catena-Poly[hexa­aqua­zinc(II) bis­[[tri­aquazincate(II)]-μ-(5-carboxyl­ato-m-phenyl­ene­di­oxy)diacetato-κ²O¹:O⁵] hepta­hydrate]

The reaction of zinc cations and (5-carb­oxy-m-phenyl­ene­dioxy)diacetate anions in water yields the title salt, {[Zn(H₂O)₆][Zn(C₁₁H₇O₈)(H₂O)₃]₂·7H₂O}_n. The cation has the Zn atom surrounded octa­hedrally by six water mol­ecules. The anion exists as a linear carboxyl­ate-bridged chain, as it uses the carb­oxy and one of the two oxyacetate arms of the trianion to connect the triaqua­zincate species. The Zn atoms in the two independent polyanionic chains exist in trigonal–bipyramidal geometries. The cation and anions are linked by extensive hydrogen bonds into a three-dimensional network structure.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.030
• wR factor = 0.082
• Data-to-parameter ratio = 14.2

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT420_ALERT_2_B D-H Without Acceptor       O11W   -   H11B   ...          ?

Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.98
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.89
PLAT142_ALERT_4_C su on b - Axis Small or Missing (x 100000) .....         10 Ang.
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)        100 Deg.
PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 =          5
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.07
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.07
PLAT415_ALERT_2_C Short Inter D-H..H-X       H11B   ..  H18     ..       2.10 Ang.
PLAT417_ALERT_2_C Short Inter D-H..H-D       H9B    ..  H18B    ..       2.12 Ang.

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.892
            Tmax scaled      0.892 Tmin scaled      0.710
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           27.48
           From the CIF: _reflns_number_total               7671
           Count of symmetry unique reflns         4596
           Completeness (_total/calc)            166.91%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      3075
           Fraction of Friedel pairs measured     0.669
           Are heavy atom types Z>Si present        yes
PLAT794_ALERT_5_G Check Predicted Bond Valency for Zn1         (2)       1.95
PLAT794_ALERT_5_G Check Predicted Bond Valency for Zn2         (2)       2.01
PLAT794_ALERT_5_G Check Predicted Bond Valency for Zn3         (2)       2.11
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          3

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

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

---

S1. Comment

The reaction of zinc cations and (5-carboxy-m-phenylenedioxy)diacetate anions in water yields the salt, [Zn(H₂O)₆]²⁺ 2[Zn(C₁₁H₇O₈)(H₂O)₃]^-.7H₂O. The cation has the zinc atom surrounded octahedrally by six water molecules. The anion exists as a linear, carboxylate-bridged chain as it uses the carboxy and one of the two oxyacetate arms of the trianion to connect the triaquazinc species. The zinc atom in the two independent polyanionic chains exists in trigonal-bipyramidal geometries. The cation and anions are linked by extensive hydrogen bonds into a three-dimensional network structure.

Related literature

There is currently only one other structure report of a metal (5-carboxy-m-phenylenedioxy)diacetate, namely a cadmium–sodium compound (Wen & Ng, 2007).

S2. Experimental

(5-Carboxy-m-phenylenedioxy)diacetic acid (0.282 g, 1 mol) and zinc nitrate hexahydrate (0.298 g, 1 mmol) were mixed in 20 ml e thanol-water (1:1, v/v) solution. The pH value was adjusted to 7 by sodium carbonate solution. The filtered solution was set aside for the growth of crystals after a week.

S3. Refinement

The water were placed in chemically sensible positions on the basis of hydrogen bonds but they were not refined. Their temperature factors tied to those of the oxygen atoms by a factor of 1.5. The carbon-bound H-atoms were generated geometrically (C—H 0.93 to 0.97 Å); they were included in the refinement in the riding model approximation, with U(H) set to 1.2U_eq(C).

Computing details

Data collection: SMART (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); 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: publCIF (Westrip, 2007).

Figures

Fig. 1. Thermal ellipsoid plot depicting the coordination geometries the zinc atoms of [Zn(H2O)6]^2+2[Zn(C11H7O8)(H2O)3]^-.7H2O; displacement ellipsoids are drawn at the 50% probability level, and H atoms as spheres of arbitrary radius. The lattice water molecules are not shown. [Translational code: (i) x – 1, y, z; (ii) 1 + x, y – 1, z.]

catena-Poly[hexaaquazinc(II) bis[[triaquazincate(II)]-µ-(5-carboxylato-m-phenylenedioxy)diacetato- κ²O¹:O⁵] heptahydrate]

Crystal data

[Zn(H2O)6][Zn(C11H7O8)(H2O)3]2·7H2O	Z = 1
Mr = 1072.75	F(000) = 554
Triclinic, P1	Dx = 1.779 Mg m^−3
Hall symbol: P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.2044 (1) Å	Cell parameters from 9439 reflections
b = 11.2959 (1) Å	θ = 2.8–27.5°
c = 13.6932 (2) Å	µ = 1.90 mm^−1
α = 70.872 (1)°	T = 295 K
β = 76.436 (1)°	Prism, colourless
γ = 74.589 (1)°	0.53 × 0.13 × 0.06 mm
V = 1001.59 (2) Å^3

Data collection

Bruker APEXII area-detector diffractometer	7671 independent reflections
Radiation source: fine-focus sealed tube	7353 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.016
φ and ω scans	θmax = 27.5°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→9
Tmin = 0.796, Tmax = 1.000	k = −14→14
14916 measured reflections	l = −17→17

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)] = 0.030	H-atom parameters constrained
wR(F^2) = 0.082	w = 1/[σ^2(Fo^2) + (0.0617P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
7671 reflections	Δρmax = 0.52 e Å^−3
542 parameters	Δρmin = −0.61 e Å^−3
3 restraints	Absolute structure: Flack (1983), with 3182 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.150 (6)

Special details

Experimental. A somewhat long crystal was used in the measurements as attempts to cut the larger ones ended up shattering the crystal. The growth of crystals could not be easily reproduced either.

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

	x	y	z	Uiso*/Ueq
Zn1	0.50020 (4)	0.49999 (3)	0.50000 (2)	0.02494 (9)
Zn2	1.09107 (4)	−0.01775 (3)	0.75462 (2)	0.02540 (9)
Zn3	0.83895 (6)	−0.22965 (4)	1.16257 (3)	0.03107 (9)
O1	0.6895 (3)	0.4346 (2)	0.38485 (17)	0.0275 (5)
O2	0.8194 (3)	0.2799 (2)	0.51287 (16)	0.0291 (5)
O3	1.1508 (4)	−0.07046 (19)	0.32384 (17)	0.0303 (5)
O4	1.2618 (4)	−0.3575 (2)	0.5234 (2)	0.0387 (6)
O5	1.3998 (4)	−0.2917 (2)	0.3622 (2)	0.0428 (7)
O6	1.0672 (4)	0.3287 (2)	0.06085 (16)	0.0298 (5)
O7	1.1763 (4)	0.3157 (2)	−0.20182 (18)	0.0332 (5)
O8	1.0586 (5)	0.4765 (2)	−0.1298 (2)	0.0483 (8)
O9	0.9041 (3)	0.05406 (19)	0.86500 (17)	0.0273 (5)
O10	0.7751 (4)	0.2131 (2)	0.73999 (16)	0.0305 (5)
O11	0.4494 (4)	0.55586 (19)	0.93352 (17)	0.0276 (5)
O12	0.3162 (4)	0.8365 (2)	0.73159 (19)	0.0320 (5)
O13	0.1907 (4)	0.7768 (2)	0.8983 (2)	0.0422 (6)
O14	0.5828 (4)	0.1589 (2)	1.19514 (16)	0.0293 (5)
O15	0.4309 (4)	0.1582 (2)	1.45986 (17)	0.0312 (5)
O16	0.5407 (5)	0.0034 (2)	1.3813 (2)	0.0493 (8)
O1W	0.4777 (4)	0.3952 (2)	0.65198 (18)	0.0347 (6)
H1A	0.5676	0.3326	0.6757	0.052*
H1B	0.3717	0.3875	0.6949	0.052*
O2W	0.7069 (4)	0.5919 (2)	0.5134 (2)	0.0326 (6)
H2A	0.7899	0.5459	0.5527	0.049*
H2B	0.6719	0.6667	0.5218	0.049*
O3W	0.3050 (4)	0.4050 (2)	0.4675 (2)	0.0353 (6)
H3A	0.2063	0.4105	0.5141	0.053*
H3B	0.3398	0.3315	0.4584	0.053*
O4W	1.1147 (4)	0.0933 (3)	0.60334 (19)	0.0406 (6)
H4A	1.2257	0.0959	0.5653	0.061*
H4B	1.0259	0.1397	0.5683	0.061*
O5W	0.8840 (4)	−0.1083 (3)	0.7440 (3)	0.0451 (7)
H5A	0.9317	−0.1700	0.7174	0.068*
H5B	0.7843	−0.0621	0.7160	0.068*
O6W	1.2974 (4)	0.0640 (3)	0.7922 (2)	0.0358 (6)
H6A	1.2680	0.1351	0.8051	0.054*
H6B	1.4065	0.0546	0.7534	0.054*
O7W	0.5925 (4)	−0.1146 (3)	1.2179 (2)	0.0450 (7)
H7A	0.5077	−0.1567	1.2609	0.068*
H7B	0.6092	−0.0632	1.2471	0.068*
O8W	0.6677 (4)	−0.3664 (2)	1.18827 (19)	0.0334 (5)
H8A	0.6994	−0.4246	1.2439	0.050*
H8B	0.7241	−0.3993	1.1389	0.050*
O9W	0.9205 (5)	−0.3172 (3)	1.3127 (2)	0.0508 (7)
H9A	0.8392	−0.3465	1.3651	0.076*
H9B	1.0280	−0.3705	1.3114	0.076*
O10W	1.0768 (4)	−0.3539 (3)	1.1004 (2)	0.0399 (6)
H10A	1.0713	−0.3919	1.0576	0.060*
H10B	1.1789	−0.3893	1.1285	0.060*
O11W	1.0123 (5)	−0.1048 (3)	1.1442 (2)	0.0496 (8)
H11A	1.0628	−0.1281	1.1997	0.074*
H11B	0.9395	−0.0292	1.1392	0.074*
O12W	0.7652 (4)	−0.1549 (2)	1.01018 (18)	0.0327 (5)
H12A	0.7790	−0.2092	0.9766	0.049*
H12B	0.8172	−0.0931	0.9702	0.049*
O13W	−0.0153 (4)	0.4100 (2)	0.6226 (2)	0.0352 (6)
H13A	0.0081	0.4151	0.6794	0.053*
H13B	−0.0582	0.3411	0.6377	0.053*
O14W	1.5912 (6)	−0.1901 (3)	0.5556 (2)	0.0608 (9)
H14A	1.4965	−0.1913	0.6062	0.091*
H14B	1.5590	−0.1303	0.5022	0.091*
O15W	1.6115 (4)	0.0755 (2)	0.6342 (2)	0.0371 (6)
H15A	1.6390	0.1426	0.6361	0.056*
H15B	1.5541	0.0906	0.5830	0.056*
O16W	0.3399 (5)	−0.0597 (4)	1.0130 (3)	0.0642 (9)
H16A	0.3490	−0.1384	1.0455	0.096*
H16B	0.3618	−0.0500	0.9470	0.096*
O17W	0.9701 (5)	−0.3302 (3)	0.6995 (3)	0.0577 (8)
H17A	1.0121	−0.3888	0.7511	0.087*
H17B	1.0556	−0.3267	0.6449	0.087*
O18W	1.2910 (5)	−0.4540 (3)	1.2606 (3)	0.0584 (8)
H18A	1.3785	−0.4062	1.2377	0.088*
H18B	1.3035	−0.4956	1.3247	0.088*
O19W	0.7759 (4)	0.6085 (3)	0.9927 (2)	0.0436 (6)
H19A	0.6812	0.6080	0.9664	0.065*
H19B	0.8822	0.5733	0.9621	0.065*
C1	0.9180 (4)	0.2574 (3)	0.3402 (2)	0.0189 (6)
C2	0.9824 (4)	0.1244 (3)	0.3748 (2)	0.0223 (6)
H2	0.9591	0.0799	0.4454	0.027*
C3	1.0815 (5)	0.0614 (3)	0.3009 (2)	0.0213 (6)
C4	1.1186 (4)	0.1252 (3)	0.1949 (2)	0.0221 (6)
H4	1.1890	0.0809	0.1468	0.026*
C5	1.0486 (4)	0.2556 (3)	0.1624 (2)	0.0213 (6)
C6	0.9513 (5)	0.3224 (3)	0.2356 (2)	0.0232 (6)
H6	0.9090	0.4108	0.2136	0.028*
C7	0.8031 (4)	0.3279 (3)	0.4184 (2)	0.0201 (6)
C8	1.1374 (5)	−0.1446 (3)	0.4299 (2)	0.0280 (7)
H81	1.0049	−0.1570	0.4575	0.034*
H82	1.1717	−0.1008	0.4713	0.034*
C9	1.2758 (5)	−0.2724 (3)	0.4360 (3)	0.0287 (7)
C10	1.1395 (5)	0.2647 (3)	−0.0181 (2)	0.0228 (6)
H101	1.0651	0.2002	−0.0075	0.027*
H102	1.2750	0.2226	−0.0152	0.027*
C11	1.1210 (5)	0.3627 (3)	−0.1237 (2)	0.0255 (6)
C12	0.7946 (4)	0.1633 (3)	0.8330 (2)	0.0205 (6)
C13	0.6929 (4)	0.2321 (3)	0.9140 (2)	0.0192 (6)
C14	0.6166 (4)	0.3631 (3)	0.8811 (2)	0.0204 (6)
H14	0.6261	0.4068	0.8101	0.024*
C15	0.5266 (5)	0.4270 (3)	0.9558 (2)	0.0203 (6)
C16	0.5108 (5)	0.3619 (3)	1.0628 (2)	0.0216 (6)
H16	0.4486	0.4055	1.1124	0.026*
C17	0.5881 (4)	0.2331 (3)	1.0936 (2)	0.0215 (6)
C18	0.6809 (4)	0.1668 (3)	1.0196 (2)	0.0214 (6)
H18	0.7342	0.0797	1.0410	0.026*
C19	0.4421 (5)	0.6258 (3)	0.8262 (2)	0.0255 (6)
H191	0.3949	0.5789	0.7924	0.031*
H192	0.5716	0.6377	0.7898	0.031*
C20	0.3055 (5)	0.7552 (3)	0.8218 (3)	0.0257 (7)
C21	0.4896 (5)	0.2183 (3)	1.2755 (2)	0.0230 (6)
H211	0.3569	0.2610	1.2651	0.028*
H212	0.5591	0.2818	1.2740	0.028*
C22	0.4887 (5)	0.1164 (3)	1.3797 (2)	0.0262 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.02845 (19)	0.02098 (16)	0.01952 (17)	0.00165 (13)	0.00168 (14)	−0.00723 (13)
Zn2	0.02831 (19)	0.02057 (16)	0.02017 (17)	0.00396 (13)	0.00093 (14)	−0.00687 (13)
Zn3	0.0371 (2)	0.02793 (17)	0.02684 (18)	−0.01000 (14)	0.00251 (14)	−0.00877 (13)
O1	0.0334 (13)	0.0195 (10)	0.0208 (11)	0.0062 (9)	−0.0004 (9)	−0.0062 (9)
O2	0.0397 (14)	0.0252 (11)	0.0163 (11)	0.0034 (9)	−0.0037 (10)	−0.0065 (9)
O3	0.0503 (15)	0.0132 (10)	0.0197 (11)	0.0030 (9)	−0.0022 (10)	−0.0047 (8)
O4	0.0476 (16)	0.0192 (11)	0.0351 (15)	0.0032 (10)	−0.0090 (12)	0.0045 (10)
O5	0.0424 (15)	0.0254 (12)	0.0460 (16)	0.0034 (11)	0.0103 (12)	−0.0114 (11)
O6	0.0452 (14)	0.0215 (10)	0.0134 (10)	0.0004 (9)	0.0024 (9)	−0.0036 (8)
O7	0.0444 (15)	0.0360 (13)	0.0164 (11)	−0.0086 (11)	−0.0006 (10)	−0.0066 (10)
O8	0.084 (2)	0.0280 (14)	0.0199 (13)	−0.0001 (13)	−0.0008 (13)	−0.0032 (10)
O9	0.0327 (12)	0.0171 (10)	0.0193 (11)	0.0057 (9)	0.0029 (9)	−0.0018 (8)
O10	0.0385 (14)	0.0295 (12)	0.0164 (11)	0.0041 (10)	−0.0020 (9)	−0.0077 (9)
O11	0.0410 (14)	0.0171 (10)	0.0186 (10)	0.0053 (9)	−0.0065 (9)	−0.0050 (8)
O12	0.0373 (14)	0.0198 (11)	0.0272 (13)	0.0067 (9)	−0.0037 (11)	−0.0023 (9)
O13	0.0489 (16)	0.0269 (12)	0.0340 (14)	0.0117 (11)	0.0027 (12)	−0.0086 (11)
O14	0.0470 (14)	0.0187 (9)	0.0111 (10)	0.0038 (9)	0.0006 (9)	−0.0017 (8)
O15	0.0392 (14)	0.0345 (12)	0.0169 (11)	−0.0066 (10)	0.0007 (9)	−0.0077 (9)
O16	0.093 (2)	0.0216 (12)	0.0236 (13)	−0.0081 (13)	−0.0045 (14)	0.0007 (10)
O1W	0.0258 (13)	0.0400 (14)	0.0219 (12)	0.0024 (10)	0.0001 (10)	0.0027 (10)
O2W	0.0360 (14)	0.0248 (12)	0.0333 (14)	−0.0025 (10)	−0.0044 (11)	−0.0074 (10)
O3W	0.0371 (15)	0.0339 (13)	0.0348 (14)	−0.0057 (10)	−0.0012 (11)	−0.0141 (11)
O4W	0.0324 (14)	0.0428 (15)	0.0239 (13)	0.0048 (11)	−0.0001 (10)	0.0074 (11)
O5W	0.0414 (17)	0.0362 (15)	0.060 (2)	−0.0015 (12)	−0.0167 (14)	−0.0154 (13)
O6W	0.0339 (14)	0.0367 (13)	0.0378 (14)	−0.0052 (10)	0.0033 (11)	−0.0196 (11)
O7W	0.0497 (17)	0.0349 (14)	0.0484 (17)	−0.0135 (12)	0.0128 (13)	−0.0196 (12)
O8W	0.0423 (14)	0.0256 (12)	0.0296 (13)	−0.0075 (10)	−0.0002 (11)	−0.0078 (10)
O9W	0.0516 (18)	0.0645 (19)	0.0272 (14)	−0.0151 (14)	0.0012 (12)	−0.0038 (13)
O10W	0.0406 (15)	0.0420 (15)	0.0324 (14)	−0.0018 (11)	−0.0030 (11)	−0.0117 (11)
O11W	0.063 (2)	0.0506 (17)	0.0454 (17)	−0.0336 (15)	0.0003 (14)	−0.0165 (14)
O12W	0.0400 (14)	0.0274 (11)	0.0269 (12)	−0.0050 (9)	0.0011 (10)	−0.0088 (9)
O13W	0.0367 (14)	0.0407 (14)	0.0301 (13)	−0.0129 (11)	−0.0093 (11)	−0.0060 (11)
O14W	0.101 (3)	0.0296 (14)	0.0300 (15)	0.0064 (15)	0.0015 (16)	−0.0034 (12)
O15W	0.0386 (15)	0.0384 (14)	0.0353 (14)	−0.0088 (11)	−0.0077 (11)	−0.0098 (11)
O16W	0.055 (2)	0.086 (2)	0.0464 (18)	−0.0137 (18)	−0.0028 (15)	−0.0156 (17)
O17W	0.082 (2)	0.0383 (16)	0.0396 (17)	0.0001 (15)	−0.0097 (16)	−0.0034 (13)
O18W	0.058 (2)	0.064 (2)	0.0541 (19)	−0.0144 (15)	−0.0220 (15)	−0.0067 (15)
O19W	0.0484 (16)	0.0448 (15)	0.0449 (16)	−0.0082 (12)	−0.0049 (12)	−0.0251 (12)
C1	0.0202 (15)	0.0184 (13)	0.0162 (13)	0.0018 (10)	−0.0030 (11)	−0.0068 (11)
C2	0.0277 (16)	0.0172 (13)	0.0181 (14)	0.0000 (11)	−0.0027 (12)	−0.0041 (11)
C3	0.0257 (16)	0.0150 (13)	0.0196 (14)	−0.0007 (11)	−0.0042 (12)	−0.0026 (11)
C4	0.0246 (16)	0.0215 (14)	0.0179 (14)	0.0005 (11)	−0.0008 (12)	−0.0086 (11)
C5	0.0248 (16)	0.0202 (13)	0.0156 (13)	−0.0018 (11)	−0.0046 (11)	−0.0021 (10)
C6	0.0313 (17)	0.0156 (12)	0.0196 (14)	−0.0010 (11)	−0.0039 (12)	−0.0039 (11)
C7	0.0235 (15)	0.0155 (12)	0.0166 (14)	0.0007 (11)	0.0017 (11)	−0.0058 (11)
C8	0.0371 (19)	0.0176 (14)	0.0206 (15)	0.0016 (12)	−0.0016 (13)	−0.0019 (12)
C9	0.0315 (18)	0.0187 (15)	0.0320 (19)	−0.0011 (12)	−0.0038 (15)	−0.0061 (13)
C10	0.0281 (16)	0.0219 (14)	0.0155 (14)	−0.0012 (11)	−0.0019 (11)	−0.0057 (11)
C11	0.0295 (17)	0.0266 (15)	0.0168 (14)	−0.0059 (12)	0.0011 (12)	−0.0046 (12)
C12	0.0221 (15)	0.0179 (13)	0.0166 (14)	−0.0035 (11)	0.0014 (11)	−0.0022 (11)
C13	0.0197 (15)	0.0183 (13)	0.0160 (13)	0.0000 (10)	−0.0013 (11)	−0.0045 (11)
C14	0.0242 (15)	0.0179 (13)	0.0142 (13)	−0.0010 (11)	−0.0033 (11)	−0.0009 (10)
C15	0.0249 (15)	0.0146 (13)	0.0198 (14)	−0.0003 (11)	−0.0043 (11)	−0.0052 (11)
C16	0.0279 (16)	0.0177 (13)	0.0176 (13)	−0.0003 (11)	−0.0027 (11)	−0.0071 (11)
C17	0.0235 (15)	0.0213 (14)	0.0166 (13)	−0.0021 (11)	−0.0024 (11)	−0.0036 (11)
C18	0.0221 (15)	0.0167 (13)	0.0192 (14)	0.0041 (11)	−0.0022 (11)	−0.0041 (11)
C19	0.0325 (18)	0.0150 (13)	0.0209 (15)	0.0051 (11)	−0.0050 (13)	−0.0019 (11)
C20	0.0322 (18)	0.0155 (13)	0.0264 (17)	−0.0011 (12)	−0.0060 (14)	−0.0042 (12)
C21	0.0272 (16)	0.0222 (14)	0.0171 (14)	−0.0011 (11)	−0.0001 (12)	−0.0079 (11)
C22	0.0289 (17)	0.0281 (16)	0.0182 (15)	−0.0058 (13)	−0.0031 (12)	−0.0025 (12)

Geometric parameters (Å, º)

Zn1—O1W	2.022 (2)	O9W—H9A	0.85
Zn1—O1	2.028 (2)	O9W—H9B	0.85
Zn1—O4^i	2.063 (3)	O10W—H10A	0.85
Zn1—O2W	2.099 (3)	O10W—H10B	0.85
Zn1—O3W	2.176 (3)	O11W—H11A	0.85
Zn2—O9	2.006 (2)	O11W—H11B	0.87
Zn2—O12^ii	2.030 (2)	O12W—H12A	0.85
Zn2—O4W	2.034 (2)	O12W—H12B	0.85
Zn2—O5W	2.075 (3)	O13W—H13A	0.86
Zn2—O6W	2.174 (3)	O13W—H13B	0.86
Zn3—O11W	2.042 (3)	O14W—H14A	0.85
Zn3—O7W	2.050 (3)	O14W—H14B	0.85
Zn3—O10W	2.110 (3)	O15W—H15A	0.84
Zn3—O9W	2.115 (3)	O15W—H15B	0.84
Zn3—O12W	2.116 (2)	O16W—H16A	0.85
Zn3—O8W	2.118 (2)	O16W—H16B	0.86
O1—C7	1.274 (4)	O17W—H17A	0.85
O2—C7	1.249 (4)	O17W—H17B	0.85
O3—C3	1.392 (3)	O18W—H18A	0.87
O3—C8	1.414 (4)	O18W—H18B	0.86
O4—C9	1.268 (4)	O19W—H19A	0.85
O4—Zn1^ii	2.063 (3)	O19W—H19B	0.85
O5—C9	1.218 (4)	C1—C6	1.375 (4)
O6—C5	1.361 (4)	C1—C2	1.401 (4)
O6—C10	1.418 (3)	C1—C7	1.503 (4)
O7—C11	1.283 (4)	C2—C3	1.380 (4)
O8—C11	1.225 (4)	C2—H2	0.9300
O9—C12	1.275 (4)	C3—C4	1.390 (4)
O10—C12	1.237 (4)	C4—C5	1.380 (4)
O11—C15	1.371 (3)	C4—H4	0.9300
O11—C19	1.429 (4)	C5—C6	1.396 (4)
O12—C20	1.274 (4)	C6—H6	0.9300
O12—Zn2^i	2.030 (2)	C8—C9	1.510 (4)
O13—C20	1.224 (4)	C8—H81	0.9700
O14—C17	1.365 (4)	C8—H82	0.9700
O14—C21	1.418 (3)	C10—C11	1.515 (4)
O15—C22	1.273 (4)	C10—H101	0.9700
O16—C22	1.226 (4)	C10—H102	0.9700
O1W—H1A	0.85	C12—C13	1.502 (4)
O1W—H1B	0.85	C13—C18	1.385 (4)
O2W—H2A	0.85	C13—C14	1.393 (4)
O2W—H2B	0.85	C14—C15	1.383 (4)
O3W—H3A	0.84	C14—H14	0.9300
O3W—H3B	0.84	C15—C16	1.400 (4)
O4W—H4A	0.85	C16—C17	1.372 (4)
O4W—H4B	0.85	C16—H16	0.9300
O5W—H5A	0.85	C17—C18	1.395 (4)
O5W—H5B	0.86	C18—H18	0.9300
O6W—H6A	0.84	C19—C20	1.521 (4)
O6W—H6B	0.84	C19—H191	0.9700
O7W—H7A	0.87	C19—H192	0.9700
O7W—H7B	0.85	C21—C22	1.512 (4)
O8W—H8A	0.86	C21—H211	0.9700
O8W—H8B	0.85	C21—H212	0.9700
O1W—Zn1—O1	122.32 (9)	H16A—O16W—H16B	109.5
O1W—Zn1—O4^i	95.06 (10)	H17A—O17W—H17B	110.7
O1—Zn1—O4^i	141.81 (10)	H18A—O18W—H18B	106.2
O1W—Zn1—O2W	93.32 (11)	H19A—O19W—H19B	110.3
O1—Zn1—O2W	90.19 (10)	C6—C1—C2	120.8 (3)
O4^i—Zn1—O2W	95.59 (10)	C6—C1—C7	120.1 (3)
O1W—Zn1—O3W	92.18 (11)	C2—C1—C7	119.1 (3)
O1—Zn1—O3W	83.45 (10)	C3—C2—C1	117.9 (3)
O4^i—Zn1—O3W	87.95 (11)	C3—C2—H2	121.0
O2W—Zn1—O3W	173.18 (10)	C1—C2—H2	121.0
O9—Zn2—O12^ii	143.70 (9)	C2—C3—C4	122.3 (3)
O9—Zn2—O4W	118.87 (10)	C2—C3—O3	124.1 (3)
O12^ii—Zn2—O4W	96.70 (10)	C4—C3—O3	113.6 (2)
O9—Zn2—O5W	90.34 (11)	C5—C4—C3	118.6 (3)
O12^ii—Zn2—O5W	93.23 (11)	C5—C4—H4	120.7
O4W—Zn2—O5W	95.78 (12)	C3—C4—H4	120.7
O9—Zn2—O6W	83.78 (9)	O6—C5—C4	124.6 (3)
O12^ii—Zn2—O6W	87.55 (10)	O6—C5—C6	115.0 (2)
O4W—Zn2—O6W	93.03 (12)	C4—C5—C6	120.3 (3)
O5W—Zn2—O6W	171.00 (12)	C1—C6—C5	120.0 (3)
O11W—Zn3—O7W	93.29 (12)	C1—C6—H6	120.0
O11W—Zn3—O10W	91.01 (12)	C5—C6—H6	120.0
O7W—Zn3—O10W	175.05 (13)	O2—C7—O1	122.6 (3)
O11W—Zn3—O9W	85.82 (13)	O2—C7—C1	119.6 (3)
O7W—Zn3—O9W	92.96 (13)	O1—C7—C1	117.8 (3)
O10W—Zn3—O9W	89.80 (11)	O3—C8—C9	108.5 (3)
O11W—Zn3—O12W	96.39 (11)	O3—C8—H81	110.0
O7W—Zn3—O12W	90.34 (11)	C9—C8—H81	110.0
O10W—Zn3—O12W	86.74 (10)	O3—C8—H82	110.0
O9W—Zn3—O12W	175.92 (12)	C9—C8—H82	110.0
O11W—Zn3—O8W	176.81 (13)	H81—C8—H82	108.4
O7W—Zn3—O8W	87.98 (10)	O5—C9—O4	121.4 (3)
O10W—Zn3—O8W	87.86 (10)	O5—C9—C8	122.0 (3)
O9W—Zn3—O8W	91.18 (11)	O4—C9—C8	116.6 (3)
O12W—Zn3—O8W	86.53 (10)	O6—C10—C11	108.4 (2)
C7—O1—Zn1	113.75 (19)	O6—C10—H101	110.0
C3—O3—C8	118.9 (2)	C11—C10—H101	110.0
C9—O4—Zn1^ii	102.3 (2)	O6—C10—H102	110.0
C5—O6—C10	117.7 (2)	C11—C10—H102	110.0
C12—O9—Zn2	116.53 (19)	H101—C10—H102	108.4
C15—O11—C19	117.6 (2)	O8—C11—O7	125.1 (3)
C20—O12—Zn2^i	102.0 (2)	O8—C11—C10	120.5 (3)
C17—O14—C21	118.0 (2)	O7—C11—C10	114.4 (3)
Zn1—O1W—H1A	122.6	O10—C12—O9	122.7 (3)
Zn1—O1W—H1B	125.9	O10—C12—C13	120.7 (3)
H1A—O1W—H1B	108.2	O9—C12—C13	116.5 (3)
Zn1—O2W—H2A	115.8	C18—C13—C14	120.8 (3)
Zn1—O2W—H2B	120.4	C18—C13—C12	120.3 (2)
H2A—O2W—H2B	109.8	C14—C13—C12	118.8 (3)
Zn1—O3W—H3A	104.6	C15—C14—C13	118.8 (3)
Zn1—O3W—H3B	123.5	C15—C14—H14	120.6
H3A—O3W—H3B	112.1	C13—C14—H14	120.6
Zn2—O4W—H4A	120.5	O11—C15—C14	124.3 (3)
Zn2—O4W—H4B	129.4	O11—C15—C16	114.6 (2)
H4A—O4W—H4B	110.1	C14—C15—C16	121.0 (3)
Zn2—O5W—H5A	113.7	C17—C16—C15	119.3 (3)
Zn2—O5W—H5B	118.3	C17—C16—H16	120.3
H5A—O5W—H5B	109.0	C15—C16—H16	120.3
Zn2—O6W—H6A	123.4	O14—C17—C16	125.0 (3)
Zn2—O6W—H6B	111.8	O14—C17—C18	114.3 (3)
H6A—O6W—H6B	111.5	C16—C17—C18	120.7 (3)
Zn3—O7W—H7A	113.4	C13—C18—C17	119.3 (3)
Zn3—O7W—H7B	116.6	C13—C18—H18	120.3
H7A—O7W—H7B	107.0	C17—C18—H18	120.3
Zn3—O8W—H8A	104.7	O11—C19—C20	108.5 (2)
Zn3—O8W—H8B	100.3	O11—C19—H191	110.0
H8A—O8W—H8B	104.5	C20—C19—H191	110.0
Zn3—O9W—H9A	121.0	O11—C19—H192	110.0
Zn3—O9W—H9B	112.6	C20—C19—H192	110.0
H9A—O9W—H9B	110.3	H191—C19—H192	108.4
Zn3—O10W—H10A	124.6	O13—C20—O12	123.3 (3)
Zn3—O10W—H10B	123.1	O13—C20—C19	122.1 (3)
H10A—O10W—H10B	109.9	O12—C20—C19	114.5 (3)
Zn3—O11W—H11A	107.3	O14—C21—C22	108.5 (2)
Zn3—O11W—H11B	108.5	O14—C21—H211	110.0
H11A—O11W—H11B	108.0	C22—C21—H211	110.0
Zn3—O12W—H12A	116.3	O14—C21—H212	110.0
Zn3—O12W—H12B	115.6	C22—C21—H212	110.0
H12A—O12W—H12B	108.5	H211—C21—H212	108.4
H13A—O13W—H13B	107.3	O16—C22—O15	125.6 (3)
H14A—O14W—H14B	109.8	O16—C22—C21	119.3 (3)
H15A—O15W—H15B	110.8	O15—C22—C21	115.2 (3)
O1W—Zn1—O1—C7	−6.0 (3)	O3—C8—C9—O4	−170.1 (3)
O4^i—Zn1—O1—C7	−172.6 (2)	C5—O6—C10—C11	172.2 (3)
O2W—Zn1—O1—C7	88.0 (2)	O6—C10—C11—O8	2.4 (4)
O3W—Zn1—O1—C7	−94.4 (2)	O6—C10—C11—O7	−177.9 (3)
O12^ii—Zn2—O9—C12	173.6 (2)	Zn2—O9—C12—O10	13.3 (4)
O4W—Zn2—O9—C12	6.3 (3)	Zn2—O9—C12—C13	−164.87 (19)
O5W—Zn2—O9—C12	−90.5 (2)	O10—C12—C13—C18	166.3 (3)
O6W—Zn2—O9—C12	96.3 (2)	O9—C12—C13—C18	−15.5 (4)
C6—C1—C2—C3	0.7 (5)	O10—C12—C13—C14	−15.7 (4)
C7—C1—C2—C3	177.7 (3)	O9—C12—C13—C14	162.5 (3)
C1—C2—C3—C4	0.0 (5)	C18—C13—C14—C15	−0.7 (5)
C1—C2—C3—O3	−178.9 (3)	C12—C13—C14—C15	−178.7 (3)
C8—O3—C3—C2	−6.6 (5)	C19—O11—C15—C14	7.4 (5)
C8—O3—C3—C4	174.4 (3)	C19—O11—C15—C16	−173.6 (3)
C2—C3—C4—C5	−1.9 (5)	C13—C14—C15—O11	178.7 (3)
O3—C3—C4—C5	177.1 (3)	C13—C14—C15—C16	−0.3 (5)
C10—O6—C5—C4	9.0 (5)	O11—C15—C16—C17	−178.3 (3)
C10—O6—C5—C6	−171.2 (3)	C14—C15—C16—C17	0.8 (5)
C3—C4—C5—O6	−177.1 (3)	C21—O14—C17—C16	0.4 (5)
C3—C4—C5—C6	3.1 (5)	C21—O14—C17—C18	−179.5 (3)
C2—C1—C6—C5	0.6 (5)	C15—C16—C17—O14	179.8 (3)
C7—C1—C6—C5	−176.4 (3)	C15—C16—C17—C18	−0.3 (5)
O6—C5—C6—C1	177.7 (3)	C14—C13—C18—C17	1.2 (5)
C4—C5—C6—C1	−2.5 (5)	C12—C13—C18—C17	179.1 (3)
Zn1—O1—C7—O2	−11.9 (4)	O14—C17—C18—C13	179.2 (3)
Zn1—O1—C7—C1	167.1 (2)	C16—C17—C18—C13	−0.7 (5)
C6—C1—C7—O2	−159.5 (3)	C15—O11—C19—C20	165.0 (3)
C2—C1—C7—O2	23.4 (4)	Zn2^i—O12—C20—O13	−5.1 (4)
C6—C1—C7—O1	21.5 (4)	Zn2^i—O12—C20—C19	172.5 (2)
C2—C1—C7—O1	−155.5 (3)	O11—C19—C20—O13	−15.8 (4)
C3—O3—C8—C9	−162.0 (3)	O11—C19—C20—O12	166.5 (3)
Zn1^ii—O4—C9—O5	5.4 (4)	C17—O14—C21—C22	175.8 (3)
Zn1^ii—O4—C9—C8	−171.9 (2)	O14—C21—C22—O16	−8.7 (4)
O3—C8—C9—O5	12.7 (5)	O14—C21—C22—O15	171.7 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1A···O10	0.85	1.90	2.742 (3)	170
O1W—H1B···O7^iii	0.85	1.89	2.711 (3)	162
O2W—H2A···O13W^iv	0.85	1.94	2.769 (4)	165
O2W—H2B···O14W^i	0.85	1.74	2.591 (4)	173
O3W—H3A···O13W	0.84	1.91	2.747 (4)	176
O3W—H3B···O15^v	0.84	1.89	2.722 (3)	171
O4W—H4A···O15^vi	0.85	1.91	2.726 (3)	161
O4W—H4B···O2	0.85	1.95	2.765 (3)	163
O5W—H5A···O17W	0.85	1.84	2.651 (4)	159
O5W—H5B···O15W^vii	0.86	1.93	2.756 (4)	163
O6W—H6A···O7^viii	0.84	1.95	2.767 (4)	164
O6W—H6B···O15W	0.84	1.92	2.737 (4)	162
O7W—H7A···O5^iii	0.87	1.90	2.726 (4)	161
O7W—H7B···O16	0.85	2.12	2.868 (4)	147
O8W—H8A···O1^ix	0.86	2.06	2.893 (3)	163
O8W—H8B···O19W^x	0.85	1.93	2.694 (4)	151
O9W—H9A···O2W^ix	0.85	2.01	2.825 (4)	162
O9W—H9B···O18W	0.85	1.96	2.768 (5)	161
O10W—H10B···O18W	0.85	1.99	2.739 (4)	146
O11W—H11A···O3^viii	0.85	2.27	3.029 (4)	148
O11W—H11A···O3^viii	0.85	2.27	3.029 (4)	148
O12W—H12A···O19W^x	0.85	2.00	2.740 (3)	144
O12W—H12B···O9	0.85	1.95	2.788 (3)	171
O13W—H13A···O7^iii	0.86	2.09	2.814 (3)	142
O13W—H13B···O10^vii	0.86	2.07	2.849 (3)	150
O14W—H14A···O12^ii	0.85	1.96	2.782 (4)	164
O14W—H14B···O16^vi	0.85	1.84	2.678 (4)	168
O15W—H15A···O2^iv	0.84	2.30	2.914 (3)	131
O15W—H15B···O15^vi	0.84	1.93	2.759 (4)	169
O16W—H16B···O6W^vii	0.86	2.17	2.937 (5)	149
O17W—H17A···O8^ix	0.85	1.86	2.693 (4)	170
O17W—H17B···O4	0.85	2.01	2.845 (4)	168
O18W—H18A···O8W^iv	0.87	2.15	2.975 (4)	156
O18W—H18B···O3W^xi	0.86	1.91	2.769 (4)	173
O19W—H19A···O11	0.85	2.10	2.915 (4)	164
O19W—H19B···O8^viii	0.85	1.95	2.759 (4)	159

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