Two new Cd^II and Zn^II coordination polymers incorporating 1-amino­benzene-3,4,5-tri­carb­oxy­lic acid: synthesis, crystal structure and characterization

Amino­benzoic acid derivatives are widely used in the preparation of new coordination polymers since they contain O-atom donors, as well as N-atom donors, and have a rich variety of coordination modes which can lead to polymers with intriguing structures and inter­esting properties. Two new coordination polymers incorporating 1-amino­benzene-3,4,5-tri­carb­oxy­lic acid (H₃abtc), namely, poly[(μ₃-1-amino-5-carb­oxy­benzene-3,4-di­carboxyl­ato)di­aqua­cadmium(II)], [Cd(C₉H₅NO₆)(H₂O)₂]_n, (I), and poly[[bis­(μ₅-1-amino­benzene-3,4,5-tri­carboxyl­ato)tri­aquatrizinc(II)] dihydrate], {[Zn₃(C₉H₄NO₆)₂(H₂O)₃]·2H₂O}_n, (II), have been prepared and structurally characterized by single-crystal X-ray diffraction. In polymer (I), each tridentate 1-amino-5-carb­oxy­benzene-3,4-di­carboxyl­ate (Habtc²⁻) ligand coordinates to three Cd^II ions to form a two-dimensional network structure, in which all of the Cd^II ions and Habtc²⁻ ligands are equivalent, respectively. Polymer (II) also exhibits a two-dimensional network structure, in which three crystallographically independent Zn^II ions are bridged by two crystallographically independent penta­dentate 1-amino­benzene-3,4,5-tri­carboxyl­ate (abtc³⁻) ligands. This indicates that changing the metal ion can influence the coordination mode of the H₃abtc-derived ligand and further influence the detailed architecture of the polymer. Moreover, the IR spectra, thermogravimetric analyses and fluorescence properties were investigated.

Computing details

For both structures, data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: publCIF (Westrip, 2010).

Poly[(µ₃-1-amino-5-carboxybenzene-3,4-dicarboxylato)diaquacadmium(II)] (I)

Crystal data

[Cd(C9H5NO6)(H2O)2]	F(000) = 728
Mr = 371.57	Dx = 2.373 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.0872 (7) Å	Cell parameters from 9796 reflections
b = 8.4024 (9) Å	θ = 2.7–27.6°
c = 17.4973 (17) Å	µ = 2.14 mm^−1
β = 93.608 (3)°	T = 293 K
V = 1039.89 (18) Å^3	Block, colorless
Z = 4	0.12 × 0.11 × 0.11 mm

Data collection

Bruker D8 VENTURE PHOTON diffractometer	2274 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.025
φ and ω scans	θmax = 27.6°, θmin = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2016)	h = −9→9
	k = −10→10
44567 measured reflections	l = −22→22
2408 independent reflections

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)] = 0.017	Hydrogen site location: mixed
wR(F^2) = 0.047	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0259P)^2 + 1.2021P] where P = (Fo^2 + 2Fc^2)/3
2408 reflections	(Δ/σ)max = 0.001
172 parameters	Δρmax = 0.89 e Å^−3
0 restraints	Δρmin = −0.68 e Å^−3

Special details

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

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

	x	y	z	Uiso*/Ueq
Cd1	0.53243 (2)	0.03978 (2)	0.30278 (2)	0.01334 (6)
O1	0.0986 (2)	0.59398 (18)	0.69228 (8)	0.0211 (3)
O2	0.0667 (2)	0.33526 (17)	0.67775 (8)	0.0190 (3)
O3	0.40891 (18)	0.17638 (16)	0.62236 (7)	0.0147 (3)
O4	0.14838 (19)	0.08829 (16)	0.55573 (8)	0.0167 (3)
O5	0.4505 (2)	0.12327 (17)	0.44511 (8)	0.0233 (3)
H5	0.487487	0.140032	0.489727	0.035*
O6	0.3975 (2)	0.26649 (18)	0.34159 (8)	0.0242 (3)
O7	0.2199 (2)	−0.05433 (19)	0.28082 (9)	0.0235 (3)
H7A	0.196320	−0.115065	0.242545	0.035*
H7B	0.127630	0.010385	0.279785	0.035*
O8	0.8638 (2)	0.08840 (18)	0.31563 (9)	0.0224 (3)
H8A	0.908445	0.052979	0.358542	0.034*
H8B	0.883435	0.188109	0.318042	0.034*
N1	0.2275 (2)	0.81742 (18)	0.43778 (9)	0.0133 (3)
H1A	0.114644	0.857017	0.448851	0.016*
H1B	0.234974	0.816377	0.386591	0.016*
C1	0.2378 (2)	0.6560 (2)	0.46868 (10)	0.0105 (3)
C2	0.1783 (2)	0.6330 (2)	0.54118 (10)	0.0118 (3)
H2	0.132091	0.718635	0.568021	0.014*
C3	0.1866 (3)	0.4828 (2)	0.57476 (10)	0.0108 (3)
C4	0.2562 (2)	0.3535 (2)	0.53438 (10)	0.0095 (3)
C5	0.3117 (2)	0.3786 (2)	0.45945 (10)	0.0100 (3)
C6	0.3032 (3)	0.5305 (2)	0.42715 (10)	0.0114 (3)
H6	0.341570	0.546872	0.377895	0.014*
C7	0.1135 (3)	0.4673 (2)	0.65348 (10)	0.0125 (3)
C8	0.2718 (3)	0.1911 (2)	0.57353 (10)	0.0120 (3)
C9	0.3905 (2)	0.2459 (2)	0.41315 (10)	0.0124 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.01794 (8)	0.01286 (8)	0.00962 (8)	0.00230 (5)	0.00405 (5)	−0.00012 (5)
O1	0.0387 (8)	0.0137 (7)	0.0121 (6)	−0.0006 (6)	0.0103 (6)	−0.0013 (5)
O2	0.0288 (7)	0.0147 (7)	0.0143 (6)	−0.0026 (6)	0.0082 (6)	0.0022 (5)
O3	0.0152 (6)	0.0148 (6)	0.0141 (6)	0.0024 (5)	0.0001 (5)	0.0041 (5)
O4	0.0180 (6)	0.0121 (6)	0.0200 (7)	−0.0017 (5)	0.0009 (5)	0.0010 (5)
O5	0.0374 (8)	0.0146 (7)	0.0182 (7)	0.0096 (6)	0.0036 (6)	0.0001 (6)
O6	0.0415 (9)	0.0206 (7)	0.0112 (6)	0.0129 (7)	0.0066 (6)	−0.0012 (6)
O7	0.0213 (7)	0.0292 (8)	0.0200 (7)	−0.0027 (6)	0.0005 (6)	−0.0075 (6)
O8	0.0282 (8)	0.0162 (7)	0.0230 (7)	−0.0027 (6)	0.0023 (6)	0.0024 (6)
N1	0.0166 (7)	0.0101 (7)	0.0137 (7)	0.0025 (6)	0.0048 (6)	0.0038 (6)
C1	0.0111 (8)	0.0083 (8)	0.0121 (8)	0.0004 (6)	0.0005 (6)	0.0021 (6)
C2	0.0137 (8)	0.0107 (8)	0.0112 (8)	0.0013 (6)	0.0025 (6)	−0.0013 (6)
C3	0.0119 (8)	0.0121 (8)	0.0084 (8)	−0.0007 (6)	0.0016 (6)	0.0000 (6)
C4	0.0095 (7)	0.0095 (8)	0.0095 (8)	0.0000 (6)	0.0001 (6)	0.0010 (6)
C5	0.0102 (7)	0.0100 (8)	0.0098 (8)	0.0012 (6)	0.0009 (6)	−0.0012 (6)
C6	0.0123 (8)	0.0135 (9)	0.0085 (8)	0.0007 (6)	0.0025 (6)	0.0011 (6)
C7	0.0126 (8)	0.0161 (9)	0.0089 (8)	0.0014 (7)	0.0022 (6)	0.0012 (7)
C8	0.0142 (8)	0.0109 (8)	0.0114 (8)	0.0019 (6)	0.0059 (6)	0.0009 (7)
C9	0.0128 (8)	0.0121 (8)	0.0125 (8)	0.0005 (7)	0.0028 (6)	−0.0022 (7)

Geometric parameters (Å, º)

Cd1—O6	2.2553 (14)	O8—H8A	0.8501
Cd1—O3^i	2.2625 (13)	O8—H8B	0.8499
Cd1—O1^ii	2.3098 (14)	N1—C1	1.460 (2)
Cd1—O7	2.3603 (16)	N1—H1A	0.8989
Cd1—O8	2.3801 (15)	N1—H1B	0.9006
Cd1—O2^ii	2.4524 (14)	C1—C2	1.375 (2)
Cd1—C7^ii	2.7105 (18)	C1—C6	1.378 (2)
O1—C7	1.271 (2)	C2—C3	1.392 (3)
O2—C7	1.241 (2)	C2—H2	0.9300
O3—C8	1.259 (2)	C3—C4	1.403 (2)
O4—C8	1.255 (2)	C3—C7	1.507 (2)
O5—C9	1.235 (2)	C4—C5	1.408 (2)
O5—H5	0.8200	C4—C8	1.527 (2)
O6—C9	1.268 (2)	C5—C6	1.396 (2)
O7—H7A	0.8501	C5—C9	1.506 (2)
O7—H7B	0.8499	C6—H6	0.9300
O6—Cd1—O3^i	124.73 (5)	C1—N1—H1B	110.8
O6—Cd1—O1^ii	140.83 (5)	H1A—N1—H1B	109.1
O3^i—Cd1—O1^ii	93.12 (5)	C2—C1—C6	120.79 (16)
O6—Cd1—O7	85.45 (6)	C2—C1—N1	117.45 (16)
O3^i—Cd1—O7	87.80 (5)	C6—C1—N1	121.76 (16)
O1^ii—Cd1—O7	86.48 (5)	C1—C2—C3	120.63 (16)
O6—Cd1—O8	105.13 (6)	C1—C2—H2	119.7
O3^i—Cd1—O8	86.49 (5)	C3—C2—H2	119.7
O1^ii—Cd1—O8	84.92 (5)	C2—C3—C4	119.79 (16)
O7—Cd1—O8	169.41 (5)	C2—C3—C7	117.16 (16)
O6—Cd1—O2^ii	88.54 (5)	C4—C3—C7	123.03 (16)
O3^i—Cd1—O2^ii	146.65 (5)	C3—C4—C5	118.72 (16)
O1^ii—Cd1—O2^ii	54.90 (5)	C3—C4—C8	118.95 (15)
O7—Cd1—O2^ii	98.20 (5)	C5—C4—C8	122.33 (15)
O8—Cd1—O2^ii	81.86 (5)	C6—C5—C4	120.44 (16)
O6—Cd1—C7^ii	115.36 (5)	C6—C5—C9	117.83 (15)
O3^i—Cd1—C7^ii	119.87 (5)	C4—C5—C9	121.66 (16)
O1^ii—Cd1—C7^ii	27.88 (5)	C1—C6—C5	119.59 (16)
O7—Cd1—C7^ii	95.13 (5)	C1—C6—H6	120.2
O8—Cd1—C7^ii	80.04 (5)	C5—C6—H6	120.2
O2^ii—Cd1—C7^ii	27.22 (5)	O2—C7—O1	122.23 (17)
C7—O1—Cd1^iii	93.88 (11)	O2—C7—C3	120.32 (16)
C7—O2—Cd1^iii	88.06 (11)	O1—C7—C3	117.42 (16)
C8—O3—Cd1^i	125.28 (12)	O2—C7—Cd1^iii	64.72 (10)
C9—O5—H5	111.6	O1—C7—Cd1^iii	58.24 (10)
C9—O6—Cd1	103.05 (12)	C3—C7—Cd1^iii	171.27 (13)
Cd1—O7—H7A	117.7	O4—C8—O3	126.66 (17)
Cd1—O7—H7B	120.1	O4—C8—C4	118.29 (16)
H7A—O7—H7B	104.7	O3—C8—C4	115.03 (16)
Cd1—O8—H8A	109.5	O5—C9—O6	121.81 (17)
Cd1—O8—H8B	109.4	O5—C9—C5	120.17 (16)
H8A—O8—H8B	104.5	O6—C9—C5	117.99 (16)
C1—N1—H1A	106.7
C6—C1—C2—C3	1.3 (3)	Cd1^iii—O1—C7—O2	10.3 (2)
N1—C1—C2—C3	−179.04 (16)	Cd1^iii—O1—C7—C3	−171.28 (14)
C1—C2—C3—C4	0.0 (3)	C2—C3—C7—O2	159.58 (18)
C1—C2—C3—C7	−178.34 (16)	C4—C3—C7—O2	−18.7 (3)
C2—C3—C4—C5	−1.6 (3)	C2—C3—C7—O1	−18.9 (3)
C7—C3—C4—C5	176.58 (16)	C4—C3—C7—O1	162.83 (18)
C2—C3—C4—C8	177.48 (16)	Cd1^i—O3—C8—O4	−2.7 (3)
C7—C3—C4—C8	−4.3 (3)	Cd1^i—O3—C8—C4	175.88 (10)
C3—C4—C5—C6	2.1 (3)	C3—C4—C8—O4	102.6 (2)
C8—C4—C5—C6	−177.02 (16)	C5—C4—C8—O4	−78.4 (2)
C3—C4—C5—C9	179.02 (16)	C3—C4—C8—O3	−76.2 (2)
C8—C4—C5—C9	−0.1 (3)	C5—C4—C8—O3	102.9 (2)
C2—C1—C6—C5	−0.9 (3)	Cd1—O6—C9—O5	0.1 (2)
N1—C1—C6—C5	179.49 (16)	Cd1—O6—C9—C5	178.32 (13)
C4—C5—C6—C1	−0.8 (3)	C6—C5—C9—O5	159.62 (18)
C9—C5—C6—C1	−177.90 (16)	C4—C5—C9—O5	−17.4 (3)
Cd1^iii—O2—C7—O1	−9.63 (19)	C6—C5—C9—O6	−18.6 (3)
Cd1^iii—O2—C7—C3	171.95 (16)	C4—C5—C9—O6	164.38 (17)

Symmetry codes: (i) −x+1, −y, −z+1; (ii) x+1/2, −y+1/2, z−1/2; (iii) x−1/2, −y+1/2, z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5···O3	0.82	2.44	3.165 (2)	148
O7—H7A···O6^iv	0.85	1.86	2.706 (2)	170
O7—H7B···O8^v	0.85	2.11	2.894 (2)	152
O8—H8A···O4^i	0.85	1.97	2.702 (2)	143
O8—H8B···O1^vi	0.85	1.85	2.687 (2)	170
N1—H1A···O4^vii	0.90	1.92	2.789 (2)	163
N1—H1B···O7^viii	0.90	2.14	2.948 (2)	148

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

Poly[[bis(µ₅-1-aminobenzene-3,4,5-tricarboxylato)triaquatrizinc(II)] dihydrate] (II)

Crystal data

[Zn3(C9H4NO6)2(H2O)3]·2H2O	Z = 2
Mr = 730.45	F(000) = 732
Triclinic, P1	Dx = 2.188 Mg m^−3
a = 7.2480 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.3135 (3) Å	Cell parameters from 9818 reflections
c = 17.2244 (6) Å	θ = 2.3–27.6°
α = 102.620 (1)°	µ = 3.32 mm^−1
β = 95.860 (1)°	T = 293 K
γ = 99.150 (1)°	Block, colorless
V = 1108.83 (7) Å^3	0.12 × 0.12 × 0.11 mm

Data collection

Bruker D8 VENTURE PHOTON diffractometer	4499 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.029
φ and ω scans	θmax = 27.6°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2016)	h = −9→9
	k = −12→12
37612 measured reflections	l = −22→22
5127 independent reflections

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)] = 0.028	Hydrogen site location: mixed
wR(F^2) = 0.075	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.036P)^2 + 1.9472P] where P = (Fo^2 + 2Fc^2)/3
5127 reflections	(Δ/σ)max = 0.001
361 parameters	Δρmax = 0.48 e Å^−3
0 restraints	Δρmin = −0.94 e Å^−3

Special details

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

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

	x	y	z	Uiso*/Ueq
Zn1	0.87219 (5)	0.69503 (3)	0.11907 (2)	0.02115 (8)
Zn2	0.60872 (4)	0.43581 (3)	0.75121 (2)	0.02023 (8)
Zn3	0.64942 (5)	0.35556 (3)	0.39787 (2)	0.02101 (8)
O1	0.8732 (5)	0.1089 (3)	−0.10728 (15)	0.0583 (8)
O2	0.9912 (4)	0.3163 (3)	−0.02030 (18)	0.0526 (7)
O3	0.6403 (3)	0.4457 (2)	0.04913 (11)	0.0239 (4)
O4	0.8967 (3)	0.49141 (19)	0.13778 (11)	0.0214 (4)
O5	0.5195 (3)	0.3817 (2)	0.20643 (12)	0.0294 (4)
O6	0.6518 (3)	0.2572 (2)	0.28748 (11)	0.0312 (5)
O7	0.3606 (3)	0.0614 (2)	0.37549 (12)	0.0342 (5)
O8	0.4556 (3)	0.2868 (2)	0.45816 (12)	0.0303 (5)
O9	0.2285 (3)	0.42890 (19)	0.57425 (12)	0.0253 (4)
O10	0.5100 (3)	0.4258 (2)	0.63313 (11)	0.0268 (4)
O11	0.0737 (3)	0.1913 (2)	0.76341 (11)	0.0236 (4)
O12	0.3554 (3)	0.3168 (2)	0.76381 (12)	0.0278 (4)
O13	0.6814 (3)	0.4505 (2)	0.87674 (12)	0.0310 (5)
H13A	0.788445	0.490823	0.904287	0.046*
H13B	0.615725	0.502643	0.905397	0.046*
O14	0.8587 (3)	0.5704 (2)	0.74974 (13)	0.0310 (5)
H14A	0.956955	0.567734	0.780509	0.046*
H14B	0.863525	0.663484	0.753459	0.046*
O15	0.7138 (3)	0.2368 (3)	0.72031 (15)	0.0449 (6)
H15A	0.658116	0.152598	0.690542	0.067*
H15B	0.820396	0.211448	0.728392	0.067*
O16	0.8303 (4)	0.8547 (3)	0.75834 (16)	0.0506 (7)
H16A	0.755036	0.867714	0.720395	0.076*
H16B	0.852306	0.925434	0.800595	0.076*
O17	0.1410 (5)	−0.5145 (5)	0.4118 (2)	0.1028 (14)
H17A	0.260734	−0.502696	0.416939	0.154*
H17B	0.107064	−0.525946	0.361789	0.154*
N1	0.6377 (3)	−0.2270 (2)	0.07737 (13)	0.0208 (4)
H1A	0.584140	−0.279830	0.027787	0.025*
H1B	0.555410	−0.246730	0.111117	0.025*
N2	0.1225 (4)	−0.2760 (2)	0.55083 (15)	0.0293 (5)
H2A	0.029846	−0.300628	0.579215	0.035*
H2B	0.099926	−0.323508	0.498405	0.035*
C1	0.8841 (5)	0.1894 (4)	−0.04009 (19)	0.0322 (7)
C2	0.7584 (4)	0.4019 (3)	0.09098 (14)	0.0162 (5)
C3	0.6059 (4)	0.2843 (3)	0.22040 (15)	0.0179 (5)
C4	0.6618 (3)	0.1819 (3)	0.14981 (14)	0.0158 (5)
C5	0.7369 (3)	0.2369 (3)	0.08828 (14)	0.0157 (5)
C6	0.7824 (4)	0.1368 (3)	0.02302 (15)	0.0190 (5)
C7	0.7446 (4)	−0.0166 (3)	0.01857 (15)	0.0196 (5)
H7A	0.770117	−0.083545	−0.025813	0.024*
C8	0.6690 (4)	−0.0699 (3)	0.08004 (15)	0.0174 (5)
C9	0.6324 (4)	0.0295 (3)	0.14634 (15)	0.0181 (5)
H9A	0.587864	−0.005792	0.188749	0.022*
C10	0.3739 (4)	0.1496 (3)	0.44142 (15)	0.0208 (5)
C11	0.3499 (4)	0.3586 (3)	0.59759 (14)	0.0175 (5)
C12	0.2152 (4)	0.2219 (3)	0.72843 (15)	0.0171 (5)
C13	0.2154 (3)	0.1308 (3)	0.64504 (14)	0.0161 (5)
C14	0.2900 (3)	0.1916 (3)	0.58424 (14)	0.0147 (5)
C15	0.2950 (4)	0.0952 (3)	0.51016 (14)	0.0169 (5)
C16	0.2331 (4)	−0.0590 (3)	0.49859 (15)	0.0203 (5)
H16C	0.237880	−0.122937	0.449427	0.024*
C17	0.1647 (4)	−0.1175 (3)	0.55947 (16)	0.0200 (5)
C18	0.1518 (4)	−0.0222 (3)	0.63174 (16)	0.0192 (5)
H18A	0.100108	−0.061119	0.671735	0.023*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.03205 (18)	0.01748 (15)	0.01903 (15)	0.00976 (12)	0.00861 (12)	0.00922 (11)
Zn2	0.01967 (15)	0.01773 (15)	0.02243 (16)	0.00263 (11)	−0.00079 (11)	0.00531 (11)
Zn3	0.03631 (18)	0.01121 (14)	0.01584 (15)	0.00254 (12)	0.00554 (12)	0.00443 (11)
O1	0.086 (2)	0.074 (2)	0.0270 (13)	0.0262 (16)	0.0323 (13)	0.0186 (13)
O2	0.0703 (18)	0.0321 (13)	0.0748 (19)	0.0152 (12)	0.0513 (15)	0.0308 (13)
O3	0.0332 (11)	0.0167 (9)	0.0243 (10)	0.0090 (8)	−0.0006 (8)	0.0092 (7)
O4	0.0237 (9)	0.0165 (8)	0.0231 (9)	0.0012 (7)	−0.0003 (7)	0.0064 (7)
O5	0.0432 (12)	0.0234 (10)	0.0286 (11)	0.0193 (9)	0.0117 (9)	0.0085 (8)
O6	0.0572 (14)	0.0271 (10)	0.0138 (9)	0.0196 (10)	0.0066 (9)	0.0050 (8)
O7	0.0542 (14)	0.0277 (11)	0.0174 (10)	0.0010 (10)	0.0066 (9)	0.0025 (8)
O8	0.0508 (13)	0.0167 (9)	0.0258 (10)	0.0031 (9)	0.0180 (9)	0.0068 (8)
O9	0.0320 (11)	0.0123 (8)	0.0318 (11)	0.0047 (7)	−0.0004 (8)	0.0076 (8)
O10	0.0288 (10)	0.0242 (10)	0.0227 (10)	−0.0088 (8)	−0.0047 (8)	0.0092 (8)
O11	0.0244 (10)	0.0245 (9)	0.0213 (9)	0.0003 (8)	0.0083 (7)	0.0050 (7)
O12	0.0264 (10)	0.0285 (10)	0.0219 (10)	−0.0066 (8)	0.0046 (8)	0.0002 (8)
O13	0.0332 (11)	0.0373 (12)	0.0229 (10)	0.0107 (9)	0.0000 (8)	0.0071 (9)
O14	0.0242 (10)	0.0246 (10)	0.0412 (12)	−0.0012 (8)	−0.0053 (9)	0.0105 (9)
O15	0.0375 (13)	0.0299 (12)	0.0576 (16)	0.0180 (10)	−0.0134 (11)	−0.0091 (11)
O16	0.0674 (18)	0.0275 (12)	0.0514 (16)	0.0003 (11)	−0.0100 (13)	0.0125 (11)
O17	0.068 (2)	0.160 (4)	0.074 (3)	0.001 (3)	0.015 (2)	0.027 (3)
N1	0.0315 (12)	0.0102 (9)	0.0203 (11)	0.0030 (8)	0.0000 (9)	0.0049 (8)
N2	0.0428 (15)	0.0104 (10)	0.0293 (13)	−0.0024 (9)	−0.0100 (11)	0.0055 (9)
C1	0.0409 (17)	0.0367 (16)	0.0387 (17)	0.0278 (14)	0.0240 (14)	0.0275 (14)
C2	0.0223 (12)	0.0130 (11)	0.0155 (11)	0.0037 (9)	0.0057 (9)	0.0067 (9)
C3	0.0230 (13)	0.0125 (11)	0.0187 (12)	0.0019 (9)	0.0062 (10)	0.0038 (9)
C4	0.0214 (12)	0.0124 (11)	0.0145 (11)	0.0047 (9)	0.0021 (9)	0.0041 (9)
C5	0.0195 (12)	0.0124 (11)	0.0168 (11)	0.0037 (9)	0.0015 (9)	0.0072 (9)
C6	0.0260 (13)	0.0182 (12)	0.0180 (12)	0.0101 (10)	0.0066 (10)	0.0097 (10)
C7	0.0307 (14)	0.0154 (11)	0.0153 (11)	0.0104 (10)	0.0055 (10)	0.0036 (9)
C8	0.0221 (12)	0.0111 (11)	0.0196 (12)	0.0049 (9)	0.0000 (10)	0.0054 (9)
C9	0.0264 (13)	0.0148 (11)	0.0158 (11)	0.0052 (10)	0.0059 (10)	0.0073 (9)
C10	0.0264 (14)	0.0210 (12)	0.0177 (12)	0.0089 (10)	0.0036 (10)	0.0071 (10)
C11	0.0275 (13)	0.0111 (11)	0.0132 (11)	0.0006 (9)	0.0031 (10)	0.0039 (9)
C12	0.0234 (13)	0.0145 (11)	0.0163 (12)	0.0055 (9)	0.0033 (9)	0.0084 (9)
C13	0.0185 (12)	0.0137 (11)	0.0170 (12)	0.0030 (9)	0.0015 (9)	0.0061 (9)
C14	0.0183 (12)	0.0112 (10)	0.0157 (11)	0.0036 (9)	0.0003 (9)	0.0060 (9)
C15	0.0213 (12)	0.0146 (11)	0.0152 (11)	0.0038 (9)	0.0005 (9)	0.0051 (9)
C16	0.0276 (14)	0.0142 (11)	0.0176 (12)	0.0056 (10)	−0.0013 (10)	0.0015 (9)
C17	0.0226 (13)	0.0106 (11)	0.0250 (13)	−0.0002 (9)	−0.0054 (10)	0.0068 (10)
C18	0.0212 (12)	0.0155 (11)	0.0216 (12)	0.0000 (9)	0.0003 (10)	0.0092 (10)

Geometric parameters (Å, º)

Zn1—O4	2.0235 (18)	O15—H15B	0.8500
Zn1—O11^i	2.0350 (19)	O16—H16A	0.8500
Zn1—O2^ii	2.046 (2)	O16—H16B	0.8501
Zn1—N1^iii	2.074 (2)	O17—H17A	0.8501
Zn1—O1^ii	2.439 (3)	O17—H17B	0.8501
Zn1—C1^ii	2.580 (3)	N1—C8	1.434 (3)
Zn2—O14	2.039 (2)	N1—H1A	0.9000
Zn2—O12	2.0458 (19)	N1—H1B	0.9000
Zn2—O10	2.0630 (19)	N2—C17	1.430 (3)
Zn2—O5^i	2.0936 (19)	N2—H2A	0.9000
Zn2—O15	2.097 (2)	N2—H2B	0.9001
Zn2—O13	2.141 (2)	C1—C6	1.499 (4)
Zn3—O6	1.9248 (19)	C2—C5	1.509 (3)
Zn3—O8	1.940 (2)	C3—C4	1.506 (3)
Zn3—O9^i	1.9926 (18)	C4—C9	1.388 (3)
Zn3—N2^iv	2.107 (2)	C4—C5	1.396 (3)
O1—C1	1.221 (4)	C5—C6	1.399 (3)
O2—C1	1.263 (4)	C6—C7	1.395 (3)
O3—C2	1.238 (3)	C7—C8	1.389 (3)
O4—C2	1.275 (3)	C7—H7A	0.9300
O5—C3	1.232 (3)	C8—C9	1.382 (3)
O6—C3	1.259 (3)	C9—H9A	0.9300
O7—C10	1.232 (3)	C10—C15	1.515 (3)
O8—C10	1.277 (3)	C11—C14	1.506 (3)
O9—C11	1.261 (3)	C12—C13	1.500 (3)
O10—C11	1.253 (3)	C13—C18	1.387 (3)
O11—C12	1.267 (3)	C13—C14	1.410 (3)
O12—C12	1.240 (3)	C14—C15	1.399 (3)
O13—H13A	0.8499	C15—C16	1.398 (3)
O13—H13B	0.8501	C16—C17	1.382 (4)
O14—H14A	0.8501	C16—H16C	0.9300
O14—H14B	0.8499	C17—C18	1.383 (4)
O15—H15A	0.8499	C18—H18A	0.9300
O4—Zn1—O11^i	96.74 (8)	C17—N2—Zn3^iv	111.86 (17)
O4—Zn1—O2^ii	97.91 (8)	C17—N2—H2A	110.9
O11^i—Zn1—O2^ii	136.57 (10)	Zn3^iv—N2—H2A	102.9
O4—Zn1—N1^iii	130.45 (8)	C17—N2—H2B	110.1
O11^i—Zn1—N1^iii	102.11 (8)	Zn3^iv—N2—H2B	106.4
O2^ii—Zn1—N1^iii	98.81 (10)	H2A—N2—H2B	114.4
O4—Zn1—O1^ii	126.91 (9)	O1—C1—O2	120.6 (3)
O11^i—Zn1—O1^ii	82.03 (8)	O1—C1—C6	121.3 (3)
O2^ii—Zn1—O1^ii	56.69 (10)	O2—C1—C6	117.9 (3)
N1^iii—Zn1—O1^ii	101.02 (9)	O1—C1—Zn1^ii	69.56 (19)
O4—Zn1—C1^ii	116.58 (8)	O2—C1—Zn1^ii	51.39 (15)
O11^i—Zn1—C1^ii	109.55 (10)	C6—C1—Zn1^ii	165.5 (2)
O2^ii—Zn1—C1^ii	28.83 (11)	O3—C2—O4	122.4 (2)
N1^iii—Zn1—C1^ii	99.45 (9)	O3—C2—C5	119.3 (2)
O1^ii—Zn1—C1^ii	27.97 (10)	O4—C2—C5	118.3 (2)
O14—Zn2—O12	173.84 (8)	O5—C3—O6	127.7 (2)
O14—Zn2—O10	93.57 (8)	O5—C3—C4	117.5 (2)
O12—Zn2—O10	90.42 (8)	O6—C3—C4	114.8 (2)
O14—Zn2—O5^i	92.74 (9)	C9—C4—C5	120.4 (2)
O12—Zn2—O5^i	82.40 (8)	C9—C4—C3	118.1 (2)
O10—Zn2—O5^i	92.22 (8)	C5—C4—C3	121.4 (2)
O14—Zn2—O15	94.18 (9)	C4—C5—C6	119.3 (2)
O12—Zn2—O15	90.32 (9)	C4—C5—C2	119.6 (2)
O10—Zn2—O15	92.70 (9)	C6—C5—C2	121.0 (2)
O5^i—Zn2—O15	171.24 (10)	C7—C6—C5	119.7 (2)
O14—Zn2—O13	90.83 (9)	C7—C6—C1	118.1 (2)
O12—Zn2—O13	84.85 (8)	C5—C6—C1	122.0 (2)
O10—Zn2—O13	173.72 (8)	C8—C7—C6	120.4 (2)
O5^i—Zn2—O13	83.08 (8)	C8—C7—H7A	119.8
O15—Zn2—O13	91.44 (9)	C6—C7—H7A	119.8
O6—Zn3—O8	121.43 (9)	C9—C8—C7	119.9 (2)
O6—Zn3—O9^i	113.23 (9)	C9—C8—N1	119.5 (2)
O8—Zn3—O9^i	119.52 (8)	C7—C8—N1	120.5 (2)
O6—Zn3—N2^iv	97.68 (9)	C8—C9—C4	120.2 (2)
O8—Zn3—N2^iv	99.62 (10)	C8—C9—H9A	119.9
O9^i—Zn3—N2^iv	96.77 (8)	C4—C9—H9A	119.9
C1—O1—Zn1^ii	82.5 (2)	O7—C10—O8	124.7 (2)
C1—O2—Zn1^ii	99.8 (2)	O7—C10—C15	119.7 (2)
C2—O4—Zn1	104.30 (15)	O8—C10—C15	115.6 (2)
C3—O5—Zn2^i	149.38 (18)	O10—C11—O9	121.3 (2)
C3—O6—Zn3	135.29 (17)	O10—C11—C14	121.8 (2)
C10—O8—Zn3	121.02 (17)	O9—C11—C14	116.9 (2)
C11—O9—Zn3^i	106.62 (16)	O12—C12—O11	121.2 (2)
C11—O10—Zn2	124.64 (16)	O12—C12—C13	120.6 (2)
C12—O11—Zn1^i	109.97 (16)	O11—C12—C13	118.0 (2)
C12—O12—Zn2	145.03 (18)	C18—C13—C14	120.3 (2)
Zn2—O13—H13A	125.2	C18—C13—C12	116.2 (2)
Zn2—O13—H13B	112.2	C14—C13—C12	123.3 (2)
H13A—O13—H13B	97.3	C15—C14—C13	118.7 (2)
Zn2—O14—H14A	120.1	C15—C14—C11	121.1 (2)
Zn2—O14—H14B	120.0	C13—C14—C11	120.1 (2)
H14A—O14—H14B	103.4	C16—C15—C14	119.9 (2)
Zn2—O15—H15A	128.7	C16—C15—C10	117.4 (2)
Zn2—O15—H15B	135.4	C14—C15—C10	122.6 (2)
H15A—O15—H15B	95.8	C17—C16—C15	120.7 (2)
H16A—O16—H16B	114.8	C17—C16—H16C	119.7
H17A—O17—H17B	104.5	C15—C16—H16C	119.7
C8—N1—Zn1^v	115.05 (16)	C16—C17—C18	119.7 (2)
C8—N1—H1A	109.9	C16—C17—N2	120.5 (2)
Zn1^v—N1—H1A	112.4	C18—C17—N2	119.6 (2)
C8—N1—H1B	109.3	C17—C18—C13	120.5 (2)
Zn1^v—N1—H1B	103.0	C17—C18—H18A	119.7
H1A—N1—H1B	106.7	C13—C18—H18A	119.7
Zn1^ii—O1—C1—O2	6.2 (3)	C3—C4—C9—C8	175.4 (2)
Zn1^ii—O1—C1—C6	−169.4 (3)	Zn3—O8—C10—O7	−23.9 (4)
Zn1^ii—O2—C1—O1	−7.5 (4)	Zn3—O8—C10—C15	154.11 (18)
Zn1^ii—O2—C1—C6	168.3 (2)	Zn2—O10—C11—O9	114.2 (2)
Zn1—O4—C2—O3	−2.8 (3)	Zn2—O10—C11—C14	−62.8 (3)
Zn1—O4—C2—C5	178.49 (17)	Zn3^i—O9—C11—O10	2.0 (3)
Zn2^i—O5—C3—O6	3.0 (6)	Zn3^i—O9—C11—C14	179.13 (17)
Zn2^i—O5—C3—C4	−178.3 (3)	Zn2—O12—C12—O11	−172.8 (2)
Zn3—O6—C3—O5	−9.9 (5)	Zn2—O12—C12—C13	12.5 (5)
Zn3—O6—C3—C4	171.37 (19)	Zn1^i—O11—C12—O12	−4.6 (3)
O5—C3—C4—C9	−135.2 (3)	Zn1^i—O11—C12—C13	170.36 (16)
O6—C3—C4—C9	43.7 (3)	O12—C12—C13—C18	132.6 (3)
O5—C3—C4—C5	43.2 (4)	O11—C12—C13—C18	−42.3 (3)
O6—C3—C4—C5	−137.9 (3)	O12—C12—C13—C14	−42.0 (4)
C9—C4—C5—C6	0.0 (4)	O11—C12—C13—C14	143.0 (2)
C3—C4—C5—C6	−178.5 (2)	C18—C13—C14—C15	1.2 (4)
C9—C4—C5—C2	176.8 (2)	C12—C13—C14—C15	175.7 (2)
C3—C4—C5—C2	−1.6 (4)	C18—C13—C14—C11	177.0 (2)
O3—C2—C5—C4	−100.9 (3)	C12—C13—C14—C11	−8.6 (4)
O4—C2—C5—C4	77.9 (3)	O10—C11—C14—C15	−99.9 (3)
O3—C2—C5—C6	76.0 (3)	O9—C11—C14—C15	83.0 (3)
O4—C2—C5—C6	−105.3 (3)	O10—C11—C14—C13	84.4 (3)
C4—C5—C6—C7	2.8 (4)	O9—C11—C14—C13	−92.7 (3)
C2—C5—C6—C7	−174.0 (2)	C13—C14—C15—C16	−2.3 (4)
C4—C5—C6—C1	−172.7 (2)	C11—C14—C15—C16	−178.0 (2)
C2—C5—C6—C1	10.5 (4)	C13—C14—C15—C10	−179.5 (2)
O1—C1—C6—C7	27.3 (4)	C11—C14—C15—C10	4.8 (4)
O2—C1—C6—C7	−148.4 (3)	O7—C10—C15—C16	8.6 (4)
Zn1^ii—C1—C6—C7	−109.1 (8)	O8—C10—C15—C16	−169.5 (2)
O1—C1—C6—C5	−157.2 (3)	O7—C10—C15—C14	−174.1 (3)
O2—C1—C6—C5	27.1 (4)	O8—C10—C15—C14	7.7 (4)
Zn1^ii—C1—C6—C5	66.5 (8)	C14—C15—C16—C17	0.7 (4)
C5—C6—C7—C8	−2.5 (4)	C10—C15—C16—C17	178.0 (2)
C1—C6—C7—C8	173.1 (3)	C15—C16—C17—C18	2.1 (4)
C6—C7—C8—C9	−0.5 (4)	C15—C16—C17—N2	−172.6 (2)
C6—C7—C8—N1	−177.2 (2)	Zn3^iv—N2—C17—C16	94.7 (3)
Zn1^v—N1—C8—C9	−93.3 (3)	Zn3^iv—N2—C17—C18	−80.0 (3)
Zn1^v—N1—C8—C7	83.5 (3)	C16—C17—C18—C13	−3.1 (4)
C7—C8—C9—C4	3.3 (4)	N2—C17—C18—C13	171.6 (2)
N1—C8—C9—C4	−180.0 (2)	C14—C13—C18—C17	1.5 (4)
C5—C4—C9—C8	−3.0 (4)	C12—C13—C18—C17	−173.3 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O13—H13A···O2^vi	0.85	2.58	3.358 (4)	154
O13—H13B···O3^i	0.85	2.17	2.964 (3)	156
O14—H14A···O4^vi	0.85	1.90	2.709 (3)	157
O14—H14B···O16	0.85	1.82	2.661 (3)	170
O15—H15A···O7^iv	0.85	2.04	2.840 (3)	156
O15—H15B···O11^vii	0.85	1.92	2.762 (3)	168
O16—H16A···O7^i	0.85	2.06	2.885 (3)	164
O16—H16B···O1^viii	0.85	2.04	2.878 (4)	171
O17—H17A···O10^iv	0.85	2.05	2.774 (4)	143
O17—H17B···O14^iv	0.85	1.92	2.717 (4)	155
N1—H1A···O3^ix	0.90	2.16	2.969 (3)	150
N1—H1B···O13^iv	0.90	2.41	3.141 (3)	139
N2—H2A···O17^x	0.90	2.00	2.736 (5)	138
N2—H2B···O17	0.90	2.14	2.919 (5)	145

Symmetry codes: (i) −x+1, −y+1, −z+1; (iv) −x+1, −y, −z+1; (vi) −x+2, −y+1, −z+1; (vii) x+1, y, z; (viii) x, y+1, z+1; (ix) −x+1, −y, −z; (x) −x, −y−1, −z+1.