The single crystal growth and sequence of reversible phase transition are described for C3H5N2Al(SO4)2·6H2O. Thermal and structural analyses combined with dielectric studies and optical observations revealed the structural phase transition at T1 = 339/340 K (I↔II) and T2 = 347/348 K (II↔III) on heating and cooling, respectively. Both phase transitions are of the first-order type. The symmetry changes from monoclinic to trigonal phase. At 293 K, the large crystals are usually divided into numerous domains of the ferroelastic type that disappear above T1 on heating and reappear below T1 on cooling. The domain structure pattern is characteristic for the transition between trigonal and monoclinic phases. The changes of entropy and clear increase of permittivity at T1 provide evidence for the order–disorder character of this phase transition. The transition at T2 seems to be displacive.
Supporting information
CCDC references: 2047334; 2047335; 2047336
For all structures, data collection: CrysAlis CCD (Oxford Diffraction, 2007); cell refinement: CrysAlis RED (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007). Program(s) used to solve structure: SHELXS2014 (Sheldrick, 2014) for I_non-standard_setting; SHELXS2013 (Sheldrick, 2013) for (II), (III). Program(s) used to refine structure: SHELXL2014 (Sheldrick, 2014) for I_non-standard_setting; SHELXL2013 (Sheldrick, 2013) for (II), (III). Molecular graphics: Mercury (Macrae, 2020) for I_non-standard_setting; SHELXTL (Sheldrick, 2008) for (II), (III).
(I_non-standard_setting)
top
Crystal data top
C3H17AlN2O14S2 | F(000) = 412 |
Mr = 396.29 | Dx = 1.776 Mg m−3 |
Monoclinic, P2/a | Mo Kα radiation, λ = 0.71073 Å |
a = 12.0026 (10) Å | Cell parameters from 4395 reflections |
b = 6.7859 (6) Å | θ = 3.0–26.0° |
c = 9.1005 (11) Å | µ = 0.50 mm−1 |
β = 88.835 (9)° | T = 290 K |
V = 741.07 (13) Å3 | Irregular, colorless |
Z = 2 | 0.25 × 0.20 × 0.13 mm |
Data collection top
Oxford Diffraction Xcalibur System diffractometer | 1082 reflections with I > 2σ(I) |
Radiation source: Enhance (Mo) X-ray Source | Rint = 0.062 |
Graphite monochromator | θmax = 26.0°, θmin = 3.0° |
Detector resolution: 10.4508 pixels mm-1 | h = −14→14 |
ω–scan | k = −8→7 |
4395 measured reflections | l = −8→11 |
1431 independent reflections | |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.050 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.121 | w = 1/[σ2(Fo2) + (0.075P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.97 | (Δ/σ)max < 0.001 |
1431 reflections | Δρmax = 0.52 e Å−3 |
125 parameters | Δρmin = −0.48 e Å−3 |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Al1 | 0.2500 | 0.26554 (15) | 0.0000 | 0.0198 (3) | |
O1 | 0.31352 (19) | 0.4649 (3) | 0.1142 (2) | 0.0280 (5) | |
H1A | 0.275 (3) | 0.568 (6) | 0.155 (4) | 0.050 (11)* | |
H1B | 0.365 (3) | 0.460 (6) | 0.145 (4) | 0.049 (13)* | |
O1A | 0.1197 (2) | 0.2657 (3) | 0.1153 (3) | 0.0289 (6) | |
H1AA | 0.093 (3) | 0.348 (5) | 0.147 (4) | 0.032 (11)* | |
H1AB | 0.091 (3) | 0.169 (5) | 0.139 (4) | 0.034 (10)* | |
O1B | 0.18848 (19) | 0.0682 (3) | −0.1164 (2) | 0.0289 (5) | |
H1BA | 0.130 (3) | 0.061 (5) | −0.139 (4) | 0.040 (11)* | |
H1BB | 0.228 (3) | −0.044 (6) | −0.153 (4) | 0.053 (11)* | |
S1 | 0.57521 (6) | 0.23069 (9) | 0.26261 (8) | 0.0227 (3) | |
O2 | 0.52020 (15) | 0.4138 (3) | 0.2171 (2) | 0.0304 (5) | |
O2A | 0.52129 (16) | 0.0634 (3) | 0.1882 (2) | 0.0365 (6) | |
O2B | 0.69411 (17) | 0.2363 (2) | 0.2168 (3) | 0.0297 (5) | |
O3 | 0.56481 (19) | 0.2052 (3) | 0.4211 (3) | 0.0390 (6) | |
N1 | 0.6636 (2) | 0.7997 (5) | 0.5045 (3) | 0.0448 (8) | |
H1 | 0.5957 | 0.8402 | 0.5078 | 0.054* | |
C2 | 0.7500 | 0.9107 (7) | 0.5000 | 0.0416 (12) | |
H2 | 0.7500 | 1.0478 | 0.5000 | 0.050* | |
C2A | 0.6956 (3) | 0.6120 (6) | 0.5030 (4) | 0.0533 (10) | |
H2A | 0.6494 | 0.5019 | 0.5058 | 0.064* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Al1 | 0.0158 (6) | 0.0190 (6) | 0.0246 (6) | 0.000 | 0.0012 (5) | 0.000 |
O1 | 0.0205 (13) | 0.0278 (12) | 0.0359 (13) | 0.0031 (9) | −0.0044 (10) | −0.0080 (9) |
O1A | 0.0240 (12) | 0.0197 (11) | 0.0423 (14) | −0.0003 (9) | 0.0150 (10) | −0.0006 (10) |
O1B | 0.0192 (12) | 0.0276 (12) | 0.0401 (13) | 0.0007 (9) | −0.0042 (10) | −0.0087 (9) |
S1 | 0.0153 (4) | 0.0198 (4) | 0.0330 (4) | 0.0010 (3) | 0.0009 (3) | 0.0003 (3) |
O2 | 0.0218 (10) | 0.0204 (10) | 0.0489 (13) | 0.0017 (9) | −0.0008 (9) | 0.0038 (9) |
O2A | 0.0205 (11) | 0.0233 (11) | 0.0658 (16) | 0.0011 (9) | −0.0057 (10) | −0.0085 (10) |
O2B | 0.0170 (11) | 0.0262 (11) | 0.0456 (13) | −0.0003 (8) | 0.0051 (9) | −0.0006 (8) |
O3 | 0.0320 (13) | 0.0514 (14) | 0.0335 (13) | 0.0023 (11) | 0.0022 (10) | 0.0070 (10) |
N1 | 0.0236 (14) | 0.074 (2) | 0.0366 (16) | 0.0073 (15) | 0.0009 (12) | −0.0106 (16) |
C2 | 0.049 (3) | 0.038 (3) | 0.038 (3) | 0.000 | −0.006 (2) | 0.000 |
C2A | 0.078 (3) | 0.049 (2) | 0.0320 (18) | −0.032 (2) | 0.005 (2) | −0.0028 (18) |
Geometric parameters (Å, º) top
Al1—O1Ai | 1.866 (2) | S1—O3 | 1.455 (2) |
Al1—O1A | 1.866 (2) | S1—O2 | 1.4706 (19) |
Al1—O1B | 1.869 (2) | S1—O2A | 1.478 (2) |
Al1—O1Bi | 1.869 (2) | S1—O2B | 1.479 (2) |
Al1—O1 | 1.877 (2) | N1—C2 | 1.282 (4) |
Al1—O1i | 1.877 (2) | N1—C2A | 1.331 (5) |
O1—H1A | 0.91 (4) | N1—H1 | 0.8600 |
O1—H1B | 0.69 (4) | C2—N1ii | 1.282 (4) |
O1A—H1AA | 0.70 (3) | C2—H2 | 0.9300 |
O1A—H1AB | 0.77 (3) | C2A—C2Aii | 1.307 (7) |
O1B—H1BA | 0.74 (4) | C2A—H2A | 0.9300 |
O1B—H1BB | 0.95 (4) | | |
| | | |
O1Ai—Al1—O1A | 179.92 (14) | H1AA—O1A—H1AB | 111 (4) |
O1Ai—Al1—O1B | 91.03 (10) | Al1—O1B—H1BA | 126 (3) |
O1A—Al1—O1B | 89.03 (10) | Al1—O1B—H1BB | 125 (2) |
O1Ai—Al1—O1Bi | 89.03 (10) | H1BA—O1B—H1BB | 109 (4) |
O1A—Al1—O1Bi | 91.03 (10) | O3—S1—O2 | 110.46 (12) |
O1B—Al1—O1Bi | 88.46 (14) | O3—S1—O2A | 109.45 (13) |
O1Ai—Al1—O1 | 88.03 (10) | O2—S1—O2A | 108.48 (13) |
O1A—Al1—O1 | 91.91 (11) | O3—S1—O2B | 110.19 (14) |
O1B—Al1—O1 | 178.99 (9) | O2—S1—O2B | 109.58 (11) |
O1Bi—Al1—O1 | 91.90 (11) | O2A—S1—O2B | 108.64 (12) |
O1Ai—Al1—O1i | 91.91 (11) | C2—N1—C2A | 109.2 (3) |
O1A—Al1—O1i | 88.02 (10) | C2—N1—H1 | 125.4 |
O1B—Al1—O1i | 91.90 (11) | C2A—N1—H1 | 125.4 |
O1Bi—Al1—O1i | 178.99 (9) | N1ii—C2—N1 | 108.0 (4) |
O1—Al1—O1i | 87.77 (15) | N1ii—C2—H2 | 126.0 |
Al1—O1—H1A | 125 (2) | N1—C2—H2 | 126.0 |
Al1—O1—H1B | 125 (3) | C2Aii—C2A—N1 | 106.77 (19) |
H1A—O1—H1B | 109 (4) | C2Aii—C2A—H2A | 126.6 |
Al1—O1A—H1AA | 127 (3) | N1—C2A—H2A | 126.6 |
Al1—O1A—H1AB | 121 (2) | | |
| | | |
C2A—N1—C2—N1ii | 0.09 (17) | C2—N1—C2A—C2Aii | −0.2 (5) |
Symmetry codes: (i) −x+1/2, y, −z; (ii) −x+3/2, y, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···S1iii | 0.91 (4) | 2.91 (4) | 3.757 (2) | 155 (3) |
O1—H1A···O2Biii | 0.91 (4) | 1.73 (4) | 2.643 (3) | 174 (3) |
O1—H1B···O2 | 0.69 (4) | 2.01 (4) | 2.692 (3) | 172 (4) |
O1A—H1AA···O2iii | 0.70 (3) | 1.94 (3) | 2.640 (3) | 175 (4) |
O1A—H1AB···S1iv | 0.77 (3) | 2.94 (3) | 3.661 (2) | 157 (3) |
O1A—H1AB···O2Aiv | 0.77 (3) | 1.84 (3) | 2.606 (3) | 178 (4) |
O1B—H1BA···S1i | 0.74 (4) | 2.96 (4) | 3.630 (2) | 152 (4) |
O1B—H1BA···O2Ai | 0.74 (4) | 1.87 (4) | 2.614 (3) | 175 (4) |
O1B—H1BB···S1v | 0.95 (4) | 2.84 (4) | 3.711 (2) | 152 (3) |
O1B—H1BB···O2Bv | 0.95 (4) | 1.70 (4) | 2.653 (3) | 177 (3) |
N1—H1···S1vi | 0.86 | 2.94 | 3.536 (3) | 128 |
N1—H1···O3vi | 0.86 | 2.04 | 2.811 (4) | 148 |
C2—H2···O3vii | 0.93 | 2.58 | 3.084 (4) | 114 |
C2—H2···O3viii | 0.93 | 2.58 | 3.084 (4) | 114 |
C2A—H2A···O3 | 0.93 | 2.39 | 3.269 (4) | 158 |
Symmetry codes: (i) −x+1/2, y, −z; (iii) x−1/2, −y+1, z; (iv) x−1/2, −y, z; (v) −x+1, −y, −z; (vi) −x+1, −y+1, −z+1; (vii) x, y+1, z; (viii) −x+3/2, y+1, −z+1. |
Crystal data top
C3H17AlN2O14S2 | Dx = 1.756 Mg m−3 |
Mr = 396.29 | Mo Kα radiation, λ = 0.71073 Å |
Trigonal, P3m1 | Cell parameters from 2491 reflections |
a = 6.8748 (5) Å | θ = 3.4–5.9° |
c = 9.1550 (12) Å | µ = 0.49 mm−1 |
V = 374.72 (7) Å3 | T = 345 K |
Z = 1 | Irregular, colorless |
F(000) = 206 | 0.25 × 0.20 × 0.13 mm |
Data collection top
Oxford Diffraction Xcalibur System diffractometer | 274 reflections with I > 2σ(I) |
Radiation source: Enhance (Mo) X-ray Source | Rint = 0.034 |
Graphite monochromator | θmax = 25.9°, θmin = 3.4° |
Detector resolution: 10.4508 pixels mm-1 | h = −8→8 |
ω–scan | k = −7→8 |
2491 measured reflections | l = −8→11 |
311 independent reflections | |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.034 | H-atom parameters constrained |
wR(F2) = 0.079 | w = 1/[σ2(Fo2) + (0.0268P)2 + 0.3072P] where P = (Fo2 + 2Fc2)/3 |
S = 1.12 | (Δ/σ)max < 0.001 |
311 reflections | Δρmax = 0.25 e Å−3 |
32 parameters | Δρmin = −0.28 e Å−3 |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Al1 | 1.0000 | 1.0000 | 1.0000 | 0.0312 (5) | |
O1 | 0.86995 (17) | 0.7399 (3) | 0.8850 (2) | 0.0418 (6) | |
H1A | 0.9349 | 0.6587 | 0.8545 | 0.050* | |
S1 | 0.3333 | 0.6667 | 0.73910 (15) | 0.0374 (4) | |
O2 | 0.44987 (18) | 0.55013 (18) | 0.7935 (3) | 0.0485 (6) | |
O3 | 0.3333 | 0.6667 | 0.5807 (5) | 0.0757 (15) | |
N1 | 0.085 (3) | 0.170 (6) | 0.506 (3) | 0.056 (7) | 0.3333 |
H1 | 0.1521 | 0.3042 | 0.5020 | 0.067* | 0.3333 |
C2 | 0.176 (4) | 0.176 (4) | 0.5000 | 0.056 (7) | 0.5 |
H2 | 0.3007 | 0.3007 | 0.5000 | 0.068* | 0.5 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Al1 | 0.0271 (7) | 0.0271 (7) | 0.0396 (11) | 0.0135 (3) | 0.000 | 0.000 |
O1 | 0.0315 (8) | 0.0366 (12) | 0.0590 (12) | 0.0183 (6) | −0.0069 (5) | −0.0138 (10) |
S1 | 0.0305 (5) | 0.0305 (5) | 0.0510 (8) | 0.0153 (2) | 0.000 | 0.000 |
O2 | 0.0328 (9) | 0.0328 (9) | 0.0831 (15) | 0.0189 (10) | −0.0020 (5) | 0.0020 (5) |
O3 | 0.090 (2) | 0.090 (2) | 0.047 (2) | 0.0449 (12) | 0.000 | 0.000 |
N1 | 0.065 (15) | 0.030 (9) | 0.062 (9) | 0.015 (5) | 0.008 (4) | 0.015 (8) |
C2 | 0.045 (7) | 0.045 (7) | 0.052 (7) | 0.002 (9) | 0.008 (4) | −0.008 (4) |
Geometric parameters (Å, º) top
Al1—O1 | 1.8728 (19) | N1—N1viii | 1.02 (4) |
Al1—O1i | 1.8728 (19) | N1—C2ix | 1.575 (11) |
Al1—O1ii | 1.8728 (19) | N1—C2x | 1.575 (11) |
Al1—O1iii | 1.8728 (19) | N1—N1xi | 1.75 (7) |
Al1—O1iv | 1.873 (2) | N1—N1x | 1.75 (7) |
Al1—O1v | 1.8728 (19) | N1—H1 | 0.8023 |
O1—H1A | 0.9154 | N1—H2 | 1.2967 |
S1—O3 | 1.450 (5) | C2—N1ix | 0.607 (15) |
S1—O2vi | 1.474 (2) | C2—C2viii | 1.21 (3) |
S1—O2vii | 1.474 (2) | C2—C2ix | 1.21 (3) |
S1—O2 | 1.474 (2) | C2—N1viii | 1.575 (11) |
N1—C2 | 0.607 (15) | C2—N1xi | 1.575 (11) |
N1—C2viii | 0.607 (15) | C2—H1 | 0.9749 |
N1—N1ix | 1.02 (4) | C2—H2 | 0.8600 |
| | | |
O1—Al1—O1i | 180.0 | C2x—N1—N1x | 20.2 (15) |
O1—Al1—O1ii | 88.53 (9) | N1xi—N1—N1x | 60.000 (6) |
O1i—Al1—O1ii | 91.47 (9) | C2—N1—H1 | 86.3 |
O1—Al1—O1iii | 91.47 (9) | C2viii—N1—H1 | 86.3 |
O1i—Al1—O1iii | 88.53 (9) | N1ix—N1—H1 | 119.4 |
O1ii—Al1—O1iii | 180.0 | N1viii—N1—H1 | 119.4 |
O1—Al1—O1iv | 91.47 (9) | C2ix—N1—H1 | 129.7 |
O1i—Al1—O1iv | 88.53 (9) | C2x—N1—H1 | 129.7 |
O1ii—Al1—O1iv | 88.53 (9) | N1xi—N1—H1 | 149.9 |
O1iii—Al1—O1iv | 91.47 (9) | N1x—N1—H1 | 149.9 |
O1—Al1—O1v | 88.53 (9) | C2—N1—H2 | 33.7 |
O1i—Al1—O1v | 91.47 (9) | C2viii—N1—H2 | 138.8 |
O1ii—Al1—O1v | 91.47 (9) | N1ix—N1—H2 | 66.9 |
O1iii—Al1—O1v | 88.53 (9) | N1viii—N1—H2 | 168.6 |
O1iv—Al1—O1v | 180.0 | C2ix—N1—H2 | 76.9 |
Al1—O1—H1A | 127.5 | C2x—N1—H2 | 174.6 |
O3—S1—O2vi | 109.73 (10) | N1xi—N1—H2 | 97.1 |
O3—S1—O2vii | 109.73 (10) | N1x—N1—H2 | 156.9 |
O2vi—S1—O2vii | 109.21 (10) | H1—N1—H2 | 52.9 |
O3—S1—O2 | 109.73 (10) | N1—C2—N1ix | 113 (10) |
O2vi—S1—O2 | 109.21 (11) | N1—C2—C2viii | 6 (3) |
O2vii—S1—O2 | 109.21 (10) | N1ix—C2—C2viii | 116 (5) |
C2—N1—C2viii | 167 (5) | N1—C2—C2ix | 116 (5) |
C2—N1—N1ix | 33 (5) | N1ix—C2—C2ix | 6 (3) |
C2viii—N1—N1ix | 151 (6) | C2viii—C2—C2ix | 120.001 (14) |
C2—N1—N1viii | 151 (6) | N1—C2—N1viii | 18 (4) |
C2viii—N1—N1viii | 33 (6) | N1ix—C2—N1viii | 96 (7) |
N1ix—N1—N1viii | 118.8 (11) | C2viii—C2—N1viii | 20.2 (16) |
C2—N1—C2ix | 43 (4) | C2ix—C2—N1viii | 99.9 (16) |
C2viii—N1—C2ix | 143 (7) | N1—C2—N1xi | 96 (7) |
N1ix—N1—C2ix | 10.8 (19) | N1ix—C2—N1xi | 18 (4) |
N1viii—N1—C2ix | 109.7 (18) | C2viii—C2—N1xi | 99.9 (16) |
C2—N1—C2x | 143 (7) | C2ix—C2—N1xi | 20.2 (16) |
C2viii—N1—C2x | 43 (4) | N1viii—C2—N1xi | 80 (3) |
N1ix—N1—C2x | 109.7 (18) | N1—C2—H1 | 55.2 |
N1viii—N1—C2x | 10.8 (19) | N1ix—C2—H1 | 167.6 |
C2ix—N1—C2x | 100 (3) | C2viii—C2—H1 | 51.7 |
C2—N1—N1xi | 64 (5) | C2ix—C2—H1 | 171.7 |
C2viii—N1—N1xi | 123 (5) | N1viii—C2—H1 | 71.9 |
N1ix—N1—N1xi | 30.6 (6) | N1xi—C2—H1 | 151.5 |
N1viii—N1—N1xi | 89.999 (5) | N1—C2—H2 | 123.3 |
C2ix—N1—N1xi | 20.2 (15) | N1ix—C2—H2 | 123.3 |
C2x—N1—N1xi | 80.1 (16) | C2viii—C2—H2 | 120.0 |
C2—N1—N1x | 123 (5) | C2ix—C2—H2 | 120.0 |
C2viii—N1—N1x | 64 (5) | N1viii—C2—H2 | 140.1 |
N1ix—N1—N1x | 89.999 (18) | N1xi—C2—H2 | 140.1 |
N1viii—N1—N1x | 30.6 (5) | H1—C2—H2 | 68.3 |
C2ix—N1—N1x | 80.1 (16) | | |
| | | |
C2viii—N1—C2—N1ix | −119 (50) | C2x—N1—C2—C2ix | −13 (5) |
N1viii—N1—C2—N1ix | −20 (7) | N1xi—N1—C2—C2ix | 0.000 (1) |
C2ix—N1—C2—N1ix | 6 (3) | N1x—N1—C2—C2ix | −6 (3) |
C2x—N1—C2—N1ix | −7 (3) | C2viii—N1—C2—N1viii | −99 (53) |
N1xi—N1—C2—N1ix | 6 (3) | N1ix—N1—C2—N1viii | 20 (7) |
N1x—N1—C2—N1ix | 0.001 (2) | C2ix—N1—C2—N1viii | 26 (10) |
N1ix—N1—C2—C2viii | 119 (50) | C2x—N1—C2—N1viii | 13 (4) |
N1viii—N1—C2—C2viii | 99 (52) | N1xi—N1—C2—N1viii | 26 (10) |
C2ix—N1—C2—C2viii | 125 (48) | N1x—N1—C2—N1viii | 20 (7) |
C2x—N1—C2—C2viii | 112 (51) | C2viii—N1—C2—N1xi | −125 (48) |
N1xi—N1—C2—C2viii | 125 (48) | N1ix—N1—C2—N1xi | −6 (3) |
N1x—N1—C2—C2viii | 119 (50) | N1viii—N1—C2—N1xi | −26 (10) |
C2viii—N1—C2—C2ix | −125 (48) | C2ix—N1—C2—N1xi | 0.000 (1) |
N1ix—N1—C2—C2ix | −6 (3) | C2x—N1—C2—N1xi | −13 (5) |
N1viii—N1—C2—C2ix | −26 (10) | N1x—N1—C2—N1xi | −6 (3) |
Symmetry codes: (i) −x+2, −y+2, −z+2; (ii) x−y+1, x, −z+2; (iii) −x+y+1, −x+2, z; (iv) −y+2, x−y+1, z; (v) y, −x+y+1, −z+2; (vi) −y+1, x−y+1, z; (vii) −x+y, −x+1, z; (viii) x−y, x, −z+1; (ix) y, −x+y, −z+1; (x) −y, x−y, z; (xi) −x+y, −x, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···S1xii | 0.92 | 2.91 | 3.7134 (9) | 147 |
O1—H1A···O2xiii | 0.92 | 1.74 | 2.6413 (17) | 170 |
N1—H1···S1 | 0.80 | 3.06 | 3.65 (4) | 132 |
N1—H1···O3 | 0.80 | 2.28 | 3.04 (4) | 159 |
C2—H1···S1 | 0.97 | 3.06 | 3.702 (15) | 125 |
C2—H1···O3 | 0.97 | 2.28 | 3.075 (18) | 139 |
N1—H2···O3xiv | 1.30 | 2.52 | 3.661 (9) | 145 |
C2—H1···O3 | 0.97 | 2.28 | 3.075 (18) | 139 |
C2—H2···O3xiv | 0.86 | 2.52 | 3.075 (18) | 123 |
Symmetry codes: (xii) x+1, y, z; (xiii) −x+y+1, −x+1, z; (xiv) −x+1, −y+1, −z+1. |
Crystal data top
C3H17AlN2O14S2 | Dx = 1.758 Mg m−3 |
Mr = 396.29 | Mo Kα radiation, λ = 0.71073 Å |
Trigonal, P3m1 | Cell parameters from 2563 reflections |
a = 6.8680 (4) Å | θ = 3.4–26.0° |
c = 9.1617 (10) Å | µ = 0.49 mm−1 |
V = 374.25 (6) Å3 | T = 350 K |
Z = 1 | Irregular, colorless |
F(000) = 206 | 0.4 × 0.36 × 0.34 mm |
Data collection top
Oxford Diffraction Xcalibur System diffractometer | 279 reflections with I > 2σ(I) |
Radiation source: Enhance (Mo) X-ray Source | Rint = 0.022 |
Graphite monochromator | θmax = 26.0°, θmin = 3.4° |
Detector resolution: 10.4508 pixels mm-1 | h = −8→8 |
ω–scan | k = −8→8 |
2563 measured reflections | l = −7→11 |
317 independent reflections | |
Refinement top
Refinement on F2 | 7 restraints |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.030 | H-atom parameters constrained |
wR(F2) = 0.080 | w = 1/[σ2(Fo2) + (0.0346P)2 + 0.2265P] where P = (Fo2 + 2Fc2)/3 |
S = 1.11 | (Δ/σ)max < 0.001 |
317 reflections | Δρmax = 0.32 e Å−3 |
32 parameters | Δρmin = −0.29 e Å−3 |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Al1 | 1.0000 | 1.0000 | 1.0000 | 0.0299 (5) | |
O1 | 0.86970 (15) | 0.7394 (3) | 0.88502 (18) | 0.0404 (5) | |
H1A | 0.9346 | 0.6587 | 0.8545 | 0.048* | |
S1 | 0.3333 | 0.6667 | 0.73902 (13) | 0.0352 (3) | |
O2 | 0.44965 (15) | 0.55035 (15) | 0.7932 (2) | 0.0470 (5) | |
O3 | 0.3333 | 0.6667 | 0.5813 (4) | 0.0726 (13) | |
N1 | 0.171 (6) | 0.085 (3) | 0.493 (2) | 0.052 (5) | 0.3333 |
H1 | 0.3289 | 0.1644 | 0.5055 | 0.062* | 0.3333 |
C2 | 0.176 (3) | 0.176 (3) | 0.5000 | 0.054 (6) | 0.5 |
H2 | 0.3006 | 0.2801 | 0.5000 | 0.065* | 0.25 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Al1 | 0.0257 (6) | 0.0257 (6) | 0.0383 (10) | 0.0128 (3) | 0.000 | 0.000 |
O1 | 0.0306 (7) | 0.0357 (11) | 0.0565 (11) | 0.0179 (5) | −0.0067 (4) | −0.0134 (9) |
S1 | 0.0281 (4) | 0.0281 (4) | 0.0492 (7) | 0.0141 (2) | 0.000 | 0.000 |
O2 | 0.0314 (7) | 0.0314 (7) | 0.0813 (13) | 0.0180 (8) | −0.0021 (5) | 0.0021 (5) |
O3 | 0.086 (2) | 0.086 (2) | 0.047 (2) | 0.0428 (10) | 0.000 | 0.000 |
N1 | 0.030 (9) | 0.058 (12) | 0.057 (8) | 0.015 (4) | −0.011 (7) | −0.006 (3) |
C2 | 0.041 (6) | 0.041 (6) | 0.053 (6) | 0.001 (9) | 0.009 (4) | −0.009 (4) |
Geometric parameters (Å, º) top
Al1—O1 | 1.8741 (17) | N1—N1viii | 1.02 (4) |
Al1—O1i | 1.8741 (17) | N1—C2ix | 1.577 (10) |
Al1—O1ii | 1.8741 (17) | N1—C2x | 1.577 (10) |
Al1—O1iii | 1.8741 (17) | N1—N1x | 1.76 (6) |
Al1—O1iv | 1.8741 (17) | N1—N1xi | 1.76 (6) |
Al1—O1v | 1.8741 (17) | N1—H1 | 0.9480 |
O1—H1A | 0.9117 | N1—H2 | 1.1819 |
S1—O3 | 1.445 (4) | C2—N1ix | 0.607 (12) |
S1—O2vi | 1.4702 (19) | C2—C2ix | 1.21 (2) |
S1—O2vii | 1.4702 (19) | C2—C2viii | 1.21 (2) |
S1—O2 | 1.4702 (19) | C2—N1xi | 1.577 (11) |
N1—C2 | 0.607 (12) | C2—N1viii | 1.577 (11) |
N1—C2viii | 0.607 (12) | C2—H1 | 1.0944 |
N1—N1ix | 1.02 (4) | C2—H2 | 0.7982 |
| | | |
O1—Al1—O1i | 180.0 | C2x—N1—N1xi | 79.9 (14) |
O1—Al1—O1ii | 88.51 (7) | N1x—N1—N1xi | 59.999 (4) |
O1i—Al1—O1ii | 91.49 (7) | C2—N1—H1 | 86.6 |
O1—Al1—O1iii | 91.49 (7) | C2viii—N1—H1 | 86.6 |
O1i—Al1—O1iii | 88.51 (7) | N1ix—N1—H1 | 118.5 |
O1ii—Al1—O1iii | 180.0 | N1viii—N1—H1 | 118.5 |
O1—Al1—O1iv | 91.49 (7) | C2ix—N1—H1 | 129.3 |
O1i—Al1—O1iv | 88.51 (7) | C2x—N1—H1 | 129.3 |
O1ii—Al1—O1iv | 88.51 (8) | N1x—N1—H1 | 149.3 |
O1iii—Al1—O1iv | 91.49 (7) | N1xi—N1—H1 | 149.3 |
O1—Al1—O1v | 88.51 (7) | C2—N1—H2 | 38.2 |
O1i—Al1—O1v | 91.49 (7) | C2viii—N1—H2 | 135.4 |
O1ii—Al1—O1v | 91.49 (7) | N1ix—N1—H2 | 70.7 |
O1iii—Al1—O1v | 88.51 (8) | N1viii—N1—H2 | 165.0 |
O1iv—Al1—O1v | 180.0 | C2ix—N1—H2 | 80.9 |
Al1—O1—H1A | 127.4 | C2x—N1—H2 | 174.5 |
O3—S1—O2vi | 109.75 (9) | N1x—N1—H2 | 160.7 |
O3—S1—O2vii | 109.75 (9) | N1xi—N1—H2 | 100.9 |
O2vi—S1—O2vii | 109.19 (9) | H1—N1—H2 | 49.0 |
O3—S1—O2 | 109.75 (9) | N1ix—C2—N1 | 115 (10) |
O2vi—S1—O2 | 109.19 (9) | N1ix—C2—C2ix | 7 (2) |
O2vii—S1—O2 | 109.19 (9) | N1—C2—C2ix | 117 (5) |
C2—N1—C2viii | 167 (4) | N1ix—C2—C2viii | 117 (5) |
C2—N1—N1ix | 33 (5) | N1—C2—C2viii | 7 (2) |
C2viii—N1—N1ix | 150 (5) | C2ix—C2—C2viii | 120.000 (11) |
C2—N1—N1viii | 150 (5) | N1ix—C2—N1xi | 19 (4) |
C2viii—N1—N1viii | 33 (5) | N1—C2—N1xi | 97 (6) |
N1ix—N1—N1viii | 118.5 (10) | C2ix—C2—N1xi | 20.0 (14) |
C2—N1—C2ix | 43 (3) | C2viii—C2—N1xi | 100.1 (14) |
C2viii—N1—C2ix | 142 (6) | N1ix—C2—N1viii | 97 (6) |
N1ix—N1—C2ix | 11.2 (16) | N1—C2—N1viii | 19 (4) |
N1viii—N1—C2ix | 109.4 (16) | C2ix—C2—N1viii | 100.1 (14) |
C2—N1—C2x | 142 (6) | C2viii—C2—N1viii | 20.0 (14) |
C2viii—N1—C2x | 43 (3) | N1xi—C2—N1viii | 80 (3) |
N1ix—N1—C2x | 109.4 (16) | N1ix—C2—H1 | 169.3 |
N1viii—N1—C2x | 11.2 (16) | N1—C2—H1 | 59.8 |
C2ix—N1—C2x | 100 (3) | C2ix—C2—H1 | 175.6 |
C2—N1—N1x | 123 (5) | C2viii—C2—H1 | 56.6 |
C2viii—N1—N1x | 63 (5) | N1xi—C2—H1 | 156.7 |
N1ix—N1—N1x | 90.00 (2) | N1viii—C2—H1 | 76.4 |
N1viii—N1—N1x | 30.8 (5) | N1ix—C2—H2 | 131.2 |
C2ix—N1—N1x | 79.9 (14) | N1—C2—H2 | 113.8 |
C2x—N1—N1x | 20.0 (14) | C2ix—C2—H2 | 128.8 |
C2—N1—N1xi | 63 (5) | C2viii—C2—H2 | 111.2 |
C2viii—N1—N1xi | 123 (5) | N1xi—C2—H2 | 148.6 |
N1ix—N1—N1xi | 30.8 (5) | N1viii—C2—H2 | 131.1 |
N1viii—N1—N1xi | 90.002 (8) | H1—C2—H2 | 54.7 |
C2ix—N1—N1xi | 20.0 (14) | | |
| | | |
C2viii—N1—C2—N1ix | −111 (43) | C2x—N1—C2—C2viii | 103 (43) |
N1viii—N1—C2—N1ix | −22 (6) | N1x—N1—C2—C2viii | 111 (43) |
C2ix—N1—C2—N1ix | 7 (2) | N1xi—N1—C2—C2viii | 118 (41) |
C2x—N1—C2—N1ix | −8 (2) | C2viii—N1—C2—N1xi | −118 (42) |
N1x—N1—C2—N1ix | −0.001 (2) | N1ix—N1—C2—N1xi | −7 (2) |
N1xi—N1—C2—N1ix | 7 (2) | N1viii—N1—C2—N1xi | −29 (8) |
C2viii—N1—C2—C2ix | −118 (42) | C2ix—N1—C2—N1xi | 0.000 (1) |
N1ix—N1—C2—C2ix | −7 (2) | C2x—N1—C2—N1xi | −15 (5) |
N1viii—N1—C2—C2ix | −29 (8) | N1x—N1—C2—N1xi | −7 (2) |
C2x—N1—C2—C2ix | −15 (5) | C2viii—N1—C2—N1viii | −89 (44) |
N1x—N1—C2—C2ix | −7 (2) | N1ix—N1—C2—N1viii | 22 (6) |
N1xi—N1—C2—C2ix | 0.000 (2) | C2ix—N1—C2—N1viii | 29 (8) |
N1ix—N1—C2—C2viii | 111 (43) | C2x—N1—C2—N1viii | 14 (3) |
N1viii—N1—C2—C2viii | 89 (44) | N1x—N1—C2—N1viii | 22 (6) |
C2ix—N1—C2—C2viii | 118 (41) | N1xi—N1—C2—N1viii | 29 (8) |
Symmetry codes: (i) −x+2, −y+2, −z+2; (ii) x−y+1, x, −z+2; (iii) −x+y+1, −x+2, z; (iv) −y+2, x−y+1, z; (v) y, −x+y+1, −z+2; (vi) −y+1, x−y+1, z; (vii) −x+y, −x+1, z; (viii) y, −x+y, −z+1; (ix) x−y, x, −z+1; (x) −x+y, −x, z; (xi) −y, x−y, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···S1xii | 0.91 | 2.91 | 3.7106 (8) | 147 |
O1—H1A···O2xiii | 0.91 | 1.74 | 2.6400 (15) | 170 |
N1—H1···S1xiv | 0.95 | 3.01 | 3.64 (4) | 125 |
N1—H1···O3xiv | 0.95 | 2.16 | 3.03 (4) | 152 |
C2—H2···S1xiv | 0.80 | 3.21 | 3.700 (13) | 122 |
C2—H2···O3xiv | 0.80 | 2.47 | 3.074 (15) | 134 |
N1—H2···O3 | 1.18 | 2.66 | 3.658 (8) | 142 |
C2—H2···O3 | 0.80 | 2.66 | 3.074 (15) | 115 |
C2—H2···O3xiv | 0.80 | 2.47 | 3.074 (15) | 134 |
Symmetry codes: (xii) x+1, y, z; (xiii) −x+y+1, −x+1, z; (xiv) −x+1, −y+1, −z+1. |