N—H...O and C—H...F hydrogen bonds in the incommensurately modulated crystal structure of adamantan-1-ammonium 4-fluorobenzoate

At low temperatures the organic salt adamantan-1-ammonium 4-fluorobenzoate, C₁₀H₁₈N⁺·C₇H₄FO₂⁻, possesses an incommensurately modulated crystal structure. The effect of the modulation on the atomic arrangement and intermolecular interactions is studied by analysing single-crystal X-ray diffraction data within the (3 + 1)-dimensional superspace approach and superspace group P2₁/n(α0γ)00. The modulation strongly affects the position of the atoms as well as their atomic displacement parameters. Nevertheless, the molecular cations and anions are built by rigid moieties, which vary their orientation with respect to each other as a function of the phase of the modulation t. Cations and anions are connected into slabs by dense N—H...O and C—H...F hydrogen-bonded networks, which are characterized by being rather rigid and which show only a little variation as a function of the phase of the modulation t.

Computing details

Figures

(I)

Crystal data

C17H22FNO2	V = 1498.06 (3) Å^3
Mr = 291.4	Z = 4
Monoclinic, P21/n(α0γ)00†	F(000) = 624
q = 0.423700a* + 0.428400c*	Dx = 1.291 Mg m^−3
a = 10.8498 (1) Å	Cu Kα radiation, λ = 1.5418 Å
b = 6.5247 (1) Å	µ = 0.75 mm^−1
c = 21.3826 (3) Å	T = 97 K
β = 98.246 (1)°	0.80 × 0.02 × 0.02 mm

† Symmetry operations: (1) x₁, x₂, x₃, x₄; (2) −x₁+1/2, x₂+1/2, −x₃+1/2, −x₄; (3) −x₁, −x₂, −x₃, −x₄; (4) x₁+1/2, −x₂+1/2, x₃+1/2, x₄.

Data collection

Oxford Diffraction CCD diffractometer	6001 reflections with I > 3σ(I)
Radiation source: X-ray tube	Rint = 0.033
Graphite monochromator	θmax = 65.7°, θmin = 3.5°
Absorption correction: empirical ?	h = −12→12
Tmin = ?, Tmax = ?	k = −7→3
29463 measured reflections	l = −25→25
11225 independent reflections

Refinement

Refinement on F	307 constraints
R[F^2 > 2σ(F^2)] = 0.051	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.071	Weighting scheme based on measured s.u.'s w = 1/(σ^2(F) + 0.000121F^2)
S = 1.76	(Δ/σ)max = 0.003
11225 reflections	Δρmax = 0.26 e Å^−3
991 parameters	Δρmin = −0.27 e Å^−3
6 restraints

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C01	−0.06259 (9)	0.38058 (15)	−0.15316 (6)	0.0306 (3)
C02	0.02518 (9)	0.29051 (15)	−0.09876 (5)	0.0310 (3)
C03	0.09126 (11)	0.41989 (16)	−0.05531 (6)	0.0390 (4)
C04	0.17229 (11)	0.34689 (17)	−0.00443 (6)	0.0428 (4)
C05	0.18623 (11)	0.14257 (17)	0.00211 (6)	0.0420 (4)
C06	0.12363 (16)	0.00717 (19)	−0.03990 (8)	0.0523 (5)
C07	0.04147 (13)	0.08249 (17)	−0.09034 (6)	0.0423 (4)
F08	0.26562 (8)	0.06883 (11)	0.05162 (4)	0.0608 (3)
O09	−0.12359 (7)	0.26017 (11)	−0.19206 (4)	0.0375 (3)
O10	−0.06978 (8)	0.57222 (12)	−0.15579 (4)	0.0418 (3)
N11	0.14166 (8)	0.13244 (13)	0.24462 (4)	0.0317 (3)
C12	0.05548 (9)	0.13331 (13)	0.29297 (5)	0.0285 (3)
C13	0.09251 (10)	−0.03906 (13)	0.34078 (5)	0.0331 (3)
C14	0.00475 (11)	−0.03839 (14)	0.39012 (6)	0.0372 (4)
C15	0.01334 (10)	0.16851 (14)	0.42492 (6)	0.0355 (3)
C16	−0.02291 (9)	0.34135 (13)	0.37675 (5)	0.0322 (3)
C17	0.06498 (9)	0.34024 (13)	0.32721 (5)	0.0307 (3)
C18	−0.07819 (9)	0.09895 (13)	0.26048 (5)	0.0307 (3)
C19	−0.16604 (9)	0.10039 (14)	0.30998 (6)	0.0349 (3)
C20	−0.15685 (10)	0.30724 (14)	0.34471 (6)	0.0351 (3)
C21	−0.12916 (11)	−0.07209 (14)	0.35808 (6)	0.0385 (4)
H03	0.080475	0.563804	−0.060677	0.0468*
H04	0.217471	0.43786	0.025433	0.0514*
H06	0.136534	−0.136056	−0.034428	0.0627*
H07	−0.004502	−0.009952	−0.119586	0.0507*
H11a	0.2175 (10)	0.1501 (13)	0.2626 (6)	0.0476*
H11b	0.1354 (10)	0.0108 (15)	0.2242 (5)	0.0476*
H11c	0.1202 (11)	0.2339 (14)	0.2166 (5)	0.0476*
H13a	0.08697	−0.168485	0.319235	0.0398*
H13b	0.176266	−0.017357	0.361068	0.0398*
H14	0.028077	−0.146646	0.419828	0.0446*
H15a	−0.042676	0.168648	0.455798	0.0425*
H15b	0.097066	0.18964	0.445341	0.0425*
H16	−0.016901	0.471243	0.398035	0.0387*
H17a	0.148861	0.360879	0.347481	0.0368*
H17b	0.042131	0.44794	0.297245	0.0368*
H18a	−0.101038	0.206473	0.23045	0.0369*
H18b	−0.083604	−0.030917	0.239188	0.0369*
H19	−0.249823	0.079757	0.289558	0.0419*
H20a	−0.180233	0.415363	0.314982	0.0421*
H20b	−0.211836	0.307131	0.37607	0.0421*
H21a	−0.184235	−0.07108	0.389397	0.0462*
H21b	−0.135038	−0.201758	0.336676	0.0462*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C01	0.0232 (5)	0.0433 (6)	0.0247 (7)	0.0005 (3)	0.0019 (4)	0.0020 (4)
C02	0.0230 (5)	0.0467 (6)	0.0234 (7)	−0.0027 (4)	0.0032 (4)	0.0014 (4)
C03	0.0354 (6)	0.0436 (6)	0.0348 (8)	0.0074 (4)	−0.0057 (5)	−0.0057 (4)
C04	0.0354 (6)	0.0522 (6)	0.0364 (8)	0.0020 (4)	−0.0101 (5)	−0.0082 (5)
C05	0.0367 (6)	0.0543 (6)	0.0314 (8)	−0.0051 (5)	−0.0080 (5)	0.0120 (5)
C06	0.0618 (11)	0.0448 (6)	0.0443 (9)	−0.0158 (7)	−0.0125 (8)	0.0165 (6)
C07	0.0453 (8)	0.0439 (6)	0.0338 (8)	−0.0171 (6)	−0.0077 (6)	0.0076 (5)
F08	0.0613 (5)	0.0646 (4)	0.0465 (5)	−0.0057 (3)	−0.0260 (4)	0.0175 (3)
O09	0.0274 (4)	0.0536 (4)	0.0284 (5)	0.0009 (3)	−0.0064 (3)	−0.0047 (3)
O10	0.0420 (4)	0.0496 (5)	0.0302 (5)	0.0002 (3)	−0.0074 (3)	0.0048 (3)
N11	0.0233 (4)	0.0460 (5)	0.0238 (5)	0.0006 (3)	−0.0038 (3)	0.0024 (4)
C12	0.0251 (5)	0.0360 (5)	0.0229 (6)	0.0030 (3)	−0.0012 (4)	0.0020 (4)
C13	0.0328 (5)	0.0378 (5)	0.0274 (7)	0.0083 (4)	−0.0009 (4)	0.0020 (4)
C14	0.0441 (6)	0.0351 (5)	0.0318 (7)	0.0075 (4)	0.0039 (5)	0.0087 (4)
C15	0.0372 (6)	0.0447 (5)	0.0241 (6)	0.0063 (4)	0.0029 (4)	0.0021 (4)
C16	0.0344 (5)	0.0337 (4)	0.0273 (6)	0.0039 (3)	−0.0002 (4)	−0.0014 (4)
C17	0.0275 (5)	0.0348 (5)	0.0273 (6)	0.0003 (3)	−0.0040 (4)	0.0023 (4)
C18	0.0252 (5)	0.0369 (5)	0.0280 (6)	0.0010 (3)	−0.0031 (4)	0.0003 (4)
C19	0.0243 (5)	0.0434 (5)	0.0357 (7)	−0.0003 (3)	−0.0002 (4)	−0.0016 (4)
C20	0.0303 (5)	0.0381 (5)	0.0363 (7)	0.0064 (3)	0.0023 (4)	0.0011 (4)
C21	0.0412 (6)	0.0353 (5)	0.0408 (8)	−0.0026 (4)	0.0119 (5)	0.0013 (4)

Geometric parameters (Å, º)

	Average	Minimum	Maximum
C01—C02	1.513 (5)	1.498 (5)	1.528 (5)
C01—O09	1.261 (4)	1.239 (5)	1.280 (4)
C01—O10	1.254 (4)	1.236 (4)	1.268 (4)
C02—C03	1.386 (5)	1.365 (5)	1.405 (5)
C02—C07	1.388 (5)	1.368 (5)	1.406 (5)
C03—C04	1.382 (6)	1.371 (6)	1.393 (6)
C04—C05	1.360 (5)	1.344 (5)	1.380 (5)
C05—C06	1.378 (6)	1.356 (6)	1.402 (6)
C05—F08	1.355 (5)	1.346 (5)	1.365 (5)
C06—C07	1.388 (6)	1.380 (7)	1.397 (6)
N11—C12	1.491 (5)	1.479 (5)	1.499 (5)
C12—C13	1.535 (4)	1.528 (4)	1.540 (4)
C12—C17	1.533 (4)	1.520 (4)	1.548 (4)
C12—C18	1.533 (4)	1.526 (4)	1.542 (4)
C13—C14	1.520 (5)	1.513 (5)	1.527 (5)
C14—C15	1.538 (4)	1.527 (4)	1.551 (4)
C14—C21	1.531 (5)	1.524 (5)	1.535 (5)
C15—C16	1.541 (5)	1.535 (5)	1.547 (4)
C16—C17	1.525 (5)	1.518 (5)	1.531 (5)
C16—C20	1.532 (5)	1.521 (5)	1.544 (5)
C18—C19	1.524 (5)	1.515 (5)	1.532 (5)
C19—C20	1.537 (4)	1.516 (4)	1.558 (4)
C19—C21	1.539 (5)	1.530 (5)	1.548 (5)
C02—C01—O09	118.6 (3)	117.0 (3)	119.7 (3)
C02—C01—O10	116.8 (3)	116.0 (3)	117.7 (3)
O09—C01—O10	124.7 (3)	123.9 (3)	125.5 (4)
C01—C02—C03	119.1 (3)	118.1 (3)	119.7 (3)
C01—C02—C07	122.4 (3)	121.7 (3)	123.1 (3)
C03—C02—C07	118.5 (3)	117.8 (4)	119.4 (3)
C02—C03—C04	121.6 (3)	120.9 (3)	122.3 (3)
C03—C04—C05	118.1 (4)	117.4 (4)	118.9 (4)
C04—C05—C06	122.6 (4)	121.4 (4)	124.1 (4)
C04—C05—F08	118.9 (4)	118.1 (4)	119.4 (4)
C06—C05—F08	118.5 (3)	117.6 (4)	119.4 (3)
C05—C06—C07	118.5 (4)	117.5 (4)	119.7 (3)
C02—C07—C06	120.5 (4)	120.1 (4)	120.8 (4)
N11—C12—C13	109.2 (3)	108.8 (3)	109.5 (3)
N11—C12—C17	109.2 (3)	108.9 (3)	109.5 (3)
N11—C12—C18	109.4 (3)	108.5 (3)	110.2 (3)
C13—C12—C17	109.6 (3)	109.1 (3)	110.2 (3)
C13—C12—C18	109.6 (2)	109.1 (3)	110.0 (2)
C17—C12—C18	109.9 (2)	109.4 (2)	110.4 (3)
C12—C13—C14	109.3 (3)	109.1 (3)	109.6 (3)
C13—C14—C15	109.8 (3)	109.6 (3)	110.0 (3)
C13—C14—C21	109.8 (3)	109.4 (3)	110.1 (3)
C15—C14—C21	109.3 (3)	108.6 (3)	109.7 (3)
C14—C15—C16	109.1 (3)	108.4 (3)	109.9 (3)
C15—C16—C17	109.6 (3)	109.4 (3)	109.9 (3)
C15—C16—C20	109.1 (3)	108.8 (3)	109.3 (3)
C17—C16—C20	109.7 (3)	109.5 (3)	110.0 (3)
C12—C17—C16	109.3 (3)	109.0 (3)	109.7 (3)
C12—C18—C19	109.3 (3)	108.8 (3)	109.7 (3)
C18—C19—C20	109.7 (3)	109.5 (3)	110.1 (3)
C18—C19—C21	109.4 (3)	109.0 (3)	109.6 (3)
C20—C19—C21	109.1 (3)	108.4 (3)	109.7 (3)
C16—C20—C19	109.6 (3)	109.0 (3)	110.0 (3)
C14—C21—C19	109.5 (3)	109.1 (3)	109.9 (3)
O10—C01—C02—C04	0.8 (3)	-9.8 (3)	9.0 (3)
O09—C01—C02—C06	0.6 (4)	-15.6 (4)	15.1 (4)
O09—C01—C02—C04	-46.8 (3)	-180.00 (6)	179.6 (3)
O10—C01—C02—C06	-8.8 (3)	-179.9 (3)	179.4 (3)