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Acta Cryst. (2009). E65, o542    [ doi:10.1107/S1600536809004590 ]

1,2-Bis(di-2-pyridylphosphinoyl)ethane

S. J. Berners-Price, M. Navarro and B. W. Skelton

Abstract top

The crystal structure of the title compound, C22H20N4O2P2, consists of two independent half-molecules, both of which lie on crystallographic inversion centres. There are no significant differences between the two molecules.

Comment top

Bidentate tertiary phosphine ligands with pyridyl substituents, such as 1,2-bis(di-2-pyridylphosphino)ethane (d2pype) are of interest because a number of studies have shown that metal complexes with these ligands exhibit selective anti-tumour properties (McKeage et al., 2000; Barnard and Berners-Price 2007; Liu et al., 2008). During the course of our work in this area, we obtained crystals of the phosphine oxide d2pypeO2 (I), which were suitable for X-ray diffraction studies.

Related literature top

For background on the antitumour properties of metal complexes of bidentate tertiary phosphine ligands with pyridyl substituents, see: McKeage et al. (2000); Barnard & Berners-Price (2007); Liu et al. (2008). The crystal structure of the parent 1,2-bis(di-2-pyridylphosphino)ethane molecule has been determined (Jones et al., 1999). The structure of 1,2-bis(di-phenylphosphino)ethane dioxide (Calcagno et al., 2000) is similar, with the two halfs of the molecule related by a pseudo-inversion centre, but this is not isomorphous with the title compound.

Experimental top

1,2-bis(di-2-pyridylphosphino)ethane (d2pype) was obtained from Strem Chemicals Inc. Single crystals of the title compound d2pypeO2 (I) suitable for X-ray crystallographic analysis were obtained as a by-product of slow evaporation of a solution of d2pype and copper (I) iodide (molar ratio 2:1) in acetonitrile-tetrahydrofuran mixture.

Refinement top

The assignments of the py ring N,C atoms were made on the basis of refinement and location of the H atoms. All H atoms were positioned geometrically and refined using a riding model with C—H = 0.95–0.99 Å and with Uiso(H) = 1.2 times Ueq(C).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis RED (Oxford Diffraction, 2008); data reduction: CrysAlis RED (Oxford Diffraction, 2008); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top
[Figure 1] Fig. 1. ORTEP drawing and atom labelling for molecule n = 1. Displacement ellipsoids of non-H atoms are drawn at the 50% probablility level. The structure of the second, n = 2, molecule is very similar.
1,2-Bis(di-2-pyridylphosphinoyl)ethane top
Crystal data top
C22H20N4O2P2Z = 2
Mr = 434.36F(000) = 452
Triclinic, P1Dx = 1.366 Mg m−3
Hall symbol: -p 1Mo Kα radiation, λ = 0.71073 Å
a = 8.3760 (6) ÅCell parameters from 2539 reflections
b = 8.8496 (8) Åθ = 3.3–32.6°
c = 16.2332 (11) ŵ = 0.23 mm−1
α = 105.627 (7)°T = 110 K
β = 92.429 (5)°Plate, colourless
γ = 112.559 (7)°0.22 × 0.10 × 0.06 mm
V = 1055.67 (16) Å3
Data collection top
Oxford Diffraction Gemini
diffractometer		4842 independent reflections
Radiation source: sealed tube2698 reflections with I > 2σ(I)
graphiteRint = 0.059
ω scansθmax = 27.5°, θmin = 3.3°
Absorption correction: gaussian
(CrysAlis RED; Oxford Diffraction, 2008)		h = −10→10
Tmin = 0.968, Tmax = 0.988k = −11→11
10983 measured reflectionsl = −21→21
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.052Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.112H-atom parameters constrained
S = 0.86 w = 1/[σ2(Fo2) + (0.0495P)2]
where P = (Fo2 + 2Fc2)/3
4842 reflections(Δ/σ)max = 0.002
271 parametersΔρmax = 0.43 e Å−3
0 restraintsΔρmin = −0.34 e Å−3
Crystal data top
C22H20N4O2P2γ = 112.559 (7)°
Mr = 434.36V = 1055.67 (16) Å3
Triclinic, P1Z = 2
a = 8.3760 (6) ÅMo Kα radiation
b = 8.8496 (8) ŵ = 0.23 mm−1
c = 16.2332 (11) ÅT = 110 K
α = 105.627 (7)°0.22 × 0.10 × 0.06 mm
β = 92.429 (5)°
Data collection top
Oxford Diffraction Gemini
diffractometer		2698 reflections with I > 2σ(I)
Absorption correction: gaussian
(CrysAlis RED; Oxford Diffraction, 2008)		Rint = 0.059
Tmin = 0.968, Tmax = 0.988θmax = 27.5°
10983 measured reflectionsStandard reflections: ?
4842 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.052H-atom parameters constrained
wR(F2) = 0.112Δρmax = 0.43 e Å−3
S = 0.86Δρmin = −0.34 e Å−3
4842 reflectionsAbsolute structure: ?
271 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
P10.18196 (9)0.21056 (9)0.45935 (4)0.02233 (18)
O10.3253 (2)0.3074 (2)0.53572 (11)0.0272 (4)
C1110.2511 (3)0.0876 (3)0.37091 (16)0.0217 (6)
N1120.1239 (3)−0.0366 (3)0.30732 (14)0.0267 (5)
C1130.1759 (4)−0.1218 (4)0.24034 (17)0.0320 (7)
H1130.0879−0.21090.1950.038*
C1140.3487 (4)−0.0891 (4)0.23254 (18)0.0320 (7)
H1140.3782−0.15280.18310.038*
C1150.4767 (4)0.0385 (4)0.29857 (19)0.0372 (8)
H1150.59690.06410.29570.045*
C1160.4284 (3)0.1287 (4)0.36902 (18)0.0313 (7)
H1160.51460.21720.41530.038*
C1210.1197 (3)0.3509 (3)0.41523 (15)0.0227 (6)
N122−0.0518 (3)0.2959 (3)0.38395 (15)0.0300 (6)
C123−0.0959 (4)0.4009 (4)0.35135 (19)0.0352 (7)
H123−0.2160.36610.32980.042*
C1240.0236 (4)0.5571 (4)0.34727 (17)0.0310 (7)
H124−0.01420.62630.32280.037*
C1250.1972 (4)0.6111 (4)0.37892 (17)0.0316 (7)
H1250.28160.71840.37730.038*
C1260.2464 (3)0.5055 (3)0.41316 (16)0.0256 (6)
H1260.36590.53880.43510.031*
C10−0.0180 (3)0.0583 (3)0.47773 (16)0.0242 (6)
H10A−0.07860.1210.51420.029*
H10B−0.0962−0.01240.42160.029*
P20.68020 (8)0.27338 (9)0.04404 (4)0.02132 (18)
O20.7095 (2)0.3187 (2)−0.03767 (11)0.0278 (4)
C2110.6499 (3)0.4398 (3)0.12649 (16)0.0213 (6)
N2120.6135 (3)0.4071 (3)0.20118 (14)0.0279 (5)
C2130.6005 (4)0.5335 (4)0.26420 (18)0.0327 (7)
H2130.57580.51380.31790.039*
C2140.6210 (3)0.6903 (4)0.2556 (2)0.0358 (7)
H2140.61110.77590.30250.043*
C2150.6559 (3)0.7211 (4)0.1781 (2)0.0347 (7)
H2150.66950.82770.17020.042*
C2160.6707 (3)0.5931 (4)0.11223 (19)0.0299 (7)
H2160.69490.610.0580.036*
C2210.8672 (3)0.2545 (3)0.09411 (16)0.0218 (6)
N2220.8365 (3)0.1354 (3)0.13511 (14)0.0285 (5)
C2230.9776 (4)0.1286 (4)0.17259 (18)0.0335 (7)
H2230.95940.04570.20220.04*
C2241.1484 (4)0.2342 (4)0.17114 (18)0.0330 (7)
H2241.24390.22270.19840.04*
C2251.1771 (3)0.3559 (4)0.12949 (18)0.0342 (7)
H2251.29290.43160.12810.041*
C2261.0340 (3)0.3661 (4)0.08959 (17)0.0278 (6)
H2261.04980.44810.05960.033*
C200.4938 (3)0.0766 (3)0.03363 (16)0.0212 (6)
H20A0.48740.05540.09050.025*
H20B0.38530.08760.01590.025*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
P10.0206 (4)0.0253 (4)0.0224 (4)0.0096 (3)0.0051 (3)0.0090 (3)
O10.0232 (9)0.0318 (11)0.0235 (10)0.0099 (9)0.0022 (8)0.0063 (8)
C1110.0238 (14)0.0239 (15)0.0205 (13)0.0105 (12)0.0034 (11)0.0107 (12)
N1120.0328 (13)0.0261 (14)0.0234 (12)0.0148 (11)0.0026 (10)0.0073 (11)
C1130.0433 (18)0.0298 (17)0.0235 (15)0.0168 (15)0.0002 (13)0.0072 (13)
C1140.0463 (18)0.0262 (17)0.0295 (16)0.0186 (15)0.0148 (14)0.0115 (14)
C1150.0328 (16)0.0311 (18)0.050 (2)0.0137 (14)0.0224 (15)0.0120 (16)
C1160.0261 (15)0.0256 (17)0.0358 (17)0.0058 (13)0.0070 (13)0.0063 (14)
C1210.0250 (14)0.0237 (15)0.0201 (14)0.0105 (12)0.0067 (11)0.0066 (12)
N1220.0216 (12)0.0288 (14)0.0420 (14)0.0083 (11)0.0007 (10)0.0181 (12)
C1230.0262 (15)0.0337 (19)0.0480 (19)0.0103 (14)0.0022 (13)0.0197 (15)
C1240.0354 (16)0.0282 (17)0.0341 (16)0.0159 (14)0.0042 (13)0.0128 (14)
C1250.0342 (16)0.0201 (16)0.0361 (17)0.0037 (13)0.0084 (13)0.0126 (13)
C1260.0239 (14)0.0268 (16)0.0232 (14)0.0083 (12)0.0031 (11)0.0065 (12)
C100.0213 (14)0.0279 (16)0.0256 (14)0.0110 (12)0.0061 (11)0.0104 (12)
P20.0193 (3)0.0198 (4)0.0227 (4)0.0056 (3)0.0010 (3)0.0071 (3)
O20.0289 (10)0.0251 (11)0.0265 (10)0.0079 (9)0.0018 (8)0.0084 (9)
C2110.0125 (12)0.0214 (15)0.0253 (14)0.0052 (11)−0.0033 (11)0.0037 (12)
N2120.0272 (12)0.0358 (15)0.0220 (12)0.0161 (11)−0.0015 (10)0.0070 (11)
C2130.0332 (16)0.044 (2)0.0234 (15)0.0229 (15)0.0014 (12)0.0042 (14)
C2140.0262 (15)0.0336 (19)0.0426 (19)0.0162 (14)0.0004 (14)−0.0008 (15)
C2150.0232 (15)0.0180 (16)0.057 (2)0.0052 (12)0.0057 (14)0.0069 (15)
C2160.0195 (14)0.0267 (17)0.0400 (17)0.0058 (12)0.0060 (12)0.0104 (14)
C2210.0225 (14)0.0214 (15)0.0208 (14)0.0089 (12)0.0039 (11)0.0053 (12)
N2220.0250 (12)0.0265 (14)0.0348 (13)0.0087 (11)0.0012 (10)0.0141 (11)
C2230.0295 (16)0.0307 (18)0.0421 (18)0.0093 (14)0.0003 (13)0.0191 (15)
C2240.0234 (15)0.0388 (19)0.0399 (18)0.0134 (14)−0.0027 (13)0.0169 (15)
C2250.0196 (14)0.0389 (19)0.0412 (18)0.0069 (13)0.0058 (13)0.0155 (15)
C2260.0240 (14)0.0279 (17)0.0321 (16)0.0069 (13)0.0059 (12)0.0157 (13)
C200.0185 (13)0.0212 (15)0.0226 (14)0.0072 (11)−0.0002 (11)0.0067 (11)
Geometric parameters (Å, °) top
P1—O11.4917 (18)P2—O21.4897 (18)
P1—C101.799 (3)P2—C201.798 (2)
P1—C1211.809 (3)P2—C2111.811 (3)
P1—C1111.815 (3)P2—C2211.819 (3)
C111—N1121.344 (3)C211—N2121.341 (3)
C111—C1161.391 (3)C211—C2161.384 (4)
N112—C1131.339 (3)N212—C2131.340 (3)
C113—C1141.381 (4)C213—C2141.378 (4)
C113—H1130.95C213—H2130.95
C114—C1151.377 (4)C214—C2151.378 (4)
C114—H1140.95C214—H2140.95
C115—C1161.380 (4)C215—C2161.382 (4)
C115—H1150.95C215—H2150.95
C116—H1160.95C216—H2160.95
C121—N1221.352 (3)C221—N2221.343 (3)
C121—C1261.383 (4)C221—C2261.386 (3)
N122—C1231.339 (3)N222—C2231.336 (3)
C123—C1241.382 (4)C223—C2241.382 (4)
C123—H1230.95C223—H2230.95
C124—C1251.371 (4)C224—C2251.372 (4)
C124—H1240.95C224—H2240.95
C125—C1261.381 (4)C225—C2261.383 (4)
C125—H1250.95C225—H2250.95
C126—H1260.95C226—H2260.95
C10—C10i1.516 (5)C20—C20ii1.536 (5)
C10—H10A0.99C20—H20A0.99
C10—H10B0.99C20—H20B0.99
O1—P1—C10115.87 (11)O2—P2—C20115.28 (11)
O1—P1—C121112.56 (12)O2—P2—C211111.60 (12)
C10—P1—C121105.88 (12)C20—P2—C211106.06 (11)
O1—P1—C111110.98 (11)O2—P2—C221112.89 (11)
C10—P1—C111105.53 (12)C20—P2—C221106.09 (12)
C121—P1—C111105.23 (11)C211—P2—C221104.05 (11)
N112—C111—C116123.1 (2)N212—C211—C216123.4 (2)
N112—C111—P1116.64 (18)N212—C211—P2116.2 (2)
C116—C111—P1120.2 (2)C216—C211—P2120.4 (2)
C113—N112—C111116.4 (2)C213—N212—C211116.5 (2)
N112—C113—C114124.6 (3)N212—C213—C214123.8 (3)
N112—C113—H113117.7N212—C213—H213118.1
C114—C113—H113117.7C214—C213—H213118.1
C115—C114—C113118.0 (3)C215—C214—C213119.1 (3)
C115—C114—H114121C215—C214—H214120.5
C113—C114—H114121C213—C214—H214120.5
C114—C115—C116119.3 (3)C214—C215—C216118.2 (3)
C114—C115—H115120.4C214—C215—H215120.9
C116—C115—H115120.4C216—C215—H215120.9
C115—C116—C111118.7 (3)C215—C216—C211119.0 (3)
C115—C116—H116120.6C215—C216—H216120.5
C111—C116—H116120.6C211—C216—H216120.5
N122—C121—C126123.0 (2)N222—C221—C226123.4 (2)
N122—C121—P1117.2 (2)N222—C221—P2118.23 (18)
C126—C121—P1119.86 (19)C226—C221—P2118.36 (19)
C123—N122—C121116.5 (2)C223—N222—C221116.2 (2)
N122—C123—C124123.6 (3)N222—C223—C224124.3 (3)
N122—C123—H123118.2N222—C223—H223117.8
C124—C123—H123118.2C224—C223—H223117.8
C125—C124—C123119.3 (3)C225—C224—C223118.6 (2)
C125—C124—H124120.4C225—C224—H224120.7
C123—C124—H124120.4C223—C224—H224120.7
C124—C125—C126118.4 (3)C224—C225—C226118.7 (3)
C124—C125—H125120.8C224—C225—H225120.6
C126—C125—H125120.8C226—C225—H225120.6
C125—C126—C121119.3 (2)C225—C226—C221118.8 (2)
C125—C126—H126120.4C225—C226—H226120.6
C121—C126—H126120.4C221—C226—H226120.6
C10i—C10—P1111.2 (2)C20ii—C20—P2111.1 (2)
C10i—C10—H10A109.4C20ii—C20—H20A109.4
P1—C10—H10A109.4P2—C20—H20A109.4
C10i—C10—H10B109.4C20ii—C20—H20B109.4
P1—C10—H10B109.4P2—C20—H20B109.4
H10A—C10—H10B108H20A—C20—H20B108
Symmetry codes: (i) −x, −y, −z+1; (ii) −x+1, −y, −z.
Acknowledgements top

The authors thank the Australian Research Council for financial assistance.

references
References top

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