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In the title compound, C32H36P22+·2Br·2CDCl3, the diphospho­nium ring of the centrosymmetric dication adopts a chair conformation. A network of weak C—H...Cl and C—H...Br inter­actions helps to establish the packing. Both bromide ions lie on crystallographic twofold rotation axes.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807052932/hb2582sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807052932/hb2582Isup2.hkl
Contains datablock I

CCDC reference: 672803

Key indicators

  • Single-crystal X-ray study
  • T = 133 K
  • Mean [sigma](C-C) = 0.003 Å
  • Some non-H atoms missing
  • R factor = 0.032
  • wR factor = 0.083
  • Data-to-parameter ratio = 26.9

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ? PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large ............. 0.88 PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.90 PLAT480_ALERT_4_C Long H...A H-Bond Reported H2A .. CL3 .. 2.93 Ang. PLAT480_ALERT_4_C Long H...A H-Bond Reported H14 .. CL1 .. 2.87 Ang. PLAT480_ALERT_4_C Long H...A H-Bond Reported H13 .. BR1 .. 2.99 Ang. PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 2 C H Cl3
Alert level G FORMU01_ALERT_2_G There is a discrepancy between the atom counts in the _chemical_formula_sum and the formula from the _atom_site* data. Atom count from _chemical_formula_sum:C34 H36 Br2 Cl6 D2 P2 Atom count from the _atom_site data: C34 H38 Br2 Cl6 P2 ABSTM02_ALERT_3_G When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.897 Tmax scaled 0.450 Tmin scaled 0.323 CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected. CELLZ01_ALERT_1_G ALERT: Large difference may be due to a symmetry error - see SYMMG tests From the CIF: _cell_formula_units_Z 4 From the CIF: _chemical_formula_sum C34 H36 Br2 Cl6 D2 P2 TEST: Compare cell contents of formula and atom_site data atom Z*formula cif sites diff C 136.00 136.00 0.00 H 144.00 152.00 -8.00 Br 8.00 8.00 0.00 Cl 24.00 24.00 0.00 D 8.00 0.00 8.00 P 8.00 8.00 0.00
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 8 ALERT level C = Check and explain 4 ALERT level G = General alerts; check 4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 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 5 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

Similar to the homologue structures known in the literature (Brown & Trefonas, 1972; Matt et al., 1996; Duraczynska & Nelson, 2005) the diphosphonium ring, in the title compound, (I), which sits on a crystallographic center of symmetry, is in a chair conformation with the torsion angles of 52.58 (17)° (C4i—P—C3—C4) and -56.00 (16)° (P—C3—C4—Pi) (i: -x,-y,-z). Each phosphorus atom has two benzyl groups attached, one of which is equatorial and the other axial. The mean P—C bond distance in (I) of 1.80 (18) Å is in accordance with the reported data for other cyclic diphosphonium salts. The P atom in (I) displays a slightly distorted tetrahedral geometry with C—P—C angles ranging from 106.61 (8)° to 113.65 (8)°. The C2—P1—C1 angle is intermediate between that of phenyl (Brown & Trefonas, 1972; Matt et al., 1996) and cyclohexyl substituted derivatives (Duraczynska & Nelson, 2005). The phenyl rings are tilted to each other with an angle of 47.42 (10)°.

Unlike the phenyl analog (Matt et al., 1996), the packing for (I) is consolidated by weak C—H···Cl and C—H···Br interactions (Table 1), linking the dication, the anions, and the deuterated solvent molecule.

Related literature top

For related literature, see: Brown & Trefonas (1972); Duraczynska & Nelson (2005); Hinton & Mann (1959); Matt et al. (1996).

Experimental top

The title compound was been prepared from the corresponding diphosphine, (PhCH2)2PCH2CH2P(CH2Ph)2, and 1,2-dibromoethane according to the procedure given by Hinton & Mann (1959). Colourless blocks of (I) were obtained from deuterated chloroform by slow evaporation at room temperature.

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 2000); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. The molecular structure of the dication in (I), with displacement ellipsoids for the non-hydrogen atoms drawn at the 50% probability level. The unlabelled atoms are generated by the symmetry operation (-x, -y, -z).
[Figure 2] Fig. 2. A packing diagram for (I), viewed along the a axis with the H bonds indicated by dashed lines.
1,1,4,4-Tetrabenzyl-1,4-diphosphinane-1,4-diium dibromide deuterochloroform disolvate top
Crystal data top
C32H36P22+·2Br·2CDCl3F(000) = 1776
Mr = 883.08Dx = 1.595 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 8675 reflections
a = 16.2692 (10) Åθ = 2.3–30.4°
b = 17.5649 (10) ŵ = 2.75 mm1
c = 13.9110 (8) ÅT = 133 K
β = 112.350 (3)°Block, colourless
V = 3676.7 (4) Å30.38 × 0.30 × 0.29 mm
Z = 4
Data collection top
Bruker SMART1000 CCD
diffractometer
5373 independent reflections
Radiation source: fine-focus sealed tube4684 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.025
Detector resolution: 8.192 pixels mm-1θmax = 30.0°, θmin = 1.8°
ω scansh = 2222
Absorption correction: multi-scan
(SADABS; Bruker, 1999)
k = 2424
Tmin = 0.360, Tmax = 0.502l = 1919
37985 measured reflections
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)] = 0.032Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.083H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0419P)2 + 6.1465P]
where P = (Fo2 + 2Fc2)/3
5373 reflections(Δ/σ)max < 0.001
200 parametersΔρmax = 1.52 e Å3
0 restraintsΔρmin = 1.05 e Å3
Crystal data top
C32H36P22+·2Br·2CDCl3V = 3676.7 (4) Å3
Mr = 883.08Z = 4
Monoclinic, C2/cMo Kα radiation
a = 16.2692 (10) ŵ = 2.75 mm1
b = 17.5649 (10) ÅT = 133 K
c = 13.9110 (8) Å0.38 × 0.30 × 0.29 mm
β = 112.350 (3)°
Data collection top
Bruker SMART1000 CCD
diffractometer
5373 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1999)
4684 reflections with I > 2σ(I)
Tmin = 0.360, Tmax = 0.502Rint = 0.025
37985 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0320 restraints
wR(F2) = 0.083H-atom parameters constrained
S = 1.05Δρmax = 1.52 e Å3
5373 reflectionsΔρmin = 1.05 e Å3
200 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
xyzUiso*/Ueq
Br10.00000.121056 (14)0.75000.02374 (7)
Br20.00000.209800 (15)0.25000.03136 (8)
P10.08262 (3)0.06365 (2)0.06148 (3)0.01914 (9)
C10.12293 (12)0.15385 (10)0.03500 (15)0.0246 (3)
H1A0.08810.16780.03820.030*
H1B0.11170.19320.07950.030*
C110.22023 (12)0.15556 (10)0.05260 (14)0.0238 (3)
C120.27929 (14)0.19798 (11)0.13390 (16)0.0291 (4)
H120.25800.22690.17730.035*
C130.36960 (15)0.19821 (13)0.15203 (19)0.0380 (5)
H130.40980.22740.20760.046*
C140.40056 (16)0.15622 (14)0.0894 (2)0.0421 (5)
H140.46240.15510.10320.050*
C150.34194 (17)0.11551 (13)0.0062 (2)0.0401 (5)
H150.36330.08750.03790.048*
C160.25188 (15)0.11585 (12)0.01245 (17)0.0316 (4)
H160.21160.08870.07020.038*
C20.13706 (12)0.03240 (10)0.19539 (14)0.0223 (3)
H2A0.15000.07770.24110.027*
H2B0.09520.00010.21320.027*
C210.22303 (11)0.01158 (10)0.21883 (13)0.0217 (3)
C220.30491 (13)0.02553 (12)0.25009 (15)0.0279 (4)
H220.30760.07930.25800.033*
C230.38249 (13)0.01563 (13)0.26965 (17)0.0331 (4)
H230.43790.01010.29120.040*
C240.37956 (13)0.09415 (13)0.25799 (16)0.0323 (4)
H240.43270.12200.27040.039*
C250.29897 (14)0.13164 (12)0.22824 (16)0.0293 (4)
H250.29680.18540.22040.035*
C260.22100 (12)0.09085 (11)0.20968 (14)0.0247 (3)
H260.16600.11710.19070.030*
C30.03415 (11)0.07968 (10)0.03025 (14)0.0222 (3)
H3A0.04030.11550.08210.027*
H3B0.05930.10500.03840.027*
C40.09037 (11)0.00863 (10)0.02692 (14)0.0214 (3)
H4A0.15330.02400.00590.026*
H4B0.07080.01330.09770.026*
Cl10.10604 (4)0.26705 (3)0.07399 (5)0.03723 (12)
Cl20.09062 (6)0.41535 (4)0.01860 (5)0.05499 (18)
Cl30.26168 (4)0.33812 (4)0.06513 (5)0.04406 (15)
C990.14538 (14)0.32753 (12)0.00011 (16)0.0311 (4)
H990.13290.30350.06940.037*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.02504 (12)0.02263 (12)0.02072 (12)0.0000.00553 (9)0.000
Br20.04348 (16)0.02395 (13)0.02526 (14)0.0000.01151 (11)0.000
P10.01808 (19)0.01810 (19)0.0191 (2)0.00022 (15)0.00459 (15)0.00208 (14)
C10.0265 (8)0.0204 (8)0.0244 (9)0.0010 (6)0.0069 (7)0.0010 (6)
C110.0285 (8)0.0206 (8)0.0227 (8)0.0028 (6)0.0101 (7)0.0015 (6)
C120.0354 (10)0.0241 (8)0.0280 (10)0.0065 (7)0.0121 (8)0.0021 (7)
C130.0337 (10)0.0371 (11)0.0396 (12)0.0147 (9)0.0099 (9)0.0022 (9)
C140.0327 (11)0.0446 (13)0.0539 (15)0.0049 (9)0.0220 (10)0.0125 (11)
C150.0479 (13)0.0375 (11)0.0479 (14)0.0006 (10)0.0329 (11)0.0038 (10)
C160.0393 (11)0.0315 (10)0.0281 (10)0.0047 (8)0.0174 (8)0.0017 (7)
C20.0225 (8)0.0241 (8)0.0193 (8)0.0018 (6)0.0069 (6)0.0002 (6)
C210.0218 (8)0.0252 (8)0.0176 (8)0.0008 (6)0.0067 (6)0.0024 (6)
C220.0262 (9)0.0288 (9)0.0260 (9)0.0028 (7)0.0069 (7)0.0036 (7)
C230.0228 (9)0.0431 (11)0.0335 (11)0.0030 (8)0.0107 (8)0.0043 (9)
C240.0273 (9)0.0427 (11)0.0294 (10)0.0093 (8)0.0138 (8)0.0051 (8)
C250.0331 (10)0.0286 (9)0.0261 (9)0.0054 (8)0.0113 (7)0.0024 (7)
C260.0238 (8)0.0261 (8)0.0225 (8)0.0006 (7)0.0067 (6)0.0009 (6)
C30.0202 (7)0.0193 (8)0.0243 (8)0.0026 (6)0.0053 (6)0.0025 (6)
C40.0213 (8)0.0214 (8)0.0208 (8)0.0012 (6)0.0070 (6)0.0020 (6)
Cl10.0334 (2)0.0369 (3)0.0452 (3)0.0021 (2)0.0192 (2)0.0015 (2)
Cl20.0842 (5)0.0376 (3)0.0367 (3)0.0212 (3)0.0157 (3)0.0044 (2)
Cl30.0367 (3)0.0499 (3)0.0516 (3)0.0161 (2)0.0235 (2)0.0209 (3)
C990.0363 (10)0.0303 (10)0.0264 (10)0.0011 (8)0.0115 (8)0.0040 (7)
Geometric parameters (Å, º) top
P1—C31.8027 (18)Cl2—C991.751 (2)
P1—C4i1.8050 (18)Cl3—C991.770 (2)
P1—C11.8053 (18)C1—H1A0.9900
P1—C21.8170 (18)C1—H1B0.9900
C1—C111.507 (3)C12—H120.9500
C11—C161.387 (3)C13—H130.9500
C11—C121.389 (3)C14—H140.9500
C12—C131.393 (3)C15—H150.9500
C13—C141.375 (4)C16—H160.9500
C14—C151.386 (4)C2—H2A0.9900
C15—C161.387 (3)C2—H2B0.9900
C2—C211.521 (2)C22—H220.9500
C21—C221.396 (3)C23—H230.9500
C21—C261.397 (3)C24—H240.9500
C22—C231.389 (3)C25—H250.9500
C23—C241.387 (3)C26—H260.9500
C24—C251.383 (3)C3—H3A0.9900
C25—C261.393 (3)C3—H3B0.9900
C3—C41.538 (2)C4—H4A0.9900
C4—P1i1.8049 (18)C4—H4B0.9900
Cl1—C991.761 (2)C99—H991.0000
C3—P1—C4i106.61 (8)C14—C13—H13120.0
C3—P1—C1104.19 (8)C12—C13—H13120.0
C4i—P1—C1110.70 (9)C13—C14—H14119.9
C3—P1—C2110.63 (9)C15—C14—H14119.9
C4i—P1—C2110.66 (8)C14—C15—H15120.1
C1—P1—C2113.65 (8)C16—C15—H15120.1
C11—C1—P1115.15 (13)C11—C16—H16119.7
C16—C11—C12119.16 (19)C15—C16—H16119.7
C16—C11—C1120.75 (17)C21—C2—H2A108.5
C12—C11—C1120.09 (17)P1—C2—H2A108.5
C11—C12—C13120.3 (2)C21—C2—H2B108.5
C14—C13—C12119.9 (2)P1—C2—H2B108.5
C13—C14—C15120.3 (2)H2A—C2—H2B107.5
C14—C15—C16119.8 (2)C23—C22—H22119.8
C11—C16—C15120.5 (2)C21—C22—H22119.8
C21—C2—P1115.04 (12)C24—C23—H23119.8
C22—C21—C26118.72 (17)C22—C23—H23119.8
C22—C21—C2121.37 (17)C25—C24—H24120.2
C26—C21—C2119.91 (16)C23—C24—H24120.2
C23—C22—C21120.44 (19)C24—C25—H25119.9
C24—C23—C22120.42 (19)C26—C25—H25119.9
C25—C24—C23119.67 (18)C25—C26—H26119.8
C24—C25—C26120.25 (19)C21—C26—H26119.8
C25—C26—C21120.48 (17)C4—C3—H3A108.2
C4—C3—P1116.16 (12)P1—C3—H3A108.2
C3—C4—P1i113.36 (12)C4—C3—H3B108.2
Cl2—C99—Cl1109.85 (12)P1—C3—H3B108.2
Cl2—C99—Cl3111.58 (12)H3A—C3—H3B107.4
Cl1—C99—Cl3108.59 (12)C3—C4—H4A108.9
C11—C1—H1A108.5P1i—C4—H4A108.9
P1—C1—H1A108.5C3—C4—H4B108.9
C11—C1—H1B108.5P1i—C4—H4B108.9
P1—C1—H1B108.5H4A—C4—H4B107.7
H1A—C1—H1B107.5Cl2—C99—H99108.9
C11—C12—H12119.9Cl1—C99—H99108.9
C13—C12—H12119.9Cl3—C99—H99108.9
C3—P1—C1—C11178.60 (14)C1—P1—C2—C2186.12 (15)
C4i—P1—C1—C1164.34 (16)P1—C2—C21—C2289.50 (19)
C2—P1—C1—C1160.91 (16)P1—C2—C21—C2690.81 (18)
P1—C1—C11—C1669.5 (2)C26—C21—C22—C231.2 (3)
P1—C1—C11—C12111.24 (18)C2—C21—C22—C23179.06 (18)
C16—C11—C12—C132.4 (3)C21—C22—C23—C240.3 (3)
C1—C11—C12—C13178.39 (18)C22—C23—C24—C251.0 (3)
C11—C12—C13—C140.1 (3)C23—C24—C25—C260.2 (3)
C12—C13—C14—C152.1 (3)C24—C25—C26—C211.3 (3)
C13—C14—C15—C161.5 (4)C22—C21—C26—C252.0 (3)
C12—C11—C16—C153.0 (3)C2—C21—C26—C25178.29 (17)
C1—C11—C16—C15177.79 (19)C4i—P1—C3—C452.58 (17)
C14—C15—C16—C111.1 (3)C1—P1—C3—C4169.70 (13)
C3—P1—C2—C21157.08 (13)C2—P1—C3—C467.81 (15)
C4i—P1—C2—C2139.15 (16)P1—C3—C4—P1i56.00 (16)
Symmetry code: (i) x, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2A···Cl3ii0.992.933.8486 (19)155
C14—H14···Cl1iii0.952.873.686 (2)145
C13—H13···Br1iv0.952.993.773 (2)141
C2—H2B···Br1v0.992.793.7553 (18)166
C4—H4B···Br1v0.992.753.6757 (18)157
C1—H1A···Br1vi0.992.863.7443 (19)149
Symmetry codes: (ii) x+1/2, y+1/2, z+1/2; (iii) x+1/2, y+1/2, z; (iv) x+1/2, y+1/2, z+1; (v) x, y, z+1; (vi) x, y, z1.

Experimental details

Crystal data
Chemical formulaC32H36P22+·2Br·2CDCl3
Mr883.08
Crystal system, space groupMonoclinic, C2/c
Temperature (K)133
a, b, c (Å)16.2692 (10), 17.5649 (10), 13.9110 (8)
β (°) 112.350 (3)
V3)3676.7 (4)
Z4
Radiation typeMo Kα
µ (mm1)2.75
Crystal size (mm)0.38 × 0.30 × 0.29
Data collection
DiffractometerBruker SMART1000 CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 1999)
Tmin, Tmax0.360, 0.502
No. of measured, independent and
observed [I > 2σ(I)] reflections
37985, 5373, 4684
Rint0.025
(sin θ/λ)max1)0.704
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.032, 0.083, 1.05
No. of reflections5373
No. of parameters200
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.52, 1.05

Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP (Siemens, 2000).

Selected bond lengths (Å) top
C3—C41.538 (2)C4—P1i1.8049 (18)
Symmetry code: (i) x, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2A···Cl3ii0.992.933.8486 (19)155
C14—H14···Cl1iii0.952.873.686 (2)145
C13—H13···Br1iv0.952.993.773 (2)141
C2—H2B···Br1v0.992.793.7553 (18)166
C4—H4B···Br1v0.992.753.6757 (18)157
C1—H1A···Br1vi0.992.863.7443 (19)149
Symmetry codes: (ii) x+1/2, y+1/2, z+1/2; (iii) x+1/2, y+1/2, z; (iv) x+1/2, y+1/2, z+1; (v) x, y, z+1; (vi) x, y, z1.
 

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