[2-(4-Methyl­piperazin-1-ylmeth­yl)phen­yl]diphenyl­phosphane

Covaci, A.; Raţ, C.I.; Silvestru, C.

doi:10.1107/S1600536809049526

organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o3193

doi:10.1107/S1600536809049526

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[2-(4-Methylpiperazin-1-ylmethyl)phenyl]diphenylphosphane

Ancuţa Covaci,^a Ciprian I. Raţ ^a and Cristian Silvestru ^a ^*

^aUniversitatea Babeş-Bolyai, Facultatea de Chimie şi Inginerie Chimicã, 11 Arany Janos, 400028 Cluj-Napoca, Romania
^*Correspondence e-mail: crat@chem.ubbcluj.ro

(Received 16 November 2009; accepted 19 November 2009; online 25 November 2009)

In the title compound, C₂₄H₂₇N₂P, the P atom is bonded to three C atoms in a trigonal–pyramidal geometry. The overall Ψ-trigonal-bipyramidal coordination of the P atom is established when the contribution of the electron lone pair and of the N—P donor–acceptor distance of 3.051 (3)Å are considered. The 4-methylpiperazinyl ring adopts a chair conformation. Intra- and intermolecular C—H⋯π hydrogen bonding leads to the consolidation of the structure.

Related literature

For organophosphorus compounds containing substituents with the capability of intramolecular donor⋯acceptor interactions, see: Alberico et al. (2007 ); Chandrasekaran et al. (2002 ); Chuit et al. (1993 ); Pretorius et al. (2004 ). For the structures of triclinic polymorphs of triphenylphosphine, see: Ziemer et al. (2000 ).

Experimental

Crystal data

C₂₄H₂₇N₂P
M_r = 374.45
Monoclinic, P 2₁ /n
a = 9.3689 (10) Å
b = 14.6735 (16) Å
c = 15.4362 (16) Å
β = 100.849 (2)°
V = 2084.2 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.14 mm⁻¹
T = 297 K
0.30 × 0.26 × 0.21 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.959, T_max = 0.971
14906 measured reflections
3667 independent reflections
2811 reflections with I > 2σ(I)
R_int = 0.064

Refinement

R[F² > 2σ(F²)] = 0.085
wR(F²) = 0.178
S = 1.20
3667 reflections
245 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

C1—P1	1.841 (4)
C13—P1	1.829 (4)
C19—P1	1.839 (4)

C13—P1—C19	101.62 (16)
C13—P1—C1	103.38 (16)
C19—P1—C1	100.26 (16)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9B⋯Cg3	0.97	2.91	3.835 (4)	160
C14—H14⋯Cg4ⁱ	0.97	2.74	3.651 (5)	166
C23—H23⋯Cg2ⁱⁱ	0.97	2.98	3.830 (5)	154
Symmetry codes: (i) -x+2, -y+1, -z; (ii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ . Cg2, Cg3, and Cg4 are the centroids of the C1–C6, C13–C18, and C19–C24 benzene rings, respectively.

Data collection: SMART (Bruker, 2000); cell refinement: SAINT-Plus (Bruker, 2001 ); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2009 ); software used to prepare material for publication: publCIF (Westrip, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809049526/wm2285sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809049526/wm2285Isup2.hkl

checkCIF report

Comment top

We report here on the preparation and structural characterization in solution and the crystalline state of an asymetric triphosphane, PPh₂[C₆H₄{CH₂N(CH₂CH₂)₂NMe}-2] (I).

Asymmetric organophosphorus(III) derivatives of the type PPh₂R, where R is a substituent capable of intramolecular coordination, were reported in the literature (Pretorius et al., 2004; Alberico et al., 2007). Nevertheless, only in the symmetrical triorganophospane P[C₆H₄(CH₂NMe₂)-2]₃ the nitrogen atom is coordinated to the phosphorous atom via N—P donor···acceptor interactions (Chuit et al., 1993; Chandrasekaran et al., 2002).

In the structure of (I) the nitrogen atom bonded to the benzyl fragment is coordinated to the phosphorous atom trans to a phenyl group. This induces chirality at the Ψ-trigonal-bipyramidal phosphorus centre, in addition to the planar chirality (the nitrogen atom acts as the pilot atom and the phenyl group as the chiral plane). (I) crystallizes in the racemic form. The (R_NA_P) isomer is shown in Fig. 1. The (S_NC_P) isomer is generated by symmetry with respect to the inversion centre.

The P—C bond lengths and C—P—C angles (Table 1) are in the range of those of triclinic PPh₃ (Ziemer et al., 2000). As expected, the P—C_Ph bond in trans-position to the P—N bond is slightly longer than the other P—C bond. The length of the P—N bond donor···acceptor interaction is in the range of values found in P[C₆H₄(CH₂NMe₂)-2]₃ (Chandrasekaran et al., 2002).

The structure displays intramolecular C–H···π bonds between one hydrogen atom of the piperazinyl group and a phenyl group (Fig. 2). Four intermolecular C–H···π bonds are established between the hydrogen atoms of the phenyl groups and π electrons of the benzene rings of neighbouring molecules. Geometrical parameters of the hydrogen bonds are listed in Table 2.

Related literature top

For organophosphorus compounds containing substituents with the capability of intramolecular donor···acceptor interactions, see: Alberico et al. (2007); Chandrasekaran et al. (2002); Chuit et al. (1993); Pretorius et al. (2004). For the structures of triclinic polymorphs of triphenylphosphine, see: Ziemer et al. (2000). Cg2, Cg3, and

Cg4 are the centroids of the benzene rings C1-C6, C13-C18, and C19-C24,

respectively.

Experimental top

To a cooled solution of [2-{4-MeN(CH₂CH₂)₂NCH₂}C₆H₄]Li (2.55 g, 13 mmol) in tetrahydrofuran (thf) (203 K) was added dropwise a solution of PPh₂Cl (2.40 ml, ρ = 1.23 g/ml, 13 mmol) in thf. The reaction mixture was stirred at 203 K for 2 h and was allowed to warm to room temperature. The solvent was removed under reduced pressure and over the resulting oily product was added dichloromethane. The obtained suspension was filtered and the dichloromethane was removed under reduced pressure. The remaining oily product solidified on addition of hexane. (I) was isolated as a colourless solid. Colourless crystals were obtained by the diffusion method from a dichloromethane/hexane mixture. Yield: 2.87 g (59%). mp 69 °C. ¹H NMR (400 MHz, CDCl₃): δ 1.96 (s, 3H, NMe), 2.26 (s,br, 8H, H_8,11+H_9,10), 3.62 (d, 2H, H₇, ⁴J_PH = 0.8 Hz), 6.88 (m, 1H, H₆), 7.09 (ddd, 1H, H₄, ³J_HH = 7.5 Hz, ⁴J_HH = 1.3 Hz), 7.18 (m, 11H, P—C₆H₅ + H₅), 7.29 (m, 1H, H₃). ¹³C NMR (100 MHz, CDCl₃): δ 45.86 (s, NMe), 52.15 (s, C_8,11), 54.24 (s, C_9,10), 61.95 (d, C₇, ³J_PC = 15.5 Hz), 127.17 (s, C₄), 128.14 (m, C₆H₅-meta+para), 128.32 (s, C₅), 129.48 (d, C₃, ³J_PC = 5.8 Hz), 133.55 (d, C₆H₅-ortho, ²J_PC = 19.6 Hz), 134.89 (s, C₆), 137.03 (d, C₂, ²J_PC = 15.9 Hz), 138.45 (d, C₆H₅-ipso, ¹J_PC = 9.9 Hz), 143.76 (d, C₁, ¹J_PC = 24.2 Hz). ³¹P NMR (162 MHz, CDCl₃): δ -16.1 (s).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2009); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top

	Fig. 1. Graphical representation of the molecular structure of R_NA_P-I. Hydrogen atoms were omitted for clarity. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Intramolecular H···π and N···P interactions in the structure of I (shown as dashed lines). All the hydrogen atoms, except for those involved in hydrogen bonds, were omitted for clarity. Cg2, Cg3, and Cg4 are the centroids of the benzene rings C1—C6, C13—C18, and C19—C24, respectively. Symmetry codes: (i) -x + 2, -y + 1, -z; (ii) -x + 3/2, y - 1/2, -z + 1/2.

[2-(4-Methylpiperazin-1-ylmethyl)phenyl]diphenylphosphane top

Crystal data top

C₂₄H₂₇N₂P	F(000) = 800
M_r = 374.45	D_x = 1.193 Mg m⁻³
Monoclinic, P2₁/n	Melting point: 342 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 9.3689 (10) Å	Cell parameters from 3207 reflections
b = 14.6735 (16) Å	θ = 2.4–23.9°
c = 15.4362 (16) Å	µ = 0.14 mm⁻¹
β = 100.849 (2)°	T = 297 K
V = 2084.2 (4) Å³	Block, colourless
Z = 4	0.30 × 0.26 × 0.21 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	3667 independent reflections
Radiation source: fine-focus sealed tube	2811 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.064
ϕ and ω scans	θ_max = 25°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −11→11
T_min = 0.959, T_max = 0.971	k = −17→17
14906 measured reflections	l = −18→18

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)] = 0.085	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.178	H-atom parameters constrained
S = 1.20	w = 1/[σ²(F_o²) + (0.0598P)² + 1.2183P] where P = (F_o² + 2F_c²)/3
3667 reflections	(Δ/σ)_max = 0.001
245 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₂₄H₂₇N₂P	V = 2084.2 (4) Å³
M_r = 374.45	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.3689 (10) Å	µ = 0.14 mm⁻¹
b = 14.6735 (16) Å	T = 297 K
c = 15.4362 (16) Å	0.30 × 0.26 × 0.21 mm
β = 100.849 (2)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	3667 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	2811 reflections with I > 2σ(I)
T_min = 0.959, T_max = 0.971	R_int = 0.064
14906 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.085	0 restraints
wR(F²) = 0.178	H-atom parameters constrained
S = 1.20	Δρ_max = 0.25 e Å⁻³
3667 reflections	Δρ_min = −0.25 e Å⁻³
245 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
C1	0.6682 (4)	0.5851 (2)	0.1668 (3)	0.0428 (9)
C2	0.5236 (4)	0.6120 (2)	0.1377 (3)	0.0486 (10)
C3	0.4311 (5)	0.6148 (3)	0.1980 (4)	0.0666 (13)
H3	0.3349	0.6325	0.1794	0.08*
C4	0.4792 (6)	0.5920 (3)	0.2845 (4)	0.0783 (16)
H4	0.4153	0.5936	0.3239	0.094*
C5	0.6207 (6)	0.5670 (3)	0.3133 (3)	0.0731 (14)
H5	0.6535	0.5525	0.3724	0.088*
C6	0.7139 (5)	0.5633 (3)	0.2549 (3)	0.0542 (11)
H6	0.8099	0.5459	0.2749	0.065*
C7	0.4705 (4)	0.6395 (3)	0.0433 (3)	0.0541 (11)
H7A	0.4805	0.5884	0.0049	0.065*
H7B	0.3683	0.6554	0.0348	0.065*
C8	0.5243 (4)	0.7993 (2)	0.0655 (3)	0.0516 (10)
H8A	0.5466	0.7889	0.1287	0.062*
H8B	0.4223	0.8152	0.0494	0.062*
C9	0.6161 (4)	0.8769 (2)	0.0421 (3)	0.0493 (10)
H9A	0.5953	0.9316	0.0726	0.059*
H9B	0.7181	0.8623	0.0615	0.059*
C10	0.6156 (5)	0.8106 (3)	−0.0969 (3)	0.0603 (12)
H10A	0.7175	0.7946	−0.0799	0.072*
H10B	0.5951	0.8207	−0.1602	0.072*
C11	0.5246 (5)	0.7335 (3)	−0.0750 (3)	0.0610 (12)
H11A	0.4226	0.7479	−0.0948	0.073*
H11B	0.5463	0.679	−0.1055	0.073*
C12	0.6772 (5)	0.9677 (3)	−0.0734 (3)	0.0725 (14)
H12A	0.6606	1.021	−0.0406	0.109*
H12B	0.6525	0.9807	−0.1354	0.109*
H12C	0.7777	0.9507	−0.0584	0.109*
C13	0.8981 (4)	0.6775 (2)	0.1019 (2)	0.0374 (9)
C14	0.9778 (4)	0.6993 (3)	0.0381 (3)	0.0526 (10)
H14	0.9738	0.6612	−0.0105	0.063*
C15	1.0624 (5)	0.7758 (3)	0.0448 (3)	0.0672 (13)
H15	1.1167	0.7885	0.0016	0.081*
C16	1.0676 (5)	0.8335 (3)	0.1143 (3)	0.0666 (13)
H16	1.1241	0.886	0.1183	0.08*
C17	0.9895 (5)	0.8137 (3)	0.1778 (3)	0.0626 (12)
H17	0.9931	0.853	0.2255	0.075*
C18	0.9055 (4)	0.7367 (3)	0.1725 (3)	0.0485 (10)
H18	0.8532	0.7241	0.2167	0.058*
C19	0.9139 (4)	0.4871 (2)	0.1368 (2)	0.0400 (9)
C20	1.0627 (4)	0.4962 (3)	0.1523 (3)	0.0554 (11)
H20	1.1033	0.5516	0.1405	0.066*
C21	1.1529 (5)	0.4251 (3)	0.1850 (3)	0.0639 (12)
H21	1.2532	0.4328	0.1942	0.077*
C22	1.0960 (5)	0.3439 (3)	0.2037 (3)	0.0582 (11)
H22	1.157	0.2964	0.2269	0.07*
C23	0.9485 (5)	0.3325 (3)	0.1881 (3)	0.0546 (11)
H23	0.9091	0.2769	0.2004	0.065*
C24	0.8585 (4)	0.4026 (2)	0.1544 (2)	0.0461 (10)
H24	0.7585	0.3935	0.143	0.055*
N1	0.5526 (3)	0.7170 (2)	0.0195 (2)	0.0432 (8)
N2	0.5876 (4)	0.8936 (2)	−0.0522 (2)	0.0534 (9)
P1	0.78585 (10)	0.57472 (7)	0.08427 (6)	0.0391 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.044 (2)	0.032 (2)	0.054 (2)	−0.0038 (17)	0.0124 (18)	0.0048 (17)
C2	0.041 (2)	0.032 (2)	0.075 (3)	−0.0081 (17)	0.017 (2)	−0.0027 (19)
C3	0.053 (3)	0.046 (3)	0.109 (4)	−0.011 (2)	0.037 (3)	0.001 (3)
C4	0.101 (4)	0.046 (3)	0.109 (5)	−0.006 (3)	0.073 (4)	0.006 (3)
C5	0.109 (4)	0.048 (3)	0.072 (3)	0.010 (3)	0.043 (3)	0.013 (2)
C6	0.069 (3)	0.044 (2)	0.055 (3)	0.009 (2)	0.025 (2)	0.007 (2)
C7	0.037 (2)	0.044 (2)	0.075 (3)	−0.0056 (18)	−0.007 (2)	−0.005 (2)
C8	0.056 (3)	0.041 (2)	0.059 (3)	0.0023 (19)	0.014 (2)	−0.0035 (19)
C9	0.049 (2)	0.036 (2)	0.062 (3)	−0.0010 (18)	0.010 (2)	−0.0048 (19)
C10	0.071 (3)	0.064 (3)	0.045 (2)	−0.002 (2)	0.008 (2)	0.001 (2)
C11	0.065 (3)	0.056 (3)	0.054 (3)	0.001 (2)	−0.007 (2)	−0.009 (2)
C12	0.072 (3)	0.059 (3)	0.091 (4)	0.003 (2)	0.029 (3)	0.021 (3)
C13	0.034 (2)	0.037 (2)	0.039 (2)	0.0023 (16)	0.0011 (16)	0.0081 (17)
C14	0.050 (2)	0.054 (3)	0.054 (2)	−0.002 (2)	0.011 (2)	0.004 (2)
C15	0.059 (3)	0.070 (3)	0.076 (3)	−0.015 (2)	0.022 (3)	0.018 (3)
C16	0.055 (3)	0.056 (3)	0.082 (3)	−0.019 (2)	−0.003 (3)	0.012 (3)
C17	0.066 (3)	0.055 (3)	0.061 (3)	−0.018 (2)	−0.004 (2)	−0.006 (2)
C18	0.048 (2)	0.050 (2)	0.045 (2)	−0.0071 (19)	0.0030 (18)	0.0022 (19)
C19	0.043 (2)	0.041 (2)	0.035 (2)	−0.0044 (17)	0.0066 (16)	−0.0081 (16)
C20	0.047 (2)	0.049 (3)	0.068 (3)	−0.001 (2)	0.005 (2)	0.002 (2)
C21	0.042 (2)	0.061 (3)	0.084 (3)	0.006 (2)	0.001 (2)	0.003 (3)
C22	0.062 (3)	0.047 (3)	0.063 (3)	0.015 (2)	0.003 (2)	0.005 (2)
C23	0.073 (3)	0.040 (2)	0.053 (3)	0.001 (2)	0.018 (2)	0.0044 (19)
C24	0.045 (2)	0.040 (2)	0.054 (2)	−0.0047 (18)	0.0112 (19)	−0.0038 (18)
N1	0.0405 (18)	0.0381 (18)	0.0483 (19)	−0.0022 (14)	0.0012 (14)	−0.0042 (14)
N2	0.055 (2)	0.046 (2)	0.058 (2)	0.0053 (16)	0.0083 (17)	0.0103 (17)
P1	0.0366 (5)	0.0398 (6)	0.0404 (6)	−0.0027 (4)	0.0058 (4)	0.0008 (4)

Geometric parameters (Å, º) top

C1—C6	1.384 (5)	C12—N2	1.448 (5)
C1—C2	1.402 (5)	C12—H12A	0.96
C1—P1	1.841 (4)	C12—H12B	0.96
C2—C3	1.386 (6)	C12—H12C	0.96
C2—C7	1.504 (6)	C13—C14	1.381 (5)
C3—C4	1.368 (7)	C13—C18	1.386 (5)
C3—H3	0.93	C13—P1	1.829 (4)
C4—C5	1.367 (7)	C14—C15	1.366 (6)
C4—H4	0.93	C14—H14	0.93
C5—C6	1.369 (6)	C15—C16	1.360 (6)
C5—H5	0.93	C15—H15	0.93
C6—H6	0.93	C16—C17	1.361 (6)
C7—N1	1.458 (5)	C16—H16	0.93
C7—H7A	0.97	C17—C18	1.370 (5)
C7—H7B	0.97	C17—H17	0.93
C8—N1	1.452 (5)	C18—H18	0.93
C8—C9	1.510 (5)	C19—C20	1.376 (5)
C8—H8A	0.97	C19—C24	1.391 (5)
C8—H8B	0.97	C19—P1	1.839 (4)
C9—N2	1.450 (5)	C20—C21	1.376 (5)
C9—H9A	0.97	C20—H20	0.93
C9—H9B	0.97	C21—C22	1.359 (6)
C10—N2	1.449 (5)	C21—H21	0.93
C10—C11	1.493 (6)	C22—C23	1.368 (6)
C10—H10A	0.97	C22—H22	0.93
C10—H10B	0.97	C23—C24	1.368 (5)
C11—N1	1.453 (5)	C23—H23	0.93
C11—H11A	0.97	C24—H24	0.93
C11—H11B	0.97	N1—P1	3.051 (3)

C6—C1—C2	118.8 (4)	H12A—C12—H12B	109.5
C6—C1—P1	123.1 (3)	N2—C12—H12C	109.5
C2—C1—P1	118.0 (3)	H12A—C12—H12C	109.5
C3—C2—C1	118.8 (4)	H12B—C12—H12C	109.5
C3—C2—C7	120.6 (4)	C14—C13—C18	117.5 (4)
C1—C2—C7	120.6 (4)	C14—C13—P1	117.3 (3)
C4—C3—C2	121.0 (5)	C18—C13—P1	125.2 (3)
C4—C3—H3	119.5	C15—C14—C13	121.4 (4)
C2—C3—H3	119.5	C15—C14—H14	119.3
C5—C4—C3	120.3 (4)	C13—C14—H14	119.3
C5—C4—H4	119.9	C16—C15—C14	120.3 (4)
C3—C4—H4	119.9	C16—C15—H15	119.8
C4—C5—C6	119.7 (5)	C14—C15—H15	119.8
C4—C5—H5	120.1	C15—C16—C17	119.4 (4)
C6—C5—H5	120.1	C15—C16—H16	120.3
C5—C6—C1	121.4 (4)	C17—C16—H16	120.3
C5—C6—H6	119.3	C16—C17—C18	120.9 (4)
C1—C6—H6	119.3	C16—C17—H17	119.5
N1—C7—C2	111.1 (3)	C18—C17—H17	119.5
N1—C7—H7A	109.4	C17—C18—C13	120.5 (4)
C2—C7—H7A	109.4	C17—C18—H18	119.8
N1—C7—H7B	109.4	C13—C18—H18	119.8
C2—C7—H7B	109.4	C20—C19—C24	117.0 (4)
H7A—C7—H7B	108	C20—C19—P1	124.4 (3)
N1—C8—C9	110.2 (3)	C24—C19—P1	118.2 (3)
N1—C8—H8A	109.6	C19—C20—C21	121.6 (4)
C9—C8—H8A	109.6	C19—C20—H20	119.2
N1—C8—H8B	109.6	C21—C20—H20	119.2
C9—C8—H8B	109.6	C22—C21—C20	120.2 (4)
H8A—C8—H8B	108.1	C22—C21—H21	119.9
N2—C9—C8	111.3 (3)	C20—C21—H21	119.9
N2—C9—H9A	109.4	C21—C22—C23	119.6 (4)
C8—C9—H9A	109.4	C21—C22—H22	120.2
N2—C9—H9B	109.4	C23—C22—H22	120.2
C8—C9—H9B	109.4	C22—C23—C24	120.3 (4)
H9A—C9—H9B	108	C22—C23—H23	119.8
N2—C10—C11	111.5 (4)	C24—C23—H23	119.8
N2—C10—H10A	109.3	C23—C24—C19	121.2 (4)
C11—C10—H10A	109.3	C23—C24—H24	119.4
N2—C10—H10B	109.3	C19—C24—H24	119.4
C11—C10—H10B	109.3	C8—N1—C11	109.7 (3)
H10A—C10—H10B	108	C8—N1—C7	111.9 (3)
N1—C11—C10	110.6 (3)	C11—N1—C7	112.3 (3)
N1—C11—H11A	109.5	C12—N2—C10	111.1 (3)
C10—C11—H11A	109.5	C12—N2—C9	110.5 (3)
N1—C11—H11B	109.5	C10—N2—C9	108.7 (3)
C10—C11—H11B	109.5	C13—P1—C19	101.62 (16)
H11A—C11—H11B	108.1	C13—P1—C1	103.38 (16)
N2—C12—H12A	109.5	C19—P1—C1	100.26 (16)
N2—C12—H12B	109.5

C6—C1—C2—C3	−0.8 (5)	C21—C22—C23—C24	−0.4 (6)
P1—C1—C2—C3	176.2 (3)	C22—C23—C24—C19	−1.2 (6)
C6—C1—C2—C7	177.8 (3)	C20—C19—C24—C23	1.9 (5)
P1—C1—C2—C7	−5.3 (5)	P1—C19—C24—C23	175.7 (3)
C1—C2—C3—C4	0.1 (6)	C9—C8—N1—C11	−57.1 (4)
C7—C2—C3—C4	−178.4 (4)	C9—C8—N1—C7	177.6 (3)
C2—C3—C4—C5	0.8 (7)	C10—C11—N1—C8	57.5 (4)
C3—C4—C5—C6	−1.1 (7)	C10—C11—N1—C7	−177.4 (3)
C4—C5—C6—C1	0.4 (7)	C2—C7—N1—C8	−67.7 (4)
C2—C1—C6—C5	0.5 (6)	C2—C7—N1—C11	168.4 (3)
P1—C1—C6—C5	−176.2 (3)	C11—C10—N2—C12	179.6 (3)
C3—C2—C7—N1	118.9 (4)	C11—C10—N2—C9	57.9 (4)
C1—C2—C7—N1	−59.6 (5)	C8—C9—N2—C12	−179.6 (3)
N1—C8—C9—N2	58.3 (4)	C8—C9—N2—C10	−57.6 (4)
N2—C10—C11—N1	−58.8 (5)	C14—C13—P1—C19	89.3 (3)
C18—C13—C14—C15	0.9 (6)	C18—C13—P1—C19	−93.1 (3)
P1—C13—C14—C15	178.7 (3)	C14—C13—P1—C1	−167.1 (3)
C13—C14—C15—C16	−1.3 (7)	C18—C13—P1—C1	10.5 (4)
C14—C15—C16—C17	1.0 (7)	C20—C19—P1—C13	−21.0 (4)
C15—C16—C17—C18	−0.2 (7)	C24—C19—P1—C13	165.6 (3)
C16—C17—C18—C13	−0.3 (6)	C20—C19—P1—C1	−127.1 (3)
C14—C13—C18—C17	−0.1 (6)	C24—C19—P1—C1	59.5 (3)
P1—C13—C18—C17	−177.7 (3)	C6—C1—P1—C13	−79.7 (3)
C24—C19—C20—C21	−0.9 (6)	C2—C1—P1—C13	103.5 (3)
P1—C19—C20—C21	−174.3 (3)	C6—C1—P1—C19	25.0 (3)
C19—C20—C21—C22	−0.7 (7)	C2—C1—P1—C19	−151.8 (3)
C20—C21—C22—C23	1.4 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9B···Cg3	0.97	2.91	3.835 (4)	160
C14—H14···Cg4ⁱ	0.97	2.74	3.651 (5)	166
C23—H23···Cg2ⁱⁱ	0.97	2.98	3.830 (5)	154

Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x+3/2, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₂₄H₂₇N₂P
M_r	374.45
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	297
a, b, c (Å)	9.3689 (10), 14.6735 (16), 15.4362 (16)
β (°)	100.849 (2)
V (Å³)	2084.2 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.14
Crystal size (mm)	0.30 × 0.26 × 0.21

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.959, 0.971
No. of measured, independent and observed [I > 2σ(I)] reflections	14906, 3667, 2811
R_int	0.064
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.085, 0.178, 1.20
No. of reflections	3667
No. of parameters	245
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.25

Computer programs: SMART (Bruker, 2000), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2009), publCIF (Westrip, 2009).

Selected geometric parameters (Å, º) top

C1—P1	1.841 (4)	C19—P1	1.839 (4)
C13—P1	1.829 (4)

C13—P1—C19	101.62 (16)	C19—P1—C1	100.26 (16)
C13—P1—C1	103.38 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9B···Cg3	0.97	2.91	3.835 (4)	160
C14—H14···Cg4ⁱ	0.97	2.74	3.651 (5)	166
C23—H23···Cg2ⁱⁱ	0.97	2.98	3.830 (5)	154

Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x+3/2, y−1/2, −z+1/2.

Acknowledgements

This work was supported by the National University Research Council (CNCSIS) of România (research project TD-40/2007).

References

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