Crystal structure of di-μ-aqua-μ-(pyrazine N,N′-dioxide)-κ2O:O-bis­(di­aqua­sodium) tetra­phenyl­borate dihydrate pyrazine N,N′-dioxide monosolvate

Boron, E.P.; Carter, K.K.; Knaust, J.M.

doi:10.1107/S205698901502071X

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ISSN: 2056-9890

Volume 71| Part 12| December 2015| Pages 1467-1470

https://doi.org/10.1107/S205698901502071X

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Crystal structure of di-μ-aqua-μ-(pyrazine N,N′-dioxide)-κ²O:O-bis(diaquasodium) tetraphenylborate dihydrate pyrazine N,N′-dioxide monosolvate

Elaine P. Boron,^a Kelsey K. Carter ^a and Jacqueline M. Knaust ^b ^*

^aChemistry Department, 520 North Main St., Meadville, PA 16335, USA, and ^bDepartment of Chemistry Mathematics and Physics, Clarion University, 840 Wood Street, Clarion, PA 16214, USA
^*Correspondence e-mail: jknaust@clarion.edu

Edited by M. Weil, Vienna University of Technology, Austria (Received 27 October 2015; accepted 1 November 2015; online 7 November 2015)

The search for novel lanthanide coordination networks using pyrazine N,N′-dioxide (pzdo, C₄H₄N₂O₂) as a structure-directing unit, led to the synthesis and the structure determination of the title compound, [Na₂(C₄H₄N₂O₂)(H₂O)₆][B(C₆H₅)₄]₂·C₄H₄N₂O₂·2H₂O. The crystal structure is comprised of discrete [{Na(H₂O)₂}₂(μ-H₂O)₂(μ-pzdo)]²⁺ cations and tetraphenylborate anions, as well as pzdo and H₂O solvent molecules. The dinuclear cation is located about a twofold rotation axis, and the symmetry-related Na^I atoms display a distorted square-pyramidal coordination sphere defined by two O atoms of terminal water ligands, two O atoms of bridging water ligands and one O atom of a bridging pzdo ligand. In the crystal, O—H⋯O hydrogen bonds link the dinuclear cation and solvent pzdo molecules (point-group symmetry -1) into rectangular grid-like layers parallel to the bc plane. Additional C—H⋯O, O—H⋯O, C—H⋯π and O—H⋯π interactions link the anion and solvent water molecules to the layers. The layers are further linked into a three-dimensional network through a combination of C—H⋯π and O—H⋯π hydrogen bonds involving the tetraphenylborate anion.

Keywords: crystal structure; sodium coordination compound; pyrazine N,N′-dioxide (pzdo); C—H⋯O interactions; O—H⋯O interactions; C—H⋯π interactions; O—H⋯π interactions.

CCDC reference: 1434594

1. Chemical context

The use of aromatic N,N′-dioxide ligands such as pyrazine N,N′-dioxide (pzdo) and 4,4′-pyridine-N,N′-dioxide (bpydo) in the synthesis of transition metal and lanthanide metal compounds with coordination networks has been of recent interest (Hill et al., 2005b ; Ma et al., 2001 ; Mantero et al., 2006 ; Sun et al., 2004 ). The coordination modes and hydrogen-bonding modes of N,N′-dioxide ligands are flexible (Ma et al., 2001; Mantero et al., 2006). Structure prediction with these ligands can be difficult, in part due to their flexible bonding, but also due to the influences of the anion and solvent (Hill et al., 2005a ; Mantero et al., 2006).

We have previously reported the structures of several three-dimensional coordination networks of the type {[Ln(pzdo)₄](ClO₄)₃}_n, with Ln = Nd (Quinn-Elmore et al., 2010a ), Dy (Quinn-Elmore et al., 2010b ), Ho (Buchner et al., 2010a ), and Er (Buchner et al., 2010b ), which all are isostructural to the previously reported La, Ce, Pr, Sm, Eu, Gd, Tb and Y coordination networks (Sun et al., 2004). In an attempt to synthesize a novel lanthanide coordination polymer with pzdo ligands and tetraphenylborate (BPh₄⁻) anions, crystals of the title compound, [{Na(H₂O)₂}₂(μ-H₂O)₂(μ-pzdo)][B(C₆H₅)₄]₂·2H₂O·pzdo, were isolated instead.

2. Structural commentary

The asymmetric unit of the title compound contains one Na^I atom, half of a coordinating pzdo ligand, two terminal water ligands, one bridging water ligand, one tetraphenylborate anion, half of a solvent pzdo molecule and one solvent water molecule (Fig. 1). The Na^I atom displays a distorted square-pyramidal coordination sphere defined by two O atoms of terminal water ligands, two O atoms of bridging water ligands and one O atom of the bridging pzdo ligand. The bridging water and pzdo ligands link two Na^I atoms to form a dinuclear cation, [{Na(H₂O)₂}₂(μ-H₂O)₂(μ-pzdo)]²⁺, that is located about a twofold rotation axis. The oxygen and nitrogen atoms of the coordinating pzdo ligand (O1, O2, N1, and N2) lie on a twofold rotation axis, and the solvent pzdo molecule (C3, C4, N3 O3) is located around an inversion center. The pzdo ligand bridges the Na^I atoms in the less commonly seen end-on fashion, while the oxygen atom (O2) of the solvent pzdo molecule is involved in O—H⋯O hydrogen-bonding interactions with another [{Na(H₂O)₂}₂(μ-H₂O)₂(μ-pzdo)]²⁺ cation.

Figure 1
The molecular entities in the crystal structure of [{Na(H₂O)₂}₂(μ-H₂O)₂(μ-pzdo)][B(Ph)₄]₂·2H₂O·pzdo drawn with displacement ellipsoids at the 50% probability level. Labeled atoms are related to unlabeled atoms by the symmetry operations: −x + 1, y, −z + $[{1\over 2}]$ for [{Na(H₂O)₂}₂(μ-H₂O)₂(μ-pzdo)]²⁺ and by −x + 1, −y + 1, −z for the solvent pzdo molecule (C3, C4, N3, and O3). Only those hydrogen atoms whose positions were refined are labeled.

3. Supramolecular features

Three unique C—H⋯O hydrogen-bonding interactions between the [{Na(H₂O)₂}₂(μ-H₂O)₂(μ-pzdo)]²⁺ cations and pzdo solvent moieties generate rectangular grid-like layers parallel to the bc plane. These interactions involve the bridging water ligand and the solvent pzdo molecule (O4—H4A⋯O3), a terminal water ligand and the solvent pzdo molecule (O5—H5B⋯O3ⁱ), and the bridging water ligand and the coordinating pzdo ligand (O4—H4B⋯ O2ⁱⁱⁱ) (see Table 1 for symmetry codes; Fig. 2). Additional interactions link the anion and solvent water molecule to the layer (Fig. 3.). The anion is linked through C—H⋯O and C—H⋯π interactions with the solvent pzdo molecule (C19—H19⋯O3^iv and C2—H2⋯Cg3^v). The solvent water molecule accepts two hydrogen bonds from coordinating water molecules (O5—H5A⋯O7 and O6—H6B⋯O7) and interacts with two anions through O—H⋯π interactions (O7—H7A⋯Cg2^v and O7—H7B⋯ Cg1^vii). While all of the aforementioned interactions occur within a layer, additional C—H⋯π and O—H⋯π interactions with the tetraphenylborate anions (C3—H3⋯Cg1ⁱ, O6—H6A⋯Cg4ⁱ, and C7—H7⋯Cg3^vi) link the layers into a complex three-dimensional network (Table 1, Fig. 4).

Table 1
Hydrogen-bond geometry (Å, °)

Cg1, Cg2, Cg3 and Cg4 are the centroids of the C5–C10, C11–C16, C17–C22 and C23–C28 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4A⋯O3	0.86 (2)	2.09 (2)	2.8855 (13)	153 (2)
O4—H4B⋯O2ⁱⁱⁱ	0.85 (2)	1.95 (2)	2.6948 (14)	144 (2)
O5—H5B⋯O3ⁱ	0.84 (2)	1.95 (2)	2.7655 (14)	163 (2)
O5—H5A⋯O7	0.86 (2)	2.00 (2)	2.8329 (16)	163 (2)
O6—H6B⋯O7	0.88 (2)	2.06 (2)	2.9055 (19)	160 (3)
C19—H19⋯O3^iv	0.95	2.55	3.4884 (16)	168
C2—H2⋯Cg3^v	0.95	2.40	3.2435 (14)	148
C3—H3⋯Cg1ⁱ	0.95	2.46	3.2788 (14)	144
O6—H6A⋯Cg4ⁱ	0.85 (3)	2.45 (3)	3.1713 (14)	144 (2)
C7—H7⋯Cg3^vi	0.95	2.66	3.5365 (14)	153
O7—H7A⋯Cg2^v	0.86 (2)	2.55 (2)	3.3871 (15)	165 (2)
O7—H7B⋯Cg1^vii	0.85 (3)	2.59 (2)	3.4337 (15)	171 (3)
Symmetry codes: (i) $[-x+1, y, -z+{\script{1\over 2}}]$ ; (iii) x, y-1, z; (iv) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (v) $[x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (vi) $[-x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (vii) $[x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ .

Figure 2
Diagram showing hydrogen-bonded [{Na(H₂O)₂}₂(μ-H₂O)₂(μ-pzdo)]²⁺ and pzdo moieties which generate a rectangular grid parallel to the bc plane. Dashed lines represent O—H⋯O interactions between coordinating water molecules and the solvent pzdo molecule (O4—H4A⋯O3 and O5—H5B⋯O3ⁱ) and between a coordinating water and the coordinating pzdo ligand (O4—H4B⋯O2ⁱⁱⁱ). [Symmetry codes: (i) −x + 1, y, −z + $[{1\over 2}]$ ; (iii) x, y − 1, z; (iv) −x + $[{1\over 2}]$ , y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ .]

Figure 3
Diagram showing interactions linking the anion and solvent water molecule to the layers. A small portion of a layer is shown with all [{Na(H₂O)₂}₂(μ-H₂O)₂(μ-pzdo)]²⁺ and pzdo moieties represented in gray, and the hydrogen-bonding interactions within the layer indicated by dashed gray lines. Two solvent water molecules and one anion are shown in blue. The C—H⋯O, O—H⋯O, C—H⋯π, and O—H⋯π interactions linking the solvent water molecules and anion to the hydrogen-bonded layers are shown as dashed green lines. [Symmetry codes: (iv) −x + $[{1\over 2}]$ , y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (viii) x − $[{1\over 2}]$ , y + $[{1\over 2}]$ , z; (ix) x − $[{1\over 2}]$ , y − $[{1\over 2}]$ , z.]

Figure 4
Diagram showing all C—H⋯O, O—H⋯O, C—H⋯π, and O—H⋯π interactions that the BPh₄⁻ anion participates in. The C—H⋯O, C—H⋯π and O—H⋯π interactions responsible for linking the anion to a layer are shown as dashed red lines. The C—H⋯π and O—H⋯π interactions responsible for linking the layers into a three-dimensional framework are shown as dashed green lines. [Symmetry codes: (i) −x + 1, y, −z + $[{1\over 2}]$ ; (iv) −x + $[{1\over 2}]$ , y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (vi) −x + $[{1\over 2}]$ , −y + $[{3\over 2}]$ , −z + 1; (viii) x − $[{1\over 2}]$ , y + $[{1\over 2}]$ , z; (ix) x − $[{1\over 2}]$ , y − $[{1\over 2}]$ , z.]

4. Database survey

A survey of the Cambridge Structural Database (CSD, Version 5.36, November 2014; Groom & Allen, 2014 ) returned hits for 37 structures with pyrazine N,N'-dioxide. Three structures are reported for the pzdo molecule. Five structures are reported for pzdo as part of a co-crystal. Fourteen structures are reported where pzdo coordinates to a transition metal and acts as a bridging ligand in a coordination network. Twelve structures are reported where pzdo coordinates to a lanthanide metal and acts as a bridging ligand in a coordination network. In all 26 reported coordination networks, pzdo bridges metal atoms in an end-to-end fashion. Two structures for mixed metal (Na^I/Tb^III and Na^I/Er^III) coordination networks with p-sulfonatocalix[4]arene are reported where the Na^I cation is coordinated by a terminal pzdo ligand, and the structure of the mixed metal coordination network (Na^I/La^III) with sulfonatocalix[4]arene is reported where pzdo is included in the structure as a clathrate (Zheng et al., 2008 ). One final structure of note deposited after the November 2014 release of the CSD is that of a mixed metal (Na^I/W^V) coordination network where pzdo bridges Na^I atoms in both end-to-end and end-on modes (Podgajny et al., 2014 ).

5. Synthesis and crystallization

Pyrazine-N,N′-dioxide was synthesized from pyrazine according to the method of Simpson et al. (1963 ). All other chemicals were obtained from commercial sources and used without further purification. Initially, NaBPh₄ (0.0821 g, 0.240 mmol), pzdo (0.0171 g, 0.152 mmol) and 40%_wt aqueous Ho(ClO₄)₃ (14.8 µl, 0.0201 mmol), were combined in 25 ml of methanol to form a cloudy solution, and colorless crystals of the title compound were obtained upon slow evaporation of the solvent. Further studies showed that crystals of the title compound can also be isolated in the absence of the lanthanide salt. In this case, NaBPh₄ (0.0257 g, 0.0750 mmol) and pzdo (0.0171 g, 0.152 mmol) were combined in 12.5 ml methanol and 1.1 ml of water to form a cloudy solution which yielded colorless crystals of the title compound upon slow evaporation of the solvent.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All aromatic H atoms were positioned geometrically and refined using a riding model with C—H = 0.95 Å and with U_iso(H) = 1.2 times U_eq(C). The positions of water H atoms were located from difference Fourier maps and the O—H distances in the water molecules were restrained to 0.85 (2) Å. U_iso parameters of water H atoms were refined freely.

Table 2
Experimental details

Crystal data
Chemical formula	[Na₂(C₄H₄N₂O₂)(H₂O)₆](BC₂₄H₂₀)₂·C₄H₄N₂O₂·2H₂O
M_r	1052.71
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	99
a, b, c (Å)	20.4224 (9), 10.1950 (4), 27.2349 (11)
β (°)	102.947 (1)
V (Å³)	5526.3 (4)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.10
Crystal size (mm)	0.50 × 0.40 × 0.25

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001 )
T_min, T_max	0.894, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	32437, 8464, 6996
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.715

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.140, 1.04
No. of reflections	8464
No. of parameters	377
No. of restraints	8
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.48, −0.21
Computer programs: SMART and SAINT (Bruker, 2007 ), SHELXS97 and SHELXL97 (Sheldrick, 2008 ), and X-SEED (Barbour, 2001 ).

Supporting information

CCDC reference: 1434594

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S205698901502071X/wm5232sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698901502071X/wm5232Isup2.hkl

checkCIF report

Computing details top

Data collection: SMART (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: X-SEED (Barbour, 2001); software used to prepare material for publication: X-SEED (Barbour, 2001).

Di-µ-aqua-µ-(pyrazine N,N'-dioxide)-κ²O:O-bis(diaquasodium) tetraphenylborate pyrazine N,N'-dioxide monosolvate dihydrate top

Crystal data top

[Na₂(C₄H₄N₂O₂)(H₂O)₆](BC₂₄H₂₀)₂·C₄H₄N₂O₂·2H₂O	F(000) = 2224
M_r = 1052.71	D_x = 1.265 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 14931 reflections
a = 20.4224 (9) Å	θ = 2.2–30.5°
b = 10.1950 (4) Å	µ = 0.10 mm⁻¹
c = 27.2349 (11) Å	T = 99 K
β = 102.947 (1)°	Block, colorless
V = 5526.3 (4) Å³	0.50 × 0.40 × 0.25 mm
Z = 4

Data collection top

Bruker SMART APEX CCD diffractometer	8464 independent reflections
Radiation source: fine-focus sealed tube	6996 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
ω scans	θ_max = 30.5°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −29→29
T_min = 0.894, T_max = 1.000	k = −14→14
32437 measured reflections	l = −37→38

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.140	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0739P)² + 3.1014P] where P = (F_o² + 2F_c²)/3
8464 reflections	(Δ/σ)_max = 0.001
377 parameters	Δρ_max = 0.48 e Å⁻³
8 restraints	Δρ_min = −0.21 e Å⁻³

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Na1	0.57681 (3)	0.53904 (5)	0.27762 (2)	0.02408 (12)
O1	0.5000	0.70101 (12)	0.2500	0.0302 (3)
O2	0.5000	1.22491 (12)	0.2500	0.0253 (3)
O3	0.48519 (5)	0.52324 (10)	0.09489 (3)	0.0272 (2)
O4	0.52081 (5)	0.44163 (9)	0.19893 (4)	0.0266 (2)
O5	0.61154 (5)	0.62448 (11)	0.35909 (4)	0.0316 (2)
O6	0.68618 (6)	0.53238 (14)	0.27608 (5)	0.0441 (3)
O7	0.75011 (6)	0.56103 (14)	0.38213 (5)	0.0434 (3)
N1	0.5000	0.82883 (14)	0.2500	0.0210 (3)
N2	0.5000	1.09705 (14)	0.2500	0.0195 (3)
N3	0.49248 (5)	0.51216 (10)	0.04872 (4)	0.0196 (2)
C1	0.53467 (6)	0.89566 (12)	0.29054 (5)	0.0214 (2)
H1	0.5591	0.8492	0.3191	0.026*
C2	0.53468 (6)	1.02966 (12)	0.29060 (5)	0.0209 (2)
H2	0.5591	1.0760	0.3192	0.025*
C3	0.54999 (6)	0.55124 (12)	0.03612 (5)	0.0215 (2)
H3	0.5855	0.5872	0.0612	0.026*
C4	0.44262 (6)	0.46070 (12)	0.01235 (5)	0.0212 (2)
H4	0.4021	0.4326	0.0207	0.025*
C5	0.28988 (5)	0.68369 (11)	0.39692 (4)	0.0165 (2)
C6	0.29439 (6)	0.74729 (12)	0.44320 (4)	0.0204 (2)
H6	0.2623	0.7264	0.4624	0.024*
C7	0.34389 (6)	0.83982 (13)	0.46232 (5)	0.0240 (2)
H7	0.3450	0.8808	0.4938	0.029*
C8	0.39154 (6)	0.87171 (13)	0.43493 (5)	0.0257 (3)
H8	0.4258	0.9337	0.4478	0.031*
C9	0.38860 (6)	0.81212 (13)	0.38855 (5)	0.0249 (3)
H9	0.4208	0.8336	0.3695	0.030*
C10	0.33829 (6)	0.72066 (12)	0.37003 (4)	0.0202 (2)
H10	0.3367	0.6819	0.3381	0.024*
C11	0.28603 (6)	0.43432 (11)	0.40579 (4)	0.0176 (2)
C12	0.28816 (6)	0.39219 (12)	0.45536 (4)	0.0203 (2)
H12	0.2577	0.4301	0.4731	0.024*
C13	0.33308 (6)	0.29710 (13)	0.47952 (5)	0.0244 (2)
H13	0.3325	0.2711	0.5129	0.029*
C14	0.37864 (7)	0.24013 (13)	0.45489 (5)	0.0281 (3)
H14	0.4094	0.1754	0.4712	0.034*
C15	0.37846 (6)	0.27962 (13)	0.40590 (5)	0.0264 (3)
H15	0.4095	0.2421	0.3886	0.032*
C16	0.33281 (6)	0.37423 (12)	0.38211 (5)	0.0217 (2)
H16	0.3333	0.3990	0.3486	0.026*
C17	0.16906 (6)	0.57084 (11)	0.39863 (4)	0.0164 (2)
C18	0.13473 (6)	0.69104 (11)	0.39796 (4)	0.0186 (2)
H18	0.1562	0.7692	0.3909	0.022*
C19	0.07050 (6)	0.69938 (12)	0.40727 (4)	0.0215 (2)
H19	0.0487	0.7820	0.4058	0.026*
C20	0.03822 (6)	0.58705 (13)	0.41870 (5)	0.0232 (2)
H20	−0.0052	0.5927	0.4257	0.028*
C21	0.07032 (6)	0.46643 (12)	0.41976 (5)	0.0211 (2)
H21	0.0488	0.3889	0.4275	0.025*
C22	0.13431 (6)	0.45933 (11)	0.40948 (4)	0.0183 (2)
H22	0.1551	0.3759	0.4098	0.022*
C23	0.21392 (6)	0.54690 (11)	0.31871 (4)	0.0181 (2)
C24	0.19493 (6)	0.66032 (12)	0.28925 (4)	0.0209 (2)
H24	0.2043	0.7439	0.3047	0.025*
C25	0.16291 (6)	0.65426 (14)	0.23831 (5)	0.0254 (3)
H25	0.1507	0.7329	0.2198	0.030*
C26	0.14892 (7)	0.53359 (14)	0.21466 (5)	0.0273 (3)
H26	0.1270	0.5290	0.1800	0.033*
C27	0.16730 (7)	0.41963 (14)	0.24223 (5)	0.0268 (3)
H27	0.1583	0.3365	0.2264	0.032*
C28	0.19901 (6)	0.42686 (12)	0.29327 (5)	0.0220 (2)
H28	0.2109	0.3477	0.3115	0.026*
B1	0.23971 (6)	0.55838 (12)	0.37996 (5)	0.0161 (2)
H4A	0.5221 (12)	0.451 (2)	0.1677 (6)	0.057 (7)*
H5A	0.6528 (8)	0.605 (2)	0.3724 (8)	0.053 (6)*
H6A	0.7091 (14)	0.514 (3)	0.2547 (9)	0.090 (9)*
H5B	0.5879 (10)	0.597 (2)	0.3788 (8)	0.059 (7)*
H4B	0.5158 (11)	0.3594 (16)	0.2028 (8)	0.059 (6)*
H7A	0.7775 (12)	0.625 (2)	0.3922 (10)	0.086 (9)*
H6B	0.7144 (13)	0.543 (3)	0.3054 (8)	0.082 (9)*
H7B	0.7749 (15)	0.496 (2)	0.3939 (12)	0.101 (11)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Na1	0.0223 (2)	0.0254 (3)	0.0240 (3)	0.00197 (19)	0.00423 (19)	0.00052 (19)
O1	0.0338 (7)	0.0136 (6)	0.0365 (7)	0.000	−0.0068 (6)	0.000
O2	0.0339 (7)	0.0137 (5)	0.0280 (6)	0.000	0.0063 (5)	0.000
O3	0.0331 (5)	0.0334 (5)	0.0162 (4)	0.0025 (4)	0.0080 (4)	−0.0001 (3)
O4	0.0377 (5)	0.0205 (4)	0.0220 (4)	0.0011 (4)	0.0075 (4)	0.0000 (3)
O5	0.0267 (5)	0.0407 (6)	0.0266 (5)	−0.0035 (4)	0.0046 (4)	0.0008 (4)
O6	0.0254 (5)	0.0644 (8)	0.0446 (7)	−0.0014 (5)	0.0124 (5)	−0.0088 (6)
O7	0.0276 (6)	0.0469 (7)	0.0502 (7)	0.0008 (5)	−0.0030 (5)	0.0040 (6)
N1	0.0220 (7)	0.0159 (6)	0.0225 (7)	0.000	−0.0004 (5)	0.000
N2	0.0217 (7)	0.0156 (6)	0.0211 (7)	0.000	0.0046 (5)	0.000
N3	0.0221 (5)	0.0196 (5)	0.0168 (4)	0.0010 (4)	0.0037 (4)	0.0005 (3)
C1	0.0214 (5)	0.0211 (6)	0.0193 (5)	−0.0001 (4)	−0.0009 (4)	0.0006 (4)
C2	0.0221 (5)	0.0205 (5)	0.0183 (5)	−0.0013 (4)	0.0009 (4)	−0.0007 (4)
C3	0.0206 (5)	0.0217 (5)	0.0203 (5)	−0.0036 (4)	0.0003 (4)	0.0004 (4)
C4	0.0180 (5)	0.0238 (6)	0.0212 (5)	−0.0020 (4)	0.0032 (4)	0.0021 (4)
C5	0.0155 (5)	0.0173 (5)	0.0158 (5)	0.0009 (4)	0.0012 (4)	0.0021 (4)
C6	0.0200 (5)	0.0217 (5)	0.0192 (5)	−0.0012 (4)	0.0037 (4)	−0.0014 (4)
C7	0.0254 (6)	0.0225 (6)	0.0216 (6)	−0.0020 (4)	0.0001 (4)	−0.0035 (4)
C8	0.0233 (6)	0.0222 (6)	0.0283 (6)	−0.0057 (5)	−0.0011 (5)	0.0019 (5)
C9	0.0207 (5)	0.0278 (6)	0.0256 (6)	−0.0041 (5)	0.0039 (4)	0.0069 (5)
C10	0.0205 (5)	0.0229 (6)	0.0167 (5)	−0.0013 (4)	0.0028 (4)	0.0026 (4)
C11	0.0165 (5)	0.0165 (5)	0.0193 (5)	−0.0002 (4)	0.0031 (4)	0.0009 (4)
C12	0.0192 (5)	0.0210 (5)	0.0209 (5)	0.0006 (4)	0.0052 (4)	0.0025 (4)
C13	0.0256 (6)	0.0237 (6)	0.0231 (6)	0.0010 (5)	0.0035 (5)	0.0066 (4)
C14	0.0271 (6)	0.0226 (6)	0.0328 (7)	0.0076 (5)	0.0030 (5)	0.0053 (5)
C15	0.0246 (6)	0.0253 (6)	0.0293 (6)	0.0074 (5)	0.0064 (5)	−0.0008 (5)
C16	0.0217 (5)	0.0219 (6)	0.0219 (5)	0.0028 (4)	0.0058 (4)	0.0005 (4)
C17	0.0165 (5)	0.0184 (5)	0.0139 (5)	0.0009 (4)	0.0025 (4)	−0.0006 (4)
C18	0.0193 (5)	0.0177 (5)	0.0179 (5)	0.0001 (4)	0.0021 (4)	−0.0011 (4)
C19	0.0202 (5)	0.0224 (6)	0.0210 (5)	0.0050 (4)	0.0028 (4)	−0.0024 (4)
C20	0.0158 (5)	0.0311 (6)	0.0231 (6)	0.0021 (4)	0.0050 (4)	0.0006 (5)
C21	0.0179 (5)	0.0240 (6)	0.0213 (5)	−0.0022 (4)	0.0037 (4)	0.0034 (4)
C22	0.0180 (5)	0.0188 (5)	0.0176 (5)	0.0002 (4)	0.0026 (4)	0.0008 (4)
C23	0.0178 (5)	0.0205 (5)	0.0168 (5)	−0.0001 (4)	0.0055 (4)	−0.0008 (4)
C24	0.0212 (5)	0.0228 (6)	0.0182 (5)	0.0005 (4)	0.0036 (4)	0.0001 (4)
C25	0.0235 (6)	0.0321 (7)	0.0198 (6)	0.0011 (5)	0.0032 (4)	0.0035 (5)
C26	0.0246 (6)	0.0402 (8)	0.0165 (5)	−0.0029 (5)	0.0032 (4)	−0.0028 (5)
C27	0.0280 (6)	0.0308 (7)	0.0218 (6)	−0.0050 (5)	0.0063 (5)	−0.0079 (5)
C28	0.0228 (6)	0.0238 (6)	0.0198 (5)	−0.0004 (4)	0.0054 (4)	−0.0023 (4)
B1	0.0162 (5)	0.0166 (5)	0.0152 (5)	0.0000 (4)	0.0033 (4)	−0.0004 (4)

Geometric parameters (Å, º) top

Na1—O6	2.2444 (13)	C9—C10	1.3954 (17)
Na1—O1	2.2857 (10)	C9—H9	0.9500
Na1—O5	2.3410 (12)	C10—H10	0.9500
Na1—O4	2.4059 (11)	C11—C16	1.4070 (16)
Na1—O4ⁱ	2.4371 (12)	C11—C12	1.4083 (16)
O1—N1	1.3031 (19)	C11—B1	1.6404 (17)
O1—Na1ⁱ	2.2857 (10)	C12—C13	1.3942 (17)
O2—N2	1.3035 (18)	C12—H12	0.9500
O3—N3	1.3040 (13)	C13—C14	1.3903 (19)
O4—Na1ⁱ	2.4371 (12)	C13—H13	0.9500
O4—H4A	0.862 (16)	C14—C15	1.3927 (19)
O4—H4B	0.854 (16)	C14—H14	0.9500
O5—H5A	0.863 (15)	C15—C16	1.3959 (17)
O5—H5B	0.844 (16)	C15—H15	0.9500
O6—H6A	0.844 (17)	C16—H16	0.9500
O6—H6B	0.880 (17)	C17—C22	1.4062 (16)
O7—H7A	0.861 (17)	C17—C18	1.4100 (16)
O7—H7B	0.855 (18)	C17—B1	1.6386 (17)
N1—C1ⁱ	1.3544 (14)	C18—C19	1.3932 (16)
N1—C1	1.3544 (14)	C18—H18	0.9500
N2—C2ⁱ	1.3583 (14)	C19—C20	1.3910 (18)
N2—C2	1.3584 (14)	C19—H19	0.9500
N3—C3	1.3552 (16)	C20—C21	1.3909 (18)
N3—C4	1.3570 (15)	C20—H20	0.9500
C1—C2	1.3661 (17)	C21—C22	1.3982 (16)
C1—H1	0.9500	C21—H21	0.9500
C2—H2	0.9500	C22—H22	0.9500
C3—C4ⁱⁱ	1.3673 (17)	C23—C28	1.4056 (17)
C3—H3	0.9500	C23—C24	1.4113 (16)
C4—C3ⁱⁱ	1.3672 (17)	C23—B1	1.6373 (17)
C4—H4	0.9500	C24—C25	1.3962 (16)
C5—C6	1.4020 (16)	C24—H24	0.9500
C5—C10	1.4073 (16)	C25—C26	1.3884 (19)
C5—B1	1.6381 (17)	C25—H25	0.9500
C6—C7	1.3953 (17)	C26—C27	1.389 (2)
C6—H6	0.9500	C26—H26	0.9500
C7—C8	1.3908 (19)	C27—C28	1.3978 (17)
C7—H7	0.9500	C27—H27	0.9500
C8—C9	1.3909 (19)	C28—H28	0.9500
C8—H8	0.9500

O6—Na1—O1	128.92 (5)	C9—C10—H10	118.8
O6—Na1—O5	86.41 (5)	C5—C10—H10	118.8
O1—Na1—O5	94.76 (4)	C16—C11—C12	115.36 (10)
O6—Na1—O4	104.32 (5)	C16—C11—B1	121.65 (10)
O1—Na1—O4	81.42 (3)	C12—C11—B1	122.49 (10)
O5—Na1—O4	168.66 (4)	C13—C12—C11	122.70 (11)
O6—Na1—O4ⁱ	150.29 (5)	C13—C12—H12	118.7
O1—Na1—O4ⁱ	80.75 (3)	C11—C12—H12	118.7
O5—Na1—O4ⁱ	89.72 (4)	C14—C13—C12	120.24 (12)
O4—Na1—O4ⁱ	79.15 (4)	C14—C13—H13	119.9
N1—O1—Na1ⁱ	136.26 (3)	C12—C13—H13	119.9
N1—O1—Na1	136.26 (3)	C13—C14—C15	118.88 (12)
Na1ⁱ—O1—Na1	87.49 (5)	C13—C14—H14	120.6
Na1—O4—Na1ⁱ	81.48 (4)	C15—C14—H14	120.6
Na1—O4—H4A	136.1 (15)	C14—C15—C16	120.17 (12)
Na1ⁱ—O4—H4A	115.0 (15)	C14—C15—H15	119.9
Na1—O4—H4B	109.9 (15)	C16—C15—H15	119.9
Na1ⁱ—O4—H4B	103.9 (15)	C15—C16—C11	122.66 (11)
H4A—O4—H4B	105 (2)	C15—C16—H16	118.7
Na1—O5—H5A	111.9 (15)	C11—C16—H16	118.7
Na1—O5—H5B	112.6 (16)	C22—C17—C18	115.62 (10)
H5A—O5—H5B	108 (2)	C22—C17—B1	121.57 (10)
Na1—O6—H6A	137 (2)	C18—C17—B1	122.22 (10)
Na1—O6—H6B	115.5 (19)	C19—C18—C17	122.44 (11)
H6A—O6—H6B	108 (3)	C19—C18—H18	118.8
H7A—O7—H7B	100 (3)	C17—C18—H18	118.8
O1—N1—C1ⁱ	120.20 (7)	C20—C19—C18	120.22 (11)
O1—N1—C1	120.20 (7)	C20—C19—H19	119.9
C1ⁱ—N1—C1	119.59 (15)	C18—C19—H19	119.9
O2—N2—C2ⁱ	120.38 (7)	C21—C20—C19	119.19 (11)
O2—N2—C2	120.38 (7)	C21—C20—H20	120.4
C2ⁱ—N2—C2	119.24 (14)	C19—C20—H20	120.4
O3—N3—C3	120.75 (10)	C20—C21—C22	119.93 (11)
O3—N3—C4	120.55 (10)	C20—C21—H21	120.0
C3—N3—C4	118.69 (10)	C22—C21—H21	120.0
N1—C1—C2	120.25 (11)	C21—C22—C17	122.59 (11)
N1—C1—H1	119.9	C21—C22—H22	118.7
C2—C1—H1	119.9	C17—C22—H22	118.7
N2—C2—C1	120.33 (11)	C28—C23—C24	115.57 (11)
N2—C2—H2	119.8	C28—C23—B1	123.30 (10)
C1—C2—H2	119.8	C24—C23—B1	120.36 (10)
N3—C3—C4ⁱⁱ	120.51 (11)	C25—C24—C23	122.44 (12)
N3—C3—H3	119.7	C25—C24—H24	118.8
C4ⁱⁱ—C3—H3	119.7	C23—C24—H24	118.8
N3—C4—C3ⁱⁱ	120.80 (11)	C26—C25—C24	120.14 (12)
N3—C4—H4	119.6	C26—C25—H25	119.9
C3ⁱⁱ—C4—H4	119.6	C24—C25—H25	119.9
C6—C5—C10	115.58 (10)	C25—C26—C27	119.20 (12)
C6—C5—B1	121.67 (10)	C25—C26—H26	120.4
C10—C5—B1	122.01 (10)	C27—C26—H26	120.4
C7—C6—C5	122.97 (11)	C26—C27—C28	120.17 (12)
C7—C6—H6	118.5	C26—C27—H27	119.9
C5—C6—H6	118.5	C28—C27—H27	119.9
C8—C7—C6	119.57 (12)	C27—C28—C23	122.48 (12)
C8—C7—H7	120.2	C27—C28—H28	118.8
C6—C7—H7	120.2	C23—C28—H28	118.8
C9—C8—C7	119.46 (11)	C23—B1—C5	112.40 (9)
C9—C8—H8	120.3	C23—B1—C17	102.54 (9)
C7—C8—H8	120.3	C5—B1—C17	113.00 (9)
C8—C9—C10	119.92 (12)	C23—B1—C11	113.87 (9)
C8—C9—H9	120.0	C5—B1—C11	102.49 (9)
C10—C9—H9	120.0	C17—B1—C11	112.96 (9)
C9—C10—C5	122.48 (11)

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

Hydrogen-bond geometry (Å, º) top

Cg1, Cg2, Cg3 and Cg4 are the centroids of the C5–C10, C11–C16, C17–C22 and C23–C28 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···O3	0.86 (2)	2.09 (2)	2.8855 (13)	153 (2)
O4—H4B···O2ⁱⁱⁱ	0.85 (2)	1.95 (2)	2.6948 (14)	144 (2)
O5—H5B···O3ⁱ	0.84 (2)	1.95 (2)	2.7655 (14)	163 (2)
O5—H5A···O7	0.86 (2)	2.00 (2)	2.8329 (16)	163 (2)
O6—H6B···O7	0.88 (2)	2.06 (2)	2.9055 (19)	160 (3)
C19—H19···O3^iv	0.95	2.55	3.4884 (16)	168
C2—H2···Cg3^v	0.95	2.40	3.2435 (14)	148
C3—H3···Cg1ⁱ	0.95	2.46	3.2788 (14)	144
O6—H6A···Cg4ⁱ	0.85 (3)	2.45 (3)	3.1713 (14)	144 (2)
C7—H7···Cg3^vi	0.95	2.66	3.5365 (14)	153
O7—H7A···Cg2^v	0.86 (2)	2.55 (2)	3.3871 (15)	165 (2)
O7—H7B···Cg1^vii	0.85 (3)	2.59 (2)	3.4337 (15)	171 (3)

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

Acknowledgements

The authors are thankful to Clarion University and Allegheny College for providing funding in support of this research. The diffractometer was funded by the NSF (grant No. 0087210), the Ohio Board of Regents (grant No. CAP-491) and by Youngstown State University. The authors would also like to acknowledge Matthias Zeller, Senior Scientist and Crystallographer at the STaRBURSTT CyberInstrumentation Consortium, for assistance with the structure analysis.

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