The crystal and mol­ecular structure of sodium 4-(2,4,6-triiso­propyl­benzo­yl)benzoate in terms of the photochemical behaviour of the anion

Contrary to the known 4-(2,4,6-triiso­propyl­benzo­yl)benzoate salts, di-μ-aqua-bis­[tetra­aqua­sodium(I)] bis­[4-(2,4,6-triiso­propyl­benzo­yl)benzoate] dihydrate, [Na₂(H₂O)₁₀](C₂₃H₂₇O₃)₂·2H₂O, (1), does not undergo a photochemical Norrish–Yang reaction in the crystalline state. In order to explain this photo­chemical inactivity, the inter­molecular inter­actions were analyzed by means of the Hirshfeld surface and intra­molecular geometrical parameters describing the possibility of a Norrish–Yang reaction were calculated. The reasons for the behaviour of the title salt are similar crystalline environments for both the o-isopropyl groups in the anion, resulting in similar geometrical parameters and orientations, and that these interaction distances differ significantly from those found in salts where the photochemical reaction occurs.

S1. Introduction

Derivatives of 2,4,6-triiso­propyl­benzo­phenone under suitable conditions can undergo an intra­molecular Norrish–Yang reaction in crystalline materials (Ito et al., 1983, 1988). This reaction, for which the equation is shown in Scheme 1, proceeds in two stages (Braslavsky, 2007). In the first stage, an H atom is transferred from a γ-C atom to the O atom of a carbonyl group, which leads to the formation of a 1,4-biradical, and in the second step, a cyclo­butane ring is created from the 1,4-biradical. The reaction is induced by radiation in the UV–vis range. Among the salts of 4-(2,4,6-triiso­propyl­benzoyl)­benzoic acid, those with organic bases were examined, viz. benzyl­ammonium (Koshima et al., 2005; Bąkowicz et al., 2014), 2-(hy­droxy­methyl)­pyrrolidinium (Koshima et al., 1994; Hirotsu et al., 1996), phenyl­ethanaminium (Koshima et al., 2008) and pyrrolidinium (Bąkowicz et al., 2014), and also the ammonium salt (Bąkowicz et al., 2014). All of these salts are photochemically active and undergo the Norrish–Yang reaction in the crystalline state, forming a four-membered ring from the 1,4-biradical. The phenyl­ethanaminium salt can additionally give a 1,5-diradical which leads to a five-membered ring (Ito et al., 2009). For the benzyl­ammonium, pyrrolidinium and ammonium salts, the course of the photochemical reaction was monitored by X-ray structure analysis and the reaction rate was evaluated using the JMAK model (Kohout, 2008; Bąkowicz et al., 2014).

However, the crystal structures of 4-(2,4,6-triiso­propyl­benzoyl)­benzoate salts containing metal cations are not known. In this paper, we present the structure of sodium 4-(2,4,6-triiso­propyl­benzoyl)­benzoate hexahydrate, (1) (see Scheme 1), and an analysis of the structure in terms of the photochemical behaviour of the salt. We also suggest the photochemical behaviour of the unstable lithium salt of 4-(2,4,6-triiso­propyl­benzoyl)­benzoic acid, denoted (2).

S2. Experimental

S2.1. Synthesis and crystallization

Sodium salt (1) and lithium salt (2) were obtained by adding sodium or lithium hydroxide, respectively, to a solution of 4-(2,4,6-triiso­propyl­benzoyl)­benzoic acid in ethanol, using a small stoichiometric excess of the former, and both were recrystallized from water.

S2.2. Data collection and refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. Since crystals of salt (1) became gradually more unstable under the influence of air, the crystal used for the X-ray data collection was covered with a thin protective layer of glue which did not inter­act with the crystal and did not give a diffraction pattern. The crystals were also unstable under X-ray radiation and therefore the measurements were carried out faster than usually. In the case of the studied salt, (1), we noticed that data collections longer than 4 h were of poor quality and accordingly we adjusted the exposure time per frame.

H atoms in the organic ion were treated as constrained. H atoms in the coordinating water molecules were refined with restrained geometry. The positions of the H atoms of crystalline water molecules were deduced on the basis of their potential hydrogen bonds and were also refined with restraints. The atomic displacement parameters of all H atoms of water molecules were treated as constrained.

S2.3. Crystal irradiation

Two other crystals of salt (1) (not covered by a protective layer) were irradiated using a 100 W mercury lamp with a water filter and glass filter BG39. Transmittance for BG39 was: 0% for 320 > λ > 680 nm, about 55% for λ σim 350 nm and 95% for λ σim 460 nm. The first crystal was irradiated for 0, 30, 45, 60 and 90 min in total and after each irradiation monitored by recording the set of diffraction patterns for several orientations of the crystal. The recorded patterns showed no features evidencing the Norrish–Yang reaction, for example, the appearance of new reflections. The second crystal was irradiated for only 3 h and its diffraction patterns also did not show any evidence of photochemical reaction. The wavelengths used for the irradiations were from the low-energy tail of the UV–vis absorption spectrum of the compound (Enkelmann et al., 1993; Novak et al., 1993). The crystals of salt (1) were also sensitive to the UV beam, which caused decreasing translational order and intensities of reflections in the monitored diffraction patterns. The instability of crystals of several other compounds under UV radiation has been studied by us previously (Turowska-Tyrk, 2003; Bąkowicz et al., 2011, 2012).

Crystals of lithium salt (2) were unstable under the influence of air to a degree precluding data collection of an acceptable quality for structure determination (even protecting them from the environment). The cell constants determined for salt (2) are a = 6.117 (3), b = 8.601 (4), c = 24.953 (7) Å, α = 90.72 (3), β = 93.52 (3) and χ = 104.27 (5)°. These are very similar to the cell parameters for salt (1) (see Table 1). This suggests that the crystals of salts (1) and (2) are isomorphous.

S3. Results and discussion

The asymmetric unit of salt (1) (Fig. 1) contains one 4-(2,4,6-triiso­propyl­benzoyl)­benzoate anion, one sodium cation coordinated by six water molecules, of which two bridge between two sodium cations, and one noncoordinating water molecule. The six-coordinated sodium cations form centrosymmetric dimeric units. The crystal structure is built of double layers of organic anions separated by single layers of inorganic cations perpendicular to the c axis. The inorganic dimerics are connected by hydrogen bonds. In the Cambridge Structural Database (CSD; ConQuest Version 1.17; Groom & Allen, 2014; Bruno et al., 2002), there are structures containing a one-, two- or three-dimensional polymeric arrangement of hexahydrated sodium units and structures containing oligomeric species. However, only in a few cases are there dimeric units as in (1) [CSD refcodes AVUNUA (reference), DOGQOG (reference), ECEPIL (reference), GEJXUQ (reference), MAJKUE (reference) and SIRGOQ (reference)] exist. Inter­estingly, for lithium hexahydrated species, there are no such dimeric, oligomeric and polymeric arrangements in the CSD.

The molecular fragment of salt (1), which could take direct part in a Norrish–Yang reaction, i.e. containing atoms O1, C7, C15, H15, C21 and H21, is surrounded by the weakly inter­acting organic species, as it is seen in Fig. 2. Moreover, there are no inter­molecular contacts for atoms O1, C15 and C21 closer than 3.6 Å. The inter­actions between the 4-(2,4,6-triiso­propyl­benzoyl)­benzoate species and the environment were visualized using Hirshfeld surface analysis (Spackman & Jayatilaka, 2009; Wolff et al., 2012), as shown in Fig. 3(a). In these visualizations, the red, white and blue colours symbolize, respectively, inter­molecular contacts close to, equal to and longer than the sum of the van der Waals radii,. As can be seen, inter­actions of the species with the environment are very similar for both o-iso­propyl groups and for both sides of the carbonyl group. These inter­actions have an impact on the molecular shape in the region of atoms O1, C7, C15, H15, C21 and H21, namely the carbonyl group is almost perpendicular to the plane of the ring of the 2,4,6-triiso­propyl­benzoyl fragment. This mutual orientation can be seen in Fig. 3(a). The above-described features of the Hirshfeld surface are consistent with the similar size of the voids near the two o-iso­propyl groups, which are shown in Fig. 3(b).

Several geometrical demands exist which should be fulfilled for a Norrish–Yang reaction to proceed in the crystalline state (Ihmels & Scheffer, 1999; Natarajan et al., 2005; Xia et al., 2005). The parameters describing them, presented in Scheme 2, are as follows: d is the distance between the γH and the O atom of a carbonyl group, D is the distance between the γC and a C atom of a carbonyl group, ω is the angular displacement of γH from the plane of a carbonyl group, Δ is the C═ O···γH angle and Θ is the C—H···O angle. Table 2 presents the ideal values of these parameters, the literature ranges observed for compounds undergoing a Norrish–Yang reaction, the values for the known 4-(2,4,6-triiso­propyl­benzoyl)­benzoate salts and for salt (1). As can be seen in this table, the values of the five geometrical parameters for salt (1), in contrast to the other to the 4-(2,4,6-triiso­propyl­benzoyl)­benzoate salts, are very similar for both o-iso­propyl groups, which is consistent with the above-discussed similar inter­molecular inter­actions. This indicates the lack of preference for one o-iso­propyl group to undergo a Norrish–Yang reaction.

The reactivity of 4-(2,4,6-triiso­propyl­benzoyl)­benzoate salts changes in the order ammonium > pyrrolidinium > benzyl­ammonium > (1) (Bąkowicz et al., 2014). Compound (1), in contrast to the known 4-(2,4,6-triiso­propyl­benzoyl)­benzoate salts, does not undergo a Norrish–Yang reaction, at least not to a degree dete­cta­ble by X-ray diffraction (see Experimental). The above order can be related to the order of the values of the geometrical parameters (see Table 2). For salt (1), the values of four of the five geometrical parameters lie close to the border literature limits, namely d and ω are close to the upper literature limits and Δ and Θ to the lower limits, i.e. all of them to such limits which are not suitable for compounds to undergo a δ-abstraction and a Norrish–Yang reaction.

The ideal values of the geometrical parameters for the formation of a four-membered ring are also valid for the formation of a five-membered ring, except for the D parameter (Cheung et al., 2000). The values of the geometrical parameters calculated for a δ-abstraction in the case of salt (1), also shown in Table 2, indicate that this salt will also not undergo a five-membered-ring formation reaction.

The data indicate that crystals of sodium and lithium 4-(2,4,6-triiso­propyl­benzoyl)­benzoate, i.e. (1) and (2), respectively, are isomorphous (see Experimental). Based on this, we can suppose that the lithium salt should exhibit the same photochemical behaviour as the sodium salt.

Contrary to other 4-(2,4,6-triiso­propyl­benzoyl)­benzoate salts with known crystal structures, salt (1) does not undergo a Norrish–Yang reaction in the crystalline state. The reason for this inactivity is connected with the values of the geometrical parameters close to the border limit for nonphotoactive compounds. This, in turn, is a result of intra­molecular inter­actions in the crystals. Salt (1), together with the other known 4-(2,4,6-triiso­propyl­benzoyl)­benzoate salts, shows to what extent it is possible to influence the reactivity of one organic species by placing it in various crystal lattices; it is even possible to inhibit the photochemical reaction.

Computing details

Data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

Figures

	Fig. 1. The molecular species in compound (I), with displacement ellipsoids drawn at the 20% probability level.
	Fig. 2. (a) The fragment of a crystal lattice and (b) hydrogen bonds in the layer of hydrated sodium anions (for clarity, only the carboxylate groups from the anions were shown) for compound (1), visualized using Mercury (Macrae et al., 2006).
	Fig. 3. (a) The Hirshfeld surface and (b) voids for the fragment of the crystal lattice of salt (1). The voids were calculated for the radius of a ball of 0.9 Å and the grid of 0.2 Å.

Di-µ-aqua-bis[tetraaquasodium(I)] bis[4-(2,4,6-triisopropylbenzoyl)benzoate] dihydrate

Crystal data

[Na2(H2O)10](C23H27O3)2·2H2O	Z = 1
Mr = 965.06	F(000) = 520
Triclinic, P1	Dx = 1.198 Mg m^−3
a = 6.1299 (6) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.7431 (9) Å	Cell parameters from 1454 reflections
c = 26.054 (3) Å	θ = 2.3–24.0°
α = 91.701 (8)°	µ = 0.10 mm^−1
β = 91.617 (8)°	T = 299 K
γ = 106.471 (9)°	Block, colourless
V = 1337.5 (3) Å^3	0.40 × 0.35 × 0.10 mm

Data collection

Agilent KM-4 with an Eos CCD detector diffractometer	4712 independent reflections
Radiation source: fine-focus sealed tube	2699 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.064
Detector resolution: 15.9718 pixels mm^-1	θmax = 25.0°, θmin = 2.4°
ω scans	h = −7→7
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −10→9
Tmin = 0.915, Tmax = 1.000	l = −30→30
8856 measured reflections

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)] = 0.079	Hydrogen site location: mixed
wR(F^2) = 0.163	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0583P)^2 + 0.1095P] where P = (Fo^2 + 2Fc^2)/3
4712 reflections	(Δ/σ)max < 0.001
334 parameters	Δρmax = 0.20 e Å^−3
18 restraints	Δρmin = −0.18 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.

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

	x	y	z	Uiso*/Ueq
O1	0.1404 (4)	0.8044 (4)	0.29801 (11)	0.0771 (9)
O2	0.3166 (4)	0.3187 (3)	0.09624 (10)	0.0660 (8)
O3	0.6720 (4)	0.4708 (3)	0.09291 (9)	0.0527 (7)
C1	0.6308 (5)	1.0743 (4)	0.30487 (12)	0.0388 (9)
C2	0.8078 (6)	1.1701 (4)	0.33607 (13)	0.0402 (9)
H2	0.8727	1.2753	0.3275	0.048*
C3	0.8910 (5)	1.1142 (4)	0.37947 (13)	0.0370 (8)
C4	0.7915 (6)	0.9567 (4)	0.39115 (13)	0.0421 (9)
H4	0.8453	0.9171	0.4201	0.051*
C5	0.6148 (6)	0.8556 (4)	0.36137 (13)	0.0386 (9)
C6	0.5343 (5)	0.9177 (4)	0.31852 (12)	0.0368 (8)
C7	0.3346 (6)	0.8121 (4)	0.28701 (13)	0.0436 (9)
C8	0.3782 (5)	0.7172 (4)	0.24152 (12)	0.0343 (8)
C9	0.1938 (5)	0.6127 (4)	0.21513 (13)	0.0422 (9)
H9	0.0473	0.6028	0.2260	0.051*
C10	0.2244 (6)	0.5237 (4)	0.17324 (13)	0.0442 (9)
H10	0.0987	0.4537	0.1561	0.053*
C11	0.4418 (5)	0.5370 (4)	0.15602 (12)	0.0328 (8)
C12	0.6262 (5)	0.6431 (4)	0.18260 (12)	0.0381 (8)
H12	0.7726	0.6544	0.1715	0.046*
C13	0.5960 (5)	0.7312 (4)	0.22482 (13)	0.0388 (9)
H13	0.7214	0.8004	0.2423	0.047*
C14	0.4789 (6)	0.4356 (4)	0.11191 (13)	0.0397 (9)
C15	0.5415 (6)	1.1416 (5)	0.25813 (14)	0.0520 (10)
H15	0.4400	1.0506	0.2385	0.062*
C16	0.3995 (9)	1.2495 (7)	0.27315 (19)	0.111 (2)
H16A	0.2834	1.1950	0.2955	0.166*
H16B	0.4947	1.3442	0.2906	0.166*
H16C	0.3297	1.2782	0.2429	0.166*
C17	0.7254 (8)	1.2210 (6)	0.22313 (16)	0.0898 (16)
H17A	0.8124	1.1491	0.2143	0.135*
H17B	0.6584	1.2495	0.1924	0.135*
H17C	0.8234	1.3155	0.2402	0.135*
C18	1.0784 (6)	1.2227 (4)	0.41362 (13)	0.0460 (9)
H18	1.1429	1.3199	0.3950	0.055*
C19	1.2711 (6)	1.1503 (5)	0.42599 (17)	0.0716 (13)
H19A	1.3848	1.2239	0.4477	0.107*
H19B	1.2124	1.0527	0.4434	0.107*
H19C	1.3377	1.1286	0.3947	0.107*
C20	0.9808 (7)	1.2714 (5)	0.46242 (15)	0.0691 (12)
H20A	1.1014	1.3402	0.4837	0.104*
H20B	0.8712	1.3269	0.4537	0.104*
H20C	0.9083	1.1778	0.4807	0.104*
C21	0.5098 (6)	0.6856 (4)	0.37746 (14)	0.0505 (10)
H21	0.4021	0.6298	0.3499	0.061*
C22	0.3753 (9)	0.6868 (6)	0.42576 (18)	0.1007 (18)
H22A	0.2656	0.7446	0.4199	0.151*
H22B	0.2981	0.5792	0.4340	0.151*
H22C	0.4776	0.7376	0.4538	0.151*
C23	0.6853 (8)	0.5961 (5)	0.3846 (2)	0.0947 (16)
H23A	0.6120	0.4897	0.3947	0.142*
H23B	0.7595	0.5916	0.3529	0.142*
H23C	0.7961	0.6501	0.4108	0.142*
Na1	0.7106 (2)	0.16169 (16)	−0.02262 (5)	0.0495 (4)
O4	0.8355 (4)	0.2101 (3)	0.07037 (11)	0.0584 (7)
HO4A	0.791 (7)	0.291 (4)	0.0760 (16)	0.088*
HO4B	0.971 (4)	0.231 (5)	0.0797 (17)	0.088*
O5	0.7487 (7)	0.4386 (4)	−0.01540 (12)	0.0804 (9)
HO5A	0.771 (9)	0.505 (5)	−0.0370 (14)	0.121*
HO5B	0.703 (9)	0.461 (6)	0.0125 (11)	0.121*
O6	1.0667 (5)	0.2167 (3)	−0.06548 (10)	0.0560 (7)
HO6A	1.145 (6)	0.304 (3)	−0.0739 (15)	0.084*
HO6B	1.043 (7)	0.156 (4)	−0.0907 (11)	0.084*
O7	0.4926 (5)	0.0655 (4)	−0.10448 (13)	0.0760 (9)
HO7A	0.459 (8)	0.132 (4)	−0.1209 (19)	0.114*
HO7B	0.387 (6)	−0.015 (4)	−0.0992 (19)	0.114*
O8	0.6689 (4)	−0.1145 (3)	−0.01261 (10)	0.0481 (7)
HO8A	0.739 (6)	−0.141 (5)	0.0108 (10)	0.072*
HO8B	0.667 (7)	−0.172 (4)	−0.0385 (10)	0.072*
O9	0.1088 (7)	0.0001 (5)	0.14832 (17)	0.1067 (12)
HO9A	0.227 (7)	−0.027 (7)	0.142 (3)	0.160*
HO9B	0.148 (10)	0.101 (2)	0.150 (3)	0.160*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0361 (16)	0.106 (2)	0.079 (2)	0.0089 (16)	0.0034 (14)	−0.0447 (17)
O2	0.0478 (16)	0.065 (2)	0.0765 (19)	0.0067 (15)	−0.0014 (14)	−0.0400 (15)
O3	0.0473 (16)	0.0507 (17)	0.0590 (17)	0.0129 (13)	0.0103 (13)	−0.0112 (12)
C1	0.037 (2)	0.042 (2)	0.035 (2)	0.0080 (18)	0.0030 (17)	0.0005 (17)
C2	0.043 (2)	0.028 (2)	0.046 (2)	0.0028 (17)	0.0054 (18)	0.0024 (16)
C3	0.0346 (19)	0.034 (2)	0.037 (2)	0.0013 (17)	0.0014 (16)	−0.0006 (16)
C4	0.049 (2)	0.036 (2)	0.038 (2)	0.0058 (18)	−0.0027 (18)	0.0060 (16)
C5	0.041 (2)	0.031 (2)	0.039 (2)	0.0025 (17)	0.0029 (17)	−0.0043 (16)
C6	0.0348 (19)	0.039 (2)	0.033 (2)	0.0057 (17)	0.0010 (16)	−0.0052 (16)
C7	0.037 (2)	0.045 (2)	0.046 (2)	0.0062 (18)	0.0031 (18)	−0.0041 (17)
C8	0.0339 (19)	0.034 (2)	0.035 (2)	0.0110 (17)	−0.0015 (16)	−0.0031 (15)
C9	0.0244 (18)	0.045 (2)	0.052 (2)	0.0028 (17)	−0.0012 (17)	−0.0082 (18)
C10	0.033 (2)	0.048 (2)	0.045 (2)	0.0042 (18)	−0.0062 (18)	−0.0135 (18)
C11	0.0315 (19)	0.0320 (19)	0.036 (2)	0.0104 (16)	−0.0011 (16)	0.0024 (15)
C12	0.0284 (19)	0.042 (2)	0.044 (2)	0.0109 (17)	0.0018 (17)	−0.0025 (17)
C13	0.0275 (19)	0.040 (2)	0.043 (2)	0.0008 (16)	−0.0035 (17)	−0.0077 (17)
C14	0.042 (2)	0.036 (2)	0.043 (2)	0.0165 (19)	−0.0042 (19)	−0.0057 (17)
C15	0.054 (2)	0.053 (3)	0.045 (2)	0.009 (2)	−0.007 (2)	0.0075 (19)
C16	0.130 (5)	0.152 (5)	0.094 (4)	0.105 (5)	0.018 (3)	0.037 (4)
C17	0.090 (4)	0.119 (4)	0.060 (3)	0.024 (3)	0.010 (3)	0.044 (3)
C18	0.047 (2)	0.041 (2)	0.039 (2)	−0.0043 (18)	−0.0041 (18)	−0.0007 (17)
C19	0.048 (3)	0.080 (3)	0.077 (3)	0.005 (2)	−0.014 (2)	−0.005 (2)
C20	0.076 (3)	0.062 (3)	0.055 (3)	0.000 (2)	−0.006 (2)	−0.018 (2)
C21	0.056 (2)	0.032 (2)	0.053 (2)	−0.0033 (19)	−0.003 (2)	−0.0002 (17)
C22	0.123 (4)	0.062 (3)	0.092 (4)	−0.020 (3)	0.042 (3)	0.006 (3)
C23	0.092 (4)	0.042 (3)	0.144 (5)	0.008 (3)	−0.011 (3)	0.018 (3)
Na1	0.0454 (8)	0.0408 (9)	0.0601 (9)	0.0081 (7)	0.0089 (7)	−0.0011 (7)
O4	0.0507 (17)	0.0569 (19)	0.0703 (19)	0.0218 (15)	−0.0064 (15)	−0.0099 (14)
O5	0.117 (3)	0.053 (2)	0.073 (2)	0.0261 (19)	0.008 (2)	0.0076 (16)
O6	0.0544 (18)	0.0521 (19)	0.0581 (18)	0.0093 (15)	0.0074 (15)	−0.0010 (13)
O7	0.080 (2)	0.067 (2)	0.078 (2)	0.0179 (18)	−0.0062 (18)	0.0105 (17)
O8	0.0517 (16)	0.0450 (17)	0.0495 (17)	0.0181 (13)	−0.0026 (13)	−0.0084 (13)
O9	0.112 (3)	0.092 (3)	0.108 (3)	0.018 (2)	−0.005 (2)	−0.017 (2)

Geometric parameters (Å, º)

O1—C7	1.216 (4)	C18—C19	1.522 (5)
O2—C14	1.255 (4)	C18—H18	0.9800
O3—C14	1.256 (4)	C19—H19A	0.9600
C1—C6	1.390 (5)	C19—H19B	0.9600
C1—C2	1.390 (4)	C19—H19C	0.9600
C1—C15	1.522 (5)	C20—H20A	0.9600
C2—C3	1.385 (4)	C20—H20B	0.9600
C2—H2	0.9300	C20—H20C	0.9600
C3—C4	1.386 (4)	C21—C23	1.510 (5)
C3—C18	1.512 (4)	C21—C22	1.525 (6)
C4—C5	1.388 (4)	C21—H21	0.9800
C4—H4	0.9300	C22—H22A	0.9600
C5—C6	1.394 (4)	C22—H22B	0.9600
C5—C21	1.519 (5)	C22—H22C	0.9600
C6—C7	1.511 (5)	C23—H23A	0.9600
C7—C8	1.500 (5)	C23—H23B	0.9600
C8—C9	1.385 (4)	C23—H23C	0.9600
C8—C13	1.389 (4)	Na1—O5	2.367 (3)
C9—C10	1.369 (5)	Na1—O8	2.378 (3)
C9—H9	0.9300	Na1—O6	2.412 (3)
C10—C11	1.392 (4)	Na1—O8^i	2.454 (3)
C10—H10	0.9300	Na1—O7	2.478 (3)
C11—C12	1.393 (4)	Na1—O4	2.507 (3)
C11—C14	1.493 (5)	Na1—Na1^i	3.504 (3)
C12—C13	1.371 (4)	O4—HO4A	0.839 (18)
C12—H12	0.9300	O4—HO4B	0.824 (18)
C13—H13	0.9300	O5—HO5A	0.809 (19)
C15—C17	1.495 (5)	O5—HO5B	0.825 (19)
C15—C16	1.505 (6)	O6—HO6A	0.821 (18)
C15—H15	0.9800	O6—HO6B	0.813 (18)
C16—H16A	0.9600	O7—HO7A	0.805 (19)
C16—H16B	0.9600	O7—HO7B	0.829 (19)
C16—H16C	0.9600	O8—Na1^i	2.454 (3)
C17—H17A	0.9600	O8—HO8A	0.813 (18)
C17—H17B	0.9600	O8—HO8B	0.826 (18)
C17—H17C	0.9600	O9—HO9A	0.845 (19)
C18—C20	1.520 (5)	O9—HO9B	0.841 (19)
C6—C1—C2	118.1 (3)	H19A—C19—H19B	109.5
C6—C1—C15	121.3 (3)	C18—C19—H19C	109.5
C2—C1—C15	120.6 (3)	H19A—C19—H19C	109.5
C3—C2—C1	122.3 (3)	H19B—C19—H19C	109.5
C3—C2—H2	118.8	C18—C20—H20A	109.5
C1—C2—H2	118.8	C18—C20—H20B	109.5
C2—C3—C4	117.5 (3)	H20A—C20—H20B	109.5
C2—C3—C18	121.1 (3)	C18—C20—H20C	109.5
C4—C3—C18	121.4 (3)	H20A—C20—H20C	109.5
C3—C4—C5	122.7 (3)	H20B—C20—H20C	109.5
C3—C4—H4	118.7	C23—C21—C5	112.2 (3)
C5—C4—H4	118.7	C23—C21—C22	111.7 (4)
C4—C5—C6	117.8 (3)	C5—C21—C22	109.8 (3)
C4—C5—C21	119.7 (3)	C23—C21—H21	107.6
C6—C5—C21	122.5 (3)	C5—C21—H21	107.6
C1—C6—C5	121.6 (3)	C22—C21—H21	107.6
C1—C6—C7	119.7 (3)	C21—C22—H22A	109.5
C5—C6—C7	118.7 (3)	C21—C22—H22B	109.5
O1—C7—C8	120.1 (3)	H22A—C22—H22B	109.5
O1—C7—C6	120.7 (3)	C21—C22—H22C	109.5
C8—C7—C6	119.3 (3)	H22A—C22—H22C	109.5
C9—C8—C13	119.0 (3)	H22B—C22—H22C	109.5
C9—C8—C7	118.5 (3)	C21—C23—H23A	109.5
C13—C8—C7	122.4 (3)	C21—C23—H23B	109.5
C10—C9—C8	120.8 (3)	H23A—C23—H23B	109.5
C10—C9—H9	119.6	C21—C23—H23C	109.5
C8—C9—H9	119.6	H23A—C23—H23C	109.5
C9—C10—C11	120.7 (3)	H23B—C23—H23C	109.5
C9—C10—H10	119.6	O5—Na1—O8	169.12 (12)
C11—C10—H10	119.6	O5—Na1—O6	89.92 (12)
C10—C11—C12	118.1 (3)	O8—Na1—O6	95.90 (10)
C10—C11—C14	121.3 (3)	O5—Na1—O8^i	88.05 (12)
C12—C11—C14	120.5 (3)	O8—Na1—O8^i	87.05 (9)
C13—C12—C11	121.3 (3)	O6—Na1—O8^i	173.87 (11)
C13—C12—H12	119.4	O5—Na1—O7	105.81 (12)
C11—C12—H12	119.4	O8—Na1—O7	83.29 (10)
C12—C13—C8	120.1 (3)	O6—Na1—O7	91.40 (11)
C12—C13—H13	120.0	O8^i—Na1—O7	83.60 (11)
C8—C13—H13	120.0	O5—Na1—O4	81.20 (11)
O2—C14—O3	123.6 (3)	O8—Na1—O4	88.54 (10)
O2—C14—C11	118.4 (3)	O6—Na1—O4	102.81 (10)
O3—C14—C11	118.1 (3)	O8^i—Na1—O4	82.59 (9)
C17—C15—C16	111.7 (4)	O7—Na1—O4	164.29 (11)
C17—C15—C1	112.9 (3)	O5—Na1—Na1^i	130.00 (11)
C16—C15—C1	111.8 (3)	O8—Na1—Na1^i	44.38 (7)
C17—C15—H15	106.7	O6—Na1—Na1^i	140.00 (10)
C16—C15—H15	106.7	O8^i—Na1—Na1^i	42.68 (6)
C1—C15—H15	106.7	O7—Na1—Na1^i	80.94 (9)
C15—C16—H16A	109.5	O4—Na1—Na1^i	83.83 (8)
C15—C16—H16B	109.5	Na1—O4—HO4A	98 (3)
H16A—C16—H16B	109.5	Na1—O4—HO4B	122 (3)
C15—C16—H16C	109.5	HO4A—O4—HO4B	108 (3)
H16A—C16—H16C	109.5	Na1—O5—HO5A	131 (4)
H16B—C16—H16C	109.5	Na1—O5—HO5B	110 (4)
C15—C17—H17A	109.5	HO5A—O5—HO5B	118 (4)
C15—C17—H17B	109.5	Na1—O6—HO6A	127 (3)
H17A—C17—H17B	109.5	Na1—O6—HO6B	106 (3)
C15—C17—H17C	109.5	HO6A—O6—HO6B	108 (3)
H17A—C17—H17C	109.5	Na1—O7—HO7A	116 (4)
H17B—C17—H17C	109.5	Na1—O7—HO7B	109 (4)
C3—C18—C20	110.3 (3)	HO7A—O7—HO7B	116 (4)
C3—C18—C19	113.0 (3)	Na1—O8—Na1^i	92.95 (9)
C20—C18—C19	111.1 (3)	Na1—O8—HO8A	119 (3)
C3—C18—H18	107.4	Na1^i—O8—HO8A	102 (3)
C20—C18—H18	107.4	Na1—O8—HO8B	119 (3)
C19—C18—H18	107.4	Na1^i—O8—HO8B	112 (3)
C18—C19—H19A	109.5	HO8A—O8—HO8B	110 (3)
C18—C19—H19B	109.5	HO9A—O9—HO9B	106 (4)

Symmetry code: (i) −x+1, −y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—HO4A···O3	0.84 (2)	1.96 (2)	2.792 (3)	176 (5)
O4—HO4B···O2^ii	0.82 (2)	2.07 (2)	2.884 (4)	170 (4)
O5—HO5A···O2^iii	0.81 (2)	2.37 (3)	3.130 (4)	158 (5)
O5—HO5B···O3	0.83 (2)	2.11 (2)	2.892 (4)	158 (5)
O6—HO6A···O3^iv	0.82 (2)	2.05 (2)	2.870 (4)	177 (4)
O6—HO6B···O9^i	0.81 (2)	2.02 (2)	2.807 (5)	164 (4)
O7—HO7B···O4^i	0.83 (2)	2.04 (2)	2.850 (4)	167 (5)
O7—HO7A···C12^iii	0.81 (2)	2.73 (2)	3.527 (4)	175 (5)
O8—HO8A···O6^v	0.81 (2)	2.07 (2)	2.882 (4)	175 (4)
O8—HO8B···O2^i	0.83 (2)	1.97 (2)	2.795 (3)	174 (4)
O9—HO9A···O7^i	0.85 (2)	2.10 (3)	2.919 (5)	162 (7)
O9—HO9B···O2	0.84 (2)	2.40 (5)	3.088 (5)	139 (6)

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