Bis{μ-2-[(4,6-bis{(2-hydroxy-5-methylphenyl)[(pyridin-2-yl)methyl]amino}-1,3,5-triazin-2-yl)[(pyridin-2-yl-κN)methyl]amino-κN]-4-methyl­phenolato-1:2κ2O:O}bis­[(nitrato-κ2O,O′)zinc]–acetonitrile–water (2/4/1)

Maheswari, P.U.; Teat, S.J.; Roubeau, O.; Reedijk, J.

doi:10.1107/S1600536811053451

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 2| February 2012| Pages m194-m195

doi:10.1107/S1600536811053451

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Bis{μ-2-[(4,6-bis{(2-hydroxy-5-methylphenyl)[(pyridin-2-yl)methyl]amino}-1,3,5-triazin-2-yl)[(pyridin-2-yl-κN)methyl]amino-κN]-4-methylphenolato-1:2κ²O:O}bis[(nitrato-κ²O,O′)zinc]–acetonitrile–water (2/4/1)

Palanisami Uma Maheswari,^a ‡ Simon J. Teat,^b Olivier Roubeau ^c and Jan Reedijk ^a,^d ^*

^aLeiden Institute of Chemistry, Leiden University, PO Box 9502, 2300 RA, Leiden, The Netherlands, ^bAdvanced Light Source, Lawrence Berkeley, National Laboratory, Berkeley, California 94720, USA, ^cInstituto de Ciencia de Materiales de Aragon, CSIC and Universidad de Zaragoza, Plaza San Francisco s/n, 50009 Zaragoza, Spain, and ^dDepartment of Chemistry, King Saud University, PO Box 2455, Riyadh, 11451, Saudi Arabia
^*Correspondence e-mail: reedijk@chem.leidenuniv.nl

(Received 9 December 2011; accepted 12 December 2011; online 21 January 2012)

The title compound, [Zn₂(C₄₂H₃₈N₉O₃)₂(NO₃)₂]·2CH₃CN·0.5H₂O, is a bis-phenolate-bridged dinuclear Zn^II complex. The asymmetric unit comprises half the zinc complex (the full complex is completed by the application of a centre of inversion), one acetonitrile solvent molecule and a quarter of a water molecule (located on a twofold axis with half-occupancy; H atoms were not located for this molecule). Each triazine-based multidentate ligand uses a phenolate group to bridge Zn^II ions, generating a Zn₂O₂ core. The Zn^II ions are five-coordinate, with an additional long Zn—O contact [2.6465 (16) Å], and include a semi-bidentate nitrate ion and a N,N′,O-tridentate mode of the ligand in the coordination sphere. Non-coordinating pyridine groups form intramolecular O—H⋯N hydrogen bonds with phenol groups. As suggested by the short O⋯O donor–acceptor distances between the disordered water molecules and phenol O atoms, these groups also participate in hydrogen bonding.

Related literature

For a related structure, see: Maheswari et al. (2007 ). For the synthesis of the ligand, see: de Hoog et al. (2002 ); Gamez et al. (2003 ). For a description of the geometry of complexes with five-coordinate metal atoms, see: Addison et al. (1984 ).

Experimental

Crystal data

[Zn₂(C₄₂H₃₈N₉O₃)₂(NO₃)₂]·2C₂H₃N·0.5H₂O
M_r = 1779.53
Monoclinic, C 2/c
a = 31.154 (3) Å
b = 15.3768 (13) Å
c = 18.0060 (16) Å
β = 100.253 (2)°
V = 8488.0 (13) Å³
Z = 4
Synchrotron radiation
λ = 0.68940 Å
μ = 0.59 mm⁻¹
T = 150 K
0.16 × 0.04 × 0.04 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.87, T_max = 0.93
47083 measured reflections
12791 independent reflections
10387 reflections with I > 2σ(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.108
S = 1.06
12791 reflections
570 parameters
H-atom parameters constrained
Δρ_max = 0.56 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Table 1
Selected bond lengths (Å)

Zn1—O1	1.9752 (10)
Zn1—O1ⁱ	2.0386 (10)
Zn1—O10	1.9743 (12)
Zn1—N4	2.4705 (12)
Zn1—N5	2.0066 (13)
Symmetry code: (i) -x+1, -y, -z+1.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯N7	0.84	1.93	2.745 (2)	164
O3—H3⋯N9	0.84	1.87	2.688 (2)	164
O1w⋯O3			2.676 (3)
O1w⋯O3ⁱⁱ			2.676 (3)
Symmetry code: (ii) $[-x+1, y, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2009 ); cell refinement: SAINT (Bruker, 2007 ); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811053451/tk5033sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811053451/tk5033Isup2.hkl

checkCIF report

Comment top

The ligand 4,4',4''-trimethyl-2,2',2''-[(1,3,5-triazine-2,4,6-triyl)tris{[(pyridin-2-yl)methyl]imino}]triphenol is a potential multidentate ligand towards metal ions. Only with zinc nitrate was a reproducible crystalline compound obtained, and its three-dimensional structure is reported here. The resulting geometry for the zinc(II) ion, Fig. 1 and Table 1, is not unusual and resembles that of an earlier reported smaller fragment 4-methyl-2-[(2-pyridylmethyl)amino]phenol(Maheswari et al., 2007). The acetonitrile molecules fill the lattice space, as does a water molecule with 50% occupancy, albeit it H-bonded to 2 phenols, Table 2. The coordination around zinc is distorted square pyramidal, with a τ value (Addison et al., 1984) of 0.33; in addition a semi-coordinating oxygen from a chelating nitrate is present at 2.6465 (16) Å [Zn1···O12].

Related literature top

For a related structure, see: Maheswari et al. (2007). For the synthesis of the ligand, see: de Hoog et al. (2002); Gamez et al. (2003). For a description of the geometry of complexes with five-coordinate metal atoms, see: Addison et al. (1984).

Experimental top

The ligand 4,4',4''-trimethyl-2,2',2''-[(1,3,5-triazine-2,4,6-triyl)tris{[(pyridin-2-yl)methyl]imino}]triphenol was prepared by reacting 2,4,6-trichloro-1,3,5-triazine with 4-methyl-2-{[(pyridine-2-yl)methyl]amino}phenol in MeOH in the ratio 1:3, as described earlier for similar compounds (de Hoog et al., 2002; Gamez et al., 2003). The ligand (1 mmol, 0.720 g) was dissolved in warm acetonitrile and Zn(NO₃)₂ (H₂O)₃ (1 mmol, 0.2434 g), also dissolved in warm acetonitrile, was added drop wise to the solution of the ligand under stirring and then filtered. The resulting clear solution is colourless and light-yellow crystals were harvested after a week.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. Molecular structure of [Zn₂(H₂L)₂(NO₃)₂](CH₃CN)₂(H₂O)_0.5 showing the intramolecular O—H···N hydrogen bonding as dashed lines. Hydrogen atoms and lattice molecules have been omitted for clarity. Unlabelled atoms are related by symmetry operation 1-x, -y, 1-z.

Bis{µ-2-[(4,6-bis{(2-hydroxy-5-methylphenyl)[(pyridin-2-yl)methyl]amino}- 1,3,5-triazin-2-yl)[(pyridin-2-yl-κN)methyl]amino-κN]-4- methylphenolato-1:2κ²O}bis[(nitrato-κ²O,O')zinc]–acetonitrile–water (2/4/1) top

Crystal data top

[Zn₂(C₄₂H₃₈N₉O₃)₂(NO₃)₂]·2C₂H₃N·0.5H₂O	F(000) = 3696
M_r = 1779.53	D_x = 1.393 Mg m⁻³
Monoclinic, C2/c	Synchrotron radiation, λ = 0.68940 Å
Hall symbol: -C 2yc	Cell parameters from 7351 reflections
a = 31.154 (3) Å	θ = 2.8–29.4°
b = 15.3768 (13) Å	µ = 0.59 mm⁻¹
c = 18.0060 (16) Å	T = 150 K
β = 100.253 (2)°	Parallelpiped, light-yellow
V = 8488.0 (13) Å³	0.16 × 0.04 × 0.04 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	12791 independent reflections
Radiation source: Daresbury SRS station 9.8	10387 reflections with I > 2σ(I)
Silicon 111 monochromator	R_int = 0.039
ω rotation with narrow frames scans	θ_max = 29.5°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −43→44
T_min = 0.87, T_max = 0.93	k = −21→21
47083 measured reflections	l = −25→25

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.108	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0554P)² + 3.4344P] where P = (F_o² + 2F_c²)/3
12791 reflections	(Δ/σ)_max = 0.001
570 parameters	Δρ_max = 0.56 e Å⁻³
0 restraints	Δρ_min = −0.37 e Å⁻³

Crystal data top

[Zn₂(C₄₂H₃₈N₉O₃)₂(NO₃)₂]·2C₂H₃N·0.5H₂O	V = 8488.0 (13) Å³
M_r = 1779.53	Z = 4
Monoclinic, C2/c	Synchrotron radiation, λ = 0.68940 Å
a = 31.154 (3) Å	µ = 0.59 mm⁻¹
b = 15.3768 (13) Å	T = 150 K
c = 18.0060 (16) Å	0.16 × 0.04 × 0.04 mm
β = 100.253 (2)°

Data collection top

Bruker APEXII CCD diffractometer	12791 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	10387 reflections with I > 2σ(I)
T_min = 0.87, T_max = 0.93	R_int = 0.039
47083 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.108	H-atom parameters constrained
S = 1.06	Δρ_max = 0.56 e Å⁻³
12791 reflections	Δρ_min = −0.37 e Å⁻³
570 parameters

Special details top

Geometry. Also a short hydrogen bond is seen for the half-occupied water to two phenol groups: O3—Ow 2.676 (3) Å.

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	Occ. (<1)
Zn1	0.458384 (5)	0.041228 (10)	0.518223 (9)	0.02346 (5)
C1	0.44079 (4)	0.23008 (8)	0.54547 (7)	0.0209 (2)
N1	0.40078 (4)	0.24336 (8)	0.55736 (7)	0.0243 (2)
C2	0.37475 (4)	0.28245 (9)	0.49918 (8)	0.0229 (2)
N2	0.38661 (4)	0.30793 (8)	0.43508 (7)	0.0246 (2)
C3	0.42888 (4)	0.29428 (9)	0.43300 (8)	0.0231 (2)
N3	0.45848 (4)	0.25762 (8)	0.48758 (6)	0.0231 (2)
N4	0.46675 (4)	0.17411 (7)	0.59659 (6)	0.0215 (2)
C4	0.51379 (4)	0.18675 (9)	0.60775 (7)	0.0222 (2)
C5	0.53898 (4)	0.13243 (9)	0.57023 (8)	0.0239 (3)
O1	0.52016 (3)	0.07228 (7)	0.52085 (6)	0.0254 (2)
C6	0.58419 (5)	0.14437 (10)	0.58511 (9)	0.0293 (3)
H6A	0.6021	0.1098	0.5594	0.035*
C7	0.60321 (5)	0.20596 (10)	0.63692 (9)	0.0331 (3)
H7A	0.6341	0.2114	0.6472	0.040*
C8	0.57822 (5)	0.25999 (10)	0.67413 (9)	0.0307 (3)
C9	0.53309 (5)	0.25013 (9)	0.65745 (8)	0.0261 (3)
H9A	0.5152	0.2876	0.6806	0.031*
C10	0.59920 (6)	0.32631 (12)	0.73076 (11)	0.0418 (4)
H10A	0.6266	0.3029	0.7589	0.063*
H10B	0.5794	0.3398	0.7659	0.063*
H10C	0.6052	0.3794	0.7043	0.063*
C11	0.44937 (5)	0.14906 (9)	0.66421 (8)	0.0244 (3)
H11A	0.4195	0.1728	0.6600	0.029*
H11B	0.4676	0.1762	0.7088	0.029*
C12	0.44780 (4)	0.05271 (9)	0.67719 (8)	0.0251 (3)
C13	0.44166 (5)	0.02155 (11)	0.74728 (9)	0.0336 (3)
H13A	0.4400	0.0607	0.7875	0.040*
C14	0.43808 (7)	−0.06705 (13)	0.75745 (11)	0.0463 (4)
H14A	0.4340	−0.0894	0.8049	0.056*
C15	0.44043 (8)	−0.12283 (12)	0.69819 (12)	0.0512 (5)
H15A	0.4379	−0.1839	0.7040	0.061*
C16	0.44652 (6)	−0.08789 (11)	0.63057 (11)	0.0418 (4)
H16A	0.4483	−0.1260	0.5897	0.050*
N5	0.45009 (4)	−0.00152 (8)	0.62001 (7)	0.0282 (2)
N6	0.33232 (4)	0.29589 (8)	0.50585 (7)	0.0258 (2)
O2	0.29522 (4)	0.41085 (8)	0.60279 (7)	0.0409 (3)
H2	0.3006	0.4215	0.5596	0.061*
C17	0.31620 (4)	0.26517 (10)	0.57091 (8)	0.0274 (3)
C18	0.29838 (5)	0.32432 (11)	0.61599 (9)	0.0311 (3)
C19	0.28357 (5)	0.29258 (12)	0.67969 (9)	0.0374 (4)
H19A	0.2702	0.3313	0.7099	0.045*
C20	0.28802 (5)	0.20607 (13)	0.69934 (9)	0.0391 (4)
H20A	0.2785	0.1867	0.7438	0.047*
C21	0.30606 (5)	0.14642 (12)	0.65563 (10)	0.0377 (4)
C22	0.31922 (5)	0.17715 (11)	0.59040 (9)	0.0322 (3)
H22A	0.3305	0.1373	0.5584	0.039*
C23	0.31110 (7)	0.05114 (14)	0.67629 (14)	0.0536 (5)
H23A	0.3254	0.0455	0.7291	0.080*
H23B	0.3289	0.0225	0.6437	0.080*
H23C	0.2823	0.0237	0.6694	0.080*
C24	0.30153 (4)	0.31816 (10)	0.43693 (8)	0.0281 (3)
H24A	0.2715	0.3083	0.4459	0.034*
H24B	0.3064	0.2785	0.3960	0.034*
C25	0.30527 (4)	0.41092 (10)	0.41109 (9)	0.0287 (3)
C26	0.30984 (5)	0.43047 (11)	0.33770 (9)	0.0332 (3)
H26A	0.3124	0.3852	0.3028	0.040*
C27	0.31063 (6)	0.51666 (12)	0.31593 (11)	0.0389 (4)
H27A	0.3136	0.5315	0.2659	0.047*
C28	0.30703 (6)	0.58063 (12)	0.36824 (11)	0.0418 (4)
H28A	0.3070	0.6403	0.3547	0.050*
C29	0.30344 (6)	0.55613 (11)	0.44057 (11)	0.0419 (4)
H29A	0.3016	0.6004	0.4767	0.050*
N7	0.30247 (5)	0.47250 (9)	0.46250 (8)	0.0351 (3)
N8	0.44353 (4)	0.31853 (8)	0.36930 (7)	0.0279 (2)
C30	0.41349 (5)	0.33489 (11)	0.30045 (8)	0.0339 (3)
C31	0.41664 (7)	0.41154 (14)	0.26101 (11)	0.0478 (5)
O3	0.44543 (6)	0.47581 (11)	0.28450 (11)	0.0692 (5)
H3	0.4637	0.4584	0.3215	0.104*
C32	0.38783 (8)	0.42351 (19)	0.19253 (13)	0.0664 (7)
H32A	0.3895	0.4752	0.1643	0.080*
C33	0.35731 (8)	0.3616 (2)	0.16589 (12)	0.0682 (7)
H33A	0.3383	0.3715	0.1193	0.082*
C34	0.35332 (7)	0.28482 (16)	0.20493 (11)	0.0535 (5)
C35	0.38230 (6)	0.27290 (13)	0.27274 (10)	0.0404 (4)
H35A	0.3807	0.2210	0.3007	0.048*
C36	0.31979 (9)	0.2168 (2)	0.17639 (15)	0.0825 (9)
H36A	0.3246	0.1954	0.1272	0.124*
H36B	0.2906	0.2422	0.1710	0.124*
H36C	0.3224	0.1683	0.2123	0.124*
C37	0.48971 (5)	0.30312 (10)	0.36586 (9)	0.0306 (3)
H37A	0.4940	0.3087	0.3129	0.037*
H37B	0.4975	0.2429	0.3826	0.037*
C38	0.51987 (5)	0.36585 (10)	0.41449 (9)	0.0313 (3)
C39	0.55425 (5)	0.33806 (12)	0.46840 (10)	0.0383 (4)
H39A	0.5595	0.2778	0.4771	0.046*
C40	0.58092 (6)	0.39966 (13)	0.50970 (12)	0.0478 (4)
H40A	0.6047	0.3822	0.5473	0.057*
C41	0.57254 (7)	0.48598 (14)	0.49561 (14)	0.0532 (5)
H41A	0.5906	0.5294	0.5227	0.064*
C42	0.53723 (7)	0.50866 (13)	0.44110 (14)	0.0532 (5)
H42A	0.5312	0.5686	0.4317	0.064*
N9	0.51116 (5)	0.44982 (9)	0.40105 (9)	0.0405 (3)
N10	0.38032 (5)	0.07108 (9)	0.43434 (9)	0.0395 (3)
O10	0.41860 (4)	0.08881 (8)	0.42993 (7)	0.0374 (3)
O11	0.35018 (5)	0.09345 (12)	0.38307 (11)	0.0715 (5)
O12	0.37223 (5)	0.03042 (9)	0.49054 (9)	0.0512 (3)
N1S	0.30136 (12)	0.78257 (19)	0.4472 (2)	0.1195 (12)
C1S	0.28966 (9)	0.85082 (18)	0.43433 (18)	0.0727 (8)
C2S	0.27491 (11)	0.9365 (2)	0.4163 (3)	0.1041 (12)
H2S1	0.2950	0.9657	0.3883	0.156*
H2S2	0.2737	0.9687	0.4629	0.156*
H2S3	0.2457	0.9345	0.3851	0.156*
O1W	0.5000	0.5976 (3)	0.2500	0.0740 (15)	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.02159 (8)	0.02630 (9)	0.02305 (9)	0.00057 (6)	0.00550 (6)	−0.00004 (6)
C1	0.0212 (6)	0.0200 (5)	0.0206 (6)	0.0003 (4)	0.0016 (4)	−0.0014 (4)
N1	0.0206 (5)	0.0284 (6)	0.0237 (6)	0.0014 (4)	0.0032 (4)	0.0023 (4)
C2	0.0206 (6)	0.0217 (6)	0.0260 (6)	0.0006 (5)	0.0027 (5)	−0.0007 (5)
N2	0.0234 (5)	0.0263 (6)	0.0237 (6)	0.0022 (4)	0.0029 (4)	0.0017 (4)
C3	0.0242 (6)	0.0226 (6)	0.0224 (6)	0.0005 (5)	0.0040 (5)	−0.0002 (5)
N3	0.0220 (5)	0.0248 (5)	0.0226 (5)	0.0012 (4)	0.0041 (4)	0.0013 (4)
N4	0.0187 (5)	0.0258 (5)	0.0199 (5)	0.0009 (4)	0.0033 (4)	0.0022 (4)
C4	0.0199 (6)	0.0248 (6)	0.0209 (6)	−0.0010 (5)	0.0011 (4)	0.0020 (5)
C5	0.0221 (6)	0.0242 (6)	0.0248 (6)	−0.0013 (5)	0.0028 (5)	0.0031 (5)
O1	0.0223 (4)	0.0265 (5)	0.0281 (5)	−0.0018 (4)	0.0062 (4)	−0.0038 (4)
C6	0.0221 (6)	0.0295 (7)	0.0365 (8)	0.0004 (5)	0.0057 (5)	0.0034 (6)
C7	0.0215 (6)	0.0353 (8)	0.0403 (8)	−0.0053 (6)	−0.0007 (6)	0.0060 (6)
C8	0.0301 (7)	0.0297 (7)	0.0295 (7)	−0.0071 (6)	−0.0024 (6)	0.0034 (6)
C9	0.0275 (7)	0.0249 (6)	0.0244 (7)	−0.0010 (5)	0.0010 (5)	0.0015 (5)
C10	0.0387 (9)	0.0403 (9)	0.0417 (9)	−0.0125 (7)	−0.0060 (7)	−0.0029 (7)
C11	0.0255 (6)	0.0287 (7)	0.0192 (6)	0.0006 (5)	0.0048 (5)	0.0007 (5)
C12	0.0216 (6)	0.0301 (7)	0.0241 (6)	−0.0010 (5)	0.0050 (5)	0.0005 (5)
C13	0.0370 (8)	0.0387 (8)	0.0274 (7)	−0.0039 (6)	0.0115 (6)	0.0012 (6)
C14	0.0649 (12)	0.0420 (9)	0.0384 (9)	−0.0031 (9)	0.0265 (9)	0.0099 (8)
C15	0.0794 (14)	0.0304 (8)	0.0531 (12)	−0.0030 (9)	0.0369 (11)	0.0074 (8)
C16	0.0603 (11)	0.0284 (8)	0.0436 (10)	−0.0030 (7)	0.0278 (8)	−0.0004 (7)
N5	0.0314 (6)	0.0267 (6)	0.0286 (6)	−0.0011 (5)	0.0113 (5)	0.0007 (5)
N6	0.0188 (5)	0.0311 (6)	0.0271 (6)	0.0016 (4)	0.0028 (4)	0.0047 (5)
O2	0.0510 (7)	0.0345 (6)	0.0394 (7)	−0.0020 (5)	0.0145 (6)	−0.0057 (5)
C17	0.0184 (6)	0.0332 (7)	0.0298 (7)	−0.0013 (5)	0.0020 (5)	0.0036 (6)
C18	0.0264 (7)	0.0370 (8)	0.0287 (7)	−0.0048 (6)	0.0016 (5)	−0.0025 (6)
C19	0.0325 (8)	0.0511 (10)	0.0287 (8)	−0.0092 (7)	0.0060 (6)	−0.0064 (7)
C20	0.0289 (8)	0.0590 (11)	0.0284 (8)	−0.0105 (7)	0.0023 (6)	0.0072 (7)
C21	0.0231 (7)	0.0458 (9)	0.0426 (9)	−0.0026 (6)	0.0017 (6)	0.0149 (7)
C22	0.0215 (6)	0.0357 (8)	0.0392 (8)	0.0019 (6)	0.0051 (6)	0.0080 (6)
C23	0.0389 (10)	0.0548 (12)	0.0685 (14)	0.0053 (8)	0.0135 (9)	0.0319 (10)
C24	0.0201 (6)	0.0310 (7)	0.0312 (7)	0.0004 (5)	−0.0007 (5)	0.0043 (6)
C25	0.0202 (6)	0.0304 (7)	0.0334 (8)	0.0026 (5)	−0.0006 (5)	0.0037 (6)
C26	0.0284 (7)	0.0350 (8)	0.0361 (8)	0.0038 (6)	0.0055 (6)	0.0051 (6)
C27	0.0350 (8)	0.0411 (9)	0.0406 (9)	0.0018 (7)	0.0070 (7)	0.0119 (7)
C28	0.0421 (9)	0.0321 (8)	0.0485 (10)	−0.0019 (7)	0.0006 (8)	0.0092 (7)
C29	0.0464 (10)	0.0316 (8)	0.0451 (10)	−0.0003 (7)	0.0014 (8)	0.0000 (7)
N7	0.0368 (7)	0.0328 (7)	0.0340 (7)	0.0005 (5)	0.0021 (6)	0.0036 (5)
N8	0.0279 (6)	0.0340 (6)	0.0224 (6)	0.0060 (5)	0.0065 (4)	0.0046 (5)
C30	0.0343 (8)	0.0455 (9)	0.0224 (7)	0.0131 (7)	0.0067 (6)	0.0043 (6)
C31	0.0452 (10)	0.0592 (12)	0.0395 (10)	0.0119 (9)	0.0089 (8)	0.0206 (9)
O3	0.0639 (10)	0.0611 (10)	0.0773 (12)	0.0008 (8)	−0.0022 (9)	0.0417 (9)
C32	0.0593 (14)	0.0960 (19)	0.0440 (12)	0.0224 (13)	0.0092 (10)	0.0364 (12)
C33	0.0544 (13)	0.120 (2)	0.0269 (9)	0.0290 (14)	−0.0009 (8)	0.0068 (11)
C34	0.0477 (11)	0.0789 (15)	0.0306 (9)	0.0197 (10)	−0.0023 (8)	−0.0115 (9)
C35	0.0397 (9)	0.0509 (10)	0.0287 (8)	0.0133 (7)	0.0014 (6)	−0.0050 (7)
C36	0.0671 (16)	0.108 (2)	0.0594 (15)	0.0119 (15)	−0.0233 (12)	−0.0309 (15)
C37	0.0304 (7)	0.0370 (8)	0.0266 (7)	0.0062 (6)	0.0109 (6)	0.0033 (6)
C38	0.0315 (7)	0.0340 (7)	0.0318 (8)	−0.0005 (6)	0.0145 (6)	0.0041 (6)
C39	0.0335 (8)	0.0372 (8)	0.0441 (9)	−0.0057 (6)	0.0065 (7)	0.0077 (7)
C40	0.0394 (9)	0.0517 (11)	0.0507 (11)	−0.0141 (8)	0.0034 (8)	0.0045 (9)
C41	0.0501 (11)	0.0463 (10)	0.0660 (14)	−0.0170 (9)	0.0178 (10)	−0.0099 (10)
C42	0.0546 (12)	0.0328 (9)	0.0757 (15)	−0.0051 (8)	0.0209 (11)	−0.0002 (9)
N9	0.0421 (8)	0.0330 (7)	0.0493 (9)	0.0022 (6)	0.0158 (7)	0.0056 (6)
N10	0.0492 (9)	0.0289 (7)	0.0376 (8)	0.0086 (6)	−0.0001 (6)	0.0016 (6)
O10	0.0399 (6)	0.0382 (6)	0.0310 (6)	0.0015 (5)	−0.0020 (5)	−0.0014 (5)
O11	0.0415 (8)	0.0744 (11)	0.0861 (12)	−0.0037 (7)	−0.0226 (8)	0.0281 (9)
O12	0.0466 (8)	0.0519 (8)	0.0579 (9)	0.0067 (6)	0.0169 (7)	0.0065 (7)
N1S	0.137 (3)	0.0659 (17)	0.172 (3)	0.0061 (17)	0.072 (2)	−0.0190 (19)
C1S	0.0600 (14)	0.0625 (16)	0.105 (2)	−0.0031 (12)	0.0395 (15)	−0.0205 (15)
C2S	0.0685 (19)	0.0724 (19)	0.175 (4)	0.0003 (15)	0.031 (2)	−0.005 (2)
O1W	0.096 (4)	0.046 (2)	0.094 (4)	0.000	0.052 (3)	0.000

Geometric parameters (Å, º) top

Zn1—Zn1ⁱ	3.0607 (4)	C21—C23	1.513 (3)
Zn1—O1	1.9752 (10)	C22—H22A	0.9500
Zn1—O1ⁱ	2.0386 (10)	C23—H23A	0.9800
Zn1—O10	1.9743 (12)	C23—H23B	0.9800
Zn1—N4	2.4705 (12)	C23—H23C	0.9800
Zn1—N5	2.0066 (13)	C24—H24A	0.9900
C1—N1	1.3176 (17)	C24—H24B	0.9900
C1—N3	1.3320 (17)	C24—C25	1.511 (2)
C1—N4	1.4061 (16)	C25—C26	1.387 (2)
N1—C2	1.3467 (17)	C25—N7	1.338 (2)
C2—N2	1.3319 (18)	C26—H26A	0.9500
C2—N6	1.3642 (17)	C26—C27	1.384 (2)
N2—C3	1.3405 (17)	C27—H27A	0.9500
C3—N3	1.3460 (17)	C27—C28	1.380 (3)
C3—N8	1.3598 (18)	C28—H28A	0.9500
N4—C4	1.4563 (16)	C28—C29	1.379 (3)
N4—C11	1.4693 (17)	C29—H29A	0.9500
C4—C5	1.3994 (19)	C29—N7	1.347 (2)
C4—C9	1.3860 (19)	N8—C30	1.4363 (19)
C5—O1	1.3433 (17)	N8—C37	1.4704 (19)
C5—C6	1.3982 (19)	C30—C31	1.389 (3)
O1—Zn1ⁱ	2.0386 (10)	C30—C35	1.389 (3)
C6—H6A	0.9500	C31—O3	1.351 (3)
C6—C7	1.386 (2)	C31—C32	1.402 (3)
C7—H7A	0.9500	O3—H3	0.8400
C7—C8	1.390 (2)	C32—H32A	0.9500
C8—C9	1.393 (2)	C32—C33	1.370 (4)
C8—C10	1.507 (2)	C33—H33A	0.9500
C9—H9A	0.9500	C33—C34	1.391 (4)
C10—H10A	0.9800	C34—C35	1.395 (2)
C10—H10B	0.9800	C34—C36	1.503 (4)
C10—H10C	0.9800	C35—H35A	0.9500
C11—H11A	0.9900	C36—H36A	0.9800
C11—H11B	0.9900	C36—H36B	0.9800
C11—C12	1.502 (2)	C36—H36C	0.9800
C12—C13	1.395 (2)	C37—H37A	0.9900
C12—N5	1.3367 (19)	C37—H37B	0.9900
C13—H13A	0.9500	C37—C38	1.512 (2)
C13—C14	1.382 (2)	C38—C39	1.379 (2)
C14—H14A	0.9500	C38—N9	1.333 (2)
C14—C15	1.381 (3)	C39—H39A	0.9500
C15—H15A	0.9500	C39—C40	1.386 (3)
C15—C16	1.375 (2)	C40—H40A	0.9500
C16—H16A	0.9500	C40—C41	1.368 (3)
C16—N5	1.349 (2)	C41—H41A	0.9500
N6—C17	1.4342 (19)	C41—C42	1.382 (3)
N6—C24	1.4677 (18)	C42—H42A	0.9500
O2—H2	0.8400	C42—N9	1.338 (3)
O2—C18	1.352 (2)	N10—O10	1.240 (2)
C17—C18	1.398 (2)	N10—O11	1.2425 (19)
C17—C22	1.397 (2)	N10—O12	1.253 (2)
C18—C19	1.398 (2)	N1S—C1S	1.122 (4)
C19—H19A	0.9500	C1S—C2S	1.414 (4)
C19—C20	1.377 (3)	C2S—H2S1	0.9800
C20—H20A	0.9500	C2S—H2S2	0.9800
C20—C21	1.391 (3)	C2S—H2S3	0.9800
C21—C22	1.394 (2)

Zn1ⁱ—Zn1—N4	117.24 (3)	C19—C20—C21	121.61 (15)
Zn1ⁱ—Zn1—O1	41.08 (3)	H20A—C20—C21	119.2
Zn1ⁱ—Zn1—O1ⁱ	39.55 (3)	C20—C21—C22	117.54 (16)
Zn1ⁱ—Zn1—N5	108.17 (4)	C20—C21—C23	122.29 (17)
Zn1ⁱ—Zn1—O10	114.54 (4)	C22—C21—C23	120.17 (18)
N4—Zn1—O1	77.47 (4)	C17—C22—C21	121.56 (16)
N4—Zn1—O1ⁱ	153.84 (4)	C17—C22—H22A	119.2
N4—Zn1—N5	76.52 (4)	C21—C22—H22A	119.2
N4—Zn1—O10	98.09 (4)	C21—C23—H23A	109.5
O1—Zn1—O1ⁱ	80.63 (4)	C21—C23—H23B	109.5
O1—Zn1—N5	109.92 (5)	C21—C23—H23C	109.5
O1ⁱ—Zn1—N5	97.94 (5)	H23A—C23—H23B	109.5
O1—Zn1—O10	113.52 (5)	H23A—C23—H23C	109.5
O1ⁱ—Zn1—O10	103.70 (5)	H23B—C23—H23C	109.5
N5—Zn1—O10	133.83 (5)	N6—C24—H24A	108.8
N1—C1—N3	127.81 (12)	N6—C24—H24B	108.8
N1—C1—N4	116.05 (12)	N6—C24—C25	113.95 (12)
N3—C1—N4	115.90 (11)	H24A—C24—H24B	107.7
C1—N1—C2	113.50 (12)	H24A—C24—C25	108.8
N1—C2—N2	125.73 (12)	H24B—C24—C25	108.8
N1—C2—N6	117.24 (12)	C24—C25—C26	121.63 (14)
N2—C2—N6	117.02 (12)	C24—C25—N7	115.90 (14)
C2—N2—C3	113.80 (12)	C26—C25—N7	122.43 (14)
N2—C3—N3	126.44 (12)	C25—C26—H26A	120.4
N2—C3—N8	117.36 (12)	C25—C26—C27	119.18 (16)
N3—C3—N8	116.20 (12)	H26A—C26—C27	120.4
C1—N3—C3	112.29 (11)	C26—C27—H27A	120.6
Zn1—N4—C1	98.19 (8)	C26—C27—C28	118.79 (17)
Zn1—N4—C4	100.98 (8)	H27A—C27—C28	120.6
Zn1—N4—C11	103.86 (8)	C27—C28—H28A	120.7
C1—N4—C4	117.14 (11)	C27—C28—C29	118.68 (16)
C1—N4—C11	116.68 (11)	H28A—C28—C29	120.7
C4—N4—C11	115.52 (10)	C28—C29—H29A	118.4
N4—C4—C5	119.39 (12)	C28—C29—N7	123.18 (17)
N4—C4—C9	119.55 (12)	H29A—C29—N7	118.4
C5—C4—C9	121.01 (12)	C25—N7—C29	117.72 (15)
C4—C5—O1	120.94 (12)	C3—N8—C30	120.74 (12)
C4—C5—C6	117.48 (13)	C3—N8—C37	117.98 (12)
O1—C5—C6	121.56 (13)	C30—N8—C37	118.94 (12)
Zn1—O1—Zn1ⁱ	99.37 (4)	N8—C30—C31	119.71 (16)
Zn1—O1—C5	119.40 (8)	N8—C30—C35	119.77 (15)
Zn1ⁱ—O1—C5	133.36 (9)	C31—C30—C35	120.50 (16)
C5—C6—H6A	119.5	C30—C31—O3	124.36 (17)
C5—C6—C7	120.94 (14)	C30—C31—C32	117.9 (2)
H6A—C6—C7	119.5	O3—C31—C32	117.69 (19)
C6—C7—H7A	119.2	C31—O3—H3	109.5
C6—C7—C8	121.58 (13)	C31—C32—H32A	119.6
H7A—C7—C8	119.2	C31—C32—C33	120.8 (2)
C7—C8—C9	117.50 (14)	H32A—C32—C33	119.6
C7—C8—C10	121.21 (14)	C32—C33—H33A	119.0
C9—C8—C10	121.29 (15)	C32—C33—C34	122.10 (19)
C4—C9—C8	121.41 (14)	H33A—C33—C34	119.0
C4—C9—H9A	119.3	C33—C34—C35	116.8 (2)
C8—C9—H9A	119.3	C33—C34—C36	122.5 (2)
C8—C10—H10A	109.5	C35—C34—C36	120.7 (2)
C8—C10—H10B	109.5	C30—C35—C34	121.77 (19)
C8—C10—H10C	109.5	C30—C35—H35A	119.1
H10A—C10—H10B	109.5	C34—C35—H35A	119.1
H10A—C10—H10C	109.5	C34—C36—H36A	109.5
H10B—C10—H10C	109.5	C34—C36—H36B	109.5
N4—C11—H11A	108.6	C34—C36—H36C	109.5
N4—C11—H11B	108.6	H36A—C36—H36B	109.5
N4—C11—C12	114.49 (11)	H36A—C36—H36C	109.5
H11A—C11—H11B	107.6	H36B—C36—H36C	109.5
H11A—C11—C12	108.6	N8—C37—H37A	109.1
H11B—C11—C12	108.6	N8—C37—H37B	109.1
C11—C12—C13	119.56 (13)	N8—C37—C38	112.62 (12)
C11—C12—N5	119.20 (12)	H37A—C37—H37B	107.8
C13—C12—N5	121.16 (14)	H37A—C37—C38	109.1
C12—C13—H13A	120.5	H37B—C37—C38	109.1
C12—C13—C14	119.08 (15)	C37—C38—C39	122.31 (15)
H13A—C13—C14	120.5	C37—C38—N9	115.30 (15)
C13—C14—H14A	120.2	C39—C38—N9	122.38 (16)
C13—C14—C15	119.56 (16)	C38—C39—H39A	120.6
H14A—C14—C15	120.2	C38—C39—C40	118.83 (17)
C14—C15—H15A	120.8	H39A—C39—C40	120.6
C14—C15—C16	118.44 (17)	C39—C40—H40A	120.4
H15A—C15—C16	120.8	C39—C40—C41	119.16 (19)
C15—C16—H16A	118.7	H40A—C40—C41	120.4
C15—C16—N5	122.51 (16)	C40—C41—H41A	120.7
H16A—C16—N5	118.7	C40—C41—C42	118.56 (19)
Zn1—N5—C12	122.17 (10)	H41A—C41—C42	120.7
Zn1—N5—C16	118.59 (11)	C41—C42—H42A	118.6
C12—N5—C16	119.25 (13)	C41—C42—N9	122.84 (19)
C2—N6—C17	120.51 (12)	H42A—C42—N9	118.6
C2—N6—C24	117.30 (12)	C38—N9—C42	118.22 (17)
C17—N6—C24	119.75 (11)	O10—N10—O11	120.00 (16)
H2—O2—C18	109.5	O10—N10—O12	119.72 (15)
N6—C17—C18	119.53 (13)	O11—N10—O12	120.29 (17)
N6—C17—C22	120.43 (14)	Zn1—O10—N10	109.88 (10)
C18—C17—C22	120.03 (14)	N1S—C1S—C2S	178.7 (4)
O2—C18—C17	124.20 (14)	C1S—C2S—H2S1	109.5
O2—C18—C19	117.62 (15)	C1S—C2S—H2S2	109.5
C17—C18—C19	118.17 (15)	C1S—C2S—H2S3	109.5
C18—C19—H19A	119.5	H2S1—C2S—H2S2	109.5
C18—C19—C20	121.01 (16)	H2S1—C2S—H2S3	109.5
H19A—C19—C20	119.5	H2S2—C2S—H2S3	109.5
C19—C20—H20A	119.2

N3—C1—N1—C2	6.8 (2)	Zn1ⁱ—Zn1—N5—C16	−58.76 (13)
N4—C1—N1—C2	−167.31 (11)	N4—Zn1—N5—C12	6.92 (11)
C1—N1—C2—N2	−1.0 (2)	N4—Zn1—N5—C16	−173.40 (13)
C1—N1—C2—N6	177.80 (12)	O1—Zn1—N5—C12	78.01 (12)
N1—C2—N2—C3	−2.4 (2)	O1ⁱ—Zn1—N5—C12	160.88 (11)
N6—C2—N2—C3	178.78 (12)	O1—Zn1—N5—C16	−102.31 (13)
C2—N2—C3—N3	0.9 (2)	O1ⁱ—Zn1—N5—C16	−19.44 (13)
C2—N2—C3—N8	179.95 (12)	O10—Zn1—N5—C12	−81.38 (13)
N1—C1—N3—C3	−8.0 (2)	O10—Zn1—N5—C16	98.30 (14)
N4—C1—N3—C3	166.17 (11)	N1—C2—N6—C17	−3.09 (19)
N2—C3—N3—C1	3.7 (2)	N1—C2—N6—C24	−165.36 (12)
N8—C3—N3—C1	−175.39 (12)	N2—C2—N6—C17	175.86 (12)
N1—C1—N4—Zn1	99.82 (11)	N2—C2—N6—C24	13.59 (18)
N1—C1—N4—C4	−153.32 (12)	C2—N6—C17—C18	121.40 (15)
N1—C1—N4—C11	−10.25 (17)	C2—N6—C17—C22	−56.99 (19)
N3—C1—N4—Zn1	−75.03 (11)	C24—N6—C17—C18	−76.76 (18)
N3—C1—N4—C4	31.83 (16)	C24—N6—C17—C22	104.84 (16)
N3—C1—N4—C11	174.90 (11)	N6—C17—C18—O2	−0.3 (2)
Zn1ⁱ—Zn1—N4—C1	121.41 (7)	N6—C17—C18—C19	−179.01 (13)
Zn1ⁱ—Zn1—N4—C4	1.58 (8)	C22—C17—C18—O2	178.12 (14)
Zn1ⁱ—Zn1—N4—C11	−118.40 (7)	C22—C17—C18—C19	−0.6 (2)
O1—Zn1—N4—C1	110.80 (8)	O2—C18—C19—C20	−176.18 (14)
O1ⁱ—Zn1—N4—C1	144.67 (9)	C17—C18—C19—C20	2.6 (2)
O1—Zn1—N4—C4	−9.03 (7)	C18—C19—C20—C21	−2.1 (2)
O1ⁱ—Zn1—N4—C4	24.84 (13)	C19—C20—C21—C22	−0.6 (2)
O1—Zn1—N4—C11	−129.01 (8)	C19—C20—C21—C23	−179.86 (16)
O1ⁱ—Zn1—N4—C11	−95.15 (11)	C20—C21—C22—C17	2.6 (2)
N5—Zn1—N4—C1	−134.86 (8)	C23—C21—C22—C17	−178.07 (15)
N5—Zn1—N4—C4	105.31 (8)	N6—C17—C22—C21	176.34 (13)
N5—Zn1—N4—C11	−14.68 (8)	C18—C17—C22—C21	−2.1 (2)
O10—Zn1—N4—C1	−1.61 (8)	C2—N6—C24—C25	−75.79 (16)
O10—Zn1—N4—C4	−121.44 (8)	C17—N6—C24—C25	121.81 (14)
O10—Zn1—N4—C11	118.57 (8)	N6—C24—C25—C26	128.15 (15)
Zn1—N4—C4—C5	5.41 (13)	N6—C24—C25—N7	−53.93 (17)
Zn1—N4—C4—C9	−172.18 (11)	C24—C25—C26—C27	176.35 (14)
C1—N4—C4—C5	−99.81 (15)	N7—C25—C26—C27	−1.4 (2)
C1—N4—C4—C9	82.59 (15)	C25—C26—C27—C28	0.3 (2)
C11—N4—C4—C5	116.69 (14)	C26—C27—C28—C29	1.0 (3)
C11—N4—C4—C9	−60.91 (16)	C27—C28—C29—N7	−1.2 (3)
N4—C4—C5—O1	3.88 (19)	C24—C25—N7—C29	−176.73 (14)
N4—C4—C5—C6	−177.27 (12)	C26—C25—N7—C29	1.2 (2)
C9—C4—C5—O1	−178.56 (12)	C28—C29—N7—C25	0.2 (3)
C9—C4—C5—C6	0.3 (2)	N2—C3—N8—C30	−16.9 (2)
C4—C5—O1—Zn1	−14.20 (17)	N2—C3—N8—C37	−179.36 (13)
C4—C5—O1—Zn1ⁱ	−156.31 (10)	N3—C3—N8—C30	162.23 (13)
C6—C5—O1—Zn1	167.00 (10)	N3—C3—N8—C37	−0.23 (19)
C6—C5—O1—Zn1ⁱ	24.9 (2)	C3—N8—C30—C31	129.60 (17)
Zn1ⁱ—Zn1—O1—C5	−153.10 (12)	C3—N8—C30—C35	−52.2 (2)
N4—Zn1—O1—Zn1ⁱ	165.58 (5)	C37—N8—C30—C31	−68.1 (2)
N4—Zn1—O1—C5	12.48 (9)	C37—N8—C30—C35	110.11 (17)
O1ⁱ—Zn1—O1—Zn1ⁱ	0.0	N8—C30—C31—O3	−3.0 (3)
O1ⁱ—Zn1—O1—C5	−153.10 (12)	N8—C30—C31—C32	177.53 (17)
N5—Zn1—O1—Zn1ⁱ	95.12 (5)	C35—C30—C31—O3	178.76 (19)
N5—Zn1—O1—C5	−57.98 (11)	C35—C30—C31—C32	−0.7 (3)
O10—Zn1—O1—Zn1ⁱ	−100.96 (5)	C30—C31—C32—C33	0.5 (3)
O10—Zn1—O1—C5	105.95 (10)	O3—C31—C32—C33	−178.9 (2)
C4—C5—C6—C7	2.0 (2)	C31—C32—C33—C34	0.1 (4)
O1—C5—C6—C7	−179.19 (14)	C32—C33—C34—C35	−0.6 (3)
C5—C6—C7—C8	−2.1 (2)	C32—C33—C34—C36	179.7 (2)
C6—C7—C8—C9	0.0 (2)	N8—C30—C35—C34	−178.04 (15)
C6—C7—C8—C10	179.56 (15)	C31—C30—C35—C34	0.2 (3)
N4—C4—C9—C8	175.07 (12)	C33—C34—C35—C30	0.5 (3)
C5—C4—C9—C8	−2.5 (2)	C36—C34—C35—C30	−179.80 (19)
C7—C8—C9—C4	2.3 (2)	C3—N8—C37—C38	−73.87 (17)
C10—C8—C9—C4	−177.28 (14)	C30—N8—C37—C38	123.35 (15)
Zn1—N4—C11—C12	20.18 (13)	N8—C37—C38—C39	125.93 (16)
C1—N4—C11—C12	126.93 (13)	N8—C37—C38—N9	−54.71 (17)
C4—N4—C11—C12	−89.40 (14)	C37—C38—C39—C40	178.78 (16)
N4—C11—C12—C13	165.30 (13)	N9—C38—C39—C40	−0.5 (3)
N4—C11—C12—N5	−18.10 (18)	C38—C39—C40—C41	−0.3 (3)
C11—C12—C13—C14	176.79 (15)	C39—C40—C41—C42	0.9 (3)
N5—C12—C13—C14	0.3 (2)	C40—C41—C42—N9	−0.7 (3)
C12—C13—C14—C15	−0.3 (3)	C37—C38—N9—C42	−178.61 (16)
C13—C14—C15—C16	0.3 (3)	C39—C38—N9—C42	0.7 (3)
C14—C15—C16—N5	−0.3 (3)	C41—C42—N9—C38	−0.1 (3)
C11—C12—N5—Zn1	2.92 (18)	O11—N10—O10—Zn1	−178.20 (14)
C11—C12—N5—C16	−176.76 (14)	O12—N10—O10—Zn1	1.63 (18)
C13—C12—N5—Zn1	179.46 (11)	Zn1ⁱ—Zn1—O10—N10	138.72 (9)
C13—C12—N5—C16	−0.2 (2)	N4—Zn1—O10—N10	−96.31 (10)
C15—C16—N5—Zn1	−179.46 (17)	O1—Zn1—O10—N10	−176.11 (10)
C15—C16—N5—C12	0.2 (3)	O1ⁱ—Zn1—O10—N10	98.28 (10)
Zn1ⁱ—Zn1—N5—C12	121.56 (11)	N5—Zn1—O10—N10	−17.26 (14)

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
O2—H2···N7	0.84	1.93	2.745 (2)	164
O3—H3···N9	0.84	1.87	2.688 (2)	164
O1w···O3			2.676 (3)
O1w···O3ⁱⁱ			2.676 (3)

Symmetry code: (ii) −x+1, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Zn₂(C₄₂H₃₈N₉O₃)₂(NO₃)₂]·2C₂H₃N·0.5H₂O
M_r	1779.53
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	150
a, b, c (Å)	31.154 (3), 15.3768 (13), 18.0060 (16)
β (°)	100.253 (2)
V (Å³)	8488.0 (13)
Z	4
Radiation type	Synchrotron, λ = 0.68940 Å
µ (mm⁻¹)	0.59
Crystal size (mm)	0.16 × 0.04 × 0.04

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.87, 0.93
No. of measured, independent and observed [I > 2σ(I)] reflections	47083, 12791, 10387
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.714

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.108, 1.06
No. of reflections	12791
No. of parameters	570
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.56, −0.37

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2007), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Zn1—O1	1.9752 (10)	Zn1—N4	2.4705 (12)
Zn1—O1ⁱ	2.0386 (10)	Zn1—N5	2.0066 (13)
Zn1—O10	1.9743 (12)

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
O2—H2···N7	0.84	1.93	2.745 (2)	164
O3—H3···N9	0.84	1.87	2.688 (2)	164
O1w···O3	.	.	2.676 (3)	.
O1w···O3ⁱⁱ	.	.	2.676 (3)	.

Symmetry code: (ii) −x+1, y, −z+1/2.

Footnotes

‡Current address: Department of Chemistry, National Institute of Technology, Tiruchirappalli 620 015, Tamilnadu, India.

Acknowledgements

The authors are indebted to Professor Patrick Gamez (ICREA, Barcelona) for many useful suggestions in the early stages of this research. The work described in this paper was supported by the Leiden University Study group WFMO (Werkgroep Fundamenteel Materialen Onderzoek).

References

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