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Crystals of n-butylammonium dihydrogenphosphate, C4H9NH3+·H2PO4-, reveal ferroelasticity at room temperature and a number of phase transitions when heated up to approximately 373 K. Some of these phase transitions show hysteresis effects. All atoms except two H atoms exist in pairs linked by the lost symmetry operations derived from the prototypic space group P2/b21/n21/a. Each of these two different H atoms is involved in an asymmetric hydrogen bond between an oxygen pair. Ferroelastic switching is concomitant with jumps of these hydrogen species from donor to acceptor O atoms. The studied structure belongs to the structural family of n-hexyl- to n-decylammonium dihydrogenphosphates and differs by localization of alternating layers from n-propyl- and n-pentylammonium dihydrogenphosphates. The studied crystal was slightly twinned; the minor domain constituted approximately 2%.
Supporting information
CCDC reference: 146100
Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: JANA98 (Petříček & Dušek, 1998); program(s) used to solve structure: SHELX86 (Sheldrick, 1985); program(s) used to refine structure: JANA2000 (Petříček & Dušek, 2000); molecular graphics: PICTUR (Dušek, 1993); software used to prepare material for publication: JANA98.
n-butylammonium dihydrogenphosphate
top
Crystal data top
C4H9NH3+H2PO4− | F(000) = 736 |
Mr = 171.13 | Dx = 1.382 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 9.1481 (9) Å | Cell parameters from 25 reflections |
b = 24.877 (2) Å | θ = 13–14° |
c = 7.225 (1) Å | µ = 0.30 mm−1 |
β = 90.82 (1)° | T = 292 K |
V = 1644.0 (4) Å3 | Plate, colourless |
Z = 8 | 0.45 × 0.30 × 0.12 mm |
Data collection top
Enraf-Nonius CAD-4-MACHIII-PC diffractometer | θmax = 27° |
ω–2θ scans | h = −11→11 |
3844 measured reflections | k = 0→31 |
3574 independent reflections | l = 0→9 |
2828 reflections with I > 3σ(I) | 3 standard reflections every 3600 min |
Rint = 0.008 | intensity decay: 2.0% |
Refinement top
Refinement on F | 0 constraints |
Least-squares matrix: full with fixed elements per cycle | H atoms treated by a mixture of independent and constrained refinement |
R[F > 3σ(F)] = 0.031 | w = 1/[σ2(Fo) + 0.0001(Fo)2] |
wR(F) = 0.042 | (Δ/σ)max = 0.01 |
S = 2.13 | Δρmax = 0.47 e Å−3 |
3574 reflections | Δρmin = −0.43 e Å−3 |
295 parameters | Extinction correction: Becker & Coppens (1974) type I, Lorentz. iso. |
42 restraints | Extinction coefficient: 0.000102 (5) |
Special details top
Refinement. The structure is a superstucture and a ferroelastic structure as well which can
be related to the prototypic space group P 2/b 21/n 21/a The structure was refined as a twin. domain fraction f: calculated from the
refinement: 0.022 (4) calculated from 33 pairs of measured intensities of well
separated intense reflections (0,0,-4) belonging to each domain. (The
intensities of these reflections were collected at different azimuthal
angles): 0.023 (1) The twinning matrix is given in _diffrn_reflns_transf_matrix_ items The H atoms except of those which are bonded to the O atoms were restrained by
the distfix and anglefix functions of JANA2000: The values for distfix were
0.90(0.022) A ng. for N—H distances. The values for distfix were 0.95(0.03) A ng. for methyl-H distances. The values for distfix were 0.95(0.013) A ng.
for methylene-H distances. The values for anglefix were 109.4 (1) °. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
P1 | 0.09616 (3) | 0.31130 (1) | 0.25570 (3) | 0.02211 (8) | |
O11 | −0.02452 (9) | 0.35502 (3) | 0.2316 (1) | 0.0366 (3) | |
O21 | 0.12834 (8) | 0.30119 (3) | 0.45762 (9) | 0.0328 (2) | |
O31 | 0.22298 (7) | 0.32869 (3) | 0.1409 (1) | 0.0316 (2) | |
O41 | 0.03056 (8) | 0.25712 (3) | 0.1798 (1) | 0.0323 (2) | |
P2 | 0.59217 (3) | 0.30782 (1) | 0.26224 (3) | 0.02258 (8) | |
O12 | 0.48010 (9) | 0.35479 (3) | 0.2623 (1) | 0.0362 (3) | |
O22 | 0.62777 (9) | 0.29711 (3) | 0.0537 (1) | 0.0358 (2) | |
O32 | 0.72505 (7) | 0.32664 (3) | 0.3659 (1) | 0.0338 (2) | |
O42 | 0.52538 (8) | 0.25686 (3) | 0.33826 (9) | 0.0305 (2) | |
N1 | 0.1798 (1) | 0.68108 (4) | 0.2670 (1) | 0.0303 (3) | |
C11 | 0.0939 (1) | 0.63077 (5) | 0.2473 (2) | 0.0339 (3) | |
C21 | 0.1884 (1) | 0.58152 (5) | 0.2530 (2) | 0.0392 (4) | |
C31 | 0.0989 (2) | 0.53041 (6) | 0.2444 (2) | 0.0557 (5) | |
C41 | 0.1873 (2) | 0.47947 (6) | 0.2484 (3) | 0.0712 (7) | |
N2 | 0.6888 (1) | 0.68074 (4) | 0.2279 (1) | 0.0292 (3) | |
C12 | 0.5990 (1) | 0.63154 (5) | 0.2477 (2) | 0.0337 (3) | |
C22 | 0.6903 (1) | 0.58153 (5) | 0.2457 (2) | 0.0386 (4) | |
C32 | 0.5977 (2) | 0.53107 (6) | 0.2545 (2) | 0.0557 (5) | |
C42 | 0.6833 (2) | 0.47948 (6) | 0.2513 (3) | 0.0703 (7) | |
H1n1 | 0.222 (1) | 0.6829 (4) | 0.377 (1) | 0.041 (3)* | |
H2n1 | 0.116 (1) | 0.7074 (4) | 0.251 (1) | 0.041 (3)* | |
H3n1 | 0.247 (1) | 0.6823 (4) | 0.179 (1) | 0.033 (3)* | |
H1c11 | 0.029 (1) | 0.6313 (5) | 0.348 (1) | 0.048 (4)* | |
H2c11 | 0.039 (1) | 0.6339 (5) | 0.136 (1) | 0.047 (4)* | |
H1c21 | 0.252 (1) | 0.5836 (6) | 0.149 (1) | 0.070 (5)* | |
H2c21 | 0.245 (1) | 0.5823 (5) | 0.365 (1) | 0.052 (4)* | |
H1c31 | 0.037 (1) | 0.5308 (6) | 0.347 (1) | 0.075 (5)* | |
H2c31 | 0.043 (1) | 0.5320 (6) | 0.135 (1) | 0.073 (5)* | |
H1c41 | 0.254 (2) | 0.4773 (7) | 0.147 (2) | 0.120 (8)* | |
H2c41 | 0.123 (2) | 0.4512 (6) | 0.241 (2) | 0.094 (6)* | |
H3c41 | 0.239 (2) | 0.4770 (7) | 0.359 (2) | 0.118 (8)* | |
H1n2 | 0.754 (1) | 0.6827 (4) | 0.322 (1) | 0.035 (3)* | |
H2n2 | 0.631 (1) | 0.7089 (4) | 0.231 (1) | 0.042 (3)* | |
H3n2 | 0.736 (1) | 0.6800 (4) | 0.122 (1) | 0.038 (3)* | |
H1c12 | 0.550 (1) | 0.6354 (5) | 0.361 (1) | 0.050 (4)* | |
H2c12 | 0.528 (1) | 0.6326 (5) | 0.149 (1) | 0.050 (4)* | |
H1c22 | 0.744 (1) | 0.5821 (6) | 0.134 (1) | 0.065 (4)* | |
H2c22 | 0.757 (1) | 0.5813 (6) | 0.350 (1) | 0.061 (4)* | |
H1c32 | 0.542 (1) | 0.5335 (6) | 0.362 (1) | 0.072 (5)* | |
H2c32 | 0.535 (1) | 0.5324 (6) | 0.151 (1) | 0.077 (5)* | |
H1c42 | 0.746 (2) | 0.4780 (7) | 0.354 (2) | 0.109 (8)* | |
H2c42 | 0.619 (2) | 0.4524 (6) | 0.258 (2) | 0.096 (6)* | |
H3c42 | 0.738 (2) | 0.4752 (7) | 0.144 (2) | 0.110 (8)* | |
HO11 | −0.094 (1) | 0.3474 (6) | 0.275 (2) | 0.047 (4)* | |
HO41 | 0.027 (2) | 0.2529 (5) | 0.051 (2) | 0.070 (5)* | |
HO12 | 0.409 (1) | 0.3463 (5) | 0.229 (2) | 0.047 (4)* | |
HO22 | 0.621 (2) | 0.2580 (6) | 0.019 (2) | 0.100 (6)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
P1 | 0.0207 (1) | 0.0272 (1) | 0.0184 (1) | −0.00188 (9) | 0.00103 (9) | 0.00152 (9) |
O11 | 0.0238 (4) | 0.0377 (4) | 0.0485 (5) | 0.0028 (3) | 0.0058 (4) | 0.0112 (4) |
O21 | 0.0430 (4) | 0.0356 (4) | 0.0196 (3) | −0.0047 (3) | −0.0024 (3) | 0.0006 (3) |
O31 | 0.0222 (3) | 0.0465 (5) | 0.0262 (4) | −0.0053 (3) | 0.0030 (3) | 0.0028 (3) |
O41 | 0.0415 (4) | 0.0337 (4) | 0.0219 (4) | −0.0110 (3) | 0.0024 (3) | −0.0024 (3) |
P2 | 0.0210 (1) | 0.0278 (1) | 0.0189 (1) | −0.00172 (9) | −0.0007 (1) | −0.00028 (9) |
O12 | 0.0231 (4) | 0.0331 (4) | 0.0523 (5) | 0.0006 (3) | −0.0054 (4) | −0.0061 (4) |
O22 | 0.0549 (5) | 0.0330 (4) | 0.0198 (3) | −0.0056 (4) | 0.0065 (3) | 0.0002 (3) |
O32 | 0.0214 (3) | 0.0509 (5) | 0.0290 (4) | −0.0057 (3) | −0.0030 (3) | −0.0011 (3) |
O42 | 0.0367 (4) | 0.0338 (4) | 0.0211 (3) | −0.0073 (3) | −0.0010 (3) | 0.0035 (3) |
N1 | 0.0303 (5) | 0.0318 (5) | 0.0289 (5) | 0.0040 (4) | 0.0003 (4) | 0.0015 (4) |
C11 | 0.0302 (6) | 0.0387 (6) | 0.0329 (6) | −0.0006 (4) | −0.0018 (5) | −0.0025 (5) |
C21 | 0.0385 (6) | 0.0342 (6) | 0.0448 (7) | −0.0015 (5) | −0.0011 (5) | −0.0006 (5) |
C31 | 0.0557 (9) | 0.0419 (8) | 0.070 (1) | −0.0122 (6) | 0.0005 (8) | −0.0047 (7) |
C41 | 0.105 (1) | 0.0332 (8) | 0.075 (1) | −0.0068 (8) | −0.002 (1) | −0.0029 (7) |
N2 | 0.0298 (4) | 0.0308 (5) | 0.0270 (5) | 0.0029 (4) | 0.0006 (4) | −0.0007 (4) |
C12 | 0.0293 (6) | 0.0389 (6) | 0.0330 (6) | −0.0029 (4) | 0.0029 (5) | 0.0025 (5) |
C22 | 0.0380 (6) | 0.0342 (6) | 0.0436 (7) | −0.0028 (5) | 0.0009 (5) | 0.0025 (5) |
C32 | 0.0567 (9) | 0.0422 (8) | 0.068 (1) | −0.0141 (6) | −0.0002 (8) | 0.0022 (7) |
C42 | 0.103 (1) | 0.0346 (8) | 0.073 (1) | −0.0112 (8) | 0.003 (1) | 0.0018 (7) |
Geometric parameters (Å, º) top
P1—O11 | 1.5576 (8) | C31—H1c31 | 0.94 (1) |
P1—O21 | 1.5052 (7) | C31—H2c31 | 0.93 (1) |
P1—O31 | 1.4996 (7) | C41—H1c41 | 0.97 (2) |
P1—O41 | 1.5710 (8) | C41—H2c41 | 0.91 (2) |
P2—O12 | 1.5546 (8) | C41—H3c41 | 0.92 (2) |
P2—O22 | 1.5687 (7) | N2—H1n2 | 0.90 (1) |
P2—O32 | 1.4940 (7) | N2—H2n2 | 0.88 (1) |
P2—O42 | 1.5138 (7) | N2—H3n2 | 0.89 (1) |
N1—C11 | 1.484 (1) | C12—H1c12 | 0.944 (9) |
C11—N1 | 1.484 (1) | C12—H2c12 | 0.956 (9) |
C11—C21 | 1.500 (2) | C22—H1c22 | 0.95 (1) |
C21—C31 | 1.513 (2) | C22—H2c22 | 0.96 (1) |
C31—C41 | 1.503 (2) | C32—H1c32 | 0.93 (1) |
N2—C12 | 1.482 (1) | C32—H2c32 | 0.93 (1) |
C12—C22 | 1.498 (2) | C42—H1c42 | 0.93 (2) |
C22—C32 | 1.516 (2) | C42—H2c42 | 0.89 (2) |
C32—C42 | 1.504 (2) | C42—H3c42 | 0.94 (2) |
O11—HO11 | 0.73 (1) | O11—O32i | 2.598 (1) |
O41—HO41 | 0.93 (2) | O21—O22ii | 2.542 (1) |
O12—HO12 | 0.72 (1) | O31—O12 | 2.582 (1) |
O22—HO22 | 1.01 (2) | O41—O42iii | 2.491 (1) |
N1—H1n1 | 0.88 (1) | O21—N2iv | 2.838 (1) |
N1—H2n1 | 0.88 (1) | O31—N2v | 2.805 (1) |
N1—H3n1 | 0.89 (1) | O41—N2vi | 2.850 (1) |
C11—H1c11 | 0.945 (9) | O22—N1v | 2.980 (1) |
C11—H2c11 | 0.949 (9) | O32—N1iv | 2.786 (1) |
C21—H1c21 | 0.96 (1) | O42—N1vi | 2.760 (1) |
C21—H2c21 | 0.955 (9) | | |
| | | |
O11—P1—O21 | 110.69 (4) | O12—P2—O22 | 105.89 (5) |
O11—P1—O31 | 106.83 (4) | O12—P2—O32 | 107.23 (4) |
O11—P1—O41 | 107.06 (4) | O12—P2—O42 | 111.09 (4) |
O21—P1—O31 | 116.24 (4) | O22—P2—O32 | 110.87 (4) |
O21—P1—O41 | 105.28 (4) | O22—P2—O42 | 107.26 (4) |
O31—P1—O41 | 110.42 (4) | O32—P2—O42 | 114.22 (4) |
Symmetry codes: (i) x−1, y, z; (ii) x−1/2, −y+1/2, z+1/2; (iii) x−1/2, −y+1/2, z−1/2; (iv) −x+1, −y+1, −z+1; (v) −x+1, −y+1, −z; (vi) −x+1/2, y−1/2, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | D···A | D—H···A |
N1v—H3n1v···O22 | 0.89 (1) | 2.980 (1) | 165 (1) |
N1iv—H1n1iv···O32 | 0.88 (1) | 2.786 (1) | 165 (1) |
N1vi—H2n1vi···O42 | 0.88 (1) | 2.760 (1) | 167 (1) |
N2iv—H1n2iv···O21 | 0.90 (1) | 2.838 (1) | 169 (1) |
N2v—H3n2v···O31 | 0.89 (1) | 2.805 (1) | 162 (1) |
N2vi—H2n2vi···O41 | 0.88 (1) | 2.850 (1) | 158 (1) |
O11—HO11···O32i | 0.73 (1) | 2.598 (1) | 175 (1) |
O41—HO41···O42iii | 0.93 (2) | 2.492 (1) | 177 (1) |
O12—HO12···O31 | 0.72 (1) | 2.582 (1) | 177 (1) |
O22ii—HO22ii···O21 | 1.00 (2) | 2.542 (1) | 174 (2) |
Symmetry codes: (i) x−1, y, z; (ii) x−1/2, −y+1/2, z+1/2; (iii) x−1/2, −y+1/2, z−1/2; (iv) −x+1, −y+1, −z+1; (v) −x+1, −y+1, −z; (vi) −x+1/2, y−1/2, −z+1/2. |
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