Bis[1,3-dihydr­oxy-2-hydroxy­methyl-2-(5-nitro-2-oxidobenzyl­ideneamino)propane-κ³N,O,O′]zinc(II) trihydrate

The Zn atom in the title compound, [Zn(C₁₁H₁₃N₂O₆)₂]·3H₂O, is chelated by the two terdentate Schiff base anions, resulting in a trans-ZnN₂O₄ octa­hedral geometry. The crystal packing is stabilized by O—H...O hydrogen bonds, leading to a three-dimensional network structure.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.023
• wR factor = 0.069
• Data-to-parameter ratio = 14.5

checkCIF/PLATON results

No syntax errors found



Alert level C
CRYSC01_ALERT_1_C The word below has not been recognised as a standard
            identifier.
            Faint
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.98
PLAT220_ALERT_2_C Large Non-Solvent    O     Ueq(max)/Ueq(min) ...       2.73 Ratio
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Zn1    -   O8      ..       7.44 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Zn1    -   N4      ..       6.22 su
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          6

Alert level G
PLAT794_ALERT_5_G Check Predicted Bond Valency for Zn1         (2)       2.10
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         12

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

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 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
   2 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

---

S1. Comment

A previous study (Ali et al., 2006) reported the structure of the complex ion found in the title compound as a bis-pyridine solvate. The use of DMSO as solvent yielded the title trihdrate (I) (Fig. 1). Two deprotonated Schiff-base ligands chelate through their phenoxy oxygen atoms, imino nitrogen and hydroxyl oxygen atoms (Table 1). The hydroxy groups of the ligands are engaged in extensive hydrogen bonding with the the uncoordinated water molecules to lead to a three-dimensional network (Table 2).

Related literature

For the same metal complex as a pyridine solvate, see: Ali et al. (2006).

S2. Experimental

The Schiff base used to make the title compound was synthesized from tris(hydroxymethyl)aminomethane and 5-nitrosalicylaldehyde. The ligand (0.23 g, 0.85 mmol) was dissolved in ethanol (25 ml) and several drops of aqueous sodium hydroxide were added to raise the pH of the solution to about 8.5. Zinc acetate (0.09 g, 0.43 mmol) was then added and the mixture heated for 5 h. The solvent was removed and the product recrystallized from DMSO to yield faint yellow blocks of (I). The water in (I) was presumably incorporated from the atmosphere.

S3. Refinement

The carbon-bound H atoms were placed at calculated positions (C–H = 0.95–0.99 Å), and they were included in the refinement in the riding model approximation with U_iso(H) = 1.2U_eq(C). The hydroxy and water H atoms were located in a difference Fourier map, and were refined with a distance restraint (O–H = 0.84±0.01 Å); their U_iso values were freely refined.

Computing details

Data collection: APEXII (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. View of the molecular structure of (I). Displacement ellipsoids are drawn at the 70% probability level (H atoms are shown as spheres of arbitrary radius).

Bis[1,3-dihydroxy-2-hydroxymethyl-2-(5-nitro-2-oxidobenzylideneamino)propane- κ³N,O,O']zinc(II) trihydrate

Crystal data

[Zn(C11H13N2O6)2]·3H2O	F(000) = 1368
Mr = 657.89	Dx = 1.621 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 8727 reflections
a = 10.7231 (2) Å	θ = 2.5–34.6°
b = 11.7429 (2) Å	µ = 0.99 mm^−1
c = 21.7538 (3) Å	T = 173 K
β = 100.227 (1)°	Irregular block, faint yellow
V = 2695.72 (8) Å^3	0.52 × 0.35 × 0.35 mm
Z = 4

Data collection

Bruker APEXII CCD diffractometer	6185 independent reflections
Radiation source: fine-focus sealed tube	5696 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
φ and ω scans	θmax = 27.5°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→13
Tmin = 0.590, Tmax = 0.722	k = −15→15
55575 measured reflections	l = −28→28

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.069	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.04P)^2 + 1.457P] where P = (Fo^2 + 2Fc^2)/3
6185 reflections	(Δ/σ)max = 0.001
427 parameters	Δρmax = 0.46 e Å^−3
12 restraints	Δρmin = −0.27 e Å^−3

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.

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

	x	y	z	Uiso*/Ueq
Zn1	0.484037 (13)	0.450449 (12)	0.344186 (6)	0.01048 (5)
O1	0.56842 (9)	0.36478 (8)	0.27965 (4)	0.01451 (18)
O2	0.37281 (9)	0.56145 (8)	0.39519 (4)	0.01370 (18)
O3	0.28019 (9)	0.73088 (8)	0.22313 (5)	0.0176 (2)
O4	0.02639 (9)	0.55207 (9)	0.31518 (5)	0.0186 (2)
O5	0.55010 (11)	0.32881 (12)	−0.00644 (5)	0.0315 (3)
O6	0.36276 (12)	0.39495 (12)	−0.00592 (5)	0.0374 (3)
O7	0.38730 (9)	0.31709 (8)	0.37207 (4)	0.01398 (18)
O8	0.60464 (9)	0.59756 (8)	0.34246 (4)	0.01519 (19)
O9	0.97710 (9)	0.50096 (9)	0.42660 (5)	0.0196 (2)
O10	0.77487 (9)	0.53162 (9)	0.53065 (4)	0.01668 (19)
O11	0.39461 (11)	−0.00756 (10)	0.59767 (5)	0.0300 (3)
O12	0.57778 (11)	0.07193 (10)	0.62595 (5)	0.0273 (2)
O1W	0.54356 (11)	0.73526 (11)	0.24683 (6)	0.0280 (2)
O2W	0.61738 (14)	0.65040 (14)	0.14354 (6)	0.0417 (3)
O3W	0.87436 (10)	0.63095 (9)	0.20693 (5)	0.0229 (2)
N1	0.46896 (12)	0.36639 (11)	0.02166 (5)	0.0201 (2)
N2	0.34315 (10)	0.50587 (9)	0.27214 (5)	0.0106 (2)
N3	0.47816 (12)	0.05985 (10)	0.58859 (6)	0.0180 (2)
N4	0.63672 (10)	0.41467 (9)	0.41535 (5)	0.0112 (2)
C1	0.54691 (12)	0.37682 (10)	0.21976 (6)	0.0125 (2)
C2	0.63983 (13)	0.33967 (12)	0.18453 (6)	0.0166 (3)
H2	0.7201	0.3149	0.2061	0.020*
C3	0.61644 (13)	0.33876 (12)	0.12065 (6)	0.0173 (3)
H3	0.6798	0.3139	0.0982	0.021*
C4	0.49776 (13)	0.37499 (11)	0.08866 (6)	0.0159 (3)
C5	0.40829 (13)	0.41975 (11)	0.12047 (6)	0.0147 (2)
H5	0.3301	0.4473	0.0979	0.018*
C6	0.43230 (12)	0.42464 (11)	0.18558 (6)	0.0120 (2)
C7	0.33752 (12)	0.48409 (11)	0.21393 (6)	0.0122 (2)
H7	0.2639	0.5094	0.1864	0.015*
C8	0.23991 (12)	0.57477 (11)	0.29063 (6)	0.0116 (2)
C9	0.29593 (12)	0.63565 (11)	0.35181 (6)	0.0143 (2)
H9A	0.3479	0.7009	0.3424	0.017*
H9B	0.2260	0.6660	0.3712	0.017*
C10	0.18367 (12)	0.66386 (11)	0.24237 (6)	0.0136 (2)
H10A	0.1339	0.6252	0.2056	0.016*
H10B	0.1255	0.7140	0.2606	0.016*
C11	0.13271 (12)	0.49241 (11)	0.29965 (6)	0.0145 (2)
H11A	0.1055	0.4486	0.2607	0.017*
H11B	0.1650	0.4378	0.3334	0.017*
C12	0.41320 (12)	0.25775 (10)	0.42287 (6)	0.0117 (2)
C13	0.31940 (12)	0.18237 (11)	0.43848 (6)	0.0153 (3)
H13	0.2401	0.1770	0.4111	0.018*
C14	0.33969 (13)	0.11756 (11)	0.49157 (6)	0.0157 (3)
H14	0.2756	0.0680	0.5009	0.019*
C15	0.45667 (13)	0.12566 (11)	0.53189 (6)	0.0147 (2)
C16	0.55135 (12)	0.19657 (11)	0.51877 (6)	0.0141 (2)
H16	0.6302	0.1997	0.5467	0.017*
C17	0.53229 (12)	0.26373 (11)	0.46495 (6)	0.0122 (2)
C18	0.63767 (12)	0.33792 (11)	0.45755 (6)	0.0129 (2)
H18	0.7142	0.3287	0.4867	0.015*
C19	0.74779 (11)	0.49089 (11)	0.41778 (6)	0.0118 (2)
C20	0.73077 (12)	0.55311 (11)	0.35481 (6)	0.0137 (2)
H20A	0.7931	0.6158	0.3566	0.016*
H20B	0.7438	0.4997	0.3213	0.016*
C21	0.87318 (12)	0.42490 (12)	0.42665 (6)	0.0155 (3)
H21A	0.8850	0.3829	0.4667	0.019*
H21B	0.8705	0.3687	0.3925	0.019*
C22	0.74665 (13)	0.57977 (11)	0.46974 (6)	0.0145 (2)
H22A	0.8096	0.6398	0.4659	0.017*
H22B	0.6621	0.6161	0.4640	0.017*
H2O	0.3294 (17)	0.5271 (16)	0.4177 (8)	0.031 (5)*
H3O	0.2450 (18)	0.7667 (16)	0.1918 (7)	0.036 (5)*
H4O	−0.0227 (18)	0.5733 (19)	0.2831 (7)	0.042 (6)*
H8O	0.5937 (19)	0.6421 (15)	0.3125 (7)	0.033 (5)*
H9O	0.9814 (19)	0.5166 (18)	0.3901 (5)	0.032 (5)*
H10O	0.8525 (9)	0.5287 (18)	0.5423 (10)	0.034 (5)*
H1W1	0.5666 (18)	0.7032 (15)	0.2156 (7)	0.028 (5)*
H1W2	0.4639 (9)	0.735 (2)	0.2426 (11)	0.049 (7)*
H2W1	0.6926 (14)	0.629 (3)	0.1600 (13)	0.079 (10)*
H2W2	0.609 (4)	0.643 (4)	0.1038 (5)	0.131 (15)*
H3W1	0.887 (2)	0.7015 (9)	0.2026 (11)	0.052 (7)*
H3W2	0.900 (2)	0.601 (2)	0.1756 (8)	0.056 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.00938 (8)	0.01265 (8)	0.00889 (8)	−0.00022 (5)	0.00021 (5)	0.00146 (5)
O1	0.0148 (4)	0.0169 (4)	0.0114 (4)	0.0034 (3)	0.0012 (3)	0.0012 (3)
O2	0.0138 (4)	0.0172 (4)	0.0101 (4)	0.0009 (3)	0.0021 (3)	0.0016 (3)
O3	0.0148 (5)	0.0183 (5)	0.0184 (5)	−0.0012 (4)	−0.0008 (4)	0.0084 (4)
O4	0.0137 (5)	0.0263 (5)	0.0170 (5)	0.0051 (4)	0.0059 (4)	0.0039 (4)
O5	0.0277 (6)	0.0523 (7)	0.0172 (5)	0.0038 (5)	0.0114 (4)	−0.0083 (5)
O6	0.0385 (7)	0.0569 (8)	0.0141 (5)	0.0253 (6)	−0.0026 (5)	−0.0056 (5)
O7	0.0144 (4)	0.0158 (4)	0.0105 (4)	−0.0031 (3)	−0.0013 (3)	0.0025 (3)
O8	0.0119 (4)	0.0175 (5)	0.0154 (5)	0.0004 (4)	0.0003 (3)	0.0065 (4)
O9	0.0102 (4)	0.0335 (6)	0.0152 (5)	−0.0036 (4)	0.0026 (4)	0.0056 (4)
O10	0.0116 (5)	0.0272 (5)	0.0110 (4)	−0.0020 (4)	0.0012 (4)	0.0021 (4)
O11	0.0308 (6)	0.0332 (6)	0.0245 (6)	−0.0131 (5)	0.0012 (5)	0.0149 (5)
O12	0.0233 (5)	0.0340 (6)	0.0215 (5)	−0.0036 (5)	−0.0049 (4)	0.0126 (5)
O1W	0.0201 (5)	0.0355 (6)	0.0271 (6)	0.0006 (5)	0.0006 (5)	0.0118 (5)
O2W	0.0358 (7)	0.0589 (9)	0.0284 (7)	0.0008 (6)	0.0000 (6)	−0.0022 (6)
O3W	0.0245 (5)	0.0215 (5)	0.0221 (5)	0.0005 (4)	0.0024 (4)	−0.0056 (4)
N1	0.0262 (6)	0.0213 (6)	0.0132 (5)	0.0032 (5)	0.0050 (5)	−0.0015 (4)
N2	0.0094 (5)	0.0112 (5)	0.0114 (5)	0.0005 (4)	0.0020 (4)	0.0005 (4)
N3	0.0196 (6)	0.0183 (6)	0.0158 (6)	−0.0007 (4)	0.0025 (5)	0.0047 (4)
N4	0.0096 (5)	0.0129 (5)	0.0110 (5)	−0.0014 (4)	0.0021 (4)	0.0000 (4)
C1	0.0133 (6)	0.0114 (5)	0.0128 (6)	−0.0008 (4)	0.0022 (5)	−0.0002 (4)
C2	0.0134 (6)	0.0191 (6)	0.0174 (6)	0.0039 (5)	0.0032 (5)	0.0004 (5)
C3	0.0180 (6)	0.0181 (6)	0.0176 (6)	0.0030 (5)	0.0076 (5)	−0.0002 (5)
C4	0.0211 (7)	0.0166 (6)	0.0107 (6)	0.0015 (5)	0.0046 (5)	−0.0004 (5)
C5	0.0160 (6)	0.0147 (6)	0.0127 (6)	0.0020 (5)	0.0009 (5)	−0.0001 (5)
C6	0.0120 (6)	0.0120 (5)	0.0124 (6)	0.0004 (4)	0.0030 (5)	−0.0004 (4)
C7	0.0101 (6)	0.0132 (5)	0.0126 (6)	0.0005 (4)	0.0001 (4)	−0.0001 (5)
C8	0.0111 (6)	0.0123 (5)	0.0117 (6)	0.0014 (4)	0.0027 (4)	−0.0001 (5)
C9	0.0168 (6)	0.0139 (6)	0.0118 (6)	0.0024 (5)	0.0013 (5)	−0.0007 (5)
C10	0.0125 (6)	0.0141 (6)	0.0140 (6)	0.0023 (5)	0.0019 (5)	0.0016 (5)
C11	0.0124 (6)	0.0153 (6)	0.0163 (6)	0.0009 (5)	0.0042 (5)	0.0005 (5)
C12	0.0131 (6)	0.0113 (5)	0.0104 (5)	−0.0001 (4)	0.0014 (4)	−0.0013 (4)
C13	0.0130 (6)	0.0178 (6)	0.0143 (6)	−0.0033 (5)	0.0002 (5)	0.0005 (5)
C14	0.0155 (6)	0.0158 (6)	0.0163 (6)	−0.0039 (5)	0.0041 (5)	0.0007 (5)
C15	0.0183 (6)	0.0135 (6)	0.0121 (6)	−0.0004 (5)	0.0026 (5)	0.0032 (5)
C16	0.0140 (6)	0.0147 (6)	0.0128 (6)	−0.0003 (5)	−0.0001 (5)	0.0009 (5)
C17	0.0129 (6)	0.0120 (5)	0.0118 (6)	−0.0008 (4)	0.0020 (5)	0.0007 (4)
C18	0.0107 (6)	0.0155 (6)	0.0115 (6)	−0.0004 (5)	−0.0004 (4)	0.0005 (5)
C19	0.0090 (5)	0.0145 (6)	0.0117 (6)	−0.0021 (4)	0.0012 (4)	0.0014 (5)
C20	0.0101 (6)	0.0175 (6)	0.0132 (6)	−0.0020 (5)	0.0012 (5)	0.0028 (5)
C21	0.0102 (6)	0.0197 (6)	0.0168 (6)	−0.0004 (5)	0.0025 (5)	0.0020 (5)
C22	0.0153 (6)	0.0161 (6)	0.0117 (6)	−0.0021 (5)	0.0016 (5)	0.0006 (5)

Geometric parameters (Å, º)

Zn1—O1	2.062 (1)	C2—C3	1.3676 (19)
Zn1—O2	2.196 (1)	C2—H2	0.9500
Zn1—O7	2.030 (1)	C3—C4	1.4038 (19)
Zn1—O8	2.162 (1)	C3—H3	0.9500
Zn1—N2	2.079 (1)	C4—C5	1.3825 (18)
Zn1—N4	2.087 (1)	C5—C6	1.3952 (18)
O1—C1	1.2898 (15)	C5—H5	0.9500
O2—C9	1.4329 (15)	C6—C7	1.4570 (17)
O2—H2O	0.837 (9)	C7—H7	0.9500
O3—C10	1.4211 (16)	C8—C10	1.5282 (17)
O3—H3O	0.832 (9)	C8—C9	1.5360 (17)
O4—C11	1.4288 (15)	C8—C11	1.5412 (17)
O4—H4O	0.834 (10)	C9—H9A	0.9900
O5—N1	1.2305 (16)	C9—H9B	0.9900
O6—N1	1.2355 (17)	C10—H10A	0.9900
O7—C12	1.2941 (15)	C10—H10B	0.9900
O8—C20	1.4300 (15)	C11—H11A	0.9900
O8—H8O	0.828 (9)	C11—H11B	0.9900
O9—C21	1.4283 (16)	C12—C13	1.4254 (18)
O9—H9O	0.824 (9)	C12—C17	1.4348 (17)
O10—C22	1.4229 (15)	C13—C14	1.3679 (18)
O10—H10O	0.826 (9)	C13—H13	0.9500
O11—N3	1.2375 (16)	C14—C15	1.4004 (18)
O12—N3	1.2301 (16)	C14—H14	0.9500
O1W—H1W1	0.852 (9)	C15—C16	1.3814 (18)
O1W—H1W2	0.843 (10)	C16—C17	1.3964 (17)
O2W—H2W1	0.860 (10)	C16—H16	0.9500
O2W—H2W2	0.857 (10)	C17—C18	1.4581 (17)
O3W—H3W1	0.848 (10)	C18—H18	0.9500
O3W—H3W2	0.851 (10)	C19—C21	1.5341 (17)
N1—C4	1.4387 (17)	C19—C20	1.5345 (17)
N2—C7	1.2828 (16)	C19—C22	1.5402 (18)
N2—C8	1.4833 (16)	C20—H20A	0.9900
N3—C15	1.4391 (17)	C20—H20B	0.9900
N4—C18	1.2853 (17)	C21—H21A	0.9900
N4—C19	1.4833 (15)	C21—H21B	0.9900
C1—C2	1.4289 (18)	C22—H22A	0.9900
C1—C6	1.4332 (17)	C22—H22B	0.9900
O7—Zn1—O1	97.84 (4)	N2—C8—C11	107.55 (10)
O7—Zn1—N2	97.20 (4)	C10—C8—C11	107.75 (10)
O1—Zn1—N2	89.28 (4)	C9—C8—C11	111.57 (10)
O7—Zn1—N4	89.90 (4)	O2—C9—C8	112.23 (10)
O1—Zn1—N4	91.46 (4)	O2—C9—H9A	109.2
N2—Zn1—N4	172.70 (4)	C8—C9—H9A	109.2
O7—Zn1—O8	163.85 (4)	O2—C9—H9B	109.2
O1—Zn1—O8	92.40 (4)	C8—C9—H9B	109.2
N2—Zn1—O8	95.37 (4)	H9A—C9—H9B	107.9
N4—Zn1—O8	77.34 (4)	O3—C10—C8	111.24 (10)
O7—Zn1—O2	87.40 (4)	O3—C10—H10A	109.4
O1—Zn1—O2	167.64 (4)	C8—C10—H10A	109.4
N2—Zn1—O2	78.92 (4)	O3—C10—H10B	109.4
N4—Zn1—O2	99.77 (4)	C8—C10—H10B	109.4
O8—Zn1—O2	85.11 (4)	H10A—C10—H10B	108.0
C1—O1—Zn1	127.78 (8)	O4—C11—C8	111.52 (11)
C9—O2—Zn1	109.20 (7)	O4—C11—H11A	109.3
C9—O2—H2O	111.3 (14)	C8—C11—H11A	109.3
Zn1—O2—H2O	114.8 (14)	O4—C11—H11B	109.3
C10—O3—H3O	105.8 (14)	C8—C11—H11B	109.3
C11—O4—H4O	111.2 (16)	H11A—C11—H11B	108.0
C12—O7—Zn1	128.83 (8)	O7—C12—C13	118.97 (11)
C20—O8—Zn1	104.71 (7)	O7—C12—C17	123.38 (11)
C20—O8—H8O	112.1 (14)	C13—C12—C17	117.66 (11)
Zn1—O8—H8O	121.1 (14)	C14—C13—C12	122.24 (12)
C21—O9—H9O	108.4 (15)	C14—C13—H13	118.9
C22—O10—H10O	109.7 (15)	C12—C13—H13	118.9
H1W1—O1W—H1W2	110 (2)	C13—C14—C15	118.78 (12)
H2W1—O2W—H2W2	108 (3)	C13—C14—H14	120.6
H3W1—O3W—H3W2	103 (2)	C15—C14—H14	120.6
O5—N1—O6	121.88 (12)	C16—C15—C14	121.40 (12)
O5—N1—C4	119.00 (12)	C16—C15—N3	119.27 (12)
O6—N1—C4	119.11 (12)	C14—C15—N3	119.32 (12)
C7—N2—C8	118.03 (10)	C15—C16—C17	120.67 (12)
C7—N2—Zn1	125.62 (9)	C15—C16—H16	119.7
C8—N2—Zn1	116.35 (8)	C17—C16—H16	119.7
O12—N3—O11	122.46 (12)	C16—C17—C12	119.24 (11)
O12—N3—C15	119.50 (12)	C16—C17—C18	115.41 (11)
O11—N3—C15	118.03 (12)	C12—C17—C18	125.33 (11)
C18—N4—C19	119.55 (11)	N4—C18—C17	126.14 (12)
C18—N4—Zn1	125.23 (9)	N4—C18—H18	116.9
C19—N4—Zn1	115.10 (8)	C17—C18—H18	116.9
O1—C1—C2	119.44 (11)	N4—C19—C21	112.33 (10)
O1—C1—C6	123.37 (11)	N4—C19—C20	106.74 (10)
C2—C1—C6	117.18 (12)	C21—C19—C20	108.39 (10)
C3—C2—C1	121.86 (12)	N4—C19—C22	108.91 (10)
C3—C2—H2	119.1	C21—C19—C22	111.78 (10)
C1—C2—H2	119.1	C20—C19—C22	108.50 (10)
C2—C3—C4	119.21 (12)	O8—C20—C19	107.46 (10)
C2—C3—H3	120.4	O8—C20—H20A	110.2
C4—C3—H3	120.4	C19—C20—H20A	110.2
C5—C4—C3	121.04 (12)	O8—C20—H20B	110.2
C5—C4—N1	119.38 (12)	C19—C20—H20B	110.2
C3—C4—N1	119.58 (12)	H20A—C20—H20B	108.5
C4—C5—C6	120.30 (12)	O9—C21—C19	110.52 (11)
C4—C5—H5	119.8	O9—C21—H21A	109.5
C6—C5—H5	119.9	C19—C21—H21A	109.5
C5—C6—C1	119.82 (12)	O9—C21—H21B	109.5
C5—C6—C7	115.63 (11)	C19—C21—H21B	109.5
C1—C6—C7	124.51 (12)	H21A—C21—H21B	108.1
N2—C7—C6	126.81 (12)	O10—C22—C19	112.71 (11)
N2—C7—H7	116.6	O10—C22—H22A	109.0
C6—C7—H7	116.6	C19—C22—H22A	109.0
N2—C8—C10	114.18 (10)	O10—C22—H22B	109.0
N2—C8—C9	107.04 (10)	C19—C22—H22B	109.0
C10—C8—C9	108.81 (10)	H22A—C22—H22B	107.8
O7—Zn1—O1—C1	112.03 (10)	C5—C6—C7—N2	−175.06 (13)
N2—Zn1—O1—C1	14.87 (11)	C1—C6—C7—N2	2.4 (2)
N4—Zn1—O1—C1	−157.87 (11)	C7—N2—C8—C10	−32.67 (16)
O8—Zn1—O1—C1	−80.48 (10)	Zn1—N2—C8—C10	148.33 (9)
O2—Zn1—O1—C1	−2.5 (2)	C7—N2—C8—C9	−153.16 (11)
O7—Zn1—O2—C9	−116.17 (8)	Zn1—N2—C8—C9	27.84 (12)
O1—Zn1—O2—C9	−0.6 (2)	C7—N2—C8—C11	86.83 (13)
N2—Zn1—O2—C9	−18.31 (8)	Zn1—N2—C8—C11	−92.17 (10)
N4—Zn1—O2—C9	154.38 (8)	Zn1—O2—C9—C8	39.50 (12)
O8—Zn1—O2—C9	78.15 (8)	N2—C8—C9—O2	−44.26 (13)
O1—Zn1—O7—C12	103.45 (11)	C10—C8—C9—O2	−168.11 (10)
N2—Zn1—O7—C12	−166.29 (10)	C11—C8—C9—O2	73.15 (13)
N4—Zn1—O7—C12	11.98 (11)	N2—C8—C10—O3	−50.24 (14)
O8—Zn1—O7—C12	−25.4 (2)	C9—C8—C10—O3	69.25 (13)
O2—Zn1—O7—C12	−87.80 (11)	C11—C8—C10—O3	−169.64 (10)
O7—Zn1—O8—C20	76.02 (16)	N2—C8—C11—O4	−177.65 (10)
O1—Zn1—O8—C20	−53.45 (8)	C10—C8—C11—O4	−54.13 (13)
N2—Zn1—O8—C20	−142.95 (8)	C9—C8—C11—O4	65.25 (13)
N4—Zn1—O8—C20	37.51 (8)	Zn1—O7—C12—C13	167.87 (9)
O2—Zn1—O8—C20	138.68 (8)	Zn1—O7—C12—C17	−12.00 (18)
O7—Zn1—N2—C7	−99.37 (11)	O7—C12—C13—C14	−179.56 (12)
O1—Zn1—N2—C7	−1.56 (11)	C17—C12—C13—C14	0.32 (19)
O8—Zn1—N2—C7	90.78 (11)	C12—C13—C14—C15	0.0 (2)
O2—Zn1—N2—C7	174.71 (11)	C13—C14—C15—C16	−0.6 (2)
O7—Zn1—N2—C8	79.54 (9)	C13—C14—C15—N3	178.61 (12)
O1—Zn1—N2—C8	177.35 (9)	O12—N3—C15—C16	3.6 (2)
O8—Zn1—N2—C8	−90.31 (9)	O11—N3—C15—C16	−176.19 (13)
O2—Zn1—N2—C8	−6.38 (8)	O12—N3—C15—C14	−175.59 (13)
O7—Zn1—N4—C18	−4.94 (11)	O11—N3—C15—C14	4.6 (2)
O1—Zn1—N4—C18	−102.78 (11)	C14—C15—C16—C17	0.8 (2)
O8—Zn1—N4—C18	165.09 (11)	N3—C15—C16—C17	−178.35 (12)
O2—Zn1—N4—C18	82.41 (11)	C15—C16—C17—C12	−0.51 (19)
O7—Zn1—N4—C19	179.02 (8)	C15—C16—C17—C18	177.86 (12)
O1—Zn1—N4—C19	81.18 (8)	O7—C12—C17—C16	179.82 (12)
O8—Zn1—N4—C19	−10.95 (8)	C13—C12—C17—C16	−0.06 (18)
O2—Zn1—N4—C19	−93.63 (8)	O7—C12—C17—C18	1.6 (2)
Zn1—O1—C1—C2	159.57 (9)	C13—C12—C17—C18	−178.24 (12)
Zn1—O1—C1—C6	−21.42 (18)	C19—N4—C18—C17	174.09 (12)
O1—C1—C2—C3	172.67 (13)	Zn1—N4—C18—C17	−1.78 (19)
C6—C1—C2—C3	−6.40 (19)	C16—C17—C18—N4	−172.61 (12)
C1—C2—C3—C4	−0.2 (2)	C12—C17—C18—N4	5.6 (2)
C2—C3—C4—C5	5.1 (2)	C18—N4—C19—C21	49.08 (15)
C2—C3—C4—N1	−175.41 (13)	Zn1—N4—C19—C21	−134.64 (9)
O5—N1—C4—C5	178.41 (13)	C18—N4—C19—C20	167.74 (11)
O6—N1—C4—C5	−2.9 (2)	Zn1—N4—C19—C20	−15.98 (12)
O5—N1—C4—C3	−1.1 (2)	C18—N4—C19—C22	−75.30 (14)
O6—N1—C4—C3	177.61 (14)	Zn1—N4—C19—C22	100.98 (10)
C3—C4—C5—C6	−3.1 (2)	Zn1—O8—C20—C19	−57.53 (10)
N1—C4—C5—C6	177.42 (12)	N4—C19—C20—O8	48.97 (13)
C4—C5—C6—C1	−3.77 (19)	C21—C19—C20—O8	170.18 (10)
C4—C5—C6—C7	173.81 (12)	C22—C19—C20—O8	−68.25 (12)
O1—C1—C6—C5	−170.72 (12)	N4—C19—C21—O9	178.03 (10)
C2—C1—C6—C5	8.31 (18)	C20—C19—C21—O9	60.34 (13)
O1—C1—C6—C7	11.9 (2)	C22—C19—C21—O9	−59.19 (14)
C2—C1—C6—C7	−169.05 (12)	N4—C19—C22—O10	70.23 (13)
C8—N2—C7—C6	175.80 (12)	C21—C19—C22—O10	−54.47 (14)
Zn1—N2—C7—C6	−5.30 (19)	C20—C19—C22—O10	−173.93 (10)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2o···O10^i	0.84 (1)	1.85 (1)	2.686 (1)	173 (2)
O3—H3o···O7^ii	0.83 (1)	1.90 (1)	2.687 (1)	158 (2)
O4—H4o···O3w^iii	0.83 (1)	1.94 (1)	2.774 (2)	175 (2)
O8—H8o···O1w	0.83 (1)	1.80 (1)	2.625 (1)	171 (2)
O9—H9o···O4^iv	0.82 (1)	1.83 (1)	2.640 (1)	168 (2)
O10—H10o···O9^v	0.83 (1)	1.87 (1)	2.685 (1)	171 (2)
O1w—H1w1···O2W	0.85 (1)	1.85 (1)	2.702 (2)	173 (2)
O1w—H1w2···O3	0.84 (1)	1.94 (1)	2.780 (2)	174 (2)
O2w—H2w1···O3W	0.86 (1)	2.03 (1)	2.863 (2)	162 (3)
O2w—H2w2···O6^vi	0.86 (1)	2.25 (1)	3.085 (2)	166 (4)
O3w—H3w1···O1^vii	0.85 (1)	2.00 (1)	2.817 (1)	163 (2)
O3w—H3w2···O11^viii	0.85 (1)	2.02 (1)	2.825 (2)	159 (2)

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