Similarity in structures of racemic and enantiomeric ibuprofen sodium dihydrates

The crystal structures of two ibuprofen sodium dihydrates, racemic sodium (RS)-2-(4-isobutylphenyl)propanoate dihydrate or (RS)-NaIBDH, Na⁺·C₁₃H₁₇O₂^-·2H₂O, and enantiomeric sodium (S)-2-(4-isobutylphenyl)propanoate dihydrate or (S)-NaIBDH, Na⁺·C₁₃H₁₇O₂^-·2H₂O, have been determined in the space groups P and P1, respectively. The unit cells of the two triclinic structures have similar lattice parameters and cell volumes. The constituent ions have similar coordination environments, but differ slightly in their hydrogen-bonding inter­actions. The dominance of the inter­actions between the O atoms and the Na⁺ cations explains the structural similarity of these two structures, despite the fact that one is heterochiral while the other is homochiral.

S1. Comment

Ibuprofen [α-methyl-4-(isobutyl)phenylacetic acid] is a chiral non-steroidal anti-inflammatory drug (NSAID). The racemic compound, (R/S)-ibuprofen, is usually formulated as tablets or suspensions, which may be purchased without a prescription. The sodium salt of racemic ibuprofen is much more water-soluble than the free acid (Gaikar & Latha, 1997), and crystallizes from water as a dihydrate. Recent publications have described the pharmacokinetics (Soergel et al., 2005), while recent patents have disclosed the formulation of ibuprofen sodium dihydrate (Gruber, 2003; Armitage et al., 1992). This paper compares the crystal structures of racemic [(R/S)-NaIBDH] and enantiomeric [(S)-NaIBDH] ibuprofen sodium dihydrates, (I) and (II), respectively, and explains their similarity.

The ibuprofen sodium dihydrate phase is stable under ambient conditions, while the anhydrous phase is highly hygroscopic. Differential scanning carlorimetry (DSC) and thermogravimetric analysis (TGA) indicate that both structures lose two water molecules in one step. (R/S)-NaIBDH loses 13.5% of weight (theoretical value 13.6%) between 317 and 365 K. The anhydrous (R/S) salt melts at 474 K. (S)-NaIBDH loses 13.1% of weight (theoretical value 13.6%) between 314 and 362 K and the anhydrous (S) salt then melts at 507 K.

The two dihydrate structures are triclinic, with similar lattice parameters and cell volumes. For comparison, the non-reduced cell is shown here for the (S)-NaIBDH structure, while the CIF file with the structure in the reduced cell is provided in the supplementary material [lattice parameters: a = 5.7767 (5), b = 6.0797 (5) and c = 23.880 (2) Å, α = 93.499 (1), β = 93.518 (1) and γ = 118.322 (1)°, cell volume = 733.01 (11) ų]. The space group of (R/S)-NaIBDH is P1, while that of (S)-NaIBDH is P1. These two structures are very similar in their packing styles, due to the similarity of the coordination interactions. In the (R/S)-NaIBDH structure, two paired R and (S) ibuprofen anions are related by a center of symmetry. The two (S) ibuprofen anions, the two Na⁺ cations and the four water molecules in the asymmetric unit of (S)-NaIBDH are related by a pseudo twofold screw axis along the a direction. However, the ring formed by the Na⁺ cations, the water molecules and the carboxylate groups gives the impression of a pseudo center of symmetry. The two structures are shown in Figs. 1 and 2.

The structures clearly show hydrophilic and hydrophobic regions. The hydrophilic regions are formed by the network of water molecules, Na⁺ cations and carboxylate groups. The carboxylate groups on the ibuprofen molecules are bridged by the Na⁺ cations to form a one-dimensional infinite chain. In the (R/S)-NaIBDH structure, each of the two chains contains only (R) or (S) molecules, respectively. Two such chains are linked by the water molecules bridging the Na⁺ cations to form a one-dimensional infinite zipper along the a direction, approximately parallel to the (012) crystallographic plane. Such zippers stack along the b direction and interact by hydrogen bonding to form wafers, the thickness of which is the same as the length of the c dimension, parallel to the ab plane. The two sides of the thick wafers consist of the disordered isobutyl groups and form the hydrophobic regions. The thick wafers stack to form the whole crystal via weak van der Waals interactions.

The water molecule bridging the two Na⁺ cations donates two lone pairs of electrons, and also donates two H atoms to form hydrogen bonds. The other water molecule donates one lone pair of electrons to an Na⁺ cation and two H atoms for hydrogen bonding. The interactions surrounding this latter water molecule are strong enough to hinder its loss on a par with the doubly coordinated water molecule, as indicated by the dehydration behavior seen in the TGA. The relatively high stability of the dihydrate phases also explains the hygroscopicity of anhydrous ibuprofen sodium. From the point of view of the hydrogen bonding, two pairs of ibuprofen anions are bridged by two water molecules to form a ring; the rings are bridged by a third water molecule to form a one-dimensional column along the a direction. In (R/S)-NaIBDH, the ring has a centrosymmetric chair conformation, while in (S)-NaIBDH, the ring is not centrosymmetric due to the O2—H2B···O3' hydrogen bonding (Figs. 3 and 4). The hydrogen-bonding geometries of the two structures are provided in Tables 1 and 2.

Each Na⁺ cation has close contact with three O atoms of the water molecules and two O atoms of two carboxylate groups to form a pyramidal coordination. Two neighboring Na⁺ cations are bridged by a pair of water O atoms to form a square plane. The Na⁺ cations are linked by carboxylate groups to form one-dimensional chains. Each carboxylate group coordinates to two Na⁺ cations and also acts as the proton acceptor for H atoms of three water molecules.

The similarities between the racemic and enantiomeric crystal structures have been observed for other organic molecules, as summarized in Table 3. Comparison shows that one type of structure has two molecules in the asymmetric unit of the enantiomeric structure, which is similar to one pair of asymmetric units in the centrosymmetric structure. In the other type, the unit cell is doubled in the racemic structure and both structures have two molecules in their asymmetric units. Although these structures are similar in packing style, differences arise from the chirality.

This research demonstrates that the dominant interaction for the packing of ibuprofen sodium dihydrate structures is the cation coordination, although the influence of chirality is also seen in the hydrogen-bonding interactions.

S2. Experimental

R/S-Ibuprofen sodium was purchased from Sigma (Saint Louis, Missouri). Enantiomeric S-ibuprofen sodium anhydrate was prepared by the method of Zhang et al. (2003). The respective dihydrate crystals of diffraction quality crystallized as thin plates by slow evaporation of a solution of the corresponding anhydrous sodium salt in water–acetonitrile (Ratio of solvents?). The crystals obtained were stored in contact with their mother liquor.

S3. Refinement

The absolute configuration was known for S-NaIBDH from the synthesis. This experiment did not attempt to determine the absolute structure. Friedel pairs were merged before refinement. The disordered iso-butyl group in (R/S)-NaIBDH was modeled as two fragments, while that in (S)-NaIBDH was modeled as one fragment, due to the instability of the constrained refinement as two fragments. The CH₂–CH₃ C—C distances in the iso-butyl group were constrained to be identical. The displacement parameters of all H atoms were constrained to be identical in each structure. Water H atoms were constrained to have identical O—H bond distances [Not identical in CIF tables?]. All other H atoms were refined using a riding model, with geometry idealized (C—H = 0.93–1.00 Å). [Please check added text.]

Computing details

For both compounds, data collection: SMART (Bruker, 2001); cell refinement: SMART; data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXL97 and SHELXTL (Bruker, 2000); software used to prepare material for publication: PLATON (Spek, 2003).

Figures

	Fig. 1. A plot of the asymmetric unit of (R/S)-ibuprofen sodium dihydrate, (I). Displacement ellipsoids are drawn at the 50% probability level. The disordered fragment with shaded bonds consists of atoms C11, C12 and C13, while that with unshaded bonds consists of atoms C11S, C12S and C13S.
	Fig. 2. A plot of the asymmetric unit of (S)- ibuprofen sodium dihydrate, (II). Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 3. Interactions in the (R/S)-ibuprofen sodium dihydrate crystal. The disordered fragment has been truncated for clarity. [Symmetry code: (i) x − 1, y + 1, z.]
	Fig. 4. Interactions in the (S)-ibuprofen sodium dihydrate crystal. [Symmetry codes: (i) x − 1, y, z − 1; (ii) x, y − 1, z − 1.]

(I) sodium (RS)-α-methyl [4-(isobutyl)phenyl]acetate dihydrate

Crystal data

Na^+·C13H17O2^−·2H2O	Z = 2
Mr = 264.29	F(000) = 284
Triclinic, P1	Dx = 1.202 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.7396 (4) Å	Cell parameters from 2507 reflections
b = 6.0284 (4) Å	θ = 1.8–27.0°
c = 23.8301 (17) Å	µ = 0.11 mm^−1
α = 83.457 (1)°	T = 173 K
β = 89.241 (1)°	Plate, colorless
γ = 63.154 (1)°	0.40 × 0.30 × 0.10 mm
V = 730.20 (9) Å^3

Data collection

Bruker SMART 1000 CCD area-detector diffractometer	3317 independent reflections
Radiation source: fine-focus sealed tube	2610 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.037
oscillation photo around ω at four ϕ scans	θmax = 27.6°, θmin = 1.7°
Absorption correction: empirical (using intensity measurements) based on ΔI (SADABS; Bruker, 2000)	h = −7→7
Tmin = 0.791, Tmax = 1.0	k = −7→7
8727 measured reflections	l = −30→30

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.135	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0626P)^2 + 0.4067P] where P = (Fo^2 + 2Fc^2)/3
3317 reflections	(Δ/σ)max < 0.001
185 parameters	Δρmax = 0.49 e Å^−3
12 restraints	Δρmin = −0.43 e Å^−3

Special details

Experimental. The single-crystal diffraction data were collected on a Bruker 1000 SMART CCD diffractometer at 173 (2) K. Oscillation photographs were taken around the ω axis at four different values of ϕ angle, 90 degrees apart. The data were indexed using SMART (Bruker, 2001) software and integrated with SAINT (Bruker, 2003) software. The structures were solved with direct methods and refined using the SHELXTL (Bruker, 2000) package. DSC employed 2920 MDSC (TA Instruments, New Castle, DE), while TGA employed 2950 T GA HR (TA Instruments, New Castle, DE), each at 5ϕC/min heating rate.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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	Occ. (<1)
Na1	0.81780 (12)	0.07127 (12)	0.05758 (3)	0.02261 (19)
O4	0.3793 (2)	0.2768 (2)	0.08114 (5)	0.0242 (3)
O3	−0.0100 (2)	0.2966 (2)	0.09916 (5)	0.0241 (3)
O2	0.7436 (2)	−0.2628 (2)	0.03320 (5)	0.0226 (3)
O1	1.2485 (2)	−0.2238 (2)	0.04190 (6)	0.0257 (3)
C1	0.2275 (3)	0.2223 (3)	0.11203 (7)	0.0189 (3)
C4	0.2462 (3)	0.2303 (3)	0.21566 (7)	0.0236 (4)
C2	0.3319 (3)	0.0606 (3)	0.16895 (7)	0.0238 (4)
C9	0.0595 (4)	0.2266 (4)	0.25309 (8)	0.0284 (4)
H9	−0.0190	0.1202	0.2487	0.0487 (18)*
C8	−0.0136 (4)	0.3757 (4)	0.29668 (8)	0.0326 (4)
H8	−0.1406	0.3687	0.3218	0.0487 (18)*
C3	0.6273 (4)	−0.1048 (4)	0.17190 (8)	0.0331 (4)
H3A	0.6795	−0.2115	0.2083	0.0487 (18)*
H3B	0.7167	0.0011	0.1682	0.0487 (18)*
H3C	0.6751	−0.2100	0.1411	0.0487 (18)*
C5	0.3531 (4)	0.3925 (4)	0.22260 (8)	0.0286 (4)
H5	0.4781	0.4014	0.1971	0.0487 (18)*
C6	0.2792 (4)	0.5412 (4)	0.26629 (8)	0.0316 (4)
H6	0.3557	0.6495	0.2704	0.0487 (18)*
C7	0.0949 (4)	0.5347 (4)	0.30430 (8)	0.0316 (4)
C10	0.0163 (5)	0.6960 (4)	0.35226 (9)	0.0428 (5)
H10A	−0.1025	0.6528	0.3764	0.0487 (18)*	0.554 (5)
H10B	−0.0824	0.8737	0.3361	0.0487 (18)*	0.554 (5)
H10D	0.0783	0.8250	0.3445	0.0487 (18)*	0.49 (5)
H10C	−0.1769	0.7842	0.3523	0.0487 (18)*	0.38 (5)
H2E	0.250 (5)	−0.043 (5)	0.1729 (10)	0.0487 (18)*
H2B	0.744 (5)	−0.279 (5)	−0.0010 (8)	0.0487 (18)*
H1A	1.392 (4)	−0.226 (5)	0.0444 (11)	0.0487 (18)*
H1B	1.271 (5)	−0.367 (4)	0.0535 (10)	0.0487 (18)*
H2A	0.827 (5)	−0.401 (4)	0.0525 (10)	0.0487 (18)*
C11	0.2456 (10)	0.6679 (10)	0.38922 (19)	0.0571 (10)	0.554 (5)
H11A	0.3565	0.7221	0.3642	0.0487 (18)*	0.554 (5)
C12	0.411 (2)	0.4300 (16)	0.4168 (4)	0.0811 (13)	0.554 (5)
H12A	0.4815	0.3108	0.3890	0.0487 (18)*	0.554 (5)
H12B	0.3123	0.3757	0.4441	0.0487 (18)*	0.554 (5)
H12C	0.5554	0.4373	0.4367	0.0487 (18)*	0.554 (5)
C13	0.1470 (14)	0.8467 (13)	0.4346 (2)	0.0811 (13)	0.554 (5)
H13A	0.2959	0.8287	0.4577	0.0487 (18)*	0.554 (5)
H13B	0.0287	0.8059	0.4588	0.0487 (18)*	0.554 (5)
H13C	0.0534	1.0196	0.4164	0.0487 (18)*	0.554 (5)
C11S	0.1178 (13)	0.5595 (12)	0.4102 (2)	0.0571 (10)	0.45
H11B	0.0217	0.4567	0.4173	0.0487 (18)*	0.446 (5)
C12S	0.0164 (17)	0.7407 (16)	0.4547 (3)	0.0811 (13)	0.45
H12D	0.0845	0.6488	0.4923	0.0487 (18)*	0.446 (5)
H12E	−0.1750	0.8189	0.4536	0.0487 (18)*	0.446 (5)
H12F	0.0747	0.8705	0.4469	0.0487 (18)*	0.446 (5)
C13S	0.391 (2)	0.372 (2)	0.4144 (5)	0.0811 (13)	0.45
H13D	0.4270	0.2696	0.3833	0.0487 (18)*	0.446 (5)
H13E	0.4271	0.2650	0.4506	0.0487 (18)*	0.446 (5)
H13F	0.5034	0.4562	0.4122	0.0487 (18)*	0.446 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Na1	0.0164 (3)	0.0218 (4)	0.0299 (4)	−0.0080 (3)	0.0013 (3)	−0.0067 (3)
O4	0.0197 (6)	0.0223 (6)	0.0271 (6)	−0.0068 (5)	0.0027 (5)	−0.0017 (5)
O3	0.0192 (6)	0.0238 (6)	0.0294 (7)	−0.0096 (5)	−0.0032 (5)	−0.0032 (5)
O2	0.0201 (6)	0.0215 (6)	0.0258 (6)	−0.0088 (5)	−0.0013 (5)	−0.0038 (5)
O1	0.0151 (6)	0.0206 (6)	0.0404 (8)	−0.0076 (5)	0.0004 (5)	−0.0016 (5)
C1	0.0203 (8)	0.0145 (7)	0.0215 (8)	−0.0066 (6)	0.0002 (6)	−0.0066 (6)
C4	0.0230 (8)	0.0234 (8)	0.0197 (8)	−0.0068 (7)	−0.0024 (6)	−0.0006 (6)
C2	0.0248 (9)	0.0222 (8)	0.0227 (9)	−0.0094 (7)	−0.0019 (7)	−0.0017 (7)
C9	0.0275 (9)	0.0298 (10)	0.0267 (9)	−0.0121 (8)	−0.0005 (7)	−0.0024 (7)
C8	0.0289 (10)	0.0379 (11)	0.0264 (9)	−0.0112 (8)	0.0059 (7)	−0.0039 (8)
C3	0.0279 (10)	0.0301 (10)	0.0270 (10)	−0.0007 (8)	−0.0044 (7)	−0.0020 (7)
C5	0.0292 (9)	0.0309 (10)	0.0265 (9)	−0.0141 (8)	0.0035 (7)	−0.0044 (7)
C6	0.0359 (10)	0.0303 (10)	0.0307 (10)	−0.0162 (8)	−0.0014 (8)	−0.0058 (8)
C7	0.0342 (10)	0.0288 (10)	0.0229 (9)	−0.0062 (8)	−0.0010 (7)	−0.0050 (7)
C10	0.0523 (14)	0.0382 (12)	0.0324 (11)	−0.0137 (10)	0.0055 (9)	−0.0131 (9)
C11	0.068 (3)	0.063 (3)	0.0354 (19)	−0.0216 (19)	0.0001 (16)	−0.0210 (17)
C12	0.095 (2)	0.084 (3)	0.0519 (16)	−0.024 (2)	−0.0128 (14)	−0.0323 (17)
C13	0.095 (2)	0.084 (3)	0.0519 (16)	−0.024 (2)	−0.0128 (14)	−0.0323 (17)
C11S	0.068 (3)	0.063 (3)	0.0354 (19)	−0.0216 (19)	0.0001 (16)	−0.0210 (17)
C12S	0.095 (2)	0.084 (3)	0.0519 (16)	−0.024 (2)	−0.0128 (14)	−0.0323 (17)
C13S	0.095 (2)	0.084 (3)	0.0519 (16)	−0.024 (2)	−0.0128 (14)	−0.0323 (17)

Geometric parameters (Å, º)

Na1—O3^i	2.3126 (13)	C5—H5	0.9500
Na1—O4	2.3428 (13)	C6—C7	1.395 (3)
Na1—O1	2.3599 (14)	C6—H6	0.9500
Na1—O2	2.3712 (14)	C7—C10	1.516 (3)
Na1—O1^ii	2.4127 (15)	C10—C11S	1.500 (6)
Na1—Na1^ii	3.3773 (13)	C10—C11	1.527 (5)
O4—C1	1.263 (2)	C10—H10A	0.9900
O3—C1	1.258 (2)	C10—H10B	0.9900
O3—Na1^iii	2.3126 (13)	C10—H10D	0.9900
O2—H2B	0.831 (17)	C10—H10C	0.9900
O2—H2A	0.833 (17)	C11—C12	1.401 (10)
O1—Na1^ii	2.4127 (15)	C11—C13	1.533 (6)
O1—H1A	0.819 (17)	C11—H11A	1.0000
O1—H1B	0.828 (17)	C12—H12A	0.9800
C1—C2	1.530 (2)	C12—H12B	0.9800
C4—C9	1.391 (3)	C12—H12C	0.9800
C4—C5	1.393 (3)	C13—H13A	0.9800
C4—C2	1.522 (2)	C13—H13B	0.9800
C2—C3	1.528 (3)	C13—H13C	0.9800
C2—H2E	0.93 (3)	C11S—C13S	1.458 (12)
C9—C8	1.387 (3)	C11S—C12S	1.527 (8)
C9—H9	0.9500	C11S—H11B	1.0000
C8—C7	1.386 (3)	C12S—H12D	0.9800
C8—H8	0.9500	C12S—H12E	0.9800
C3—H3A	0.9800	C12S—H12F	0.9800
C3—H3B	0.9800	C13S—H13D	0.9800
C3—H3C	0.9800	C13S—H13E	0.9800
C5—C6	1.387 (3)	C13S—H13F	0.9800
O3^i—Na1—O4	101.04 (5)	C11S—C10—C11	48.8 (3)
O3^i—Na1—O1	88.45 (5)	C7—C10—C11	114.3 (2)
O4—Na1—O1	166.04 (5)	C11S—C10—H10A	62.2
O3^i—Na1—O2	162.24 (5)	C7—C10—H10A	108.7
O4—Na1—O2	88.90 (5)	C11—C10—H10A	108.7
O1—Na1—O2	79.43 (5)	C11S—C10—H10B	135.5
O3^i—Na1—O1^ii	106.65 (5)	C7—C10—H10B	108.7
O4—Na1—O1^ii	97.04 (5)	C11—C10—H10B	108.7
O1—Na1—O1^ii	89.92 (5)	H10A—C10—H10B	107.6
O2—Na1—O1^ii	86.43 (5)	C11S—C10—H10D	108.4
O3^i—Na1—Na1^ii	100.70 (4)	C7—C10—H10D	108.3
O4—Na1—Na1^ii	139.96 (5)	C11—C10—H10D	62.8
O1—Na1—Na1^ii	45.59 (4)	H10A—C10—H10D	141.9
O2—Na1—Na1^ii	80.05 (4)	H10B—C10—H10D	50.9
O1^ii—Na1—Na1^ii	44.33 (3)	C11S—C10—H10C	108.4
C1—O4—Na1	136.24 (11)	C7—C10—H10C	108.4
C1—O3—Na1^iii	125.73 (11)	C11—C10—H10C	137.2
Na1—O2—H2B	116.8 (18)	H10A—C10—H10C	51.4
Na1—O2—H2A	116.5 (18)	H10B—C10—H10C	58.8
H2B—O2—H2A	111 (3)	H10D—C10—H10C	107.4
Na1—O1—Na1^ii	90.08 (5)	C12—C11—C10	118.3 (5)
Na1—O1—H1A	134.1 (19)	C12—C11—C13	107.0 (5)
Na1^ii—O1—H1A	94.0 (18)	C10—C11—C13	110.2 (4)
Na1—O1—H1B	110.1 (18)	C12—C11—H10D	152.1
Na1^ii—O1—H1B	121.4 (18)	C13—C11—H10D	98.6
H1A—O1—H1B	106 (3)	C12—C11—H11A	106.9
O3—C1—O4	123.67 (15)	C10—C11—H11A	106.9
O3—C1—C2	116.90 (15)	C13—C11—H11A	106.9
O4—C1—C2	119.42 (14)	H10D—C11—H11A	75.1
C9—C4—C5	117.90 (17)	C11—C12—H12A	109.5
C9—C4—C2	120.84 (16)	C11—C12—H12B	109.5
C5—C4—C2	121.26 (16)	H12A—C12—H12B	109.5
C4—C2—C3	111.82 (15)	C11—C12—H12C	109.5
C4—C2—C1	108.66 (14)	H12A—C12—H12C	109.5
C3—C2—C1	113.59 (15)	H12B—C12—H12C	109.5
C4—C2—H2E	108.8 (16)	C11—C13—H13A	109.5
C3—C2—H2E	108.4 (16)	C11—C13—H13B	109.5
C1—C2—H2E	105.3 (15)	H13A—C13—H13B	109.5
C8—C9—C4	121.01 (18)	C11—C13—H13C	109.5
C8—C9—H9	119.5	H13A—C13—H13C	109.5
C4—C9—H9	119.5	H13B—C13—H13C	109.5
C7—C8—C9	121.34 (18)	C13S—C11S—C10	115.6 (7)
C7—C8—H8	119.3	C13S—C11S—C12S	118.8 (6)
C9—C8—H8	119.3	C10—C11S—C12S	110.5 (5)
C2—C3—H3A	109.5	C13S—C11S—H11B	103.2
C2—C3—H3B	109.5	C10—C11S—H11B	103.2
H3A—C3—H3B	109.5	C12S—C11S—H11B	103.2
C2—C3—H3C	109.5	C11S—C12S—H12D	109.5
H3A—C3—H3C	109.5	C11S—C12S—H12E	109.5
H3B—C3—H3C	109.5	H12D—C12S—H12E	109.5
C6—C5—C4	120.82 (17)	C11S—C12S—H12F	109.5
C6—C5—H5	119.6	H12D—C12S—H12F	109.5
C4—C5—H5	119.6	H12E—C12S—H12F	109.5
C5—C6—C7	121.23 (18)	C11S—C13S—H13D	109.5
C5—C6—H6	119.4	C11S—C13S—H13E	109.5
C7—C6—H6	119.4	H13D—C13S—H13E	109.5
C8—C7—C6	117.68 (17)	C11S—C13S—H13F	109.5
C8—C7—C10	121.28 (19)	H13D—C13S—H13F	109.5
C6—C7—C10	121.05 (19)	H13E—C13S—H13F	109.5
C11S—C10—C7	115.6 (3)

Symmetry codes: (i) x+1, y, z; (ii) −x+2, −y, −z; (iii) x−1, y, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O3^iv	0.83 (2)	1.86 (2)	2.6907 (17)	176 (3)
O1—H1B···O4^iv	0.83 (2)	1.98 (2)	2.7998 (17)	172 (3)
O1—H1A···O2^i	0.82 (2)	1.95 (2)	2.7507 (17)	166 (3)
O2—H2B···O4^v	0.83 (2)	2.04 (2)	2.8438 (18)	162 (3)

Symmetry codes: (i) x+1, y, z; (iv) x+1, y−1, z; (v) −x+1, −y, −z.

(II) sodium S-α-Methyl-4-(isobutyl)phenylacetate dihydrate

Crystal data

Na^+·C13H17O2^−·2H2O	Z = 2
Mr = 264.29	F(000) = 284
Triclinic, P1	Dx = 1.197 Mg m^−3
Hall symbol: P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.7767 (5) Å	Cell parameters from 3725 reflections
b = 6.0835 (5) Å	θ = 1.9–27.0°
c = 23.880 (2) Å	µ = 0.11 mm^−1
α = 83.151 (1)°	T = 173 K
β = 86.482 (1)°	Plate, colorless
γ = 61.612 (1)°	0.30 × 0.30 × 0.10 mm
V = 733.00 (11) Å^3

Data collection

Bruker SMART 1000 CCD area-detector diffractometer	2589 independent reflections
Radiation source: fine-focus sealed tube	2350 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
oscillation photo around ω at four ϕ scans	θmax = 25.0°, θmin = 1.7°
Absorption correction: empirical (using intensity measurements) based on ΔI (SADABS; Bruker, 2000)	h = −6→6
Tmin = 0.822, Tmax = 1.0	k = −7→7
7383 measured reflections	l = −28→28

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.113	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0737P)^2 + 0.1763P] where P = (Fo^2 + 2Fc^2)/3
2589 reflections	(Δ/σ)max < 0.001
356 parameters	Δρmax = 0.57 e Å^−3
37 restraints	Δρmin = −0.30 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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
Na1	0.8101 (2)	1.0604 (2)	0.74213 (6)	0.0229 (3)
O1'	0.6838 (5)	0.7400 (5)	0.76335 (13)	0.0271 (6)
O3	0.4009 (5)	1.3279 (5)	0.70443 (12)	0.0269 (6)
O3'	1.0901 (5)	0.5648 (5)	0.88818 (13)	0.0325 (7)
C1'	1.2463 (7)	0.6008 (7)	0.91531 (16)	0.0218 (8)
C7'	1.4239 (9)	0.0957 (8)	1.10835 (19)	0.0349 (9)
O4'	1.4752 (5)	0.5512 (5)	0.89860 (12)	0.0307 (6)
O4	0.0412 (5)	1.2862 (5)	0.72135 (12)	0.0278 (6)
C4	0.1772 (8)	1.3740 (7)	0.58729 (16)	0.0241 (8)
C1	0.2351 (7)	1.2636 (7)	0.69105 (15)	0.0196 (7)
C2	0.2763 (7)	1.1577 (7)	0.63408 (16)	0.0239 (8)
H2E	0.4662	1.0557	0.6285	0.065 (2)*
C2'	1.1606 (8)	0.7045 (8)	0.97265 (17)	0.0270 (8)
H2F	1.2466	0.8063	0.9775	0.065 (2)*
C4'	1.2584 (7)	0.4873 (7)	1.01917 (16)	0.0244 (8)
C5'	1.4482 (8)	0.4513 (7)	1.05721 (17)	0.0306 (8)
H5A	1.5235	0.5577	1.0532	0.065 (2)*
C8	0.2591 (8)	1.6015 (8)	0.50525 (17)	0.0346 (9)
H8	0.3792	1.6209	0.4801	0.065 (2)*
C9'	1.1546 (8)	0.3191 (7)	1.02605 (16)	0.0297 (8)
H9A	1.0293	0.3358	1.0009	0.065 (2)*
C9	0.3501 (8)	1.4087 (7)	0.54911 (16)	0.0299 (8)
H9	0.5299	1.3015	0.5528	0.065 (2)*
C6	−0.1804 (8)	1.7322 (7)	0.53724 (16)	0.0319 (9)
H6	−0.3597	1.8416	0.5339	0.065 (2)*
C6'	1.5283 (8)	0.2605 (8)	1.10103 (17)	0.0337 (9)
H6A	1.6547	0.2426	1.1261	0.065 (2)*
C10	−0.1055 (10)	1.9738 (9)	0.45030 (18)	0.0469 (12)
H10B	0.0444	1.9669	0.4283	0.065 (2)*
H10A	−0.1917	2.1339	0.4660	0.065 (2)*
C5	−0.0912 (7)	1.5400 (7)	0.58090 (16)	0.0276 (8)
H5	−0.2113	1.5214	0.6062	0.065 (2)*
C3	0.1498 (9)	0.9882 (7)	0.63103 (17)	0.0347 (9)
H3A	0.1863	0.9241	0.5949	0.065 (2)*
H3B	−0.0371	1.0834	0.6361	0.065 (2)*
H3C	0.2207	0.8508	0.6602	0.065 (2)*
C3'	0.8648 (8)	0.8721 (8)	0.97741 (18)	0.0386 (10)
H3D	0.8229	0.9298	1.0142	0.065 (2)*
H3E	0.7750	0.7784	0.9717	0.065 (2)*
H3F	0.8102	1.0139	0.9493	0.065 (2)*
C8'	1.2363 (8)	0.1287 (8)	1.06984 (17)	0.0329 (9)
H18A	1.1639	0.0199	1.0736	0.065 (2)*
C7	−0.0067 (9)	1.7648 (8)	0.49833 (17)	0.0326 (9)
C11	−0.2987 (15)	1.9620 (11)	0.4107 (3)	0.089 (2)
H11	−0.4547	1.9791	0.4325	0.065 (2)*
C10'	1.5115 (10)	−0.1107 (10)	1.15591 (19)	0.0470 (12)
H10C	1.6433	−0.1022	1.1775	0.065 (2)*
H10D	1.5947	−0.2708	1.1402	0.065 (2)*
C13	−0.383 (2)	2.1818 (15)	0.3643 (3)	0.105 (3)
H13A	−0.5117	2.1814	0.3407	0.065 (2)*
H13B	−0.2328	2.1647	0.3420	0.065 (2)*
H13C	−0.4582	2.3369	0.3812	0.065 (2)*
C12	−0.177 (2)	1.7143 (14)	0.3849 (3)	0.127 (4)
H12A	−0.1112	1.5778	0.4143	0.065 (2)*
H12B	−0.0351	1.7032	0.3602	0.065 (2)*
H12C	−0.3081	1.7055	0.3638	0.065 (2)*
C11'	1.2894 (13)	−0.1031 (11)	1.1964 (2)	0.088 (2)
H11A	1.1636	−0.1220	1.1743	0.065 (2)*
C12'	1.141 (2)	0.1438 (14)	1.2220 (3)	0.128 (4)
H12D	1.0486	0.2764	1.1928	0.065 (2)*
H12E	1.2628	0.1782	1.2399	0.065 (2)*
H12F	1.0170	0.1333	1.2494	0.065 (2)*
O2	1.2223 (5)	0.7038 (5)	0.77081 (11)	0.0231 (6)
H2B	1.204 (12)	0.659 (12)	0.8051 (10)	0.065 (2)*
C13'	1.3995 (18)	−0.3255 (15)	1.2423 (3)	0.104 (3)
H13D	1.5092	−0.3029	1.2672	0.065 (2)*
H13E	1.5014	−0.4784	1.2251	0.065 (2)*
H13F	1.2567	−0.3343	1.2634	0.065 (2)*
O2'	0.2274 (5)	1.1389 (5)	0.83852 (12)	0.0246 (6)
H2D	0.197 (13)	1.264 (8)	0.856 (3)	0.065 (2)*
O1	0.7491 (5)	1.1429 (5)	0.83743 (12)	0.0259 (6)
Na1'	0.6547 (2)	0.8031 (2)	0.86123 (6)	0.0241 (3)
H1A	0.651 (11)	1.266 (8)	0.856 (2)	0.065 (2)*
H1C	0.789 (10)	0.611 (8)	0.747 (3)	0.065 (2)*
H1D	0.545 (7)	0.725 (13)	0.765 (3)	0.065 (2)*
H2C	0.203 (12)	1.198 (11)	0.8041 (10)	0.065 (2)*
H2A	1.277 (12)	0.591 (9)	0.748 (2)	0.065 (2)*
H1B	0.904 (6)	1.115 (12)	0.844 (3)	0.065 (2)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Na1	0.0199 (7)	0.0215 (8)	0.0306 (8)	−0.0126 (6)	0.0003 (6)	−0.0021 (6)
O1'	0.0206 (13)	0.0238 (14)	0.0409 (16)	−0.0128 (11)	0.0028 (12)	−0.0092 (12)
O3	0.0209 (13)	0.0266 (14)	0.0354 (15)	−0.0115 (11)	−0.0043 (11)	−0.0074 (11)
O3'	0.0250 (13)	0.0281 (15)	0.0415 (16)	−0.0075 (11)	−0.0061 (11)	−0.0132 (12)
C1'	0.0211 (18)	0.0152 (18)	0.0253 (18)	−0.0060 (15)	−0.0009 (15)	0.0002 (15)
C7'	0.039 (2)	0.029 (2)	0.030 (2)	−0.0104 (18)	0.0029 (18)	−0.0064 (17)
O4'	0.0304 (15)	0.0265 (14)	0.0397 (16)	−0.0172 (12)	0.0124 (12)	−0.0095 (12)
O4	0.0299 (14)	0.0255 (14)	0.0334 (15)	−0.0173 (12)	0.0089 (12)	−0.0087 (11)
C4	0.031 (2)	0.023 (2)	0.0230 (19)	−0.0154 (17)	0.0002 (15)	−0.0066 (16)
C1	0.0244 (18)	0.0122 (16)	0.0210 (17)	−0.0080 (14)	−0.0027 (15)	0.0009 (14)
C2	0.0232 (18)	0.0213 (19)	0.0250 (19)	−0.0084 (15)	0.0012 (15)	−0.0043 (15)
C2'	0.033 (2)	0.026 (2)	0.0262 (19)	−0.0156 (17)	0.0006 (16)	−0.0069 (16)
C4'	0.0225 (18)	0.024 (2)	0.0249 (19)	−0.0089 (16)	0.0039 (15)	−0.0069 (16)
C5'	0.0299 (19)	0.033 (2)	0.032 (2)	−0.0161 (17)	0.0010 (16)	−0.0078 (17)
C8	0.043 (2)	0.040 (2)	0.029 (2)	−0.027 (2)	0.0078 (17)	−0.0048 (18)
C9'	0.034 (2)	0.034 (2)	0.0249 (18)	−0.0178 (17)	−0.0018 (15)	−0.0049 (16)
C9	0.0301 (19)	0.033 (2)	0.030 (2)	−0.0178 (17)	0.0005 (16)	−0.0055 (16)
C6	0.034 (2)	0.031 (2)	0.028 (2)	−0.0125 (17)	−0.0019 (16)	−0.0029 (16)
C6'	0.031 (2)	0.039 (2)	0.028 (2)	−0.0128 (18)	−0.0045 (16)	−0.0049 (17)
C10	0.067 (3)	0.035 (3)	0.032 (2)	−0.021 (2)	0.000 (2)	0.004 (2)
C5	0.0271 (19)	0.030 (2)	0.0253 (18)	−0.0130 (16)	0.0027 (15)	−0.0029 (15)
C3	0.054 (3)	0.030 (2)	0.029 (2)	−0.026 (2)	−0.0065 (18)	−0.0018 (16)
C3'	0.039 (2)	0.032 (2)	0.030 (2)	−0.0053 (18)	0.0066 (17)	−0.0037 (17)
C8'	0.039 (2)	0.031 (2)	0.031 (2)	−0.0191 (18)	−0.0004 (16)	−0.0005 (16)
C7	0.045 (2)	0.032 (2)	0.0236 (19)	−0.020 (2)	−0.0030 (17)	−0.0012 (17)
C11	0.115 (6)	0.088 (5)	0.065 (4)	−0.054 (5)	−0.038 (4)	0.035 (4)
C10'	0.059 (3)	0.038 (3)	0.036 (2)	−0.017 (2)	−0.008 (2)	0.004 (2)
C13	0.143 (8)	0.093 (6)	0.068 (5)	−0.051 (5)	−0.046 (5)	0.035 (4)
C12	0.239 (13)	0.103 (6)	0.059 (4)	−0.095 (8)	−0.055 (6)	0.009 (4)
C11'	0.098 (5)	0.092 (5)	0.051 (4)	−0.034 (4)	0.003 (3)	0.022 (4)
C12'	0.149 (8)	0.102 (6)	0.058 (4)	−0.008 (6)	0.039 (5)	0.014 (4)
O2	0.0217 (13)	0.0215 (14)	0.0281 (14)	−0.0118 (11)	0.0004 (11)	−0.0023 (11)
C13'	0.124 (7)	0.097 (6)	0.066 (4)	−0.041 (5)	0.006 (4)	0.032 (4)
O2'	0.0219 (13)	0.0216 (14)	0.0307 (14)	−0.0099 (11)	−0.0018 (11)	−0.0048 (11)
O1	0.0215 (13)	0.0253 (14)	0.0358 (15)	−0.0143 (12)	0.0026 (11)	−0.0067 (12)
Na1'	0.0204 (7)	0.0235 (8)	0.0309 (8)	−0.0126 (6)	−0.0006 (6)	−0.0011 (6)

Geometric parameters (Å, º)

Na1—O3	2.302 (3)	C10—C7	1.516 (6)
Na1—O4^i	2.327 (3)	C10—C11	1.539 (5)
Na1—O1	2.358 (3)	C10—H10B	0.9700
Na1—O1'	2.379 (3)	C10—H10A	0.9700
Na1—O2	2.404 (3)	C5—H5	0.9300
Na1—Na1'	3.3623 (16)	C3—H3A	0.9600
O1'—Na1'	2.396 (3)	C3—H3B	0.9600
O1'—H1C	0.849 (17)	C3—H3C	0.9600
O1'—H1D	0.849 (18)	C3'—H3D	0.9600
O3—C1	1.264 (4)	C3'—H3E	0.9600
O3'—C1'	1.255 (5)	C3'—H3F	0.9600
O3'—Na1'	2.313 (3)	C8'—H18A	0.9300
C1'—O4'	1.259 (5)	C11—C12	1.518 (5)
C1'—C2'	1.531 (5)	C11—C13	1.531 (5)
C7'—C6'	1.386 (6)	C11—H11	0.9800
C7'—C8'	1.390 (6)	C10'—C11'	1.544 (5)
C7'—C10'	1.500 (6)	C10'—H10C	0.9700
O4'—Na1'^i	2.300 (3)	C10'—H10D	0.9700
O4—C1	1.255 (5)	C13—H13A	0.9600
O4—Na1^ii	2.327 (3)	C13—H13B	0.9600
C4—C9	1.384 (5)	C13—H13C	0.9600
C4—C5	1.397 (6)	C12—H12A	0.9600
C4—C2	1.523 (6)	C12—H12B	0.9600
C1—C2	1.531 (5)	C12—H12C	0.9600
C2—C3	1.531 (5)	C11'—C12'	1.515 (5)
C2—H2E	0.9800	C11'—C13'	1.533 (5)
C2'—C4'	1.522 (6)	C11'—H11A	0.9800
C2'—C3'	1.523 (6)	C12'—H12D	0.9600
C2'—H2F	0.9800	C12'—H12E	0.9600
C4'—C5'	1.386 (6)	C12'—H12F	0.9600
C4'—C9'	1.402 (6)	O2—H2B	0.849 (17)
C5'—C6'	1.384 (6)	O2—H2A	0.849 (17)
C5'—H5A	0.9300	C13'—H13D	0.9600
C8—C7	1.383 (6)	C13'—H13E	0.9600
C8—C9	1.392 (6)	C13'—H13F	0.9600
C8—H8	0.9300	O2'—Na1'	2.380 (3)
C9'—C8'	1.382 (6)	O2'—H2D	0.849 (17)
C9'—H9A	0.9300	O2'—H2C	0.849 (17)
C9—H9	0.9300	O1—Na1'	2.376 (3)
C6—C5	1.386 (5)	O1—H1A	0.849 (17)
C6—C7	1.393 (6)	O1—H1B	0.849 (18)
C6—H6	0.9300	Na1'—O4'^ii	2.300 (3)
C6'—H6A	0.9300
O3—Na1—O4^i	103.28 (11)	C2—C3—H3B	109.5
O3—Na1—O1	102.33 (11)	H3A—C3—H3B	109.5
O4^i—Na1—O1	92.95 (10)	C2—C3—H3C	109.5
O3—Na1—O1'	90.03 (11)	H3A—C3—H3C	109.5
O4^i—Na1—O1'	165.27 (11)	H3B—C3—H3C	109.5
O1—Na1—O1'	90.27 (11)	C2'—C3'—H3D	109.5
O3—Na1—O2	165.58 (11)	C2'—C3'—H3E	109.5
O4^i—Na1—O2	87.31 (10)	H3D—C3'—H3E	109.5
O1—Na1—O2	86.63 (10)	C2'—C3'—H3F	109.5
O1'—Na1—O2	78.53 (10)	H3D—C3'—H3F	109.5
O3—Na1—Na1'	101.66 (8)	H3E—C3'—H3F	109.5
O4^i—Na1—Na1'	134.88 (8)	C9'—C8'—C7'	121.6 (4)
O1—Na1—Na1'	44.96 (7)	C9'—C8'—H18A	119.2
O1'—Na1—Na1'	45.46 (8)	C7'—C8'—H18A	119.2
O2—Na1—Na1'	76.60 (7)	C8—C7—C6	117.8 (4)
O3—Na1—H1B	118.1 (11)	C8—C7—C10	121.1 (4)
O4^i—Na1—H1B	79.5 (11)	C6—C7—C10	121.1 (4)
O1—Na1—H1B	18.8 (7)	C12—C11—C13	110.3 (6)
O1'—Na1—H1B	100.0 (13)	C12—C11—C10	111.6 (6)
O2—Na1—H1B	73.1 (12)	C13—C11—C10	109.0 (5)
Na1'—Na1—H1B	55.6 (12)	C12—C11—H11	108.6
Na1—O1'—Na1'	89.50 (10)	C13—C11—H11	108.6
Na1—O1'—H1C	110 (5)	C10—C11—H11	108.6
Na1'—O1'—H1C	128 (4)	C7'—C10'—C11'	114.7 (4)
Na1—O1'—H1D	139 (4)	C7'—C10'—H10C	108.6
Na1'—O1'—H1D	93 (4)	C11'—C10'—H10C	108.6
H1C—O1'—H1D	101 (6)	C7'—C10'—H10D	108.6
C1—O3—Na1	125.6 (2)	C11'—C10'—H10D	108.6
C1'—O3'—Na1'	134.9 (3)	H10C—C10'—H10D	107.6
O3'—C1'—O4'	123.6 (4)	C11—C13—H13A	109.5
O3'—C1'—C2'	119.2 (3)	C11—C13—H13B	109.5
O4'—C1'—C2'	117.2 (3)	H13A—C13—H13B	109.5
C6'—C7'—C8'	117.4 (4)	C11—C13—H13C	109.5
C6'—C7'—C10'	121.1 (4)	H13A—C13—H13C	109.5
C8'—C7'—C10'	121.5 (4)	H13B—C13—H13C	109.5
C1'—O4'—Na1'^i	132.1 (2)	C11—C12—H12A	109.5
C1—O4—Na1^ii	136.2 (2)	C11—C12—H12B	109.5
C9—C4—C5	118.1 (4)	H12A—C12—H12B	109.5
C9—C4—C2	121.0 (4)	C11—C12—H12C	109.5
C5—C4—C2	121.0 (3)	H12A—C12—H12C	109.5
O4—C1—O3	123.4 (3)	H12B—C12—H12C	109.5
O4—C1—C2	119.8 (3)	C12'—C11'—C13'	111.1 (6)
O3—C1—C2	116.8 (3)	C12'—C11'—C10'	112.7 (6)
C4—C2—C3	111.5 (3)	C13'—C11'—C10'	110.3 (5)
C4—C2—C1	109.1 (3)	C12'—C11'—H11A	107.5
C3—C2—C1	113.4 (3)	C13'—C11'—H11A	107.5
C4—C2—H2E	107.5	C10'—C11'—H11A	107.5
C3—C2—H2E	107.5	C11'—C12'—H12D	109.5
C1—C2—H2E	107.5	C11'—C12'—H12E	109.5
C4'—C2'—C3'	111.1 (3)	H12D—C12'—H12E	109.5
C4'—C2'—C1'	109.3 (3)	C11'—C12'—H12F	109.5
C3'—C2'—C1'	113.3 (3)	H12D—C12'—H12F	109.5
C4'—C2'—H2F	107.7	H12E—C12'—H12F	109.5
C3'—C2'—H2F	107.7	Na1—O2—H2B	107 (4)
C1'—C2'—H2F	107.7	Na1—O2—H2A	113 (4)
C5'—C4'—C9'	117.3 (4)	H2B—O2—H2A	116 (7)
C5'—C4'—C2'	121.6 (4)	C11'—C13'—H13D	109.5
C9'—C4'—C2'	121.1 (3)	C11'—C13'—H13E	109.5
C6'—C5'—C4'	121.5 (4)	H13D—C13'—H13E	109.5
C6'—C5'—H5A	119.2	C11'—C13'—H13F	109.5
C4'—C5'—H5A	119.2	H13D—C13'—H13F	109.5
C7—C8—C9	121.2 (4)	H13E—C13'—H13F	109.5
C7—C8—H8	119.4	Na1'—O2'—H2D	110 (5)
C9—C8—H8	119.4	Na1'—O2'—H2C	116 (4)
C8'—C9'—C4'	120.8 (4)	H2D—O2'—H2C	104 (6)
C8'—C9'—H9A	119.6	Na1—O1—Na1'	90.51 (11)
C4'—C9'—H9A	119.6	Na1—O1—H1A	137 (4)
C4—C9—C8	121.0 (4)	Na1'—O1—H1A	111 (4)
C4—C9—H9	119.5	Na1—O1—H1B	98 (4)
C8—C9—H9	119.5	Na1'—O1—H1B	117 (5)
C5—C6—C7	121.3 (4)	H1A—O1—H1B	104 (6)
C5—C6—H6	119.3	O4'^ii—Na1'—O3'	101.98 (12)
C7—C6—H6	119.3	O4'^ii—Na1'—O1	164.49 (11)
C5'—C6'—C7'	121.3 (4)	O3'—Na1'—O1	86.92 (11)
C5'—C6'—H6A	119.3	O4'^ii—Na1'—O2'	90.50 (11)
C7'—C6'—H6A	119.3	O3'—Na1'—O2'	164.50 (12)
C7—C10—C11	114.1 (4)	O1—Na1'—O2'	78.95 (10)
C7—C10—H10B	108.7	O4'^ii—Na1'—O1'	101.09 (11)
C11—C10—H10B	108.7	O3'—Na1'—O1'	101.23 (11)
C7—C10—H10A	108.7	O1—Na1'—O1'	89.42 (10)
C11—C10—H10A	108.7	O2'—Na1'—O1'	85.11 (10)
H10B—C10—H10A	107.6	O4'^ii—Na1'—Na1	145.54 (9)
C6—C5—C4	120.6 (3)	O3'—Na1'—Na1	92.81 (9)
C6—C5—H5	119.7	O1—Na1'—Na1	44.53 (8)
C4—C5—H5	119.7	O2'—Na1'—Na1	81.62 (8)
C2—C3—H3A	109.5	O1'—Na1'—Na1	45.04 (7)

Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2B···O3′	0.85 (2)	2.15 (2)	2.990 (4)	170 (6)
O2′—H2D···O3′^iii	0.85 (2)	1.88 (2)	2.723 (4)	173 (7)
O1—H1A···O4′^iii	0.85 (2)	1.92 (2)	2.766 (4)	171 (6)
O1′—H1C···O4^iv	0.85 (2)	1.96 (2)	2.806 (4)	172 (6)
O1′—H1D···O2^ii	0.85 (2)	1.92 (2)	2.771 (4)	177 (6)
O2′—H2C···O4	0.85 (2)	2.14 (3)	2.940 (4)	158 (6)
O2—H2A···O3^iv	0.85 (2)	1.84 (2)	2.688 (4)	176 (6)
O1—H1B···O2′^i	0.85 (2)	1.93 (3)	2.753 (4)	162 (6)

Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z; (iii) x−1, y+1, z; (iv) x+1, y−1, z.