2D coordination polymers of cadmium(II) and zinc(II) derived from N,N′-bis­(glycin­yl)pyromellitic di­imide: microwave-assisted synthesis, structures, spectroscopic properties and influence of metal-ion size

Two new two-dimensional (2D) coordination polymers (CPs), namely, poly[di­aqua­[μ₄-2,2′-(1,3,5,7-tetra­oxo-1,2,3,5,6,7-hexa­hydro­pyrrolo­[3,4-f]iso­indole-2,6-di­yl)di­ace­tato-κ⁴O:O′:O′′:O′′′]cadmium(II)], [Cd(C₁₄H₆N₂O₈)(H₂O)₂]_n (1), and poly[[tetra­aqua­[μ₄-2,2′-(1,3,5,7-tetra­oxo-1,2,3,5,6,7-hexa­hydro­pyrrolo­[3,4-f]iso­in­dole-2,6-di­yl)di­acetato-κ⁴O:O′:O′′:O′′′][μ₂-2,2′-(1,3,5,7-tetra­oxo-1,2,3,5,6,7-hexa­hy­dro­pyrrolo­[3,4-f]iso­indole-2,6-di­yl)di­acetato-κ²O:O′]dizinc(II)] dihydrate], {[Zn(C₁₄H₆N₂O₈(H₂O)₂]·H₂O}_n (2), have been synthesized by the microwave-irradiated reaction of Cd(CH₃COO)₂·2H₂O and Zn(CH₃COO)₂·2H₂O, res­pectively, with N,N′-bis­(glycin­yl)pyromellitic di­imide {BGPD, namely, 2,2′-(1,3,5,7-tetra­oxo-1,2,3,5,6,7-hexa­hydro­pyrrolo­[3,4-f]iso­indole-2,6-di­yl)di­acetic acid, H₂L}. In the crystal structure of 1, the Cd^II ion is six-coordinated by four carboxyl­ate O atoms from four symmetry-related L²⁻ dianions and two coordinated water mol­ecules, furnishing an octa­hedral coordination geometry. The bridging L²⁻ dianion links four symmetry-related Cd^II cations into a 2D layer-like structure with a 3,4-connected bex topology. In the crystal structure of 2, the Zn^II ion is five-coordinated by three carboxyl­ate O atoms from three different L²⁻ dianions and two coordination water mol­ecules, furnishing a trigonal bi­py­ramidal coordination geometry. Two crystallographically independent ligands serve as μ₄- and μ₂-bridges, res­pec­tively, to connect the Zn^II ions, thereby forming a 2D layer with a 3,3-con­nected hcb topology. Crystal structure analysis reveals the presence of n→π* inter­actions between two carbonyl groups of the pyromellitic di­imide moieties in 1 and 2. CP 1 exhibits an enhanced fluorescence emission com­pared with free H₂L. The framework of 2 decom­poses from 720 K, indicating its high thermal stability. A com­parative analysis of a series of structures based on the BGPD ligand indicates that the metal-ion size has a great influence on the connection modes of the metal ions due to different steric effects, which, in turn, affects the structures of the SBUs (secondary building units) and frameworks.

Computing details

Poly[diaqua[µ₄-2,2'-(1,3,5,7-tetraoxo-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindole-2,6-diyl)diacetato-κ⁴O,O':O'',O''']cadmium(II)] (1)

Crystal data

[Cd(C14H6N2O8)(H2O)2]	Z = 1
Mr = 478.64	F(000) = 236
Triclinic, P1	Dx = 2.127 Mg m^−3
a = 4.9317 (15) Å	Mo Kα radiation, λ = 0.71073 Å
b = 5.441 (2) Å	Cell parameters from 4112 reflections
c = 14.014 (5) Å	θ = 2.9–27.3°
α = 84.255 (10)°	µ = 1.53 mm^−1
β = 88.521 (9)°	T = 298 K
γ = 87.532 (9)°	Block, colorless
V = 373.8 (2) Å^3	0.13 × 0.11 × 0.04 mm

Data collection

Bruker APEXII CCD diffractometer	1663 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.055
φ and ω scans	θmax = 27.5°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −6→6
Tmin = 0.686, Tmax = 0.746	k = −7→7
10027 measured reflections	l = −18→18
1714 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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.075	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0462P)^2 + 0.0531P] where P = (Fo^2 + 2Fc^2)/3
1714 reflections	(Δ/σ)max < 0.001
124 parameters	Δρmax = 0.95 e Å^−3
0 restraints	Δρmin = −0.64 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
C1	0.9646 (6)	0.6523 (5)	0.6275 (2)	0.0210 (6)
C2	1.0944 (6)	0.6578 (6)	0.7249 (2)	0.0255 (6)
H2A	1.2457	0.5376	0.7299	0.031*
H2B	1.1666	0.8198	0.7281	0.031*
C3	0.9307 (6)	0.3945 (6)	0.8707 (2)	0.0219 (6)
C4	0.7091 (5)	0.4231 (5)	0.9445 (2)	0.0207 (6)
C5	0.5705 (5)	0.6495 (5)	0.9205 (2)	0.0197 (5)
C6	0.6998 (5)	0.7689 (5)	0.8297 (2)	0.0200 (6)
C7	0.3559 (6)	0.7338 (5)	0.9754 (2)	0.0210 (6)
H7	0.2628	0.8841	0.9596	0.025*
Cd1	0.5000	0.5000	0.5000	0.02113 (12)
N1	0.9111 (5)	0.6058 (5)	0.80638 (18)	0.0223 (5)
O1	0.7256 (4)	0.5874 (5)	0.62675 (16)	0.0310 (5)
O2	1.1127 (4)	0.7175 (4)	0.55563 (15)	0.0260 (5)
O3	0.6400 (5)	0.9627 (4)	0.78525 (16)	0.0291 (5)
O4	1.1000 (5)	0.2292 (5)	0.86703 (17)	0.0334 (5)
O5	0.6122 (6)	0.8467 (5)	0.40317 (19)	0.0408 (6)
H5A	0.5183	0.8945	0.3565	0.049*
H5B	0.7055	0.9374	0.4318	0.049*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0207 (13)	0.0224 (14)	0.0196 (14)	0.0032 (10)	0.0020 (11)	−0.0036 (11)
C2	0.0180 (13)	0.0403 (18)	0.0182 (14)	−0.0060 (12)	0.0027 (11)	−0.0006 (12)
C3	0.0199 (13)	0.0277 (15)	0.0183 (14)	−0.0015 (11)	0.0005 (10)	−0.0038 (11)
C4	0.0185 (12)	0.0247 (14)	0.0190 (14)	−0.0004 (10)	0.0007 (10)	−0.0038 (11)
C5	0.0215 (13)	0.0219 (14)	0.0154 (13)	−0.0026 (10)	0.0004 (10)	0.0003 (10)
C6	0.0180 (12)	0.0264 (15)	0.0160 (13)	−0.0032 (10)	−0.0006 (10)	−0.0029 (11)
C7	0.0217 (13)	0.0200 (13)	0.0209 (14)	0.0011 (10)	−0.0021 (11)	−0.0010 (11)
Cd1	0.02157 (17)	0.02575 (18)	0.01623 (17)	−0.00171 (11)	0.00209 (10)	−0.00321 (11)
N1	0.0198 (11)	0.0299 (13)	0.0168 (12)	0.0004 (9)	0.0005 (9)	−0.0007 (10)
O1	0.0215 (10)	0.0520 (15)	0.0212 (11)	−0.0077 (9)	0.0004 (8)	−0.0094 (10)
O2	0.0274 (11)	0.0298 (11)	0.0199 (11)	0.0009 (8)	0.0067 (8)	−0.0008 (9)
O3	0.0334 (12)	0.0272 (12)	0.0249 (11)	0.0005 (9)	0.0016 (9)	0.0057 (9)
O4	0.0296 (11)	0.0364 (13)	0.0319 (13)	0.0104 (9)	0.0066 (9)	0.0002 (10)
O5	0.0542 (15)	0.0329 (13)	0.0351 (14)	−0.0176 (11)	−0.0078 (12)	0.0057 (11)

Geometric parameters (Å, º)

C1—O1	1.246 (4)	C6—O3	1.199 (4)
C1—O2	1.260 (3)	C6—N1	1.393 (4)
C1—C2	1.527 (4)	C7—C4^i	1.380 (4)
C2—N1	1.451 (4)	C7—H7	0.9300
C2—H2A	0.9700	Cd1—O1^ii	2.222 (2)
C2—H2B	0.9700	Cd1—O1	2.222 (2)
C3—O4	1.205 (4)	Cd1—O5	2.290 (2)
C3—N1	1.390 (4)	Cd1—O5^ii	2.290 (2)
C3—C4	1.500 (4)	Cd1—O2^iii	2.360 (2)
C4—C7^i	1.380 (4)	Cd1—O2^iv	2.360 (2)
C4—C5	1.398 (4)	O2—Cd1^v	2.360 (2)
C5—C7	1.382 (4)	O5—H5A	0.8258
C5—C6	1.508 (4)	O5—H5B	0.8279
O1—C1—O2	126.8 (3)	O1^ii—Cd1—O1	180.00 (11)
O1—C1—C2	117.6 (2)	O1^ii—Cd1—O5	83.92 (9)
O2—C1—C2	115.6 (2)	O1—Cd1—O5	96.09 (9)
N1—C2—C1	114.4 (2)	O1^ii—Cd1—O5^ii	96.08 (9)
N1—C2—H2A	108.7	O1—Cd1—O5^ii	83.91 (9)
C1—C2—H2A	108.7	O5—Cd1—O5^ii	180.00 (13)
N1—C2—H2B	108.7	O1^ii—Cd1—O2^iii	90.25 (8)
C1—C2—H2B	108.7	O1—Cd1—O2^iii	89.75 (8)
H2A—C2—H2B	107.6	O5—Cd1—O2^iii	89.41 (9)
O4—C3—N1	125.3 (3)	O5^ii—Cd1—O2^iii	90.59 (9)
O4—C3—C4	128.6 (3)	O1^ii—Cd1—O2^iv	89.75 (8)
N1—C3—C4	106.0 (2)	O1—Cd1—O2^iv	90.25 (8)
C7^i—C4—C5	123.1 (3)	O5—Cd1—O2^iv	90.59 (9)
C7^i—C4—C3	129.1 (3)	O5^ii—Cd1—O2^iv	89.41 (9)
C5—C4—C3	107.8 (3)	O2^iii—Cd1—O2^iv	180.0
C7—C5—C4	122.4 (3)	C3—N1—C6	112.9 (2)
C7—C5—C6	129.8 (3)	C3—N1—C2	124.3 (3)
C4—C5—C6	107.8 (2)	C6—N1—C2	122.9 (3)
O3—C6—N1	125.7 (3)	C1—O1—Cd1	126.8 (2)
O3—C6—C5	128.9 (3)	C1—O2—Cd1^v	126.77 (19)
N1—C6—C5	105.5 (2)	Cd1—O5—H5A	119.8
C4^i—C7—C5	114.6 (3)	Cd1—O5—H5B	111.3
C4^i—C7—H7	122.7	H5A—O5—H5B	124.4
C5—C7—H7	122.7
O1—C1—C2—N1	−5.1 (4)	C6—C5—C7—C4^i	−179.3 (3)
O2—C1—C2—N1	174.1 (3)	O4—C3—N1—C6	−178.3 (3)
O4—C3—C4—C7^i	−1.0 (5)	C4—C3—N1—C6	−0.4 (3)
N1—C3—C4—C7^i	−178.9 (3)	O4—C3—N1—C2	−0.1 (5)
O4—C3—C4—C5	177.6 (3)	C4—C3—N1—C2	177.8 (2)
N1—C3—C4—C5	−0.2 (3)	O3—C6—N1—C3	−179.4 (3)
C7^i—C4—C5—C7	−0.2 (5)	C5—C6—N1—C3	0.8 (3)
C3—C4—C5—C7	−179.0 (3)	O3—C6—N1—C2	2.4 (5)
C7^i—C4—C5—C6	179.4 (3)	C5—C6—N1—C2	−177.5 (2)
C3—C4—C5—C6	0.6 (3)	C1—C2—N1—C3	111.9 (3)
C7—C5—C6—O3	−1.1 (5)	C1—C2—N1—C6	−70.0 (4)
C4—C5—C6—O3	179.3 (3)	O2—C1—O1—Cd1	11.6 (5)
C7—C5—C6—N1	178.7 (3)	C2—C1—O1—Cd1	−169.2 (2)
C4—C5—C6—N1	−0.9 (3)	O1—C1—O2—Cd1^v	−111.4 (3)
C4—C5—C7—C4^i	0.2 (5)	C2—C1—O2—Cd1^v	69.4 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O3^vi	0.83	2.21	3.018 (4)	167
O5—H5B···O2^vii	0.83	2.14	2.896 (3)	152
C7—H7···O4^viii	0.93	2.30	3.186 (4)	159

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

Poly[[tetraaqua[µ₄-2,2'-(1,3,5,7-tetraoxo-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindole-2,6-diyl)diacetato-κ⁴O,O':O'',O'''] [µ₂-2,2'-(1,3,5,7-tetraoxo-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindole-2,6-diyl)diacetato-κ²O:O']dizinc(II)] dihydrate] (2)

Crystal data

[Zn(C14H6N2O8)(H2O)2]·H2O	F(000) = 912
Mr = 449.63	Dx = 1.877 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 10.7680 (12) Å	Cell parameters from 2916 reflections
b = 5.0511 (5) Å	θ = 2.7–26.4°
c = 29.334 (3) Å	µ = 1.62 mm^−1
β = 94.409 (2)°	T = 298 K
V = 1590.8 (3) Å^3	Needle, colorless
Z = 4	0.44 × 0.07 × 0.02 mm

Data collection

Bruker APEXII CCD diffractometer	2458 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.061
φ and ω scans	θmax = 27.6°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −14→14
Tmin = 0.580, Tmax = 0.746	k = −6→6
13203 measured reflections	l = −37→34
3664 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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.115	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0543P)^2] where P = (Fo^2 + 2Fc^2)/3
3664 reflections	(Δ/σ)max < 0.001
253 parameters	Δρmax = 0.80 e Å^−3
0 restraints	Δρmin = −0.41 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
C1	0.4391 (3)	0.5990 (7)	0.32345 (11)	0.0262 (7)
C2	0.4188 (4)	0.4497 (7)	0.36730 (11)	0.0305 (8)
H2A	0.3331	0.3892	0.3663	0.037*
H2B	0.4723	0.2950	0.3693	0.037*
C3	0.5506 (3)	0.5913 (7)	0.43788 (11)	0.0256 (7)
C4	0.5366 (3)	0.7987 (7)	0.47309 (10)	0.0240 (7)
C5	0.4266 (3)	0.9369 (6)	0.46195 (11)	0.0224 (7)
C6	0.3684 (3)	0.8204 (7)	0.41857 (11)	0.0237 (7)
C7	0.3861 (3)	1.1407 (6)	0.48843 (11)	0.0237 (7)
H7	0.3120	1.2310	0.4809	0.028*
C8	0.6129 (3)	0.6407 (6)	0.01487 (11)	0.0242 (7)
H8	0.6855	0.7310	0.0244	0.029*
C9	0.5658 (3)	0.4378 (6)	0.03991 (10)	0.0209 (7)
C10	0.6156 (3)	0.3236 (7)	0.08485 (11)	0.0253 (7)
C11	0.4569 (3)	0.3004 (7)	0.02579 (11)	0.0227 (7)
C12	0.4355 (3)	0.0962 (7)	0.06104 (11)	0.0250 (7)
C13	0.5431 (3)	−0.0332 (7)	0.13647 (11)	0.0303 (8)
H13A	0.6287	−0.0918	0.1423	0.036*
H13B	0.4914	−0.1896	0.1319	0.036*
C14	0.5044 (3)	0.1145 (6)	0.17844 (11)	0.0234 (7)
N1	0.4448 (3)	0.6117 (5)	0.40763 (9)	0.0250 (6)
N2	0.5332 (3)	0.1231 (5)	0.09482 (9)	0.0260 (6)
O1	0.4113 (2)	0.4631 (5)	0.28711 (8)	0.0330 (6)
O2	0.4782 (3)	0.8266 (5)	0.32493 (9)	0.0423 (7)
O3	0.6330 (2)	0.4309 (5)	0.43547 (8)	0.0374 (6)
O4	0.2732 (2)	0.8867 (5)	0.39645 (8)	0.0319 (6)
O5	0.4946 (2)	0.3628 (4)	0.17535 (7)	0.0277 (5)
O6	0.4889 (2)	−0.0166 (5)	0.21364 (8)	0.0371 (6)
O7	0.7086 (2)	0.3868 (5)	0.10783 (8)	0.0362 (6)
O8	0.3545 (2)	−0.0681 (5)	0.06077 (8)	0.0362 (6)
O9	0.6513 (2)	0.5687 (5)	0.25468 (9)	0.0377 (6)
O10	0.2783 (3)	0.6020 (6)	0.20164 (9)	0.0523 (8)
O11	0.6808 (2)	0.1287 (5)	0.31092 (9)	0.0423 (7)
H11A	0.7108	0.0940	0.3379	0.051*
H11B	0.6150	0.0357	0.3075	0.051*
H10A	0.2749	0.5711	0.1730	0.051*
H10B	0.2480	0.7579	0.2037	0.051*
H9A	0.6572	0.4504	0.2758	0.051*
H9B	0.6957	0.5197	0.2333	0.051*
Zn1	0.46404 (4)	0.59945 (7)	0.22872 (2)	0.02526 (14)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0284 (17)	0.030 (2)	0.0200 (18)	0.0034 (15)	0.0033 (13)	0.0024 (15)
C2	0.048 (2)	0.025 (2)	0.0183 (18)	−0.0046 (16)	−0.0007 (15)	−0.0012 (14)
C3	0.0332 (18)	0.0266 (18)	0.0174 (17)	0.0014 (16)	0.0051 (13)	0.0033 (15)
C4	0.0271 (17)	0.0267 (18)	0.0186 (17)	0.0007 (14)	0.0045 (13)	−0.0015 (14)
C5	0.0251 (16)	0.0262 (19)	0.0160 (16)	−0.0010 (13)	0.0021 (13)	0.0031 (13)
C6	0.0269 (17)	0.0243 (18)	0.0203 (17)	−0.0049 (14)	0.0048 (14)	0.0025 (14)
C7	0.0206 (16)	0.0294 (19)	0.0210 (17)	0.0036 (14)	0.0013 (13)	0.0015 (14)
C8	0.0226 (16)	0.0278 (19)	0.0220 (18)	−0.0027 (14)	0.0014 (13)	−0.0030 (14)
C9	0.0254 (16)	0.0212 (18)	0.0159 (16)	−0.0001 (13)	0.0003 (12)	−0.0016 (13)
C10	0.0296 (18)	0.0269 (19)	0.0196 (18)	0.0039 (14)	0.0028 (14)	−0.0009 (15)
C11	0.0264 (17)	0.0221 (17)	0.0197 (17)	−0.0036 (13)	0.0031 (13)	−0.0005 (14)
C12	0.0322 (17)	0.0225 (18)	0.0211 (17)	0.0045 (15)	0.0067 (14)	−0.0019 (14)
C13	0.052 (2)	0.0177 (18)	0.0218 (19)	0.0033 (16)	0.0070 (16)	0.0000 (14)
C14	0.0312 (17)	0.0195 (17)	0.0189 (17)	−0.0001 (14)	−0.0006 (13)	−0.0003 (14)
N1	0.0361 (15)	0.0246 (15)	0.0143 (14)	−0.0001 (12)	0.0013 (11)	−0.0016 (12)
N2	0.0389 (16)	0.0226 (16)	0.0166 (14)	0.0001 (13)	0.0037 (12)	−0.0001 (12)
O1	0.0429 (14)	0.0386 (15)	0.0176 (13)	−0.0120 (12)	0.0027 (10)	−0.0016 (11)
O2	0.0609 (18)	0.0298 (15)	0.0381 (16)	−0.0123 (13)	0.0156 (13)	0.0004 (12)
O3	0.0435 (15)	0.0333 (16)	0.0353 (15)	0.0096 (12)	0.0024 (12)	−0.0073 (11)
O4	0.0301 (13)	0.0392 (15)	0.0253 (13)	0.0004 (11)	−0.0062 (10)	−0.0009 (11)
O5	0.0435 (14)	0.0195 (13)	0.0209 (12)	0.0018 (10)	0.0076 (10)	0.0008 (9)
O6	0.0693 (18)	0.0215 (13)	0.0217 (13)	0.0015 (13)	0.0118 (12)	0.0042 (11)
O7	0.0357 (14)	0.0445 (17)	0.0271 (14)	−0.0013 (12)	−0.0058 (11)	0.0005 (12)
O8	0.0426 (15)	0.0297 (15)	0.0368 (15)	−0.0135 (12)	0.0057 (12)	0.0036 (11)
O9	0.0365 (14)	0.0407 (17)	0.0363 (15)	0.0027 (11)	0.0055 (11)	0.0031 (12)
O10	0.0451 (16)	0.067 (2)	0.0419 (17)	0.0212 (14)	−0.0135 (13)	−0.0174 (15)
O11	0.0368 (14)	0.0511 (18)	0.0379 (15)	−0.0088 (12)	−0.0039 (12)	0.0113 (13)
Zn1	0.0361 (2)	0.0216 (2)	0.0185 (2)	0.00141 (17)	0.00540 (16)	0.00126 (16)

Geometric parameters (Å, º)

C1—O2	1.224 (4)	C10—N2	1.392 (4)
C1—O1	1.284 (4)	C11—C8^ii	1.392 (4)
C1—C2	1.521 (4)	C11—C12	1.491 (4)
C2—N1	1.448 (4)	C12—O8	1.204 (4)
C2—H2A	0.9700	C12—N2	1.395 (4)
C2—H2B	0.9700	C13—N2	1.451 (4)
C3—O3	1.208 (4)	C13—C14	1.525 (4)
C3—N1	1.393 (4)	C13—H13A	0.9700
C3—C4	1.487 (4)	C13—H13B	0.9700
C4—C7^i	1.385 (4)	C14—O6	1.249 (4)
C4—C5	1.391 (4)	C14—O5	1.261 (4)
C5—C7	1.381 (4)	O1—Zn1	1.970 (2)
C5—C6	1.495 (5)	O5—Zn1	2.017 (2)
C6—O4	1.217 (4)	O6—Zn1^iii	2.011 (2)
C6—N1	1.390 (4)	O9—Zn1	2.106 (2)
C7—C4^i	1.385 (4)	O9—H9A	0.8592
C7—H7	0.9300	O9—H9B	0.8537
C8—C9	1.380 (4)	O10—Zn1	2.095 (3)
C8—C11^ii	1.392 (4)	O10—H10A	0.8518
C8—H8	0.9300	O10—H10B	0.8559
C9—C11	1.398 (4)	O11—H11A	0.8498
C9—C10	1.500 (4)	O11—H11B	0.8495
C10—O7	1.207 (4)	Zn1—O6^iv	2.012 (3)
O2—C1—O1	126.1 (3)	O8—C12—C11	128.5 (3)
O2—C1—C2	120.5 (3)	N2—C12—C11	106.1 (3)
O1—C1—C2	113.4 (3)	N2—C13—C14	114.0 (3)
N1—C2—C1	112.3 (3)	N2—C13—H13A	108.8
N1—C2—H2A	109.1	C14—C13—H13A	108.8
C1—C2—H2A	109.1	N2—C13—H13B	108.8
N1—C2—H2B	109.1	C14—C13—H13B	108.8
C1—C2—H2B	109.1	H13A—C13—H13B	107.7
H2A—C2—H2B	107.9	O6—C14—O5	124.8 (3)
O3—C3—N1	125.5 (3)	O6—C14—C13	118.0 (3)
O3—C3—C4	128.9 (3)	O5—C14—C13	117.1 (3)
N1—C3—C4	105.6 (3)	C6—N1—C3	112.3 (3)
C7^i—C4—C5	121.9 (3)	C6—N1—C2	122.4 (3)
C7^i—C4—C3	129.4 (3)	C3—N1—C2	125.2 (3)
C5—C4—C3	108.7 (3)	C10—N2—C12	112.3 (3)
C7—C5—C4	122.8 (3)	C10—N2—C13	124.5 (3)
C7—C5—C6	130.0 (3)	C12—N2—C13	123.2 (3)
C4—C5—C6	107.2 (3)	C1—O1—Zn1	118.1 (2)
O4—C6—N1	125.1 (3)	C14—O5—Zn1	123.5 (2)
O4—C6—C5	128.8 (3)	C14—O6—Zn1^iii	136.2 (2)
N1—C6—C5	106.1 (3)	Zn1—O9—H9A	109.1
C5—C7—C4^i	115.3 (3)	Zn1—O9—H9B	109.3
C5—C7—H7	122.4	H9A—O9—H9B	108.3
C4^i—C7—H7	122.4	Zn1—O10—H10A	109.9
C9—C8—C11^ii	114.8 (3)	Zn1—O10—H10B	109.7
C9—C8—H8	122.6	H10A—O10—H10B	104.4
C11^ii—C8—H8	122.6	H11A—O11—H11B	104.5
C8—C9—C11	123.1 (3)	O1—Zn1—O6^iv	125.49 (10)
C8—C9—C10	129.2 (3)	O1—Zn1—O5	122.87 (10)
C11—C9—C10	107.7 (3)	O6^iv—Zn1—O5	111.61 (9)
O7—C10—N2	126.1 (3)	O1—Zn1—O10	90.07 (11)
O7—C10—C9	127.9 (3)	O6^iv—Zn1—O10	92.86 (11)
N2—C10—C9	105.9 (3)	O5—Zn1—O10	85.27 (10)
C8^ii—C11—C9	122.2 (3)	O1—Zn1—O9	89.54 (10)
C8^ii—C11—C12	129.8 (3)	O6^iv—Zn1—O9	90.61 (10)
C9—C11—C12	108.0 (3)	O5—Zn1—O9	91.60 (10)
O8—C12—N2	125.3 (3)	O10—Zn1—O9	175.99 (11)
O2—C1—C2—N1	2.8 (5)	C9—C11—C12—N2	0.3 (3)
O1—C1—C2—N1	−177.1 (3)	N2—C13—C14—O6	167.6 (3)
O3—C3—C4—C7^i	0.1 (6)	N2—C13—C14—O5	−14.8 (5)
N1—C3—C4—C7^i	178.2 (3)	O4—C6—N1—C3	176.8 (3)
O3—C3—C4—C5	−179.8 (3)	C5—C6—N1—C3	−3.7 (3)
N1—C3—C4—C5	−1.6 (3)	O4—C6—N1—C2	0.8 (5)
C7^i—C4—C5—C7	−0.8 (5)	C5—C6—N1—C2	−179.8 (3)
C3—C4—C5—C7	179.1 (3)	O3—C3—N1—C6	−178.4 (3)
C7^i—C4—C5—C6	179.6 (3)	C4—C3—N1—C6	3.4 (3)
C3—C4—C5—C6	−0.6 (3)	O3—C3—N1—C2	−2.5 (5)
C7—C5—C6—O4	2.3 (6)	C4—C3—N1—C2	179.3 (3)
C4—C5—C6—O4	−178.0 (3)	C1—C2—N1—C6	70.7 (4)
C7—C5—C6—N1	−177.1 (3)	C1—C2—N1—C3	−104.8 (4)
C4—C5—C6—N1	2.6 (3)	O7—C10—N2—C12	−179.0 (3)
C4—C5—C7—C4^i	0.7 (5)	C9—C10—N2—C12	−0.1 (3)
C6—C5—C7—C4^i	−179.7 (3)	O7—C10—N2—C13	3.8 (5)
C11^ii—C8—C9—C11	0.2 (5)	C9—C10—N2—C13	−177.2 (3)
C11^ii—C8—C9—C10	−179.8 (3)	O8—C12—N2—C10	177.3 (3)
C8—C9—C10—O7	−0.8 (6)	C11—C12—N2—C10	−0.1 (3)
C11—C9—C10—O7	179.2 (3)	O8—C12—N2—C13	−5.5 (5)
C8—C9—C10—N2	−179.8 (3)	C11—C12—N2—C13	177.1 (3)
C11—C9—C10—N2	0.2 (3)	C14—C13—N2—C10	74.7 (4)
C8—C9—C11—C8^ii	−0.2 (5)	C14—C13—N2—C12	−102.1 (4)
C10—C9—C11—C8^ii	179.8 (3)	O2—C1—O1—Zn1	12.3 (5)
C8—C9—C11—C12	179.7 (3)	C2—C1—O1—Zn1	−167.8 (2)
C10—C9—C11—C12	−0.3 (3)	O6—C14—O5—Zn1	4.7 (5)
C8^ii—C11—C12—O8	2.8 (6)	C13—C14—O5—Zn1	−172.8 (2)
C9—C11—C12—O8	−177.1 (3)	O5—C14—O6—Zn1^iii	165.7 (2)
C8^ii—C11—C12—N2	−179.8 (3)	C13—C14—O6—Zn1^iii	−16.9 (5)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O9—H9B···O11^v	0.85	2.01	2.756 (4)	146
O9—H9A···O11	0.86	1.93	2.771 (4)	166
O10—H10A···O4^vi	0.85	2.26	3.086 (3)	162
O10—H10B···O1^vii	0.86	2.04	2.776 (4)	144
O11—H11A···O7^viii	0.85	2.04	2.856 (3)	160
O11—H11B···O2^iii	0.85	1.91	2.719 (4)	158
C7—H7···O8^ix	0.93	2.33	3.222 (4)	162
C8—H8···O3^v	0.93	2.42	3.338 (4)	168
C13—H13B···O5^iii	0.97	2.59	3.313 (4)	131

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