.0007 (7)	0.0072 (7)	0.0020 (6)
C45	0.0165 (9)	0.0192 (8)	0.0231 (9)	0.0022 (7)	0.0063 (8)	0.0022 (7)
C46	0.0227 (9)	0.0156 (7)	0.0205 (9)	0.0016 (7)	0.0093 (8)	−0.0009 (6)
C51	0.0262 (10)	0.0300 (9)	0.0292 (10)	0.0014 (8)	0.0011 (8)	0.0062 (8)
C52	0.0260 (10)	0.0269 (9)	0.0275 (9)	0.0029 (7)	0.0070 (8)	0.0034 (7)
C61	0.0239 (10)	0.0180 (8)	0.0294 (9)	−0.0006 (7)	0.0087 (8)	0.0017 (7)
C62	0.0351 (11)	0.0312 (9)	0.0287 (10)	−0.0044 (8)	0.0115 (9)	0.0024 (8)

Geometric parameters (Å, º) top

P1—O3	1.4691 (10)	C33—C34	1.389 (2)
P1—O1	1.5734 (10)	C33—H33	0.9500
P1—O2	1.5822 (10)	C34—C35	1.376 (2)
P1—C44	1.7902 (16)	C34—H34	0.9500
O1—C51	1.4553 (17)	C35—C36	1.381 (2)
O2—C61	1.4644 (16)	C35—H35	0.9500
C11—C16	1.3865 (19)	C36—H36	0.9500
C11—C12	1.397 (2)	C41—C42	1.3972 (19)
C11—C41	1.493 (2)	C41—C46	1.397 (2)
C12—C13	1.397 (2)	C42—C43	1.389 (2)
C12—H12	0.9500	C42—H42	0.9500
C13—N14	1.3524 (18)	C43—C44	1.394 (2)
C13—C21	1.493 (2)	C43—H43	0.9500
N14—C15	1.3520 (18)	C44—C45	1.4053 (19)
C15—C16	1.387 (2)	C45—C46	1.386 (2)
C15—C31	1.4928 (19)	C45—H45	0.9500
C16—H16	0.9500	C46—H46	0.9500
C21—N22	1.3472 (18)	C51—C52	1.503 (2)
C21—C26	1.395 (2)	C51—H51A	0.9900
N22—C23	1.3429 (19)	C51—H51B	0.9900
C23—C24	1.384 (2)	C52—H52A	0.9800
C23—H23	0.9500	C52—H52B	0.9800
C24—C25	1.381 (2)	C52—H52C	0.9800
C24—H24	0.9500	C61—C62	1.503 (2)
C25—C26	1.379 (2)	C61—H61A	0.9900
C25—H25	0.9500	C61—H61B	0.9900
C26—H26	0.9500	C62—H62A	0.9800
C31—N32	1.3491 (18)	C62—H62B	0.9800
C31—C36	1.384 (2)	C62—H62C	0.9800
N32—C33	1.3414 (19)

O3—P1—O1	116.57 (6)	C33—C34—H34	121.0
O3—P1—O2	114.70 (6)	C34—C35—C36	119.57 (15)
O1—P1—O2	101.19 (6)	C34—C35—H35	120.2
O3—P1—C44	113.77 (7)	C36—C35—H35	120.2
O1—P1—C44	102.29 (6)	C35—C36—C31	119.17 (15)
O2—P1—C44	106.77 (6)	C35—C36—H36	120.4
C51—O1—P1	121.89 (9)	C31—C36—H36	120.4
C61—O2—P1	118.05 (9)	C42—C41—C46	118.52 (14)
C16—C11—C12	117.61 (14)	C42—C41—C11	121.62 (14)
C16—C11—C41	119.81 (13)	C46—C41—C11	119.86 (13)
C12—C11—C41	122.57 (13)	C43—C42—C41	120.96 (14)
C11—C12—C13	119.64 (14)	C43—C42—H42	119.5
C11—C12—H12	120.2	C41—C42—H42	119.5
C13—C12—H12	120.2	C42—C43—C44	120.62 (14)
N14—C13—C12	122.12 (14)	C42—C43—H43	119.7
N14—C13—C21	116.23 (13)	C44—C43—H43	119.7
C12—C13—C21	121.62 (13)	C43—C44—C45	118.44 (14)
C15—N14—C13	118.11 (13)	C43—C44—P1	121.22 (11)
N14—C15—C16	122.29 (13)	C45—C44—P1	120.34 (12)
N14—C15—C31	117.10 (13)	C46—C45—C44	120.79 (14)
C16—C15—C31	120.59 (13)	C46—C45—H45	119.6
C11—C16—C15	120.22 (13)	C44—C45—H45	119.6
C11—C16—H16	119.9	C45—C46—C41	120.65 (13)
C15—C16—H16	119.9	C45—C46—H46	119.7
N22—C21—C26	122.35 (14)	C41—C46—H46	119.7
N22—C21—C13	116.81 (13)	O1—C51—C52	107.47 (12)
C26—C21—C13	120.83 (14)	O1—C51—H51A	110.2
C23—N22—C21	116.92 (13)	C52—C51—H51A	110.2
N22—C23—C24	124.10 (15)	O1—C51—H51B	110.2
N22—C23—H23	117.9	C52—C51—H51B	110.2
C24—C23—H23	117.9	H51A—C51—H51B	108.5
C25—C24—C23	118.39 (15)	C51—C52—H52A	109.5
C25—C24—H24	120.8	C51—C52—H52B	109.5
C23—C24—H24	120.8	H52A—C52—H52B	109.5
C26—C25—C24	118.71 (15)	C51—C52—H52C	109.5
C26—C25—H25	120.6	H52A—C52—H52C	109.5
C24—C25—H25	120.6	H52B—C52—H52C	109.5
C25—C26—C21	119.51 (15)	O2—C61—C62	108.30 (12)
C25—C26—H26	120.2	O2—C61—H61A	110.0
C21—C26—H26	120.2	C62—C61—H61A	110.0
N32—C31—C36	122.19 (14)	O2—C61—H61B	110.0
N32—C31—C15	116.16 (13)	C62—C61—H61B	110.0
C36—C31—C15	121.60 (13)	H61A—C61—H61B	108.4
C33—N32—C31	117.64 (13)	C61—C62—H62A	109.5
N32—C33—C34	123.48 (15)	C61—C62—H62B	109.5
N32—C33—H33	118.3	H62A—C62—H62B	109.5
C34—C33—H33	118.3	C61—C62—H62C	109.5
C35—C34—C33	117.94 (15)	H62A—C62—H62C	109.5
C35—C34—H34	121.0	H62B—C62—H62C	109.5

O3—P1—O1—C51	64.82 (12)	N14—C15—C31—C36	−2.4 (2)
O2—P1—O1—C51	−60.30 (12)	C16—C15—C31—C36	176.11 (13)
C44—P1—O1—C51	−170.42 (11)	C36—C31—N32—C33	0.3 (2)
O3—P1—O2—C61	59.59 (11)	C15—C31—N32—C33	177.95 (12)
O1—P1—O2—C61	−174.05 (10)	C31—N32—C33—C34	−0.9 (2)
C44—P1—O2—C61	−67.41 (11)	N32—C33—C34—C35	0.7 (2)
C16—C11—C12—C13	0.5 (2)	C33—C34—C35—C36	0.1 (2)
C41—C11—C12—C13	−178.66 (13)	C34—C35—C36—C31	−0.6 (2)
C11—C12—C13—N14	0.1 (2)	N32—C31—C36—C35	0.4 (2)
C11—C12—C13—C21	178.06 (13)	C15—C31—C36—C35	−177.07 (14)
C12—C13—N14—C15	−0.6 (2)	C16—C11—C41—C42	145.39 (14)
C21—C13—N14—C15	−178.60 (12)	C12—C11—C41—C42	−35.5 (2)
C13—N14—C15—C16	0.4 (2)	C16—C11—C41—C46	−33.99 (19)
C13—N14—C15—C31	178.91 (12)	C12—C11—C41—C46	145.12 (14)
C12—C11—C16—C15	−0.6 (2)	C46—C41—C42—C43	1.4 (2)
C41—C11—C16—C15	178.51 (13)	C11—C41—C42—C43	−177.99 (13)
N14—C15—C16—C11	0.2 (2)	C41—C42—C43—C44	−0.1 (2)
C31—C15—C16—C11	−178.24 (12)	C42—C43—C44—C45	−1.2 (2)
N14—C13—C21—N22	174.58 (12)	C42—C43—C44—P1	178.75 (11)
C12—C13—C21—N22	−3.5 (2)	O3—P1—C44—C43	6.93 (14)
N14—C13—C21—C26	−4.2 (2)	O1—P1—C44—C43	−119.67 (12)
C12—C13—C21—C26	177.82 (13)	O2—P1—C44—C43	134.48 (11)
C26—C21—N22—C23	1.4 (2)	O3—P1—C44—C45	−173.13 (11)
C13—C21—N22—C23	−177.27 (12)	O1—P1—C44—C45	60.27 (12)
C21—N22—C23—C24	−0.6 (2)	O2—P1—C44—C45	−45.58 (13)
N22—C23—C24—C25	−0.5 (2)	C43—C44—C45—C46	1.3 (2)
C23—C24—C25—C26	0.6 (2)	P1—C44—C45—C46	−178.67 (11)
C24—C25—C26—C21	0.2 (2)	C44—C45—C46—C41	0.0 (2)
N22—C21—C26—C25	−1.3 (2)	C42—C41—C46—C45	−1.3 (2)
C13—C21—C26—C25	177.38 (14)	C11—C41—C46—C45	178.09 (13)
N14—C15—C31—N32	179.95 (12)	P1—O1—C51—C52	−166.13 (10)
C16—C15—C31—N32	−1.51 (19)	P1—O2—C61—C62	135.67 (11)

Experimental details

Crystal data
Chemical formula	C₂₅H₂₄N₃O₃P
M_r	445.44
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	120
a, b, c (Å)	12.5290 (4), 13.0264 (4), 14.5681 (5)
β (°)	111.674 (3)
V (Å³)	2209.53 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.16
Crystal size (mm)	0.40 × 0.40 × 0.30

Data collection
Diffractometer	Oxford Diffraction Xcalibur (Sapphire2) diffractometer
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2009)
T_min, T_max	0.957, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	23115, 3886, 2809
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.075, 1.02
No. of reflections	3886
No. of parameters	291
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.36

Computer programs: CrysAlis CCD (Oxford Diffraction, 2009), CrysAlis RED (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

This work was supported by CEITEC–Central European Institute of Technology (CZ.1.05/1.1.00/02.0068) and GACR P207/11/0555.

References

Andres, R. P. & Schubert, U. S. (2004). Adv. Mater. 16, 1043–1068. Web of Science CrossRef CAS Google Scholar
Constable, E. C. (2007). Chem. Soc. Rev. 36, 246–253. Web of Science CrossRef PubMed CAS Google Scholar
Constable, E. C. (2008). Coord. Chem. Rev. 252, 842–855. Web of Science CrossRef CAS Google Scholar
Eryazici, I., Moorefield, C. N. & Newkome, G. R. (2008). Chem. Rev. 108, 1834–1895. Web of Science CrossRef PubMed CAS Google Scholar
Heller, M. & Schubert, U. S. (2003). Eur. J. Org. Chem. pp. 947–961. CrossRef Google Scholar
Hofmeier, H. & Schubert, U. S. (2004). Chem. Soc. Rev. 33, 373–399. Web of Science CrossRef PubMed CAS Google Scholar
Oxford Diffraction (2009). CrysAlis RED and CrysAlis CCD. Oxford Diffraction Ltd, Yarnton, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar