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In P(CH3)4(HCO3) the hydrogen carbonate ions form hydrogen-bonded head-to-tail dimers, as in the corresponding compounds of the heavier alkali metals.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802013168/mg6011sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536802013168/mg6011Isup2.hkl
Contains datablock I

CCDC reference: 197473

Key indicators

  • Single-crystal X-ray study
  • T = 100 K
  • Mean [sigma](O-C) = 0.002 Å
  • R factor = 0.040
  • wR factor = 0.087
  • Data-to-parameter ratio = 25.0

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Red Alert Alert Level A:
DIFF_020 Alert A _diffrn_standards_interval_count and _diffrn_standards_interval_time are missing. Number of measurements between standards or time (min) between standards. DIFF_022 Alert A _diffrn_standards_decay_% is missing Percentage decrease in standards intensity.
2 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
0 Alert Level C = Please check

Comment top

The hydrogen carbonates of the alkali metals sodium (Sharma, 1965), potassium (Thomas et al., 1974) and caesium (Kaduk, 1993) have been characterized by single-crystal structure determination. Whereas the hydrogen carbonate ions form hydrogen-bonded infinite chains in the sodium compound, the larger separation of the anions in the compounds of the heavier alkali metals leads to the formation of dimers.

The tetramethylphosphonium ion can be considered to behave like a large alkali metal, and in fact, the hydrogen carbonate ions do form dimers in the title compound, too (Fig. 1). The geometry of the tetramethylphosphonium cation is as expected (Margraf et al., 2002). In the hydrogen carbonate moiety, the C5—O3 bond involving the hydrogen bond acceptor is slightly longer than the C5—O2 bond that does not take part in the hydrogen bonding. The packing resembles that of the antifluorite type. The hydrogen carbonate dimers are surrounded by eight tetramethylphosphonium ions with the P atoms forming a strongly distorted parallelepiped. The centers of half of these parallelepipeds are occupied by hydrogen carbonate dimers (Fig. 2).

Experimental top

The title compound was obtained by accident by exposure of a solution of tetramethylphosphonium superoxide in liquid ammonia to air. Some of the mother liquor containing crystals was taken and immersed in cooled perfluorinated polyether oil. A suitable crystal was chosen under a microscope and picked up with a nylon loop attached to a prealigned goniometer head, which was transferred in liquid nitrogen to the diffractometer and mounted in a cooling stream.

Computing details top

Data collection: SMART32 (Bruker, 2000); cell refinement: SAINT32 (Bruker, 2000); data reduction: SAINT32; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2000) and ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. Packing diagram of the title compound, with the atom-numbering scheme shown. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. View of the polyhedra surrounding the hydrogen carbonate dimers. The C atoms of the phosphonium ions have been omitted for clarity.
Tetramethylphosphonium hydrogen carbonate top
Crystal data top
C4H12P+·CHO3F(000) = 328
Mr = 152.12Dx = 1.279 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2752 reflections
a = 6.862 (2) Åθ = 2.7–33.1°
b = 10.293 (3) ŵ = 0.29 mm1
c = 11.540 (3) ÅT = 100 K
β = 104.296 (6)°Plate, colorless
V = 789.9 (4) Å30.02 × 0.01 × 0.01 mm
Z = 4
Data collection top
Bruker SMART APEX
diffractometer
2211 reflections with I > 2s(I)
Radiation source: fine-focus sealed tubeRint = 0.073
Graphite monochromatorθmax = 35.0°, θmin = 2.7°
ω scansh = 1011
12209 measured reflectionsk = 1614
3349 independent 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)] = 0.040Hydrogen site location: difference Fourier map
wR(F2) = 0.087All H-atom parameters refined
S = 0.89 w = 1/[σ2(Fo2) + (0.0024P)2 + 0.2026P]
where P = (Fo2 + 2Fc2)/3
3349 reflections(Δ/σ)max = 0.002
134 parametersΔρmax = 0.68 e Å3
0 restraintsΔρmin = 0.41 e Å3
Crystal data top
C4H12P+·CHO3V = 789.9 (4) Å3
Mr = 152.12Z = 4
Monoclinic, P21/nMo Kα radiation
a = 6.862 (2) ŵ = 0.29 mm1
b = 10.293 (3) ÅT = 100 K
c = 11.540 (3) Å0.02 × 0.01 × 0.01 mm
β = 104.296 (6)°
Data collection top
Bruker SMART APEX
diffractometer
2211 reflections with I > 2s(I)
12209 measured reflectionsRint = 0.073
3349 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0400 restraints
wR(F2) = 0.087All H-atom parameters refined
S = 0.89Δρmax = 0.68 e Å3
3349 reflectionsΔρmin = 0.41 e Å3
134 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
H10.115 (3)1.0544 (14)0.6208 (14)0.038 (4)*
H20.016 (2)1.1410 (15)0.7021 (14)0.032 (4)*
H30.114 (2)1.0581 (14)0.6028 (14)0.036 (4)*
H40.012 (2)0.7152 (15)0.7346 (13)0.030 (4)*
H50.101 (2)0.7688 (15)0.6457 (13)0.032 (4)*
H60.126 (3)0.7828 (16)0.6236 (16)0.044 (5)*
H70.264 (2)0.8672 (16)0.9167 (13)0.032 (4)*
H80.361 (2)0.9243 (14)0.8233 (13)0.033 (4)*
H90.273 (2)1.0133 (15)0.9068 (12)0.029 (4)*
H100.292 (2)0.9464 (14)0.7782 (14)0.032 (4)*
H110.151 (2)1.0337 (16)0.8696 (13)0.031 (4)*
H120.160 (2)0.8881 (15)0.8936 (12)0.025 (4)*
H130.046 (3)0.4116 (19)1.0549 (16)0.050 (6)*
P10.02215 (4)0.93307 (3)0.75964 (2)0.01603 (8)
O10.03657 (14)0.33387 (10)1.03510 (8)0.0227 (2)
O20.08090 (14)0.21693 (9)0.90765 (8)0.0278 (2)
O30.08918 (12)0.43273 (9)0.89652 (7)0.02142 (18)
C10.00857 (19)1.06363 (14)0.65730 (10)0.0219 (2)
C20.0057 (2)0.78268 (14)0.68134 (11)0.0226 (3)
C30.26042 (17)0.93423 (14)0.86445 (10)0.0191 (2)
C40.17291 (18)0.95161 (14)0.83490 (11)0.0207 (3)
C50.04973 (17)0.32669 (12)0.94090 (9)0.0181 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
P10.01543 (13)0.01815 (17)0.01475 (12)0.00080 (12)0.00421 (9)0.00139 (11)
O10.0303 (5)0.0172 (5)0.0252 (4)0.0017 (4)0.0154 (4)0.0001 (3)
O20.0377 (5)0.0182 (5)0.0307 (5)0.0008 (4)0.0146 (4)0.0065 (4)
O30.0286 (4)0.0185 (5)0.0205 (4)0.0006 (4)0.0124 (3)0.0003 (3)
C10.0240 (6)0.0243 (7)0.0181 (5)0.0043 (5)0.0062 (4)0.0015 (5)
C20.0218 (6)0.0242 (7)0.0215 (5)0.0019 (5)0.0052 (5)0.0052 (5)
C30.0173 (5)0.0220 (7)0.0176 (5)0.0003 (5)0.0038 (4)0.0001 (5)
C40.0184 (5)0.0238 (8)0.0215 (5)0.0007 (5)0.0083 (4)0.0018 (5)
C50.0169 (5)0.0202 (7)0.0170 (5)0.0013 (4)0.0040 (4)0.0021 (4)
Geometric parameters (Å, º) top
P1—C11.7762 (13)C1—H30.921 (16)
P1—C41.7767 (12)C2—H40.936 (16)
P1—C31.7777 (12)C2—H50.938 (15)
P1—C21.7787 (14)C2—H60.927 (17)
O1—C51.3623 (14)C3—H70.912 (16)
O1—H130.840 (19)C3—H80.938 (16)
O2—C51.2287 (15)C3—H90.942 (15)
O3—C51.2630 (14)C4—H100.915 (16)
C1—H10.932 (17)C4—H110.931 (16)
C1—H20.943 (16)C4—H120.930 (15)
C1—P1—C4108.76 (6)H4—C2—H6107.1 (14)
C1—P1—C3109.62 (7)H5—C2—H6110.1 (13)
C4—P1—C3110.13 (6)P1—C3—H7108.2 (9)
C1—P1—C2109.83 (7)P1—C3—H8109.0 (9)
C4—P1—C2110.02 (7)H7—C3—H8110.6 (13)
C3—P1—C2108.47 (7)P1—C3—H9107.9 (9)
C5—O1—H13110.4 (12)H7—C3—H9109.0 (13)
P1—C1—H1107.7 (9)H8—C3—H9112.0 (13)
P1—C1—H2106.7 (9)P1—C4—H10107.1 (9)
H1—C1—H2113.0 (13)P1—C4—H11104.1 (10)
P1—C1—H3107.2 (10)H10—C4—H11112.6 (13)
H1—C1—H3111.8 (13)P1—C4—H12109.5 (9)
H2—C1—H3110.1 (13)H10—C4—H12112.7 (12)
P1—C2—H4109.2 (9)H11—C4—H12110.4 (12)
P1—C2—H5110.9 (10)O2—C5—O3126.63 (11)
H4—C2—H5110.2 (13)O2—C5—O1116.27 (11)
P1—C2—H6109.2 (10)O3—C5—O1117.11 (11)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H13···O3i0.840 (19)1.75 (2)2.5817 (14)173.3 (18)
Symmetry code: (i) x, y+1, z+2.

Experimental details

Crystal data
Chemical formulaC4H12P+·CHO3
Mr152.12
Crystal system, space groupMonoclinic, P21/n
Temperature (K)100
a, b, c (Å)6.862 (2), 10.293 (3), 11.540 (3)
β (°) 104.296 (6)
V3)789.9 (4)
Z4
Radiation typeMo Kα
µ (mm1)0.29
Crystal size (mm)0.02 × 0.01 × 0.01
Data collection
DiffractometerBruker SMART APEX
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2s(I)] reflections
12209, 3349, 2211
Rint0.073
(sin θ/λ)max1)0.807
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.040, 0.087, 0.89
No. of reflections3349
No. of parameters134
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.68, 0.41

Computer programs: SMART32 (Bruker, 2000), SAINT32 (Bruker, 2000), SAINT32, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 2000) and ORTEP-3 (Farrugia, 1997), SHELXL97.

Selected geometric parameters (Å, º) top
P1—C11.7762 (13)O1—C51.3623 (14)
P1—C41.7767 (12)O2—C51.2287 (15)
P1—C31.7777 (12)O3—C51.2630 (14)
P1—C21.7787 (14)
C1—P1—C4108.76 (6)C3—P1—C2108.47 (7)
C1—P1—C3109.62 (7)O2—C5—O3126.63 (11)
C4—P1—C3110.13 (6)O2—C5—O1116.27 (11)
C1—P1—C2109.83 (7)O3—C5—O1117.11 (11)
C4—P1—C2110.02 (7)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H13···O3i0.840 (19)1.75 (2)2.5817 (14)173.3 (18)
Symmetry code: (i) x, y+1, z+2.
 

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