Redetermination of bis­(diphenyl­phosphino)methane at 293 (2) K

The structure of the title compound, C₂₅H₂₂P₂, at 293 K is isostructural with those determined at 153 K [Di Nicola, Effendy, Faza­roh, Pettinari, Skelton, Somers & White (2005), Inorg. Chim. Acta, 358, 720-734] and 233 K [Schmidbaur, Reber, Schier, Wagner & Muller (1998), Inorg. Chim. Acta, 147, 143-150]. The diphenyl­phosphine groups are staggered relative to the PCP backbone such that the lone pairs are at an angle of 75.12 (7)° to each other. There are no classical inter­molecular inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• R factor = 0.049
• wR factor = 0.120
• Data-to-parameter ratio = 21.2

checkCIF/PLATON results

No syntax errors found



Alert level C
ABSTM02_ALERT_3_C  The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
            Tmin and Tmax reported:      0.840     1.000
            Tmin(prime) and Tmax expected:      0.949     0.962
            RR(prime) =      0.852
            Please check that your absorption correction is appropriate.
PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large .............       0.85
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.96
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C221   -   C226    ..       5.05 su
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for       C211

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Bis(diphenylphosphino)methane, (I), is a ubiquitous ligand in organometallic chemistry, with 1988 compounds reported in the Cambridge Structural Data base (Version 5.28, January, 2007; Allen, 2002). Its crystal structure has been previously determined at 153 K (Di Nicola et al., 2005) and 233 K (Schmidbauer et al., 1998). We present here the structure of the title compound at 293 K, where the precision of the geometric parameters is slightly improved.

The structure of the title compound at 293 K (Fig. 1) is isostructural with those determined at 153 K and 233 K. The bond lengths and angles are as expected (Table 1). Each of the diphenylphosphine moieties adopts a gauche conformation relative to the bridging methylene group, with the P atom lone pair pointing in the direction opposite to the methylene H atoms. The resulting configuration forms a nearly planar `W' made up of atoms C121—P1—C1—P2—C222, with two phenyl groups positioned on the plane but only somewhat one coplanar, and two positioned on either side of the plane, as indicated by the P—C—P—C torsion angles (Table 1).

The vector defined by the P atom and the centroid of the ipso-C atoms of the organic groups bound to the P atom can be used to estimate the vector between the P atom and its lone pair for phosphines (Powell, 1989; Martin & Orpen, 1996). The angle between the vectors P1···centroid(C_ipso)₃ and P2···centroid(C_ipso)₃ is 75.12 (7)°.

There are no intermolecular interactions in the crystal structure of (I). The phenyl groups pack in a herring-bone pattern (Fig. 2).

Related literature

For related literature, see: Allen (2002); de Carvalho et al. (1999); Di Nicola et al. (2005); Martin & Orpen (1996); Peppe (2004); Powell (1989).

S2. Experimental

The title compound was obtained unintentionally as colourless blocks by the slow evaporation of tetrahydrofuran from a solution of the white powder precipitated from the reaction of dibromo-bromomethyl-indium(III) (de Carvalho et al., 1999; Peppe, 2004) with bis(diphenylphosphino)methane monoxide in dioxane.

S3. Refinement

All H atoms were located in a difference Fourier map and were placed in idealized positions and refined using a riding model, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C) for phenyl H atoms and C—H = 0.97 Å and U_iso(H) = 1.2U_eq(C) for methylene H atoms.

Computing details

Data collection: APEX2, BIS and COSMO (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT and SADABS (Bruker, 2006); program(s) used to solve structure: SHELXTL (Bruker, 2006); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2007).

Figures

	Fig. 1. A view of (I) at 293 K, showing the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Views parallel to (a) the a axis and (b) the b axis of the unit cell of (I). Molecules in front are shown with black outlines and those behind are shown with grey outlines; atoms have arbitrary radii.

bis(diphenylphosphino)methane

Crystal data

C25H22P2	Dx = 1.22 Mg m^−3
Mr = 384.37	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 2940 reflections
a = 9.8918 (3) Å	θ = 2.9–23.0°
b = 10.3368 (4) Å	µ = 0.21 mm^−1
c = 40.9389 (15) Å	T = 293 K
V = 4186.0 (3) Å^3	Block, colourless
Z = 8	0.24 × 0.24 × 0.18 mm
F(000) = 1616

Data collection

Bruker SMART CCD area-detector diffractometer	2927 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.041
φ and ω scans	θmax = 28.3°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2006)	h = −13→10
Tmin = 0.840, Tmax = 1	k = −13→13
18346 measured reflections	l = −48→54
5171 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.120	H-atom parameters constrained
S = 1.16	w = 1/[σ^2(Fo^2) + (0.0432P)^2] where P = (Fo^2 + 2Fc^2)/3
5171 reflections	(Δ/σ)max < 0.001
244 parameters	Δρmax = 0.30 e Å^−3
0 restraints	Δρmin = −0.20 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.8024 (2)	0.4568 (2)	0.12237 (5)	0.0592 (5)
H1A	0.7404	0.4616	0.1041	0.071*
H1B	0.8132	0.543	0.1314	0.071*
P1	0.96755 (6)	0.39319 (6)	0.108800 (12)	0.05699 (18)
P2	0.73568 (5)	0.34517 (6)	0.153963 (12)	0.05689 (18)
C111	0.9209 (2)	0.2701 (2)	0.07883 (4)	0.0564 (5)
C112	0.7969 (2)	0.2573 (2)	0.06361 (5)	0.0753 (7)
H112	0.728	0.3154	0.0686	0.09*
C113	0.7734 (3)	0.1599 (3)	0.04116 (6)	0.0982 (9)
H113	0.6888	0.1529	0.0314	0.118*
C114	0.8717 (5)	0.0747 (3)	0.03322 (7)	0.1090 (11)
H114	0.8555	0.0107	0.0177	0.131*
C115	0.9944 (4)	0.0834 (3)	0.04806 (7)	0.1048 (10)
H115	1.0621	0.0243	0.0429	0.126*
C116	1.0189 (3)	0.1797 (2)	0.07069 (6)	0.0801 (7)
H116	1.1031	0.184	0.0807	0.096*
C121	1.02816 (19)	0.5252 (2)	0.08259 (4)	0.0538 (5)
C122	1.0619 (2)	0.5114 (2)	0.04966 (5)	0.0628 (6)
H122	1.0501	0.4318	0.0395	0.075*
C123	1.1129 (2)	0.6149 (3)	0.03200 (5)	0.0766 (7)
H123	1.1345	0.6041	0.0101	0.092*
C124	1.1318 (2)	0.7329 (3)	0.04649 (7)	0.0846 (7)
H124	1.1655	0.8021	0.0345	0.102*
C125	1.1002 (3)	0.7479 (3)	0.07903 (7)	0.0867 (8)
H125	1.1129	0.8277	0.0891	0.104*
C126	1.0499 (2)	0.6454 (2)	0.09677 (5)	0.0714 (6)
H126	1.0299	0.6571	0.1188	0.086*
C211	0.8150 (2)	0.4150 (2)	0.19062 (4)	0.0526 (5)
C212	0.9291 (2)	0.3579 (3)	0.20334 (6)	0.0802 (7)
H212	0.9646	0.2849	0.1932	0.096*
C213	0.9921 (3)	0.4073 (3)	0.23097 (7)	0.0996 (9)
H213	1.0698	0.3681	0.2391	0.12*
C214	0.9397 (3)	0.5135 (3)	0.24619 (6)	0.0900 (9)
H214	0.981	0.5455	0.2649	0.108*
C215	0.8273 (3)	0.5730 (3)	0.23410 (6)	0.0865 (8)
H215	0.7923	0.646	0.2443	0.104*
C216	0.7658 (2)	0.5235 (2)	0.20641 (5)	0.0692 (6)
H216	0.6892	0.5644	0.1982	0.083*
C221	0.5605 (2)	0.3984 (2)	0.15895 (4)	0.0568 (5)
C222	0.5074 (2)	0.5138 (2)	0.14730 (5)	0.0695 (6)
H222	0.5635	0.5711	0.1362	0.083*
C223	0.3728 (3)	0.5455 (3)	0.15183 (6)	0.0864 (8)
H223	0.3398	0.6238	0.144	0.104*
C224	0.2882 (3)	0.4627 (4)	0.16777 (7)	0.0928 (9)
H224	0.1976	0.484	0.1705	0.111*
C225	0.3374 (3)	0.3469 (3)	0.17984 (6)	0.0885 (8)
H225	0.2802	0.2903	0.1908	0.106*
C226	0.4733 (2)	0.3153 (2)	0.17545 (5)	0.0693 (6)
H226	0.5061	0.2375	0.1837	0.083*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0728 (14)	0.0612 (14)	0.0436 (10)	0.0072 (11)	0.0088 (9)	−0.0010 (9)
P1	0.0604 (3)	0.0673 (4)	0.0432 (3)	0.0049 (3)	0.0014 (2)	0.0001 (3)
P2	0.0648 (4)	0.0594 (4)	0.0464 (3)	−0.0003 (3)	0.0049 (2)	−0.0015 (3)
C111	0.0624 (13)	0.0606 (14)	0.0462 (11)	0.0033 (11)	0.0105 (10)	0.0032 (9)
C112	0.0679 (15)	0.0940 (19)	0.0641 (14)	−0.0084 (13)	0.0102 (12)	−0.0125 (13)
C113	0.100 (2)	0.122 (3)	0.0720 (17)	−0.0489 (19)	0.0117 (15)	−0.0204 (18)
C114	0.172 (4)	0.084 (2)	0.0704 (19)	−0.038 (2)	0.032 (2)	−0.0190 (15)
C115	0.164 (3)	0.074 (2)	0.0755 (18)	0.027 (2)	0.035 (2)	−0.0087 (15)
C116	0.0928 (18)	0.0824 (19)	0.0652 (14)	0.0204 (15)	0.0094 (12)	−0.0022 (13)
C121	0.0511 (11)	0.0643 (15)	0.0461 (10)	0.0031 (10)	0.0019 (9)	−0.0016 (9)
C122	0.0674 (14)	0.0672 (16)	0.0539 (12)	−0.0025 (11)	0.0084 (10)	−0.0040 (11)
C123	0.0845 (17)	0.088 (2)	0.0571 (13)	−0.0011 (14)	0.0175 (12)	0.0061 (13)
C124	0.0933 (19)	0.0726 (19)	0.0879 (18)	−0.0035 (15)	0.0238 (14)	0.0098 (15)
C125	0.0991 (19)	0.0681 (18)	0.0930 (19)	−0.0101 (15)	0.0133 (15)	−0.0110 (14)
C126	0.0867 (17)	0.0712 (17)	0.0562 (12)	−0.0049 (13)	0.0094 (11)	−0.0086 (12)
C211	0.0523 (12)	0.0606 (14)	0.0450 (10)	−0.0053 (10)	0.0059 (9)	0.0076 (9)
C212	0.0807 (17)	0.0864 (19)	0.0734 (15)	0.0126 (14)	−0.0096 (13)	−0.0005 (13)
C213	0.0875 (19)	0.123 (3)	0.088 (2)	0.0104 (18)	−0.0303 (16)	0.0082 (19)
C214	0.089 (2)	0.127 (3)	0.0545 (14)	−0.0161 (18)	−0.0143 (13)	−0.0048 (15)
C215	0.0851 (18)	0.109 (2)	0.0659 (15)	−0.0035 (16)	−0.0066 (14)	−0.0264 (14)
C216	0.0660 (14)	0.0867 (18)	0.0550 (12)	0.0042 (12)	−0.0044 (11)	−0.0086 (12)
C221	0.0594 (13)	0.0693 (15)	0.0417 (10)	−0.0097 (11)	−0.0016 (9)	−0.0059 (10)
C222	0.0576 (14)	0.0847 (18)	0.0662 (14)	0.0012 (13)	−0.0001 (10)	0.0054 (12)
C223	0.0724 (17)	0.109 (2)	0.0774 (16)	0.0110 (16)	−0.0011 (13)	0.0039 (15)
C224	0.0590 (16)	0.137 (3)	0.0826 (18)	−0.0002 (18)	−0.0035 (14)	−0.0097 (19)
C225	0.0703 (17)	0.115 (2)	0.0800 (17)	−0.0315 (17)	0.0130 (14)	−0.0094 (17)
C226	0.0729 (15)	0.0776 (18)	0.0574 (13)	−0.0116 (13)	−0.0001 (11)	−0.0066 (11)

Geometric parameters (Å, º)

P1—C1	1.8463 (19)	C124—H124	0.93
P2—C1	1.855 (2)	C125—C126	1.378 (3)
C1—H1A	0.97	C125—H125	0.93
C1—H1B	0.97	C126—H126	0.93
P1—C111	1.827 (2)	C211—C212	1.376 (3)
P1—C121	1.836 (2)	C211—C216	1.383 (3)
P2—C211	1.841 (2)	C212—C213	1.389 (3)
P2—C221	1.829 (2)	C212—H212	0.93
C111—C112	1.382 (3)	C213—C214	1.365 (4)
C111—C116	1.387 (3)	C213—H213	0.93
C112—C113	1.384 (3)	C214—C215	1.364 (3)
C112—H112	0.93	C214—H214	0.93
C113—C114	1.351 (4)	C215—C216	1.384 (3)
C113—H113	0.93	C215—H215	0.93
C114—C115	1.361 (4)	C216—H216	0.93
C114—H114	0.93	C221—C222	1.388 (3)
C115—C116	1.381 (4)	C221—C226	1.392 (3)
C115—H115	0.93	C222—C223	1.384 (3)
C116—H116	0.93	C222—H222	0.93
C121—C126	1.389 (3)	C223—C224	1.364 (4)
C121—C122	1.396 (3)	C223—H223	0.93
C122—C123	1.386 (3)	C224—C225	1.384 (4)
C122—H122	0.93	C224—H224	0.93
C123—C124	1.369 (3)	C225—C226	1.394 (3)
C123—H123	0.93	C225—H225	0.93
C124—C125	1.377 (3)	C226—H226	0.93
P1—C1—P2	107.63 (10)	C126—C125—C124	120.3 (2)
P1—C1—H1A	110.2	C126—C125—H125	119.8
P2—C1—H1A	110.2	C124—C125—H125	119.8
P1—C1—H1B	110.2	C125—C126—C121	121.6 (2)
P2—C1—H1B	110.2	C125—C126—H126	119.2
H1A—C1—H1B	108.5	C121—C126—H126	119.2
C1—P1—C111	103.12 (10)	C212—C211—C216	117.3 (2)
C1—P1—C121	101.53 (9)	C212—C211—P2	119.32 (17)
C1—P2—C211	99.94 (9)	C216—C211—P2	123.34 (16)
C1—P2—C221	103.17 (9)	C211—C212—C213	121.3 (2)
C111—P1—C121	101.98 (9)	C211—C212—H212	119.4
C211—P2—C221	101.22 (9)	C213—C212—H212	119.4
C112—C111—C116	116.6 (2)	C214—C213—C212	119.8 (3)
C112—C111—P1	126.39 (17)	C214—C213—H213	120.1
C116—C111—P1	117.01 (17)	C212—C213—H213	120.1
C111—C112—C113	121.2 (2)	C215—C214—C213	120.4 (2)
C111—C112—H112	119.4	C215—C214—H214	119.8
C113—C112—H112	119.4	C213—C214—H214	119.8
C114—C113—C112	120.9 (3)	C214—C215—C216	119.2 (3)
C114—C113—H113	119.6	C214—C215—H215	120.4
C112—C113—H113	119.6	C216—C215—H215	120.4
C113—C114—C115	119.5 (3)	C211—C216—C215	121.9 (2)
C113—C114—H114	120.3	C211—C216—H216	119.1
C115—C114—H114	120.3	C215—C216—H216	119.1
C114—C115—C116	120.2 (3)	C222—C221—C226	117.6 (2)
C114—C115—H115	119.9	C222—C221—P2	125.34 (16)
C116—C115—H115	119.9	C226—C221—P2	117.10 (18)
C115—C116—C111	121.6 (3)	C223—C222—C221	121.4 (2)
C115—C116—H116	119.2	C223—C222—H222	119.3
C111—C116—H116	119.2	C221—C222—H222	119.3
C126—C121—C122	117.2 (2)	C224—C223—C222	120.4 (3)
C126—C121—P1	118.13 (15)	C224—C223—H223	119.8
C122—C121—P1	124.51 (17)	C222—C223—H223	119.8
C123—C122—C121	120.8 (2)	C223—C224—C225	119.9 (2)
C123—C122—H122	119.6	C223—C224—H224	120.1
C121—C122—H122	119.6	C225—C224—H224	120.1
C124—C123—C122	120.8 (2)	C224—C225—C226	119.7 (2)
C124—C123—H123	119.6	C224—C225—H225	120.1
C122—C123—H123	119.6	C226—C225—H225	120.1
C123—C124—C125	119.2 (2)	C221—C226—C225	121.0 (2)
C123—C124—H124	120.4	C221—C226—H226	119.5
C125—C124—H124	120.4	C225—C226—H226	119.5
P2—C1—P1—C111	82.33 (11)	C124—C125—C126—C121	−0.6 (4)
P2—C1—P1—C121	−172.30 (10)	C122—C121—C126—C125	1.2 (3)
P1—C1—P2—C211	87.31 (11)	P1—C121—C126—C125	177.45 (19)
P1—C1—P2—C221	−168.57 (10)	C221—P2—C211—C212	153.94 (18)
P1—C1—P2—Cg1	138.70 (12)	C1—P2—C211—C212	−100.36 (18)
P2—C1—P1—Cg2	135.46 (12)	C221—P2—C211—C216	−26.07 (19)
C121—P1—C111—C112	−88.10 (19)	C1—P2—C211—C216	79.64 (18)
C1—P1—C111—C112	16.9 (2)	C216—C211—C212—C213	0.1 (3)
C121—P1—C111—C116	92.48 (17)	P2—C211—C212—C213	−179.9 (2)
C1—P1—C111—C116	−162.49 (16)	C211—C212—C213—C214	0.8 (4)
C116—C111—C112—C113	−0.7 (3)	C212—C213—C214—C215	−1.2 (4)
P1—C111—C112—C113	179.87 (18)	C213—C214—C215—C216	0.8 (4)
C111—C112—C113—C114	−0.6 (4)	C212—C211—C216—C215	−0.5 (3)
C112—C113—C114—C115	1.4 (4)	P2—C211—C216—C215	179.48 (18)
C113—C114—C115—C116	−0.9 (4)	C214—C215—C216—C211	0.1 (4)
C114—C115—C116—C111	−0.4 (4)	C211—P2—C221—C222	89.39 (18)
C112—C111—C116—C115	1.2 (3)	C1—P2—C221—C222	−13.7 (2)
P1—C111—C116—C115	−179.32 (18)	C211—P2—C221—C226	−91.44 (16)
C111—P1—C121—C126	168.52 (16)	C1—P2—C221—C226	165.43 (15)
C1—P1—C121—C126	62.25 (18)	C226—C221—C222—C223	0.0 (3)
C111—P1—C121—C122	−15.51 (19)	P2—C221—C222—C223	179.12 (17)
C1—P1—C121—C122	−121.78 (17)	C221—C222—C223—C224	−0.6 (4)
C126—C121—C122—C123	−1.0 (3)	C222—C223—C224—C225	0.8 (4)
P1—C121—C122—C123	−177.01 (17)	C223—C224—C225—C226	−0.4 (4)
C121—C122—C123—C124	0.3 (3)	C222—C221—C226—C225	0.5 (3)
C122—C123—C124—C125	0.3 (4)	P2—C221—C226—C225	−178.78 (16)
C123—C124—C125—C126	−0.2 (4)	C224—C225—C226—C221	−0.3 (3)