Crystal structure of poly[di-aqua-bis-(μ5-benzene-1,3-di-carboxyl-ato)(N,N-di-methyl-formamide)-cadmium(II)disodium(I)].

The title compound, [CdNa2(C8H4O4)2(C3H7NO)(H2O)2] n or [CdNa2(1,3-bdc)2(DMF)(H2O)2] n , is a new CdII-NaI heterobimetallic coordination polymer. The asymmetric unit consists of one CdII atom, two NaI atoms, two 1,3-bdc ligands, two coordinated water mol-ecules and one coordinated DMF mol-ecule. The CdII atom exhibits a seven-coordinate geometry, while the NaI atoms can be considered to be penta-coordinate. The metal ions and their symmetry-related equivalents are connected via chelating-bridging carboxyl-ate groups of the 1,3-bdc ligands to generate a three-dimensional framework. In the crystal, there are classical O-H⋯O hydrogen bonds involving the coordinated water mol-ecules and the 1,3-bdc carboxyl-ate groups and π-π stacking between the benzene rings of the 1,3-bdc ligands present within the frameworks.

Chemical context

Porous coordination polymers or metal–organic frameworks (MOFs) constructed from d 10 transition metals and benzene polycarboxyl­ate bridging ligands have been widely studied (Yaghi et al., 1999 ▸; Lin et al., 2008 ▸; Seco et al., 2017 ▸) due to the varieties of coordination framework topologies and also potential applications in gas adsorption (Suh et al., 2012 ▸), photoluminescence (Wang et al., 2012 ▸) and photocatalysis (Wu et al., 2017 ▸). Among the most common ligands in this class, the rigid and planar backbone of benzene di­carboxyl­ates such as benzene-1,3-di­carb­oxy­lic acid (1,3-H2bdc) and benzene-1,4-di­carb­oxy­lic acid (1,4-H2bdc) are widely employed in the construction of these solids owing to their rich coordination modes. Studies incorporating alkaline metal ions into d 10-MOFs with one type of bridging ligand to construct novel heterobimetallic d 10-alkaline metal ion MOFs have been undertaken (Lin et al., 2010a ▸,b ▸). The alkali metal ions could provide an unpredictable coordination number and pH-dependent self-assembly in the construction of coordination frameworks with various types of topology and dimensionality (Borah et al., 2011 ▸; Chen et al., 2011 ▸). However, the members of three-dimensional coordination framework heterobi­metallic ZnII or CdII /NaI MOFs with benzene­polycarboxyl­ate ligands are still limited; previous reports include [ZnNa(1,2,4-btc)] where 1,2,4-btc = benzene-1,2,4-tri­carboxyl­ate (Wang et al., 2004 ▸), [Zn2Na2(1,4-bdc)3·(DMF)2·(m-H2O)2] where 1,4-bdcH2 = benzene-1,4-di­carb­oxy­lic acid (Xu et al., 2004 ▸), {[CdNa(1,3-bdc)2]·[NH2(CH3)2]} where 1,3-bdcH2 = benzene-1,3-di­carb­oxy­lic acid (Che et al., 2007 ▸), [CdNa(OH-1,3-bdc)2(H2O)2]·2H2O where OH-1,3-bdcH2 = 5-hy­droxy­benzene-1,3-di­carb­oxy­lic acid (Du et al., 2013 ▸) and [Cd8Na(ntc)6(H2O)8] where ntcH3 = 5-nitro­benzene-1,2,3-tri­carb­oxy­lic acid (Yang et al., 2014 ▸). With the aim of searching for new members of this heterobimetallic MOFs system containing benzene-1,3-di­carb­oxy­lic acid (1,3-bdcH2), we explored mixed sources of ZnII/CdII–NaI with this ligand. The expected products are prepared by using a direct synthetic method, mixing metal nitrate salts, 1,3-bdcH2 and NaOH (mole ratio 1:1:2) in water, methanol and DMF solvents. However, only the CdII–NaI MOF product has been successfully synthesized. As part of our ongoing studies on this complex, we describe here the synthesis and crystal structure of a novel three-dimensional heterobimetallic CdII–NaI MOF, [CdNa2(1,3-bdc)2(DMF)(H2O)2] (I).

Structural commentary

The title compound (I) crystallizes in the tetra­gonal crystal system with polar P43 space group. The asymmetric unit of (I) consists of one CdII ion, two crystallographically independent Na(I) ions, two 1,3-bdc ligands, two coordinated water mol­ecules and one DMF mol­ecules, as shown in Fig. 1 ▸. Each CdII ion is coordinated by seven carboxyl­ate oxygen atoms from four different 1,3-bdc ligands with the Cd—O bond distances range between 2.301 (3) and 2.555 (3) Å (Table 1 ▸). The Na1 ion is surrounded by three carboxyl­ate oxygen atoms of three different 1,3-bdc ligands, one oxygen atom from a water mol­ecule, and one DMF mol­ecule with the Na—O bond distances ranging between 2.304 (7) and 2.498 (11) Å, while the Na2 ion adopts a five-coordinate [4 + 1] coordination with four oxygen atoms from three different 1,3-bdc ligands and one oxygen atom from a water mol­ecule. The Na—O bond distances are in the range 2.275 (5) to 2.354 (8) Å. Fig. 2 ▸ shows the coordination modes of the 1,3-bdc ligand in compound (I). The 1,3-bdc mol­ecule is fully deprotonated and coordinated to the CdII and NaI ions in a μ5-coordination mode, creating a one-dimensional heterobimetallic chain running parallel to the c axis, Fig. 3 ▸. Adjacent chains are further connected through the 1,3-bdc ligands in the a- and b-axis directions, generating a three-dimensional framework structure as shown in Fig. 4 ▸. The coordinated water and DMF mol­ecules adopt a monodentate coordination mode and serve as a terminal pendant ligand pointing inside the channels.

Figure 1

Asymmetric unit of (I) with the atomic-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

Table 1

Selected geometric parameters (Å, °)

Cd1—O1	2.301 (3)	Na1—O4i	2.441 (5)
Cd1—O2	2.555 (3)	Na1—O9	2.304 (7)
Cd1—O3i	2.496 (3)	Na1—O11B	2.498 (11)
Cd1—O4i	2.385 (3)	Na1—O11A	2.475 (18)
Cd1—O5	2.284 (4)	Na2—O4iv	2.655 (5)
Cd1—O7ii	2.396 (3)	Na2—O5	2.277 (5)
Cd1—O8ii	2.472 (3)	Na2—O7ii	2.282 (4)
Na1—O1	2.368 (5)	Na2—O8v	2.275 (5)
Na1—O3iii	2.339 (5)	Na2—O10	2.354 (8)
O1—Cd1—O2	53.12 (15)	O1—Na1—O4i	77.84 (17)
O1—Cd1—O3i	131.59 (15)	O1—Na1—O11B	104.1 (3)
O1—Cd1—O4i	80.31 (12)	O3iii—Na1—O1	151.1 (2)
O1—Cd1—O7ii	125.91 (12)	O3iii—Na1—O4i	94.59 (15)
O1—Cd1—O8ii	92.04 (13)	O3iii—Na1—O11B	82.9 (3)
O3i—Cd1—O2	173.00 (16)	O4i—Na1—O11B	177.4 (3)
O4i—Cd1—O2	132.60 (15)	O9—Na1—O1	95.8 (2)
O4i—Cd1—O3i	53.37 (13)	O9—Na1—O3iii	112.0 (2)
O4i—Cd1—O7ii	122.40 (12)	O9—Na1—O4i	88.3 (2)
O4i—Cd1—O8ii	78.81 (13)	O9—Na1—O11B	93.2 (4)
O5—Cd1—O1	125.67 (14)	O5—Na2—O4iv	95.45 (19)
O5—Cd1—O2	90.36 (16)	O5—Na2—O7ii	83.03 (18)
O5—Cd1—O3i	82.65 (15)	O5—Na2—O10	104.5 (2)
O5—Cd1—O4i	128.83 (14)	O7ii—Na2—O4iv	94.98 (14)
O5—Cd1—O7ii	80.41 (12)	O7ii—Na2—O10	80.5 (2)
O5—Cd1—O8ii	133.24 (16)	O8v—Na2—O4iv	77.02 (13)
O7ii—Cd1—O2	85.03 (15)	O8v—Na2—O5	110.18 (16)
O7ii—Cd1—O3i	94.01 (14)	O8v—Na2—O7ii	164.93 (18)
O7ii—Cd1—O8ii	53.55 (14)	O8v—Na2—O10	102.3 (2)
O8ii—Cd1—O2	93.07 (11)	O10—Na2—O4iv	158.8 (2)
O8ii—Cd1—O3i	91.92 (10)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .

Figure 2

Coordination mode of the μ5-1,3-bdc bridging ligands found in (I). All hydrogen atoms are omitted for clarity.

Figure 3

Perspective view along the crystallographic c axis of (a) the three-dimensional framework of (I) (the coordination polyhedra for CdII and NaI are pink and green, respectively) and (b) helical chain-like structure of the Cd—Na clusters (dark blue = Cd, blue = Na and red = O).

Figure 4

Perspective view of the three-dimensional framework of (I) (the coordination polyhedra for CdII and NaI are pink and green, respectively). All hydrogen atoms are omitted for clarity.

Supra­molecular features

In the crystal of (I), classical O—H⋯O hydrogen bonds and aromatic π–π stacking inter­actions are observed and these inter­actions presumably help to stabilize the frameworks. All water mol­ecules are shown to act as O—H⋯O hydrogen-bond donors towards the carboxyl­ate groups of the 1,3-bdc ligands (Table 2 ▸). The π–π stacking inter­actions are between symmetry-related aromatic rings of the 1,3-bdc ligands with a Cg1⋯Cg2i distance of 3.588 (3) Å and a dihedral angle of 3.8 (4)° [Cg1 and Cg2 are the centroids of the C1–C6 and C9–C14 rings, respectively; symmetry code: (i) –y, x, z – 1/4].

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O9—H9B⋯O6	0.90	2.22	3.074 (8)	159
O10—H10B⋯O6v	0.86	2.29	3.073 (8)	152

Symmetry code: (v) .

Database survey

To the best of our knowledge of structures closely related to (I), only the three-dimensional coordination framework {[CdNa(1,3-bdc)2]·[NH2(CH3)2]} has been reported (Che et al., 2007 ▸). This compound crystallized in the centrosymmetric space group C2/c. The CdII and NaI centers are linked by a 1,3-bdc ligand in a μ4-coordination mode. The DMF solvent decomposes under solvothermal synthesis, with the construction of a 3D coordination framework with open channels containing NH2(CH3)2 mol­ecules. In comparison, compound (I) contains coordinated H2O and DMF mol­ecules projecting into the framework channels. Other related three-dimensional heterobimetallic d 10–NaI coordination frameworks containing benzene­polycarboxyl­ate ligands have been published, such as [CdNa(OH-1,3-bdc)2(H2O)2]·2H2O where OH-1,3-bdcH2 = 5-hy­droxy-benzene-1,3-di­carb­oxy­lic acid (Du et al., 2013 ▸), [Zn2Na2(1,4-bdc)3·(DMF)2·(m-H2O)2] where 1,4-bdcH2 = benzene-1,4-di­carb­oxy­lic acid (Xu et al., 2004 ▸), [ZnNa(1,2,4-btc)] where 1,2,4-btc = 1,2,4-benzene­tri­carboxyl­ate (Wang et al., 2004 ▸), and [Cd8Na(ntc)6(H2O)8] where ntcH3 = 5-nitro­benzene-1,2,3-tri­carb­oxy­lic acid (Yang et al., 2014 ▸). The three-dimensional coordination framework topologies of these compounds are the result of the construction of different types of metal centers, geometries and carboxyl­ate ligand derivatives. It is found that the carboxyl­ate ligand derivatives in the structure of these related compounds exhibit a μ4-coordination mode.

Synthesis and crystallization

A mixture solution of 1,3-bdcH2 (1.0 mmol) and NaOH (2.0 mmol) in 10 mL of distilled water was slowly dropped to a methano­lic solution (10 ml) of Cd(NO3)2·4H2O (1.0 mmol). The reaction mixture was stirred at 333 K for 30 min and allowed to cool to room temperature and then filtered. The filtrate was allowed to stand to slowly evaporate at ambient temperature. Colorless block-shaped crystals suitable for single crystal X-ray diffraction were obtained after three days (76% yield based on Cd).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3 ▸. All hydrogen atoms except those of water mol­ecules were generated geometrically and refined isotropically using a riding model, with C—H = 0.93 Å and U iso(H) = 1.2U eq(C). The coordinated DMF mol­ecule was found to be disordered with two sets of sites with a refined occupancy ratio of 0.382 (10) and 0.618 (10).

Table 3

Experimental details

Crystal data
Chemical formula	[CdNa2(C8H4O4)2(C3H7NO)(H2O)2]
M r	595.73
Crystal system, space group	Tetragonal, P43
Temperature (K)	296
a, c (Å)	10.1437 (8), 21.4664 (15)
V (Å3)	2208.8 (4)
Z	4
Radiation type	Mo Kα
μ (mm−1)	1.09
Crystal size (mm)	0.35 × 0.21 × 0.16
Data collection
Diffractometer	Bruker APEXII D8 QUEST CMOS
Absorption correction	Multi-scan (SADABS, Bruker, 2013 ▸)
T min, T max	0.647, 0.704
No. of measured, independent and observed [I > 2σ(I)] reflections	56814, 5708, 5301
R int	0.074
(sin θ/λ)max (Å−1)	0.676
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.028, 0.068, 1.03
No. of reflections	5708
No. of parameters	351
No. of restraints	160
H-atom treatment	H-atom parameters constrained
Δρmax, Δρmin (e Å−3)	0.52, −0.45
Absolute structure	Flack x determined using 2427 quotients [(I +)−(I −)]/[(I +)+(I −)] (Parsons et al., 2013 ▸)
Absolute structure parameter	0.081 (13)

Computer programs: APEX2 and SAINT (Bruker, 2013 ▸), SHELXT (Sheldrick, 2015a ▸), SHELXL (Sheldrick, 2015b ▸) and OLEX2 (Dolomanov et al., 2009 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017013871/pj2046sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989017013871/pj2046Isup2.hkl

CCDC reference: 1576543

Additional supporting information: crystallographic information; 3D view; checkCIF report

[CdNa2(C8H4O4)2(C3H7NO)(H2O)2]	Dx = 1.791 Mg m−3
Mr = 595.73	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P43	Cell parameters from 9769 reflections
a = 10.1437 (8) Å	θ = 2.7–28.3°
c = 21.4664 (15) Å	µ = 1.09 mm−1
V = 2208.8 (4) Å3	T = 296 K
Z = 4	Block, colourless
F(000) = 1192	0.35 × 0.21 × 0.16 mm

Bruker APEXII D8 QUEST CMOS diffractometer	5301 reflections with I > 2σ(I)
Detector resolution: 10.5 pixels mm-1	Rint = 0.074
ω and φ scans	θmax = 28.7°, θmin = 2.8°
Absorption correction: multi-scan (SADABS, Bruker, 2013)	h = −13→13
Tmin = 0.647, Tmax = 0.704	k = −12→13
56814 measured reflections	l = −28→29
5708 independent reflections

Refinement on F2	H-atom parameters constrained
Least-squares matrix: full	w = 1/[σ2(Fo2) + (0.0375P)2 + 0.6193P] where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.028	(Δ/σ)max < 0.001
wR(F2) = 0.068	Δρmax = 0.52 e Å−3
S = 1.03	Δρmin = −0.45 e Å−3
5708 reflections	Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
351 parameters	Extinction coefficient: 0.0050 (7)
160 restraints	Absolute structure: Flack x determined using 2427 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Hydrogen site location: mixed	Absolute structure parameter: 0.081 (13)

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cd1	0.08591 (2)	0.23028 (2)	0.49814 (3)	0.02155 (9)
Na1	0.1091 (4)	0.2329 (2)	0.33008 (17)	0.0575 (9)
Na2	0.1037 (2)	0.2125 (3)	0.66027 (15)	0.0510 (8)
O1	0.0894 (3)	0.3769 (3)	0.41640 (17)	0.0357 (8)
O2	0.0886 (4)	0.4817 (3)	0.5052 (3)	0.0458 (10)
O3	0.1045 (3)	0.9851 (3)	0.5013 (2)	0.0349 (6)
O4	0.0482 (4)	1.0819 (3)	0.41384 (15)	0.0354 (8)
O5	0.2394 (3)	0.2174 (5)	0.57576 (19)	0.0502 (10)
O6	0.3488 (3)	0.2217 (4)	0.4890 (2)	0.0490 (10)
O7	0.9433 (3)	0.2411 (4)	0.58696 (16)	0.0337 (7)
O8	0.8424 (3)	0.2200 (3)	0.4971 (2)	0.0319 (6)
O9	0.3263 (6)	0.1781 (9)	0.3477 (3)	0.111 (2)
H9A	0.3381	0.0906	0.3450	0.166*
H9B	0.3540	0.2025	0.3857	0.166*
O10	0.0517 (7)	0.4353 (7)	0.6789 (3)	0.118 (2)
H10A	0.0182	0.4694	0.6461	0.178*
H10B	0.1218	0.4773	0.6885	0.178*
C1	0.0879 (4)	0.6114 (4)	0.4125 (2)	0.0251 (8)
C2	0.0830 (4)	0.7316 (4)	0.4438 (2)	0.0236 (8)
H2	0.0798	0.7328	0.4871	0.028*
C3	0.0829 (4)	0.8496 (4)	0.4111 (2)	0.0225 (8)
C4	0.0860 (5)	0.8478 (4)	0.3463 (2)	0.0312 (10)
H4	0.0847	0.9267	0.3242	0.037*
C5	0.0909 (5)	0.7295 (4)	0.3148 (2)	0.0364 (12)
H5	0.0935	0.7284	0.2715	0.044*
C6	0.0918 (5)	0.6114 (4)	0.3481 (2)	0.0335 (10)
H6	0.0951	0.5317	0.3268	0.040*
C7	0.0881 (4)	0.4829 (4)	0.4476 (3)	0.0314 (10)
C8	0.0788 (4)	0.9796 (4)	0.4444 (2)	0.0249 (8)
C9	0.4717 (4)	0.2316 (4)	0.5837 (2)	0.0257 (8)
C10	0.5928 (4)	0.2363 (4)	0.5534 (2)	0.0245 (9)
H10	0.5962	0.2377	0.5101	0.029*
C11	0.7089 (4)	0.2390 (4)	0.58795 (19)	0.0220 (8)
C12	0.7034 (4)	0.2399 (5)	0.6526 (2)	0.0286 (9)
H12	0.7809	0.2424	0.6758	0.034*
C13	0.5834 (4)	0.2370 (4)	0.6825 (2)	0.0327 (10)
H13	0.5802	0.2389	0.7258	0.039*
C14	0.4674 (4)	0.2313 (4)	0.6486 (2)	0.0285 (9)
H14	0.3867	0.2273	0.6691	0.034*
C15	0.3461 (4)	0.2229 (4)	0.5460 (2)	0.0300 (9)
C16	0.8396 (4)	0.2330 (4)	0.5549 (2)	0.0227 (8)
O11B	0.1647 (14)	0.3817 (14)	0.2412 (5)	0.082 (3)	0.618 (10)
N1	0.3469 (8)	0.4165 (5)	0.1823 (3)	0.0859 (17)
C17B	0.2980 (15)	0.3983 (11)	0.2335 (6)	0.088 (3)	0.618 (10)
H17B	0.3526	0.3957	0.2683	0.106*	0.618 (10)
C18B	0.2609 (14)	0.4209 (11)	0.1244 (7)	0.093 (3)	0.618 (10)
H18A	0.2369	0.3328	0.1127	0.140*	0.618 (10)
H18B	0.3088	0.4617	0.0910	0.140*	0.618 (10)
H18C	0.1828	0.4711	0.1330	0.140*	0.618 (10)
C19B	0.4849 (13)	0.4221 (13)	0.1669 (8)	0.099 (3)	0.618 (10)
H19A	0.5354	0.4346	0.2043	0.149*	0.618 (10)
H19B	0.5005	0.4943	0.1390	0.149*	0.618 (10)
H19C	0.5109	0.3411	0.1473	0.149*	0.618 (10)
C18A	0.439 (2)	0.424 (2)	0.2384 (9)	0.105 (5)	0.382 (10)
H18D	0.3884	0.4164	0.2760	0.157*	0.382 (10)
H18E	0.4851	0.5063	0.2380	0.157*	0.382 (10)
H18F	0.5015	0.3527	0.2364	0.157*	0.382 (10)
C19A	0.433 (3)	0.417 (3)	0.1269 (10)	0.110 (6)	0.382 (10)
H19D	0.4565	0.5063	0.1169	0.165*	0.382 (10)
H19E	0.3865	0.3786	0.0923	0.165*	0.382 (10)
H19F	0.5109	0.3670	0.1353	0.165*	0.382 (10)
C17A	0.2249 (19)	0.401 (2)	0.1936 (11)	0.098 (4)	0.382 (10)
H17A	0.1610	0.3926	0.1628	0.117*	0.382 (10)
O11A	0.198 (3)	0.396 (2)	0.2554 (10)	0.102 (5)	0.382 (10)

	U11	U22	U33	U12	U13	U23
Cd1	0.02087 (14)	0.02266 (15)	0.02112 (12)	0.00064 (10)	−0.00023 (11)	−0.00002 (11)
Na1	0.096 (2)	0.0428 (14)	0.0337 (16)	−0.0075 (12)	0.0048 (15)	−0.0055 (8)
Na2	0.0289 (10)	0.0944 (19)	0.0298 (14)	−0.0066 (10)	−0.0059 (9)	0.0114 (12)
O1	0.0375 (18)	0.0144 (13)	0.055 (2)	−0.0009 (11)	−0.0018 (15)	0.0020 (13)
O2	0.062 (2)	0.0262 (15)	0.049 (3)	−0.0022 (14)	−0.001 (2)	0.0105 (18)
O3	0.0471 (16)	0.0271 (13)	0.0305 (15)	0.0009 (12)	−0.0002 (19)	−0.0023 (17)
O4	0.055 (2)	0.0144 (13)	0.0365 (18)	0.0024 (13)	0.0009 (15)	0.0005 (12)
O5	0.0156 (15)	0.083 (3)	0.052 (2)	−0.0012 (16)	−0.0008 (14)	0.005 (2)
O6	0.0319 (17)	0.079 (3)	0.036 (3)	−0.0123 (16)	−0.0103 (17)	0.007 (2)
O7	0.0159 (13)	0.048 (2)	0.0369 (17)	−0.0016 (13)	−0.0045 (12)	0.0016 (15)
O8	0.0263 (13)	0.0429 (15)	0.0265 (13)	0.0009 (11)	0.0044 (17)	0.0006 (18)
O9	0.087 (4)	0.193 (8)	0.052 (3)	0.004 (5)	−0.013 (3)	0.003 (4)
O10	0.113 (5)	0.122 (5)	0.120 (6)	−0.002 (4)	−0.047 (4)	0.049 (4)
C1	0.025 (2)	0.0149 (17)	0.035 (2)	−0.0004 (15)	0.0015 (16)	0.0031 (16)
C2	0.025 (2)	0.0183 (19)	0.027 (2)	−0.0009 (15)	−0.0013 (15)	0.0021 (14)
C3	0.026 (2)	0.0151 (18)	0.026 (2)	−0.0021 (14)	−0.0009 (16)	0.0006 (15)
C4	0.041 (3)	0.022 (2)	0.030 (2)	0.0029 (18)	0.0003 (19)	0.0024 (17)
C5	0.055 (3)	0.028 (2)	0.027 (2)	0.002 (2)	0.0015 (19)	−0.0009 (16)
C6	0.038 (3)	0.020 (2)	0.042 (3)	0.0019 (18)	0.001 (2)	−0.0050 (18)
C7	0.022 (2)	0.0180 (19)	0.054 (3)	−0.0016 (15)	−0.0008 (19)	0.0063 (19)
C8	0.0244 (19)	0.0190 (19)	0.031 (2)	−0.0021 (15)	0.0077 (16)	−0.0011 (16)
C9	0.0167 (18)	0.027 (2)	0.033 (2)	−0.0001 (15)	−0.0045 (16)	0.0025 (17)
C10	0.0184 (19)	0.030 (2)	0.026 (2)	−0.0022 (16)	−0.0008 (14)	0.0035 (15)
C11	0.0165 (17)	0.0230 (19)	0.0265 (19)	−0.0025 (14)	−0.0009 (15)	0.0003 (15)
C12	0.023 (2)	0.039 (2)	0.024 (2)	−0.0001 (17)	−0.0057 (16)	−0.0027 (18)
C13	0.032 (2)	0.041 (3)	0.024 (2)	−0.002 (2)	0.0034 (16)	−0.0011 (17)
C14	0.019 (2)	0.034 (2)	0.032 (2)	0.0019 (17)	0.0061 (16)	−0.0008 (18)
C15	0.0143 (18)	0.029 (2)	0.046 (3)	−0.0017 (15)	−0.0069 (18)	0.0079 (19)
C16	0.0159 (17)	0.0210 (18)	0.031 (2)	−0.0006 (14)	0.0001 (15)	0.0015 (15)
O11B	0.125 (6)	0.051 (6)	0.068 (6)	−0.015 (4)	0.025 (4)	−0.027 (5)
N1	0.135 (5)	0.030 (2)	0.093 (3)	0.000 (3)	0.035 (3)	−0.001 (2)
C17B	0.127 (6)	0.047 (5)	0.091 (4)	−0.012 (4)	0.028 (3)	−0.004 (3)
C18B	0.143 (6)	0.041 (6)	0.095 (5)	0.012 (5)	0.029 (4)	−0.008 (4)
C19B	0.135 (5)	0.048 (6)	0.115 (7)	0.001 (4)	0.036 (4)	0.017 (6)
C18A	0.144 (7)	0.073 (12)	0.098 (5)	−0.018 (7)	0.030 (5)	0.008 (6)
C19A	0.136 (8)	0.099 (18)	0.095 (5)	0.006 (9)	0.035 (5)	0.005 (7)
C17A	0.137 (5)	0.057 (10)	0.100 (6)	−0.008 (4)	0.040 (4)	−0.029 (6)
O11A	0.155 (10)	0.052 (9)	0.100 (6)	−0.039 (9)	0.046 (6)	−0.037 (7)

Cd1—O1	2.301 (3)	C1—C7	1.505 (6)
Cd1—O2	2.555 (3)	C2—H2	0.9300
Cd1—O3i	2.496 (3)	C2—C3	1.388 (5)
Cd1—O4i	2.385 (3)	C3—C4	1.391 (6)
Cd1—O5	2.284 (4)	C3—C8	1.501 (5)
Cd1—O7ii	2.396 (3)	C4—H4	0.9300
Cd1—O8ii	2.472 (3)	C4—C5	1.379 (6)
Na1—Na2iii	3.914 (6)	C5—H5	0.9300
Na1—O1	2.368 (5)	C5—C6	1.395 (7)
Na1—O3iv	2.339 (5)	C6—H6	0.9300
Na1—O4i	2.441 (5)	C9—C10	1.390 (6)
Na1—O9	2.304 (7)	C9—C14	1.395 (6)
Na1—O11B	2.498 (11)	C9—C15	1.511 (6)
Na1—O11A	2.475 (18)	C10—H10	0.9300
Na2—Cd1v	3.791 (3)	C10—C11	1.392 (5)
Na2—Na1v	3.914 (6)	C11—C12	1.390 (6)
Na2—O4vi	2.655 (5)	C11—C16	1.505 (5)
Na2—O5	2.277 (5)	C12—H12	0.9300
Na2—O7ii	2.282 (4)	C12—C13	1.376 (6)
Na2—O8vii	2.275 (5)	C13—H13	0.9300
Na2—O10	2.354 (8)	C13—C14	1.385 (6)
O1—C7	1.266 (6)	C14—H14	0.9300
O2—C7	1.237 (8)	O11B—C17B	1.373 (18)
O3—Cd1viii	2.495 (3)	N1—C17B	1.221 (13)
O3—Na1vii	2.339 (5)	N1—C18B	1.517 (15)
O3—C8	1.250 (6)	N1—C19B	1.439 (14)
O4—Cd1viii	2.385 (3)	N1—C18A	1.526 (18)
O4—Na1viii	2.442 (5)	N1—C19A	1.473 (17)
O4—Na2ix	2.655 (5)	N1—C17A	1.271 (19)
O4—C8	1.266 (5)	C17B—H17B	0.9300
O5—C15	1.259 (6)	C18B—H18A	0.9600
O6—C15	1.224 (7)	C18B—H18B	0.9600
O7—Cd1x	2.396 (3)	C18B—H18C	0.9600
O7—Na2x	2.282 (4)	C19B—H19A	0.9600
O7—C16	1.259 (5)	C19B—H19B	0.9600
O8—Cd1x	2.472 (3)	C19B—H19C	0.9600
O8—Na2iv	2.275 (5)	C18A—H18D	0.9600
O8—C16	1.248 (6)	C18A—H18E	0.9600
O9—H9A	0.8971	C18A—H18F	0.9600
O9—H9B	0.8991	C19A—H19D	0.9600
O10—H10A	0.8544	C19A—H19E	0.9600
O10—H10B	0.8548	C19A—H19F	0.9600
C1—C2	1.393 (6)	C17A—H17A	0.9300
C1—C6	1.383 (7)	C17A—O11A	1.36 (2)
O1—Cd1—O2	53.12 (15)	Na2—O10—H10B	109.5
O1—Cd1—O3i	131.59 (15)	H10A—O10—H10B	109.2
O1—Cd1—O4i	80.31 (12)	C2—C1—C7	121.2 (4)
O1—Cd1—O7ii	125.91 (12)	C6—C1—C2	118.9 (4)
O1—Cd1—O8ii	92.04 (13)	C6—C1—C7	120.0 (4)
O3i—Cd1—O2	173.00 (16)	C1—C2—H2	119.6
O4i—Cd1—O2	132.60 (15)	C3—C2—C1	120.7 (4)
O4i—Cd1—O3i	53.37 (13)	C3—C2—H2	119.6
O4i—Cd1—O7ii	122.40 (12)	C2—C3—C4	119.7 (4)
O4i—Cd1—O8ii	78.81 (13)	C2—C3—C8	121.1 (4)
O5—Cd1—O1	125.67 (14)	C4—C3—C8	119.2 (3)
O5—Cd1—O2	90.36 (16)	C3—C4—H4	119.9
O5—Cd1—O3i	82.65 (15)	C5—C4—C3	120.2 (4)
O5—Cd1—O4i	128.83 (14)	C5—C4—H4	119.9
O5—Cd1—O7ii	80.41 (12)	C4—C5—H5	120.1
O5—Cd1—O8ii	133.24 (16)	C4—C5—C6	119.8 (5)
O7ii—Cd1—O2	85.03 (15)	C6—C5—H5	120.1
O7ii—Cd1—O3i	94.01 (14)	C1—C6—C5	120.8 (4)
O7ii—Cd1—O8ii	53.55 (14)	C1—C6—H6	119.6
O8ii—Cd1—O2	93.07 (11)	C5—C6—H6	119.6
O8ii—Cd1—O3i	91.92 (10)	O1—C7—C1	118.1 (5)
O1—Na1—Na2iii	77.99 (11)	O2—C7—O1	121.4 (4)
O1—Na1—O4i	77.84 (17)	O2—C7—C1	120.5 (4)
O1—Na1—O11B	104.1 (3)	O3—C8—O4	121.4 (4)
O1—Na1—O11A	97.1 (6)	O3—C8—C3	119.9 (4)
O3iv—Na1—Na2iii	77.96 (14)	O4—C8—C3	118.7 (4)
O3iv—Na1—O1	151.1 (2)	C10—C9—C14	119.7 (4)
O3iv—Na1—O4i	94.59 (15)	C10—C9—C15	119.8 (4)
O3iv—Na1—O11B	82.9 (3)	C14—C9—C15	120.5 (4)
O3iv—Na1—O11A	93.0 (6)	C9—C10—H10	120.0
O4i—Na1—Na2iii	41.86 (11)	C9—C10—C11	120.0 (4)
O4i—Na1—O11B	177.4 (3)	C11—C10—H10	120.0
O4i—Na1—O11A	171.5 (7)	C10—C11—C16	119.6 (4)
O9—Na1—Na2iii	130.1 (2)	C12—C11—C10	119.9 (4)
O9—Na1—O1	95.8 (2)	C12—C11—C16	120.4 (4)
O9—Na1—O3iv	112.0 (2)	C11—C12—H12	120.0
O9—Na1—O4i	88.3 (2)	C13—C12—C11	120.1 (4)
O9—Na1—O11B	93.2 (4)	C13—C12—H12	120.0
O9—Na1—O11A	85.4 (8)	C12—C13—H13	119.7
O11B—Na1—Na2iii	136.6 (4)	C12—C13—C14	120.5 (4)
O11A—Na1—Na2iii	144.3 (8)	C14—C13—H13	119.7
Cd1v—Na2—Na1v	55.94 (8)	C9—C14—H14	120.1
O4vi—Na2—Cd1v	38.59 (8)	C13—C14—C9	119.9 (4)
O4vi—Na2—Na1v	37.86 (11)	C13—C14—H14	120.1
O5—Na2—Cd1v	102.07 (15)	O5—C15—C9	117.2 (4)
O5—Na2—Na1v	57.70 (14)	O6—C15—O5	121.7 (4)
O5—Na2—O4vi	95.45 (19)	O6—C15—C9	121.1 (4)
O5—Na2—O7ii	83.03 (18)	O7—C16—C11	118.4 (4)
O5—Na2—O10	104.5 (2)	O8—C16—O7	122.1 (4)
O7ii—Na2—Cd1v	133.31 (13)	O8—C16—C11	119.5 (3)
O7ii—Na2—Na1v	92.36 (13)	C17B—O11B—Na1	112.8 (9)
O7ii—Na2—O4vi	94.98 (14)	C17B—N1—C18B	120.6 (10)
O7ii—Na2—O10	80.5 (2)	C17B—N1—C19B	127.4 (12)
O8vii—Na2—Cd1v	38.84 (9)	C19B—N1—C18B	111.8 (9)
O8vii—Na2—Na1v	89.00 (13)	C19A—N1—C18A	106.0 (13)
O8vii—Na2—O4vi	77.02 (13)	C17A—N1—C18A	116.8 (12)
O8vii—Na2—O5	110.18 (16)	C17A—N1—C19A	136.9 (17)
O8vii—Na2—O7ii	164.93 (18)	O11B—C17B—H17B	119.1
O8vii—Na2—O10	102.3 (2)	N1—C17B—O11B	121.8 (13)
O10—Na2—Cd1v	139.3 (2)	N1—C17B—H17B	119.1
O10—Na2—Na1v	161.7 (2)	N1—C18B—H18A	109.5
O10—Na2—O4vi	158.8 (2)	N1—C18B—H18B	109.5
Cd1—O1—Na1	101.49 (13)	N1—C18B—H18C	109.5
C7—O1—Cd1	98.4 (3)	H18A—C18B—H18B	109.5
C7—O1—Na1	159.7 (3)	H18A—C18B—H18C	109.5
C7—O2—Cd1	87.1 (3)	H18B—C18B—H18C	109.5
Na1vii—O3—Cd1viii	117.93 (19)	N1—C19B—H19A	109.5
C8—O3—Cd1viii	90.1 (3)	N1—C19B—H19B	109.5
C8—O3—Na1vii	143.6 (3)	N1—C19B—H19C	109.5
Cd1viii—O4—Na1viii	97.02 (13)	H19A—C19B—H19B	109.5
Cd1viii—O4—Na2ix	97.42 (13)	H19A—C19B—H19C	109.5
Na1viii—O4—Na2ix	100.28 (18)	H19B—C19B—H19C	109.5
C8—O4—Cd1viii	94.9 (3)	N1—C18A—H18D	109.5
C8—O4—Na1viii	146.5 (3)	N1—C18A—H18E	109.5
C8—O4—Na2ix	109.1 (3)	N1—C18A—H18F	109.5
Na2—O5—Cd1	99.83 (14)	H18D—C18A—H18E	109.5
C15—O5—Cd1	102.4 (3)	H18D—C18A—H18F	109.5
C15—O5—Na2	157.7 (3)	H18E—C18A—H18F	109.5
Na2x—O7—Cd1x	96.46 (14)	N1—C19A—H19D	109.5
C16—O7—Cd1x	93.8 (3)	N1—C19A—H19E	109.5
C16—O7—Na2x	164.5 (3)	N1—C19A—H19F	109.5
Na2iv—O8—Cd1x	105.91 (16)	H19D—C19A—H19E	109.5
C16—O8—Cd1x	90.5 (2)	H19D—C19A—H19F	109.5
C16—O8—Na2iv	149.8 (3)	H19E—C19A—H19F	109.5
Na1—O9—H9A	110.8	N1—C17A—H17A	123.6
Na1—O9—H9B	112.4	N1—C17A—O11A	113 (2)
H9A—O9—H9B	106.7	O11A—C17A—H17A	123.6
Na2—O10—H10A	109.8	C17A—O11A—Na1	136.8 (17)
Cd1—O1—C7—O2	1.6 (5)	C4—C3—C8—O3	−164.6 (4)
Cd1—O1—C7—C1	−179.3 (3)	C4—C3—C8—O4	15.9 (6)
Cd1—O2—C7—O1	−1.5 (4)	C4—C5—C6—C1	0.0 (7)
Cd1—O2—C7—C1	179.5 (4)	C6—C1—C2—C3	−0.5 (6)
Cd1viii—O3—C8—O4	−5.0 (4)	C6—C1—C7—O1	−1.3 (6)
Cd1viii—O3—C8—C3	175.5 (3)	C6—C1—C7—O2	177.8 (5)
Cd1viii—O4—C8—O3	5.2 (4)	C7—C1—C2—C3	180.0 (4)
Cd1viii—O4—C8—C3	−175.2 (3)	C7—C1—C6—C5	179.6 (4)
Cd1—O5—C15—O6	−6.1 (6)	C8—C3—C4—C5	179.5 (4)
Cd1—O5—C15—C9	173.6 (3)	C9—C10—C11—C12	−1.4 (6)
Cd1x—O7—C16—O8	1.9 (4)	C9—C10—C11—C16	175.0 (4)
Cd1x—O7—C16—C11	−178.2 (3)	C10—C9—C14—C13	0.6 (7)
Cd1x—O8—C16—O7	−1.9 (4)	C10—C9—C15—O5	179.3 (4)
Cd1x—O8—C16—C11	178.3 (3)	C10—C9—C15—O6	−1.0 (7)
Na1—O1—C7—O2	−166.8 (7)	C10—C11—C12—C13	0.5 (7)
Na1—O1—C7—C1	12.2 (11)	C10—C11—C16—O7	177.1 (4)
Na1vii—O3—C8—O4	−147.3 (4)	C10—C11—C16—O8	−3.1 (6)
Na1vii—O3—C8—C3	33.1 (7)	C11—C12—C13—C14	1.0 (7)
Na1viii—O4—C8—O3	115.7 (5)	C12—C11—C16—O7	−6.5 (6)
Na1viii—O4—C8—C3	−64.7 (7)	C12—C11—C16—O8	173.4 (4)
Na1—O11B—C17B—N1	148.4 (9)	C12—C13—C14—C9	−1.5 (7)
Na2ix—O4—C8—O3	−94.4 (4)	C14—C9—C10—C11	0.8 (6)
Na2ix—O4—C8—C3	85.2 (4)	C14—C9—C15—O5	1.0 (6)
Na2—O5—C15—O6	−179.4 (8)	C14—C9—C15—O6	−179.2 (5)
Na2—O5—C15—C9	0.4 (13)	C15—C9—C10—C11	−177.4 (4)
Na2x—O7—C16—O8	−129.6 (10)	C15—C9—C14—C13	178.9 (4)
Na2x—O7—C16—C11	50.2 (13)	C16—C11—C12—C13	−175.9 (4)
Na2iv—O8—C16—O7	122.2 (5)	N1—C17A—O11A—Na1	−116 (3)
Na2iv—O8—C16—C11	−57.7 (7)	C17B—N1—C17A—O11A	6.5 (16)
C1—C2—C3—C4	0.9 (6)	C18B—N1—C17B—O11B	−0.2 (17)
C1—C2—C3—C8	−179.5 (4)	C18B—N1—C17A—O11A	−174 (2)
C2—C1—C6—C5	0.0 (7)	C19B—N1—C17B—O11B	−173.3 (11)
C2—C1—C7—O1	178.3 (4)	C18A—N1—C17B—O11B	175.3 (18)
C2—C1—C7—O2	−2.6 (6)	C18A—N1—C17A—O11A	2 (3)
C2—C3—C4—C5	−0.9 (7)	C19A—N1—C17B—O11B	−142 (6)
C2—C3—C8—O3	15.8 (6)	C19A—N1—C17A—O11A	174 (2)
C2—C3—C8—O4	−163.7 (4)	C17A—N1—C17B—O11B	0.1 (14)
C3—C4—C5—C6	0.5 (7)

D—H···A	D—H	H···A	D···A	D—H···A
O9—H9B···O6	0.90	2.22	3.074 (8)	159
O10—H10B···O6vii	0.86	2.29	3.073 (8)	152
C4—H4···O3xi	0.93	2.49	3.385 (6)	161
C6—H6···O1	0.93	2.48	2.791 (5)	100
C6—H6···O11B	0.93	2.48	3.347 (14)	155
C10—H10···O10iv	0.93	2.59	3.277 (8)	131
C14—H14···O8vii	0.93	2.48	3.366 (5)	159
C18B—H18A···Cg3iv	-	2.54	3.387 (11)	148
C19B—H19B···Cg4xii	-	2.93	3.696 (15)	138
C19A—H19D···Cg4xii	-	2.67	3.53 (4)	151