Crystal structure of bis­(μ-N-hy­droxy­picolin­amid­ato)bis­[bis­(N-hy­droxy­picolinamide)­sodium]

Safyanova, I.S.; Ohui, K.A.; Omelchenko, I.V.

doi:10.1107/S2056989016019095

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Volume 73| Part 1| January 2017| Pages 24-27

https://doi.org/10.1107/S2056989016019095

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Crystal structure of bis(μ-N-hydroxypicolinamidato)bis[bis(N-hydroxypicolinamide)sodium]

Inna S. Safyanova,^a Kateryna A. Ohui ^a ^* and Irina V. Omelchenko ^b

^aDepartment of Chemistry, National Taras Shevchenko University of Kyiv, Volodymyrska Street 64, 01601 Kiev, Ukraine, and ^bSSI "Institute for Single Crystals", National Academy of Sciences of Ukraine, Nauki ave. 60, Kharkiv, 61001, Ukraine
^*Correspondence e-mail: safyanova_inna@mail.ru

Edited by D.-J. Xu, Zhejiang University (Yuquan Campus), China (Received 23 November 2016; accepted 30 November 2016; online 1 January 2017)

The title compound, [Na₂(C₆H₅N₂O₂)₂(C₆H₆N₂O₂)₄], is a centrosymmetric coordination dimer based on the sodium(I) salt of N-hydroxypicolinamide. The molecule has an {Na₂O₆(μ-O)₂} core with two bridging carbonyl O atoms and two hydroxamate O atoms of two mono-deprotonated residues of N-hydroxypicolinamide, while two neutral N-hydroxypicolinamide molecules are coordinated in a monodentate manner to each sodium ion via the carbonyl O atoms [the Na—O distances range from 2.3044 (2) to 2.3716 (2) Å]. The pentacoordinated sodium ion exhibits a distorted trigonal–pyramidal coordination polyhedron. In the crystal, the coordination dimers are linked into chains along the c axis via N—H⋯O and N—H⋯N hydrogen bonds; the chains are linked into a two-dimensional framework parallel to (100) via weak C—H⋯O and π–π stacking interactions.

Keywords: crystal structure; hydroxamic acids; hydrogen bonds; π–π stacking.

CCDC reference: 1520114

1. Chemical context

Hydroxamic acids as a class of organic compounds originate from Lossen's invention (Lossen, 1869 ). The coordination ability of hydroxamic acids has led to their extensive use in coordination and supramolecular chemistry (Świątek-Kozłowska et al., 2000 ; Dobosz et al., 1999 ). In particular, over the past two decades they have often been used as frameworks of metallacrowns (Golenya et al., 2012a ; Safyanova et al., 2015 ; Stemmler et al., 1999 ; Jankolovits et al., 2013a ,b ) and as building blocks of coordination polymers (Gumienna-Kontecka et al., 2007 ; Golenya et al., 2014 ; Pavlishchuk et al., 2010 , 2011 ). They have also been studied intensively in biology and medicine due to their various biological activities, especially their metal-chelating ability and inhibition of a series of metalloenzymes (Codd, 2008 ; Griffith et al., 2005 ; Marmion et al., 2013 ).

N-Hydroxypicolinamide (or picoline-2-hydroxamic acid, H₂PicHA) has been used extensively for the synthesis of polynuclear complexes, especially various metallacrowns (Stemmler et al., 1999; Seda et al., 2007 ; Jankolovits et al., 2013a; Golenya et al., 2012a; Gumienna-Kontecka et al., 2013 ). A large number of polynuclear metal complexes based on this ligand has been investigated. The Cambridge Structural Database (Groom et al., 2016 ) contains data on the crystal structures of over 20 coordination compounds based on o-PicHA. The crystal and molecular structure of N-hydroxypicolinamide monohydrate was the subject of two recent independent investigations (Chaiyaveij et al., 2015 ; Safyanova et al., 2016 ).

In the course of the synthesis of hydroxamate metal complexes, especially metallacrowns, in some cases alkaline metal hydroxamates appear to be more preferable starting materials than the parent hydroxamic acids due to their better solubility in water. During our synthetic attempts using the sodium salt of N-hydroxypicolinamide, we noticed that the elementary analysis data differ noticeably from those expected for the monosodium salt or its hydrates, which might affect the reagent ratio in the synthesis of coordination compounds. In order to find out the reason for this deviation in the analytical data, we undertook a single crystal X-ray analysis of the sodium salt of N-hydroxypicolinamide. Herein we present the crystal and molecular structure of the title compound.

2. Structural commentary

The molecular structure of title compound is shown in Fig. 1. The structure determination revealed that the dinuclear hydroxamate acid salt was obtained, with the ratio of neutral and deprotonated N-hydroxypicolinamide being 2:1. A centrosymmetric dimeric structure is formed by non-planar subunits interconnected through the bridging carbonyl O atoms belonging to the deprotonated residues of N-hydroxypicolinamide [the Na—μ-O distances are Na1—O5 = 2.3044 (14) Å and Na1—O5ⁱ = 2.3558 (14) Å; symmetry code: (i) 1 − x, −y, 1 − z] . Coordination of the μ-O carbonyl and hydroxamate O atoms of the same anion lead to the formation of five-membered chelate rings [Na1—O6ⁱ = 2.3716 (14) Å and O5ⁱ—Na—O6ⁱ = 70.26 (5)°]. Two neutral N-hydroxypicolinamide molecules coordinate in a monodentate manner to each sodium ion via the carbonyl O atoms [Na1—O1 = 2.3300 (16) Å and Na1—O3 = 2.3225 (15) Å]. As a result, each pentacoordinated sodium ion reveals a distorted trigonal–pyramidal coordination polyhedron (τ₅ = 0.50; Addison et al., 1984 ) with O1, O3, and O5ⁱ atoms forming the equatorial plane. The distance between the equatorial plane and the Na atom is 0.408 (1) Å and the deviation of the O—Na—O angles from ideal values are up to 23.47 (5)°. The Na—O bond lengths are in the range 2.3044 (14)—2.3716 (14) Å, which is common for pentacoordinated sodium cations (Groom et al., 2016; Golenya et al., 2012b ; Malinkin et al., 2012a ,b ). The central Na₂(μ-O)₂ core is virtually planar and approaches a square [the O—Na—O angles are 86.43 (5) and 93.57 (5)°].

Figure 1
The centrosymmetric molecular unit of the title compound, with displacement ellipsoids drawn at the 50% probability level. H atoms are shown as spheres of undefined radius.

The deprotonated hydroxamate atom O6 acts as an acceptor of two hydrogen bonds (Table 1) in which the O—H groups of the protonated hydroxamic groups of two neutral molecules of N-hydroxypicolinamide act as donors [O2—H2⋯O6(1 − x, −y, 1 − z) = 1.65 (2) Å and 169 (2)°; O4—H4⋯O6(1 − x, −y, 1 − z) = 1.66 (3) Å and 177 (3)°]. The nearly coplanar pyridine rings of two neutral molecules of N-hydroxypicolinamide coordinating to the same sodium ion reveal intramolecular stacking interactions in unusual `head-to-head' manner [angle between planes = 10.00 (7)°, intercentroid distance = 3.801 (1) Å, mean interplanar separation = 3.760 (1) Å, mean plane shift = 0.508 (4) Å].

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N2	0.80 (3)	2.35 (3)	2.688 (3)	106 (2)
N3—H3⋯N4	0.86 (3)	2.30 (3)	2.681 (3)	107 (2)
N5—H5⋯N6	0.84 (2)	2.25 (2)	2.670 (3)	111.1 (17)
O2—H2⋯O6ⁱ	0.91 (2)	1.65 (2)	2.549 (2)	169 (2)
O4—H4⋯O6ⁱ	0.91 (3)	1.66 (3)	2.5744 (19)	177 (3)
N1—H1⋯N6ⁱⁱ	0.80 (2)	2.55 (3)	3.224 (2)	143 (2)
N5—H5⋯O2ⁱⁱⁱ	0.84 (2)	2.35 (2)	3.058 (2)	142.6 (19)
C5—H5A⋯O4^iv	0.93	2.61	3.341 (3)	136
C17—H17⋯N2ⁱⁱⁱ	0.93	2.60	3.330 (3)	136
Symmetry codes: (i) -x+1, -y, -z+1; (ii) x, y, z+1; (iii) x, y, z-1; (iv) -x+1, -y+1, -z+2.

The deprotonated N-hydroxypicolinamide residue adopts a strongly flattened conformation with a dihedral angle of only 0.6 (2)° between the hydroxamic group and the pyridine ring. At the same time, the corresponding dihedral angles in both neutral N-hydroxypicolinamide molecules are noticeably greater [17.5 (2) and 8.9 (2)°], indicating a deviation of the hydroxamic group from the plane of pyridine rings. The configuration about the hydroxamic C—N bond is Z and that about the C—C bond between the pyridine and hydroxamic groups is E for both the neutral and deprotonated hydroxamates. Intramolecular N—H⋯N attractive contacts between the hydroxamate group and the nitrogen atom of pyridine ring [2.25 (2)–2.35 (3) Å] are present in both the neutral and deprotonated N-hydroxypicolinamide molecules (Table 1).

The bond lengths and angles within both the neutral and deprotonated hydroxamic groups are within normal ranges. The C—N and C—C bond lengths in the pyridine moiety are typical for 2-substituted pyridine derivatives (Moroz et al., 2012 ; Strotmeyer et al., 2003 ; Fritsky et al., 2004 ).

3. Supramolecular features

In the crystal (Fig. 2), the dimeric molecules are linked into chains along the c axis via two pairs of classical intermolecular N5—H5⋯O2(x, y, z − 1) and N1—H1⋯N6(x, y, z − 1) hydrogen bonds supported by a pair of weak non-classical C17—H17⋯N2(x, y, z − 1) hydrogen bonds (Table 1). The chains are linked into a two-dimensional framework parallel to (100) by weaker interactions, namely a C5—H5A⋯O4(−x + 1, −y + 1, −z + 2) hydrogen bond and π–π stacking between the N4/C7–C11 pyridine ring and the deprotonated O5/C18/N5/O6 hydroxamic group [angle between planes = 4.89 (7)°, intercentroid distance = 3.766 (1) Å, mean interplanar separation = 3.385 (2) Å, mean plane shift = 1.644 (4) Å]. Intermolecular π–π stacking between the same deprotonated hydroxamic group and the N2/C1–C5 pyridine ring [angle between planes = 10.78 (8)°, intercentroid distance = 3.823 (1) Å, mean interplanar separation = 3.589 (2) Å, mean plane shift = 1.319 (4) Å] links the frameworks into a three-dimensional structure.

Figure 2
A packing diagram of the title compound. Hydrogen bonds are indicated by dashed lines. [The outline of the unit cell and axes should be added]

4. Database survey

A search of the Cambridge Structural Database (Groom et al., 2016) for metal complexes based on N-hydroxypicolinamide revealed the crystal structures of over 20 compounds, mostly belonging to the metallacrown (MC) family. In particular, heterometallic copper(II) 15-metallacrown-5 complexes with encapsulated Gd^III and Eu^III ions (Stemmler et al., 1999), Ca²⁺, Pr³⁺ and Nd³⁺ ions (Safyanova et al., 2015), UO₂²⁺ (Stemmler et al., 1996 ), and Pb²⁺ and Hg²⁺ ions (Seda et al., 2007; Saf'yanova et al., 2014 ) have been structurally characterized. Nickel(II) 15-metallacrown-5 complexes with Eu³⁺ (Jankolovits et al., 2013b), Sm³⁺ and Pb²⁺ ions (Seda et al., 2006a ) in the central cavity have also been synthesized and structurally characterized. Homo-[12-MC_Zn(II),picHA-4](OTf)_1.25(OH)_0.75 (Jankolovits et al., 2013a) and heterometallic zinc(II) 12-metallacrown-4 complexes including sandwich compounds Dy^III[12-MC_Zn(II),picHA-4]₂(OH)₃(py)₂ (Jankolovits et al., 2014 ) and Tb^III[12-MC_Zn(II),picHA-4]₂·[24 MC_Zn(II),picHA-8]·(pyridine)₈·(triflate)₃ (Jankolovits et al., 2011 ) have also been reported. Three structures of collapsed copper(II) metallacrowns have been reported (Golenya et al., 2012a) as well as a trinuclear mixed-ligand copper(II) complex with pyridine (Seda et al., 2006b ) and 2,2′-dipyridine (Gumienna-Kontecka et al., 2013), and mono- and binuclear complexes with platinum(II) (Griffith et al., 2005). In addition, a tetranuclear Zn₄(picHA)₂(OAc)₄(DMF)₂ collapsed metallacrown complex has been structurally characterized (Jankolovits et al., 2013a).

5. Synthesis and crystallization

The title compound was obtained by the reaction of N-hydroxypicolinamide (0.156 g, 1 mmol, dissolved in 5 ml of water) with sodium hydrogen carbonate (1 M aqueous solution, 1 ml). Colorless crystals suitable for X-ray diffraction were obtained from the resulting aqueous solution by slow evaporation at ambient temperature within 48 h (yield 78%).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All hydrogen atoms were found in the difference Fourier maps; H atoms of pyridine rings were constrained to ride on their parent atoms with C—H = 0.93 Å and U_iso = 1.2U_eq(C), and H atoms of the N—H and O—H groups were refined isotropically.

Table 2
Experimental details

Crystal data
Chemical formula	[Na₂(C₆H₅N₂O₂)₂(C₆H₆N₂O₂)₄]
M_r	872.73
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	298
a, b, c (Å)	9.7997 (7), 10.0959 (7), 11.0401 (8)
α, β, γ (°)	96.618 (6), 102.741 (6), 113.902 (7)
V (Å³)	948.02 (13)
Z	1
Radiation type	Mo Kα
μ (mm⁻¹)	0.14
Crystal size (mm)	0.3 × 0.3 × 0.3

Data collection
Diffractometer	Agilent Xcalibur Sapphire3
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2013 )
T_min, T_max	0.965, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	12244, 5514, 3066
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.064, 0.144, 0.96
No. of reflections	5521
No. of parameters	300
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.23
Computer programs: CrysAlis PRO (Agilent, 2013), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 1520114

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989016019095/xu5895sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989016019095/xu5895Isup2.hkl

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Agilent, 2013); cell refinement: CrysAlis PRO (Agilent, 2013); data reduction: CrysAlis PRO (Agilent, 2013); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Bis(µ-N-hydroxypicolinamidato)bis[bis(N-hydroxypicolinamide)sodium] top

Crystal data top

[Na₂(C₆H₅N₂O₂)₂(C₆H₆N₂O₂)₄]	Z = 1
M_r = 872.73	F(000) = 452
Triclinic, P1	D_x = 1.529 Mg m⁻³
a = 9.7997 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.0959 (7) Å	Cell parameters from 2896 reflections
c = 11.0401 (8) Å	θ = 3.2–31.6°
α = 96.618 (6)°	µ = 0.14 mm⁻¹
β = 102.741 (6)°	T = 298 K
γ = 113.902 (7)°	Block, clear colourless
V = 948.02 (13) Å³	0.3 × 0.3 × 0.3 mm

Data collection top

Agilent Xcalibur Sapphire3 diffractometer	5514 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3066 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
Detector resolution: 16.1827 pixels mm^-1	θ_max = 30.0°, θ_min = 3.0°
ω scans	h = −13→13
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	k = −14→14
T_min = 0.965, T_max = 1.000	l = −15→15
12244 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.064	w = 1/[σ²(F_o²) + (0.0618P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.144	(Δ/σ)_max < 0.001
S = 0.96	Δρ_max = 0.23 e Å⁻³
5521 reflections	Δρ_min = −0.23 e Å⁻³
300 parameters

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.

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

	x	y	z	U_iso*/U_eq
Na1	0.46101 (9)	0.10567 (8)	0.60562 (6)	0.0406 (2)
O1	0.23043 (17)	0.04309 (17)	0.66132 (12)	0.0517 (4)
O2	0.33418 (18)	0.01016 (16)	0.90258 (13)	0.0445 (4)
H2	0.426 (3)	0.053 (3)	0.883 (2)	0.066 (8)*
O3	0.56164 (19)	0.36282 (15)	0.66630 (13)	0.0555 (4)
O4	0.74368 (18)	0.39266 (18)	0.90321 (14)	0.0516 (4)
H4	0.681 (3)	0.293 (3)	0.876 (3)	0.107 (11)*
O5	0.39508 (16)	0.03347 (14)	0.38677 (12)	0.0413 (3)
O6	0.42798 (15)	−0.11024 (13)	0.17918 (12)	0.0374 (3)
N1	0.2660 (2)	0.10347 (19)	0.87255 (16)	0.0397 (4)
H1	0.250 (3)	0.145 (3)	0.930 (2)	0.075 (9)*
N2	0.1263 (2)	0.28298 (18)	0.84096 (15)	0.0445 (4)
N3	0.6408 (2)	0.45461 (19)	0.87873 (17)	0.0428 (4)
H3	0.643 (3)	0.517 (3)	0.940 (2)	0.068 (8)*
N4	0.4699 (2)	0.60614 (18)	0.85596 (16)	0.0454 (4)
N5	0.34178 (18)	−0.03212 (17)	0.17342 (15)	0.0325 (4)
H5	0.301 (2)	−0.018 (2)	0.104 (2)	0.049 (6)*
N6	0.16908 (19)	0.11506 (18)	0.13287 (14)	0.0391 (4)
C1	0.1203 (2)	0.19678 (19)	0.73700 (17)	0.0327 (4)
C2	0.0281 (3)	0.1793 (3)	0.61794 (19)	0.0515 (6)
H2A	0.0291	0.1203	0.5472	0.062*
C3	−0.0661 (3)	0.2507 (3)	0.6045 (2)	0.0596 (6)
H3A	−0.1316	0.2385	0.5248	0.072*
C4	−0.0623 (2)	0.3393 (2)	0.7094 (2)	0.0483 (5)
H4A	−0.1247	0.3889	0.7029	0.058*
C5	0.0357 (3)	0.3532 (2)	0.8243 (2)	0.0522 (6)
H5A	0.0399	0.4154	0.8954	0.063*
C6	0.2119 (2)	0.1080 (2)	0.75329 (17)	0.0337 (4)
C7	0.4699 (2)	0.52978 (19)	0.74923 (18)	0.0358 (4)
C8	0.3960 (3)	0.5331 (3)	0.6301 (2)	0.0583 (6)
H8	0.3977	0.4771	0.5579	0.070*
C9	0.3190 (3)	0.6209 (3)	0.6188 (2)	0.0679 (7)
H9	0.2696	0.6265	0.5387	0.082*
C10	0.3159 (3)	0.6994 (2)	0.7263 (2)	0.0515 (6)
H10	0.2635	0.7584	0.7214	0.062*
C11	0.3925 (3)	0.6887 (2)	0.8421 (2)	0.0502 (6)
H11	0.3905	0.7424	0.9155	0.060*
C12	0.5611 (2)	0.44067 (19)	0.76097 (18)	0.0371 (4)
C13	0.2335 (2)	0.11871 (18)	0.25376 (16)	0.0301 (4)
C14	0.2116 (3)	0.1935 (3)	0.3547 (2)	0.0540 (6)
H14	0.2580	0.1948	0.4382	0.065*
C15	0.1199 (3)	0.2665 (3)	0.3297 (2)	0.0595 (6)
H15	0.1045	0.3184	0.3964	0.071*
C16	0.0524 (2)	0.2621 (2)	0.2072 (2)	0.0431 (5)
H16	−0.0103	0.3101	0.1881	0.052*
C17	0.0792 (2)	0.1845 (2)	0.11211 (19)	0.0465 (5)
H17	0.0316	0.1803	0.0280	0.056*
C18	0.3310 (2)	0.03654 (18)	0.27692 (16)	0.0299 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Na1	0.0567 (5)	0.0543 (5)	0.0255 (4)	0.0397 (4)	0.0115 (3)	0.0068 (3)
O1	0.0587 (9)	0.0844 (10)	0.0293 (8)	0.0518 (9)	0.0114 (7)	0.0031 (7)
O2	0.0571 (10)	0.0604 (9)	0.0423 (8)	0.0450 (8)	0.0217 (7)	0.0219 (7)
O3	0.0912 (12)	0.0558 (9)	0.0339 (8)	0.0507 (9)	0.0141 (8)	0.0025 (7)
O4	0.0543 (9)	0.0553 (9)	0.0494 (9)	0.0368 (8)	0.0044 (7)	0.0007 (7)
O5	0.0575 (9)	0.0562 (8)	0.0241 (7)	0.0395 (7)	0.0098 (6)	0.0101 (6)
O6	0.0486 (8)	0.0475 (7)	0.0333 (7)	0.0374 (7)	0.0128 (6)	0.0101 (6)
N1	0.0550 (11)	0.0544 (10)	0.0294 (9)	0.0410 (9)	0.0154 (8)	0.0121 (8)
N2	0.0551 (11)	0.0550 (10)	0.0325 (9)	0.0366 (9)	0.0089 (8)	0.0040 (8)
N3	0.0558 (11)	0.0469 (10)	0.0349 (10)	0.0347 (9)	0.0103 (8)	0.0035 (8)
N4	0.0634 (12)	0.0487 (9)	0.0362 (10)	0.0343 (9)	0.0198 (8)	0.0082 (8)
N5	0.0432 (9)	0.0423 (9)	0.0234 (8)	0.0307 (8)	0.0079 (7)	0.0079 (7)
N6	0.0462 (10)	0.0531 (10)	0.0313 (9)	0.0343 (8)	0.0124 (7)	0.0101 (7)
C1	0.0354 (10)	0.0400 (10)	0.0292 (10)	0.0206 (8)	0.0130 (8)	0.0101 (8)
C2	0.0690 (15)	0.0727 (14)	0.0288 (11)	0.0515 (13)	0.0081 (10)	0.0065 (10)
C3	0.0722 (16)	0.0826 (16)	0.0386 (13)	0.0562 (14)	0.0033 (11)	0.0097 (11)
C4	0.0554 (13)	0.0542 (12)	0.0515 (14)	0.0399 (11)	0.0139 (11)	0.0153 (10)
C5	0.0673 (15)	0.0583 (13)	0.0402 (12)	0.0424 (12)	0.0105 (11)	−0.0001 (10)
C6	0.0342 (10)	0.0436 (10)	0.0273 (9)	0.0216 (9)	0.0092 (8)	0.0061 (8)
C7	0.0418 (11)	0.0306 (9)	0.0348 (10)	0.0162 (8)	0.0118 (8)	0.0049 (8)
C8	0.0881 (18)	0.0653 (14)	0.0330 (12)	0.0537 (14)	0.0065 (11)	0.0004 (10)
C9	0.0954 (19)	0.0793 (16)	0.0420 (14)	0.0639 (16)	−0.0008 (13)	0.0063 (12)
C10	0.0547 (14)	0.0495 (12)	0.0598 (15)	0.0335 (11)	0.0152 (11)	0.0112 (11)
C11	0.0666 (15)	0.0522 (12)	0.0471 (13)	0.0377 (12)	0.0257 (11)	0.0072 (10)
C12	0.0485 (12)	0.0324 (9)	0.0336 (11)	0.0202 (9)	0.0144 (9)	0.0065 (8)
C13	0.0333 (10)	0.0323 (9)	0.0279 (9)	0.0171 (8)	0.0104 (7)	0.0067 (7)
C14	0.0792 (16)	0.0755 (15)	0.0311 (11)	0.0598 (14)	0.0132 (10)	0.0079 (10)
C15	0.0878 (18)	0.0793 (16)	0.0399 (13)	0.0650 (15)	0.0215 (12)	0.0066 (11)
C16	0.0480 (12)	0.0487 (11)	0.0483 (13)	0.0333 (10)	0.0191 (10)	0.0143 (10)
C17	0.0543 (13)	0.0663 (13)	0.0350 (11)	0.0420 (11)	0.0115 (10)	0.0161 (10)
C18	0.0342 (10)	0.0327 (9)	0.0270 (9)	0.0183 (8)	0.0101 (7)	0.0063 (7)

Geometric parameters (Å, º) top

Na1—O5	2.3044 (14)	C1—C2	1.367 (3)
Na1—O3	2.3225 (15)	C1—C6	1.503 (2)
Na1—O1	2.3300 (16)	C2—C3	1.377 (3)
Na1—O5ⁱ	2.3558 (14)	C2—H2A	0.9300
Na1—O6ⁱ	2.3716 (14)	C3—C4	1.363 (3)
Na1—Na1ⁱ	3.3964 (13)	C3—H3A	0.9300
O1—C6	1.232 (2)	C4—C5	1.365 (3)
O2—N1	1.388 (2)	C4—H4A	0.9300
O2—H2	0.91 (2)	C5—H5A	0.9300
O3—C12	1.235 (2)	C7—C8	1.366 (3)
O4—N3	1.383 (2)	C7—C12	1.501 (3)
O4—H4	0.91 (3)	C8—C9	1.378 (3)
O5—C18	1.247 (2)	C8—H8	0.9300
O5—Na1ⁱ	2.3558 (14)	C9—C10	1.362 (3)
O6—N5	1.3666 (18)	C9—H9	0.9300
O6—Na1ⁱ	2.3716 (14)	C10—C11	1.372 (3)
N1—C6	1.320 (2)	C10—H10	0.9300
N1—H1	0.80 (2)	C11—H11	0.9300
N2—C1	1.333 (2)	C13—C14	1.379 (3)
N2—C5	1.339 (2)	C13—C18	1.500 (2)
N3—C12	1.319 (3)	C14—C15	1.379 (3)
N3—H3	0.86 (2)	C14—H14	0.9300
N4—C7	1.332 (2)	C15—C16	1.355 (3)
N4—C11	1.336 (2)	C15—H15	0.9300
N5—C18	1.314 (2)	C16—C17	1.372 (3)
N5—H5	0.84 (2)	C16—H16	0.9300
N6—C17	1.330 (2)	C17—H17	0.9300
N6—C13	1.334 (2)

O5—Na1—O3	109.39 (6)	N2—C5—C4	124.16 (19)
O5—Na1—O1	107.77 (5)	N2—C5—H5A	117.9
O3—Na1—O1	98.10 (6)	C4—C5—H5A	117.9
O5—Na1—O5ⁱ	86.43 (5)	O1—C6—N1	123.81 (17)
O3—Na1—O5ⁱ	126.64 (6)	O1—C6—C1	121.78 (17)
O1—Na1—O5ⁱ	125.87 (6)	N1—C6—C1	114.39 (16)
O5—Na1—O6ⁱ	156.53 (5)	N4—C7—C8	123.26 (18)
O3—Na1—O6ⁱ	87.61 (5)	N4—C7—C12	118.11 (17)
O1—Na1—O6ⁱ	84.80 (5)	C8—C7—C12	118.58 (17)
O5ⁱ—Na1—O6ⁱ	70.26 (5)	C7—C8—C9	118.8 (2)
C6—O1—Na1	127.13 (13)	C7—C8—H8	120.6
N1—O2—H2	102.4 (15)	C9—C8—H8	120.6
C12—O3—Na1	129.55 (13)	C10—C9—C8	119.3 (2)
N3—O4—H4	103.9 (19)	C10—C9—H9	120.4
C18—O5—Na1	151.93 (12)	C8—C9—H9	120.4
C18—O5—Na1ⁱ	114.42 (11)	C9—C10—C11	118.0 (2)
Na1—O5—Na1ⁱ	93.57 (5)	C9—C10—H10	121.0
N5—O6—Na1ⁱ	110.28 (9)	C11—C10—H10	121.0
C6—N1—O2	121.64 (15)	N4—C11—C10	124.06 (19)
C6—N1—H1	121.1 (19)	N4—C11—H11	118.0
O2—N1—H1	116.7 (19)	C10—C11—H11	118.0
C1—N2—C5	116.66 (17)	O3—C12—N3	123.70 (18)
C12—N3—O4	121.18 (16)	O3—C12—C7	121.61 (18)
C12—N3—H3	119.5 (17)	N3—C12—C7	114.69 (16)
O4—N3—H3	118.2 (17)	N6—C13—C14	122.09 (17)
C7—N4—C11	116.62 (18)	N6—C13—C18	117.42 (15)
C18—N5—O6	121.82 (15)	C14—C13—C18	120.49 (17)
C18—N5—H5	116.6 (14)	C13—C14—C15	118.87 (19)
O6—N5—H5	121.3 (14)	C13—C14—H14	120.6
C17—N6—C13	117.46 (16)	C15—C14—H14	120.6
N2—C1—C2	123.00 (17)	C16—C15—C14	119.55 (19)
N2—C1—C6	118.12 (16)	C16—C15—H15	120.2
C2—C1—C6	118.77 (16)	C14—C15—H15	120.2
C1—C2—C3	118.83 (19)	C15—C16—C17	118.02 (18)
C1—C2—H2A	120.6	C15—C16—H16	121.0
C3—C2—H2A	120.6	C17—C16—H16	121.0
C4—C3—C2	119.3 (2)	N6—C17—C16	124.00 (19)
C4—C3—H3A	120.3	N6—C17—H17	118.0
C2—C3—H3A	120.3	C16—C17—H17	118.0
C3—C4—C5	117.99 (19)	O5—C18—N5	123.20 (16)
C3—C4—H4A	121.0	O5—C18—C13	121.78 (15)
C5—C4—H4A	121.0	N5—C18—C13	115.02 (15)

Na1ⁱ—O6—N5—C18	1.8 (2)	Na1—O3—C12—C7	−113.54 (18)
C5—N2—C1—C2	0.4 (3)	O4—N3—C12—O3	6.3 (3)
C5—N2—C1—C6	−175.88 (18)	O4—N3—C12—C7	−172.72 (16)
N2—C1—C2—C3	−1.8 (3)	N4—C7—C12—O3	177.27 (19)
C6—C1—C2—C3	174.5 (2)	C8—C7—C12—O3	−5.1 (3)
C1—C2—C3—C4	1.6 (4)	N4—C7—C12—N3	−3.7 (3)
C2—C3—C4—C5	−0.1 (4)	C8—C7—C12—N3	173.90 (19)
C1—N2—C5—C4	1.2 (3)	C17—N6—C13—C14	−1.3 (3)
C3—C4—C5—N2	−1.4 (4)	C17—N6—C13—C18	178.22 (17)
Na1—O1—C6—N1	−72.4 (2)	N6—C13—C14—C15	0.2 (3)
Na1—O1—C6—C1	109.31 (18)	C18—C13—C14—C15	−179.3 (2)
O2—N1—C6—O1	−7.4 (3)	C13—C14—C15—C16	0.6 (4)
O2—N1—C6—C1	170.99 (16)	C14—C15—C16—C17	−0.3 (4)
N2—C1—C6—O1	−169.34 (18)	C13—N6—C17—C16	1.7 (3)
C2—C1—C6—O1	14.2 (3)	C15—C16—C17—N6	−0.9 (3)
N2—C1—C6—N1	12.2 (3)	Na1—O5—C18—N5	175.36 (18)
C2—C1—C6—N1	−164.23 (19)	Na1ⁱ—O5—C18—N5	0.2 (2)
C11—N4—C7—C8	0.0 (3)	Na1—O5—C18—C13	−5.3 (4)
C11—N4—C7—C12	177.53 (17)	Na1ⁱ—O5—C18—C13	179.48 (12)
N4—C7—C8—C9	0.8 (4)	O6—N5—C18—O5	−1.4 (3)
C12—C7—C8—C9	−176.6 (2)	O6—N5—C18—C13	179.24 (14)
C7—C8—C9—C10	−1.3 (4)	N6—C13—C18—O5	−179.72 (17)
C8—C9—C10—C11	0.9 (4)	C14—C13—C18—O5	−0.2 (3)
C7—N4—C11—C10	−0.5 (3)	N6—C13—C18—N5	−0.4 (2)
C9—C10—C11—N4	0.0 (4)	C14—C13—C18—N5	179.15 (19)
Na1—O3—C12—N3	67.5 (3)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N2	0.80 (3)	2.35 (3)	2.688 (3)	106 (2)
N3—H3···N4	0.86 (3)	2.30 (3)	2.681 (3)	107 (2)
N5—H5···N6	0.84 (2)	2.25 (2)	2.670 (3)	111.1 (17)
O2—H2···O6ⁱ	0.91 (2)	1.65 (2)	2.549 (2)	169 (2)
O4—H4···O6ⁱ	0.91 (3)	1.66 (3)	2.5744 (19)	177 (3)
N1—H1···N6ⁱⁱ	0.80 (2)	2.55 (3)	3.224 (2)	143 (2)
N5—H5···O2ⁱⁱⁱ	0.84 (2)	2.35 (2)	3.058 (2)	142.6 (19)
C5—H5A···O4^iv	0.93	2.61	3.341 (3)	136
C17—H17···N2ⁱⁱⁱ	0.93	2.60	3.330 (3)	136

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

Acknowledgements

Financial support from the European Community's Seventh Framework Program (FP7/2007–2013) under grant agreement PIRSES-GA-2013–611488 is gratefully acknowledged. KAO acknowledges for the DAAD fellowship (Leonhard-Euler-Program).

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