Download citation
Download citation
link to html
The crystal structures of ammonium tetraphenylborate, NH4+·BPh4, are determined by neutron diffraction at 20 and 293 K. At both temperatures, all four N—H vectors of the ammonium ion are time-average-oriented at the midpoints of the phenyl rings of neighboring anions. The N—H...Ph distances, H...M 2.067 and N...M 3.023 Å, are exceptionally short (M = aromatic midpoint). Even at 20 K the ammonium ion performs large amplitude motions which allow the N—H vectors to sample the entire face of the aromatic system.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768199012318/ka0046sup1.cif
Contains datablocks lt, rt, default

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108768199012318/ka0046ltsup2.hkl
Contains datablock lt

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108768199012318/ka0046rtsup3.hkl
Contains datablock rt

CCDC references: 144361; 144362

Computing details top

For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997).

(lt) ammonium tetraphenylborate top
Crystal data top
NH4+·C24H20BDx = 1.132 Mg m3
Mr = 337.27Neutron radiation, λ = 0.8469 Å
Tetragonal, I42mCell parameters from 354 reflections
a = 11.1208 (8) Åθ = 3.1–44.4°
c = 8.0033 (7) ŵ = 0.06 mm1
V = 989.79 (13) Å3T = 20 K
Z = 2Block, colorless transparent
F(000) = 3601.72 × 1.00 × 0.83 mm
Data collection top
D9
diffractometer
Rint = 0.030
Radiation source: ILL high flux neutron reactorθmax = 45.1°, θmin = 3.1°
area detector scansh = 1018
Absorption correction: gaussiank = 618
Tmin = 0.761, Tmax = 0.826l = 013
1278 measured reflections3 standard reflections every 50 reflections
736 independent reflections intensity decay: none
639 reflections with I > 2σ(I)
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.038H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.066 w = 1/[σ2(Fo2) + 5.0563P]
where P = (Fo2 + 2Fc2)/3
S = 1.10(Δ/σ)max < 0.001
736 reflectionsΔρmax = 1.38 e Å3
65 parametersΔρmin = 1.14 e Å3
0 restraintsAbsolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.0 (2)
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
B0.00000.00000.00000.0034 (5)
N0.00000.00000.50000.0080 (3)
C10.08200 (9)0.08200 (9)0.12672 (18)0.0048 (2)
C20.04000 (9)0.19147 (9)0.19306 (14)0.00640 (16)
C30.10202 (9)0.25438 (9)0.31756 (14)0.00746 (17)
C40.20961 (10)0.20961 (10)0.38113 (19)0.0079 (2)
H20.0455 (2)0.2280 (2)0.1484 (3)0.0209 (5)
H30.0649 (3)0.3379 (2)0.3653 (4)0.0239 (5)
H40.2569 (3)0.2569 (3)0.4807 (5)0.0228 (7)
H50.0491 (5)0.0491 (5)0.4288 (12)0.092 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
B0.0033 (7)0.0033 (7)0.0036 (12)0.0000.0000.000
N0.0085 (5)0.0085 (5)0.0070 (8)0.0000.0000.000
C10.0050 (3)0.0050 (3)0.0044 (5)0.0004 (4)0.0008 (3)0.0008 (3)
C20.0069 (3)0.0055 (4)0.0067 (3)0.0002 (3)0.0007 (3)0.0017 (4)
C30.0085 (4)0.0064 (4)0.0074 (4)0.0000 (3)0.0003 (4)0.0018 (3)
C40.0082 (3)0.0082 (3)0.0073 (5)0.0010 (5)0.0016 (4)0.0016 (4)
H20.0149 (9)0.0235 (11)0.0243 (11)0.0074 (8)0.0058 (9)0.0055 (9)
H30.0270 (12)0.0175 (10)0.0274 (11)0.0062 (9)0.0025 (11)0.0096 (9)
H40.0233 (9)0.0233 (9)0.0217 (16)0.0011 (13)0.0079 (10)0.0079 (10)
H50.104 (5)0.104 (5)0.069 (5)0.059 (6)0.029 (3)0.029 (3)
Geometric parameters (Å, º) top
B—C1i1.6406 (14)C2—C31.3993 (14)
B—C1ii1.6406 (14)C2—H21.095 (3)
B—C1iii1.6406 (14)C3—C41.3922 (13)
B—C11.6407 (14)C3—H31.086 (3)
N—H50.960 (7)C4—C3iv1.3922 (13)
C1—C21.4078 (13)C4—H41.089 (4)
C1—C2iv1.4078 (13)
C1i—B—C1ii103.64 (10)C3—C2—C1122.50 (10)
C1i—B—C1iii112.46 (5)C3—C2—H2118.37 (17)
C1ii—B—C1iii112.46 (5)C1—C2—H2119.11 (17)
C1i—B—C1112.46 (5)C4—C3—C2120.34 (11)
C1ii—B—C1112.46 (5)C4—C3—H3120.28 (19)
C1iii—B—C1103.64 (10)C2—C3—H3119.38 (18)
C2—C1—C2iv115.56 (13)C3—C4—C3iv118.76 (14)
C2—C1—B121.96 (6)C3—C4—H4120.62 (7)
C2iv—C1—B121.96 (6)C3iv—C4—H4120.62 (7)
C1i—B—C1—C236.02 (9)C1iii—B—C1—C2iv85.70 (11)
C1ii—B—C1—C2152.58 (14)C2iv—C1—C2—C30.4 (2)
C1iii—B—C1—C285.70 (11)B—C1—C2—C3171.48 (10)
C1i—B—C1—C2iv152.57 (14)C1—C2—C3—C40.03 (17)
C1ii—B—C1—C2iv36.02 (9)C2—C3—C4—C3iv0.5 (2)
Symmetry codes: (i) y, x, z; (ii) y, x, z; (iii) x, y, z; (iv) y, x, z.
(rt) ammonium tetraphenylborate top
Crystal data top
NH4+·C24H20BDx = 1.101 Mg m3
Mr = 337.27Neutron radiation, λ = 0.8469 Å
Tetragonal, I42mCell parameters from 124 reflections
a = 11.2255 (15) Åθ = 3.1–25.6°
c = 8.0745 (13) ŵ = 0.06 mm1
V = 1017.5 (3) Å3T = 293 K
Z = 2Block, colorless transparent
F(000) = 3601.72 × 1.00 × 0.83 mm
Data collection top
D9
diffractometer
Rint = 0.039
Radiation source: ILL high flux neutron reactorθmax = 34.8°, θmin = 3.0°
area detector scansh = 1015
Absorption correction: gaussiank = 615
Tmin = 0.777, Tmax = 0.826l = 010
662 measured reflections3 standard reflections every 50 reflections
418 independent reflections intensity decay: none
364 reflections with I > 2σ(I)
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.069H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.116 w = 1/[σ2(Fo2) + 7.8251P]
where P = (Fo2 + 2Fc2)/3
S = 1.23(Δ/σ)max < 0.001
418 reflectionsΔρmax = 0.64 e Å3
65 parametersΔρmin = 0.57 e Å3
0 restraintsAbsolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.4 (4)
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
B0.00000.00000.00000.0211 (17)
N0.00000.00000.50000.0421 (16)
C10.0811 (2)0.0811 (2)0.1255 (5)0.0255 (8)
C20.0399 (3)0.1897 (3)0.1917 (4)0.0359 (7)
C30.1009 (4)0.2518 (3)0.3156 (5)0.0459 (9)
C40.2077 (3)0.2077 (3)0.3782 (8)0.0535 (14)
H20.0444 (8)0.2267 (7)0.1447 (12)0.063 (2)
H30.0670 (10)0.3354 (9)0.3603 (13)0.081 (3)
H40.2557 (11)0.2557 (11)0.4756 (17)0.091 (5)
H50.0456 (17)0.0456 (17)0.437 (3)0.162 (12)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
B0.017 (2)0.017 (2)0.028 (5)0.0000.0000.000
N0.049 (3)0.049 (3)0.027 (4)0.0000.0000.000
C10.0269 (11)0.0269 (11)0.0226 (15)0.0040 (14)0.0007 (11)0.0007 (11)
C20.0427 (16)0.0307 (15)0.0344 (13)0.0021 (11)0.0002 (15)0.0093 (14)
C30.060 (2)0.0385 (17)0.0393 (17)0.0135 (15)0.0004 (19)0.0108 (16)
C40.057 (2)0.057 (2)0.047 (3)0.027 (3)0.0068 (18)0.0068 (18)
H20.064 (5)0.051 (4)0.075 (5)0.011 (3)0.004 (5)0.016 (4)
H30.091 (7)0.065 (5)0.087 (7)0.002 (5)0.011 (6)0.027 (5)
H40.105 (7)0.105 (7)0.062 (8)0.043 (9)0.022 (5)0.022 (5)
H50.167 (16)0.167 (16)0.15 (2)0.026 (17)0.060 (12)0.060 (12)
Geometric parameters (Å, º) top
B—C11.638 (4)C2—C31.398 (5)
B—C1i1.638 (4)C2—H21.101 (9)
B—C1ii1.638 (4)C3—C41.393 (5)
B—C1iii1.638 (4)C3—H31.074 (10)
N—H50.89 (2)C4—C3iv1.393 (5)
C1—C21.409 (4)C4—H41.095 (14)
C1—C2iv1.409 (4)
C1—B—C1i112.49 (14)C3—C2—C1122.9 (4)
C1—B—C1ii112.49 (14)C3—C2—H2118.6 (5)
C1i—B—C1ii103.6 (3)C1—C2—H2118.5 (5)
C1—B—C1iii103.6 (3)C4—C3—C2120.2 (4)
C1i—B—C1iii112.49 (14)C4—C3—H3119.5 (7)
C1ii—B—C1iii112.49 (14)C2—C3—H3120.2 (7)
C2—C1—C2iv115.1 (4)C3iv—C4—C3118.7 (5)
C2—C1—B122.21 (19)C3iv—C4—H4120.6 (2)
C2iv—C1—B122.21 (19)C3—C4—H4120.6 (2)
Symmetry codes: (i) y, x, z; (ii) y, x, z; (iii) x, y, z; (iv) y, x, z.
 

Follow Acta Cryst. B
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds