4-Di­phenyl­phosphanyl-8-methyl-1,5-naphthyridine

Chen, C.; Wang, K.-Y.; Liu, J.-F.; Wang, D.-F.; Zhu, H.-J.

doi:10.1107/S1600536813013196

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 6| June 2013| Page o928

doi:10.1107/S1600536813013196

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4-Diphenylphosphanyl-8-methyl-1,5-naphthyridine

Chen Chen,^a Kun-Yan Wang,^a Jin-Fang Liu,^a Dan-Feng Wang ^a and Hong-Jun Zhu ^a ^*

^aDepartment of Applied Chemistry, College of Science, Nanjing University of Technology, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: zhuhjnjut@hotmail.com

(Received 8 May 2013; accepted 14 May 2013; online 18 May 2013)

In the title compound, C₂₁H₁₇N₂P, the dihedral angles between the 1,5-naphthyridine ring system (r.m.s. deviation = 0.005 Å) and the phenyl rings are 89.18 (8) and 77.39 (8)°. The phenyl rings are almost perpendicular, making a dihedral angle of 88.12 (8)°. The only possible intermolecular interaction is a very weak aromatic π–π stacking interaction [centroid–centroid separation = 3.898 (2) Å].

Related literature

For further synthetic details and background to the role of the title compound as an intermediate in the synthesis of OLED materials, see: Chen et al. (2012 ).

Experimental

Crystal data

C₂₁H₁₇N₂P
M_r = 328.34
Triclinic, $[P \overline 1]$
a = 7.2320 (14) Å
b = 7.4470 (15) Å
c = 16.780 (3) Å
α = 99.78 (3)°
β = 93.35 (3)°
γ = 98.58 (3)°
V = 877.4 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.16 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.954, T_max = 0.984
3500 measured reflections
3224 independent reflections
2285 reflections with I > 2σ(I)
R_int = 0.023
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.155
S = 1.00
3224 reflections
217 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); 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/S1600536813013196/hb7082sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813013196/hb7082Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813013196/hb7082Isup3.cml

checkCIF report

Comment top

The tittle compound, (I), is an intermediate for manufacturing OLED materials (Chen et al., 2012). We now report its crystal structure (Fig. 1).

The 1,5-naphthyridine ring system is nearly planar with an r.m.s. deviation of 0.005Å; its mean plane is oriented with respect to the two phenyl rings at 89.18 (8) and 77.39 (8)°. The two phenyl rings are twisted to each other with a dihedral angle of 88.12 (8)°. The crystal packing of the molecules in the crystal is influenced by van der Waals forces (Fig. 2).

Related literature top

For further synthetic details and background to the role of the title compound as an intermediate in the synthesis of OLED materials, see: Chen et al. (2012).

Experimental top

The title compund was synthesized according to the published procedure (Chen et al., 2012). Yellow blocks were obtained by dissolving it (0.5 g) in tetrahydrofuran (20 ml) and evaporating the solvent slowly at room temperature for about 5 d.

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); 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 displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. A packing diagram of (I).

4-Diphenylphosphanyl-8-methyl-1,5-naphthyridine top

Crystal data top

C₂₁H₁₇N₂P	Z = 2
M_r = 328.34	F(000) = 344
Triclinic, P1	D_x = 1.243 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.2320 (14) Å	Cell parameters from 25 reflections
b = 7.4470 (15) Å	θ = 10–14°
c = 16.780 (3) Å	µ = 0.16 mm⁻¹
α = 99.78 (3)°	T = 293 K
β = 93.35 (3)°	Block, yellow
γ = 98.58 (3)°	0.30 × 0.20 × 0.10 mm
V = 877.4 (3) Å³

Data collection top

Enraf–Nonius CAD-4 diffractometer	2285 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.023
Graphite monochromator	θ_max = 25.4°, θ_min = 1.2°
ω/2θ scans	h = 0→8
Absorption correction: ψ scan (North et al., 1968)	k = −8→8
T_min = 0.954, T_max = 0.984	l = −20→20
3500 measured reflections	3 standard reflections every 200 reflections
3224 independent reflections	intensity decay: 1%

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.155	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.096P)²] where P = (F_o² + 2F_c²)/3
3224 reflections	(Δ/σ)_max = 0.001
217 parameters	Δρ_max = 0.17 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₂₁H₁₇N₂P	γ = 98.58 (3)°
M_r = 328.34	V = 877.4 (3) Å³
Triclinic, P1	Z = 2
a = 7.2320 (14) Å	Mo Kα radiation
b = 7.4470 (15) Å	µ = 0.16 mm⁻¹
c = 16.780 (3) Å	T = 293 K
α = 99.78 (3)°	0.30 × 0.20 × 0.10 mm
β = 93.35 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	2285 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.023
T_min = 0.954, T_max = 0.984	3 standard reflections every 200 reflections
3500 measured reflections	intensity decay: 1%
3224 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.155	H-atom parameters constrained
S = 1.00	Δρ_max = 0.17 e Å⁻³
3224 reflections	Δρ_min = −0.23 e Å⁻³
217 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
P	0.18105 (10)	0.17196 (9)	0.71974 (4)	0.0529 (2)
N1	0.2284 (3)	0.3164 (3)	0.89550 (13)	0.0603 (6)
C1	−0.0068 (5)	−0.0965 (4)	0.59708 (17)	0.0711 (8)
H1B	−0.1116	−0.0650	0.6223	0.085*
N2	0.2453 (3)	−0.1579 (3)	0.92992 (13)	0.0569 (6)
C2	−0.0308 (6)	−0.2312 (5)	0.5287 (2)	0.0906 (11)
H2B	−0.1507	−0.2917	0.5087	0.109*
C3	0.1213 (7)	−0.2762 (5)	0.4901 (2)	0.0976 (13)
H3A	0.1048	−0.3655	0.4432	0.117*
C4	0.2974 (6)	−0.1907 (5)	0.5202 (2)	0.0914 (11)
H4A	0.4009	−0.2230	0.4942	0.110*
C5	0.3227 (5)	−0.0553 (4)	0.58980 (18)	0.0734 (8)
H5A	0.4433	0.0028	0.6098	0.088*
C6	0.1710 (4)	−0.0060 (3)	0.62951 (15)	0.0579 (7)
C7	0.4103 (3)	0.3111 (3)	0.71826 (14)	0.0501 (6)
C8	0.5758 (4)	0.2855 (4)	0.75679 (17)	0.0644 (7)
H8A	0.5754	0.1889	0.7854	0.077*
C9	0.7416 (4)	0.4013 (4)	0.75339 (19)	0.0757 (8)
H9A	0.8516	0.3842	0.7806	0.091*
C10	0.7445 (5)	0.5412 (4)	0.7101 (2)	0.0822 (10)
H10A	0.8568	0.6181	0.7071	0.099*
C11	0.5835 (5)	0.5682 (4)	0.6713 (2)	0.0844 (10)
H11A	0.5859	0.6635	0.6419	0.101*
C12	0.4175 (4)	0.4557 (3)	0.67539 (17)	0.0652 (7)
H12A	0.3080	0.4764	0.6491	0.078*
C13	0.2210 (3)	0.0390 (3)	0.79998 (14)	0.0476 (6)
C14	0.2313 (3)	0.1306 (3)	0.88168 (14)	0.0468 (6)
C15	0.2393 (5)	0.3962 (4)	0.97172 (18)	0.0744 (9)
H15A	0.2379	0.5226	0.9827	0.089*
C16	0.2527 (4)	0.3065 (4)	1.03778 (18)	0.0736 (8)
H16A	0.2609	0.3736	1.0903	0.088*
C17	0.2539 (3)	0.1222 (4)	1.02590 (15)	0.0557 (6)
C18	0.2437 (3)	0.0284 (3)	0.94493 (15)	0.0478 (6)
C19	0.2366 (4)	−0.2382 (3)	0.85361 (17)	0.0638 (7)
H19A	0.2389	−0.3645	0.8426	0.077*
C20	0.2241 (4)	−0.1471 (3)	0.78760 (16)	0.0576 (6)
H20A	0.2179	−0.2133	0.7350	0.069*
C21	0.2657 (4)	0.0179 (4)	1.09549 (16)	0.0724 (8)
H21A	0.2718	0.1022	1.1460	0.109*
H21B	0.3761	−0.0394	1.0935	0.109*
H21C	0.1565	−0.0752	1.0911	0.109*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P	0.0594 (4)	0.0457 (4)	0.0574 (4)	0.0135 (3)	0.0070 (3)	0.0149 (3)
N1	0.0850 (16)	0.0364 (11)	0.0630 (14)	0.0140 (10)	0.0175 (12)	0.0113 (10)
C1	0.086 (2)	0.0568 (16)	0.0678 (18)	−0.0071 (15)	−0.0020 (16)	0.0218 (14)
N2	0.0624 (14)	0.0436 (11)	0.0676 (14)	0.0070 (10)	0.0070 (11)	0.0191 (10)
C2	0.124 (3)	0.066 (2)	0.070 (2)	−0.022 (2)	−0.013 (2)	0.0194 (17)
C3	0.166 (4)	0.0558 (19)	0.061 (2)	−0.009 (2)	0.003 (2)	0.0081 (15)
C4	0.136 (3)	0.065 (2)	0.077 (2)	0.024 (2)	0.029 (2)	0.0121 (17)
C5	0.091 (2)	0.0604 (17)	0.0681 (18)	0.0135 (15)	0.0148 (16)	0.0055 (14)
C6	0.0759 (18)	0.0475 (14)	0.0505 (14)	0.0035 (13)	0.0023 (13)	0.0162 (11)
C7	0.0615 (15)	0.0364 (12)	0.0539 (14)	0.0121 (11)	0.0124 (12)	0.0061 (10)
C8	0.0623 (17)	0.0624 (17)	0.0735 (18)	0.0144 (14)	0.0100 (14)	0.0214 (14)
C9	0.0608 (18)	0.087 (2)	0.076 (2)	0.0133 (16)	0.0077 (15)	0.0024 (17)
C10	0.082 (2)	0.069 (2)	0.088 (2)	−0.0125 (17)	0.0211 (19)	0.0113 (17)
C11	0.100 (3)	0.0589 (18)	0.096 (2)	−0.0019 (17)	0.017 (2)	0.0296 (17)
C12	0.0796 (19)	0.0476 (14)	0.0709 (18)	0.0105 (14)	0.0071 (14)	0.0175 (13)
C13	0.0499 (14)	0.0399 (12)	0.0547 (14)	0.0068 (10)	0.0084 (11)	0.0121 (10)
C14	0.0460 (13)	0.0402 (12)	0.0560 (14)	0.0065 (10)	0.0102 (11)	0.0121 (10)
C15	0.113 (3)	0.0438 (15)	0.0681 (18)	0.0187 (15)	0.0194 (17)	0.0057 (13)
C16	0.098 (2)	0.0628 (18)	0.0591 (17)	0.0169 (16)	0.0137 (16)	0.0018 (14)
C17	0.0519 (15)	0.0614 (16)	0.0563 (15)	0.0096 (12)	0.0090 (12)	0.0152 (12)
C18	0.0437 (13)	0.0456 (13)	0.0576 (14)	0.0082 (10)	0.0116 (11)	0.0158 (11)
C19	0.082 (2)	0.0361 (13)	0.0733 (18)	0.0077 (12)	0.0043 (15)	0.0130 (12)
C20	0.0713 (17)	0.0409 (13)	0.0591 (15)	0.0070 (12)	0.0045 (13)	0.0072 (11)
C21	0.0725 (19)	0.090 (2)	0.0609 (17)	0.0143 (16)	0.0112 (14)	0.0279 (15)

Geometric parameters (Å, º) top

P—C7	1.823 (3)	C9—C10	1.367 (4)
P—C6	1.825 (3)	C9—H9A	0.9300
P—C13	1.836 (2)	C10—C11	1.358 (5)
N1—C15	1.308 (3)	C10—H10A	0.9300
N1—C14	1.367 (3)	C11—C12	1.369 (4)
C1—C2	1.374 (4)	C11—H11A	0.9300
C1—C6	1.392 (4)	C12—H12A	0.9300
C1—H1B	0.9300	C13—C20	1.370 (3)
N2—C19	1.312 (3)	C13—C14	1.416 (3)
N2—C18	1.369 (3)	C14—C18	1.413 (3)
C2—C3	1.364 (5)	C15—C16	1.394 (4)
C2—H2B	0.9300	C15—H15A	0.9300
C3—C4	1.362 (5)	C16—C17	1.355 (4)
C3—H3A	0.9300	C16—H16A	0.9300
C4—C5	1.391 (4)	C17—C18	1.411 (3)
C4—H4A	0.9300	C17—C21	1.513 (3)
C5—C6	1.380 (4)	C19—C20	1.399 (3)
C5—H5A	0.9300	C19—H19A	0.9300
C7—C8	1.381 (4)	C20—H20A	0.9300
C7—C12	1.390 (3)	C21—H21A	0.9600
C8—C9	1.379 (4)	C21—H21B	0.9600
C8—H8A	0.9300	C21—H21C	0.9600

C7—P—C6	102.31 (12)	C10—C11—H11A	119.8
C7—P—C13	102.97 (11)	C12—C11—H11A	119.8
C6—P—C13	100.69 (11)	C11—C12—C7	121.0 (3)
C15—N1—C14	115.8 (2)	C11—C12—H12A	119.5
C2—C1—C6	121.5 (3)	C7—C12—H12A	119.5
C2—C1—H1B	119.3	C20—C13—C14	116.6 (2)
C6—C1—H1B	119.3	C20—C13—P	125.1 (2)
C19—N2—C18	116.9 (2)	C14—C13—P	117.97 (16)
C3—C2—C1	119.9 (3)	N1—C14—C18	122.9 (2)
C3—C2—H2B	120.0	N1—C14—C13	117.7 (2)
C1—C2—H2B	120.0	C18—C14—C13	119.5 (2)
C4—C3—C2	120.2 (3)	N1—C15—C16	125.1 (2)
C4—C3—H3A	119.9	N1—C15—H15A	117.4
C2—C3—H3A	119.9	C16—C15—H15A	117.4
C3—C4—C5	120.1 (4)	C17—C16—C15	120.3 (3)
C3—C4—H4A	119.9	C17—C16—H16A	119.8
C5—C4—H4A	119.9	C15—C16—H16A	119.8
C6—C5—C4	120.8 (3)	C16—C17—C18	117.2 (2)
C6—C5—H5A	119.6	C16—C17—C21	122.4 (3)
C4—C5—H5A	119.6	C18—C17—C21	120.4 (2)
C5—C6—C1	117.5 (3)	N2—C18—C17	119.3 (2)
C5—C6—P	125.9 (2)	N2—C18—C14	122.1 (2)
C1—C6—P	116.6 (2)	C17—C18—C14	118.6 (2)
C8—C7—C12	117.7 (2)	N2—C19—C20	124.6 (2)
C8—C7—P	125.38 (19)	N2—C19—H19A	117.7
C12—C7—P	116.9 (2)	C20—C19—H19A	117.7
C9—C8—C7	120.8 (3)	C13—C20—C19	120.4 (2)
C9—C8—H8A	119.6	C13—C20—H20A	119.8
C7—C8—H8A	119.6	C19—C20—H20A	119.8
C10—C9—C8	120.1 (3)	C17—C21—H21A	109.5
C10—C9—H9A	120.0	C17—C21—H21B	109.5
C8—C9—H9A	120.0	H21A—C21—H21B	109.5
C11—C10—C9	120.0 (3)	C17—C21—H21C	109.5
C11—C10—H10A	120.0	H21A—C21—H21C	109.5
C9—C10—H10A	120.0	H21B—C21—H21C	109.5
C10—C11—C12	120.4 (3)

C6—C1—C2—C3	−1.3 (5)	C7—P—C13—C14	76.6 (2)
C1—C2—C3—C4	1.4 (5)	C6—P—C13—C14	−178.00 (19)
C2—C3—C4—C5	−0.9 (5)	C15—N1—C14—C18	0.5 (4)
C3—C4—C5—C6	0.3 (5)	C15—N1—C14—C13	−179.6 (2)
C4—C5—C6—C1	−0.2 (4)	C20—C13—C14—N1	−180.0 (2)
C4—C5—C6—P	−178.5 (2)	P—C13—C14—N1	−6.0 (3)
C2—C1—C6—C5	0.7 (4)	C20—C13—C14—C18	−0.1 (3)
C2—C1—C6—P	179.2 (2)	P—C13—C14—C18	173.91 (17)
C7—P—C6—C5	19.7 (3)	C14—N1—C15—C16	−0.2 (5)
C13—P—C6—C5	−86.2 (2)	N1—C15—C16—C17	−0.5 (5)
C7—P—C6—C1	−158.59 (19)	C15—C16—C17—C18	0.9 (4)
C13—P—C6—C1	95.5 (2)	C15—C16—C17—C21	−179.2 (3)
C6—P—C7—C8	−91.8 (2)	C19—N2—C18—C17	−179.6 (2)
C13—P—C7—C8	12.4 (2)	C19—N2—C18—C14	0.7 (3)
C6—P—C7—C12	88.9 (2)	C16—C17—C18—N2	179.7 (2)
C13—P—C7—C12	−166.89 (19)	C21—C17—C18—N2	−0.2 (3)
C12—C7—C8—C9	0.7 (4)	C16—C17—C18—C14	−0.6 (4)
P—C7—C8—C9	−178.5 (2)	C21—C17—C18—C14	179.5 (2)
C7—C8—C9—C10	−1.4 (4)	N1—C14—C18—N2	179.6 (2)
C8—C9—C10—C11	1.0 (5)	C13—C14—C18—N2	−0.3 (3)
C9—C10—C11—C12	0.0 (5)	N1—C14—C18—C17	−0.1 (4)
C10—C11—C12—C7	−0.7 (5)	C13—C14—C18—C17	180.0 (2)
C8—C7—C12—C11	0.3 (4)	C18—N2—C19—C20	−0.7 (4)
P—C7—C12—C11	179.6 (2)	C14—C13—C20—C19	0.1 (4)
C7—P—C13—C20	−110.0 (2)	P—C13—C20—C19	−173.4 (2)
C6—P—C13—C20	−4.6 (3)	N2—C19—C20—C13	0.3 (4)

Experimental details

Crystal data
Chemical formula	C₂₁H₁₇N₂P
M_r	328.34
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.2320 (14), 7.4470 (15), 16.780 (3)
α, β, γ (°)	99.78 (3), 93.35 (3), 98.58 (3)
V (Å³)	877.4 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.16
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.954, 0.984
No. of measured, independent and observed [I > 2σ(I)] reflections	3500, 3224, 2285
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.155, 1.00
No. of reflections	3224
No. of parameters	217
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.23

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

The authors thank the Center of Testing and Analysis, Nanjing University, for support.

References

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