Chloro­bis­(naphthalen-1-yl)phosphane

Foi, A.; Suarez, S.A.; Doctorovich, F.

doi:10.1107/S1600536811033782

organic compounds

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ISSN: 2056-9890

Volume 67| Part 9| September 2011| Page o2524

doi:10.1107/S1600536811033782

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Chlorobis(naphthalen-1-yl)phosphane

Ana Foi,^a Sebastian A. Suarez ^a and Fabio Doctorovich ^a ^*

^aDepartamento de Química Inorgánica, Analítica y Química Física/INQUIMAE-CONICET, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Argentina
^*Correspondence e-mail: doctorovich@qi.fcen.uba.ar

(Received 29 July 2011; accepted 18 August 2011; online 31 August 2011)

In the title compound, C₂₀H₁₄ClP, the dihedral angle between the naphthyl rings is 81.77 (6)°. The crystal packing suggests weak π–π stacking interactions between the naphthyl rings in adjacent units [minimum ring centroid separation 3.7625 (13) Å].

Related literature

For the structure of a similar compound, see: Schiemenz et al. (2003 ). For details of the synthetic procedures, see: Wesemann et al. (1992 ).

Experimental

Crystal data

C₂₀H₁₄ClP
M_r = 320.76
Monoclinic, P 2₁ /c
a = 12.4335 (6) Å
b = 10.4510 (4) Å
c = 11.9293 (7) Å
β = 93.180 (5)°
V = 1547.74 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.34 mm⁻¹
T = 298 K
0.30 × 0.20 × 0.10 mm

Data collection

Oxford Gemini E CCD diffractometer
8306 measured reflections
3531 independent reflections
1723 reflections with I > 2σ(I)
R_int = 0.041

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.079
S = 0.78
3531 reflections
199 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS86 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811033782/zs2136sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811033782/zs2136Isup2.hkl

checkCIF report

Comment top

The title compound, C₂₀H₁₄ClP, was obtained in the course of our continuing studies on the synthesis of phosphonium salts, with the aim of using them as building blocks in crystal engineering. In the structure (Fig. 1), the dihedral angle between the naphthyl rings is 81.77 (6)°, corresponding to torsion angles C1—P1—C11—C12 and C11—P1—C1—C2 of 100.58 (18)° and 2.03 (18)° respectively while an intramolecular C—H···Cl hydrogen-bonding interaction [C12—H12···Cl1, 3.128 (2) Å] stabilizes the conformation of one of the naphthyl rings [torsion angle Cl1—P1—C11—C12 = -1.68 (18)°]. Both of these naphthyl ring systems are essentially planar, with mean deviations from their least-square planes of 0.071 (2) Å for the C1–C10 system and 0.021 (2) Å for the C11–C20 system. The structural analysis of the title compound shows no significant bond differences compared to those found in similar structures, e.g. the P—Cl distance [2.0867 (8) Å cf. 2.10 (6) Å] and the P—C distances [P1—C1, 1.8294 (18) Å and P1–C11, 1.8309 (19) Å] comparing with 1.84 (3) Å.

A comparison with the previously reported structure of bis(8-diethylaminonaphth-1-yl)phosphine (Schiemenz et al., 2003) which shows no evidence of π–π stacking interactions, differs from that of the title compound which shows weak interactions between the naphthalene rings in adjacent molecules [minimum ring centroid separation, 3.7625 (13) Å]. It is likely that due to the presence of Cl instead of the group N(CH₃)₂ there is less steric repulsion between the substituents, which is evidenced by a smaller separation between the naphthyl moieties, allowing the π–π interactions between the aromatic rings to take place.

Related literature top

For the structure of a similar compound, see: Schiemenz et al. (2003). For details of the synthetic procedures, see: Wesemann et al. (1992).

Experimental top

The title compound was obtained as a by product in the synthesis of tris(1-naphthyl)phosphine (Wesemann et al., 1992). The synthesis was carried out in two steps. 7.27 mmol of 2-bromonaphthalene and 7.37 mmol of n-butyllithium were added to 20 ml of diethyl ether at -30°C, in order to obtain the naphthyllithium intermediate. 2.4 mmol of PCl₃ dissolved in 10 ml of diethyl ether were added to the reaction mixture and refluxed for 2 h. The by product chlorobis(1-naphthyl)phosphine was separated from the major product of the synthesis (tris(1-naphthyl)phosphine), after recrystallization of the reaction mixture from toluene.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS86 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. Molecular conformation and atom numbering scheme for the title compound. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Crystal packing for the title compound viewed along a (A) and along b (B)
	Fig. 3. Packing arrangement for different bis(1-naphthyl)phosphines. A = the title compound; B = bis(8-diethylaminonaphth-1-yl)phosphine.

Chlorobis(naphthalen-1-yl)phosphane top

Crystal data top

C₂₀H₁₄ClP	F(000) = 664
M_r = 320.76	D_x = 1.377 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2101 reflections
a = 12.4335 (6) Å	θ = 3.6–28.6°
b = 10.4510 (4) Å	µ = 0.34 mm⁻¹
c = 11.9293 (7) Å	T = 298 K
β = 93.180 (5)°	Prism, colourless
V = 1547.74 (13) Å³	0.30 × 0.20 × 0.10 mm
Z = 4

Data collection top

Oxford Gemini E CCD diffractometer	R_int = 0.041
Graphite monochromator	θ_max = 28.7°, θ_min = 3.7°
ω scans	h = −16→16
8306 measured reflections	k = −14→12
3531 independent reflections	l = −15→11
1723 reflections with I > 2σ(I)

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.079	H-atom parameters constrained
S = 0.78	w = 1/[σ²(F_o²) + (0.0359P)²] where P = (F_o² + 2F_c²)/3
3531 reflections	(Δ/σ)_max < 0.001
199 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₂₀H₁₄ClP	V = 1547.74 (13) Å³
M_r = 320.76	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.4335 (6) Å	µ = 0.34 mm⁻¹
b = 10.4510 (4) Å	T = 298 K
c = 11.9293 (7) Å	0.30 × 0.20 × 0.10 mm
β = 93.180 (5)°

Data collection top

Oxford Gemini E CCD diffractometer	1723 reflections with I > 2σ(I)
8306 measured reflections	R_int = 0.041
3531 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.079	H-atom parameters constrained
S = 0.78	Δρ_max = 0.24 e Å⁻³
3531 reflections	Δρ_min = −0.22 e Å⁻³
199 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
Cl1	0.85651 (5)	−0.90729 (5)	0.04716 (6)	0.0721 (2)
P1	0.80969 (4)	−0.75005 (5)	−0.05171 (5)	0.04255 (16)
C6	0.60540 (16)	−0.85615 (17)	−0.10376 (16)	0.0369 (5)
C12	0.89415 (16)	−0.63352 (18)	0.14784 (19)	0.0462 (6)
H12	0.8979	−0.7154	0.1783	0.055*
C5	0.49261 (17)	−0.86465 (19)	−0.09499 (18)	0.0444 (6)
C1	0.66389 (14)	−0.76001 (17)	−0.03965 (15)	0.0357 (5)
C17	0.79619 (16)	−0.46293 (19)	−0.11219 (18)	0.0470 (6)
H17	0.7693	−0.5296	−0.1572	0.056*
C16	0.84215 (14)	−0.49050 (17)	−0.00446 (17)	0.0335 (5)
C15	0.88282 (15)	−0.38650 (17)	0.06173 (19)	0.0403 (5)
C14	0.92955 (17)	−0.4102 (2)	0.1698 (2)	0.0509 (6)
H14	0.9573	−0.3424	0.2127	0.061*
C7	0.65511 (18)	−0.94555 (18)	−0.17321 (17)	0.0468 (6)
H7	0.7291	−0.941	−0.1808	0.056*
C4	0.44061 (17)	−0.7756 (2)	−0.02860 (19)	0.0532 (6)
H4	0.3663	−0.7801	−0.0242	0.064*
C2	0.60878 (16)	−0.67670 (18)	0.02485 (17)	0.0454 (5)
H2	0.6467	−0.6145	0.0665	0.054*
C20	0.87568 (16)	−0.26148 (18)	0.0175 (2)	0.0511 (6)
H20	0.9025	−0.1932	0.0605	0.061*
C13	0.93470 (16)	−0.5302 (2)	0.21200 (18)	0.0526 (6)
H13	0.9652	−0.5442	0.2839	0.063*
C19	0.83054 (17)	−0.2391 (2)	−0.0863 (2)	0.0593 (6)
H19	0.8263	−0.1559	−0.1139	0.071*
C9	0.4862 (2)	−1.0482 (2)	−0.2178 (2)	0.0663 (7)
H9	0.4475	−1.1132	−0.2548	0.08*
C3	0.49639 (18)	−0.6832 (2)	0.02937 (19)	0.0551 (6)
H3	0.4602	−0.6243	0.072	0.066*
C11	0.84924 (15)	−0.61702 (16)	0.04156 (17)	0.0352 (5)
C18	0.79022 (18)	−0.3405 (2)	−0.1522 (2)	0.0580 (6)
H18	0.7592	−0.3247	−0.2235	0.07*
C8	0.5971 (2)	−1.0381 (2)	−0.22923 (19)	0.0602 (7)
H8	0.6314	−1.0951	−0.2754	0.072*
C10	0.43458 (19)	−0.9638 (2)	−0.1532 (2)	0.0589 (7)
H10	0.3606	−0.9709	−0.147	0.071*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0613 (4)	0.0341 (3)	0.1182 (6)	0.0056 (3)	−0.0207 (4)	0.0046 (3)
P1	0.0398 (3)	0.0334 (3)	0.0549 (4)	−0.0021 (3)	0.0067 (2)	−0.0070 (3)
C6	0.0423 (13)	0.0346 (10)	0.0333 (13)	−0.0041 (10)	−0.0034 (10)	0.0071 (10)
C12	0.0440 (13)	0.0444 (12)	0.0503 (16)	−0.0002 (11)	0.0027 (11)	0.0071 (11)
C5	0.0425 (13)	0.0484 (12)	0.0412 (14)	−0.0072 (11)	−0.0072 (11)	0.0142 (11)
C1	0.0362 (11)	0.0328 (10)	0.0380 (12)	−0.0014 (10)	0.0018 (9)	0.0063 (10)
C17	0.0461 (13)	0.0416 (11)	0.0529 (15)	−0.0009 (10)	0.0000 (11)	0.0017 (11)
C16	0.0280 (11)	0.0334 (10)	0.0393 (13)	−0.0003 (9)	0.0025 (9)	−0.0014 (9)
C15	0.0331 (12)	0.0357 (11)	0.0527 (16)	−0.0050 (9)	0.0097 (11)	−0.0059 (10)
C14	0.0430 (13)	0.0547 (13)	0.0550 (16)	−0.0107 (12)	0.0028 (11)	−0.0173 (12)
C7	0.0523 (14)	0.0397 (11)	0.0479 (15)	−0.0039 (11)	−0.0019 (11)	−0.0005 (11)
C4	0.0331 (12)	0.0712 (16)	0.0551 (15)	−0.0007 (12)	0.0019 (11)	0.0176 (13)
C2	0.0436 (13)	0.0438 (12)	0.0490 (15)	0.0001 (11)	0.0050 (11)	−0.0024 (11)
C20	0.0451 (12)	0.0332 (11)	0.0761 (18)	−0.0052 (11)	0.0132 (12)	−0.0090 (12)
C13	0.0489 (14)	0.0661 (15)	0.0416 (15)	−0.0051 (13)	−0.0094 (11)	−0.0038 (12)
C19	0.0557 (14)	0.0374 (12)	0.086 (2)	0.0037 (12)	0.0155 (14)	0.0115 (14)
C9	0.081 (2)	0.0539 (15)	0.0604 (19)	−0.0191 (15)	−0.0293 (15)	0.0065 (13)
C3	0.0475 (14)	0.0598 (14)	0.0590 (17)	0.0084 (12)	0.0114 (12)	−0.0032 (13)
C11	0.0297 (11)	0.0346 (11)	0.0414 (14)	−0.0005 (9)	0.0030 (10)	−0.0017 (10)
C18	0.0612 (16)	0.0551 (14)	0.0568 (17)	0.0069 (13)	−0.0050 (12)	0.0136 (13)
C8	0.0814 (19)	0.0456 (13)	0.0519 (16)	−0.0036 (14)	−0.0105 (14)	−0.0060 (12)
C10	0.0493 (15)	0.0670 (15)	0.0583 (18)	−0.0176 (14)	−0.0157 (13)	0.0184 (14)

Geometric parameters (Å, º) top

Cl1—P1	2.0867 (8)	C14—H14	0.93
P1—C1	1.8293 (18)	C7—C8	1.360 (3)
P1—C11	1.8309 (18)	C7—H7	0.93
C6—C5	1.415 (3)	C4—C3	1.356 (3)
C6—C7	1.414 (3)	C4—H4	0.93
C6—C1	1.436 (2)	C2—C3	1.403 (3)
C12—C11	1.368 (3)	C2—H2	0.93
C12—C13	1.401 (3)	C20—C19	1.351 (3)
C12—H12	0.93	C20—H20	0.93
C5—C4	1.403 (3)	C13—H13	0.93
C5—C10	1.422 (3)	C19—C18	1.396 (3)
C1—C2	1.370 (2)	C19—H19	0.93
C17—C18	1.366 (3)	C9—C10	1.356 (3)
C17—C16	1.407 (3)	C9—C8	1.397 (3)
C17—H17	0.93	C9—H9	0.93
C16—C15	1.420 (2)	C3—H3	0.93
C16—C11	1.433 (2)	C18—H18	0.93
C15—C14	1.406 (3)	C8—H8	0.93
C15—C20	1.410 (3)	C10—H10	0.93
C14—C13	1.352 (3)

C1—P1—C11	103.26 (9)	C5—C4—H4	119.3
C1—P1—Cl1	99.06 (6)	C1—C2—C3	121.38 (19)
C11—P1—Cl1	101.38 (7)	C1—C2—H2	119.3
C5—C6—C7	117.98 (19)	C3—C2—H2	119.3
C5—C6—C1	118.65 (19)	C19—C20—C15	121.2 (2)
C7—C6—C1	123.35 (18)	C19—C20—H20	119.4
C11—C12—C13	121.68 (18)	C15—C20—H20	119.4
C11—C12—H12	119.2	C14—C13—C12	120.2 (2)
C13—C12—H12	119.2	C14—C13—H13	119.9
C4—C5—C6	119.33 (19)	C12—C13—H13	119.9
C4—C5—C10	121.5 (2)	C20—C19—C18	120.1 (2)
C6—C5—C10	119.2 (2)	C20—C19—H19	119.9
C2—C1—C6	119.30 (17)	C18—C19—H19	119.9
C2—C1—P1	122.45 (14)	C10—C9—C8	120.5 (2)
C6—C1—P1	118.21 (14)	C10—C9—H9	119.7
C18—C17—C16	121.5 (2)	C8—C9—H9	119.7
C18—C17—H17	119.3	C4—C3—C2	119.8 (2)
C16—C17—H17	119.3	C4—C3—H3	120.1
C17—C16—C15	117.73 (18)	C2—C3—H3	120.1
C17—C16—C11	123.52 (18)	C12—C11—C16	119.01 (17)
C15—C16—C11	118.75 (18)	C12—C11—P1	123.34 (14)
C14—C15—C20	121.36 (19)	C16—C11—P1	117.34 (15)
C14—C15—C16	119.43 (18)	C17—C18—C19	120.3 (2)
C20—C15—C16	119.2 (2)	C17—C18—H18	119.9
C13—C14—C15	120.92 (19)	C19—C18—H18	119.9
C13—C14—H14	119.5	C7—C8—C9	120.3 (2)
C15—C14—H14	119.5	C7—C8—H8	119.8
C8—C7—C6	121.4 (2)	C9—C8—H8	119.8
C8—C7—H7	119.3	C9—C10—C5	120.5 (2)
C6—C7—H7	119.3	C9—C10—H10	119.7
C3—C4—C5	121.44 (19)	C5—C10—H10	119.7
C3—C4—H4	119.3

C7—C6—C5—C4	−178.67 (18)	P1—C1—C2—C3	177.53 (15)
C1—C6—C5—C4	3.0 (3)	C14—C15—C20—C19	−179.9 (2)
C7—C6—C5—C10	1.7 (3)	C16—C15—C20—C19	0.3 (3)
C1—C6—C5—C10	−176.61 (17)	C15—C14—C13—C12	0.6 (3)
C5—C6—C1—C2	−2.3 (3)	C11—C12—C13—C14	0.4 (3)
C7—C6—C1—C2	179.54 (18)	C15—C20—C19—C18	−0.2 (3)
C5—C6—C1—P1	179.99 (13)	C5—C4—C3—C2	−1.0 (3)
C7—C6—C1—P1	1.8 (2)	C1—C2—C3—C4	1.8 (3)
C11—P1—C1—C2	2.03 (18)	C13—C12—C11—C16	−0.9 (3)
Cl1—P1—C1—C2	106.09 (15)	C13—C12—C11—P1	172.55 (16)
C11—P1—C1—C6	179.72 (14)	C17—C16—C11—C12	−179.13 (19)
Cl1—P1—C1—C6	−76.22 (14)	C15—C16—C11—C12	0.5 (3)
C18—C17—C16—C15	−0.3 (3)	C17—C16—C11—P1	7.0 (3)
C18—C17—C16—C11	179.33 (19)	C15—C16—C11—P1	−173.42 (14)
C17—C16—C15—C14	−179.87 (18)	C1—P1—C11—C12	100.58 (18)
C11—C16—C15—C14	0.5 (3)	Cl1—P1—C11—C12	−1.68 (18)
C17—C16—C15—C20	0.0 (3)	C1—P1—C11—C16	−85.83 (16)
C11—C16—C15—C20	−179.64 (18)	Cl1—P1—C11—C16	171.91 (14)
C20—C15—C14—C13	179.1 (2)	C16—C17—C18—C19	0.3 (3)
C16—C15—C14—C13	−1.1 (3)	C20—C19—C18—C17	0.0 (3)
C5—C6—C7—C8	−0.7 (3)	C6—C7—C8—C9	−1.0 (3)
C1—C6—C7—C8	177.49 (18)	C10—C9—C8—C7	1.7 (3)
C6—C5—C4—C3	−1.5 (3)	C8—C9—C10—C5	−0.7 (3)
C10—C5—C4—C3	178.2 (2)	C4—C5—C10—C9	179.4 (2)
C6—C1—C2—C3	−0.1 (3)	C6—C5—C10—C9	−1.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···Cl1	0.93	2.58	3.128 (2)	118

Experimental details

Crystal data
Chemical formula	C₂₀H₁₄ClP
M_r	320.76
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	12.4335 (6), 10.4510 (4), 11.9293 (7)
β (°)	93.180 (5)
V (Å³)	1547.74 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.34
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Oxford Gemini E CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	8306, 3531, 1723
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.676

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.079, 0.78
No. of reflections	3531
No. of parameters	199
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.22

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SHELXS86 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Acknowledgements

The authors thank ANPCyT for grant No. PME-2006-01113 and R. Baggio for his helpful suggestions.

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