A pair of diastereomeric 1:2 salts of (R)- and (S)-2-methyl­piperazine with (2S,3S)-tartaric acid

The crystal structures of a pair of diastereomeric 1:2 salts of (R)- and (S)-2-methyl­piperazine with (2S,3S)-tartaric acid, namely (R)-2-methyl­piperazinediium bis­[hydrogen (2S,3S)-tartrate] monohydrate, (I), and (S)-2-methyl­piperazinediium bis­[hydrogen (2S,3S)-tartrate] monohydrate, (II), both C₅H₁₄N₂²⁺·2C₄H₅O₆^-·H₂O, each reveal the formation of well-defined head-to-tail-connected hydrogen tartrate chains; these chains are linked into a two-dimensional sheet via inter­molecular hydrogen bonds involving hydr­oxy groups and water mol­ecules, resulting in a layer structure. The (R)-2-methyl­piperazinediium ions lie between the hydrogen tartrate layers in the most stable equatorial conformation in (I), whereas in (II), these ions are in an unstable axial position inside the more inter­connected layers and form a larger number of inter­molecular hydrogen bonds than are observed in (I).

S1. Comment

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···O8^v and O9—H10···O11^viii 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 U_eq for all non-H atoms can be used in the calculation of solid state entropies (Madsen & Larsen, 2007). The U_eq 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.

Related literature

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).

S2. Experimental

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.

S3. Refinement

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 U_iso(H) values of 1.5U_eq(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 U_iso(H) values of 1.2U_eq(C) or 1.5U_eq(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.

Computing details

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).

Figures

	Fig. 1. The asymmetric unit of (I), showing 50% probability displacement ellipsoids. H atoms are shown as spheres.
	Fig. 2. The asymmetric unit of (II), showing 50% probability displacement ellipsoids. H atoms are shown as spheres.
	Fig. 3. Head-to-tail-connected hydrogen tartrate chains in (I), showing the adoption of mutually orthogonal skew lines. (Symmetry codes as in Table 2.)
	Fig. 4. Head-to-tail-connected hydrogen tartrate chains in (II), showing the adoption of mutually orthogonal skew lines. (Symmetry codes as in Table 4.)
	Fig. 5. The packing of (I) along the a axis, showing the regular layers of hydrogen tartrate and piperazinium ions interconnected in the equatorial position by hydrogen bonds. (Symmetry codes as in Table 2.)
	Fig. 6. The packing of (II) along the a axis, showing the greater number of interconnected layers of hydrogen tartrate and piperazinium ions interconnected in the axial position by hydrogen bonds. (Symmetry codes as in Table 4.)
	Fig. 7. A perspective view of the partial packing of (I), showing the piperazinium ions lying in the most stable equatorial conformation, stabilized by five intermolecular hydrogen bonds formed of two tartrate ions and two water molecules. (Symmetry codes as in Table 2.)
	Fig. 8. A perspective view of the partial packing of (II), showing how the piperazinium ions lie between the hydrogen tartrate layers in the unstable axial conformation, stabilized by eight intermolecular hydrogen bonds formed by five tartrate ions and a water molecule. (Symmetry codes as in Table 4.)
	Fig. 9. Ratio between Ueq of (II) and (I), showing the comparison of differences in the Ueq values of non-H atoms.

(I) (R)-2-methylpiperazinediium bis[hydrogen (2S,3S)-tartrate] monohydrate

Crystal data

C5H14N2^2+·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) Å^3	Prism, colourless
Z = 4	0.60 × 0.60 × 0.60 mm

Data collection

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

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.025	w = 1/[σ^2(Fo^2) + (0.0302P)^2 + 0.6376P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 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+0.001xFc^2λ^3/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

Special details

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.

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

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2^i	0.90 (2)	2.03 (2)	2.7484 (19)	136 (2)
N1—H1A···O10^i	0.90 (2)	2.39 (2)	3.1814 (19)	146 (2)
O1W—H1W···O11^ii	0.84 (2)	1.90 (2)	2.7227 (17)	168 (2)
N1—H1B···O1W^iii	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···O8^iv	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···O3^iv	0.77 (2)	2.28 (2)	2.9474 (17)	146 (2)
O5—H5A···O7^ii	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···O11^v	0.82 (2)	2.14 (2)	2.9389 (17)	163 (2)
O2—H2C···O1^vi	0.86 (2)	2.59 (2)	3.1283 (17)	121.5 (18)
O2—H2C···O12^vi	0.86 (2)	1.78 (2)	2.6249 (17)	165 (2)
O9—H9A···O12^iii	0.91 (2)	1.69 (2)	2.5878 (17)	169 (2)
C1—H1D···O8^iv	0.99	2.32	3.085 (2)	133
C1—H1E···O10^i	0.99	2.48	3.2930 (19)	139
C2—H2D···O12^iii	0.99	2.60	3.5216 (19)	155
C2—H2E···O3	0.99	2.44	3.2288 (19)	136
C2—H2E···O7^vii	0.99	2.32	3.095 (2)	135
C4—H4B···O10^i	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.

(II) (S)-2-methylpiperazinediium bis[hydrogen (2S,3S)-tartrate] monohydrate

Crystal data

C5H14N2^2+·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) Å^3	Prism, colourless
Z = 4	0.60 × 0.50 × 0.30 mm

Data collection

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

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.035	w = 1/[σ^2(Fo^2) + (0.0421P)^2 + 0.7169P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 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+0.001xFc^2λ^3/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

Special details

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.

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

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O10^i	0.89 (3)	2.31 (3)	2.846 (3)	119 (3)
N1—H1A···O12^ii	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···O6^iii	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···O4^iv	0.77 (3)	2.30 (3)	2.972 (2)	148 (3)
O1W—H1W···O7^v	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···O4^iv	0.98 (3)	2.20 (3)	2.914 (3)	129 (2)
N2—H2B···O8^iv	0.98 (3)	1.85 (3)	2.732 (3)	149 (3)
O2—H2C···O12^vi	0.83 (4)	2.19 (4)	2.909 (2)	145 (3)
O1W—H2W···O3^iii	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···O10^vii	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···O8^iv	0.94 (3)	1.59 (3)	2.527 (2)	171 (4)
O9—H9A···O11^viii	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···O6^iii	0.99	2.47	3.044 (3)	117
C4—H4B···O3^ix	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.