Poly[di­aqua­bis­(μ-hydrogen benzene-1,2,4-tri­carboxyl­ato)copper(II)disodium]: a novel 4,5,6-connected trinodal net

Yang, A.P.; LaDuca, R.L.

doi:10.1107/S2414314618006764

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 3| Part 5| May 2018| x180676

https://doi.org/10.1107/S2414314618006764

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Poly[diaquabis(μ-hydrogen benzene-1,2,4-tricarboxylato)copper(II)disodium]: a novel 4,5,6-connected trinodal net

Annabeth P. Yang ^a and Robert L. LaDuca ^a ^*

^aE-35A Holmes Hall, Michigan State University, 919 E. Shaw Lane, East Lansing, MI 48825, USA
^*Correspondence e-mail: laduca@msu.edu

Edited by A. J. Lough, University of Toronto, Canada (Received 19 April 2018; accepted 2 May 2018; online 15 May 2018)

In the title compound, [CuNa₂(C₉H₄O₆)₂(H₂O)₄]_n, the Cu^II cations are square-planar coordinated by carboxylate O-atom donors from four different hydrogen benzene-1,2,4-tricarboxylate (btcH) ligands, thereby forming [Cu(btcH)₂]_n²ⁿ⁻ coordination polymer ribbons. These are connected by octahedrally coordinated and hydrated Na^I cations within Na₂(μ-H₂O)₂ clusters to construct the full [Na₂(H₂O)₄Cu(btcH)₂]_n three-dimensional coordination polymer.

Keywords: crystal structure.

CCDC reference: 1841075

Structure description

The title coordination polymer was isolated during an attempt to prepare a copper benzene-1,2,4-tricarboxylate (btc) coordination polymer containing N,N′-bis(pyridin-3-ylmethyl)piperazine (3-bpmp) ligands. The 3-bpmp ligand has been used to construct coordination polymers with rare topologies, such as the (4⁴6²)(4⁴6⁶) tcs topology in {[Zn₂(hydrogen pyromellitate)₂(H₂O)₂(H₂-3-bpmp)]·H₂O}_n (Blake et al., 2011 ).

The asymmetric unit of the title compound contains a Cu^II cation on a crystallographic inversion center, a protonated hydrogen benzene-1,2,4-tricarboxylate (btcH) ligand, an Na^I cation on a general position, and two aqua ligands bound to the Na atom. Operation of the inversion center affords a square-planar coordination geometry at the Cu^II cation, ligated by carboxylate O-atom donors from four different btcH ligands. The Na atom is coordinated in an octahedral geometry, with a mer disposition of three bound water molecules and a mer disposition of carboxylate O-atom donors from three different btcH ligands. A depiction of the coordination geometries and btcH ligand is shown in Fig. 1. Bond lengths and angles within the coordination spheres at Cu^II and Na^I are listed in Table 1.

Table 1
Selected geometric parameters (Å, °)

Cu1—O1	1.944 (2)	Na1—O3^v	2.413 (3)
Cu1—O1ⁱ	1.944 (2)	Na1—O5	2.390 (2)
Cu1—O3ⁱⁱ	1.9681 (19)	Na1—O7	2.473 (3)
Cu1—O3ⁱⁱⁱ	1.9681 (19)	Na1—O8	2.354 (3)
Na1—O2^iv	2.571 (3)	Na1—O8^vi	2.413 (3)

O1—Cu1—O1ⁱ	180	O5—Na1—O8^vi	150.41 (10)
O1ⁱ—Cu1—O3ⁱⁱⁱ	87.13 (9)	O7—Na1—O2^iv	96.31 (10)
O1ⁱ—Cu1—O3ⁱⁱ	92.88 (9)	O8^vi—Na1—O2^iv	66.08 (9)
O1—Cu1—O3ⁱⁱⁱ	92.87 (9)	O8—Na1—O2^iv	72.51 (9)
O1—Cu1—O3ⁱⁱ	87.13 (9)	O8—Na1—O3^v	115.87 (9)
O3ⁱⁱⁱ—Cu1—O3ⁱⁱ	180.00 (14)	O8^vi—Na1—O3^v	97.25 (9)
O3^v—Na1—O2^iv	162.81 (9)	O8—Na1—O5	89.37 (9)
O3^v—Na1—O7	77.27 (10)	O8—Na1—O7	165.87 (11)
O5—Na1—O2^iv	89.20 (8)	O8^vi—Na1—O7	85.02 (9)
O5—Na1—O3^v	105.37 (9)	O8—Na1—O8^vi	97.79 (8)
O5—Na1—O7	81.70 (9)
Symmetry codes: (i) -x, -y+1, -z; (ii) x-1, y, z; (iii) -x+1, -y+1, -z; (iv) -x+1, -y+2, -z+1; (v) -x+1, -y+1, -z+1; (vi) -x+1, -y+2, -z+2.

Figure 1
The coordination environments within the title compound, showing the octahedral coordination at the Na^I cation and the square-planar coordination at the Cu^II cation. Displacement ellipsoids are drawn at the 50% probability level.Symmetry codes are as listed in Table 2

The Cu^II cations are conjoined by pairs of btcH ligands via their deprotonated carboxylate termini to construct anionic [Cu(btcH)₂]_n²ⁿ⁻ coordination polymer ribbons oriented parallel to [100] (Fig. 2). Within the [Cu(btcH)₂]_n²ⁿ⁻ ribbons, the Cu⋯Cu internuclear distance of 6.9035 (7) Å coincides with the a lattice parameter. The protonated carboxylate groups of the btcH ligands project towards the periphery of the ribbon motifs.

Figure 2
[Cu(btcH)₂]_n²ⁿ⁻ coordination polymer ribbon parallel to [100] in the title compound.

Pairs of bridging water molecules create cationic Na₂(μ-H₂O)₂²⁺ clusters with an Na⋯Na distance of 3.140 (5) Å (Fig. 3). These clusters conjoin adjacent anionic [Cu(btcH)₂]_n²ⁿ⁻ ribbons into an [Na₂(H₂O)₄Cu(btcH)₂]_n three-dimensional coordination polymer network (Fig. 4). Ancillary structural stabilization is provided by hydrogen bonding between the protonated btcH carboxylate group and non-bridging water molecules bound to the Na^I cations (Table 2).

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O6—H6⋯O7	0.70 (4)	1.91 (4)	2.613 (3)	177 (5)
O7—H7A⋯O4^iv	0.68 (4)	2.01 (4)	2.685 (4)	169 (4)
O7—H7B⋯O1^vii	0.81 (5)	2.02 (5)	2.816 (4)	168 (4)
O8—H8A⋯O4^viii	0.84 (2)	1.90 (2)	2.736 (3)	170 (4)
O8—H8B⋯O2^ix	0.81 (2)	2.54 (3)	2.720 (3)	94 (3)
Symmetry codes: (iv) -x+1, -y+2, -z+1; (vii) -x, -y+1, -z+1; (viii) -x+2, -y+2, -z+1; (ix) x, y, z+1.

Figure 3
Cationic Na₂(μ-H₂O)₂²⁺ cluster in the title compound.

Figure 4
Connection of [Cu(btcH)₂]_n²ⁿ⁻ coordination polymer ribbons by Na^I cations to construct the [Na₂(H₂O)₄Cu(btcH)₂]_n three-dimensional coordination polymer structure of the title compound. Individual [Cu(btcH)₂]_n²ⁿ⁻ ribbons are drawn in red.

Treating the Cu^II atoms as 4-connected nodes, the btcH ligands as 5-connected nodes, and the Na₂(μ-H₂O)₂²⁺ clusters as 6-connected nodes results in a 4,5,6-connected {4².8⁴}{4⁶.6⁶.8³}{4⁸.6²}₂ topology (Fig. 5) for the underlying network of the [Na₂(H₂O)₄Cu(btcH)₂]_n three-dimensional coordination polymer, as determined by TOPOS (Blatov et al., 2014 ).

Figure 5
Schematic perspective of the 4,5,6-connected {4².8⁴}{4⁶.6⁶.8³}{4⁸.6²}₂ topology network of the [Na₂(H₂O)₄Cu(btcH)₂]_n three-dimensional coordination polymer within the title compound. The 4-connected Cu^II atom nodes are depicted as blue spheres. The 5-connected btcH ligand nodes are depicted as orange spheres. The 6-connected Na₂(μ-H₂O)₂²⁺ cluster modes are depicted as green spheres.

Synthesis and crystallization

Cu(NO₃)₂·2.5H₂O (86 mg, 0.37 mmol), benzene-1,2,4-tricarboxylic acid (78 mg, 0.37 mol), N,N′-bis(pyridin-3-ylmethyl)piperazine (99 mg, 0.37 mol) and 0.75 ml of a 1.0 M NaOH solution were placed in 10 ml distilled H₂O in a Teflon-lined acid digestion bomb. The bomb was sealed and heated in an oven at 393 K for 24 h, and then cooled slowly to 278 K. Blue crystals of the title compound (47 mg, 21% yield based on copper) were isolated after washing with distilled water and acetone, and drying in air.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3.

Table 3
Experimental details

Crystal data
Chemical formula	[CuNa₂(C₉H₄O₆)₂(H₂O)₄]
M_r	597.83
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	173
a, b, c (Å)	6.9048 (9), 7.0555 (9), 11.8449 (15)
α, β, γ (°)	105.071 (2), 93.073 (2), 109.955 (2)
V (Å³)	517.26 (11)
Z	1
Radiation type	Mo Kα
μ (mm⁻¹)	1.19
Crystal size (mm)	0.26 × 0.08 × 0.03

Data collection
Diffractometer	Bruker SMART CCD 1K area detector
Absorption correction	Multi-scan (SADABS; Bruker, 2015 )
T_min, T_max	0.659, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	4640, 1906, 1606
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.099, 1.07
No. of reflections	1906
No. of parameters	199
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.48, −0.35
Computer programs: COSMO (Bruker, 2009 ), SAINT (Bruker, 2013 ), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ) within OLEX2 (Dolomanov et al., 2009 ) and Crystal Maker (Palmer, 2018 ).

Structural data

CCDC reference: 1841075

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314618006764/lh4034sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618006764/lh4034Isup2.hkl

checkCIF report

Computing details top

Data collection: COSMO (Bruker, 2009); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b) within OLEX2 (Dolomanov et al., 2009); molecular graphics: Crystal Maker (Palmer, 2018); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Poly[diaquabis(µ-hydrogen benzene-1,2,4-tricarboxylato)copper(II)disodium] top

Crystal data top

[CuNa₂(C₉H₄O₆)₂(H₂O)₄]	Z = 1
M_r = 597.83	F(000) = 301
Triclinic, P1	D_x = 1.913 Mg m⁻³
a = 6.9048 (9) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.0555 (9) Å	Cell parameters from 2453 reflections
c = 11.8449 (15) Å	θ = 3.2–25.4°
α = 105.071 (2)°	µ = 1.19 mm⁻¹
β = 93.073 (2)°	T = 173 K
γ = 109.955 (2)°	Needle, blue
V = 517.26 (11) Å³	0.26 × 0.08 × 0.03 mm

Data collection top

Bruker SMART CCD 1K area detector diffractometer	1906 independent reflections
Radiation source: sealed X-ray tube	1606 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
Detector resolution: 7.9 pixels mm^-1	θ_max = 25.4°, θ_min = 1.8°
ω scans	h = −8→8
Absorption correction: multi-scan (SADABS; Bruker, 2015)	k = −8→8
T_min = 0.659, T_max = 0.745	l = −13→14
4640 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.099	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0511P)² + 0.245P] where P = (F_o² + 2F_c²)/3
1906 reflections	(Δ/σ)_max < 0.001
199 parameters	Δρ_max = 0.48 e Å⁻³
3 restraints	Δρ_min = −0.35 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. The structure was refined by Least Squares using version 2014/6 of XL (Sheldrick, 2015b) incorporated in Olex2 (Dolomanov et al., 2009). All non-hydrogen atoms were refined anisotropically. Hydrogen atom positions were calculated geometrically and refined using the riding model, except for the Hydrogen atom on the oxygen atoms which was found by difference Fourier methods and refined isotropically.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cu1	0.0000	0.5000	0.0000	0.01725 (19)
Na1	0.38930 (19)	0.8360 (2)	0.87662 (11)	0.0247 (3)
O1	0.2019 (3)	0.5155 (3)	0.12631 (18)	0.0188 (5)
O2	0.4758 (4)	0.7631 (4)	0.09054 (19)	0.0265 (6)
O3	0.8109 (3)	0.5155 (3)	0.11767 (18)	0.0181 (5)
O4	0.9730 (4)	0.8616 (4)	0.1695 (2)	0.0322 (6)
O5	0.4966 (4)	0.7908 (4)	0.68605 (19)	0.0248 (6)
O6	0.2072 (4)	0.7132 (4)	0.5602 (2)	0.0242 (6)
H6	0.167 (7)	0.722 (7)	0.614 (4)	0.039 (13)*
O7	0.0503 (4)	0.7544 (5)	0.7571 (2)	0.0221 (6)
H7A	0.032 (6)	0.846 (6)	0.770 (3)	0.021 (12)*
H7B	−0.036 (7)	0.673 (7)	0.783 (4)	0.038 (12)*
O8	0.7418 (4)	0.9752 (4)	0.9649 (2)	0.0264 (6)
H8A	0.836 (5)	1.038 (5)	0.931 (3)	0.028*
H8B	0.770 (5)	0.877 (4)	0.973 (3)	0.028*
C1	0.5084 (5)	0.6815 (5)	0.2697 (3)	0.0143 (6)
C2	0.7216 (5)	0.7167 (5)	0.2844 (3)	0.0162 (7)
C3	0.8280 (5)	0.7616 (5)	0.3969 (3)	0.0188 (7)
H3	0.965 (6)	0.780 (5)	0.411 (3)	0.020 (9)*
C4	0.7268 (5)	0.7724 (5)	0.4942 (3)	0.0192 (7)
H4	0.806 (5)	0.811 (5)	0.574 (3)	0.027 (10)*
C5	0.5150 (5)	0.7383 (5)	0.4802 (3)	0.0166 (7)
C6	0.4076 (5)	0.6917 (5)	0.3678 (3)	0.0170 (7)
H6A	0.259 (5)	0.667 (5)	0.358 (2)	0.011 (8)*
C7	0.3906 (5)	0.6523 (5)	0.1510 (3)	0.0170 (7)
C8	0.8432 (5)	0.7000 (5)	0.1818 (3)	0.0168 (7)
C9	0.4075 (5)	0.7501 (5)	0.5861 (3)	0.0185 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0163 (3)	0.0219 (3)	0.0148 (3)	0.0074 (2)	0.0044 (2)	0.0065 (2)
Na1	0.0207 (7)	0.0273 (8)	0.0196 (7)	0.0028 (6)	0.0047 (6)	0.0038 (6)
O1	0.0145 (12)	0.0263 (13)	0.0133 (11)	0.0032 (10)	0.0001 (9)	0.0083 (9)
O2	0.0271 (14)	0.0285 (14)	0.0205 (12)	0.0020 (11)	0.0016 (10)	0.0131 (11)
O3	0.0180 (12)	0.0211 (13)	0.0141 (11)	0.0060 (10)	0.0045 (9)	0.0045 (9)
O4	0.0325 (15)	0.0225 (13)	0.0456 (16)	0.0085 (12)	0.0266 (12)	0.0148 (11)
O5	0.0221 (13)	0.0342 (14)	0.0159 (13)	0.0084 (11)	0.0031 (10)	0.0067 (10)
O6	0.0214 (14)	0.0392 (15)	0.0161 (13)	0.0144 (12)	0.0080 (11)	0.0095 (11)
O7	0.0241 (14)	0.0211 (14)	0.0246 (14)	0.0096 (12)	0.0104 (11)	0.0092 (11)
O8	0.0256 (14)	0.0350 (16)	0.0280 (13)	0.0152 (12)	0.0114 (11)	0.0181 (12)
C1	0.0179 (16)	0.0127 (15)	0.0137 (15)	0.0060 (13)	0.0031 (12)	0.0052 (12)
C2	0.0173 (16)	0.0130 (16)	0.0208 (17)	0.0054 (13)	0.0064 (13)	0.0086 (13)
C3	0.0132 (17)	0.0218 (18)	0.0221 (17)	0.0067 (14)	0.0022 (13)	0.0072 (14)
C4	0.0193 (18)	0.0186 (17)	0.0166 (17)	0.0041 (14)	−0.0008 (14)	0.0047 (14)
C5	0.0202 (17)	0.0134 (16)	0.0159 (16)	0.0047 (13)	0.0039 (13)	0.0057 (13)
C6	0.0169 (17)	0.0150 (16)	0.0179 (17)	0.0053 (13)	0.0026 (13)	0.0040 (13)
C7	0.0190 (18)	0.0204 (17)	0.0162 (16)	0.0114 (14)	0.0074 (13)	0.0068 (13)
C8	0.0138 (16)	0.0207 (18)	0.0179 (16)	0.0072 (14)	0.0017 (13)	0.0081 (14)
C9	0.0224 (18)	0.0156 (16)	0.0177 (17)	0.0062 (14)	0.0064 (14)	0.0055 (13)

Geometric parameters (Å, º) top

Cu1—O1	1.944 (2)	O6—H6	0.70 (4)
Cu1—O1ⁱ	1.944 (2)	O6—C9	1.320 (4)
Cu1—O3ⁱⁱ	1.9681 (19)	O7—H7A	0.68 (4)
Cu1—O3ⁱⁱⁱ	1.9681 (19)	O7—H7B	0.81 (5)
Na1—O2^iv	2.571 (3)	O8—Na1^vi	2.413 (3)
Na1—O3^v	2.413 (3)	O8—H8A	0.842 (18)
Na1—O5	2.390 (2)	O8—H8B	0.808 (18)
Na1—O7	2.473 (3)	C1—C2	1.400 (4)
Na1—O8	2.354 (3)	C1—C6	1.385 (4)
Na1—O8^vi	2.413 (3)	C1—C7	1.514 (4)
O1—C7	1.292 (4)	C2—C3	1.389 (4)
O2—Na1^vii	2.787 (3)	C2—C8	1.516 (4)
O2—Na1^iv	2.571 (3)	C3—H3	0.91 (4)
O2—C7	1.222 (4)	C3—C4	1.379 (4)
O3—Cu1^viii	1.9681 (19)	C4—H4	0.99 (4)
O3—Na1^v	2.413 (3)	C4—C5	1.392 (4)
O3—C8	1.261 (4)	C5—C6	1.390 (4)
O4—C8	1.236 (4)	C5—C9	1.489 (4)
O5—C9	1.219 (4)	C6—H6A	0.98 (3)

O1—Cu1—O1ⁱ	180.0	Na1—O8—Na1^vi	82.21 (8)
O1ⁱ—Cu1—O3ⁱⁱⁱ	87.13 (9)	Na1^vi—O8—H8A	122 (2)
O1ⁱ—Cu1—O3ⁱⁱ	92.88 (9)	Na1—O8—H8A	121 (3)
O1—Cu1—O3ⁱⁱⁱ	92.87 (9)	Na1—O8—H8B	107 (3)
O1—Cu1—O3ⁱⁱ	87.13 (9)	Na1^vi—O8—H8B	118 (3)
O3ⁱⁱⁱ—Cu1—O3ⁱⁱ	180.00 (14)	H8A—O8—H8B	105 (3)
O3^v—Na1—O2^iv	162.81 (9)	C2—C1—C7	121.4 (3)
O3^v—Na1—O7	77.27 (10)	C6—C1—C2	119.1 (3)
O5—Na1—O2^iv	89.20 (8)	C6—C1—C7	119.3 (3)
O5—Na1—O3^v	105.37 (9)	C1—C2—C8	122.9 (3)
O5—Na1—O7	81.70 (9)	C3—C2—C1	119.5 (3)
O5—Na1—O8^vi	150.41 (10)	C3—C2—C8	117.5 (3)
O7—Na1—O2^iv	96.31 (10)	C2—C3—H3	123 (2)
O8^vi—Na1—O2^iv	66.08 (9)	C4—C3—C2	121.0 (3)
O8—Na1—O2^iv	72.51 (9)	C4—C3—H3	116 (2)
O8—Na1—O3^v	115.87 (9)	C3—C4—H4	120 (2)
O8^vi—Na1—O3^v	97.25 (9)	C3—C4—C5	119.8 (3)
O8—Na1—O5	89.37 (9)	C5—C4—H4	120 (2)
O8—Na1—O7	165.87 (11)	C4—C5—C9	119.2 (3)
O8^vi—Na1—O7	85.02 (9)	C6—C5—C4	119.4 (3)
O8—Na1—O8^vi	97.79 (8)	C6—C5—C9	121.3 (3)
C7—O1—Cu1	122.27 (19)	C1—C6—C5	121.1 (3)
Na1^iv—O2—Na1^vii	71.48 (7)	C1—C6—H6A	119.4 (17)
C7—O2—Na1^iv	132.9 (2)	C5—C6—H6A	119.5 (17)
C7—O2—Na1^vii	139.5 (2)	O1—C7—C1	115.1 (3)
Cu1^viii—O3—Na1^v	109.41 (9)	O2—C7—O1	126.2 (3)
C8—O3—Cu1^viii	114.38 (19)	O2—C7—C1	118.6 (3)
C8—O3—Na1^v	135.22 (19)	O3—C8—C2	116.0 (3)
C9—O5—Na1	133.8 (2)	O4—C8—O3	124.3 (3)
C9—O6—H6	107 (4)	O4—C8—C2	119.6 (3)
Na1—O7—H7A	106 (3)	O5—C9—O6	123.9 (3)
Na1—O7—H7B	106 (3)	O5—C9—C5	123.1 (3)
H7A—O7—H7B	107 (4)	O6—C9—C5	113.0 (3)

Cu1^ix—Na1—O5—C9	59.0 (3)	O8—Na1—O5—C9	−168.1 (3)
Cu1^ix—Na1—O8—Na1^vi	−66.87 (8)	O8^vi—Na1—O5—C9	−63.3 (4)
Cu1—O1—C7—O2	−12.0 (4)	O8^vi—Na1—O8—Na1^vi	0.0
Cu1—O1—C7—C1	164.65 (18)	C1—C2—C3—C4	−0.1 (5)
Cu1^viii—O3—C8—O4	4.1 (4)	C1—C2—C8—O3	−74.2 (4)
Cu1^viii—O3—C8—C2	−171.8 (2)	C1—C2—C8—O4	109.7 (4)
Na1^vii—Cu1—O1—C7	12.9 (2)	C2—C1—C6—C5	0.7 (5)
Na1^x—Cu1—O1—C7	−167.1 (2)	C2—C1—C7—O1	143.0 (3)
Na1^vi—Na1—O5—C9	−138.8 (3)	C2—C1—C7—O2	−40.1 (4)
Na1^iv—O2—C7—O1	114.2 (3)	C2—C3—C4—C5	−0.1 (5)
Na1^vii—O2—C7—O1	−0.6 (5)	C3—C2—C8—O3	103.4 (3)
Na1^iv—O2—C7—C1	−62.4 (4)	C3—C2—C8—O4	−72.7 (4)
Na1^vii—O2—C7—C1	−177.12 (19)	C3—C4—C5—C6	0.6 (5)
Na1^v—O3—C8—O4	171.2 (2)	C3—C4—C5—C9	179.9 (3)
Na1^v—O3—C8—C2	−4.7 (4)	C4—C5—C6—C1	−1.0 (5)
Na1—O5—C9—O6	−2.0 (5)	C4—C5—C9—O5	0.8 (5)
Na1—O5—C9—C5	177.6 (2)	C4—C5—C9—O6	−179.6 (3)
O1ⁱ—Cu1—O1—C7	23 (9)	C6—C1—C2—C3	−0.2 (4)
O2^ix—Na1—O5—C9	146.4 (3)	C6—C1—C2—C8	177.4 (3)
O2^iv—Na1—O5—C9	−95.6 (3)	C6—C1—C7—O1	−42.6 (4)
O2^iv—Na1—O8—Na1^vi	61.83 (8)	C6—C1—C7—O2	134.3 (3)
O2^ix—Na1—O8—Na1^vi	−60.30 (8)	C6—C5—C9—O5	−179.9 (3)
O3ⁱⁱⁱ—Cu1—O1—C7	52.4 (2)	C6—C5—C9—O6	−0.3 (4)
O3ⁱⁱ—Cu1—O1—C7	−127.6 (2)	C7—C1—C2—C3	174.2 (3)
O3^v—Na1—O5—C9	75.2 (3)	C7—C1—C2—C8	−8.2 (4)
O3^v—Na1—O8—Na1^vi	−102.00 (10)	C7—C1—C6—C5	−173.8 (3)
O5—Na1—O8—Na1^vi	151.19 (10)	C8—C2—C3—C4	−177.8 (3)
O7—Na1—O5—C9	0.9 (3)	C9—C5—C6—C1	179.8 (3)
O7—Na1—O8—Na1^vi	100.6 (4)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O6—H6···O7	0.70 (4)	1.91 (4)	2.613 (3)	177 (5)
O7—H7A···O4^iv	0.68 (4)	2.01 (4)	2.685 (4)	169 (4)
O7—H7B···O1^x	0.81 (5)	2.02 (5)	2.816 (4)	168 (4)
O8—H8A···O4^xi	0.84 (2)	1.90 (2)	2.736 (3)	170 (4)
O8—H8B···O2^ix	0.81 (2)	2.54 (3)	2.720 (3)	94 (3)

Symmetry codes: (iv) −x+1, −y+2, −z+1; (ix) x, y, z+1; (x) −x, −y+1, −z+1; (xi) −x+2, −y+2, −z+1.

Funding information

Funding for this work was provided by the Honors College of Michigan State University.

References

Blake, K. M., Lucas, J. S. & LaDuca, R. L. (2011). Cryst. Growth Des. 11, 1287–1293. Web of Science CSD CrossRef CAS Google Scholar
Blatov, V. A., Shevchenko, A. P. & Proserpio, D. M. (2014). Cryst. Growth Des. 11, 3576–3586. CrossRef Google Scholar
Bruker (2009). COSMO. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2013). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2015). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Palmer, D. (2018). CrystalMaker. CrystalMaker Software, Bicester, Oxfordshire, England. Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar

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