A two-dimensional zinc(II) coordination polymer based on mixed dimethyl succinate and bi­pyridine ligands: synthesis, structure, thermostability and luminescence properties

From the viewpoint of crystal engineering, the construction of crystalline polymeric materials requires a rational choice of organic bridging ligands for the self-assembly process. Multi­carboxyl­ate ligands are of particular inter­est due to their strong coordination activity towards metal ions, as well as their various coordination modes and versatile conformations. The structural chemistry of di­carboxyl­ate-based coordination polymers of transition metals has been developed through the grafting of N-containing organic linkers into carboxyl­ate-bridged transition metal networks. A new luminescent two-dimensional zinc(II) coordination polymer containing bridging 2,2-di­methyl­succinate and 4,4′-bi­pyridine ligands, namely poly[[aqua­(μ₂-4,4′-bi­pyridine-κ²N:N′)bis­(μ₃-2,2-di­methyl­butane­dioato)-κ⁴O¹,O^1′:O⁴:O^4′;κ⁵O¹:O¹,O⁴:O⁴,O^4′-dizinc(II)] dihydrate], {[Zn₂(C₆H₈O₄)₂(C₁₀H₈N₂)(H₂O)]·2H₂O}_n, has been synthesized under hydro­thermal conditions and characterized by single-crystal X-ray diffraction and elemental, IR and thermogravimetric analyses. In the structure, the 2,2-di­­methyl­succinate ligands link linear tetra­nuclear Zn^II subunits into one-dimensional chains along the c axis. 4,4′-Bi­pyridine acts as a tethering ligand expanding these one-dimensional chains into a two-dimensional layered structure. Hydrogen-bonding inter­actions between the water mol­ecules (both coordinated and free) and carboxyl­ate O atoms strengthen the packing of the layers. Furthermore, the luminescence properties of the complex were investigated. The compound exhibits a blue photoluminescence in the solid state at room temperature and may be a good candidate for potential hybrid inorganic–organic photoactive materials.

Computing details

Data collection: APEX2 (Bruker, 2012); cell refinement: APEX2 (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Poly[[aqua(µ₂-4,4'-bipyridine-κ²N:N')bis(µ₃-2,2-dimethylbutanedioato)-κ⁴O¹,O^1':O⁴:O^4';κ⁵O¹:O¹,O⁴:O⁴,O^4'-dizinc(II)] dihydrate]

Crystal data

[Zn2(C6H8O4)2(C10H8N2)(H2O)]·2H2O	Z = 2
Mr = 629.02	F(000) = 648
Triclinic, P1	Dx = 1.694 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.2372 (15) Å	Cell parameters from 6239 reflections
b = 9.7244 (16) Å	θ = 2.4–27.3°
c = 14.511 (2) Å	µ = 2.01 mm^−1
α = 79.099 (2)°	T = 296 K
β = 83.298 (2)°	Block, colorless
γ = 75.012 (2)°	0.20 × 0.20 × 0.20 mm
V = 1233.2 (3) Å^3

Data collection

Bruker SMART APEXII CCD area-detector diffractometer	4309 independent reflections
Radiation source: fine-focus sealed tube	3680 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
phi and ω scans	θmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −10→10
Tmin = 0.689, Tmax = 0.689	k = −11→11
12084 measured reflections	l = −17→17

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.084	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0325P)^2 + 1.9247P] where P = (Fo^2 + 2Fc^2)/3
4309 reflections	(Δ/σ)max = 0.001
352 parameters	Δρmax = 0.63 e Å^−3
10 restraints	Δρmin = −0.44 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.

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 > 2sigma(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
Zn1	0.52906 (4)	0.95918 (4)	0.89274 (2)	0.02272 (11)
Zn2	0.55734 (4)	1.09196 (4)	0.59956 (2)	0.02182 (11)
O5	0.4641 (2)	0.8759 (2)	1.03849 (15)	0.0242 (5)
O3	0.4019 (2)	0.9778 (2)	0.63422 (15)	0.0274 (5)
O7	0.5796 (3)	1.0741 (2)	0.76166 (15)	0.0275 (5)
O4	0.3968 (3)	0.8307 (2)	0.53468 (15)	0.0333 (6)
O2	0.4578 (2)	0.8031 (2)	0.83284 (16)	0.0281 (5)
O8	0.7037 (3)	1.1928 (2)	0.65191 (15)	0.0301 (5)
O1	0.3015 (2)	1.0061 (2)	0.85345 (15)	0.0282 (5)
O9	0.7400 (3)	0.8256 (3)	0.90525 (17)	0.0353 (6)
O6	0.6229 (3)	0.6602 (3)	1.05799 (19)	0.0409 (6)
N1	0.3692 (3)	1.2859 (3)	0.60279 (19)	0.0253 (6)
N2	0.7430 (3)	0.8960 (3)	0.59911 (18)	0.0239 (6)
C1	0.8579 (4)	0.8902 (4)	0.5333 (2)	0.0322 (8)
H1	0.8557	0.9702	0.4864	0.039*
C2	0.9787 (4)	0.7734 (4)	0.5307 (2)	0.0313 (8)
H2	1.0540	0.7754	0.4823	0.038*
C3	0.9886 (3)	0.6529 (3)	0.6001 (2)	0.0235 (7)
C4	0.8709 (4)	0.6590 (4)	0.6692 (3)	0.0336 (8)
H4	0.8719	0.5813	0.7178	0.040*
C5	0.7524 (4)	0.7798 (4)	0.6662 (2)	0.0318 (8)
H5	0.6751	0.7804	0.7134	0.038*
C6	0.2647 (4)	1.2964 (4)	0.6744 (2)	0.0328 (8)
H6	0.2755	1.2220	0.7258	0.039*
C7	0.1416 (4)	1.4117 (4)	0.6762 (2)	0.0326 (8)
H7	0.0723	1.4135	0.7282	0.039*
C8	1.1196 (3)	0.5255 (3)	0.6011 (2)	0.0233 (7)
C9	1.2301 (4)	0.5148 (4)	0.5272 (3)	0.0350 (8)
H9	1.2229	0.5882	0.4753	0.042*
C10	0.3502 (4)	1.3958 (4)	0.5306 (3)	0.0356 (8)
H10	0.4220	1.3917	0.4800	0.043*
C17	0.5011 (3)	0.7415 (3)	1.0770 (2)	0.0233 (7)
C18	0.3817 (3)	0.6789 (3)	1.1416 (2)	0.0234 (7)
C19	0.2650 (3)	0.7931 (3)	1.1886 (2)	0.0239 (7)
H19A	0.2260	0.8744	1.1408	0.029*
H19B	0.1819	0.7523	1.2173	0.029*
C20	0.6719 (3)	1.1538 (3)	0.7373 (2)	0.0226 (7)
C11	0.3313 (4)	0.8882 (3)	0.8217 (2)	0.0231 (7)
C12	0.2138 (3)	0.8483 (4)	0.7730 (2)	0.0250 (7)
C22	0.4545 (4)	0.5540 (4)	1.2146 (3)	0.0380 (9)
H22A	0.5269	0.4841	1.1836	0.057*
H22B	0.3788	0.5099	1.2496	0.057*
H22C	0.5038	0.5892	1.2566	0.057*
C21	0.2995 (4)	0.6238 (4)	1.0753 (3)	0.0406 (9)
H21A	0.2535	0.7030	1.0294	0.061*
H21B	0.2235	0.5808	1.1111	0.061*
H21C	0.3701	0.5530	1.0441	0.061*
C13	0.2896 (4)	0.7810 (3)	0.6870 (2)	0.0255 (7)
H13A	0.3618	0.6921	0.7089	0.031*
H13B	0.2136	0.7555	0.6573	0.031*
C16	0.0840 (4)	0.9776 (4)	0.7445 (3)	0.0394 (9)
H16A	0.0130	0.9475	0.7143	0.059*
H16B	0.1220	1.0505	0.7018	0.059*
H16C	0.0353	1.0161	0.7995	0.059*
C15	0.1528 (4)	0.7321 (4)	0.8425 (2)	0.0362 (9)
H15A	0.0783	0.7047	0.8139	0.054*
H15B	0.1084	0.7702	0.8985	0.054*
H15C	0.2337	0.6491	0.8586	0.054*
C14	0.3691 (3)	0.8713 (3)	0.6133 (2)	0.0223 (7)
O10	0.0815 (3)	1.1063 (3)	0.9783 (2)	0.0474 (7)
O11	0.0566 (3)	0.4152 (3)	0.9257 (3)	0.0650 (9)
H11A	0.149 (3)	0.413 (5)	0.919 (4)	0.098*
H11B	0.052 (5)	0.335 (3)	0.923 (5)	0.098*
H9A	0.803 (5)	0.849 (6)	0.932 (3)	0.098*
H9B	0.713 (6)	0.763 (5)	0.947 (3)	0.098*
H10A	0.140 (5)	1.071 (6)	0.935 (3)	0.098*
H10B	0.011 (4)	1.159 (3)	0.950 (3)	0.098*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0231 (2)	0.0236 (2)	0.0225 (2)	−0.00651 (15)	−0.00045 (14)	−0.00590 (15)
Zn2	0.0229 (2)	0.01995 (19)	0.0216 (2)	−0.00289 (15)	−0.00022 (14)	−0.00491 (14)
O5	0.0314 (12)	0.0196 (11)	0.0214 (11)	−0.0062 (10)	0.0016 (9)	−0.0051 (9)
O3	0.0293 (12)	0.0271 (12)	0.0273 (12)	−0.0109 (10)	0.0033 (10)	−0.0055 (10)
O7	0.0311 (12)	0.0304 (12)	0.0227 (12)	−0.0110 (11)	−0.0009 (9)	−0.0042 (10)
O4	0.0480 (15)	0.0258 (12)	0.0202 (12)	0.0000 (11)	0.0050 (10)	−0.0061 (10)
O2	0.0230 (12)	0.0291 (12)	0.0327 (13)	−0.0043 (10)	−0.0053 (10)	−0.0069 (10)
O8	0.0355 (13)	0.0314 (13)	0.0230 (12)	−0.0086 (11)	−0.0007 (10)	−0.0038 (10)
O1	0.0285 (12)	0.0304 (12)	0.0284 (12)	−0.0095 (10)	0.0036 (10)	−0.0117 (10)
O9	0.0287 (13)	0.0363 (14)	0.0379 (14)	−0.0027 (11)	−0.0013 (11)	−0.0067 (11)
O6	0.0256 (13)	0.0288 (13)	0.0603 (18)	−0.0004 (11)	0.0081 (12)	−0.0033 (12)
N1	0.0254 (14)	0.0216 (13)	0.0267 (15)	−0.0027 (12)	0.0001 (11)	−0.0043 (11)
N2	0.0220 (13)	0.0229 (13)	0.0258 (14)	−0.0038 (11)	−0.0005 (11)	−0.0045 (11)
C1	0.0301 (18)	0.0281 (18)	0.0307 (19)	−0.0028 (15)	0.0006 (15)	0.0061 (15)
C2	0.0223 (17)	0.0331 (18)	0.0306 (18)	0.0005 (15)	0.0043 (14)	0.0003 (15)
C3	0.0215 (16)	0.0220 (16)	0.0268 (17)	−0.0035 (13)	−0.0026 (13)	−0.0054 (13)
C4	0.0321 (19)	0.0255 (17)	0.0343 (19)	−0.0017 (15)	0.0060 (15)	0.0044 (15)
C5	0.0287 (18)	0.0294 (18)	0.0317 (19)	−0.0021 (15)	0.0082 (14)	−0.0045 (15)
C6	0.0342 (19)	0.0258 (17)	0.0307 (19)	−0.0008 (15)	0.0013 (15)	0.0031 (15)
C7	0.0288 (18)	0.0307 (18)	0.0289 (18)	0.0017 (15)	0.0060 (14)	0.0007 (15)
C8	0.0220 (16)	0.0209 (15)	0.0275 (17)	−0.0046 (13)	−0.0031 (13)	−0.0051 (13)
C9	0.037 (2)	0.0258 (18)	0.0312 (19)	0.0012 (16)	0.0084 (15)	0.0031 (15)
C10	0.0340 (19)	0.0289 (18)	0.035 (2)	−0.0003 (16)	0.0121 (15)	−0.0018 (15)
C17	0.0252 (17)	0.0232 (16)	0.0241 (17)	−0.0077 (14)	−0.0031 (13)	−0.0070 (13)
C18	0.0243 (16)	0.0193 (15)	0.0269 (17)	−0.0050 (13)	−0.0016 (13)	−0.0050 (13)
C19	0.0223 (16)	0.0253 (16)	0.0238 (16)	−0.0070 (14)	0.0004 (13)	−0.0032 (13)
C20	0.0207 (16)	0.0192 (15)	0.0253 (17)	0.0000 (13)	0.0003 (13)	−0.0054 (13)
C11	0.0248 (17)	0.0294 (17)	0.0151 (15)	−0.0092 (15)	0.0043 (12)	−0.0035 (13)
C12	0.0223 (16)	0.0309 (17)	0.0228 (16)	−0.0070 (14)	0.0012 (13)	−0.0082 (14)
C22	0.041 (2)	0.0240 (18)	0.042 (2)	−0.0002 (16)	0.0023 (17)	−0.0012 (16)
C21	0.042 (2)	0.048 (2)	0.042 (2)	−0.0225 (19)	0.0024 (17)	−0.0203 (18)
C13	0.0308 (18)	0.0275 (17)	0.0214 (16)	−0.0108 (15)	0.0013 (13)	−0.0085 (13)
C16	0.0261 (18)	0.046 (2)	0.044 (2)	0.0013 (17)	−0.0059 (16)	−0.0155 (18)
C15	0.035 (2)	0.051 (2)	0.0277 (19)	−0.0232 (18)	0.0044 (15)	−0.0068 (17)
C14	0.0172 (15)	0.0208 (16)	0.0243 (17)	0.0030 (13)	−0.0045 (12)	−0.0009 (13)
O10	0.0325 (15)	0.0582 (18)	0.0568 (18)	−0.0110 (13)	0.0111 (13)	−0.0313 (15)
O11	0.0408 (17)	0.0526 (19)	0.097 (3)	−0.0143 (15)	−0.0067 (18)	0.0056 (19)

Geometric parameters (Å, º)

Zn1—O9	2.049 (2)	C6—H6	0.9300
Zn1—O5^i	2.060 (2)	C7—C8^iii	1.390 (5)
Zn1—O7	2.084 (2)	C7—H7	0.9300
Zn1—O1	2.153 (2)	C8—C9	1.390 (5)
Zn1—O2	2.155 (2)	C8—C7^iv	1.390 (5)
Zn1—O5	2.190 (2)	C9—C10^iv	1.378 (5)
Zn1—C11	2.497 (3)	C9—H9	0.9300
Zn1—Zn1^i	3.3065 (8)	C10—C9^iii	1.378 (5)
Zn2—O4^ii	1.989 (2)	C10—H10	0.9300
Zn2—O3	1.998 (2)	C17—C18	1.534 (4)
Zn2—O8	2.139 (2)	C18—C22	1.518 (5)
Zn2—N2	2.210 (3)	C18—C19	1.535 (4)
Zn2—N1	2.213 (3)	C18—C21	1.538 (5)
Zn2—O7	2.355 (2)	C19—C20^i	1.508 (4)
Zn2—C20	2.599 (3)	C19—H19A	0.9700
O5—C17	1.294 (4)	C19—H19B	0.9700
O5—Zn1^i	2.060 (2)	C20—C19^i	1.508 (4)
O3—C14	1.248 (4)	C11—C12	1.527 (4)
O7—C20	1.273 (4)	C12—C16	1.526 (5)
O4—C14	1.254 (4)	C12—C13	1.531 (4)
O4—Zn2^ii	1.989 (2)	C12—C15	1.542 (5)
O2—C11	1.253 (4)	C22—H22A	0.9600
O8—C20	1.250 (4)	C22—H22B	0.9600
O1—C11	1.268 (4)	C22—H22C	0.9600
O9—H9A	0.841 (19)	C21—H21A	0.9600
O9—H9B	0.838 (19)	C21—H21B	0.9600
O6—C17	1.232 (4)	C21—H21C	0.9600
N1—C6	1.333 (4)	C13—C14	1.499 (4)
N1—C10	1.339 (4)	C13—H13A	0.9700
N2—C5	1.336 (4)	C13—H13B	0.9700
N2—C1	1.339 (4)	C16—H16A	0.9600
C1—C2	1.374 (5)	C16—H16B	0.9600
C1—H1	0.9300	C16—H16C	0.9600
C2—C3	1.384 (5)	C15—H15A	0.9600
C2—H2	0.9300	C15—H15B	0.9600
C3—C4	1.388 (5)	C15—H15C	0.9600
C3—C8	1.490 (4)	O10—H10A	0.848 (19)
C4—C5	1.381 (5)	O10—H10B	0.818 (19)
C4—H4	0.9300	O11—H11A	0.840 (19)
C5—H5	0.9300	O11—H11B	0.803 (18)
C6—C7	1.377 (5)
O9—Zn1—O5^i	103.06 (10)	N1—C6—C7	123.3 (3)
O9—Zn1—O7	95.35 (9)	N1—C6—H6	118.3
O5^i—Zn1—O7	92.54 (9)	C7—C6—H6	118.3
O9—Zn1—O1	151.38 (10)	C6—C7—C8^iii	120.7 (3)
O5^i—Zn1—O1	105.29 (8)	C6—C7—H7	119.6
O7—Zn1—O1	87.29 (9)	C8^iii—C7—H7	119.6
O9—Zn1—O2	90.81 (9)	C9—C8—C7^iv	115.6 (3)
O5^i—Zn1—O2	164.35 (9)	C9—C8—C3	121.8 (3)
O7—Zn1—O2	93.35 (9)	C7^iv—C8—C3	122.6 (3)
O1—Zn1—O2	60.57 (8)	C10^iv—C9—C8	120.3 (3)
O9—Zn1—O5	90.24 (9)	C10^iv—C9—H9	119.9
O5^i—Zn1—O5	77.90 (9)	C8—C9—H9	119.9
O7—Zn1—O5	169.83 (8)	N1—C10—C9^iii	123.6 (3)
O1—Zn1—O5	91.87 (8)	N1—C10—H10	118.2
O2—Zn1—O5	95.06 (8)	C9^iii—C10—H10	118.2
O9—Zn1—C11	120.89 (10)	O6—C17—O5	122.7 (3)
O5^i—Zn1—C11	135.71 (10)	O6—C17—C18	119.1 (3)
O7—Zn1—C11	88.84 (9)	O5—C17—C18	118.0 (3)
O1—Zn1—C11	30.53 (9)	C22—C18—C17	110.9 (3)
O2—Zn1—C11	30.11 (9)	C22—C18—C19	110.9 (3)
O5—Zn1—C11	95.58 (9)	C17—C18—C19	112.9 (2)
O9—Zn1—Zn1^i	98.25 (7)	C22—C18—C21	109.7 (3)
O5^i—Zn1—Zn1^i	40.36 (6)	C17—C18—C21	104.5 (3)
O7—Zn1—Zn1^i	132.81 (6)	C19—C18—C21	107.5 (3)
O1—Zn1—Zn1^i	100.71 (6)	C20^i—C19—C18	113.0 (3)
O2—Zn1—Zn1^i	131.18 (6)	C20^i—C19—H19A	109.0
O5—Zn1—Zn1^i	37.53 (5)	C18—C19—H19A	109.0
C11—Zn1—Zn1^i	120.69 (7)	C20^i—C19—H19B	109.0
O4^ii—Zn2—O3	120.07 (10)	C18—C19—H19B	109.0
O4^ii—Zn2—O8	94.35 (10)	H19A—C19—H19B	107.8
O3—Zn2—O8	145.33 (9)	O8—C20—O7	119.4 (3)
O4^ii—Zn2—N2	93.37 (9)	O8—C20—C19^i	120.6 (3)
O3—Zn2—N2	92.76 (9)	O7—C20—C19^i	119.8 (3)
O8—Zn2—N2	88.93 (9)	O8—C20—Zn2	54.80 (16)
O4^ii—Zn2—N1	87.81 (10)	O7—C20—Zn2	64.67 (16)
O3—Zn2—N1	86.31 (9)	C19^i—C20—Zn2	173.5 (2)
O8—Zn2—N1	91.37 (9)	O2—C11—O1	119.0 (3)
N2—Zn2—N1	178.76 (10)	O2—C11—C12	120.2 (3)
O4^ii—Zn2—O7	152.01 (9)	O1—C11—C12	120.7 (3)
O3—Zn2—O7	87.64 (8)	O2—C11—Zn1	59.66 (16)
O8—Zn2—O7	57.76 (8)	O1—C11—Zn1	59.59 (16)
N2—Zn2—O7	88.76 (9)	C12—C11—Zn1	176.9 (2)
N1—Zn2—O7	90.38 (9)	C16—C12—C11	112.3 (3)
O4^ii—Zn2—C20	122.80 (10)	C16—C12—C13	110.6 (3)
O3—Zn2—C20	116.83 (10)	C11—C12—C13	109.2 (3)
O8—Zn2—C20	28.52 (9)	C16—C12—C15	109.4 (3)
N2—Zn2—C20	89.20 (9)	C11—C12—C15	107.5 (3)
N1—Zn2—C20	90.48 (10)	C13—C12—C15	107.7 (3)
O7—Zn2—C20	29.25 (9)	C18—C22—H22A	109.5
C17—O5—Zn1^i	122.42 (19)	C18—C22—H22B	109.5
C17—O5—Zn1	124.48 (19)	H22A—C22—H22B	109.5
Zn1^i—O5—Zn1	102.10 (9)	C18—C22—H22C	109.5
C14—O3—Zn2	139.7 (2)	H22A—C22—H22C	109.5
C20—O7—Zn1	130.2 (2)	H22B—C22—H22C	109.5
C20—O7—Zn2	86.08 (18)	C18—C21—H21A	109.5
Zn1—O7—Zn2	142.47 (11)	C18—C21—H21B	109.5
C14—O4—Zn2^ii	139.9 (2)	H21A—C21—H21B	109.5
C11—O2—Zn1	90.23 (19)	C18—C21—H21C	109.5
C20—O8—Zn2	96.68 (19)	H21A—C21—H21C	109.5
C11—O1—Zn1	89.88 (19)	H21B—C21—H21C	109.5
Zn1—O9—H9A	119 (4)	C14—C13—C12	117.0 (3)
Zn1—O9—H9B	95 (4)	C14—C13—H13A	108.1
H9A—O9—H9B	102 (2)	C12—C13—H13A	108.1
C6—N1—C10	116.5 (3)	C14—C13—H13B	108.1
C6—N1—Zn2	121.9 (2)	C12—C13—H13B	108.1
C10—N1—Zn2	121.6 (2)	H13A—C13—H13B	107.3
C5—N2—C1	115.9 (3)	C12—C16—H16A	109.5
C5—N2—Zn2	122.8 (2)	C12—C16—H16B	109.5
C1—N2—Zn2	121.3 (2)	H16A—C16—H16B	109.5
N2—C1—C2	124.2 (3)	C12—C16—H16C	109.5
N2—C1—H1	117.9	H16A—C16—H16C	109.5
C2—C1—H1	117.9	H16B—C16—H16C	109.5
C1—C2—C3	120.1 (3)	C12—C15—H15A	109.5
C1—C2—H2	120.0	C12—C15—H15B	109.5
C3—C2—H2	120.0	H15A—C15—H15B	109.5
C2—C3—C4	116.0 (3)	C12—C15—H15C	109.5
C2—C3—C8	121.7 (3)	H15A—C15—H15C	109.5
C4—C3—C8	122.2 (3)	H15B—C15—H15C	109.5
C5—C4—C3	120.4 (3)	O3—C14—O4	125.9 (3)
C5—C4—H4	119.8	O3—C14—C13	118.8 (3)
C3—C4—H4	119.8	O4—C14—C13	115.3 (3)
N2—C5—C4	123.5 (3)	H10A—O10—H10B	103 (2)
N2—C5—H5	118.3	H11A—O11—H11B	105 (2)
C4—C5—H5	118.3
O9—Zn1—O5—C17	−41.0 (2)	C1—N2—C5—C4	−0.6 (5)
O5^i—Zn1—O5—C17	−144.3 (3)	Zn2—N2—C5—C4	−177.1 (3)
O7—Zn1—O5—C17	−164.5 (4)	C3—C4—C5—N2	−0.3 (6)
O1—Zn1—O5—C17	110.4 (2)	C10—N1—C6—C7	0.6 (5)
O2—Zn1—O5—C17	49.8 (2)	Zn2—N1—C6—C7	−176.1 (3)
C11—Zn1—O5—C17	80.1 (2)	N1—C6—C7—C8^iii	0.2 (6)
Zn1^i—Zn1—O5—C17	−144.3 (3)	C2—C3—C8—C9	−7.1 (5)
O9—Zn1—O5—Zn1^i	103.31 (11)	C4—C3—C8—C9	174.1 (3)
O5^i—Zn1—O5—Zn1^i	0.000 (1)	C2—C3—C8—C7^iv	171.4 (3)
O7—Zn1—O5—Zn1^i	−20.2 (5)	C4—C3—C8—C7^iv	−7.4 (5)
O1—Zn1—O5—Zn1^i	−105.23 (9)	C7^iv—C8—C9—C10^iv	1.1 (5)
O2—Zn1—O5—Zn1^i	−165.85 (9)	C3—C8—C9—C10^iv	179.7 (3)
C11—Zn1—O5—Zn1^i	−135.61 (10)	C6—N1—C10—C9^iii	−0.6 (5)
O4^ii—Zn2—O3—C14	52.2 (3)	Zn2—N1—C10—C9^iii	176.1 (3)
O8—Zn2—O3—C14	−135.4 (3)	Zn1^i—O5—C17—O6	−102.5 (3)
N2—Zn2—O3—C14	−43.3 (3)	Zn1—O5—C17—O6	35.0 (4)
N1—Zn2—O3—C14	137.5 (3)	Zn1^i—O5—C17—C18	83.6 (3)
O7—Zn2—O3—C14	−132.0 (3)	Zn1—O5—C17—C18	−138.9 (2)
C20—Zn2—O3—C14	−133.8 (3)	O6—C17—C18—C22	33.0 (4)
O9—Zn1—O7—C20	−62.9 (3)	O5—C17—C18—C22	−152.8 (3)
O5^i—Zn1—O7—C20	40.5 (3)	O6—C17—C18—C19	158.3 (3)
O1—Zn1—O7—C20	145.7 (3)	O5—C17—C18—C19	−27.5 (4)
O2—Zn1—O7—C20	−154.0 (3)	O6—C17—C18—C21	−85.2 (4)
O5—Zn1—O7—C20	60.2 (6)	O5—C17—C18—C21	89.0 (3)
C11—Zn1—O7—C20	176.2 (3)	C22—C18—C19—C20^i	54.5 (4)
Zn1^i—Zn1—O7—C20	43.6 (3)	C17—C18—C19—C20^i	−70.7 (3)
O9—Zn1—O7—Zn2	99.73 (19)	C21—C18—C19—C20^i	174.5 (3)
O5^i—Zn1—O7—Zn2	−156.90 (18)	Zn2—O8—C20—O7	2.0 (3)
O1—Zn1—O7—Zn2	−51.70 (18)	Zn2—O8—C20—C19^i	−174.5 (2)
O2—Zn1—O7—Zn2	8.59 (18)	Zn1—O7—C20—O8	167.7 (2)
O5—Zn1—O7—Zn2	−137.2 (4)	Zn2—O7—C20—O8	−1.8 (3)
C11—Zn1—O7—Zn2	−21.19 (18)	Zn1—O7—C20—C19^i	−15.8 (4)
Zn1^i—Zn1—O7—Zn2	−153.81 (12)	Zn2—O7—C20—C19^i	174.7 (3)
O4^ii—Zn2—O7—C20	−4.3 (3)	Zn1—O7—C20—Zn2	169.5 (2)
O3—Zn2—O7—C20	−176.60 (18)	O4^ii—Zn2—C20—O8	−4.3 (2)
O8—Zn2—O7—C20	1.07 (16)	O3—Zn2—C20—O8	−178.09 (17)
N2—Zn2—O7—C20	90.59 (18)	N2—Zn2—C20—O8	89.22 (19)
N1—Zn2—O7—C20	−90.30 (18)	N1—Zn2—C20—O8	−91.98 (19)
O4^ii—Zn2—O7—Zn1	−171.03 (16)	O7—Zn2—C20—O8	178.1 (3)
O3—Zn2—O7—Zn1	16.62 (18)	O4^ii—Zn2—C20—O7	177.63 (16)
O8—Zn2—O7—Zn1	−165.7 (2)	O3—Zn2—C20—O7	3.8 (2)
N2—Zn2—O7—Zn1	−76.19 (18)	O8—Zn2—C20—O7	−178.1 (3)
N1—Zn2—O7—Zn1	102.92 (19)	N2—Zn2—C20—O7	−88.88 (17)
C20—Zn2—O7—Zn1	−166.8 (3)	N1—Zn2—C20—O7	89.92 (17)
O9—Zn1—O2—C11	−177.27 (18)	O4^ii—Zn2—C20—C19^i	42.4 (19)
O5^i—Zn1—O2—C11	30.1 (4)	O3—Zn2—C20—C19^i	−131.4 (19)
O7—Zn1—O2—C11	−81.86 (18)	O8—Zn2—C20—C19^i	46.7 (19)
O1—Zn1—O2—C11	3.12 (17)	N2—Zn2—C20—C19^i	135.9 (19)
O5—Zn1—O2—C11	92.41 (18)	N1—Zn2—C20—C19^i	−45.3 (19)
Zn1^i—Zn1—O2—C11	81.00 (18)	O7—Zn2—C20—C19^i	−135 (2)
O4^ii—Zn2—O8—C20	176.40 (18)	Zn1—O2—C11—O1	−5.3 (3)
O3—Zn2—O8—C20	3.0 (3)	Zn1—O2—C11—C12	176.4 (2)
N2—Zn2—O8—C20	−90.31 (19)	Zn1—O1—C11—O2	5.3 (3)
N1—Zn2—O8—C20	88.49 (19)	Zn1—O1—C11—C12	−176.4 (2)
O7—Zn2—O8—C20	−1.10 (17)	O9—Zn1—C11—O2	3.2 (2)
O9—Zn1—O1—C11	−3.9 (3)	O5^i—Zn1—C11—O2	−168.84 (16)
O5^i—Zn1—O1—C11	−175.80 (17)	O7—Zn1—C11—O2	98.72 (18)
O7—Zn1—O1—C11	92.31 (18)	O1—Zn1—C11—O2	−174.6 (3)
O2—Zn1—O1—C11	−3.08 (17)	O5—Zn1—C11—O2	−90.46 (17)
O5—Zn1—O1—C11	−97.84 (18)	Zn1^i—Zn1—C11—O2	−120.17 (16)
Zn1^i—Zn1—O1—C11	−134.58 (16)	O9—Zn1—C11—O1	177.82 (16)
O4^ii—Zn2—N1—C6	168.5 (3)	O5^i—Zn1—C11—O1	5.8 (2)
O3—Zn2—N1—C6	48.2 (3)	O7—Zn1—C11—O1	−86.64 (18)
O8—Zn2—N1—C6	−97.2 (3)	O2—Zn1—C11—O1	174.6 (3)
N2—Zn2—N1—C6	7 (5)	O5—Zn1—C11—O1	84.19 (18)
O7—Zn2—N1—C6	−39.4 (3)	Zn1^i—Zn1—C11—O1	54.48 (19)
C20—Zn2—N1—C6	−68.7 (3)	O9—Zn1—C11—C12	−86 (4)
O4^ii—Zn2—N1—C10	−8.0 (3)	O5^i—Zn1—C11—C12	102 (4)
O3—Zn2—N1—C10	−128.4 (3)	O7—Zn1—C11—C12	10 (4)
O8—Zn2—N1—C10	86.3 (3)	O1—Zn1—C11—C12	96 (4)
N2—Zn2—N1—C10	−170 (5)	O2—Zn1—C11—C12	−89 (4)
O7—Zn2—N1—C10	144.0 (3)	O5—Zn1—C11—C12	−179 (100)
C20—Zn2—N1—C10	114.8 (3)	Zn1^i—Zn1—C11—C12	151 (4)
O4^ii—Zn2—N2—C5	−164.4 (3)	O2—C11—C12—C16	−165.9 (3)
O3—Zn2—N2—C5	−44.0 (3)	O1—C11—C12—C16	15.8 (4)
O8—Zn2—N2—C5	101.3 (3)	Zn1—C11—C12—C16	−79 (4)
N1—Zn2—N2—C5	−2 (5)	O2—C11—C12—C13	−42.9 (4)
O7—Zn2—N2—C5	43.6 (3)	O1—C11—C12—C13	138.8 (3)
C20—Zn2—N2—C5	72.8 (3)	Zn1—C11—C12—C13	44 (4)
O4^ii—Zn2—N2—C1	19.3 (3)	O2—C11—C12—C15	73.7 (4)
O3—Zn2—N2—C1	139.6 (3)	O1—C11—C12—C15	−104.6 (3)
O8—Zn2—N2—C1	−75.0 (3)	Zn1—C11—C12—C15	161 (4)
N1—Zn2—N2—C1	−179 (100)	C16—C12—C13—C14	65.6 (4)
O7—Zn2—N2—C1	−132.8 (3)	C11—C12—C13—C14	−58.5 (4)
C20—Zn2—N2—C1	−103.5 (3)	C15—C12—C13—C14	−174.9 (3)
C5—N2—C1—C2	1.4 (5)	Zn2—O3—C14—O4	−29.8 (5)
Zn2—N2—C1—C2	178.0 (3)	Zn2—O3—C14—C13	150.1 (3)
N2—C1—C2—C3	−1.3 (6)	Zn2^ii—O4—C14—O3	−21.0 (5)
C1—C2—C3—C4	0.3 (5)	Zn2^ii—O4—C14—C13	159.0 (3)
C1—C2—C3—C8	−178.5 (3)	C12—C13—C14—O3	17.3 (4)
C2—C3—C4—C5	0.4 (5)	C12—C13—C14—O4	−162.8 (3)
C8—C3—C4—C5	179.2 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O11—H11A···O6^v	0.84 (2)	2.09 (3)	2.887 (4)	159 (5)
O11—H11B···O10^vi	0.80 (2)	2.17 (3)	2.911 (4)	153 (6)
O9—H9A···O10^i	0.84 (2)	1.94 (2)	2.766 (4)	166 (5)
O9—H9B···O6	0.84 (2)	1.95 (2)	2.768 (4)	165 (6)
O9—H9B···O5	0.84 (2)	2.60 (5)	3.006 (3)	111 (5)
O10—H10A···O1	0.85 (2)	1.84 (2)	2.674 (3)	166 (5)

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