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The title compound, C36H30NP2+·HSO4·CHCl3, consists of discrete ions and well separated chloroform solvate molecules. The central feature of the structure is O—H...O hydrogen bonding between two hydrogensulfate ions related by a crystallographic inversion centre. The chloroform solvate molecule takes part in a well defined C—H...O hydrogen bond.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101006710/de1168sup1.cif
Contains datablocks default1, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270101006710/de1168Isup2.hkl
Contains datablock I

CCDC reference: 173362

Comment top

Herein we report the structure of [Ph3P=N=PPh3]+[HSO4]-·CHCl3, (I), solated from chloroform and heptane as a by-product of the recrystallization of (PPN)[Re3Cl9(SO4)], which was prepared from the reaction of (Re3Cl9)x, PPNCl, and H2SO4 in water. \sch

The structure consists of discrete ions and well separated solvate molecules of chloroform. The location of the H atom on atom O(1) of the hydrosulfate is unequivocal as indicated by the longer S—O1 distance [1.541 (3) Å] compared with the other S—O bond lengths [average 1.428 (11) Å]. In 30 hydrosulfate ions reported in the Cambridge Structural Database (CSD; Allen & Kennard, 1993) the corresponding values averaged 1.53 (3) and 1.43 (2) Å, respectively. The central feature of the structure is hydrogen bonding between two hydrosulfate ions related by a crystallographic inversion centre (Fig. 1). Due to the symmetry considerations both hydrogen bonds have identical parameters. The O1···O2 (1 - x, 2 - y, 1 - z) distance is 2.633 (4) Å while the O—H···O angle is 155 (1)°. The corresponding values for 23 similar HSO4-—HSO4- hydrogen-bonding interactions in structures reported to the CSD comprised 2.58 (4) Å and 164 (10)°. The only structure with two symmetrical hydrogen bonds between two hydrosulfate moieties [average O···O separation 2.63 (1) Å, O—H.·O angle 150 (2)°] was reported for [Fe(TTP)(HSO4)].1/2C6H6 (TTP = tetraphenylporphinato) (Scheidt et al., 1988). The environment about the S atom is distorted tetrahedral with the O—S—O angles ranging from 105.38 (19)–113.5 (3)°. The [Ph3P NPPh3]+ cation is rather typical. The P—N distance [average 1.589 (3) Å] is slightly longer than the average PN distance of 1.576 (18) Å obtained by averaging 562 P—N distances in PPN+ ions reported to the CSD. The P—N—P angle in (I) [134.42 (19)°] is noticeably smaller than the average angle of 143 (8)° found in the same 562 PPN+ cations. The large s.u.'s calculated for the two parameters for complexes reported to the CSD reveal that the geometry about the N atom in PPN+ ions may vary substantially. Both phosphorus atoms in (I) are tetrahedral with the average C—P—C and C—P—N angles averaging 109 (3)°.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SMART; data reduction: SHELXTL (Sheldrick, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The structure of (I) showing hydrogen bonds between symmetry-related species. The displacement ellipsoids are shown at 30% probability level.
(I) top
Crystal data top
C36H30NP2+·HO4S·CHCl3Z = 4
Mr = 754.99F(000) = 1560
Monoclinic, P21/nDx = 1.397 Mg m3
a = 15.3399 (13) ÅMo Kα radiation, λ = 0.71073 Å
b = 16.2211 (13) ŵ = 0.44 mm1
c = 15.6888 (13) ÅT = 173 K
β = 113.101 (1)°Prism, colorless
V = 3590.8 (5) Å30.43 × 0.20 × 0.20 mm
Data collection top
CCD area detector
diffractometer
6269 independent reflections
Radiation source: fine-focus sealed tube4010 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.058
ϕ and ω scansθmax = 25.0°, θmin = 2.5°
Absorption correction: empirical (using intensity measurements)
(SADABS; Blessing, 1995)
h = 1816
Tmin = 0.832, Tmax = 0.917k = 1919
27441 measured reflectionsl = 1818
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)] = 0.061Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.153H-atom parameters constrained
S = 0.99 w = 1/[σ2(Fo2) + (0.084P)2]
where P = (Fo2 + 2Fc2)/3
6269 reflections(Δ/σ)max = 0.001
434 parametersΔρmax = 0.45 e Å3
0 restraintsΔρmin = 0.42 e Å3
Crystal data top
C36H30NP2+·HO4S·CHCl3V = 3590.8 (5) Å3
Mr = 754.99Z = 4
Monoclinic, P21/nMo Kα radiation
a = 15.3399 (13) ŵ = 0.44 mm1
b = 16.2211 (13) ÅT = 173 K
c = 15.6888 (13) Å0.43 × 0.20 × 0.20 mm
β = 113.101 (1)°
Data collection top
CCD area detector
diffractometer
6269 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Blessing, 1995)
4010 reflections with I > 2σ(I)
Tmin = 0.832, Tmax = 0.917Rint = 0.058
27441 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0610 restraints
wR(F2) = 0.153H-atom parameters constrained
S = 0.99Δρmax = 0.45 e Å3
6269 reflectionsΔρmin = 0.42 e Å3
434 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
S0.62658 (8)1.06605 (8)0.54548 (8)0.0474 (3)
Cl10.65012 (9)0.38986 (8)0.07487 (9)0.0670 (4)
Cl20.54802 (11)0.47980 (9)0.09140 (15)0.1184 (7)
Cl30.63338 (10)0.32483 (10)0.10125 (9)0.0806 (4)
P10.76240 (7)1.07083 (6)0.09653 (6)0.0264 (2)
P20.81761 (6)0.90164 (5)0.07528 (6)0.0253 (2)
O10.5433 (2)1.09141 (18)0.4556 (2)0.0535 (8)
H10.51291.04920.42930.080*
O20.5849 (2)1.02619 (18)0.60232 (19)0.0534 (8)
O30.6862 (3)1.0120 (3)0.5218 (3)0.1013 (15)
O40.6717 (2)1.1414 (2)0.5866 (2)0.0760 (10)
N0.8105 (2)0.98327 (17)0.12825 (19)0.0269 (7)
C10.8511 (2)1.1492 (2)0.1124 (2)0.0293 (8)
C20.8233 (3)1.2309 (2)0.0915 (3)0.0503 (12)
H20.75871.24560.07440.060*
C30.8884 (3)1.2905 (3)0.0955 (3)0.0544 (12)
H30.86871.34600.07970.065*
C40.9828 (3)1.2695 (2)0.1226 (3)0.0416 (10)
H41.02801.31030.12490.050*
C51.0110 (3)1.1898 (3)0.1460 (3)0.0415 (10)
H51.07611.17580.16600.050*
C60.9454 (3)1.1292 (2)0.1410 (3)0.0345 (9)
H60.96561.07390.15730.041*
C70.6957 (2)1.0986 (2)0.1645 (3)0.0301 (8)
C80.6251 (3)1.1578 (2)0.1326 (3)0.0430 (10)
H80.61091.18330.07420.052*
C90.5751 (3)1.1798 (3)0.1862 (3)0.0510 (12)
H90.52651.22010.16440.061*
C100.5962 (3)1.1429 (3)0.2714 (3)0.0488 (11)
H100.56231.15840.30820.059*
C110.6657 (3)1.0842 (3)0.3031 (3)0.0466 (11)
H110.67921.05870.36130.056*
C120.7166 (3)1.0619 (2)0.2507 (3)0.0366 (9)
H120.76551.02180.27330.044*
C130.6795 (2)1.0750 (2)0.0222 (2)0.0267 (8)
C140.6999 (3)1.1116 (2)0.0916 (2)0.0307 (9)
H140.75791.14050.07650.037*
C150.6360 (3)1.1066 (2)0.1837 (3)0.0376 (10)
H150.65061.13140.23130.045*
C160.5513 (3)1.0654 (2)0.2052 (3)0.0386 (10)
H160.50761.06160.26790.046*
C170.5299 (3)1.0296 (2)0.1361 (3)0.0369 (9)
H170.47111.00190.15140.044*
C180.5932 (3)1.0337 (2)0.0450 (3)0.0323 (9)
H180.57821.00850.00230.039*
C190.9351 (2)0.8591 (2)0.1341 (2)0.0261 (8)
C200.9878 (3)0.8797 (2)0.2259 (3)0.0344 (9)
H200.96090.91480.25760.041*
C211.0785 (3)0.8501 (2)0.2715 (3)0.0396 (10)
H211.11420.86550.33400.048*
C221.1174 (3)0.7979 (2)0.2263 (3)0.0396 (10)
H221.18000.77760.25760.048*
C231.0649 (3)0.7751 (2)0.1352 (3)0.0425 (10)
H231.09130.73860.10430.051*
C240.9736 (3)0.8057 (2)0.0890 (3)0.0354 (9)
H240.93760.79010.02670.043*
C250.8036 (2)0.9188 (2)0.0427 (2)0.0265 (8)
C260.8717 (3)0.9693 (2)0.0550 (3)0.0331 (9)
H260.92440.98820.00260.040*
C270.8626 (3)0.9918 (2)0.1432 (3)0.0417 (10)
H270.90911.02590.15120.050*
C280.7853 (3)0.9645 (3)0.2199 (3)0.0435 (11)
H280.77900.97980.28050.052*
C290.7181 (3)0.9152 (2)0.2078 (3)0.0422 (10)
H290.66510.89680.26030.051*
C300.7268 (3)0.8922 (2)0.1196 (3)0.0337 (9)
H300.68000.85820.11200.040*
C310.7331 (2)0.8259 (2)0.0769 (2)0.0293 (9)
C320.7270 (3)0.7497 (2)0.0337 (3)0.0369 (10)
H320.76700.73770.00200.044*
C330.6629 (3)0.6919 (3)0.0372 (3)0.0486 (11)
H330.65850.64000.00770.058*
C340.6048 (3)0.7089 (3)0.0834 (3)0.0578 (13)
H340.56070.66870.08570.069*
C350.6106 (3)0.7835 (3)0.1260 (4)0.0624 (14)
H350.57050.79490.15790.075*
C360.6742 (3)0.8422 (3)0.1229 (3)0.0455 (11)
H360.67760.89390.15240.055*
C370.6432 (3)0.4145 (3)0.0361 (4)0.0650 (14)
H370.70280.44370.03000.078*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S0.0450 (7)0.0622 (8)0.0416 (6)0.0159 (6)0.0240 (6)0.0122 (6)
Cl10.0726 (9)0.0568 (8)0.0678 (9)0.0134 (7)0.0233 (7)0.0080 (6)
Cl20.0750 (10)0.0618 (10)0.1699 (18)0.0057 (8)0.0044 (11)0.0618 (10)
Cl30.0753 (10)0.1052 (12)0.0591 (9)0.0124 (8)0.0238 (8)0.0106 (8)
P10.0283 (5)0.0266 (5)0.0269 (5)0.0005 (4)0.0136 (4)0.0018 (4)
P20.0273 (5)0.0244 (5)0.0269 (5)0.0001 (4)0.0134 (4)0.0011 (4)
O10.0511 (18)0.063 (2)0.0432 (18)0.0076 (15)0.0155 (15)0.0158 (15)
O20.062 (2)0.068 (2)0.0311 (16)0.0005 (16)0.0187 (15)0.0097 (14)
O30.104 (3)0.139 (4)0.085 (3)0.083 (3)0.064 (3)0.036 (2)
O40.055 (2)0.092 (3)0.080 (3)0.024 (2)0.0251 (19)0.001 (2)
N0.0297 (17)0.0275 (17)0.0243 (17)0.0013 (13)0.0116 (14)0.0028 (13)
C10.030 (2)0.031 (2)0.027 (2)0.0005 (17)0.0119 (18)0.0051 (16)
C20.034 (2)0.036 (2)0.075 (3)0.002 (2)0.014 (2)0.002 (2)
C30.054 (3)0.026 (2)0.073 (3)0.006 (2)0.014 (3)0.000 (2)
C40.047 (3)0.039 (2)0.041 (2)0.019 (2)0.018 (2)0.0107 (19)
C50.031 (2)0.045 (3)0.049 (3)0.004 (2)0.016 (2)0.004 (2)
C60.033 (2)0.033 (2)0.036 (2)0.0008 (18)0.0122 (19)0.0009 (18)
C70.029 (2)0.030 (2)0.032 (2)0.0023 (17)0.0134 (18)0.0055 (17)
C80.057 (3)0.035 (2)0.048 (3)0.003 (2)0.033 (2)0.0024 (19)
C90.058 (3)0.042 (3)0.065 (3)0.007 (2)0.038 (3)0.008 (2)
C100.060 (3)0.052 (3)0.049 (3)0.010 (2)0.037 (3)0.022 (2)
C110.052 (3)0.064 (3)0.028 (2)0.011 (2)0.021 (2)0.011 (2)
C120.036 (2)0.046 (2)0.027 (2)0.0066 (19)0.0105 (19)0.0032 (18)
C130.029 (2)0.0254 (19)0.029 (2)0.0026 (16)0.0141 (17)0.0012 (16)
C140.031 (2)0.030 (2)0.032 (2)0.0035 (17)0.0146 (19)0.0016 (17)
C150.043 (2)0.036 (2)0.037 (2)0.0042 (19)0.020 (2)0.0084 (18)
C160.039 (2)0.046 (2)0.028 (2)0.008 (2)0.010 (2)0.0011 (19)
C170.031 (2)0.040 (2)0.040 (3)0.0018 (18)0.013 (2)0.0040 (19)
C180.033 (2)0.036 (2)0.034 (2)0.0013 (17)0.020 (2)0.0003 (18)
C190.0265 (19)0.0226 (19)0.030 (2)0.0007 (15)0.0120 (17)0.0070 (16)
C200.038 (2)0.034 (2)0.036 (2)0.0005 (18)0.019 (2)0.0060 (18)
C210.037 (2)0.044 (2)0.031 (2)0.001 (2)0.006 (2)0.0090 (19)
C220.032 (2)0.036 (2)0.048 (3)0.0075 (18)0.013 (2)0.014 (2)
C230.039 (2)0.040 (2)0.051 (3)0.0100 (19)0.021 (2)0.001 (2)
C240.035 (2)0.035 (2)0.036 (2)0.0019 (18)0.014 (2)0.0010 (18)
C250.032 (2)0.026 (2)0.025 (2)0.0061 (16)0.0144 (18)0.0013 (15)
C260.028 (2)0.037 (2)0.036 (2)0.0013 (17)0.0140 (19)0.0025 (18)
C270.039 (2)0.049 (3)0.046 (3)0.012 (2)0.026 (2)0.017 (2)
C280.058 (3)0.045 (3)0.036 (3)0.017 (2)0.028 (2)0.011 (2)
C290.052 (3)0.039 (2)0.029 (2)0.010 (2)0.009 (2)0.0004 (18)
C300.040 (2)0.026 (2)0.034 (2)0.0009 (18)0.014 (2)0.0002 (17)
C310.028 (2)0.029 (2)0.028 (2)0.0024 (16)0.0082 (17)0.0076 (16)
C320.043 (2)0.034 (2)0.033 (2)0.0043 (19)0.014 (2)0.0042 (18)
C330.054 (3)0.034 (2)0.050 (3)0.009 (2)0.012 (2)0.003 (2)
C340.040 (3)0.052 (3)0.080 (4)0.017 (2)0.022 (3)0.009 (3)
C350.059 (3)0.056 (3)0.094 (4)0.008 (2)0.053 (3)0.001 (3)
C360.045 (3)0.040 (2)0.064 (3)0.003 (2)0.035 (2)0.002 (2)
C370.048 (3)0.052 (3)0.086 (4)0.013 (2)0.016 (3)0.017 (3)
Geometric parameters (Å, º) top
S—O31.418 (3)C11—C121.386 (5)
S—O41.428 (4)C13—C141.380 (5)
S—O21.439 (3)C13—C181.399 (5)
S—O11.541 (3)C14—C151.394 (5)
Cl1—C371.749 (5)C15—C161.380 (5)
Cl2—C371.736 (5)C16—C171.378 (5)
Cl3—C371.749 (5)C17—C181.380 (5)
P1—N1.588 (3)C19—C241.387 (5)
P1—C131.798 (4)C19—C201.387 (5)
P1—C71.801 (4)C20—C211.378 (5)
P1—C11.807 (4)C21—C221.381 (5)
P2—N1.590 (3)C22—C231.388 (5)
P2—C311.793 (4)C23—C241.393 (5)
P2—C251.800 (3)C25—C301.382 (5)
P2—C191.809 (3)C25—C261.399 (5)
C1—C61.374 (5)C26—C271.384 (5)
C1—C21.392 (5)C27—C281.389 (6)
C2—C31.374 (5)C28—C291.376 (6)
C3—C41.382 (6)C29—C301.388 (5)
C4—C51.367 (5)C31—C361.386 (5)
C5—C61.386 (5)C31—C321.396 (5)
C7—C81.386 (5)C32—C331.375 (5)
C7—C121.395 (5)C33—C341.378 (6)
C8—C91.389 (5)C34—C351.369 (6)
C9—C101.381 (6)C35—C361.377 (6)
C10—C111.368 (6)
O3—S—O4113.5 (3)C14—C13—C18119.3 (3)
O3—S—O2112.0 (2)C14—C13—P1123.1 (3)
O4—S—O2111.08 (19)C18—C13—P1117.4 (3)
O3—S—O1108.3 (2)C13—C14—C15120.5 (3)
O4—S—O1105.38 (19)C16—C15—C14119.6 (3)
O2—S—O1106.06 (17)C17—C16—C15120.2 (4)
N—P1—C13114.28 (15)C16—C17—C18120.5 (4)
N—P1—C7109.91 (16)C17—C18—C13119.9 (3)
C13—P1—C7105.57 (17)C24—C19—C20119.3 (3)
N—P1—C1110.71 (16)C24—C19—P2121.1 (3)
C13—P1—C1107.73 (16)C20—C19—P2119.6 (3)
C7—P1—C1108.37 (16)C21—C20—C19120.9 (4)
N—P2—C31111.41 (16)C20—C21—C22119.9 (4)
N—P2—C25113.83 (15)C21—C22—C23120.0 (4)
C31—P2—C25108.98 (17)C22—C23—C24119.9 (4)
N—P2—C19108.06 (16)C19—C24—C23120.0 (4)
C31—P2—C19108.20 (16)C30—C25—C26119.3 (3)
C25—P2—C19106.07 (16)C30—C25—P2124.5 (3)
P1—N—P2134.42 (19)C26—C25—P2115.9 (3)
C6—C1—C2119.2 (3)C27—C26—C25120.3 (4)
C6—C1—P1121.2 (3)C26—C27—C28120.0 (4)
C2—C1—P1119.5 (3)C29—C28—C27119.8 (4)
C3—C2—C1120.6 (4)C28—C29—C30120.6 (4)
C2—C3—C4119.7 (4)C25—C30—C29120.1 (4)
C5—C4—C3119.9 (4)C36—C31—C32119.2 (3)
C4—C5—C6120.6 (4)C36—C31—P2120.0 (3)
C1—C6—C5119.8 (4)C32—C31—P2120.8 (3)
C8—C7—C12119.7 (3)C33—C32—C31119.8 (4)
C8—C7—P1120.3 (3)C32—C33—C34120.3 (4)
C12—C7—P1119.9 (3)C35—C34—C33120.1 (4)
C7—C8—C9119.9 (4)C34—C35—C36120.3 (4)
C10—C9—C8119.9 (4)C35—C36—C31120.2 (4)
C11—C10—C9120.4 (4)Cl2—C37—Cl1110.3 (3)
C10—C11—C12120.4 (4)Cl2—C37—Cl3110.6 (3)
C11—C12—C7119.6 (4)Cl1—C37—Cl3110.5 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O2i0.841.852.633 (4)155.2
Symmetry code: (i) x+1, y+2, z+1.

Experimental details

Crystal data
Chemical formulaC36H30NP2+·HO4S·CHCl3
Mr754.99
Crystal system, space groupMonoclinic, P21/n
Temperature (K)173
a, b, c (Å)15.3399 (13), 16.2211 (13), 15.6888 (13)
β (°) 113.101 (1)
V3)3590.8 (5)
Z4
Radiation typeMo Kα
µ (mm1)0.44
Crystal size (mm)0.43 × 0.20 × 0.20
Data collection
DiffractometerCCD area detector
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(SADABS; Blessing, 1995)
Tmin, Tmax0.832, 0.917
No. of measured, independent and
observed [I > 2σ(I)] reflections
27441, 6269, 4010
Rint0.058
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.061, 0.153, 0.99
No. of reflections6269
No. of parameters434
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.45, 0.42

Computer programs: SMART (Siemens, 1996), SMART, SHELXTL (Sheldrick, 1997), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O2i0.841.852.633 (4)155.2
Symmetry code: (i) x+1, y+2, z+1.
 

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