Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109046460/eg3031sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109046460/eg3031Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109046460/eg3031IIsup3.hkl |
CCDC references: 765469; 765470
For related literature, see: Bruun & Larsen (1999); Gawronski & Gawronska (1999); Katagiri et al. (2009); Madsen & Larsen (2007); Ryttersgaard & Larsen (1998); Sakurai et al. (2006); Spek (2009).
Enantiomeric pure (2S,3S)-tartaric acid, (R)- and (S)-2-methylpiperazine were manufactured by Toray Fine Chemicals Co. Ltd (Japan). Both salts were prepared by heating 2 mmol quantities of (2S,3S)-tartaric acid and 1 mmol (R)-2-methylpiperazine [for (I)] or (S)-2-methylpiperazine [for (II)] under reflux in the smallest possible amount of water. Subsequent cooling to room temperature yielded a crop of colorless prisms [m.p. 455–456 K for (I) and 460–461 K for (II)]. Their melting points were measured using a melting point apparatus. The solubility of these salts in water was established by the equilibration method, i.e. by preparing a saturated solution at 303 K and determining its concentration.
In the refinement of both (I) and (II), H atoms attached to O and N atoms were located by difference Fourier analysis and refined with Uiso(H) values of 1.5Ueq(N,O). The positions of other H atoms were calculated geometrically and refined as riding, with C—H bond lengths of 0.98–1.00 Å, and with Uiso(H) values of 1.2Ueq(C) or 1.5Ueq(methyl C). In both (I) and (II), in the absence of significant anomalous scattering effects, Friedel pairs were merged, and the absolute configurations was assigned from the known configuration of (2S,3S)- tartaric acid.
For both compounds, data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and PLATON (Spek, 2009); software used to prepare material for publication: Yadokari-XG 2009 (Wakita, 2001; Kabuto et al., 2009).
C5H14N22+·2C4H5O6−·H2O | F(000) = 888 |
Mr = 418.36 | Dx = 1.582 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71075 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 25752 reflections |
a = 7.5571 (2) Å | θ = 3.5–27.5° |
b = 7.7903 (3) Å | µ = 0.14 mm−1 |
c = 29.8324 (8) Å | T = 108 K |
V = 1756.30 (9) Å3 | Prism, colourless |
Z = 4 | 0.60 × 0.60 × 0.60 mm |
Rigaku R-AXIS RAPID diffractometer | 2331 independent reflections |
Radiation source: rotating anode | 2271 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
ω scans | θmax = 27.5°, θmin = 3.0° |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −9→9 |
Tmin = 0.919, Tmax = 0.919 | k = −10→10 |
26023 measured reflections | l = −37→38 |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.025 | w = 1/[σ2(Fo2) + (0.0302P)2 + 0.6376P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.062 | (Δ/σ)max < 0.001 |
S = 1.11 | Δρmax = 0.33 e Å−3 |
2331 reflections | Δρmin = −0.19 e Å−3 |
291 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.099 (3) |
Primary atom site location: structure-invariant direct methods | Absolute structure: see text |
Secondary atom site location: difference Fourier map |
C5H14N22+·2C4H5O6−·H2O | V = 1756.30 (9) Å3 |
Mr = 418.36 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 7.5571 (2) Å | µ = 0.14 mm−1 |
b = 7.7903 (3) Å | T = 108 K |
c = 29.8324 (8) Å | 0.60 × 0.60 × 0.60 mm |
Rigaku R-AXIS RAPID diffractometer | 2331 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 2271 reflections with I > 2σ(I) |
Tmin = 0.919, Tmax = 0.919 | Rint = 0.024 |
26023 measured reflections |
R[F2 > 2σ(F2)] = 0.025 | 0 restraints |
wR(F2) = 0.062 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.11 | Δρmax = 0.33 e Å−3 |
2331 reflections | Δρmin = −0.19 e Å−3 |
291 parameters | Absolute structure: see text |
Experimental. Higashi, T. (1995). Program for Absorption Correction. Rigaku Corporation, Tokyo, Japan. |
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. |
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. |
x | y | z | Uiso*/Ueq | ||
N1 | 0.0917 (2) | 0.02318 (18) | 0.11013 (5) | 0.0126 (3) | |
H1A | 0.081 (3) | 0.042 (3) | 0.0804 (7) | 0.019* | |
H1B | 0.102 (3) | −0.093 (3) | 0.1142 (7) | 0.019* | |
N2 | 0.08325 (18) | 0.36636 (19) | 0.14444 (5) | 0.0094 (3) | |
H2A | 0.093 (3) | 0.354 (3) | 0.1737 (7) | 0.014* | |
H2B | 0.076 (3) | 0.473 (3) | 0.1385 (7) | 0.014* | |
O1 | 0.37535 (15) | 0.58168 (16) | 0.03444 (4) | 0.0106 (2) | |
H1C | 0.374 (3) | 0.613 (3) | 0.0081 (7) | 0.016* | |
O2 | 0.67895 (15) | 0.56716 (16) | −0.02386 (4) | 0.0105 (2) | |
H2C | 0.786 (3) | 0.598 (3) | −0.0301 (7) | 0.016* | |
O3 | 0.37191 (16) | 0.23774 (16) | 0.22492 (4) | 0.0116 (2) | |
H3A | 0.377 (3) | 0.346 (3) | 0.2214 (7) | 0.017* | |
O4 | 0.37805 (17) | 0.46728 (15) | 0.30267 (4) | 0.0133 (3) | |
H4A | 0.469 (3) | 0.502 (3) | 0.2954 (8) | 0.020* | |
O5 | 0.01431 (14) | 0.22908 (16) | 0.30431 (4) | 0.0118 (2) | |
H5A | −0.117 (3) | 0.263 (3) | 0.3010 (7) | 0.018* | |
O9 | 0.61255 (17) | 0.21613 (15) | 0.05092 (4) | 0.0129 (2) | |
H9A | 0.585 (3) | 0.104 (3) | 0.0454 (7) | 0.019* | |
O6 | 0.02777 (16) | 0.32806 (19) | 0.23426 (4) | 0.0178 (3) | |
O10 | 0.55030 (16) | 0.24894 (16) | −0.02226 (4) | 0.0149 (3) | |
O7 | 0.70272 (15) | 0.32862 (16) | 0.30073 (4) | 0.0144 (2) | |
O11 | 0.78684 (15) | 0.79983 (16) | 0.05636 (4) | 0.0134 (2) | |
O8 | 0.60285 (17) | 0.06174 (16) | 0.31247 (4) | 0.0140 (2) | |
O12 | 0.51470 (16) | 0.89873 (16) | 0.04456 (4) | 0.0139 (3) | |
C1 | 0.2426 (2) | 0.3002 (2) | 0.12048 (5) | 0.0114 (3) | |
H1D | 0.3501 | 0.3563 | 0.1326 | 0.014* | |
H1E | 0.2338 | 0.3283 | 0.0882 | 0.014* | |
C2 | 0.2571 (2) | 0.1083 (2) | 0.12630 (5) | 0.0125 (3) | |
H2D | 0.3598 | 0.0648 | 0.1091 | 0.015* | |
H2E | 0.2761 | 0.0807 | 0.1583 | 0.015* | |
C3 | −0.0669 (2) | 0.0886 (2) | 0.13440 (5) | 0.0119 (3) | |
H3B | −0.0564 | 0.0616 | 0.1667 | 0.014* | |
H3C | −0.1745 | 0.0313 | 0.1228 | 0.014* | |
C4 | −0.0833 (2) | 0.2816 (2) | 0.12816 (5) | 0.0101 (3) | |
H4B | −0.0973 | 0.3064 | 0.0955 | 0.012* | |
C5 | −0.2433 (2) | 0.3506 (2) | 0.15276 (5) | 0.0141 (3) | |
H5B | −0.2353 | 0.3198 | 0.1846 | 0.021* | |
H5C | −0.3510 | 0.3007 | 0.1399 | 0.021* | |
H5D | −0.2473 | 0.4758 | 0.1498 | 0.021* | |
C6 | 0.6054 (2) | 0.3044 (2) | 0.01313 (5) | 0.0093 (3) | |
C7 | 0.6750 (2) | 0.4865 (2) | 0.01857 (5) | 0.0084 (3) | |
H7A | 0.7970 | 0.4833 | 0.0315 | 0.010* | |
C8 | 0.5540 (2) | 0.5927 (2) | 0.04898 (5) | 0.0087 (3) | |
H8A | 0.5613 | 0.5445 | 0.0800 | 0.010* | |
C9 | 0.6245 (2) | 0.7788 (2) | 0.05014 (5) | 0.0092 (3) | |
C10 | 0.0967 (2) | 0.2597 (2) | 0.26679 (5) | 0.0102 (3) | |
C11 | 0.2898 (2) | 0.2035 (2) | 0.26652 (5) | 0.0093 (3) | |
H11A | 0.2923 | 0.0764 | 0.2712 | 0.011* | |
C12 | 0.3910 (2) | 0.2864 (2) | 0.30557 (5) | 0.0096 (3) | |
H12A | 0.3325 | 0.2498 | 0.3341 | 0.011* | |
C13 | 0.5816 (2) | 0.2182 (2) | 0.30619 (5) | 0.0095 (3) | |
O1W | 0.08688 (17) | 0.66356 (16) | 0.09223 (4) | 0.0123 (2) | |
H1W | −0.006 (3) | 0.692 (3) | 0.0789 (7) | 0.018* | |
H2W | 0.165 (3) | 0.639 (3) | 0.0718 (7) | 0.018* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0155 (7) | 0.0093 (6) | 0.0130 (6) | 0.0006 (6) | 0.0024 (6) | −0.0014 (5) |
N2 | 0.0112 (6) | 0.0074 (6) | 0.0096 (6) | −0.0003 (6) | −0.0005 (5) | 0.0004 (5) |
O1 | 0.0077 (5) | 0.0119 (6) | 0.0124 (5) | −0.0006 (5) | 0.0003 (4) | 0.0002 (5) |
O2 | 0.0101 (5) | 0.0115 (6) | 0.0100 (5) | −0.0008 (5) | 0.0012 (4) | 0.0031 (4) |
O3 | 0.0133 (5) | 0.0109 (6) | 0.0107 (5) | 0.0001 (5) | 0.0040 (4) | 0.0006 (4) |
O4 | 0.0088 (5) | 0.0081 (6) | 0.0229 (6) | −0.0001 (5) | 0.0031 (5) | −0.0011 (5) |
O5 | 0.0080 (5) | 0.0160 (6) | 0.0114 (5) | −0.0001 (5) | 0.0009 (4) | 0.0019 (5) |
O9 | 0.0186 (6) | 0.0073 (5) | 0.0127 (5) | −0.0025 (5) | −0.0024 (5) | 0.0009 (4) |
O6 | 0.0130 (5) | 0.0279 (7) | 0.0125 (5) | 0.0050 (6) | −0.0011 (4) | 0.0048 (5) |
O10 | 0.0183 (6) | 0.0139 (6) | 0.0124 (5) | −0.0031 (5) | −0.0021 (4) | −0.0029 (5) |
O7 | 0.0082 (5) | 0.0121 (6) | 0.0228 (6) | −0.0005 (5) | 0.0014 (4) | −0.0010 (5) |
O11 | 0.0097 (5) | 0.0113 (6) | 0.0193 (5) | −0.0008 (5) | −0.0022 (4) | −0.0009 (5) |
O8 | 0.0143 (5) | 0.0103 (5) | 0.0174 (5) | 0.0019 (5) | −0.0004 (5) | 0.0004 (5) |
O12 | 0.0119 (6) | 0.0072 (6) | 0.0226 (6) | 0.0008 (5) | −0.0023 (5) | 0.0005 (5) |
C1 | 0.0103 (7) | 0.0125 (7) | 0.0115 (6) | −0.0008 (6) | 0.0010 (5) | −0.0005 (6) |
C2 | 0.0113 (7) | 0.0140 (8) | 0.0120 (7) | 0.0026 (7) | 0.0011 (6) | −0.0007 (6) |
C3 | 0.0123 (7) | 0.0082 (7) | 0.0151 (7) | −0.0009 (6) | 0.0034 (6) | −0.0021 (6) |
C4 | 0.0093 (7) | 0.0107 (7) | 0.0104 (6) | 0.0005 (6) | −0.0010 (5) | −0.0007 (6) |
C5 | 0.0117 (7) | 0.0158 (8) | 0.0148 (7) | 0.0037 (7) | −0.0009 (6) | −0.0037 (6) |
C6 | 0.0075 (6) | 0.0086 (7) | 0.0117 (7) | 0.0014 (6) | 0.0007 (6) | −0.0011 (6) |
C7 | 0.0100 (7) | 0.0064 (7) | 0.0087 (6) | 0.0002 (6) | 0.0002 (5) | 0.0008 (6) |
C8 | 0.0085 (7) | 0.0073 (7) | 0.0104 (6) | 0.0004 (6) | 0.0005 (6) | −0.0003 (6) |
C9 | 0.0119 (7) | 0.0082 (7) | 0.0077 (6) | 0.0003 (6) | 0.0007 (6) | −0.0008 (6) |
C10 | 0.0100 (7) | 0.0094 (7) | 0.0113 (6) | −0.0018 (7) | −0.0004 (5) | −0.0015 (6) |
C11 | 0.0094 (7) | 0.0090 (7) | 0.0094 (6) | −0.0003 (6) | 0.0011 (5) | 0.0009 (6) |
C12 | 0.0090 (7) | 0.0080 (7) | 0.0118 (6) | 0.0001 (6) | 0.0004 (6) | 0.0005 (6) |
C13 | 0.0096 (7) | 0.0112 (7) | 0.0076 (6) | 0.0006 (6) | −0.0002 (5) | −0.0016 (6) |
O1W | 0.0118 (5) | 0.0120 (6) | 0.0132 (5) | 0.0024 (5) | 0.0010 (5) | 0.0015 (4) |
N1—C3 | 1.490 (2) | C1—C2 | 1.509 (2) |
N1—C2 | 1.495 (2) | C1—H1D | 0.9900 |
N1—H1A | 0.90 (2) | C1—H1E | 0.9900 |
N1—H1B | 0.91 (3) | C2—H2D | 0.9900 |
N2—C1 | 1.492 (2) | C2—H2E | 0.9900 |
N2—C4 | 1.502 (2) | C3—C4 | 1.520 (2) |
N2—H2A | 0.88 (2) | C3—H3B | 0.9900 |
N2—H2B | 0.85 (2) | C3—H3C | 0.9900 |
O1—C8 | 1.4203 (19) | C4—C5 | 1.514 (2) |
O1—H1C | 0.82 (2) | C4—H4B | 1.0000 |
O2—C7 | 1.4134 (17) | C5—H5B | 0.9800 |
O2—H2C | 0.86 (2) | C5—H5C | 0.9800 |
O3—C11 | 1.4127 (17) | C5—H5D | 0.9800 |
O3—H3A | 0.85 (3) | C6—C7 | 1.522 (2) |
O4—C12 | 1.4149 (19) | C7—C8 | 1.531 (2) |
O4—H4A | 0.77 (3) | C7—H7A | 1.0000 |
O5—C10 | 1.3028 (19) | C8—C9 | 1.545 (2) |
O5—H5A | 1.03 (2) | C8—H8A | 1.0000 |
O9—C6 | 1.3216 (19) | C10—C11 | 1.524 (2) |
O9—H9A | 0.91 (2) | C11—C12 | 1.536 (2) |
O6—C10 | 1.223 (2) | C11—H11A | 1.0000 |
O10—C6 | 1.2143 (18) | C12—C13 | 1.536 (2) |
O7—C13 | 1.266 (2) | C12—H12A | 1.0000 |
O11—C9 | 1.252 (2) | O1W—H1W | 0.84 (2) |
O8—C13 | 1.243 (2) | O1W—H2W | 0.87 (2) |
O12—C9 | 1.261 (2) | ||
C3—N1—C2 | 111.33 (12) | C4—C5—H5C | 109.5 |
C3—N1—H1A | 110.4 (15) | H5B—C5—H5C | 109.5 |
C2—N1—H1A | 108.6 (15) | C4—C5—H5D | 109.5 |
C3—N1—H1B | 110.1 (15) | H5B—C5—H5D | 109.5 |
C2—N1—H1B | 108.7 (15) | H5C—C5—H5D | 109.5 |
H1A—N1—H1B | 108 (2) | O10—C6—O9 | 124.81 (15) |
C1—N2—C4 | 111.69 (12) | O10—C6—C7 | 122.87 (14) |
C1—N2—H2A | 111.8 (14) | O9—C6—C7 | 112.33 (12) |
C4—N2—H2A | 109.8 (14) | O2—C7—C6 | 109.05 (12) |
C1—N2—H2B | 106.9 (15) | O2—C7—C8 | 107.65 (12) |
C4—N2—H2B | 107.8 (15) | C6—C7—C8 | 111.14 (12) |
H2A—N2—H2B | 109 (2) | O2—C7—H7A | 109.7 |
C8—O1—H1C | 106.8 (16) | C6—C7—H7A | 109.7 |
C7—O2—H2C | 109.6 (14) | C8—C7—H7A | 109.7 |
C11—O3—H3A | 108.4 (15) | O1—C8—C7 | 110.74 (12) |
C12—O4—H4A | 108 (2) | O1—C8—C9 | 113.04 (13) |
C10—O5—H5A | 109.2 (12) | C7—C8—C9 | 108.33 (12) |
C6—O9—H9A | 109.4 (14) | O1—C8—H8A | 108.2 |
N2—C1—C2 | 110.21 (14) | C7—C8—H8A | 108.2 |
N2—C1—H1D | 109.6 | C9—C8—H8A | 108.2 |
C2—C1—H1D | 109.6 | O11—C9—O12 | 124.59 (16) |
N2—C1—H1E | 109.6 | O11—C9—C8 | 117.66 (14) |
C2—C1—H1E | 109.6 | O12—C9—C8 | 117.74 (13) |
H1D—C1—H1E | 108.1 | O6—C10—O5 | 123.92 (15) |
N1—C2—C1 | 109.98 (14) | O6—C10—C11 | 121.91 (14) |
N1—C2—H2D | 109.7 | O5—C10—C11 | 114.17 (13) |
C1—C2—H2D | 109.7 | O3—C11—C10 | 111.77 (12) |
N1—C2—H2E | 109.7 | O3—C11—C12 | 111.61 (13) |
C1—C2—H2E | 109.7 | C10—C11—C12 | 110.59 (12) |
H2D—C2—H2E | 108.2 | O3—C11—H11A | 107.5 |
N1—C3—C4 | 110.13 (14) | C10—C11—H11A | 107.5 |
N1—C3—H3B | 109.6 | C12—C11—H11A | 107.5 |
C4—C3—H3B | 109.6 | O4—C12—C11 | 109.77 (13) |
N1—C3—H3C | 109.6 | O4—C12—C13 | 114.21 (13) |
C4—C3—H3C | 109.6 | C11—C12—C13 | 109.29 (12) |
H3B—C3—H3C | 108.1 | O4—C12—H12A | 107.8 |
N2—C4—C5 | 110.90 (13) | C11—C12—H12A | 107.8 |
N2—C4—C3 | 109.09 (14) | C13—C12—H12A | 107.8 |
C5—C4—C3 | 110.89 (14) | O8—C13—O7 | 126.30 (16) |
N2—C4—H4B | 108.6 | O8—C13—C12 | 117.51 (15) |
C5—C4—H4B | 108.6 | O7—C13—C12 | 116.18 (14) |
C3—C4—H4B | 108.6 | H1W—O1W—H2W | 107 (2) |
C4—C5—H5B | 109.5 | ||
C4—N2—C1—C2 | −57.75 (17) | O1—C8—C9—O11 | −170.15 (13) |
C3—N1—C2—C1 | −57.87 (17) | C7—C8—C9—O11 | −47.05 (18) |
N2—C1—C2—N1 | 56.63 (16) | O1—C8—C9—O12 | 9.52 (19) |
C2—N1—C3—C4 | 58.55 (17) | C7—C8—C9—O12 | 132.63 (14) |
C1—N2—C4—C5 | −179.89 (13) | O6—C10—C11—O3 | −1.0 (2) |
C1—N2—C4—C3 | 57.69 (17) | O5—C10—C11—O3 | 179.26 (14) |
N1—C3—C4—N2 | −57.33 (17) | O6—C10—C11—C12 | 124.02 (17) |
N1—C3—C4—C5 | −179.76 (12) | O5—C10—C11—C12 | −55.72 (18) |
O10—C6—C7—O2 | −5.5 (2) | O3—C11—C12—O4 | 67.41 (17) |
O9—C6—C7—O2 | 174.48 (13) | C10—C11—C12—O4 | −57.70 (17) |
O10—C6—C7—C8 | 113.06 (17) | O3—C11—C12—C13 | −58.57 (17) |
O9—C6—C7—C8 | −67.00 (16) | C10—C11—C12—C13 | 176.33 (12) |
O2—C7—C8—O1 | 68.02 (16) | O4—C12—C13—O8 | 174.12 (14) |
C6—C7—C8—O1 | −51.34 (16) | C11—C12—C13—O8 | −62.50 (18) |
O2—C7—C8—C9 | −56.47 (15) | O4—C12—C13—O7 | −5.04 (19) |
C6—C7—C8—C9 | −175.83 (12) | C11—C12—C13—O7 | 118.34 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2i | 0.90 (2) | 2.03 (2) | 2.7484 (19) | 136 (2) |
N1—H1A···O10i | 0.90 (2) | 2.39 (2) | 3.1814 (19) | 146 (2) |
O1W—H1W···O11ii | 0.84 (2) | 1.90 (2) | 2.7227 (17) | 168 (2) |
N1—H1B···O1Wiii | 0.92 (2) | 2.01 (2) | 2.8522 (19) | 152.1 (19) |
O1W—H2W···O1 | 0.87 (2) | 1.99 (2) | 2.8516 (17) | 169 (2) |
N2—H2A···O6 | 0.88 (2) | 1.88 (2) | 2.7285 (19) | 160 (2) |
N2—H2B···O1W | 0.85 (2) | 2.03 (2) | 2.7906 (19) | 149 (2) |
O3—H3A···O8iv | 0.85 (2) | 1.97 (2) | 2.7661 (18) | 156 (2) |
O4—H4A···O7 | 0.77 (2) | 2.23 (2) | 2.6815 (17) | 118 (2) |
O4—H4A···O3iv | 0.77 (2) | 2.28 (2) | 2.9474 (17) | 146 (2) |
O5—H5A···O7ii | 1.03 (2) | 1.46 (2) | 2.4814 (16) | 172.3 (19) |
O1—H1C···O2 | 0.82 (2) | 2.52 (2) | 2.8813 (16) | 107.9 (18) |
O1—H1C···O11v | 0.82 (2) | 2.14 (2) | 2.9389 (17) | 163 (2) |
O2—H2C···O1vi | 0.86 (2) | 2.59 (2) | 3.1283 (17) | 121.5 (18) |
O2—H2C···O12vi | 0.86 (2) | 1.78 (2) | 2.6249 (17) | 165 (2) |
O9—H9A···O12iii | 0.91 (2) | 1.69 (2) | 2.5878 (17) | 169 (2) |
C1—H1D···O8iv | 0.99 | 2.32 | 3.085 (2) | 133 |
C1—H1E···O10i | 0.99 | 2.48 | 3.2930 (19) | 139 |
C2—H2D···O12iii | 0.99 | 2.60 | 3.5216 (19) | 155 |
C2—H2E···O3 | 0.99 | 2.44 | 3.2288 (19) | 136 |
C2—H2E···O7vii | 0.99 | 2.32 | 3.095 (2) | 135 |
C4—H4B···O10i | 1.00 | 2.49 | 3.3252 (19) | 141 |
C5—H5B···O6 | 0.98 | 2.48 | 3.1841 (19) | 128 |
Symmetry codes: (i) x−1/2, −y+1/2, −z; (ii) x−1, y, z; (iii) x, y−1, z; (iv) −x+1, y+1/2, −z+1/2; (v) x−1/2, −y+3/2, −z; (vi) x+1/2, −y+3/2, −z; (vii) −x+1, y−1/2, −z+1/2. |
C5H14N22+·2C4H5O6−·H2O | F(000) = 888 |
Mr = 418.36 | Dx = 1.573 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71075 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 26172 reflections |
a = 7.6062 (3) Å | θ = 3.0–27.6° |
b = 7.6426 (3) Å | µ = 0.14 mm−1 |
c = 30.3987 (11) Å | T = 103 K |
V = 1767.11 (12) Å3 | Prism, colourless |
Z = 4 | 0.60 × 0.50 × 0.30 mm |
Rigaku R-AXIS RAPID diffractometer | 2342 independent reflections |
Radiation source: rotating anode | 2193 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.063 |
ω scans | θmax = 27.5°, θmin = 3.3° |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −9→9 |
Tmin = 0.920, Tmax = 0.959 | k = −9→9 |
27022 measured reflections | l = −39→39 |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.035 | w = 1/[σ2(Fo2) + (0.0421P)2 + 0.7169P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.088 | (Δ/σ)max < 0.001 |
S = 1.07 | Δρmax = 0.28 e Å−3 |
2342 reflections | Δρmin = −0.19 e Å−3 |
291 parameters | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0134 (17) |
Primary atom site location: structure-invariant direct methods | Absolute structure: see text |
Secondary atom site location: difference Fourier map |
C5H14N22+·2C4H5O6−·H2O | V = 1767.11 (12) Å3 |
Mr = 418.36 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 7.6062 (3) Å | µ = 0.14 mm−1 |
b = 7.6426 (3) Å | T = 103 K |
c = 30.3987 (11) Å | 0.60 × 0.50 × 0.30 mm |
Rigaku R-AXIS RAPID diffractometer | 2342 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 2193 reflections with I > 2σ(I) |
Tmin = 0.920, Tmax = 0.959 | Rint = 0.063 |
27022 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.088 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.28 e Å−3 |
2342 reflections | Δρmin = −0.19 e Å−3 |
291 parameters | Absolute structure: see text |
Experimental. Higashi, T. (1995). Program for Absorption Correction. Rigaku Corporation, Tokyo, Japan. |
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. |
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. |
x | y | z | Uiso*/Ueq | ||
N1 | 0.8714 (3) | 0.4953 (3) | 0.09996 (7) | 0.0219 (4) | |
H1A | 0.935 (5) | 0.450 (4) | 0.0782 (10) | 0.033* | |
H1B | 0.894 (4) | 0.436 (4) | 0.1250 (10) | 0.033* | |
N2 | 0.6229 (3) | 0.7550 (3) | 0.12585 (7) | 0.0213 (4) | |
H2A | 0.601 (4) | 0.806 (4) | 0.0997 (9) | 0.032* | |
H2B | 0.545 (5) | 0.803 (4) | 0.1485 (9) | 0.032* | |
O3 | 0.0952 (2) | 0.1001 (2) | 0.16180 (6) | 0.0225 (4) | |
H3A | 0.127 (4) | 0.145 (4) | 0.1381 (10) | 0.034* | |
O2 | 0.3118 (2) | 1.2459 (2) | 0.05752 (6) | 0.0247 (4) | |
H2C | 0.268 (5) | 1.342 (5) | 0.0511 (10) | 0.037* | |
O4 | 0.4632 (2) | 0.0755 (2) | 0.15900 (5) | 0.0218 (3) | |
H4A | 0.569 (5) | 0.125 (4) | 0.1621 (10) | 0.033* | |
O1 | 0.3273 (2) | 0.8915 (2) | 0.07987 (5) | 0.0225 (4) | |
H1C | 0.353 (5) | 0.971 (4) | 0.0938 (10) | 0.034* | |
O5 | 0.3245 (2) | 0.4512 (2) | 0.21533 (5) | 0.0236 (4) | |
H5A | 0.341 (5) | 0.571 (4) | 0.2091 (9) | 0.035* | |
O9 | −0.0416 (3) | 0.9843 (2) | 0.01529 (5) | 0.0232 (4) | |
H9A | −0.144 (5) | 0.968 (4) | 0.0246 (10) | 0.035* | |
O6 | 0.1732 (2) | 0.4390 (2) | 0.15176 (5) | 0.0252 (4) | |
O10 | −0.0263 (2) | 1.1501 (2) | 0.07587 (5) | 0.0242 (4) | |
O7 | 0.2317 (2) | −0.1186 (2) | 0.24897 (5) | 0.0260 (4) | |
O11 | 0.6483 (2) | 0.9240 (2) | 0.04364 (5) | 0.0253 (4) | |
O8 | 0.4003 (2) | −0.2358 (2) | 0.19634 (5) | 0.0236 (4) | |
O12 | 0.5442 (2) | 1.0270 (2) | −0.01993 (5) | 0.0234 (4) | |
C1 | 0.5714 (3) | 0.5675 (3) | 0.12247 (8) | 0.0230 (5) | |
H1D | 0.4457 | 0.5591 | 0.1143 | 0.028* | |
H1E | 0.5872 | 0.5100 | 0.1514 | 0.028* | |
C2 | 0.6810 (3) | 0.4757 (3) | 0.08857 (8) | 0.0234 (5) | |
H2D | 0.6495 | 0.3500 | 0.0876 | 0.028* | |
H2E | 0.6583 | 0.5266 | 0.0592 | 0.028* | |
C3 | 0.9251 (3) | 0.6837 (3) | 0.10287 (7) | 0.0217 (5) | |
H3B | 0.9122 | 0.7392 | 0.0736 | 0.026* | |
H3C | 1.0504 | 0.6909 | 0.1115 | 0.026* | |
C4 | 0.8140 (3) | 0.7826 (3) | 0.13628 (7) | 0.0220 (5) | |
H4B | 0.8391 | 0.9100 | 0.1322 | 0.026* | |
C5 | 0.8526 (4) | 0.7390 (3) | 0.18414 (7) | 0.0254 (5) | |
H5B | 0.7749 | 0.8074 | 0.2032 | 0.038* | |
H5C | 0.9754 | 0.7676 | 0.1908 | 0.038* | |
H5D | 0.8326 | 0.6139 | 0.1892 | 0.038* | |
C6 | 0.0401 (3) | 1.0875 (3) | 0.04296 (7) | 0.0199 (4) | |
C7 | 0.2319 (3) | 1.1199 (3) | 0.03011 (7) | 0.0199 (4) | |
H7A | 0.2381 | 1.1593 | −0.0012 | 0.024* | |
C8 | 0.3355 (3) | 0.9491 (3) | 0.03560 (7) | 0.0201 (5) | |
H8A | 0.2765 | 0.8583 | 0.0171 | 0.024* | |
C9 | 0.5247 (3) | 0.9702 (3) | 0.01824 (7) | 0.0199 (5) | |
C13 | 0.3311 (3) | −0.1080 (3) | 0.21661 (7) | 0.0206 (5) | |
C12 | 0.3726 (3) | 0.0777 (3) | 0.20004 (7) | 0.0199 (5) | |
H12A | 0.4475 | 0.1384 | 0.2223 | 0.024* | |
C11 | 0.2002 (3) | 0.1783 (3) | 0.19506 (7) | 0.0201 (4) | |
H11A | 0.1348 | 0.1702 | 0.2235 | 0.024* | |
C10 | 0.2313 (3) | 0.3712 (3) | 0.18505 (7) | 0.0208 (5) | |
O1W | 0.7681 (2) | 0.2438 (2) | 0.17149 (6) | 0.0244 (4) | |
H2W | 0.867 (5) | 0.187 (4) | 0.1682 (10) | 0.037* | |
H1W | 0.760 (4) | 0.268 (4) | 0.1985 (10) | 0.037* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0176 (11) | 0.0227 (9) | 0.0253 (10) | 0.0014 (8) | 0.0007 (8) | −0.0019 (8) |
N2 | 0.0193 (10) | 0.0215 (9) | 0.0232 (9) | 0.0021 (8) | −0.0012 (8) | 0.0010 (8) |
O3 | 0.0202 (9) | 0.0230 (8) | 0.0242 (8) | −0.0014 (7) | −0.0025 (7) | −0.0001 (7) |
O2 | 0.0218 (9) | 0.0206 (8) | 0.0318 (8) | −0.0015 (7) | −0.0048 (7) | −0.0024 (7) |
O4 | 0.0173 (8) | 0.0237 (8) | 0.0246 (8) | −0.0025 (7) | 0.0036 (6) | −0.0001 (6) |
O1 | 0.0197 (8) | 0.0242 (8) | 0.0235 (8) | 0.0003 (7) | 0.0000 (7) | 0.0019 (6) |
O5 | 0.0264 (10) | 0.0190 (8) | 0.0255 (8) | −0.0022 (7) | −0.0040 (7) | 0.0002 (6) |
O9 | 0.0140 (8) | 0.0293 (9) | 0.0262 (8) | −0.0026 (7) | 0.0001 (7) | −0.0022 (7) |
O6 | 0.0234 (9) | 0.0246 (8) | 0.0276 (8) | −0.0008 (7) | −0.0040 (7) | 0.0025 (7) |
O10 | 0.0218 (9) | 0.0249 (8) | 0.0259 (8) | 0.0003 (7) | 0.0030 (7) | −0.0003 (7) |
O7 | 0.0291 (10) | 0.0241 (8) | 0.0247 (8) | 0.0034 (8) | 0.0065 (7) | 0.0026 (6) |
O11 | 0.0155 (8) | 0.0337 (9) | 0.0266 (8) | 0.0011 (8) | −0.0007 (6) | 0.0050 (7) |
O8 | 0.0237 (9) | 0.0187 (8) | 0.0285 (8) | 0.0015 (7) | 0.0041 (7) | −0.0001 (7) |
O12 | 0.0198 (9) | 0.0282 (8) | 0.0222 (8) | −0.0014 (7) | −0.0007 (6) | 0.0018 (6) |
C1 | 0.0167 (11) | 0.0237 (11) | 0.0286 (11) | −0.0013 (10) | 0.0009 (9) | −0.0014 (9) |
C2 | 0.0194 (12) | 0.0259 (12) | 0.0250 (11) | −0.0010 (10) | −0.0006 (9) | −0.0027 (9) |
C3 | 0.0180 (12) | 0.0215 (11) | 0.0256 (11) | −0.0001 (9) | 0.0009 (9) | 0.0004 (9) |
C4 | 0.0190 (12) | 0.0212 (11) | 0.0258 (11) | −0.0008 (9) | −0.0002 (9) | 0.0006 (9) |
C5 | 0.0248 (13) | 0.0267 (12) | 0.0248 (11) | −0.0018 (11) | −0.0027 (9) | −0.0008 (9) |
C6 | 0.0186 (11) | 0.0201 (10) | 0.0210 (10) | 0.0015 (9) | −0.0012 (9) | 0.0024 (8) |
C7 | 0.0162 (11) | 0.0213 (10) | 0.0221 (10) | −0.0013 (9) | −0.0011 (8) | −0.0005 (8) |
C8 | 0.0166 (11) | 0.0231 (11) | 0.0208 (10) | 0.0008 (9) | −0.0001 (8) | 0.0005 (8) |
C9 | 0.0156 (11) | 0.0198 (10) | 0.0242 (10) | 0.0004 (9) | 0.0003 (8) | −0.0017 (8) |
C13 | 0.0180 (11) | 0.0203 (10) | 0.0236 (10) | 0.0003 (9) | −0.0021 (9) | 0.0004 (8) |
C12 | 0.0182 (12) | 0.0209 (10) | 0.0207 (10) | 0.0003 (9) | −0.0001 (9) | 0.0003 (8) |
C11 | 0.0189 (11) | 0.0197 (10) | 0.0216 (10) | −0.0016 (9) | −0.0012 (8) | −0.0010 (8) |
C10 | 0.0162 (11) | 0.0220 (10) | 0.0241 (10) | 0.0006 (9) | 0.0021 (9) | −0.0017 (8) |
O1W | 0.0190 (9) | 0.0280 (9) | 0.0263 (8) | 0.0007 (8) | 0.0008 (7) | −0.0023 (7) |
N1—C2 | 1.496 (3) | C1—C2 | 1.500 (3) |
N1—C3 | 1.500 (3) | C1—H1D | 0.9900 |
N1—H1A | 0.89 (3) | C1—H1E | 0.9900 |
N1—H1B | 0.90 (3) | C2—H2D | 0.9900 |
N2—C1 | 1.489 (3) | C2—H2E | 0.9900 |
N2—C4 | 1.502 (3) | C3—C4 | 1.522 (3) |
N2—H2A | 0.90 (3) | C3—H3B | 0.9900 |
N2—H2B | 0.98 (3) | C3—H3C | 0.9900 |
O3—C11 | 1.420 (3) | C4—C5 | 1.521 (3) |
O3—H3A | 0.83 (3) | C4—H4B | 1.0000 |
O2—C7 | 1.411 (3) | C5—H5B | 0.9800 |
O2—H2C | 0.83 (4) | C5—H5C | 0.9800 |
O4—C12 | 1.425 (3) | C5—H5D | 0.9800 |
O4—H4A | 0.89 (4) | C6—C7 | 1.530 (3) |
O1—C8 | 1.417 (3) | C7—C8 | 1.533 (3) |
O1—H1C | 0.76 (3) | C7—H7A | 1.0000 |
O5—C10 | 1.312 (3) | C8—C9 | 1.542 (3) |
O5—H5A | 0.94 (3) | C8—H8A | 1.0000 |
O9—C6 | 1.310 (3) | C13—C12 | 1.539 (3) |
O9—H9A | 0.84 (4) | C12—C11 | 1.528 (3) |
O6—C10 | 1.220 (3) | C12—H12A | 1.0000 |
O10—C6 | 1.218 (3) | C11—C10 | 1.524 (3) |
O7—C13 | 1.244 (3) | C11—H11A | 1.0000 |
O11—C9 | 1.267 (3) | O1W—H2W | 0.88 (4) |
O8—C13 | 1.269 (3) | O1W—H1W | 0.84 (3) |
O12—C9 | 1.248 (3) | ||
C2—N1—C3 | 111.94 (19) | C4—C5—H5C | 109.5 |
C2—N1—H1A | 108 (2) | H5B—C5—H5C | 109.5 |
C3—N1—H1A | 106 (2) | C4—C5—H5D | 109.5 |
C2—N1—H1B | 109 (2) | H5B—C5—H5D | 109.5 |
C3—N1—H1B | 112 (2) | H5C—C5—H5D | 109.5 |
H1A—N1—H1B | 109 (3) | O10—C6—O9 | 124.5 (2) |
C1—N2—C4 | 113.82 (19) | O10—C6—C7 | 122.8 (2) |
C1—N2—H2A | 108 (2) | O9—C6—C7 | 112.67 (19) |
C4—N2—H2A | 108 (2) | O2—C7—C6 | 111.71 (19) |
C1—N2—H2B | 104.6 (19) | O2—C7—C8 | 107.17 (18) |
C4—N2—H2B | 112.4 (19) | C6—C7—C8 | 108.94 (19) |
H2A—N2—H2B | 110 (3) | O2—C7—H7A | 109.7 |
C11—O3—H3A | 106 (2) | C6—C7—H7A | 109.7 |
C7—O2—H2C | 107 (2) | C8—C7—H7A | 109.7 |
C12—O4—H4A | 110 (2) | O1—C8—C7 | 110.21 (18) |
C8—O1—H1C | 106 (2) | O1—C8—C9 | 113.50 (19) |
C10—O5—H5A | 112.5 (19) | C7—C8—C9 | 110.70 (19) |
C6—O9—H9A | 108 (2) | O1—C8—H8A | 107.4 |
N2—C1—C2 | 110.6 (2) | C7—C8—H8A | 107.4 |
N2—C1—H1D | 109.5 | C9—C8—H8A | 107.4 |
C2—C1—H1D | 109.5 | O12—C9—O11 | 125.2 (2) |
N2—C1—H1E | 109.5 | O12—C9—C8 | 117.8 (2) |
C2—C1—H1E | 109.5 | O11—C9—C8 | 117.05 (19) |
H1D—C1—H1E | 108.1 | O7—C13—O8 | 125.9 (2) |
N1—C2—C1 | 109.39 (19) | O7—C13—C12 | 116.3 (2) |
N1—C2—H2D | 109.8 | O8—C13—C12 | 117.8 (2) |
C1—C2—H2D | 109.8 | O4—C12—C11 | 109.52 (18) |
N1—C2—H2E | 109.8 | O4—C12—C13 | 112.02 (19) |
C1—C2—H2E | 109.8 | C11—C12—C13 | 108.73 (19) |
H2D—C2—H2E | 108.2 | O4—C12—H12A | 108.8 |
N1—C3—C4 | 111.4 (2) | C11—C12—H12A | 108.8 |
N1—C3—H3B | 109.3 | C13—C12—H12A | 108.8 |
C4—C3—H3B | 109.3 | O3—C11—C10 | 110.63 (19) |
N1—C3—H3C | 109.3 | O3—C11—C12 | 109.95 (18) |
C4—C3—H3C | 109.3 | C10—C11—C12 | 111.9 (2) |
H3B—C3—H3C | 108.0 | O3—C11—H11A | 108.1 |
N2—C4—C5 | 111.0 (2) | C10—C11—H11A | 108.1 |
N2—C4—C3 | 109.08 (18) | C12—C11—H11A | 108.1 |
C5—C4—C3 | 115.0 (2) | O6—C10—O5 | 125.4 (2) |
N2—C4—H4B | 107.1 | O6—C10—C11 | 121.4 (2) |
C5—C4—H4B | 107.1 | O5—C10—C11 | 113.21 (19) |
C3—C4—H4B | 107.1 | H2W—O1W—H1W | 106 (3) |
C4—C5—H5B | 109.5 | ||
C4—N2—C1—C2 | −56.8 (2) | O1—C8—C9—O12 | −177.3 (2) |
C3—N1—C2—C1 | −58.1 (3) | C7—C8—C9—O12 | −52.8 (3) |
N2—C1—C2—N1 | 56.8 (2) | O1—C8—C9—O11 | 4.5 (3) |
C2—N1—C3—C4 | 57.1 (3) | C7—C8—C9—O11 | 129.0 (2) |
C1—N2—C4—C5 | −73.8 (2) | O7—C13—C12—O4 | −170.5 (2) |
C1—N2—C4—C3 | 53.9 (2) | O8—C13—C12—O4 | 9.5 (3) |
N1—C3—C4—N2 | −53.0 (2) | O7—C13—C12—C11 | −49.3 (3) |
N1—C3—C4—C5 | 72.4 (3) | O8—C13—C12—C11 | 130.7 (2) |
O10—C6—C7—O2 | −7.4 (3) | O4—C12—C11—O3 | 58.0 (2) |
O9—C6—C7—O2 | 173.59 (19) | C13—C12—C11—O3 | −64.7 (2) |
O10—C6—C7—C8 | 110.8 (2) | O4—C12—C11—C10 | −65.4 (2) |
O9—C6—C7—C8 | −68.2 (2) | C13—C12—C11—C10 | 171.88 (18) |
O2—C7—C8—O1 | 61.2 (2) | O3—C11—C10—O6 | −1.6 (3) |
C6—C7—C8—O1 | −59.8 (2) | C12—C11—C10—O6 | 121.4 (2) |
O2—C7—C8—C9 | −65.1 (2) | O3—C11—C10—O5 | 178.51 (19) |
C6—C7—C8—C9 | 173.83 (18) | C12—C11—C10—O5 | −58.5 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O10i | 0.89 (3) | 2.31 (3) | 2.846 (3) | 119 (3) |
N1—H1A···O12ii | 0.89 (3) | 1.96 (3) | 2.770 (3) | 150 (3) |
N1—H1B···O1W | 0.90 (3) | 2.25 (3) | 3.007 (3) | 141 (3) |
N1—H1B···O6iii | 0.90 (3) | 2.27 (3) | 2.817 (3) | 118 (2) |
O1—H1C···O2 | 0.77 (3) | 2.39 (3) | 2.795 (2) | 114 (3) |
O1—H1C···O4iv | 0.77 (3) | 2.30 (3) | 2.972 (2) | 148 (3) |
O1W—H1W···O7v | 0.84 (3) | 1.82 (3) | 2.637 (2) | 163 (3) |
N2—H2A···O1 | 0.90 (3) | 2.26 (3) | 2.846 (3) | 122 (2) |
N2—H2A···O11 | 0.90 (3) | 1.96 (3) | 2.820 (3) | 159 (3) |
N2—H2B···O4iv | 0.98 (3) | 2.20 (3) | 2.914 (3) | 129 (2) |
N2—H2B···O8iv | 0.98 (3) | 1.85 (3) | 2.732 (3) | 149 (3) |
O2—H2C···O12vi | 0.83 (4) | 2.19 (4) | 2.909 (2) | 145 (3) |
O1W—H2W···O3iii | 0.87 (4) | 1.87 (4) | 2.736 (2) | 171 (3) |
O3—H3A···O6 | 0.83 (3) | 2.31 (3) | 2.675 (2) | 107 (2) |
O3—H3A···O10vii | 0.83 (3) | 2.22 (3) | 2.797 (2) | 126 (3) |
O4—H4A···O1W | 0.89 (4) | 1.79 (4) | 2.679 (2) | 174 (3) |
O5—H5A···O8iv | 0.94 (3) | 1.59 (3) | 2.527 (2) | 171 (4) |
O9—H9A···O11viii | 0.84 (4) | 1.72 (4) | 2.553 (3) | 177 (3) |
C1—H1D···O6 | 0.99 | 2.54 | 3.306 (3) | 134 |
C1—H1E···O1W | 0.99 | 2.53 | 3.253 (3) | 130 |
C3—H3C···O6iii | 0.99 | 2.47 | 3.044 (3) | 117 |
C4—H4B···O3ix | 1.00 | 2.59 | 3.326 (3) | 130 |
C11—H11A···O7 | 1.00 | 2.45 | 2.809 (3) | 100 |
C12—H12A···O5 | 1.00 | 2.58 | 2.915 (3) | 100 |
Symmetry codes: (i) x+1, y−1, z; (ii) x+1/2, −y+3/2, −z; (iii) x+1, y, z; (iv) x, y+1, z; (v) −x+1, y+1/2, −z+1/2; (vi) x−1/2, −y+5/2, −z; (vii) x, y−1, z; (viii) x−1, y, z; (ix) x+1, y+1, z. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C5H14N22+·2C4H5O6−·H2O | C5H14N22+·2C4H5O6−·H2O |
Mr | 418.36 | 418.36 |
Crystal system, space group | Orthorhombic, P212121 | Orthorhombic, P212121 |
Temperature (K) | 108 | 103 |
a, b, c (Å) | 7.5571 (2), 7.7903 (3), 29.8324 (8) | 7.6062 (3), 7.6426 (3), 30.3987 (11) |
V (Å3) | 1756.30 (9) | 1767.11 (12) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.14 | 0.14 |
Crystal size (mm) | 0.60 × 0.60 × 0.60 | 0.60 × 0.50 × 0.30 |
Data collection | ||
Diffractometer | Rigaku R-AXIS RAPID diffractometer | Rigaku R-AXIS RAPID diffractometer |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.919, 0.919 | 0.920, 0.959 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 26023, 2331, 2271 | 27022, 2342, 2193 |
Rint | 0.024 | 0.063 |
(sin θ/λ)max (Å−1) | 0.649 | 0.649 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.062, 1.11 | 0.035, 0.088, 1.07 |
No. of reflections | 2331 | 2342 |
No. of parameters | 291 | 291 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.33, −0.19 | 0.28, −0.19 |
Absolute structure | See text | See text |
Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996) and PLATON (Spek, 2009), Yadokari-XG 2009 (Wakita, 2001; Kabuto et al., 2009).
C1—N2—C4—C5 | −179.89 (13) | C6—C7—C8—C9 | −175.83 (12) |
N1—C3—C4—C5 | −179.76 (12) | O3—C11—C12—O4 | 67.41 (17) |
O2—C7—C8—O1 | 68.02 (16) | C10—C11—C12—C13 | 176.33 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2i | 0.90 (2) | 2.03 (2) | 2.7484 (19) | 136 (2) |
N1—H1A···O10i | 0.90 (2) | 2.39 (2) | 3.1814 (19) | 146 (2) |
O1W—H1W···O11ii | 0.84 (2) | 1.90 (2) | 2.7227 (17) | 168 (2) |
N1—H1B···O1Wiii | 0.92 (2) | 2.01 (2) | 2.8522 (19) | 152.1 (19) |
O1W—H2W···O1 | 0.87 (2) | 1.99 (2) | 2.8516 (17) | 169 (2) |
N2—H2A···O6 | 0.88 (2) | 1.88 (2) | 2.7285 (19) | 160 (2) |
N2—H2B···O1W | 0.85 (2) | 2.03 (2) | 2.7906 (19) | 149 (2) |
O3—H3A···O8iv | 0.85 (2) | 1.97 (2) | 2.7661 (18) | 156 (2) |
O4—H4A···O3iv | 0.77 (2) | 2.28 (2) | 2.9474 (17) | 146 (2) |
O5—H5A···O7ii | 1.03 (2) | 1.46 (2) | 2.4814 (16) | 172.3 (19) |
O1—H1C···O11v | 0.82 (2) | 2.14 (2) | 2.9389 (17) | 163 (2) |
O2—H2C···O12vi | 0.86 (2) | 1.78 (2) | 2.6249 (17) | 165 (2) |
O9—H9A···O12iii | 0.91 (2) | 1.69 (2) | 2.5878 (17) | 169 (2) |
Symmetry codes: (i) x−1/2, −y+1/2, −z; (ii) x−1, y, z; (iii) x, y−1, z; (iv) −x+1, y+1/2, −z+1/2; (v) x−1/2, −y+3/2, −z; (vi) x+1/2, −y+3/2, −z. |
C1—N2—C4—C5 | −73.8 (2) | C6—C7—C8—C9 | 173.83 (18) |
N1—C3—C4—C5 | 72.4 (3) | O4—C12—C11—O3 | 58.0 (2) |
O2—C7—C8—O1 | 61.2 (2) | C13—C12—C11—C10 | 171.88 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O10i | 0.89 (3) | 2.31 (3) | 2.846 (3) | 119 (3) |
N1—H1A···O12ii | 0.89 (3) | 1.96 (3) | 2.770 (3) | 150 (3) |
N1—H1B···O1W | 0.90 (3) | 2.25 (3) | 3.007 (3) | 141 (3) |
N1—H1B···O6iii | 0.90 (3) | 2.27 (3) | 2.817 (3) | 118 (2) |
O1—H1C···O4iv | 0.77 (3) | 2.30 (3) | 2.972 (2) | 148 (3) |
O1W—H1W···O7v | 0.84 (3) | 1.82 (3) | 2.637 (2) | 163 (3) |
N2—H2A···O1 | 0.90 (3) | 2.26 (3) | 2.846 (3) | 122 (2) |
N2—H2A···O11 | 0.90 (3) | 1.96 (3) | 2.820 (3) | 159 (3) |
N2—H2B···O4iv | 0.98 (3) | 2.20 (3) | 2.914 (3) | 129 (2) |
N2—H2B···O8iv | 0.98 (3) | 1.85 (3) | 2.732 (3) | 149 (3) |
O2—H2C···O12vi | 0.83 (4) | 2.19 (4) | 2.909 (2) | 145 (3) |
O1W—H2W···O3iii | 0.87 (4) | 1.87 (4) | 2.736 (2) | 171 (3) |
O3—H3A···O10vii | 0.83 (3) | 2.22 (3) | 2.797 (2) | 126 (3) |
O4—H4A···O1W | 0.89 (4) | 1.79 (4) | 2.679 (2) | 174 (3) |
O5—H5A···O8iv | 0.94 (3) | 1.59 (3) | 2.527 (2) | 171 (4) |
O9—H9A···O11viii | 0.84 (4) | 1.72 (4) | 2.553 (3) | 177 (3) |
Symmetry codes: (i) x+1, y−1, z; (ii) x+1/2, −y+3/2, −z; (iii) x+1, y, z; (iv) x, y+1, z; (v) −x+1, y+1/2, −z+1/2; (vi) x−1/2, −y+5/2, −z; (vii) x, y−1, z; (viii) x−1, y, z. |
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Tartaric acid is one of the most readily available enantiomerically pure compounds, and is potentially useful as achiral resolving reagent for racemic amines (Gawronski & Gawronska, 1999). In the diastereomeric salts consisting of chiral amines and tartaric acids, hydrogen tartrates are often connected by an intermolecular hydrogen bond to the carboxylate group from another carboxylic acid to afford a one-dimensional chain structure, which leads to the construction of a two-dimensional sheet formed via intermolecular hydrogen bonds between hydroxy groups (Ryttersgaard & Larsen, 1998). Moreover, the chiral environment created by the layer of hydrogen tartrate ions is assumed to discriminate between the two ammonium enantiomers inside the layer, along with water molecules organizing the layer structure for the target amines (Bruun & Larsen, 1999; Sakurai et al., 2006). To evaluate their potential for use in this way, we report here the crystal structures of a pair of diastereomeric 1:2 salts, (I) and (II), of (2S,3S)- tartaric acid with (R)- and (S)-2-methylpiperazine, respectively.
In the crystal structures of both compounds, the N atoms of the 2-methylpiperazine molecule each have two H atoms, showing that these amines are completely converted to quaternary ammonium cations (Figs. 1 and 2). The C1—N2—C4—C5 and N1—C3—C4—C5 torsion angles are 179.89 (13) and 179.76 (12)° in (I), and 73.8 (2) and 72.4 (3)° in (II), respectively, indicating that the methyl groups are in the most stable equatorial position in the chair conformation of the piperazine ring in (I), whereas in (II), the methyl groups are in unstable axial position (Tables 1 and 3). Although all the tartaric acid was present as tartrate in the 1:1 salts (Katagiri et al., 2009), it was found that the two symmetrically independent tartaric acid units are present as hydrogen tartrate ions in (I) and (II) owing to the loss of a single H atom. The conformations of the hydrogen tartrate ions have roughly the same geometry around the C7—C8 and C11—C12 axes; the relevent torsion angles are given in Tables 1 and 3. The present structures of both (I) and (II) conform to the general structure for hydrogen tartrate salts, namely, these hydrogen tartrate ions form a one-dimensional chain structure (Figs. 3 and 4) connected by strong intermolecular hydrogen bonds [O5—H7···O7ii and O9—H10···O12iii in (I), and O5—H7···O8v and O9—H10···O11viii in (II); geometric details and symmetry codes are given in Tables 2 and 4). These two symmetrically independent chains are, however, skew lines that are orthogonal to each other, unlike in the case of most frequently reported types (Bruun & Larsen,1999).
Strong intermolecular O—H···O and N—H···O hydrogen bonds are observed in the packing structures, and, particularly, the piperadinium ions are tightly hydrogen bonded to water molecules and hydrogen tartrate ions in both (I) and (II) (Figs. 5 and 6, and Tables 2 and 4). The solubility of 12.7 g/100 g H2O for (I) is less than that of 33.0 g/100 g H2O for (II) at 303 K, and the crystal density of 1.582 Mg m-3 for (I) is slightly greater than that of 1.573 Mg m-3 for (II). The high packing efficiency of (I) is also evident in its higher `packing coefficient' (Spek, 2009) (75.7%), which differs by just 0.7% from the value found for (II) (75.2%), indicating that the less soluble salt (I) has a slight advantage in close packing. In contrast, there are more hydrogen bonds in the more soluble salt (II) than in the less soluble salt (I), indicating the same behavior as has been observed for 1:1 salts (Katagiri et al., 2009). The large number of hydrogen bonds in (II) is attributed to the contribution of the hydrogen bonds around the N atoms in the piperazinium ions (Figs. 7 and 8). Furthermore, the melting point of 460–461 K for (II) is higher than that of 455–456 K for (I), also suggesting that the more soluble salt (II) is stabilized to a greater extent by intermolecular hydrogen bonds.
In the less soluble salt (I), the hydrogen tartrate chains construct a two-dimensional sheet via intermolecular hydrogen bonds with the hydroxy groups, leading to the formation of a layer structure. No interaction is observed between the hydrogen tartrate layers (Fig. 5). The piperazinium ions lie between the hydrogen tartrate layers in the most stable equatorial conformation, anchored by five intermolecular hydrogen bonds formed by two tartrate ions and two water molecules (Fig. 7). The water molecules fill the structural void between the hydrogen tartrate layers. In contrast to the structure of (I), there are two independent forms of assembly of the hydrogen tartrate ions in the more soluble salt (II), and the layers are more interconnected (Fig. 6). One type of hydrogen tartrate chain is assembled by hydrogen bonds with the hydroxy groups to create a double-chain unit; no hydrogen bonds are formed between these double chains. The other type forms a sheet structure by hydrogen bonding via water molecules. Moreover, there are obvious hydrogen bonds between the hydrogen tartrate sheets, indicating that the layer-to-layer spacing is narrower than that in (I). The piperazinium ions lie between the hydrogen tartrate layers in an unstable axial conformation, which is stabilized by eight intermolecular hydrogen bonds constructed of five tartrates and a water molecule (Fig. 8). These hydrogen bonds are bifurcated and are thus estimated to be weaker than those of ordinary hydrogen bonds constituted geometrically with a single donor and acceptor. The water molecules behave as a hinge for the sheet structure of the hydrogen tartrate. The more soluble salt (II) is structurally disadvantaged in close packing, and adopts a less dense structure supported by intermolecular hydrogen bonds. These structural properties were similar to those of 1:1 salts.
The large contribution of the hydrogen bonds in the salt (II) showed a slight advantage of enthalpies. On the other hand, it has been reported that a comparison of vibrational movements observed as the equivalent isotropic parameters Ueq for all non-H atoms can be used in the calculation of solid state entropies (Madsen & Larsen, 2007). The Ueq values of the salt (II) are almost double those in (I) (Fig. 9). These results explain that the higher melting point of the less dense (II) is correlated not only with a difference in their enthalpies but also with that in their entropies.