Home Crystal structure of ethane-1,2-diylbis(diphenylphosphine oxide) – dihydrogenperoxide (1/2), C26H28O6P2
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Crystal structure of ethane-1,2-diylbis(diphenylphosphine oxide) – dihydrogenperoxide (1/2), C26H28O6P2

  • See Mun Lee , Kong Mun Lo and Edward R.T. Tiekink ORCID logo EMAIL logo
Published/Copyright: August 21, 2020

Abstract

C26H28O6P2, monoclinic, C2/c (no. 15), a = 12.8582(1) Å, b = 12.4664(1) Å, c = 15.4358(1) Å, β = 95.738(1)°, V = 2461.89(3) Å3, Z = 4, Rgt(F) = 0.0296, wRref(F2) = 0.0809, T = 100(2) K.

CCDC no.: 2023123

Table 1 contains crystallographic data and Table 2 contains the list of the atoms including atomic coordinates and displacement parameters.

Table 1:

Data collection and handling.

Crystal:Colourless block
Size:0.21 × 0.18 × 0.16 mm
Wavelength:Cu Kα radiation (1.54184 Å)
μ:1.94 mm−1
Diffractometer, scan mode:XtaLAB Synergy, ω
θmax, completeness:67.0°, >99%
N(hkl)measured, N(hkl)unique, Rint:15092, 2209, 0.023
Criterion for Iobs, N(hkl)gt:Iobs > 2 σ(Iobs), 2150
N(param)refined:160
Programs:CrysAlisPRO [1], SHELX [2], [3], WinGX/ORTEP [4]
Table 2:

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2).

AtomxyzUiso*/Ueq
P10.63489(2)0.26828(3)0.59742(2)0.01656(13)
O10.59865(7)0.38168(7)0.58138(6)0.0237(2)
O20.43878(8)0.50768(9)0.61936(7)0.0340(3)
H2O0.4859(13)0.4626(14)0.6090(13)0.051*
O30.35955(8)0.48151(8)0.54863(7)0.0288(2)
H3O0.3763(15)0.5234(14)0.5092(10)0.043*
C10.70133(10)0.21716(10)0.50803(8)0.0189(3)
H1A0.7223600.1419030.5205300.023*
H1B0.6521740.2174430.4544030.023*
C20.72539(10)0.25872(11)0.69350(9)0.0191(3)
C30.72370(12)0.33851(12)0.75690(9)0.0271(3)
H30.6737940.3948170.7498300.033*
C40.79545(14)0.33498(15)0.83033(10)0.0392(4)
H40.7943860.3887610.8738410.047*
C50.86859(13)0.25311(16)0.84022(10)0.0404(4)
H50.9185170.2520280.8899320.048*
C60.86953(11)0.17316(15)0.77849(10)0.0330(4)
H60.9190170.1165370.7863640.040*
C70.79819(10)0.17552(12)0.70497(9)0.0242(3)
H70.7988360.1205520.6624060.029*
C80.52740(10)0.17782(11)0.60555(8)0.0199(3)
C90.54213(13)0.07445(14)0.63811(14)0.0473(5)
H90.6101430.0511410.6597480.057*
C100.45788(14)0.00518(14)0.63914(15)0.0505(5)
H100.468471−0.0653310.6616400.061*
C110.35935(11)0.03781(12)0.60787(10)0.0289(3)
H110.301837−0.0098740.6087410.035*
C120.34422(11)0.13987(12)0.57526(10)0.0294(3)
H120.2760950.1623180.5531350.035*
C130.42762(11)0.21037(12)0.57440(10)0.0247(3)
H130.4162770.2810340.5524290.030*

Source of material

1,2-Bis(diphenylphosphino)ethane (Sigma-Aldrich, 0.98 g, 2.5 mmol) was dissolved in 95% ethanol (100 mL). To this solution was added 30% hydrogen peroxide in excess (Merck, 0.50 mL). The mixture was stirred at room temperature for 1 h and filtered. The filtrate was evaporated slowly at room temperature until white crystalline solids were formed. Yield: 0.84 g (68.7%). M. pt (Stuart SMP30 digital melting point apparatus; uncorrected): 420–422 K. IR (Bruker Vertex 70v FTIR Spectrometer; cm−1): 3206 (b) ν(O–H), 1465 (s) ν(C=C), 1185 (m) ν(P=O), 1088 (m) ν(P–Ar). 1H NMR (Bruker Ascend 400 MHz NMR spectrometer; CDCl3; ppm relative to Me4Si): δ 1.86 (s, 2H, OH), 2.51 (s, 4H, CH2), 7.43–7.72 (20H, Ph—H). 13C{1H} NMR (as for 1H NMR): 21.9 (d, CH2, J = 66 Hz) 128.8, 130.8, 131.2, 131.9, 132.4, 132.6 (Ph—C).

Experimental details

The C-bound H atoms were geometrically placed (C—H = 0.95–0.99 Å) and refined as riding with Uiso(H) = 1.2Ueq(C). The O-bound H atoms were refined with O—H = 0.84 ± 0.01 Å, and with Uiso(H) = 1.5Ueq(O).

Comment

The title compound Ph2P(=O)CH2CH2P(=O)Ph2 ⋅ 2H2O2, (I), was generated during a successful attempt to oxidise Ph2PCH2CH2PPh2 for the purpose of coordinating the oxidised species to various neutral organotin species, studies which, hitherto, have focussed upon mono-functional triorganophosphaneoxide adducts [5], [6].

The molecular structures of the constituents of (I) are shown in the upper part of the figure (70% displacement ellipsoids; unlabelled atoms are related by the symmetry operation (i) 3/2 − x, 1/2 − y, 1 − z). The ethane-1,2-diylbis(diphenylphosphine oxide) molecule is disposed about a centre of inversion located at the mid-point of the C1—C1i bond. The P1 atom is tetrahedrally coordinated by methylene-C [P1—C1 = 1.8099(13) Å], phenyl-C [P1—C2, C8 = 1.7951(14) & 1.7978(13) Å] and oxide-O1 [P1—O1 = 1.5013(9) Å] atoms. The angles in the C3O donor set range from a narrow 104.90(6)°, for C1—P1—C8, to a wide 111.97(6)° for C8—P1—O1; the angles involving the O1 atom are uniformly wider than those involving C atoms only. The O2—O3 bond in the hydrogen peroxide molecule is 1.4539(15) Å.

While there are several triorganophosphaneoxide analogues of (I) in the crystallographic literature, the most closely related structure is that of the only diphosphane analogue, i.e. Cy2P(=O)CH2CH2P(=O)Cy2⋅H2O2 [7]. Here, the diphosphane molecule is disposed about a centre of inversion, as for (I), but crystallises with only one H2O2 molecule per diphosphane species.

In the crystal and as shown in the lower view of the figure, the hydrogen peroxide molecule employs both hydrogen atoms to bridge oxide atoms of translationally-related molecules [O2—H2o⋯O1: H2o⋯O1 = 1.851(17) Å, O2⋯O1 = 2.6977(14) Å with angle at H2o = 171.7(18)° and O3—H3o⋯O1ii: H3o⋯O1ii = 1.884(16) Å, O3⋯O1ii = 2.7278(14) Å with angle at H3o = 175.1(19)° for (ii) 1 − x, 1 − y, 1 − z]. The hydrogen bonding results in a linear, supramolecular chain sustained by 10-membered {⋯HOOH⋯O}2 synthons which have a chair conformation; the chain is close to being parallel to [1 −1 0]. As the chains appear to pack in the crystal without directional interactions between them, the molecular packing was further analysed by calculating the Hirshfeld surfaces as well as the full- and delineated two-dimensional fingerprint plots for the individual molecules using the program Crystal Explorer 17 [8] and standard protocols [9]. There are only two types of contributors to the calculated Hirshfeld surface of the H2O2 molecule, namely H⋯O/O⋯H which makes up 66.7% of all contacts with the remainder, i.e. 33.3%, being due to H⋯H contacts. For the diphosphane molecule, the contribution from H⋯H contacts increases to 54.8% with H⋯O/O⋯H contacts accounting for 17.0% of all contacts. The only other contributions to the surface are from H⋯C/C⋯H [20.4%] and C⋯C [7.8%] contacts.

Acknowledgements

Sunway University Sdn Bhd is thanked for financial support of this work through Grant No. STR-RCTR-RCCM-001-2019.

References

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Received: 2020-07-20
Accepted: 2020-08-13
Published Online: 2020-08-21
Published in Print: 2020-10-27

©2020 See Mun Lee et al., published by De Gruyter, Berlin/Boston

This work is licensed under the Creative Commons Attribution 4.0 International License.

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  77. Crystal structure of bis{N-methyl-N′-[3-(4-methoxyphenyl)-1-methylpropane-1-ylidene]carbamohydrazonothioato}zinc(II), C26H36N6O2S2Zn
  78. Crystal structure of (2-carboxy-4-(3-carboxy-5-carboxylatophenoxy)benzoato-κ2O,O′)bis(1,10-phenantroline-κ2N,N′)cobalt(II), C40H24N4O9Co
  79. The crystal structure of (3S,8R,10R,14R)-17-((2S,5S)-5-(2-hydroxypropan-2-yl)-2-methyltetrahydrofuran-2-yl)-4,4,8,10,14-pentamethyl-12-oxohexadecahydro-1H-cyclopenta[a]phenanthren-3-yl acetate, C32H52O5
  80. Crystal structure of (μ2-1,1′-bis(diphenylphosphino)ferrocene-κ2P,P′)-bis[(Z)N-(3-fluorophenyl)-O-methylthiocarbamato-S]digold(I) chloroform solvate, C50H42Au2F2FeN2O2P2S2, CHCl3
  81. Crystal structure of poly[bis(μ2-1,4-di(1H-imidazol-1-yl)benzene-κ2N:N′)-(μ2-tetraoxidomolybdato(VI)-κ2O:O′)cobalt(II)], C24H20N8O4MoCo
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