A neutral cubane with a Zn^II₄O₄ core: tetra­benzoato­tetra­kis(μ₃-hydroxydi-2-pyridylmethano­lato)tetra­zinc(II)–acetone–methanol (1/2/1)

In the title compound, [Zn₄(C₁₁H₉N₂O₂)₄(C₇H₅O₂)₄]·2(CH₃)₂CO·CH₃OH, the tetra­nuclear mol­ecule lies on a fourfold inversion axis. Zn^II ions and μ₃-O atoms in the cubane core occupy alternating vertices, forming two inter­penetrating tetra­hedra. Each Zn^II ion is further coordinated by two N atoms from two different (py)₂C(OH)O ligands (py is pyrid­yl) and one O atom from a monodentate benzoate ligand, forming a distorted octa­hedral environment. The (py)₂C(OH)O ligand acts in an η¹:η³:η¹:μ₃ manner, forming two five-membered ZnNCCO chelating rings with two different Zn^II atoms sharing a common C—O bond, and an alkoxide-type bond to a third Zn^II ion. There are four symmetry-related intra­molecular O—H...O hydrogen bonds between the two types of ligands. In the asymmetric unit, there is a half-occupancy acetone solvent mol­ecule and a half-occupancy methanol solvent molecule that lies on a twofold rotation axis.

Key indicators

• Single-crystal X-ray study
• T = 170 K
• Mean [sigma](C-C) = 0.005 Å
• Disorder in solvent or counterion
• R factor = 0.034
• wR factor = 0.110
• Data-to-parameter ratio = 18.9

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT432_ALERT_2_B Short Inter X...Y Contact  O2S    ..  C1S     ..       2.90 Ang.
PLAT432_ALERT_2_B Short Inter X...Y Contact  O2S    ..  C1S     ..       2.90 Ang.

Alert level C
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       3.30
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.53 Ratio
PLAT415_ALERT_2_C Short Inter D-H..H-X       H9     ..  H2S     ..       2.12 Ang.
PLAT432_ALERT_2_C Short Inter X...Y Contact  O2S    ..  C3S     ..       3.00 Ang.
PLAT432_ALERT_2_C Short Inter X...Y Contact  O2S    ..  C3S     ..       3.00 Ang.
PLAT432_ALERT_2_C Short Inter X...Y Contact  C3S    ..  C21S    ..       3.12 Ang.
PLAT041_ALERT_1_C Calc. and Reported SumFormula    Strings  Differ          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       4.00 Ratio
PLAT076_ALERT_1_C Occupancy       0.50 less than 1.0 for Sp.pos  .        O2S
PLAT076_ALERT_1_C Occupancy       0.50 less than 1.0 for Sp.pos  .       C21S
PLAT952_ALERT_1_C Reported and Calculated Lmax Values Differ by ..          2

Alert level G
FORMU01_ALERT_1_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and _chemical_formula_moiety. This is
            usually due to the moiety formula being in the wrong format.
            Atom count from _chemical_formula_sum:   C316 H288 N32 O76 Zn16
            Atom count from _chemical_formula_moiety:C79 H72 N8 O19 Zn4
REFLT03_ALERT_1_G ALERT: Expected hkl max differ from CIF values
           From the CIF: _diffrn_reflns_theta_max           28.29
           From the CIF: _reflns_number_total               4628
           From the CIF: _diffrn_reflns_limit_ max hkl   18.   18.   48.
           From the CIF: _diffrn_reflns_limit_ min hkl  -18.   -9.  -48.
           TEST1: Expected hkl limits for theta max
           Calculated maximum hkl   19.   19.   50.
           Calculated minimum hkl  -19.  -19.  -50.
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           28.29
           From the CIF: _reflns_number_total               4628
           Count of symmetry unique reflns         2628
           Completeness (_total/calc)            176.10%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      2000
           Fraction of Friedel pairs measured     0.761
           Are heavy atom types Z>Si present        yes
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          5
PLAT066_ALERT_1_G Predicted and Reported Transmissions Identical .          ?
PLAT302_ALERT_4_G Note Anion/Solvent Disorder ....................      50.00 Perc.
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          6

   0 ALERT level A = In general: serious problem
   2 ALERT level B = Potentially serious problem
  11 ALERT level C = Check and explain
   7 ALERT level G = General alerts; check

   8 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   8 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Transition metal ions have, recently, received attention as the major cationic contributors to the inorganic composition of natural water and biological fluids (Daniele, et al., 2008). While the main interest is focused on the interaction of transition metal ions with biologically active molecules such as amino acids, proteins, sugars and nucleotides, the study on the interaction of the transition metal ions with fulvic acids and humic acids, mainly found in soil, is in incipient stages. As models to examine the interaction, therefore, we have previously used copper(II) benzoate as a building block and reported the structures of copper(II) benzoates with quinoxaline, 6-methylquinoline, and 3-methylquinoline (Lee, et al., 2008; Yu, et al., 2008; Park, et al., 2008). In this work, we have employed zinc(II) benzoate as a building block and di-2-pyridyl ketone as a ligand. We report herein the structure of the product of zinc(II) benzoate with di-2-pyridyl ketone.

The crystal structure contains tetranuclear [Zn₄(O₂CPh)₄{(py)₂C(OH)O}₄] molecules (Fig. 1), similar to the corresponding Mn₄ cubane compound (Stoumpos, et al., 2008). The tetramolecular molecule lies on a fourfold inversion center and hence the asymmetric unit contains a quarter of a molecule. Zn^II ions and µ₃-O atoms in the cubane [Zn^II₄(µ₃-OR)₄]⁴⁺ core occupy alternate vertices. Thus, the molecule consists of two interpenetrating tetrahedra: one contains four µ₃-O atoms originating from the (py)₂C(OH)O ligands, and the other contains four Zn^II atoms. Each Zn^II center is coordinated by two N atoms from two different (py)₂C(OH)O ligands and one O atom from a monodentate PhCO₂^- ligand to form a distorted octahedral geometry. The (py)₂C(OH)O ligands acts as η¹:η³:η¹:µ₃ to form two five-membered ZnNCCO chelating rings with two different Zn^II ions sharing a common C—O edge and an alkoxide-type bond to a third Zn^II ion. This ligation mode is common for the hydrated di-2-pyridyl ketone, (py)₂C(OH)O^- (Papaefstathiou & Perlepes, 2002; Papatriantafyllopoulou, et al., 2007). There are intramolecular hydrogen bonds interactions between the protonated O atom of the (py)₂C(OH)O ligand and the uncoordinated O atom of the monodentate PhCO₂ group.

Related literature

For background to transition metal ions as the major cationic contributors to the inorganic composition of natural water and biological fluids, see: Daniele et al. (2008); For related crystal structures, see: Lee et al. (2008); Park et al. (2008); Yu et al. (2008); Stoumpos et al. (2008); Papaefstathiou & Perlepes (2002); Papatriantafyllopoulou et al., (2007).

S2. Experimental

38.0 mg (0.125 mmol) of Zn(NO₃)₂^.6H₂O and 35.5 mg (0.25 mmol) of C₆H₅COONH₄ were dissolved in 4 ml water and carefully layered by 4 ml solution of a mixture of acetone, methanol and ethanol (2/2/2) of di-2-pyridyl ketone ligand (46.1 mg, 0.25 mmol). Crystals of the title compound suitable for X-ray analysis were obtained in a few weeks.

S3. Refinement

H atoms were placed in calculated positions with C—H distances of 0.93–0.98 Å and O—H = 0.82 Å. They were included in the refinement in a riding-motion approximation with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(C_methyl and O).

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

Fig. 1. Partially labeled molecular structure of the title complex. Displacement ellipsoids areshown at the 30% probability level. The green dotted lines represent hydrogen bonds. Solvent molecules are not shown.

Tetrabenzoatotetrakis(µ₃-hydroxydi-2-pyridylmethanolato)tetrazinc(II)– acetone–methanol (1/2/1)

Crystal data

[Zn4(C11H9N2O2)4(C7H5O2)4]·2C3H6O·CH4O	Dx = 1.458 Mg m^−3
Mr = 6795.70	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I42d	Cell parameters from 8208 reflections
Hall symbol: I -4 2bw	θ = 2.8–27.0°
a = 14.3201 (4) Å	µ = 1.30 mm^−1
c = 37.730 (2) Å	T = 170 K
V = 7737.1 (5) Å^3	Polyhedron, colorless
Z = 1	0.10 × 0.08 × 0.05 mm
F(000) = 3496

Data collection

Bruker SMART CCD diffractometer	4628 independent reflections
Radiation source: fine-focus sealed tube	4279 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
ϕ and ω scans	θmax = 28.3°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −18→18
Tmin = 0.883, Tmax = 0.937	k = −9→18
22787 measured reflections	l = −48→48

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.034	H-atom parameters constrained
wR(F^2) = 0.110	w = 1/[σ^2(Fo^2) + (0.0787P)^2 + 0.4409P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max = 0.001
4628 reflections	Δρmax = 1.37 e Å^−3
245 parameters	Δρmin = −0.42 e Å^−3
5 restraints	Absolute structure: Flack (1983), 2045 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.002 (13)

Special details

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Zn1	0.61621 (2)	0.51226 (2)	0.470190 (8)	0.01677 (10)
O1	0.50301 (15)	0.59983 (13)	0.47540 (5)	0.0177 (4)
O2	0.53176 (14)	0.75354 (15)	0.45808 (6)	0.0237 (5)
H2O	0.5908	0.7429	0.4575	0.036*
O3	0.73924 (15)	0.58089 (15)	0.47172 (6)	0.0257 (4)
O4	0.71640 (16)	0.73233 (17)	0.46138 (9)	0.0390 (6)
N1	0.58789 (18)	0.55925 (18)	0.41603 (6)	0.0197 (5)
N2	0.67260 (17)	0.38313 (19)	0.45377 (6)	0.0204 (5)
C1	0.6300 (2)	0.5287 (2)	0.38641 (8)	0.0262 (6)
H1	0.6712	0.4768	0.3881	0.031*
C2	0.6162 (3)	0.5691 (3)	0.35381 (9)	0.0366 (8)
H2	0.6465	0.5455	0.3333	0.044*
C3	0.5566 (3)	0.6455 (3)	0.35178 (10)	0.0404 (10)
H3	0.5448	0.6748	0.3296	0.049*
C4	0.5141 (3)	0.6789 (3)	0.38253 (8)	0.0331 (8)
H4	0.4741	0.7318	0.3818	0.040*
C5	0.5320 (2)	0.6328 (2)	0.41431 (8)	0.0210 (6)
C6	0.4901 (2)	0.6676 (2)	0.44992 (7)	0.0187 (5)
C7	0.6154 (2)	0.3128 (2)	0.44535 (7)	0.0192 (5)
C8	0.6484 (2)	0.2278 (2)	0.43286 (9)	0.0256 (6)
H8	0.6064	0.1783	0.4277	0.031*
C9	0.7445 (3)	0.2165 (2)	0.42796 (10)	0.0325 (8)
H9	0.7685	0.1604	0.4181	0.039*
C10	0.8032 (2)	0.2871 (3)	0.43751 (10)	0.0330 (8)
H10	0.8689	0.2797	0.4353	0.040*
C11	0.7658 (2)	0.3707 (2)	0.45060 (9)	0.0280 (7)
H11	0.8069	0.4197	0.4574	0.034*
C12	0.7640 (2)	0.6651 (2)	0.47105 (9)	0.0227 (6)
C13	0.8626 (2)	0.6836 (2)	0.48381 (8)	0.0237 (6)
C14	0.9023 (2)	0.7726 (2)	0.48046 (11)	0.0341 (8)
H14	0.8676	0.8218	0.4699	0.041*
C15	0.9924 (3)	0.7888 (3)	0.49264 (12)	0.0461 (10)
H15	1.0196	0.8489	0.4900	0.055*
C16	1.0423 (3)	0.7181 (3)	0.50846 (13)	0.0474 (11)
H16	1.1039	0.7295	0.5168	0.057*
C17	1.0032 (3)	0.6313 (3)	0.51216 (11)	0.0398 (8)
H17	1.0374	0.5829	0.5234	0.048*
C18	0.9141 (2)	0.6138 (3)	0.49960 (9)	0.0306 (7)
H18	0.8882	0.5530	0.5019	0.037*
O1S	0.9292 (16)	1.1086 (15)	0.3972 (6)	0.218 (6)*	0.50
C1S	0.9466 (13)	1.0280 (17)	0.3923 (6)	0.218 (6)*	0.50
C2S	0.965 (2)	0.972 (2)	0.4275 (8)	0.218 (6)*	0.50
H2S1	1.0259	0.9886	0.4372	0.328*	0.50
H2S2	0.9634	0.9045	0.4224	0.328*	0.50
H2S3	0.9160	0.9865	0.4448	0.328*	0.50
C3S	0.9503 (19)	0.975 (2)	0.3559 (7)	0.218 (6)*	0.50
H3S1	0.8956	0.9340	0.3537	0.328*	0.50
H3S2	1.0073	0.9370	0.3547	0.328*	0.50
H3S3	0.9504	1.0201	0.3364	0.328*	0.50
O2S	0.7500	1.0096 (11)	0.3750	0.110 (5)*	0.50
H2S	0.7197	1.0292	0.3574	0.164*	0.25
C21S	0.7500	0.9049 (11)	0.3750	0.139 (10)*	0.50
H21A	0.7999	0.8821	0.3595	0.208*	0.25
H21B	0.6896	0.8821	0.3664	0.208*	0.25
H21C	0.7605	0.8821	0.3992	0.208*	0.25

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.01658 (17)	0.01739 (17)	0.01634 (15)	0.00064 (12)	0.00086 (12)	0.00068 (12)
O1	0.0189 (9)	0.0175 (9)	0.0167 (9)	0.0029 (8)	0.0001 (8)	0.0034 (7)
O2	0.0206 (10)	0.0193 (10)	0.0311 (11)	−0.0009 (9)	0.0009 (8)	−0.0005 (9)
O3	0.0216 (11)	0.0258 (11)	0.0296 (11)	−0.0035 (9)	0.0013 (9)	−0.0002 (10)
O4	0.0214 (11)	0.0262 (13)	0.0693 (19)	−0.0015 (9)	−0.0062 (11)	0.0019 (12)
N1	0.0201 (12)	0.0213 (12)	0.0176 (11)	0.0003 (9)	0.0009 (9)	0.0007 (9)
N2	0.0182 (12)	0.0232 (12)	0.0199 (11)	0.0025 (11)	0.0015 (9)	0.0025 (10)
C1	0.0244 (15)	0.0299 (16)	0.0244 (14)	0.0035 (13)	0.0059 (12)	0.0000 (12)
C2	0.044 (2)	0.044 (2)	0.0218 (15)	0.0112 (18)	0.0101 (15)	0.0016 (14)
C3	0.050 (2)	0.048 (2)	0.0227 (16)	0.0158 (19)	0.0113 (16)	0.0114 (15)
C4	0.0378 (19)	0.0376 (18)	0.0238 (15)	0.0120 (16)	0.0058 (14)	0.0085 (13)
C5	0.0206 (14)	0.0214 (14)	0.0211 (14)	0.0008 (12)	0.0015 (10)	0.0043 (11)
C6	0.0199 (14)	0.0168 (13)	0.0194 (12)	0.0026 (12)	0.0006 (11)	0.0040 (10)
C7	0.0206 (14)	0.0207 (13)	0.0163 (12)	0.0010 (12)	0.0005 (11)	0.0006 (10)
C8	0.0267 (15)	0.0255 (16)	0.0245 (15)	0.0056 (13)	−0.0002 (12)	−0.0017 (12)
C9	0.0317 (18)	0.0298 (17)	0.0361 (18)	0.0124 (15)	0.0060 (15)	−0.0024 (14)
C10	0.0231 (16)	0.0371 (19)	0.0388 (19)	0.0086 (14)	0.0068 (14)	0.0018 (15)
C11	0.0214 (15)	0.0312 (17)	0.0315 (17)	−0.0005 (13)	0.0033 (12)	0.0037 (14)
C12	0.0192 (14)	0.0267 (15)	0.0221 (14)	−0.0017 (11)	0.0049 (12)	−0.0030 (13)
C13	0.0204 (15)	0.0263 (16)	0.0246 (14)	−0.0009 (12)	0.0040 (12)	−0.0069 (12)
C14	0.0275 (18)	0.0260 (17)	0.049 (2)	−0.0028 (14)	0.0040 (14)	−0.0056 (14)
C15	0.0283 (18)	0.0291 (18)	0.081 (3)	−0.0061 (16)	−0.001 (2)	−0.0103 (19)
C16	0.0218 (17)	0.048 (2)	0.072 (3)	−0.0035 (16)	−0.0083 (18)	−0.020 (2)
C17	0.0292 (17)	0.038 (2)	0.052 (2)	0.0050 (16)	−0.0075 (17)	−0.0062 (17)
C18	0.0270 (16)	0.0290 (16)	0.0357 (17)	−0.0039 (14)	−0.0012 (13)	−0.0028 (14)

Geometric parameters (Å, º)

Zn1—O3	2.018 (2)	C9—C10	1.365 (5)
Zn1—O1	2.059 (2)	C9—H9	0.9500
Zn1—O1^i	2.0776 (19)	C10—C11	1.401 (5)
Zn1—N2	2.111 (3)	C10—H10	0.9500
Zn1—N1	2.189 (2)	C11—H11	0.9500
Zn1—O1^ii	2.351 (2)	C12—C13	1.515 (4)
O1—C6	1.378 (3)	C13—C18	1.378 (5)
O1—Zn1^iii	2.0777 (19)	C13—C14	1.401 (5)
O1—Zn1^ii	2.352 (2)	C14—C15	1.389 (5)
O2—C6	1.402 (4)	C14—H14	0.9500
O2—H2O	0.8587	C15—C16	1.376 (6)
O3—C12	1.257 (4)	C15—H15	0.9500
O4—C12	1.235 (4)	C16—C17	1.371 (6)
N1—C5	1.325 (4)	C16—H16	0.9500
N1—C1	1.343 (4)	C17—C18	1.384 (5)
N2—C7	1.336 (4)	C17—H17	0.9500
N2—C11	1.352 (4)	C18—H18	0.9500
C1—C2	1.374 (5)	O1S—C1S	1.195 (10)
C1—H1	0.9500	C1S—C2S	1.57 (2)
C2—C3	1.391 (5)	C1S—C3S	1.57 (2)
C2—H2	0.9500	C2S—H2S1	0.9800
C3—C4	1.394 (5)	C2S—H2S2	0.9800
C3—H3	0.9500	C2S—H2S3	0.9800
C4—C5	1.392 (4)	C3S—H3S1	0.9800
C4—H4	0.9500	C3S—H3S2	0.9800
C5—C6	1.553 (4)	C3S—H3S3	0.9800
C6—C7^ii	1.546 (4)	O2S—C21S	1.499 (2)
C7—C8	1.388 (4)	O2S—H2S	0.8400
C7—C6^ii	1.546 (4)	C21S—H21A	0.9800
C8—C9	1.398 (5)	C21S—H21B	0.9800
C8—H8	0.9500	C21S—H21C	0.9800
O3—Zn1—O1	112.83 (9)	C7—C8—H8	120.6
O3—Zn1—O1^i	96.98 (9)	C9—C8—H8	120.6
O1—Zn1—O1^i	83.16 (8)	C10—C9—C8	119.1 (3)
O3—Zn1—N2	95.80 (9)	C10—C9—H9	120.5
O1—Zn1—N2	149.64 (9)	C8—C9—H9	120.5
O1^i—Zn1—N2	103.94 (9)	C9—C10—C11	119.4 (3)
O3—Zn1—N1	92.22 (9)	C9—C10—H10	120.3
O1—Zn1—N1	75.88 (9)	C11—C10—H10	120.3
O1^i—Zn1—N1	159.01 (9)	N2—C11—C10	121.4 (3)
N2—Zn1—N1	93.79 (10)	N2—C11—H11	119.3
O3—Zn1—O1^ii	164.53 (8)	C10—C11—H11	119.3
O1—Zn1—O1^ii	80.57 (8)	O4—C12—O3	126.7 (3)
O1^i—Zn1—O1^ii	76.33 (8)	O4—C12—C13	118.1 (3)
N2—Zn1—O1^ii	72.80 (8)	O3—C12—C13	115.2 (3)
N1—Zn1—O1^ii	98.82 (8)	C18—C13—C14	118.8 (3)
C6—O1—Zn1	117.87 (17)	C18—C13—C12	120.6 (3)
C6—O1—Zn1^iii	126.55 (17)	C14—C13—C12	120.6 (3)
Zn1—O1—Zn1^iii	104.24 (9)	C15—C14—C13	119.9 (4)
C6—O1—Zn1^ii	108.97 (17)	C15—C14—H14	120.0
Zn1—O1—Zn1^ii	98.51 (8)	C13—C14—H14	120.1
Zn1^iii—O1—Zn1^ii	94.78 (7)	C16—C15—C14	120.2 (4)
C6—O2—H2O	104.9	C16—C15—H15	119.9
C12—O3—Zn1	135.5 (2)	C14—C15—H15	119.9
C5—N1—C1	119.3 (3)	C17—C16—C15	119.9 (4)
C5—N1—Zn1	113.71 (19)	C17—C16—H16	120.0
C1—N1—Zn1	126.4 (2)	C15—C16—H16	120.0
C7—N2—C11	119.1 (3)	C16—C17—C18	120.5 (4)
C7—N2—Zn1	119.66 (19)	C16—C17—H17	119.8
C11—N2—Zn1	121.3 (2)	C18—C17—H17	119.8
N1—C1—C2	122.9 (3)	C13—C18—C17	120.6 (4)
N1—C1—H1	118.6	C13—C18—H18	119.7
C2—C1—H1	118.5	C17—C18—H18	119.7
C1—C2—C3	118.0 (3)	O1S—C1S—C2S	114 (2)
C1—C2—H2	121.0	O1S—C1S—C3S	128 (2)
C3—C2—H2	121.0	C2S—C1S—C3S	119 (2)
C2—C3—C4	119.4 (3)	C1S—C2S—H2S1	109.5
C2—C3—H3	120.3	C1S—C2S—H2S2	109.4
C4—C3—H3	120.3	H2S1—C2S—H2S2	109.5
C5—C4—C3	118.3 (3)	C1S—C2S—H2S3	109.5
C5—C4—H4	120.9	H2S1—C2S—H2S3	109.5
C3—C4—H4	120.9	H2S2—C2S—H2S3	109.5
N1—C5—C4	122.0 (3)	C1S—C3S—H3S1	109.5
N1—C5—C6	116.5 (2)	C1S—C3S—H3S2	109.4
C4—C5—C6	121.4 (3)	H3S1—C3S—H3S2	109.5
O1—C6—O2	114.1 (2)	C1S—C3S—H3S3	109.5
O1—C6—C7^ii	109.6 (2)	H3S1—C3S—H3S3	109.5
O2—C6—C7^ii	106.3 (2)	H3S2—C3S—H3S3	109.5
O1—C6—C5	109.0 (2)	C21S—O2S—H2S	109.5
O2—C6—C5	107.9 (2)	O2S—C21S—H21A	109.00
C7^ii—C6—C5	109.8 (2)	O2S—C21S—H21B	109.00
N2—C7—C8	122.1 (3)	H21A—C21S—H21B	110.00
N2—C7—C6^ii	115.9 (2)	O2S—C21S—H21C	109.00
C8—C7—C6^ii	122.0 (3)	H21A—C21S—H21C	109.00
C7—C8—C9	118.8 (3)	H21B—C21S—H21C	109.00

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2O···O4	0.86	1.81	2.664 (3)	172