Poly[[di-μ-aqua-(μ-4-formyl-2-meth­oxy­phenol­ato)disodium] 4-formyl-2-meth­oxy­phenolate]

In the title coordination polymer, {[Na₂(C₈H₇O₃)(H₂O)₄](C₈H₇O₃)}_n, all the non-H atoms except the water O atoms lie on a crystallographic mirror plane. One sodium cation is bonded to four water O atoms and one vanillinate O atom in a distorted square-based pyramidal arrangement; the other Na⁺ ion is six-coordinated by four water O atoms and two vanillinate O atoms in an irregular geometry. One of the vanillinate anions is directly bonded to two sodium ions, whilst the other only inter­acts with the polymeric network by way of hydrogen bonds. In the crystal, a two-dimensional polymeric array is formed; this is reinforced by O—H...O hydrogen bonds, which generate R₂¹(6) and R₂²(20) loops.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.044
• wR factor = 0.119
• Data-to-parameter ratio = 11.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.84 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.11 Ratio
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C13
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C14
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C12
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.58
PLAT309_ALERT_2_C Single Bonded Oxygen (C-O .GT. 1.3 Ang) ........         O5
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          2
PLAT927_ALERT_1_C Reported and Calculated  wR2 * 100.0 Differ by .      -0.27

Alert level G
FORMU01_ALERT_1_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and _chemical_formula_moiety. This is
            usually due to the moiety formula being in the wrong format.
            Atom count from _chemical_formula_sum:   C16 H22 Na2 O10
            Atom count from _chemical_formula_moiety:C16 H22 Na2 O4
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         12
PLAT960_ALERT_3_G Number of Intensities with I .LT. - 2*sig(I) ..           2

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   9 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   6 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check


checkCIF publication errors

Alert level A
PUBL024_ALERT_1_A The number of authors is greater than 5.
              Please specify the role of each of the co-authors
              for your paper.

Author Response: Each of the six authors has been involved in this study.

   1 ALERT level A = Data missing that is essential or data in wrong format
   0 ALERT level G = General alerts. Data that may be required is missing

---

S1. Comment

The crystal structures of vanillin-I (Velavan et al., 1995), the polymorphic forms of isovanillin (Iwasaki, 1973), o-vanillin (Iwasaki et al., 1976) and other vanillin derivatives (Usman et al., 2002; Li et al., 1999) have been reported. We now report the title compound, (I).

The basic polymeric fragment of (I), with asymmetric unit formula [Na₂(H₂O)₂(C₈H₇O₃)₂]_n, is illustrated in Fig. 1. The Na⁺ cations are of two coordination types. In the first of these coordination, the Na1 coordination by four O atoms from two equivalent water molecules (O1, O2, O1^iv and O2^iv) and the bonded carboxylate O atom from vanillin ligand (O6) (Table 1). In the second coordination, cation Na2 is coordinated by four O atoms from two equivalent water molecules (O1, O2, O1^vii and O2^vii) and two O atoms from vanillin ligand (O7^vi and O8^vi) [symmetry codes: (iv) x, 1/2 - y, z; (vi) 3/2 - x, -y, 1/2 + z; (vii) x, -1/2 - y, z]. The vanillin ligand five-membered (O7^vi/C11^vi/C12^vi/O8^vi/Na2) chelates to the Na atom through the methoxy and hydroxy groups. Two adjacent Na⁺ cations are linked together by two H₂O bridges to form a four-membered ring with an Na₂O₂ core. The Na1···Na2 separation is 3.7595 (8) Å. Adjacent Na₂O₂ binuclear motifs are further joined by the vanillin ligand through carboxyl atoms O6, O7 and O8, to produce a one-dimensional chain along the c axis, with an Na1···Na2ⁱⁱ separation of 9.890Å [symmetry code: (ii) 3/2 - x, 1 - y, z - 1/2]; this compares with the corresponding Na···Na distance of 8.006 (3)Å in the three-dimensional Na-terephthalate polymer [Na₂(C₈H₄O₄)] (Kaduk, 2000). These chains are connected by the water O atoms [Na1···Na2^v = 3.7595 (8) Å; symmetry code: (v) x, 1 + y, z], generating a two-dimensional layer architecture in the crystallographic bc plane (Fig. 2).

Water atom O1 in the molecule at (x, y, z) acts as a hydrogen-bond donor, via H1B, to atom O8ⁱ so forming a C(10)[R₂²(20)] (Bernstein et al., 1995) chain of rings running parallel to the [0–10] direction and centrosymmetric R₂²(20) rings centred at (1/2, 1/2+n/2, 1/2) (n = zero or integer). The combination of O1—H1B···O8ⁱ and O1^ix—H1B^ix···O8ⁱ hydrogen bonds produce R₂¹(6) ring (Fig. 3). Water atom O2 in the molecule at (x, y, z) acts as a hydrogen-bond donor, via H2A, to atom O4ⁱⁱ, while O1ⁱⁱ acts as donor to O5ⁱⁱ, and in this manner a C₂²(12) chain running parallel to the [00–1] direction. The combination of O2—H2A···O4ⁱⁱ, O1ⁱⁱ—H1Aⁱⁱ···O5ⁱⁱ and O2^ix—H2A^ix···O4ⁱⁱ hydrogen bonds produce R₂¹(6) and R₂²(20) rings (Fig. 4).

Related literature

For related crystal structures, see: Velavan et al. (1995); Iwasaki (1973); Iwasaki et al. (1976); Usman et al. (2002); Li et al. (1999); Kaduk (2000). For graph-set notation, see: Bernstein et al. (1995).

S2. Experimental

Sodium hydroxide (0.66 g, 0.0165 mmol) was dissolved in a mixture of distilled water (10 ml) and ethanol (8 ml). The solution was cooled to room temperature. Half of the mixture of vanillin (1 g, 0.00658 mmol) and acetone (0.19 g, 0.00329 mmol) added to the above solution and stirred at room temperature for 15 minute then the remaining mixture was added and stirred for 2 h under the same conditions. The greenish-yellow precipitate obtained was filtered and recystalized from methanol to yield colourless blocks of (I).

S3. Refinement

All H atoms bound to C atoms were refined using a riding model, with C—H = 0.93Å and U_iso(H) = 1.2U_eq(C) for aromatic C, and C—H = 0.96Å and U_iso(H) = 1.5U_eq(C) for methyl C atoms. Water H atom was located in difference maps and refined subject to a restraint of O—H = 0.83 (2) Å.

Computing details

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999) and SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. A view of the asymmetric unit of (I), showing displacement ellipsoids drawn at the 30% probability level. Hydrogen bonds are indicated by dashed lines.
	Fig. 2. View of part of the crystal structure of compound (I), showing the formation of a coordination polymer chain parallel to the bc plane. For the sake of clarity, the noncoordinated molecule and all H atoms have been omitted. [Symmetry codes: (ii) 3/2 - x, 1 - y, z - 1/2; (iv) x, 3/2 - y, z; (v) x, 1 + y, z; (vi) 3/2 - x, 1 - y, 1/2 + z; (vii) x, 1/2 - y, z; (viii) x, y - 1, z.]
	Fig. 3. Part of the crystal structure of (I), showing the formation of R2^1(6) and R2^2(20) rings. For the sake of clarity, the noncoordinated molecule and H atoms have been omitted. [Symmetry codes: (i) 1 - x, 1 - y, 1 - z; (ix) x, 1/2 - y, z.]
	Fig. 4. Part of the crystal structure of (I), showing the formation of R2^1(6) and R2^2(20) rings. H atoms not involved in these interactions have been omitted for clarity. [Symmetry codes: (ii) 3/2 - x, 1 - y, z - 1/2; (ix) x, 1/2 - y, z.]

Poly[[di-µ-aqua-(µ-4-formyl-2-methoxyphenolato)disodium] 4-formyl-2-methoxyphenolate]

Crystal data

[Na2(C8H7O3)(H2O)4](C8H7O3)	F(000) = 880
Mr = 420.32	Dx = 1.488 Mg m^−3
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 5113 reflections
a = 12.2281 (6) Å	θ = 3.0–31.1°
b = 6.7681 (3) Å	µ = 0.16 mm^−1
c = 22.6734 (10) Å	T = 296 K
V = 1876.47 (15) Å^3	Block, colourles
Z = 4	0.42 × 0.33 × 0.24 mm

Data collection

Bruker APEXII CCD diffractometer	2121 independent reflections
Radiation source: fine-focus sealed tube	1825 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
phi and ω scans	θmax = 26.5°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −15→15
Tmin = 0.938, Tmax = 0.962	k = −8→4
10469 measured reflections	l = −19→28

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.044	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.119	w = 1/[σ^2(Fo^2) + (0.0476P)^2 + 1.7283P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.001
2121 reflections	Δρmax = 0.63 e Å^−3
180 parameters	Δρmin = −0.67 e Å^−3
12 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0138 (14)

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	Occ. (<1)
C1	0.6494 (2)	0.7500	0.97772 (12)	0.0327 (7)
C2	0.7164 (2)	0.7500	0.92725 (13)	0.0321 (7)
H2	0.7920	0.7500	0.9315	0.039*
C3	0.6713 (2)	0.7500	0.87213 (12)	0.0263 (6)
C4	0.5554 (2)	0.7500	0.86488 (12)	0.0260 (6)
C5	0.4908 (2)	0.7500	0.91595 (13)	0.0317 (7)
H5	0.4151	0.7500	0.9123	0.038*
C6	0.5368 (2)	0.7500	0.97117 (13)	0.0331 (7)
H6	0.4921	0.7500	1.0044	0.040*
C7	0.6978 (3)	0.7500	1.03533 (14)	0.0505 (10)
H7	0.7738	0.7500	1.0370	0.061*
C8	0.8444 (2)	0.7500	0.82464 (14)	0.0345 (7)
H8A	0.8757	0.7214	0.7868	0.052*	0.50
H8B	0.8669	0.6512	0.8525	0.052*	0.50
H8C	0.8689	0.8774	0.8377	0.052*	0.50
C9	0.6086 (3)	0.7500	0.49146 (15)	0.0582 (12)
C10	0.7012 (2)	0.7500	0.45577 (13)	0.0318 (7)
H10	0.7704	0.7500	0.4728	0.038*
C11	0.6907 (2)	0.7500	0.39567 (12)	0.0258 (6)
C12	0.5862 (2)	0.7500	0.36734 (13)	0.0336 (7)
C13	0.4958 (3)	0.7500	0.40446 (17)	0.092 (2)
H13	0.4260	0.7500	0.3882	0.111*
C14	0.5076 (3)	0.7500	0.46474 (18)	0.099 (2)
H14	0.4452	0.7500	0.4882	0.118*
C15	0.6143 (3)	0.7500	0.55467 (17)	0.0725 (15)
H15	0.5477	0.7500	0.5745	0.087*
C16	0.8841 (2)	0.7500	0.38079 (14)	0.0364 (7)
H16A	0.8962	0.8710	0.4019	0.055*	0.50
H16B	0.9364	0.7389	0.3494	0.055*	0.50
H16C	0.8922	0.6401	0.4072	0.055*	0.50
O1	0.59561 (12)	0.4859 (3)	0.73010 (7)	0.0386 (4)
H1A	0.5721 (19)	0.552 (4)	0.7574 (10)	0.047 (8)*
H1B	0.5423 (18)	0.426 (4)	0.7162 (11)	0.060 (9)*
O2	0.83431 (12)	0.4956 (3)	0.68524 (7)	0.0353 (4)
H2A	0.835 (2)	0.439 (4)	0.6534 (9)	0.047 (8)*
H2B	0.8935 (17)	0.557 (4)	0.6870 (11)	0.051 (8)*
O3	0.72906 (16)	0.7500	0.82013 (9)	0.0352 (5)
O4	0.6492 (2)	0.7500	1.08231 (10)	0.0528 (7)
O5	0.51190 (16)	0.7500	0.81191 (8)	0.0319 (5)
O6	0.6945 (2)	0.7500	0.58503 (11)	0.0611 (8)
O7	0.77607 (16)	0.7500	0.35679 (9)	0.0367 (5)
O8	0.57840 (16)	0.7500	0.31048 (8)	0.0325 (5)
Na1	0.69720 (10)	0.7500	0.68819 (5)	0.0353 (3)
Na2	0.75745 (10)	0.2500	0.75268 (5)	0.0343 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0341 (15)	0.0405 (18)	0.0234 (14)	0.000	−0.0004 (11)	0.000
C2	0.0253 (13)	0.0429 (18)	0.0282 (14)	0.000	−0.0014 (11)	0.000
C3	0.0260 (13)	0.0284 (15)	0.0245 (13)	0.000	0.0031 (10)	0.000
C4	0.0265 (13)	0.0271 (15)	0.0245 (13)	0.000	−0.0018 (10)	0.000
C5	0.0241 (13)	0.0400 (17)	0.0309 (15)	0.000	0.0014 (11)	0.000
C6	0.0322 (14)	0.0404 (18)	0.0268 (14)	0.000	0.0053 (11)	0.000
C7	0.0400 (17)	0.084 (3)	0.0279 (16)	0.000	−0.0038 (13)	0.000
C8	0.0274 (14)	0.0409 (18)	0.0352 (16)	0.000	0.0065 (12)	0.000
C9	0.0366 (17)	0.110 (4)	0.0276 (17)	0.000	0.0020 (13)	0.000
C10	0.0299 (14)	0.0375 (17)	0.0281 (14)	0.000	−0.0045 (11)	0.000
C11	0.0268 (13)	0.0240 (14)	0.0267 (13)	0.000	0.0007 (10)	0.000
C12	0.0295 (14)	0.0457 (19)	0.0256 (14)	0.000	−0.0029 (11)	0.000
C13	0.0249 (16)	0.219 (7)	0.0333 (18)	0.000	−0.0012 (14)	0.000
C14	0.0368 (19)	0.218 (6)	0.041 (2)	0.000	0.0087 (17)	0.000
C15	0.047 (2)	0.138 (5)	0.0322 (19)	0.000	0.0065 (16)	0.000
C16	0.0245 (13)	0.0486 (19)	0.0363 (16)	0.000	−0.0056 (12)	0.000
O1	0.0325 (8)	0.0420 (10)	0.0413 (9)	−0.0063 (7)	0.0053 (7)	−0.0109 (8)
O2	0.0347 (8)	0.0402 (9)	0.0311 (8)	−0.0032 (7)	0.0039 (6)	−0.0014 (7)
O3	0.0256 (10)	0.0557 (15)	0.0243 (10)	0.000	0.0028 (8)	0.000
O4	0.0623 (16)	0.0727 (19)	0.0233 (11)	0.000	−0.0007 (10)	0.000
O5	0.0266 (9)	0.0442 (13)	0.0249 (10)	0.000	−0.0030 (8)	0.000
O6	0.0559 (16)	0.099 (2)	0.0287 (12)	0.000	−0.0051 (11)	0.000
O7	0.0243 (10)	0.0597 (15)	0.0262 (10)	0.000	−0.0024 (8)	0.000
O8	0.0291 (10)	0.0442 (13)	0.0242 (10)	0.000	−0.0039 (8)	0.000
Na1	0.0336 (6)	0.0352 (7)	0.0371 (7)	0.000	0.0020 (5)	0.000
Na2	0.0337 (6)	0.0422 (7)	0.0272 (6)	0.000	0.0001 (5)	0.000

Geometric parameters (Å, º)

C1—C6	1.385 (4)	C12—C13	1.390 (5)
C1—C2	1.407 (4)	C13—C14	1.374 (6)
C1—C7	1.434 (4)	C13—H13	0.9300
C2—C3	1.366 (4)	C14—H14	0.9300
C2—H2	0.9300	C15—O6	1.198 (5)
C3—O3	1.374 (3)	C15—H15	0.9300
C3—C4	1.427 (4)	C16—O7	1.428 (3)
C4—O5	1.314 (3)	C16—H16A	0.9600
C4—C5	1.402 (4)	C16—H16B	0.9600
C5—C6	1.372 (4)	C16—H16C	0.9600
C5—H5	0.9300	O1—H1A	0.817 (17)
C6—H6	0.9300	O1—H1B	0.830 (17)
C7—O4	1.220 (4)	O2—H2A	0.816 (17)
C7—H7	0.9300	O2—H2B	0.836 (17)
C8—O3	1.414 (3)	Na1—O1	2.3751 (18)
C8—H8A	0.9600	Na1—O2	2.4043 (18)
C8—H8B	0.9600	Na1—O6	2.339 (3)
C8—H8C	0.9600	Na1—O1^i	2.3751 (18)
C9—C14	1.376 (5)	Na1—O2^i	2.4043 (18)
C9—C10	1.391 (4)	Na2—O1	2.5938 (19)
C9—C15	1.435 (5)	Na2—O2	2.4462 (18)
C10—C11	1.369 (4)	Na2—O2^ii	2.4462 (18)
C10—H10	0.9300	Na2—O1^ii	2.5938 (19)
C11—O7	1.366 (3)	Na2—O7^iii	2.396 (2)
C11—C12	1.430 (4)	Na2—O8^iii	2.397 (2)
C12—O8	1.293 (3)
C6—C1—C2	119.4 (3)	H16A—C16—H16C	109.5
C6—C1—C7	120.6 (3)	H16B—C16—H16C	109.5
C2—C1—C7	120.0 (3)	Na1—O1—Na2	98.23 (6)
C3—C2—C1	120.6 (3)	Na1—O1—H1A	94.3 (19)
C3—C2—H2	119.7	Na2—O1—H1A	117.2 (19)
C1—C2—H2	119.7	Na1—O1—H1B	129 (2)
C2—C3—O3	125.3 (2)	Na2—O1—H1B	112 (2)
C2—C3—C4	120.4 (2)	H1A—O1—H1B	106 (2)
O3—C3—C4	114.3 (2)	Na1—O2—Na2	101.61 (6)
O5—C4—C5	121.8 (2)	Na1—O2—H2A	111.6 (19)
O5—C4—C3	120.5 (2)	Na2—O2—H2A	104.0 (19)
C5—C4—C3	117.7 (2)	Na1—O2—H2B	104.2 (19)
C6—C5—C4	121.5 (3)	Na2—O2—H2B	129.9 (19)
C6—C5—H5	119.2	H2A—O2—H2B	105 (2)
C4—C5—H5	119.2	C3—O3—C8	116.8 (2)
C5—C6—C1	120.3 (3)	C3—O3—Na1	141.66 (16)
C5—C6—H6	119.8	C8—O3—Na1	101.57 (16)
C1—C6—H6	119.8	C15—O6—Na1	125.9 (3)
O4—C7—C1	126.4 (3)	C11—O7—C16	117.4 (2)
O4—C7—H7	116.8	C11—O7—Na2^iv	120.33 (16)
C1—C7—H7	116.8	C16—O7—Na2^iv	122.24 (17)
O3—C8—H8A	109.5	C12—O8—Na2^iv	118.88 (18)
O3—C8—H8B	109.5	O6—Na1—O1^i	113.13 (7)
H8A—C8—H8B	109.5	O6—Na1—O1	113.13 (7)
O3—C8—H8C	109.5	O1^i—Na1—O1	97.63 (9)
H8A—C8—H8C	109.5	O6—Na1—O2^i	88.96 (7)
H8B—C8—H8C	109.5	O1^i—Na1—O2^i	80.61 (6)
C14—C9—C10	118.3 (3)	O1—Na1—O2^i	156.19 (8)
C14—C9—C15	118.9 (4)	O6—Na1—O2	88.96 (7)
C10—C9—C15	122.8 (3)	O1^i—Na1—O2	156.19 (8)
C11—C10—C9	120.2 (3)	O1—Na1—O2	80.61 (5)
C11—C10—H10	119.9	O2^i—Na1—O2	91.48 (9)
C9—C10—H10	119.9	O6—Na1—O3	173.38 (9)
O7—C11—C10	124.8 (3)	O1^i—Na1—O3	70.78 (5)
O7—C11—C12	113.1 (2)	O1—Na1—O3	70.78 (5)
C10—C11—C12	122.1 (3)	O2^i—Na1—O3	86.42 (5)
O8—C12—C13	123.0 (3)	O2—Na1—O3	86.42 (5)
O8—C12—C11	120.9 (3)	O7^iii—Na2—O8^iii	66.71 (7)
C13—C12—C11	116.0 (3)	O7^iii—Na2—O2^ii	132.97 (5)
C14—C13—C12	121.3 (3)	O8^iii—Na2—O2^ii	91.15 (6)
C14—C13—H13	119.4	O7^iii—Na2—O2	132.97 (5)
C12—C13—H13	119.4	O8^iii—Na2—O2	91.15 (6)
C13—C14—C9	122.1 (4)	O2^ii—Na2—O2	85.60 (9)
C13—C14—H14	118.9	O7^iii—Na2—O1^ii	93.66 (6)
C9—C14—H14	118.9	O8^iii—Na2—O1^ii	138.31 (5)
O6—C15—C9	127.8 (4)	O2^ii—Na2—O1^ii	75.61 (6)
O6—C15—H15	116.1	O2—Na2—O1^ii	126.01 (7)
C9—C15—H15	116.1	O7^iii—Na2—O1	93.66 (6)
O7—C16—H16A	109.5	O8^iii—Na2—O1	138.31 (5)
O7—C16—H16B	109.5	O2^ii—Na2—O1	126.01 (7)
H16A—C16—H16B	109.5	O2—Na2—O1	75.61 (5)
O7—C16—H16C	109.5	O1^ii—Na2—O1	75.98 (8)
C6—C1—C2—C3	0.000 (2)	C10—C11—O7—Na2^iv	180.0
C7—C1—C2—C3	180.000 (1)	C12—C11—O7—Na2^iv	0.0
C1—C2—C3—O3	180.000 (1)	C13—C12—O8—Na2^iv	180.0
C1—C2—C3—C4	0.000 (1)	C11—C12—O8—Na2^iv	0.0
C2—C3—C4—O5	180.000 (1)	C15—O6—Na1—O1^i	−54.92 (6)
O3—C3—C4—O5	0.000 (1)	C15—O6—Na1—O1	54.92 (6)
C2—C3—C4—C5	0.000 (1)	C15—O6—Na1—O2^i	−134.25 (4)
O3—C3—C4—C5	180.000 (1)	C15—O6—Na1—O2	134.25 (4)
O5—C4—C5—C6	180.000 (1)	Na2—O1—Na1—O6	99.60 (9)
C3—C4—C5—C6	0.000 (2)	Na2—O1—Na1—O1^i	−141.19 (5)
C4—C5—C6—C1	0.000 (2)	Na2—O1—Na1—O2^i	−57.16 (18)
C2—C1—C6—C5	0.000 (2)	Na2—O1—Na1—O2	14.80 (6)
C7—C1—C6—C5	180.000 (1)	Na2—O1—Na1—O3	−74.67 (6)
C6—C1—C7—O4	0.000 (2)	Na2—O2—Na1—O6	−129.53 (7)
C2—C1—C7—O4	180.000 (2)	Na2—O2—Na1—O1^i	71.75 (18)
C14—C9—C10—C11	0.0	Na2—O2—Na1—O1	−15.88 (7)
C15—C9—C10—C11	180.0	Na2—O2—Na1—O2^i	141.54 (5)
C9—C10—C11—O7	180.0	Na2—O2—Na1—O3	55.22 (6)
C9—C10—C11—C12	0.0	C3—O3—Na1—O1^i	52.85 (5)
O7—C11—C12—O8	0.0	C8—O3—Na1—O1^i	−127.15 (5)
C10—C11—C12—O8	180.0	C3—O3—Na1—O1	−52.85 (5)
O7—C11—C12—C13	180.0	C8—O3—Na1—O1	127.15 (5)
C10—C11—C12—C13	0.0	C3—O3—Na1—O2^i	134.14 (4)
O8—C12—C13—C14	180.0	C8—O3—Na1—O2^i	−45.86 (4)
C11—C12—C13—C14	0.0	C3—O3—Na1—O2	−134.14 (4)
C12—C13—C14—C9	0.000 (1)	C8—O3—Na1—O2	45.86 (4)
C10—C9—C14—C13	0.000 (1)	Na1—O2—Na2—O7^iii	−66.66 (11)
C15—C9—C14—C13	180.0	Na1—O2—Na2—O8^iii	−125.21 (6)
C14—C9—C15—O6	180.0	Na1—O2—Na2—O2^ii	143.73 (5)
C10—C9—C15—O6	0.000 (1)	Na1—O2—Na2—O1^ii	75.08 (9)
C2—C3—O3—C8	0.000 (1)	Na1—O2—Na2—O1	14.79 (6)
C4—C3—O3—C8	180.000 (1)	Na1—O1—Na2—O7^iii	118.71 (6)
C2—C3—O3—Na1	180.000 (1)	Na1—O1—Na2—O8^iii	60.30 (12)
C4—C3—O3—Na1	0.000 (1)	Na1—O1—Na2—O2^ii	−88.29 (9)
C9—C15—O6—Na1	180.0	Na1—O1—Na2—O2	−14.81 (6)
C10—C11—O7—C16	0.0	Na1—O1—Na2—O1^ii	−148.42 (4)
C12—C11—O7—C16	180.0

Symmetry codes: (i) x, −y+3/2, z; (ii) x, −y+1/2, z; (iii) −x+3/2, −y+1, z+1/2; (iv) −x+3/2, −y+1, z−1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O5	0.82 (2)	1.97 (2)	2.772 (2)	169 (3)
O1—H1B···O8^v	0.83 (2)	1.99 (2)	2.815 (2)	172 (3)
O2—H2A···O4^iv	0.82 (2)	2.07 (2)	2.872 (2)	168 (3)
O2—H2B···O5^vi	0.84 (2)	1.95 (2)	2.772 (2)	168 (3)

Symmetry codes: (iv) −x+3/2, −y+1, z−1/2; (v) −x+1, −y+1, −z+1; (vi) x+1/2, y, −z+3/2.