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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

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100006326/qa0290sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100006326/qa0290Isup2.hkl
Contains datablock I

CCDC reference: 146100

Computing details top

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+H2PO4F(000) = 736
Mr = 171.13Dx = 1.382 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 9.1481 (9) ÅCell parameters from 25 reflections
b = 24.877 (2) Åθ = 13–14°
c = 7.225 (1) ŵ = 0.30 mm1
β = 90.82 (1)°T = 292 K
V = 1644.0 (4) Å3Plate, colourless
Z = 80.45 × 0.30 × 0.12 mm
Data collection top
Enraf-Nonius CAD-4-MACHIII-PC
diffractometer
θmax = 27°
ω–2θ scansh = 1111
3844 measured reflectionsk = 031
3574 independent reflectionsl = 09
2828 reflections with I > 3σ(I)3 standard reflections every 3600 min
Rint = 0.008 intensity decay: 2.0%
Refinement top
Refinement on F0 constraints
Least-squares matrix: full with fixed elements per cycleH atoms treated by a mixture of independent and constrained refinement
R[F > 3σ(F)] = 0.031w = 1/[σ2(Fo) + 0.0001(Fo)2]
wR(F) = 0.042(Δ/σ)max = 0.01
S = 2.13Δρmax = 0.47 e Å3
3574 reflectionsΔρmin = 0.43 e Å3
295 parametersExtinction correction: Becker & Coppens (1974) type I, Lorentz. iso.
42 restraintsExtinction 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
xyzUiso*/Ueq
P10.09616 (3)0.31130 (1)0.25570 (3)0.02211 (8)
O110.02452 (9)0.35502 (3)0.2316 (1)0.0366 (3)
O210.12834 (8)0.30119 (3)0.45762 (9)0.0328 (2)
O310.22298 (7)0.32869 (3)0.1409 (1)0.0316 (2)
O410.03056 (8)0.25712 (3)0.1798 (1)0.0323 (2)
P20.59217 (3)0.30782 (1)0.26224 (3)0.02258 (8)
O120.48010 (9)0.35479 (3)0.2623 (1)0.0362 (3)
O220.62777 (9)0.29711 (3)0.0537 (1)0.0358 (2)
O320.72505 (7)0.32664 (3)0.3659 (1)0.0338 (2)
O420.52538 (8)0.25686 (3)0.33826 (9)0.0305 (2)
N10.1798 (1)0.68108 (4)0.2670 (1)0.0303 (3)
C110.0939 (1)0.63077 (5)0.2473 (2)0.0339 (3)
C210.1884 (1)0.58152 (5)0.2530 (2)0.0392 (4)
C310.0989 (2)0.53041 (6)0.2444 (2)0.0557 (5)
C410.1873 (2)0.47947 (6)0.2484 (3)0.0712 (7)
N20.6888 (1)0.68074 (4)0.2279 (1)0.0292 (3)
C120.5990 (1)0.63154 (5)0.2477 (2)0.0337 (3)
C220.6903 (1)0.58153 (5)0.2457 (2)0.0386 (4)
C320.5977 (2)0.53107 (6)0.2545 (2)0.0557 (5)
C420.6833 (2)0.47948 (6)0.2513 (3)0.0703 (7)
H1n10.222 (1)0.6829 (4)0.377 (1)0.041 (3)*
H2n10.116 (1)0.7074 (4)0.251 (1)0.041 (3)*
H3n10.247 (1)0.6823 (4)0.179 (1)0.033 (3)*
H1c110.029 (1)0.6313 (5)0.348 (1)0.048 (4)*
H2c110.039 (1)0.6339 (5)0.136 (1)0.047 (4)*
H1c210.252 (1)0.5836 (6)0.149 (1)0.070 (5)*
H2c210.245 (1)0.5823 (5)0.365 (1)0.052 (4)*
H1c310.037 (1)0.5308 (6)0.347 (1)0.075 (5)*
H2c310.043 (1)0.5320 (6)0.135 (1)0.073 (5)*
H1c410.254 (2)0.4773 (7)0.147 (2)0.120 (8)*
H2c410.123 (2)0.4512 (6)0.241 (2)0.094 (6)*
H3c410.239 (2)0.4770 (7)0.359 (2)0.118 (8)*
H1n20.754 (1)0.6827 (4)0.322 (1)0.035 (3)*
H2n20.631 (1)0.7089 (4)0.231 (1)0.042 (3)*
H3n20.736 (1)0.6800 (4)0.122 (1)0.038 (3)*
H1c120.550 (1)0.6354 (5)0.361 (1)0.050 (4)*
H2c120.528 (1)0.6326 (5)0.149 (1)0.050 (4)*
H1c220.744 (1)0.5821 (6)0.134 (1)0.065 (4)*
H2c220.757 (1)0.5813 (6)0.350 (1)0.061 (4)*
H1c320.542 (1)0.5335 (6)0.362 (1)0.072 (5)*
H2c320.535 (1)0.5324 (6)0.151 (1)0.077 (5)*
H1c420.746 (2)0.4780 (7)0.354 (2)0.109 (8)*
H2c420.619 (2)0.4524 (6)0.258 (2)0.096 (6)*
H3c420.738 (2)0.4752 (7)0.144 (2)0.110 (8)*
HO110.094 (1)0.3474 (6)0.275 (2)0.047 (4)*
HO410.027 (2)0.2529 (5)0.051 (2)0.070 (5)*
HO120.409 (1)0.3463 (5)0.229 (2)0.047 (4)*
HO220.621 (2)0.2580 (6)0.019 (2)0.100 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
P10.0207 (1)0.0272 (1)0.0184 (1)0.00188 (9)0.00103 (9)0.00152 (9)
O110.0238 (4)0.0377 (4)0.0485 (5)0.0028 (3)0.0058 (4)0.0112 (4)
O210.0430 (4)0.0356 (4)0.0196 (3)0.0047 (3)0.0024 (3)0.0006 (3)
O310.0222 (3)0.0465 (5)0.0262 (4)0.0053 (3)0.0030 (3)0.0028 (3)
O410.0415 (4)0.0337 (4)0.0219 (4)0.0110 (3)0.0024 (3)0.0024 (3)
P20.0210 (1)0.0278 (1)0.0189 (1)0.00172 (9)0.0007 (1)0.00028 (9)
O120.0231 (4)0.0331 (4)0.0523 (5)0.0006 (3)0.0054 (4)0.0061 (4)
O220.0549 (5)0.0330 (4)0.0198 (3)0.0056 (4)0.0065 (3)0.0002 (3)
O320.0214 (3)0.0509 (5)0.0290 (4)0.0057 (3)0.0030 (3)0.0011 (3)
O420.0367 (4)0.0338 (4)0.0211 (3)0.0073 (3)0.0010 (3)0.0035 (3)
N10.0303 (5)0.0318 (5)0.0289 (5)0.0040 (4)0.0003 (4)0.0015 (4)
C110.0302 (6)0.0387 (6)0.0329 (6)0.0006 (4)0.0018 (5)0.0025 (5)
C210.0385 (6)0.0342 (6)0.0448 (7)0.0015 (5)0.0011 (5)0.0006 (5)
C310.0557 (9)0.0419 (8)0.070 (1)0.0122 (6)0.0005 (8)0.0047 (7)
C410.105 (1)0.0332 (8)0.075 (1)0.0068 (8)0.002 (1)0.0029 (7)
N20.0298 (4)0.0308 (5)0.0270 (5)0.0029 (4)0.0006 (4)0.0007 (4)
C120.0293 (6)0.0389 (6)0.0330 (6)0.0029 (4)0.0029 (5)0.0025 (5)
C220.0380 (6)0.0342 (6)0.0436 (7)0.0028 (5)0.0009 (5)0.0025 (5)
C320.0567 (9)0.0422 (8)0.068 (1)0.0141 (6)0.0002 (8)0.0022 (7)
C420.103 (1)0.0346 (8)0.073 (1)0.0112 (8)0.003 (1)0.0018 (7)
Geometric parameters (Å, º) top
P1—O111.5576 (8)C31—H1c310.94 (1)
P1—O211.5052 (7)C31—H2c310.93 (1)
P1—O311.4996 (7)C41—H1c410.97 (2)
P1—O411.5710 (8)C41—H2c410.91 (2)
P2—O121.5546 (8)C41—H3c410.92 (2)
P2—O221.5687 (7)N2—H1n20.90 (1)
P2—O321.4940 (7)N2—H2n20.88 (1)
P2—O421.5138 (7)N2—H3n20.89 (1)
N1—C111.484 (1)C12—H1c120.944 (9)
C11—N11.484 (1)C12—H2c120.956 (9)
C11—C211.500 (2)C22—H1c220.95 (1)
C21—C311.513 (2)C22—H2c220.96 (1)
C31—C411.503 (2)C32—H1c320.93 (1)
N2—C121.482 (1)C32—H2c320.93 (1)
C12—C221.498 (2)C42—H1c420.93 (2)
C22—C321.516 (2)C42—H2c420.89 (2)
C32—C421.504 (2)C42—H3c420.94 (2)
O11—HO110.73 (1)O11—O32i2.598 (1)
O41—HO410.93 (2)O21—O22ii2.542 (1)
O12—HO120.72 (1)O31—O122.582 (1)
O22—HO221.01 (2)O41—O42iii2.491 (1)
N1—H1n10.88 (1)O21—N2iv2.838 (1)
N1—H2n10.88 (1)O31—N2v2.805 (1)
N1—H3n10.89 (1)O41—N2vi2.850 (1)
C11—H1c110.945 (9)O22—N1v2.980 (1)
C11—H2c110.949 (9)O32—N1iv2.786 (1)
C21—H1c210.96 (1)O42—N1vi2.760 (1)
C21—H2c210.955 (9)
O11—P1—O21110.69 (4)O12—P2—O22105.89 (5)
O11—P1—O31106.83 (4)O12—P2—O32107.23 (4)
O11—P1—O41107.06 (4)O12—P2—O42111.09 (4)
O21—P1—O31116.24 (4)O22—P2—O32110.87 (4)
O21—P1—O41105.28 (4)O22—P2—O42107.26 (4)
O31—P1—O41110.42 (4)O32—P2—O42114.22 (4)
Symmetry codes: (i) x1, y, z; (ii) x1/2, y+1/2, z+1/2; (iii) x1/2, y+1/2, z1/2; (iv) x+1, y+1, z+1; (v) x+1, y+1, z; (vi) x+1/2, y1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HD···AD—H···A
N1v—H3n1v···O220.89 (1)2.980 (1)165 (1)
N1iv—H1n1iv···O320.88 (1)2.786 (1)165 (1)
N1vi—H2n1vi···O420.88 (1)2.760 (1)167 (1)
N2iv—H1n2iv···O210.90 (1)2.838 (1)169 (1)
N2v—H3n2v···O310.89 (1)2.805 (1)162 (1)
N2vi—H2n2vi···O410.88 (1)2.850 (1)158 (1)
O11—HO11···O32i0.73 (1)2.598 (1)175 (1)
O41—HO41···O42iii0.93 (2)2.492 (1)177 (1)
O12—HO12···O310.72 (1)2.582 (1)177 (1)
O22ii—HO22ii···O211.00 (2)2.542 (1)174 (2)
Symmetry codes: (i) x1, y, z; (ii) x1/2, y+1/2, z+1/2; (iii) x1/2, y+1/2, z1/2; (iv) x+1, y+1, z+1; (v) x+1, y+1, z; (vi) x+1/2, y1/2, z+1/2.
 

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