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
CCDC reference: 197473
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean (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
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
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.
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.
Tetramethylphosphonium hydrogen carbonate
top
Crystal data top
C4H12P+·CHO3− | F(000) = 328 |
Mr = 152.12 | Dx = 1.279 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 2752 reflections |
a = 6.862 (2) Å | θ = 2.7–33.1° |
b = 10.293 (3) Å | µ = 0.29 mm−1 |
c = 11.540 (3) Å | T = 100 K |
β = 104.296 (6)° | Plate, colorless |
V = 789.9 (4) Å3 | 0.02 × 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 tube | Rint = 0.073 |
Graphite monochromator | θmax = 35.0°, θmin = 2.7° |
ω scans | h = −10→11 |
12209 measured reflections | k = −16→14 |
3349 independent reflections | l = −18→18 |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.040 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.087 | All 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 parameters | Δρmax = 0.68 e Å−3 |
0 restraints | Δρmin = −0.41 e Å−3 |
Crystal data top
C4H12P+·CHO3− | V = 789.9 (4) Å3 |
Mr = 152.12 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 6.862 (2) Å | µ = 0.29 mm−1 |
b = 10.293 (3) Å | T = 100 K |
c = 11.540 (3) Å | 0.02 × 0.01 × 0.01 mm |
β = 104.296 (6)° | |
Data collection top
Bruker SMART APEX diffractometer | 2211 reflections with I > 2s(I) |
12209 measured reflections | Rint = 0.073 |
3349 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.087 | All H-atom parameters refined |
S = 0.89 | Δρmax = 0.68 e Å−3 |
3349 reflections | Δρmin = −0.41 e Å−3 |
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 | x | y | z | Uiso*/Ueq | |
H1 | 0.115 (3) | 1.0544 (14) | 0.6208 (14) | 0.038 (4)* | |
H2 | 0.016 (2) | 1.1410 (15) | 0.7021 (14) | 0.032 (4)* | |
H3 | −0.114 (2) | 1.0581 (14) | 0.6028 (14) | 0.036 (4)* | |
H4 | −0.012 (2) | 0.7152 (15) | 0.7346 (13) | 0.030 (4)* | |
H5 | 0.101 (2) | 0.7688 (15) | 0.6457 (13) | 0.032 (4)* | |
H6 | −0.126 (3) | 0.7828 (16) | 0.6236 (16) | 0.044 (5)* | |
H7 | 0.264 (2) | 0.8672 (16) | 0.9167 (13) | 0.032 (4)* | |
H8 | 0.361 (2) | 0.9243 (14) | 0.8233 (13) | 0.033 (4)* | |
H9 | 0.273 (2) | 1.0133 (15) | 0.9068 (12) | 0.029 (4)* | |
H10 | −0.292 (2) | 0.9464 (14) | 0.7782 (14) | 0.032 (4)* | |
H11 | −0.151 (2) | 1.0337 (16) | 0.8696 (13) | 0.031 (4)* | |
H12 | −0.160 (2) | 0.8881 (15) | 0.8936 (12) | 0.025 (4)* | |
H13 | −0.046 (3) | 0.4116 (19) | 1.0549 (16) | 0.050 (6)* | |
P1 | 0.02215 (4) | 0.93307 (3) | 0.75964 (2) | 0.01603 (8) | |
O1 | −0.03657 (14) | 0.33387 (10) | 1.03510 (8) | 0.0227 (2) | |
O2 | 0.08090 (14) | 0.21693 (9) | 0.90765 (8) | 0.0278 (2) | |
O3 | 0.08918 (12) | 0.43273 (9) | 0.89652 (7) | 0.02142 (18) | |
C1 | 0.00857 (19) | 1.06363 (14) | 0.65730 (10) | 0.0219 (2) | |
C2 | −0.0057 (2) | 0.78268 (14) | 0.68134 (11) | 0.0226 (3) | |
C3 | 0.26042 (17) | 0.93423 (14) | 0.86445 (10) | 0.0191 (2) | |
C4 | −0.17291 (18) | 0.95161 (14) | 0.83490 (11) | 0.0207 (3) | |
C5 | 0.04973 (17) | 0.32669 (12) | 0.94090 (9) | 0.0181 (2) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
P1 | 0.01543 (13) | 0.01815 (17) | 0.01475 (12) | 0.00080 (12) | 0.00421 (9) | −0.00139 (11) |
O1 | 0.0303 (5) | 0.0172 (5) | 0.0252 (4) | −0.0017 (4) | 0.0154 (4) | −0.0001 (3) |
O2 | 0.0377 (5) | 0.0182 (5) | 0.0307 (5) | −0.0008 (4) | 0.0146 (4) | −0.0065 (4) |
O3 | 0.0286 (4) | 0.0185 (5) | 0.0205 (4) | −0.0006 (4) | 0.0124 (3) | 0.0003 (3) |
C1 | 0.0240 (6) | 0.0243 (7) | 0.0181 (5) | 0.0043 (5) | 0.0062 (4) | 0.0015 (5) |
C2 | 0.0218 (6) | 0.0242 (7) | 0.0215 (5) | −0.0019 (5) | 0.0052 (5) | −0.0052 (5) |
C3 | 0.0173 (5) | 0.0220 (7) | 0.0176 (5) | −0.0003 (5) | 0.0038 (4) | 0.0001 (5) |
C4 | 0.0184 (5) | 0.0238 (8) | 0.0215 (5) | 0.0007 (5) | 0.0083 (4) | −0.0018 (5) |
C5 | 0.0169 (5) | 0.0202 (7) | 0.0170 (5) | −0.0013 (4) | 0.0040 (4) | −0.0021 (4) |
Geometric parameters (Å, º) top
P1—C1 | 1.7762 (13) | C1—H3 | 0.921 (16) |
P1—C4 | 1.7767 (12) | C2—H4 | 0.936 (16) |
P1—C3 | 1.7777 (12) | C2—H5 | 0.938 (15) |
P1—C2 | 1.7787 (14) | C2—H6 | 0.927 (17) |
O1—C5 | 1.3623 (14) | C3—H7 | 0.912 (16) |
O1—H13 | 0.840 (19) | C3—H8 | 0.938 (16) |
O2—C5 | 1.2287 (15) | C3—H9 | 0.942 (15) |
O3—C5 | 1.2630 (14) | C4—H10 | 0.915 (16) |
C1—H1 | 0.932 (17) | C4—H11 | 0.931 (16) |
C1—H2 | 0.943 (16) | C4—H12 | 0.930 (15) |
| | | |
C1—P1—C4 | 108.76 (6) | H4—C2—H6 | 107.1 (14) |
C1—P1—C3 | 109.62 (7) | H5—C2—H6 | 110.1 (13) |
C4—P1—C3 | 110.13 (6) | P1—C3—H7 | 108.2 (9) |
C1—P1—C2 | 109.83 (7) | P1—C3—H8 | 109.0 (9) |
C4—P1—C2 | 110.02 (7) | H7—C3—H8 | 110.6 (13) |
C3—P1—C2 | 108.47 (7) | P1—C3—H9 | 107.9 (9) |
C5—O1—H13 | 110.4 (12) | H7—C3—H9 | 109.0 (13) |
P1—C1—H1 | 107.7 (9) | H8—C3—H9 | 112.0 (13) |
P1—C1—H2 | 106.7 (9) | P1—C4—H10 | 107.1 (9) |
H1—C1—H2 | 113.0 (13) | P1—C4—H11 | 104.1 (10) |
P1—C1—H3 | 107.2 (10) | H10—C4—H11 | 112.6 (13) |
H1—C1—H3 | 111.8 (13) | P1—C4—H12 | 109.5 (9) |
H2—C1—H3 | 110.1 (13) | H10—C4—H12 | 112.7 (12) |
P1—C2—H4 | 109.2 (9) | H11—C4—H12 | 110.4 (12) |
P1—C2—H5 | 110.9 (10) | O2—C5—O3 | 126.63 (11) |
H4—C2—H5 | 110.2 (13) | O2—C5—O1 | 116.27 (11) |
P1—C2—H6 | 109.2 (10) | O3—C5—O1 | 117.11 (11) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H13···O3i | 0.840 (19) | 1.75 (2) | 2.5817 (14) | 173.3 (18) |
Symmetry code: (i) −x, −y+1, −z+2. |
Experimental details
Crystal data |
Chemical formula | C4H12P+·CHO3− |
Mr | 152.12 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 100 |
a, b, c (Å) | 6.862 (2), 10.293 (3), 11.540 (3) |
β (°) | 104.296 (6) |
V (Å3) | 789.9 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.29 |
Crystal size (mm) | 0.02 × 0.01 × 0.01 |
|
Data collection |
Diffractometer | Bruker SMART APEX diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2s(I)] reflections | 12209, 3349, 2211 |
Rint | 0.073 |
(sin θ/λ)max (Å−1) | 0.807 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.087, 0.89 |
No. of reflections | 3349 |
No. of parameters | 134 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.68, −0.41 |
Selected geometric parameters (Å, º) topP1—C1 | 1.7762 (13) | O1—C5 | 1.3623 (14) |
P1—C4 | 1.7767 (12) | O2—C5 | 1.2287 (15) |
P1—C3 | 1.7777 (12) | O3—C5 | 1.2630 (14) |
P1—C2 | 1.7787 (14) | | |
| | | |
C1—P1—C4 | 108.76 (6) | C3—P1—C2 | 108.47 (7) |
C1—P1—C3 | 109.62 (7) | O2—C5—O3 | 126.63 (11) |
C4—P1—C3 | 110.13 (6) | O2—C5—O1 | 116.27 (11) |
C1—P1—C2 | 109.83 (7) | O3—C5—O1 | 117.11 (11) |
C4—P1—C2 | 110.02 (7) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H13···O3i | 0.840 (19) | 1.75 (2) | 2.5817 (14) | 173.3 (18) |
Symmetry code: (i) −x, −y+1, −z+2. |
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).