Diethyl [4-(2,2':6',2''-terpyridine-4'-yl)phen-yl]phospho-nate.

The title compound, C25H24N3O3P, was obtained by catalytic phospho-nation of 4'-(4-bromphen-yl)-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 anti-periplanar 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)°.

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 = 445.44

Monoclinic,

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 ▶) 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[F 2 > 2σ(F 2)] = 0.030

wR(F 2) = 0.075

S = 1.02

3886 reflections

291 parameters

H-atom parameters constrained

Δρmax = 0.26 e Å−3

Δρmin = −0.36 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2009 ▶); 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.

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

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

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813031541/nc2320Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C25H24N3O3P	F(000) = 936
Mr = 445.44	Dx = 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

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

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(Fo2) + (0.0428P)2] where P = (Fo2 + 2Fc2)/3
3886 reflections	(Δ/σ)max = 0.001
291 parameters	Δρmax = 0.26 e Å−3
0 restraints	Δρmin = −0.36 e Å−3

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)