A novel zinc(II) complex with the ligand 2,2′,2′′-(1,4,7-triazanonane-1,4,7-triyl)triacetate (NOTA)

Pereira-García, I.; Macías, A.; Bastida, R.; Valencia, L.

doi:10.1107/S1600536808041895

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 1| January 2009| Pages m84-m85

doi:10.1107/S1600536808041895

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A novel zinc(II) complex with the ligand 2,2′,2′′-(1,4,7-triazanonane-1,4,7-triyl)triacetate (NOTA)

Iria Pereira-García,^a Alejandro Macías,^a ^* Rufina Bastida ^a and Laura Valencia ^a

^aDepartamento de Química Inorgánica, Facultade de Química, Avd. das Ciencias s/n, Universidade de Santiago de Compostela, 15706-Santiago de Compostela, A Coruña, Galicia, Spain
^*Correspondence e-mail: alejandroalberto.macias@usc.es

(Received 20 October 2008; accepted 9 December 2008; online 17 December 2008)

The zinc(II) complex with NOTA [2,2′,2′′-(1,4,7-triazanonane-1,4,7-triyl)triacetate] has previously been synthesized and studied in solution, but was not isolated. The corresponding title Zn^II complex pentasodium(I) bis{[2,2′,2′′-(1,4,7-triazanonane-1,4,7-triyl)triacetato]zinc(II)} tris(perchlorate) methanol solvate, Na₅[Zn(C₁₂H₁₈N₃O₆)]₂(ClO₄)₃·CH₃OH, was crystallized as a sodium perchlorate double salt in methanol solution. The asymmetric unit contains two independent [Zn(NOTA)]⁻ complex anion entities, five sodium cations, three perchlorate anions and a methanol solvent molecule. The two Zn^II cations exhibit a distorted trigonal-prismatic N₃O₃ coordination with a bifacial arrangement of the donor atoms. Neither the methanol solvent molecule nor the perchlorate anions appear to be coordinated to the Zn centres. The crystal structure shows a layer arrangement parallel to (001) generated by interactions between the [Zn(NOTA)]⁻ units, the Na⁺ cations, two ClO₄⁻ units and the methanole molecule, leading to an overall layer composition of [Na₅[Zn(C₁₂H₁₈N₃O₆)]₂(ClO₄)₂^.CH₃OH]⁺. The third ClO₄ anion is isolated and situated between the layers without any significant interactions.

Related literature

Details on the synthesis of NOTA are given by Desreux (1980 ). For NOTA complexes of Al, Cr, Fe, Co, Ni, Cu, Ga and In characterized by X-ray diffraction studies, see: Boeyens & Van der Merwe (1997 ); Bossek et al. (1995 ); Clarke & Martell (1991 ); Craig et al. (1989 ); Jyo et al. (1990 ); Van der Merwe et al. (1983 , 1985 ); Moore et al. (1990 ); Wieghardt et al. (1982 ). For general background, see: Geraldes et al. (1985 ).

Experimental

Crystal data

Na₅[Zn(C₁₂H₁₈N₃O₆)]₂(ClO₄)₃·CH₄O
M_r = 1176.67
Orthorhombic, P n a 2₁
a = 16.8879 (5) Å
b = 9.4723 (3) Å
c = 26.4552 (9) Å
V = 4232.0 (2) Å³
Z = 4
Mo Kα radiation
μ = 1.47 mm⁻¹
T = 100 (2) K
0.22 × 0.10 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.738, T_max = 0.867
31309 measured reflections
9954 independent reflections
8605 reflections with I > 2σ(I)
R_int = 0.036

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.084
S = 1.07
9954 reflections
601 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.56 e Å⁻³
Δρ_min = −0.58 e Å⁻³
Absolute structure: Flack (1983 ), 4585 Friedel pairs
Flack parameter: 0.383 (7)

Table 1
Selected bond lengths (Å)

Zn1—O5	2.027 (3)
Zn1—O1	2.062 (2)
Zn1—O3	2.066 (2)
Zn1—N2	2.160 (3)
Zn1—N3	2.172 (3)
Zn1—N1	2.189 (3)
Zn2—O23	2.047 (3)
Zn2—O21	2.057 (3)
Zn2—O25	2.072 (3)
Zn2—N22	2.198 (3)
Zn2—N21	2.201 (3)
Zn2—N23	2.201 (3)

Data collection: APEX2 (Bruker, 2005 ); cell refinement: APEX2; data reduction: SHELXTL (Sheldrick, 2008 ); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808041895/wm2202sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808041895/wm2202Isup2.hkl

checkCIF report

Comment top

NOTA (1,4,7-triazacyclononane-N, N', N''-triacetate) has a well-known preference for small metal ions, and many metal NOTA complexes (M = Al, Cr, Fe, Co, Ni, Cu, Ga and In) have been structurally characterized: (Boeyens & Van der Merwe, 1997; Bossek et al., 1995; Clarke & Martell, 1991; Craig et al., 1989; Jyo et al., 1990; Van der Merwe et al., 1983, 1985; Moore et al., 1990; Wieghardt et al., 1982).

Our starting objective was the synthesis of NOTA (1,4,7-triazacyclononane-N,N',N''-triacetate) complexes in aqueous solutions and its isolation as salts of the type [X][M(NOTA)], where X⁺ is a monovalent cation and M is Zn^II or Cd(II). We also developed a species distribution diagram for NOTA complexes in aqueous solution based on the experimental data obtained by Geraldes et al. (1985). From these experiments we concluded that the anionic salts [Zn(NOTA)]^- and [Cd(NOTA)]^-, due to their extreme solubility in aqueous solution, do not precipitate as neither sodium nor the alkylammonium salts. These difficulties for isolating the complexes led us to synthesize the Zn^II and Cd(II) NOTA complexes in methanol, a solvent in which the sodium salts are less soluble than in aqueous solution. A Zn^II complex with a 1:1 composition was prepared by reaction of the NOTA ligand L with hydrous Zn^II perchlorate in a 1:1 molar ratio of metal:ligand. This complex was synthesized by a single-step procedure as described and the reaction revealed a pure product that was also characterized by ESI-MS and ¹H-NMR spectroscopy.

The molecular structure of the complex entity [Zn(NOTA)]^- and selected bond lengths (Å) and angles (°) of the coordination environment of Zn^II are given in Fig. 1 and Table 1, respectively. The asymmetric unit contains two independent mononuclear complex [Zn(NOTA)]^- entities, five sodium cations, three perchlorate anions and a methanol solvent molecule. The coordination environment, distances and angles of both independent [Zn(NOTA)]^- molecules are similar. When the metal centre coordination requirements do not favour an octahedral environment, the metal core geometry in NOTA complexes is trigonal-prismatic (Wieghardt et al., 1982). Thus, the Zn^II centres present a six-coordinated N₃O₃ core in a distorted trigonal-prismatic arrangement. Each Zn atom is bound to three N atoms from the macrocyclic backbone and three O atoms from the pendant-arms. Like in all the other known structures of NOTA complexes, in the [Zn(NOTA)]^- entities the donor atoms are disposed in a bifacial arrangement. Three N atoms occupy one facial plane of the prism, and three O atoms belong to the other plane. The average Zn—N and Zn—O bond lengths are 2.187 Å and 2.055 Å, respectively. These bond lengths are in the range found for M–N and M–O bonds in other NOTA complexes with divalent transition metals.

The crystal structure shows a layer arrangement parallel (001) generated by interactions between the [Zn(NOTA)]^- units, the Na⁺ cations, two ClO₄^- units and the methanol molecule, leading to an overall layer composition of [Na₅[Zn(C₁₂H₁₈N₃O₆)]₂(ClO₄)₂^.CH₃OH]⁺. The third ClO₄ anion is isolated and situated between the layers without any significant interactions (Fig. 2).

Related literature top

Details on the synthesis of NOTA are given by Desreux (1980). For NOTA complexes of Al, Cr, Fe, Co, Ni, Cu, Ga and In characterized by X-ray diffraction studies, see: Boeyens & Van der Merwe (1997); Bossek et al. (1995); Clarke & Martell (1991); Craig et al. (1989); Jyo et al. (1990); Van der Merwe et al. (1983, 1985); Moore et al. (1990); Wieghardt et al. (1982). For general background, see: Geraldes et al. (1985).

For related literature, see: Boeyens & Van der Merwe (1997); Van der Merwe, Boeyens & Hancock (1983, 1985).

Experimental top

Synthesis of the macrocycle NOTAH₃: The ligand NOTA was prepared from its triazamacrocycle precursor TACN by alkylation with bromoacetic acid using a modification of a previously reported method (Desreux, 1980). TACN and NaOH were dissolved in water, and to the solution was added a bromoacetic acid/ NaOH aqueous solution at 273 K. The reaction mixture temperature was raised to 323 K, and a NaOH aqueous solution was added. The mixture was maintained at 323 K under stirring for 5 d. Then, concentrated hydrobromic acid was added until a pH of ~ 7 was reached. NOTAH₃ does not precipitate from aqueous solutions in a well-defined state, thus a purification stage was needed. After a liquid-liquid extraction with n-butanol, a white powder characterized as a salt of the expected ligand was finally obtained. C₁₂H₂₁N₃O₆.(CH₂BrCOOH)₃:MS (ESI, m/z) 304 [H(LH₃)]⁺, 326 {Na(LH₃)]}⁺, 348 [Na₂(LH₂)]⁺; ¹H NMR data: (250 MHz, D₂O, SiMe₄): d 3.5 (s, 12 H from –CH₂– in the ring), d 3.9 (s, 6 H from CH₂BrCOOH), d 4.3 (s, 6 H from –CH₂– in pendants).

Synthesis of the metal complexes: Hydrated zinc perchlorate was added to a solution of the purified ligand NOTAH₃ in methanol. The reaction mixture was heated and then cooled. A concentrated NaOH methanolic solution was added until a pH of 7 was reached. Single crystals were obtained by the diffusion vapour-phase crystallization method in a MeOH/Et₂O solvent system. The Zn^II complex was characterized by ESI-MS, ¹HNMR, COSY NMR and X-ray diffraction. Na[ZnL]1.5(NaClO₄).0.5MeOH: MS(ESI, m/z) 366 [Zn(LH₂)]⁺, 388 {Na[Zn(LH)]}⁺. Colour: colourless.

The correspondent Cd(II) complex was also obtained in methanolic solution, but it has not been isolated in crystalline form.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: SHELXTL (Sheldrick, 2008); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure of one [Zn(NOTA)]^- complex with atom labelling and displacement ellipsoids drawn at the 50% probability level. The structure of the second [Zn(NOTA)]^- entity is very similar.
	Fig. 2. The crystal structure of the title compound in a projection along [010], emphasizing the layer arrangement parallel (001) as generated by interactions between the [Zn(NOTA)]^- units, the Na⁺ cations, two ClO₄^- units and the methanol molecule. The third ClO₄ anion is isolated and situated between the layers without any significant interactions.

pentasodium(I) bis[(1,4,7-triazacyclononane-N,N',N''-triacetato)zinc(II)] tris(perchlorate) methanol solvate top

Crystal data top

Na₅[Zn(C₁₂H₁₈N₃O₆)]₂(ClO₄)₃·CH₄O	F(000) = 2392
M_r = 1176.67	D_x = 1.847 Mg m⁻³
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 9827 reflections
a = 16.8879 (5) Å	θ = 2.4–27.7°
b = 9.4723 (3) Å	µ = 1.47 mm⁻¹
c = 26.4552 (9) Å	T = 100 K
V = 4232.0 (2) Å³	Prism, colourless
Z = 4	0.22 × 0.10 × 0.10 mm

Data collection top

Bruker APEXII CCD diffractometer	9954 independent reflections
Radiation source: fine-focus sealed tube	8605 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
ω and ϕ scans	θ_max = 28.3°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −21→22
T_min = 0.738, T_max = 0.867	k = −12→12
31309 measured reflections	l = −35→32

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.039	w = 1/[σ²(F_o²) + (0.0392P)² + 1.4688P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.084	(Δ/σ)_max = 0.001
S = 1.07	Δρ_max = 0.56 e Å⁻³
9954 reflections	Δρ_min = −0.58 e Å⁻³
601 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.00024 (8)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 4585 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.383 (7)

Crystal data top

Na₅[Zn(C₁₂H₁₈N₃O₆)]₂(ClO₄)₃·CH₄O	V = 4232.0 (2) Å³
M_r = 1176.67	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 16.8879 (5) Å	µ = 1.47 mm⁻¹
b = 9.4723 (3) Å	T = 100 K
c = 26.4552 (9) Å	0.22 × 0.10 × 0.10 mm

Data collection top

Bruker APEXII CCD diffractometer	9954 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	8605 reflections with I > 2σ(I)
T_min = 0.738, T_max = 0.867	R_int = 0.036
31309 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.084	Δρ_max = 0.56 e Å⁻³
S = 1.07	Δρ_min = −0.58 e Å⁻³
9954 reflections	Absolute structure: Flack (1983), 4585 Friedel pairs
601 parameters	Absolute structure parameter: 0.383 (7)
1 restraint

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. 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
Zn1	1.07460 (2)	0.01616 (4)	0.917626 (16)	0.00860 (9)
N1	1.12568 (18)	−0.1518 (3)	0.96418 (12)	0.0120 (7)
N2	1.12185 (18)	0.1482 (3)	0.97696 (12)	0.0118 (7)
N3	0.97800 (19)	−0.0083 (3)	0.97112 (12)	0.0129 (7)
O1	1.16120 (14)	−0.0640 (3)	0.87080 (10)	0.0118 (5)
O2	1.21023 (15)	−0.2696 (3)	0.84582 (10)	0.0149 (6)
O3	1.08723 (14)	0.2045 (3)	0.87911 (10)	0.0109 (5)
O4	1.14849 (15)	0.4106 (3)	0.88043 (10)	0.0138 (6)
O5	0.98658 (14)	−0.0531 (3)	0.87180 (10)	0.0127 (6)
O6	0.85724 (14)	−0.0775 (3)	0.86305 (10)	0.0134 (6)
C1	1.1941 (2)	−0.0791 (4)	0.98715 (16)	0.0161 (8)
H1A	1.2341	−0.0596	0.9607	0.019*
H1B	1.2187	−0.1417	1.0127	0.019*
C2	1.1699 (2)	0.0601 (4)	1.01240 (15)	0.0174 (8)
H2A	1.1386	0.0398	1.0432	0.021*
H2B	1.2179	0.1128	1.0226	0.021*
C3	1.0484 (2)	0.2058 (4)	1.00086 (15)	0.0134 (8)
H3A	1.0233	0.2739	0.9774	0.016*
H3B	1.0629	0.2573	1.0321	0.016*
C4	0.9891 (2)	0.0898 (4)	1.01387 (15)	0.0169 (9)
H4A	1.0082	0.0367	1.0437	0.020*
H4B	0.9376	0.1332	1.0227	0.020*
C5	0.9838 (2)	−0.1590 (4)	0.98620 (15)	0.0157 (8)
H5A	0.9663	−0.2188	0.9576	0.019*
H5B	0.9474	−0.1764	1.0149	0.019*
C6	1.0663 (2)	−0.2020 (4)	1.00137 (14)	0.0156 (8)
H6A	1.0787	−0.1621	1.0350	0.019*
H6B	1.0692	−0.3061	1.0039	0.019*
C7	1.1508 (2)	−0.2609 (4)	0.92774 (14)	0.0152 (8)
H7A	1.1064	−0.3272	0.9217	0.018*
H7B	1.1955	−0.3151	0.9421	0.018*
C8	1.1760 (2)	−0.1946 (4)	0.87764 (14)	0.0095 (7)
C9	1.1674 (2)	0.2606 (4)	0.95153 (14)	0.0140 (8)
H9A	1.2228	0.2292	0.9470	0.017*
H9B	1.1678	0.3460	0.9731	0.017*
C10	1.1323 (2)	0.2972 (4)	0.90042 (14)	0.0107 (8)
C11	0.9056 (2)	0.0144 (4)	0.94157 (15)	0.0128 (8)
H11A	0.8936	0.1166	0.9399	0.015*
H11B	0.8605	−0.0336	0.9582	0.015*
C12	0.9163 (2)	−0.0434 (4)	0.88855 (15)	0.0120 (8)
Zn2	0.60272 (2)	0.05820 (4)	0.708125 (16)	0.00988 (9)
N21	0.53471 (18)	−0.0972 (3)	0.66409 (11)	0.0111 (7)
N22	0.68311 (18)	0.0323 (3)	0.64345 (12)	0.0137 (7)
N23	0.54514 (19)	0.2003 (3)	0.65352 (12)	0.0141 (7)
O21	0.52931 (15)	−0.0254 (3)	0.76249 (10)	0.0134 (6)
O22	0.45361 (15)	−0.2103 (3)	0.78197 (10)	0.0168 (6)
O23	0.70301 (16)	−0.0144 (3)	0.74292 (10)	0.0160 (6)
O24	0.83384 (17)	−0.0339 (3)	0.73661 (12)	0.0267 (7)
O25	0.60456 (15)	0.2484 (3)	0.74679 (10)	0.0142 (6)
O26	0.55583 (15)	0.4664 (3)	0.74935 (10)	0.0145 (6)
C21	0.5825 (2)	−0.1491 (4)	0.62115 (14)	0.0129 (8)
H21A	0.5636	−0.1044	0.5895	0.015*
H21B	0.5754	−0.2524	0.6178	0.015*
C22	0.6700 (2)	−0.1160 (4)	0.62845 (16)	0.0162 (8)
H22A	0.6920	−0.1791	0.6548	0.019*
H22B	0.6986	−0.1350	0.5965	0.019*
C23	0.6640 (2)	0.1362 (4)	0.60296 (15)	0.0161 (8)
H23A	0.6354	0.0882	0.5752	0.019*
H23B	0.7136	0.1761	0.5891	0.019*
C24	0.6130 (2)	0.2540 (4)	0.62434 (16)	0.0160 (8)
H24A	0.6460	0.3145	0.6465	0.019*
H24B	0.5933	0.3132	0.5962	0.019*
C25	0.4863 (2)	0.1230 (4)	0.62259 (15)	0.0151 (8)
H25A	0.5090	0.1028	0.5888	0.018*
H25B	0.4386	0.1823	0.6179	0.018*
C26	0.4633 (2)	−0.0149 (4)	0.64821 (15)	0.0132 (8)
H26A	0.4303	0.0058	0.6783	0.016*
H26B	0.4312	−0.0725	0.6246	0.016*
C27	0.5128 (2)	−0.2061 (4)	0.70054 (15)	0.0145 (8)
H27A	0.5563	−0.2757	0.7034	0.017*
H27B	0.4650	−0.2564	0.6884	0.017*
C28	0.4961 (2)	−0.1420 (4)	0.75278 (14)	0.0121 (8)
C29	0.7628 (2)	0.0498 (4)	0.66439 (15)	0.0175 (9)
H29A	0.7774	0.1510	0.6637	0.021*
H29B	0.8013	−0.0023	0.6432	0.021*
C30	0.7672 (2)	−0.0043 (4)	0.71825 (16)	0.0165 (9)
C31	0.5101 (2)	0.3140 (4)	0.68376 (14)	0.0140 (8)
H31A	0.4565	0.2856	0.6950	0.017*
H31B	0.5048	0.3998	0.6627	0.017*
C32	0.5604 (2)	0.3469 (4)	0.72938 (15)	0.0140 (8)
Cl1P	0.90733 (6)	0.49270 (10)	0.94241 (4)	0.0164 (2)
Cl2P	0.76010 (6)	0.50986 (10)	0.57365 (4)	0.0207 (2)
Cl3P	0.85405 (6)	0.29914 (10)	0.79612 (4)	0.0198 (2)
O1P	0.87409 (16)	0.4307 (3)	0.81979 (11)	0.0225 (7)
O2P	0.78137 (15)	0.2457 (3)	0.81750 (11)	0.0215 (7)
O3P	0.91798 (15)	0.2025 (3)	0.80605 (11)	0.0199 (6)
O4P	0.84347 (19)	0.3166 (3)	0.74240 (12)	0.0322 (8)
O5P	0.98116 (16)	0.4732 (3)	0.91612 (13)	0.0264 (7)
O6P	0.92441 (19)	0.5250 (3)	0.99436 (12)	0.0300 (8)
O7P	0.86528 (16)	0.6093 (3)	0.91977 (11)	0.0196 (6)
O8P	0.86005 (19)	0.3672 (3)	0.93927 (13)	0.0326 (8)
O9P	0.81100 (17)	0.6321 (3)	0.57245 (13)	0.0307 (7)
O10P	0.7577 (3)	0.4429 (4)	0.52517 (14)	0.0578 (12)
O11P	0.68191 (19)	0.5555 (3)	0.58564 (16)	0.0445 (10)
O12P	0.78848 (18)	0.4105 (3)	0.61010 (12)	0.0303 (8)
C1S	0.7491 (3)	0.6009 (5)	0.71492 (18)	0.0350 (12)
H1S1	0.7719	0.5133	0.7016	0.053*
H1S2	0.7837	0.6804	0.7064	0.053*
H1S3	0.6967	0.6160	0.6999	0.053*
O1S	0.74181 (18)	0.5907 (3)	0.76745 (11)	0.0238 (7)
H1S	0.708 (3)	0.650 (5)	0.7779 (19)	0.036*
Na1	0.94165 (8)	0.95334 (15)	0.78618 (6)	0.0129 (3)
Na2	0.84425 (8)	0.67402 (15)	0.83292 (6)	0.0180 (3)
Na3	0.52011 (8)	0.11140 (16)	0.83393 (6)	0.0175 (3)
Na4	0.66600 (9)	0.40410 (15)	0.80596 (6)	0.0146 (3)
Na5	0.74113 (8)	−0.00225 (14)	0.82877 (6)	0.0121 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.00958 (19)	0.00826 (19)	0.0080 (2)	−0.00044 (15)	−0.00002 (19)	−0.00020 (19)
N1	0.0161 (16)	0.0096 (15)	0.0102 (16)	−0.0003 (12)	−0.0014 (13)	−0.0001 (13)
N2	0.0135 (16)	0.0102 (16)	0.0117 (16)	−0.0013 (12)	−0.0008 (13)	−0.0011 (13)
N3	0.0172 (18)	0.0110 (16)	0.0106 (16)	−0.0007 (12)	0.0024 (14)	−0.0027 (13)
O1	0.0138 (13)	0.0109 (13)	0.0106 (13)	0.0039 (10)	0.0041 (11)	0.0003 (11)
O2	0.0156 (14)	0.0128 (14)	0.0164 (14)	0.0043 (10)	0.0033 (12)	−0.0003 (11)
O3	0.0119 (13)	0.0117 (13)	0.0092 (13)	−0.0018 (10)	−0.0016 (11)	0.0001 (11)
O4	0.0160 (14)	0.0092 (13)	0.0162 (14)	−0.0019 (10)	0.0031 (11)	0.0019 (11)
O5	0.0076 (13)	0.0175 (14)	0.0129 (14)	−0.0008 (10)	0.0012 (11)	−0.0014 (11)
O6	0.0137 (13)	0.0096 (13)	0.0169 (14)	−0.0006 (10)	−0.0021 (12)	0.0009 (11)
C1	0.011 (2)	0.021 (2)	0.016 (2)	0.0011 (15)	−0.0043 (16)	0.0070 (17)
C2	0.023 (2)	0.019 (2)	0.010 (2)	−0.0010 (17)	−0.0045 (17)	0.0019 (17)
C3	0.0168 (19)	0.0116 (18)	0.012 (2)	−0.0009 (15)	0.0002 (17)	−0.0036 (15)
C4	0.018 (2)	0.021 (2)	0.012 (2)	−0.0015 (16)	0.0039 (17)	−0.0072 (17)
C5	0.019 (2)	0.019 (2)	0.0092 (19)	−0.0068 (16)	0.0041 (16)	0.0022 (16)
C6	0.023 (2)	0.014 (2)	0.010 (2)	−0.0046 (16)	0.0002 (17)	0.0041 (15)
C7	0.020 (2)	0.0091 (18)	0.016 (2)	0.0005 (14)	0.0023 (17)	−0.0012 (15)
C8	0.0067 (17)	0.0114 (18)	0.0104 (19)	0.0003 (13)	−0.0034 (15)	−0.0009 (15)
C9	0.016 (2)	0.0124 (19)	0.014 (2)	−0.0023 (15)	−0.0031 (16)	−0.0035 (16)
C10	0.0114 (18)	0.0064 (17)	0.0142 (19)	0.0013 (13)	0.0013 (15)	−0.0013 (14)
C11	0.0127 (19)	0.0101 (18)	0.016 (2)	−0.0017 (14)	0.0032 (16)	−0.0029 (16)
C12	0.014 (2)	0.0089 (18)	0.013 (2)	0.0000 (14)	−0.0019 (16)	0.0032 (15)
Zn2	0.0111 (2)	0.0108 (2)	0.0077 (2)	0.00016 (16)	0.00000 (19)	−0.00050 (18)
N21	0.0112 (16)	0.0143 (17)	0.0078 (16)	0.0000 (12)	0.0030 (13)	−0.0013 (13)
N22	0.0101 (16)	0.0163 (16)	0.0148 (17)	−0.0048 (12)	−0.0013 (14)	−0.0020 (14)
N23	0.0176 (17)	0.0144 (16)	0.0103 (16)	−0.0007 (13)	−0.0013 (14)	−0.0003 (14)
O21	0.0161 (14)	0.0144 (14)	0.0095 (14)	−0.0014 (11)	0.0025 (11)	0.0012 (11)
O22	0.0164 (14)	0.0139 (14)	0.0202 (15)	0.0009 (11)	0.0064 (12)	0.0014 (12)
O23	0.0185 (15)	0.0166 (14)	0.0130 (15)	0.0031 (11)	−0.0027 (12)	−0.0022 (12)
O24	0.0146 (15)	0.0318 (18)	0.034 (2)	0.0028 (12)	−0.0097 (14)	−0.0080 (15)
O25	0.0163 (14)	0.0130 (14)	0.0133 (14)	0.0019 (11)	−0.0037 (12)	−0.0006 (11)
O26	0.0136 (14)	0.0102 (13)	0.0197 (15)	−0.0007 (10)	0.0038 (12)	−0.0048 (11)
C21	0.016 (2)	0.0158 (19)	0.0072 (18)	−0.0027 (15)	0.0010 (15)	−0.0052 (15)
C22	0.017 (2)	0.018 (2)	0.014 (2)	0.0015 (16)	0.0035 (17)	−0.0061 (17)
C23	0.018 (2)	0.020 (2)	0.0105 (19)	−0.0059 (16)	0.0012 (17)	0.0003 (17)
C24	0.017 (2)	0.016 (2)	0.014 (2)	−0.0064 (15)	−0.0006 (17)	−0.0004 (17)
C25	0.016 (2)	0.014 (2)	0.015 (2)	−0.0009 (15)	−0.0052 (17)	0.0031 (16)
C26	0.014 (2)	0.0134 (19)	0.0118 (19)	−0.0017 (14)	−0.0033 (16)	−0.0011 (16)
C27	0.0155 (19)	0.0154 (19)	0.013 (2)	−0.0046 (14)	0.0017 (16)	−0.0016 (16)
C28	0.0121 (19)	0.0119 (19)	0.0122 (19)	0.0024 (15)	0.0004 (16)	0.0007 (15)
C29	0.010 (2)	0.028 (2)	0.015 (2)	−0.0014 (16)	−0.0020 (16)	−0.0045 (17)
C30	0.018 (2)	0.0094 (18)	0.022 (2)	−0.0006 (14)	−0.0025 (18)	−0.0039 (16)
C31	0.016 (2)	0.0107 (19)	0.015 (2)	0.0041 (14)	−0.0009 (17)	0.0030 (16)
C32	0.0125 (19)	0.0163 (19)	0.0131 (19)	0.0000 (15)	0.0081 (16)	0.0014 (16)
Cl1P	0.0172 (5)	0.0118 (4)	0.0201 (5)	0.0008 (4)	0.0043 (4)	0.0007 (4)
Cl2P	0.0179 (5)	0.0190 (5)	0.0250 (6)	−0.0022 (4)	−0.0024 (4)	0.0056 (4)
Cl3P	0.0173 (5)	0.0157 (5)	0.0264 (6)	−0.0003 (4)	−0.0004 (4)	−0.0019 (4)
O1P	0.0213 (15)	0.0160 (15)	0.0302 (18)	−0.0028 (12)	−0.0018 (13)	−0.0033 (13)
O2P	0.0113 (15)	0.0157 (14)	0.0376 (19)	−0.0009 (11)	0.0024 (13)	0.0032 (13)
O3P	0.0133 (14)	0.0142 (15)	0.0322 (17)	0.0006 (11)	−0.0025 (13)	−0.0011 (13)
O4P	0.041 (2)	0.0296 (18)	0.0256 (17)	0.0040 (15)	−0.0028 (15)	−0.0033 (15)
O5P	0.0209 (15)	0.0348 (16)	0.0236 (16)	0.0103 (12)	0.0060 (15)	0.0010 (15)
O6P	0.040 (2)	0.0317 (18)	0.0178 (16)	0.0064 (14)	0.0047 (15)	0.0021 (14)
O7P	0.0225 (15)	0.0153 (13)	0.0211 (15)	0.0024 (11)	−0.0027 (14)	0.0028 (13)
O8P	0.0323 (19)	0.0170 (16)	0.048 (2)	−0.0055 (13)	0.0015 (16)	0.0053 (15)
O9P	0.0257 (17)	0.0278 (17)	0.0384 (19)	−0.0113 (13)	−0.0034 (15)	0.0137 (15)
O10P	0.093 (3)	0.054 (3)	0.026 (2)	0.006 (2)	−0.011 (2)	−0.0121 (19)
O11P	0.0185 (17)	0.0303 (19)	0.085 (3)	0.0005 (14)	0.0062 (18)	0.022 (2)
O12P	0.0276 (18)	0.0225 (17)	0.041 (2)	−0.0039 (13)	−0.0087 (15)	0.0138 (14)
C1S	0.041 (3)	0.032 (3)	0.032 (3)	0.005 (2)	−0.002 (2)	0.001 (2)
O1S	0.0243 (17)	0.0277 (17)	0.0193 (16)	0.0010 (13)	0.0058 (14)	−0.0048 (13)
Na1	0.0106 (7)	0.0141 (8)	0.0140 (8)	−0.0015 (6)	−0.0006 (6)	0.0006 (6)
Na2	0.0176 (8)	0.0149 (8)	0.0216 (8)	0.0011 (6)	0.0059 (7)	−0.0020 (7)
Na3	0.0161 (8)	0.0166 (8)	0.0198 (9)	0.0007 (6)	−0.0018 (7)	−0.0064 (7)
Na4	0.0157 (8)	0.0149 (8)	0.0130 (8)	0.0000 (6)	0.0011 (6)	−0.0036 (6)
Na5	0.0136 (8)	0.0104 (7)	0.0124 (8)	−0.0001 (5)	−0.0012 (6)	−0.0002 (6)

Geometric parameters (Å, º) top

Zn1—O5	2.027 (3)	O24—Na5	2.913 (3)
Zn1—O1	2.062 (2)	O25—C32	1.280 (4)
Zn1—O3	2.066 (2)	O25—Na4	2.388 (3)
Zn1—N2	2.160 (3)	O25—Na3	3.005 (3)
Zn1—N3	2.172 (3)	O26—C32	1.251 (4)
Zn1—N1	2.189 (3)	O26—Na1^v	2.291 (3)
N1—C7	1.475 (5)	O26—Na4	2.460 (3)
N1—C1	1.477 (5)	C21—C22	1.524 (5)
N1—C6	1.483 (5)	C21—H21A	0.9900
N2—C9	1.475 (5)	C21—H21B	0.9900
N2—C3	1.495 (5)	C22—H22A	0.9900
N2—C2	1.495 (5)	C22—H22B	0.9900
N3—C11	1.467 (5)	C23—C24	1.519 (5)
N3—C4	1.476 (5)	C23—H23A	0.9900
N3—C5	1.485 (5)	C23—H23B	0.9900
O1—C8	1.276 (4)	C24—H24A	0.9900
O1—Na4ⁱ	2.289 (3)	C24—H24B	0.9900
O2—C8	1.244 (4)	C25—C26	1.523 (5)
O2—Na5ⁱⁱ	2.268 (3)	C25—H25A	0.9900
O2—Na2ⁱ	2.461 (3)	C25—H25B	0.9900
O3—C10	1.291 (4)	C26—H26A	0.9900
O3—Na3ⁱ	2.399 (3)	C26—H26B	0.9900
O3—Na4ⁱ	2.564 (3)	C27—C28	1.536 (5)
O4—C10	1.228 (4)	C27—H27A	0.9900
O4—Na5ⁱ	2.252 (3)	C27—H27B	0.9900
O4—Na3ⁱ	2.501 (3)	C29—C30	1.516 (6)
O5—C12	1.271 (4)	C29—H29A	0.9900
O5—Na1ⁱⁱⁱ	2.390 (3)	C29—H29B	0.9900
O6—C12	1.246 (4)	C30—Na5	2.957 (4)
O6—Na5	2.275 (3)	C31—C32	1.508 (5)
O6—Na2ⁱⁱⁱ	2.495 (3)	C31—H31A	0.9900
O6—Na1ⁱⁱⁱ	2.501 (3)	C31—H31B	0.9900
C1—C2	1.533 (6)	C32—Na4	2.753 (4)
C1—H1A	0.9900	Cl1P—O8P	1.435 (3)
C1—H1B	0.9900	Cl1P—O6P	1.437 (3)
C2—H2A	0.9900	Cl1P—O5P	1.440 (3)
C2—H2B	0.9900	Cl1P—O7P	1.444 (3)
C3—C4	1.527 (5)	Cl2P—O11P	1.425 (3)
C3—H3A	0.9900	Cl2P—O12P	1.430 (3)
C3—H3B	0.9900	Cl2P—O10P	1.431 (4)
C4—H4A	0.9900	Cl2P—O9P	1.442 (3)
C4—H4B	0.9900	Cl3P—O1P	1.435 (3)
C5—C6	1.507 (5)	Cl3P—O3P	1.440 (3)
C5—H5A	0.9900	Cl3P—O4P	1.442 (3)
C5—H5B	0.9900	Cl3P—O2P	1.443 (3)
C6—H6A	0.9900	Cl3P—Na3ⁱ	3.0957 (17)
C6—H6B	0.9900	Cl3P—Na4	3.3378 (18)
C7—C8	1.527 (5)	O1P—Na2	2.385 (3)
C7—H7A	0.9900	O1P—Na3ⁱ	2.526 (3)
C7—H7B	0.9900	O2P—Na5	2.463 (3)
C8—Na2ⁱ	3.083 (4)	O2P—Na4	2.478 (3)
C9—C10	1.516 (5)	O3P—Na1ⁱⁱⁱ	2.451 (3)
C9—H9A	0.9900	O3P—Na3ⁱ	2.574 (3)
C9—H9B	0.9900	O5P—Na3ⁱ	2.409 (4)
C10—Na3ⁱ	2.727 (4)	O7P—Na2	2.404 (3)
C11—C12	1.516 (5)	C1S—O1S	1.398 (6)
C11—H11A	0.9900	C1S—H1S1	0.9800
C11—H11B	0.9900	C1S—H1S2	0.9800
C12—Na1ⁱⁱⁱ	2.742 (4)	C1S—H1S3	0.9800
Zn2—O23	2.047 (3)	O1S—Na4	2.409 (3)
Zn2—O21	2.057 (3)	O1S—Na2	2.572 (3)
Zn2—O25	2.072 (3)	O1S—H1S	0.85 (5)
Zn2—N22	2.198 (3)	Na1—O24^vi	2.247 (3)
Zn2—N21	2.201 (3)	Na1—O26^vii	2.291 (3)
Zn2—N23	2.201 (3)	Na1—O22ⁱ	2.313 (3)
Zn2—Na3	3.6439 (16)	Na1—O5^vi	2.390 (3)
N21—C27	1.460 (5)	Na1—O3P^vi	2.451 (3)
N21—C21	1.477 (5)	Na1—O6^vi	2.501 (3)
N21—C26	1.496 (5)	Na1—C12^vi	2.742 (4)
N22—C29	1.465 (5)	Na2—O22ⁱ	2.312 (3)
N22—C22	1.476 (5)	Na2—O2^iv	2.461 (3)
N22—C23	1.490 (5)	Na2—O6^vi	2.495 (3)
N23—C31	1.467 (5)	Na2—C8^iv	3.083 (4)
N23—C24	1.473 (5)	Na3—O3^iv	2.399 (3)
N23—C25	1.480 (5)	Na3—O5P^iv	2.409 (4)
O21—C28	1.265 (4)	Na3—O4^iv	2.501 (3)
O21—Na3	2.297 (3)	Na3—O1P^iv	2.526 (3)
O22—C28	1.237 (4)	Na3—O3P^iv	2.574 (3)
O22—Na2^iv	2.312 (3)	Na3—C10^iv	2.727 (4)
O22—Na1^iv	2.313 (3)	Na3—Cl3P^iv	3.0957 (17)
O23—C30	1.269 (5)	Na4—O1^iv	2.289 (3)
O23—Na5	2.364 (3)	Na4—O3^iv	2.564 (3)
O24—C30	1.257 (5)	Na5—O4^iv	2.252 (3)
O24—Na1ⁱⁱⁱ	2.247 (3)	Na5—O2^viii	2.268 (3)

O5—Zn1—O1	92.38 (10)	N23—C24—H24A	109.1
O5—Zn1—O3	93.47 (10)	C23—C24—H24A	109.1
O1—Zn1—O3	87.04 (10)	N23—C24—H24B	109.1
O5—Zn1—N2	153.25 (11)	C23—C24—H24B	109.1
O1—Zn1—N2	112.82 (11)	H24A—C24—H24B	107.8
O3—Zn1—N2	79.63 (11)	N23—C25—C26	110.5 (3)
O5—Zn1—N3	78.72 (11)	N23—C25—H25A	109.6
O1—Zn1—N3	152.26 (11)	C26—C25—H25A	109.6
O3—Zn1—N3	119.42 (11)	N23—C25—H25B	109.6
N2—Zn1—N3	82.29 (12)	C26—C25—H25B	109.6
O5—Zn1—N1	112.96 (11)	H25A—C25—H25B	108.1
O1—Zn1—N1	77.94 (11)	N21—C26—C25	111.5 (3)
O3—Zn1—N1	149.83 (11)	N21—C26—H26A	109.3
N2—Zn1—N1	82.32 (12)	C25—C26—H26A	109.3
N3—Zn1—N1	81.47 (12)	N21—C26—H26B	109.3
O5—Zn1—Na4ⁱ	83.44 (8)	C25—C26—H26B	109.3
O1—Zn1—Na4ⁱ	40.66 (8)	H26A—C26—H26B	108.0
O3—Zn1—Na4ⁱ	48.41 (7)	N21—C27—C28	111.2 (3)
N2—Zn1—Na4ⁱ	109.47 (9)	N21—C27—H27A	109.4
N3—Zn1—Na4ⁱ	157.82 (9)	C28—C27—H27A	109.4
N1—Zn1—Na4ⁱ	117.97 (9)	N21—C27—H27B	109.4
C7—N1—C1	111.8 (3)	C28—C27—H27B	109.4
C7—N1—C6	113.8 (3)	H27A—C27—H27B	108.0
C1—N1—C6	113.9 (3)	O22—C28—O21	126.0 (4)
C7—N1—Zn1	104.7 (2)	O22—C28—C27	117.5 (3)
C1—N1—Zn1	101.6 (2)	O21—C28—C27	116.5 (3)
C6—N1—Zn1	109.9 (2)	N22—C29—C30	111.2 (3)
C9—N2—C3	111.2 (3)	N22—C29—H29A	109.4
C9—N2—C2	114.0 (3)	C30—C29—H29A	109.4
C3—N2—C2	112.9 (3)	N22—C29—H29B	109.4
C9—N2—Zn1	106.2 (2)	C30—C29—H29B	109.4
C3—N2—Zn1	102.3 (2)	H29A—C29—H29B	108.0
C2—N2—Zn1	109.4 (2)	O24—C30—O23	123.3 (4)
C11—N3—C4	114.9 (3)	O24—C30—C29	118.8 (4)
C11—N3—C5	109.8 (3)	O23—C30—C29	117.8 (3)
C4—N3—C5	113.0 (3)	O24—C30—Na5	75.7 (2)
C11—N3—Zn1	105.3 (2)	O23—C30—Na5	50.56 (19)
C4—N3—Zn1	109.7 (2)	C29—C30—Na5	156.9 (3)
C5—N3—Zn1	103.2 (2)	N23—C31—C32	111.2 (3)
C8—O1—Zn1	114.3 (2)	N23—C31—H31A	109.4
C8—O1—Na4ⁱ	137.8 (2)	C32—C31—H31A	109.4
Zn1—O1—Na4ⁱ	103.41 (11)	N23—C31—H31B	109.4
C8—O2—Na5ⁱⁱ	141.8 (2)	C32—C31—H31B	109.4
C8—O2—Na2ⁱ	108.1 (2)	H31A—C31—H31B	108.0
Na5ⁱⁱ—O2—Na2ⁱ	96.39 (10)	O26—C32—O25	122.9 (4)
C10—O3—Zn1	115.6 (2)	O26—C32—C31	119.3 (3)
C10—O3—Na3ⁱ	90.2 (2)	O25—C32—C31	117.7 (3)
Zn1—O3—Na3ⁱ	145.57 (12)	O26—C32—Na4	63.3 (2)
C10—O3—Na4ⁱ	107.2 (2)	O25—C32—Na4	60.11 (19)
Zn1—O3—Na4ⁱ	94.54 (9)	C31—C32—Na4	173.9 (3)
Na3ⁱ—O3—Na4ⁱ	99.25 (10)	O8P—Cl1P—O6P	110.1 (2)
C10—O4—Na5ⁱ	138.8 (2)	O8P—Cl1P—O5P	110.33 (19)
C10—O4—Na3ⁱ	86.9 (2)	O6P—Cl1P—O5P	108.4 (2)
Na5ⁱ—O4—Na3ⁱ	109.63 (12)	O8P—Cl1P—O7P	109.66 (18)
C12—O5—Zn1	116.9 (2)	O6P—Cl1P—O7P	109.42 (18)
C12—O5—Na1ⁱⁱⁱ	91.8 (2)	O5P—Cl1P—O7P	108.90 (18)
Zn1—O5—Na1ⁱⁱⁱ	142.31 (13)	O11P—Cl2P—O12P	111.1 (2)
C12—O6—Na5	145.5 (2)	O11P—Cl2P—O10P	107.9 (3)
C12—O6—Na2ⁱⁱⁱ	119.2 (2)	O12P—Cl2P—O10P	108.8 (2)
Na5—O6—Na2ⁱⁱⁱ	95.30 (10)	O11P—Cl2P—O9P	108.29 (19)
C12—O6—Na1ⁱⁱⁱ	87.4 (2)	O12P—Cl2P—O9P	110.07 (19)
Na5—O6—Na1ⁱⁱⁱ	97.50 (11)	O10P—Cl2P—O9P	110.7 (2)
Na2ⁱⁱⁱ—O6—Na1ⁱⁱⁱ	84.29 (9)	O1P—Cl3P—O3P	107.20 (16)
N1—C1—C2	111.8 (3)	O1P—Cl3P—O4P	111.07 (19)
N1—C1—H1A	109.3	O3P—Cl3P—O4P	110.22 (18)
C2—C1—H1A	109.3	O1P—Cl3P—O2P	109.51 (18)
N1—C1—H1B	109.3	O3P—Cl3P—O2P	110.08 (17)
C2—C1—H1B	109.3	O4P—Cl3P—O2P	108.74 (18)
H1A—C1—H1B	107.9	O1P—Cl3P—Na3ⁱ	53.68 (12)
N2—C2—C1	110.6 (3)	O3P—Cl3P—Na3ⁱ	55.65 (11)
N2—C2—H2A	109.5	O4P—Cl3P—Na3ⁱ	113.53 (14)
C1—C2—H2A	109.5	O2P—Cl3P—Na3ⁱ	137.71 (13)
N2—C2—H2B	109.5	O1P—Cl3P—Na4	86.08 (12)
C1—C2—H2B	109.5	O3P—Cl3P—Na4	152.71 (13)
H2A—C2—H2B	108.1	O4P—Cl3P—Na4	85.68 (13)
N2—C3—C4	112.2 (3)	O2P—Cl3P—Na4	42.67 (11)
N2—C3—H3A	109.2	Na3ⁱ—Cl3P—Na4	139.04 (5)
C4—C3—H3A	109.2	Cl3P—O1P—Na2	148.54 (18)
N2—C3—H3B	109.2	Cl3P—O1P—Na3ⁱ	99.08 (15)
C4—C3—H3B	109.2	Na2—O1P—Na3ⁱ	109.71 (11)
H3A—C3—H3B	107.9	Cl3P—O2P—Na5	128.06 (16)
N3—C4—C3	111.3 (3)	Cl3P—O2P—Na4	114.08 (15)
N3—C4—H4A	109.4	Na5—O2P—Na4	112.04 (11)
C3—C4—H4A	109.4	Cl3P—O3P—Na1ⁱⁱⁱ	134.07 (16)
N3—C4—H4B	109.4	Cl3P—O3P—Na3ⁱ	96.85 (13)
C3—C4—H4B	109.4	Na1ⁱⁱⁱ—O3P—Na3ⁱ	127.71 (11)
H4A—C4—H4B	108.0	Cl1P—O5P—Na3ⁱ	135.67 (19)
N3—C5—C6	113.1 (3)	Cl1P—O7P—Na2	131.63 (17)
N3—C5—H5A	109.0	O1S—C1S—H1S1	109.5
C6—C5—H5A	109.0	O1S—C1S—H1S2	109.5
N3—C5—H5B	109.0	H1S1—C1S—H1S2	109.5
C6—C5—H5B	109.0	O1S—C1S—H1S3	109.5
H5A—C5—H5B	107.8	H1S1—C1S—H1S3	109.5
N1—C6—C5	111.2 (3)	H1S2—C1S—H1S3	109.5
N1—C6—H6A	109.4	C1S—O1S—Na4	121.1 (3)
C5—C6—H6A	109.4	C1S—O1S—Na2	126.1 (3)
N1—C6—H6B	109.4	Na4—O1S—Na2	107.33 (12)
C5—C6—H6B	109.4	C1S—O1S—H1S	110 (3)
H6A—C6—H6B	108.0	Na4—O1S—H1S	90 (3)
N1—C7—C8	111.1 (3)	Na2—O1S—H1S	91 (3)
N1—C7—H7A	109.4	O24^vi—Na1—O26^vii	114.58 (12)
C8—C7—H7A	109.4	O24^vi—Na1—O22ⁱ	95.52 (12)
N1—C7—H7B	109.4	O26^vii—Na1—O22ⁱ	103.68 (11)
C8—C7—H7B	109.4	O24^vi—Na1—O5^vi	144.28 (12)
H7A—C7—H7B	108.0	O26^vii—Na1—O5^vi	98.30 (10)
O2—C8—O1	123.3 (3)	O22ⁱ—Na1—O5^vi	89.56 (11)
O2—C8—C7	118.9 (3)	O24^vi—Na1—O3P^vi	86.63 (11)
O1—C8—C7	117.8 (3)	O26^vii—Na1—O3P^vi	84.76 (10)
O2—C8—Na2ⁱ	49.36 (18)	O22ⁱ—Na1—O3P^vi	169.35 (12)
O1—C8—Na2ⁱ	93.7 (2)	O5^vi—Na1—O3P^vi	82.72 (10)
C7—C8—Na2ⁱ	128.1 (2)	O24^vi—Na1—O6^vi	91.09 (11)
N2—C9—C10	111.6 (3)	O26^vii—Na1—O6^vi	149.84 (11)
N2—C9—H9A	109.3	O22ⁱ—Na1—O6^vi	88.43 (10)
C10—C9—H9A	109.3	O5^vi—Na1—O6^vi	53.64 (9)
N2—C9—H9B	109.3	O3P^vi—Na1—O6^vi	81.09 (10)
C10—C9—H9B	109.3	O22ⁱ—Na2—O1P	83.69 (11)
H9A—C9—H9B	108.0	O22ⁱ—Na2—O7P	118.49 (11)
O4—C10—O3	122.5 (3)	O1P—Na2—O7P	82.05 (11)
O4—C10—C9	119.8 (3)	O22ⁱ—Na2—O2^iv	139.51 (11)
O3—C10—C9	117.7 (3)	O1P—Na2—O2^iv	124.75 (11)
O4—C10—Na3ⁱ	66.3 (2)	O7P—Na2—O2^iv	95.57 (10)
O3—C10—Na3ⁱ	61.58 (18)	O22ⁱ—Na2—O6^vi	88.60 (10)
C9—C10—Na3ⁱ	156.8 (3)	O1P—Na2—O6^vi	160.03 (11)
N3—C11—C12	109.9 (3)	O7P—Na2—O6^vi	85.54 (10)
N3—C11—H11A	109.7	O2^iv—Na2—O6^vi	71.91 (9)
C12—C11—H11A	109.7	O22ⁱ—Na2—O1S	100.97 (11)
N3—C11—H11B	109.7	O1P—Na2—O1S	75.38 (11)
C12—C11—H11B	109.7	O7P—Na2—O1S	131.66 (11)
H11A—C11—H11B	108.2	O2^iv—Na2—O1S	65.65 (10)
O6—C12—O5	122.7 (4)	O6^vi—Na2—O1S	124.31 (11)
O6—C12—C11	119.9 (3)	O21—Na3—O5P^iv	125.00 (12)
O5—C12—C11	117.4 (3)	O3^iv—Na3—O5P^iv	85.47 (10)
O6—C12—Na1ⁱⁱⁱ	65.6 (2)	O21—Na3—O4^iv	107.40 (10)
O5—C12—Na1ⁱⁱⁱ	60.57 (19)	O3^iv—Na3—O4^iv	53.55 (8)
C11—C12—Na1ⁱⁱⁱ	159.4 (2)	O5P^iv—Na3—O4^iv	76.41 (10)
O23—Zn2—O21	93.15 (11)	O21—Na3—O1P^iv	81.67 (11)
O23—Zn2—O25	93.30 (10)	O3^iv—Na3—O1P^iv	130.54 (10)
O21—Zn2—O25	89.92 (10)	O5P^iv—Na3—O1P^iv	79.32 (11)
O23—Zn2—N22	78.54 (11)	O4^iv—Na3—O1P^iv	154.94 (12)
O21—Zn2—N22	150.85 (11)	O21—Na3—O3P^iv	101.30 (11)
O25—Zn2—N22	118.18 (11)	O3^iv—Na3—O3P^iv	87.80 (9)
O23—Zn2—N21	116.44 (11)	O5P^iv—Na3—O3P^iv	107.67 (11)
O21—Zn2—N21	78.35 (11)	O4^iv—Na3—O3P^iv	141.14 (10)
O25—Zn2—N21	148.30 (11)	O1P^iv—Na3—O3P^iv	53.95 (9)
N22—Zn2—N21	80.53 (11)	O21—Na3—C10^iv	131.52 (12)
O23—Zn2—N23	150.03 (12)	O3^iv—Na3—C10^iv	28.26 (9)
O21—Zn2—N23	115.34 (11)	O5P^iv—Na3—C10^iv	73.33 (11)
O25—Zn2—N23	78.41 (11)	O4^iv—Na3—C10^iv	26.73 (9)
N22—Zn2—N23	80.23 (12)	O1P^iv—Na3—C10^iv	145.51 (12)
N21—Zn2—N23	80.27 (12)	O3P^iv—Na3—C10^iv	115.66 (11)
O23—Zn2—Na3	87.28 (8)	O21—Na3—O25	65.18 (9)
O21—Zn2—Na3	35.31 (8)	O3^iv—Na3—O25	81.04 (9)
O25—Zn2—Na3	55.57 (8)	O5P^iv—Na3—O25	164.93 (10)
N22—Zn2—Na3	164.36 (9)	O4^iv—Na3—O25	90.11 (9)
N21—Zn2—Na3	112.10 (8)	O1P^iv—Na3—O25	114.70 (10)
N23—Zn2—Na3	110.23 (9)	O3P^iv—Na3—O25	78.61 (9)
C27—N21—C21	114.3 (3)	C10^iv—Na3—O25	91.59 (10)
C27—N21—C26	110.4 (3)	O21—Na3—Cl3P^iv	87.13 (8)
C21—N21—C26	113.4 (3)	O3^iv—Na3—Cl3P^iv	112.97 (8)
C27—N21—Zn2	104.8 (2)	O5P^iv—Na3—Cl3P^iv	97.78 (9)
C21—N21—Zn2	110.2 (2)	O4^iv—Na3—Cl3P^iv	165.21 (9)
C26—N21—Zn2	102.8 (2)	O1P^iv—Na3—Cl3P^iv	27.24 (7)
C29—N22—C22	110.3 (3)	O3P^iv—Na3—Cl3P^iv	27.50 (6)
C29—N22—C23	113.3 (3)	C10^iv—Na3—Cl3P^iv	138.69 (9)
C22—N22—C23	113.7 (3)	O25—Na3—Cl3P^iv	93.66 (7)
C29—N22—Zn2	105.1 (2)	O1^iv—Na4—O25	152.16 (11)
C22—N22—Zn2	102.9 (2)	O1^iv—Na4—O1S	81.39 (10)
C23—N22—Zn2	110.6 (2)	O25—Na4—O1S	114.02 (11)
C31—N23—C24	110.2 (3)	O1^iv—Na4—O26	105.71 (10)
C31—N23—C25	113.2 (3)	O25—Na4—O26	54.58 (9)
C24—N23—C25	113.8 (3)	O1S—Na4—O26	88.20 (11)
C31—N23—Zn2	105.6 (2)	O1^iv—Na4—O2P	109.63 (11)
C24—N23—Zn2	102.2 (2)	O25—Na4—O2P	92.77 (10)
C25—N23—Zn2	110.9 (2)	O1S—Na4—O2P	94.51 (11)
C28—O21—Zn2	117.5 (2)	O26—Na4—O2P	144.57 (11)
C28—O21—Na3	129.0 (2)	O1^iv—Na4—O3^iv	71.43 (9)
Zn2—O21—Na3	113.50 (12)	O25—Na4—O3^iv	91.22 (10)
C28—O22—Na2^iv	138.5 (2)	O1S—Na4—O3^iv	152.81 (11)
C28—O22—Na1^iv	127.0 (2)	O26—Na4—O3^iv	99.40 (10)
Na2^iv—O22—Na1^iv	92.88 (11)	O2P—Na4—O3^iv	94.12 (10)
C30—O23—Zn2	116.8 (2)	O1^iv—Na4—C32	131.19 (12)
C30—O23—Na5	104.9 (2)	O25—Na4—C32	27.70 (10)
Zn2—O23—Na5	129.88 (13)	O1S—Na4—C32	100.22 (12)
C30—O24—Na1ⁱⁱⁱ	164.3 (3)	O26—Na4—C32	27.03 (10)
C30—O24—Na5	79.6 (2)	O2P—Na4—C32	118.75 (12)
Na1ⁱⁱⁱ—O24—Na5	87.28 (11)	O3^iv—Na4—C32	98.08 (11)
C32—O25—Zn2	116.6 (2)	O1^iv—Na4—Cl3P	106.80 (8)
C32—O25—Na4	92.2 (2)	O25—Na4—Cl3P	100.27 (8)
Zn2—O25—Na4	150.14 (13)	O1S—Na4—Cl3P	71.34 (8)
C32—O25—Na3	108.3 (2)	O26—Na4—Cl3P	138.03 (9)
Zn2—O25—Na3	89.79 (9)	O2P—Na4—Cl3P	23.25 (7)
Na4—O25—Na3	88.28 (9)	O3^iv—Na4—Cl3P	115.65 (7)
C32—O26—Na1^v	122.2 (2)	C32—Na4—Cl3P	120.02 (9)
C32—O26—Na4	89.6 (2)	O4^iv—Na5—O2^viii	94.98 (11)
Na1^v—O26—Na4	117.22 (12)	O4^iv—Na5—O6	118.54 (12)
N21—C21—C22	111.3 (3)	O2^viii—Na5—O6	79.66 (10)
N21—C21—H21A	109.4	O4^iv—Na5—O23	114.38 (11)
C22—C21—H21A	109.4	O2^viii—Na5—O23	94.71 (11)
N21—C21—H21B	109.4	O6—Na5—O23	127.05 (11)
C22—C21—H21B	109.4	O4^iv—Na5—O2P	84.12 (10)
H21A—C21—H21B	108.0	O2^viii—Na5—O2P	174.83 (12)
N22—C22—C21	112.1 (3)	O6—Na5—O2P	96.27 (10)
N22—C22—H22A	109.2	O23—Na5—O2P	90.30 (11)
C21—C22—H22A	109.2	O4^iv—Na5—O24	157.10 (11)
N22—C22—H22B	109.2	O2^viii—Na5—O24	101.07 (10)
C21—C22—H22B	109.2	O6—Na5—O24	80.68 (10)
H22A—C22—H22B	107.9	O23—Na5—O24	48.48 (9)
N22—C23—C24	109.9 (3)	O2P—Na5—O24	81.29 (10)
N22—C23—H23A	109.7	O4^iv—Na5—C30	134.93 (12)
C24—C23—H23A	109.7	O2^viii—Na5—C30	102.99 (11)
N22—C23—H23B	109.7	O6—Na5—C30	105.29 (11)
C24—C23—H23B	109.7	O23—Na5—C30	24.50 (10)
H23A—C23—H23B	108.2	O2P—Na5—C30	81.10 (11)
N23—C24—C23	112.5 (3)	O24—Na5—C30	24.72 (9)

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

Experimental details

Crystal data
Chemical formula	Na₅[Zn(C₁₂H₁₈N₃O₆)]₂(ClO₄)₃·CH₄O
M_r	1176.67
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	100
a, b, c (Å)	16.8879 (5), 9.4723 (3), 26.4552 (9)
V (Å³)	4232.0 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.47
Crystal size (mm)	0.22 × 0.10 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.738, 0.867
No. of measured, independent and observed [I > 2σ(I)] reflections	31309, 9954, 8605
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.084, 1.07
No. of reflections	9954
No. of parameters	601
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.56, −0.58
Absolute structure	Flack (1983), 4585 Friedel pairs
Absolute structure parameter	0.383 (7)

Computer programs: APEX2 (Bruker, 2005), SHELXTL (Sheldrick, 2008), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected bond lengths (Å) top

Zn1—O5	2.027 (3)	Zn2—O23	2.047 (3)
Zn1—O1	2.062 (2)	Zn2—O21	2.057 (3)
Zn1—O3	2.066 (2)	Zn2—O25	2.072 (3)
Zn1—N2	2.160 (3)	Zn2—N22	2.198 (3)
Zn1—N3	2.172 (3)	Zn2—N21	2.201 (3)
Zn1—N1	2.189 (3)	Zn2—N23	2.201 (3)

Acknowledgements

We thank the Xunta de Galicia (Spain; Project PGIDIT07PXIB209039PR) for financial support. The X-ray data were collected at the Unidade de Raios X, RIAIDT, University of Santiago de Compostela, Spain.

References

Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343–350. CrossRef Web of Science IUCr Journals Google Scholar
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Volume 65| Part 1| January 2009| Pages m84-m85

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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

A novel zinc(II) complex with the ligand 2,2′,2′′-(1,4,7-tri­azanonane-1,4,7-triyl)tri­acetate (NOTA)

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

A novel zinc(II) complex with the ligand 2,2′,2′′-(1,4,7-triazanonane-1,4,7-triyl)triacetate (NOTA)