Controllable assembly of a three-dimensional metal-organic supra­molecular framework displaying hydrogen-bonding and [pi]-[pi] stacking inter­actions

The complex poly[[aqua­([mu]₂-phthalato-[kappa]²O¹:O²){[mu]₃-2-[3-(pyri­din-2-yl)-1H-pyrazol-1-yl]acetato-[kappa]⁴N²,N³:O:O'}{[mu]₂-2-[3-(pyri­din-2-yl)-1H-pyrazol-1-yl]acetato-[kappa]³N²,N³:O}dizinc(II)] dihydrate], {[Zn₂(C₁₀H₈N₃O₂)₂(C₈H₄O₄)(H₂O)]·2H₂O}_n, has been prepared by solvothermal reaction of 2-[3-(pyridin-2-yl)-1H-pyrazol-1-yl]aceto­nitrile (PPAN) with zinc(II). Under hydro­thermal conditions, PPAN is hydrolyzed to 2-[3-(pyridin-2-yl)-1H-pyrazol-1-yl]acetate (PPAA^-). The structure determination reveals that the complex is a one-dimensional double chain containing cationic [Zn₄(PPAA)₄]⁴⁺ structural units, which are further extended by bridging phthalate ligands. The one-dimensional chains are extended into a three-dimensional supra­molecular architecture via hydrogen-bonding and [pi]-[pi] stacking inter­actions.

Computing details

Data collection: SMART (Bruker, 2003); cell refinement: SMART (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Berndt, 2005); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and TOPOS (Blatov, 2004).

Poly[[aqua(µ₂-phthalato-κ²O¹:O²){µ₃-2-[3-(pyridin-2-yl)-1H-pyrazol-1-yl]acetato-κ⁴N²,N³:O:O'}{µ₂-2-[3-(pyridin-2-yl)-1H-pyrazol-1-yl]acetato-κ³N²,N³:O}dizinc(II)] dihydrate]

Crystal data

[Zn2(C10H8N3O2)2(C8H4O4)(H2O)]·2H2O	Z = 2
Mr = 753.29	F(000) = 768
Triclinic, P1	Dx = 1.735 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 11.1541 (9) Å	Cell parameters from 2559 reflections
b = 11.6710 (9) Å	θ = 2.3–26.5°
c = 12.2073 (10) Å	µ = 1.74 mm^−1
α = 93.545 (1)°	T = 296 K
β = 106.904 (1)°	Block, colourless
γ = 106.283 (1)°	0.28 × 0.22 × 0.20 mm
V = 1441.6 (2) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	5588 independent reflections
Radiation source: fine-focus sealed tube	4285 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.018
phi and ω scans	θmax = 26.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→11
Tmin = 0.642, Tmax = 0.722	k = −14→14
7932 measured reflections	l = −13→15

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.083	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0316P)^2 + 1.1689P] where P = (Fo^2 + 2Fc^2)/3
5588 reflections	(Δ/σ)max = 0.001
424 parameters	Δρmax = 0.35 e Å^−3
0 restraints	Δρmin = −0.58 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.

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 > σ(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	0.68849 (4)	1.24620 (3)	1.04076 (3)	0.02612 (11)
Zn2	0.74757 (4)	1.01217 (3)	0.78177 (3)	0.02846 (11)
O1	0.6764 (2)	1.08982 (18)	0.94965 (18)	0.0298 (5)
O2	0.6941 (2)	0.91106 (19)	0.90539 (19)	0.0332 (5)
O3	0.3447 (3)	0.6212 (2)	0.7597 (2)	0.0432 (6)
O4	0.3664 (2)	0.81022 (19)	0.82676 (19)	0.0338 (5)
O5	0.7978 (2)	0.9000 (2)	0.68999 (19)	0.0339 (5)
O6	0.9827 (3)	1.0414 (2)	0.6973 (2)	0.0519 (7)
O7	1.0288 (2)	0.8665 (2)	0.86991 (19)	0.0392 (6)
O8	1.1118 (2)	0.71330 (19)	0.87391 (19)	0.0342 (5)
O9	0.9370 (2)	1.0910 (2)	0.9059 (2)	0.0395 (6)
H9A	0.9362	1.1010	0.9752	0.059*
H9B	0.9991	1.0674	0.8956	0.059*
O10	0.6428 (3)	0.6587 (3)	0.6064 (3)	0.0738 (9)
H10A	0.6555	0.6220	0.5505	0.111*
H10B	0.6907	0.7319	0.6305	0.111*
O11	0.5969 (3)	0.5153 (3)	0.4052 (3)	0.0807 (10)
H11A	0.5246	0.4637	0.4023	0.121*
H11B	0.6482	0.4894	0.3781	0.121*
N1	0.2799 (2)	0.5869 (2)	1.0166 (2)	0.0270 (6)
N2	0.5080 (2)	0.7579 (2)	1.0667 (2)	0.0274 (6)
N3	0.6339 (3)	0.8308 (2)	1.1024 (2)	0.0291 (6)
N4	0.7504 (3)	1.1819 (2)	0.7324 (2)	0.0312 (6)
N5	0.5418 (3)	0.9839 (2)	0.6784 (2)	0.0308 (6)
N6	0.4229 (3)	0.8981 (3)	0.6396 (2)	0.0339 (6)
C1	0.1604 (3)	0.5040 (3)	0.9920 (3)	0.0331 (8)
H1	0.0867	0.5231	0.9496	0.040*
C2	0.1424 (3)	0.3926 (3)	1.0265 (3)	0.0372 (8)
H2	0.0579	0.3384	1.0088	0.045*
C3	0.2507 (3)	0.3618 (3)	1.0878 (3)	0.0372 (8)
H3	0.2408	0.2866	1.1119	0.045*
C4	0.3749 (3)	0.4458 (3)	1.1128 (3)	0.0342 (8)
H4	0.4499	0.4271	1.1529	0.041*
C5	0.3861 (3)	0.5575 (3)	1.0776 (3)	0.0264 (7)
C6	0.5121 (3)	0.6531 (3)	1.1034 (3)	0.0276 (7)
C7	0.6419 (3)	0.6599 (3)	1.1640 (3)	0.0372 (8)
H7	0.6714	0.5995	1.1979	0.045*
C8	0.7159 (3)	0.7747 (3)	1.1623 (3)	0.0362 (8)
H8	0.8067	0.8080	1.1965	0.043*
C9	0.6627 (3)	0.9570 (3)	1.0887 (3)	0.0312 (7)
H9A'	0.7439	1.0026	1.1492	0.037*
H9B'	0.5928	0.9853	1.1005	0.037*
C10	0.6770 (3)	0.9854 (3)	0.9726 (3)	0.0262 (7)
C11	0.8588 (4)	1.2765 (3)	0.7555 (3)	0.0402 (9)
H11	0.9403	1.2658	0.7895	0.048*
C12	0.8552 (4)	1.3895 (3)	0.7310 (3)	0.0479 (10)
H12	0.9328	1.4536	0.7478	0.058*
C13	0.7349 (4)	1.4055 (3)	0.6816 (3)	0.0495 (10)
H13	0.7298	1.4812	0.6655	0.059*
C14	0.6224 (4)	1.3090 (3)	0.6560 (3)	0.0456 (10)
H14	0.5402	1.3185	0.6224	0.055*
C15	0.6324 (3)	1.1966 (3)	0.6809 (3)	0.0333 (8)
C16	0.5187 (3)	1.0876 (3)	0.6528 (3)	0.0334 (8)
C17	0.3853 (4)	1.0674 (4)	0.5991 (4)	0.0527 (11)
H17	0.3440	1.1243	0.5733	0.063*
C18	0.3275 (4)	0.9467 (4)	0.5922 (4)	0.0519 (11)
H18	0.2379	0.9051	0.5603	0.062*
C19	0.4091 (4)	0.7724 (3)	0.6505 (3)	0.0391 (8)
H19A	0.4921	0.7587	0.6548	0.047*
H19B	0.3429	0.7225	0.5808	0.047*
C20	0.3706 (3)	0.7307 (3)	0.7546 (3)	0.0305 (7)
C21	0.9536 (3)	0.8387 (3)	0.6254 (3)	0.0273 (7)
C22	0.9278 (3)	0.8234 (3)	0.5055 (3)	0.0367 (8)
H22	0.8877	0.8730	0.4617	0.044*
C23	0.9609 (4)	0.7359 (3)	0.4514 (3)	0.0441 (9)
H23	0.9433	0.7267	0.3715	0.053*
C24	1.0204 (4)	0.6616 (3)	0.5155 (3)	0.0434 (9)
H24	1.0418	0.6017	0.4788	0.052*
C25	1.0477 (3)	0.6767 (3)	0.6339 (3)	0.0332 (8)
H25	1.0889	0.6271	0.6766	0.040*
C26	1.0152 (3)	0.7647 (3)	0.6911 (3)	0.0267 (7)
C27	0.9123 (3)	0.9366 (3)	0.6772 (3)	0.0281 (7)
C28	1.0533 (3)	0.7832 (3)	0.8212 (3)	0.0288 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0291 (2)	0.02265 (19)	0.0305 (2)	0.01162 (15)	0.01078 (17)	0.01038 (16)
Zn2	0.0321 (2)	0.0268 (2)	0.0318 (2)	0.01405 (16)	0.01254 (18)	0.00948 (16)
O1	0.0369 (13)	0.0230 (11)	0.0328 (13)	0.0118 (10)	0.0128 (11)	0.0094 (10)
O2	0.0444 (14)	0.0288 (12)	0.0352 (13)	0.0179 (11)	0.0192 (11)	0.0073 (10)
O3	0.0535 (16)	0.0316 (13)	0.0565 (17)	0.0199 (12)	0.0275 (14)	0.0151 (12)
O4	0.0427 (14)	0.0325 (13)	0.0329 (13)	0.0147 (11)	0.0188 (11)	0.0075 (10)
O5	0.0285 (13)	0.0388 (13)	0.0361 (14)	0.0160 (10)	0.0093 (11)	−0.0013 (11)
O6	0.0654 (18)	0.0271 (14)	0.074 (2)	0.0082 (13)	0.0443 (16)	0.0096 (13)
O7	0.0473 (15)	0.0492 (15)	0.0253 (12)	0.0259 (12)	0.0075 (11)	0.0057 (11)
O8	0.0294 (12)	0.0341 (13)	0.0393 (14)	0.0122 (10)	0.0068 (11)	0.0173 (11)
O9	0.0390 (14)	0.0490 (15)	0.0311 (13)	0.0137 (12)	0.0119 (11)	0.0079 (11)
O10	0.067 (2)	0.0526 (18)	0.097 (3)	0.0043 (15)	0.038 (2)	−0.0133 (17)
O11	0.094 (3)	0.063 (2)	0.085 (2)	0.0108 (18)	0.045 (2)	−0.0064 (18)
N1	0.0274 (14)	0.0245 (13)	0.0314 (15)	0.0093 (11)	0.0105 (12)	0.0103 (11)
N2	0.0260 (14)	0.0234 (13)	0.0343 (16)	0.0076 (11)	0.0107 (12)	0.0109 (11)
N3	0.0272 (15)	0.0273 (14)	0.0315 (15)	0.0058 (11)	0.0090 (12)	0.0100 (12)
N4	0.0357 (16)	0.0310 (15)	0.0315 (16)	0.0124 (13)	0.0148 (13)	0.0089 (12)
N5	0.0327 (16)	0.0323 (15)	0.0317 (16)	0.0129 (12)	0.0134 (13)	0.0098 (12)
N6	0.0331 (16)	0.0394 (16)	0.0313 (16)	0.0118 (13)	0.0118 (13)	0.0118 (13)
C1	0.0273 (18)	0.0306 (18)	0.042 (2)	0.0096 (14)	0.0102 (16)	0.0109 (15)
C2	0.0315 (19)	0.0274 (17)	0.048 (2)	0.0013 (14)	0.0129 (17)	0.0080 (16)
C3	0.045 (2)	0.0240 (17)	0.047 (2)	0.0114 (16)	0.0180 (19)	0.0141 (16)
C4	0.0323 (19)	0.0277 (17)	0.043 (2)	0.0116 (15)	0.0092 (16)	0.0108 (15)
C5	0.0277 (17)	0.0254 (16)	0.0288 (18)	0.0105 (13)	0.0102 (14)	0.0078 (13)
C6	0.0314 (18)	0.0249 (16)	0.0312 (18)	0.0121 (13)	0.0124 (15)	0.0122 (14)
C7	0.0295 (18)	0.0336 (18)	0.049 (2)	0.0119 (15)	0.0079 (17)	0.0212 (17)
C8	0.0248 (18)	0.0381 (19)	0.042 (2)	0.0097 (15)	0.0044 (16)	0.0131 (16)
C9	0.039 (2)	0.0209 (16)	0.0362 (19)	0.0079 (14)	0.0162 (16)	0.0092 (14)
C10	0.0199 (16)	0.0261 (16)	0.0321 (18)	0.0050 (13)	0.0090 (14)	0.0072 (14)
C11	0.044 (2)	0.037 (2)	0.040 (2)	0.0102 (17)	0.0159 (18)	0.0111 (17)
C12	0.060 (3)	0.036 (2)	0.046 (2)	0.0055 (19)	0.021 (2)	0.0120 (18)
C13	0.081 (3)	0.032 (2)	0.046 (2)	0.024 (2)	0.026 (2)	0.0159 (18)
C14	0.057 (3)	0.041 (2)	0.050 (2)	0.027 (2)	0.021 (2)	0.0195 (19)
C15	0.042 (2)	0.0349 (18)	0.0309 (19)	0.0196 (16)	0.0156 (16)	0.0100 (15)
C16	0.037 (2)	0.0367 (19)	0.0322 (19)	0.0192 (16)	0.0114 (16)	0.0136 (15)
C17	0.035 (2)	0.053 (2)	0.075 (3)	0.0235 (19)	0.013 (2)	0.031 (2)
C18	0.029 (2)	0.063 (3)	0.063 (3)	0.0155 (19)	0.0084 (19)	0.026 (2)
C19	0.048 (2)	0.0338 (19)	0.040 (2)	0.0131 (16)	0.0215 (18)	0.0049 (16)
C20	0.0248 (17)	0.0369 (19)	0.0341 (19)	0.0129 (14)	0.0115 (15)	0.0101 (15)
C21	0.0250 (17)	0.0311 (17)	0.0294 (18)	0.0122 (14)	0.0105 (14)	0.0068 (14)
C22	0.043 (2)	0.045 (2)	0.0300 (19)	0.0226 (17)	0.0120 (16)	0.0123 (16)
C23	0.058 (3)	0.055 (2)	0.0252 (19)	0.026 (2)	0.0150 (18)	0.0028 (17)
C24	0.053 (2)	0.038 (2)	0.044 (2)	0.0179 (18)	0.021 (2)	−0.0007 (17)
C25	0.0335 (19)	0.0273 (17)	0.041 (2)	0.0127 (14)	0.0119 (16)	0.0094 (15)
C26	0.0248 (17)	0.0250 (16)	0.0322 (18)	0.0081 (13)	0.0112 (14)	0.0078 (14)
C27	0.0335 (19)	0.0326 (18)	0.0239 (17)	0.0163 (15)	0.0108 (15)	0.0090 (14)
C28	0.0205 (16)	0.0316 (17)	0.0352 (19)	0.0080 (13)	0.0092 (14)	0.0113 (15)

Geometric parameters (Å, º)

Zn1—O4^i	1.976 (2)	C2—C3	1.378 (5)
Zn1—O1	2.027 (2)	C2—H2	0.9300
Zn1—O8^ii	2.067 (2)	C3—C4	1.390 (5)
Zn1—N1^i	2.083 (2)	C3—H3	0.9300
Zn1—N2^i	2.188 (3)	C4—C5	1.381 (4)
Zn2—O5	1.970 (2)	C4—H4	0.9300
Zn2—O2	2.091 (2)	C5—C6	1.463 (4)
Zn2—N4	2.100 (3)	C6—C7	1.398 (4)
Zn2—O9	2.117 (2)	C7—C8	1.367 (5)
Zn2—N5	2.193 (3)	C7—H7	0.9300
O1—C10	1.269 (3)	C8—H8	0.9300
O2—C10	1.248 (4)	C9—C10	1.518 (4)
O3—C20	1.239 (4)	C9—H9A'	0.9700
O4—C20	1.260 (4)	C9—H9B'	0.9700
O4—Zn1^i	1.976 (2)	C11—C12	1.379 (5)
O5—C27	1.286 (4)	C11—H11	0.9300
O6—C27	1.219 (4)	C12—C13	1.372 (5)
O7—C28	1.243 (4)	C12—H12	0.9300
O8—C28	1.275 (3)	C13—C14	1.370 (6)
O8—Zn1^ii	2.067 (2)	C13—H13	0.9300
O9—H9A	0.8500	C14—C15	1.392 (4)
O9—H9B	0.8499	C14—H14	0.9300
O10—H10A	0.8501	C15—C16	1.461 (5)
O10—H10B	0.8502	C16—C17	1.384 (5)
O11—H11A	0.8503	C17—C18	1.361 (5)
O11—H11B	0.8505	C17—H17	0.9300
N1—C1	1.346 (4)	C18—H18	0.9300
N1—C5	1.350 (4)	C19—C20	1.520 (4)
N1—Zn1^i	2.083 (2)	C19—H19A	0.9700
N2—C6	1.336 (4)	C19—H19B	0.9700
N2—N3	1.347 (4)	C21—C22	1.397 (4)
N2—Zn1^i	2.188 (3)	C21—C26	1.400 (4)
N3—C8	1.343 (4)	C21—C27	1.515 (4)
N3—C9	1.449 (4)	C22—C23	1.373 (5)
N4—C11	1.332 (4)	C22—H22	0.9300
N4—C15	1.347 (4)	C23—C24	1.382 (5)
N5—C16	1.343 (4)	C23—H23	0.9300
N5—N6	1.348 (4)	C24—C25	1.376 (5)
N6—C18	1.346 (4)	C24—H24	0.9300
N6—C19	1.450 (4)	C25—C26	1.394 (4)
C1—C2	1.370 (4)	C25—H25	0.9300
C1—H1	0.9300	C26—C28	1.504 (4)
O4^i—Zn1—O1	102.25 (9)	N3—C8—C7	107.8 (3)
O4^i—Zn1—O8^ii	95.14 (9)	N3—C8—H8	126.1
O1—Zn1—O8^ii	93.45 (9)	C7—C8—H8	126.1
O4^i—Zn1—N1^i	131.84 (9)	N3—C9—C10	115.7 (3)
O1—Zn1—N1^i	125.11 (9)	N3—C9—H9A'	108.4
O8^ii—Zn1—N1^i	90.61 (9)	C10—C9—H9A'	108.4
O4^i—Zn1—N2^i	95.46 (10)	N3—C9—H9B'	108.4
O1—Zn1—N2^i	92.51 (9)	C10—C9—H9B'	108.4
O8^ii—Zn1—N2^i	166.47 (9)	H9A'—C9—H9B'	107.4
N1^i—Zn1—N2^i	76.04 (9)	O2—C10—O1	121.8 (3)
O5—Zn2—O2	102.80 (9)	O2—C10—C9	121.3 (3)
O5—Zn2—N4	118.97 (10)	O1—C10—C9	116.8 (3)
O2—Zn2—N4	138.14 (9)	N4—C11—C12	122.8 (4)
O5—Zn2—O9	96.30 (9)	N4—C11—H11	118.6
O2—Zn2—O9	88.00 (9)	C12—C11—H11	118.6
N4—Zn2—O9	90.03 (10)	C13—C12—C11	118.6 (4)
O5—Zn2—N5	102.00 (10)	C13—C12—H12	120.7
O2—Zn2—N5	92.93 (9)	C11—C12—H12	120.7
N4—Zn2—N5	76.64 (10)	C14—C13—C12	119.4 (3)
O9—Zn2—N5	160.97 (9)	C14—C13—H13	120.3
C10—O1—Zn1	135.4 (2)	C12—C13—H13	120.3
C10—O2—Zn2	103.61 (18)	C13—C14—C15	119.3 (4)
C20—O4—Zn1^i	116.6 (2)	C13—C14—H14	120.4
C27—O5—Zn2	118.0 (2)	C15—C14—H14	120.4
C28—O8—Zn1^ii	126.9 (2)	N4—C15—C14	121.2 (3)
Zn2—O9—H9A	113.8	N4—C15—C16	115.5 (3)
Zn2—O9—H9B	116.7	C14—C15—C16	123.3 (3)
H9A—O9—H9B	116.6	N5—C16—C17	110.5 (3)
H10A—O10—H10B	116.6	N5—C16—C15	117.5 (3)
H11A—O11—H11B	116.6	C17—C16—C15	131.9 (3)
C1—N1—C5	117.8 (3)	C18—C17—C16	105.3 (3)
C1—N1—Zn1^i	124.0 (2)	C18—C17—H17	127.3
C5—N1—Zn1^i	118.1 (2)	C16—C17—H17	127.3
C6—N2—N3	105.8 (2)	N6—C18—C17	107.9 (3)
C6—N2—Zn1^i	113.7 (2)	N6—C18—H18	126.0
N3—N2—Zn1^i	140.23 (19)	C17—C18—H18	126.0
C8—N3—N2	111.1 (3)	N6—C19—C20	115.4 (3)
C8—N3—C9	128.4 (3)	N6—C19—H19A	108.4
N2—N3—C9	119.9 (2)	C20—C19—H19A	108.4
C11—N4—C15	118.6 (3)	N6—C19—H19B	108.4
C11—N4—Zn2	124.6 (2)	C20—C19—H19B	108.4
C15—N4—Zn2	116.6 (2)	H19A—C19—H19B	107.5
C16—N5—N6	105.5 (3)	O3—C20—O4	126.0 (3)
C16—N5—Zn2	112.5 (2)	O3—C20—C19	116.8 (3)
N6—N5—Zn2	141.5 (2)	O4—C20—C19	117.2 (3)
C18—N6—N5	110.7 (3)	C22—C21—C26	119.5 (3)
C18—N6—C19	127.9 (3)	C22—C21—C27	117.0 (3)
N5—N6—C19	121.4 (3)	C26—C21—C27	123.5 (3)
N1—C1—C2	123.1 (3)	C23—C22—C21	120.8 (3)
N1—C1—H1	118.5	C23—C22—H22	119.6
C2—C1—H1	118.5	C21—C22—H22	119.6
C1—C2—C3	119.3 (3)	C22—C23—C24	120.1 (3)
C1—C2—H2	120.3	C22—C23—H23	120.0
C3—C2—H2	120.3	C24—C23—H23	120.0
C2—C3—C4	118.4 (3)	C25—C24—C23	119.8 (3)
C2—C3—H3	120.8	C25—C24—H24	120.1
C4—C3—H3	120.8	C23—C24—H24	120.1
C5—C4—C3	119.4 (3)	C24—C25—C26	121.4 (3)
C5—C4—H4	120.3	C24—C25—H25	119.3
C3—C4—H4	120.3	C26—C25—H25	119.3
N1—C5—C4	122.0 (3)	C25—C26—C21	118.5 (3)
N1—C5—C6	114.6 (3)	C25—C26—C28	120.0 (3)
C4—C5—C6	123.4 (3)	C21—C26—C28	121.5 (3)
N2—C6—C7	110.4 (3)	O6—C27—O5	125.3 (3)
N2—C6—C5	117.0 (3)	O6—C27—C21	119.9 (3)
C7—C6—C5	132.6 (3)	O5—C27—C21	114.7 (3)
C8—C7—C6	105.0 (3)	O7—C28—O8	124.6 (3)
C8—C7—H7	127.5	O7—C28—C26	118.4 (3)
C6—C7—H7	127.5	O8—C28—C26	117.0 (3)
O4^i—Zn1—O1—C10	−21.5 (3)	N2—N3—C9—C10	−86.5 (4)
O8^ii—Zn1—O1—C10	74.5 (3)	Zn2—O2—C10—O1	8.9 (3)
N1^i—Zn1—O1—C10	167.7 (3)	Zn2—O2—C10—C9	−168.0 (2)
N2^i—Zn1—O1—C10	−117.6 (3)	Zn1—O1—C10—O2	−165.5 (2)
O5—Zn2—O2—C10	172.44 (19)	Zn1—O1—C10—C9	11.5 (4)
N4—Zn2—O2—C10	−11.4 (3)	N3—C9—C10—O2	−16.3 (4)
O9—Zn2—O2—C10	76.4 (2)	N3—C9—C10—O1	166.6 (3)
N5—Zn2—O2—C10	−84.5 (2)	C15—N4—C11—C12	1.4 (5)
O2—Zn2—O5—C27	−126.1 (2)	Zn2—N4—C11—C12	−173.8 (3)
N4—Zn2—O5—C27	56.8 (2)	N4—C11—C12—C13	0.4 (6)
O9—Zn2—O5—C27	−36.8 (2)	C11—C12—C13—C14	−1.1 (6)
N5—Zn2—O5—C27	138.0 (2)	C12—C13—C14—C15	0.1 (6)
C6—N2—N3—C8	−1.2 (4)	C11—N4—C15—C14	−2.5 (5)
Zn1^i—N2—N3—C8	−174.2 (3)	Zn2—N4—C15—C14	173.1 (3)
C6—N2—N3—C9	−172.5 (3)	C11—N4—C15—C16	176.9 (3)
Zn1^i—N2—N3—C9	14.5 (5)	Zn2—N4—C15—C16	−7.6 (4)
O5—Zn2—N4—C11	−79.1 (3)	C13—C14—C15—N4	1.8 (5)
O2—Zn2—N4—C11	105.1 (3)	C13—C14—C15—C16	−177.5 (3)
O9—Zn2—N4—C11	18.1 (3)	N6—N5—C16—C17	0.7 (4)
N5—Zn2—N4—C11	−175.6 (3)	Zn2—N5—C16—C17	−173.2 (3)
O5—Zn2—N4—C15	105.6 (2)	N6—N5—C16—C15	−177.4 (3)
O2—Zn2—N4—C15	−70.1 (3)	Zn2—N5—C16—C15	8.7 (4)
O9—Zn2—N4—C15	−157.2 (2)	N4—C15—C16—N5	−1.2 (5)
N5—Zn2—N4—C15	9.1 (2)	C14—C15—C16—N5	178.2 (3)
O5—Zn2—N5—C16	−126.7 (2)	N4—C15—C16—C17	−178.8 (4)
O2—Zn2—N5—C16	129.6 (2)	C14—C15—C16—C17	0.6 (6)
N4—Zn2—N5—C16	−9.4 (2)	N5—C16—C17—C18	−0.4 (5)
O9—Zn2—N5—C16	37.2 (4)	C15—C16—C17—C18	177.4 (4)
O5—Zn2—N5—N6	62.8 (3)	N5—N6—C18—C17	0.5 (5)
O2—Zn2—N5—N6	−41.0 (3)	C19—N6—C18—C17	−179.1 (3)
N4—Zn2—N5—N6	−180.0 (4)	C16—C17—C18—N6	−0.1 (5)
O9—Zn2—N5—N6	−133.4 (3)	C18—N6—C19—C20	−83.4 (5)
C16—N5—N6—C18	−0.8 (4)	N5—N6—C19—C20	96.9 (4)
Zn2—N5—N6—C18	170.2 (3)	Zn1^i—O4—C20—O3	−0.7 (4)
C16—N5—N6—C19	178.9 (3)	Zn1^i—O4—C20—C19	178.4 (2)
Zn2—N5—N6—C19	−10.1 (5)	N6—C19—C20—O3	172.7 (3)
C5—N1—C1—C2	0.4 (5)	N6—C19—C20—O4	−6.4 (5)
Zn1^i—N1—C1—C2	177.1 (3)	C26—C21—C22—C23	0.6 (5)
N1—C1—C2—C3	−1.0 (5)	C27—C21—C22—C23	−179.3 (3)
C1—C2—C3—C4	0.3 (5)	C21—C22—C23—C24	0.1 (6)
C2—C3—C4—C5	1.1 (5)	C22—C23—C24—C25	−0.8 (6)
C1—N1—C5—C4	1.0 (5)	C23—C24—C25—C26	0.9 (6)
Zn1^i—N1—C5—C4	−175.9 (2)	C24—C25—C26—C21	−0.2 (5)
C1—N1—C5—C6	−178.6 (3)	C24—C25—C26—C28	−176.6 (3)
Zn1^i—N1—C5—C6	4.5 (4)	C22—C21—C26—C25	−0.6 (5)
C3—C4—C5—N1	−1.8 (5)	C27—C21—C26—C25	179.4 (3)
C3—C4—C5—C6	177.8 (3)	C22—C21—C26—C28	175.8 (3)
N3—N2—C6—C7	0.5 (4)	C27—C21—C26—C28	−4.2 (5)
Zn1^i—N2—C6—C7	175.6 (2)	Zn2—O5—C27—O6	−15.0 (4)
N3—N2—C6—C5	178.8 (3)	Zn2—O5—C27—C21	169.14 (19)
Zn1^i—N2—C6—C5	−6.1 (4)	C22—C21—C27—O6	−81.8 (4)
N1—C5—C6—N2	1.4 (4)	C26—C21—C27—O6	98.2 (4)
C4—C5—C6—N2	−178.2 (3)	C22—C21—C27—O5	94.3 (4)
N1—C5—C6—C7	179.2 (3)	C26—C21—C27—O5	−85.7 (4)
C4—C5—C6—C7	−0.4 (6)	Zn1^ii—O8—C28—O7	−76.6 (4)
N2—C6—C7—C8	0.3 (4)	Zn1^ii—O8—C28—C26	101.6 (3)
C5—C6—C7—C8	−177.7 (3)	C25—C26—C28—O7	176.3 (3)
N2—N3—C8—C7	1.4 (4)	C21—C26—C28—O7	0.0 (5)
C9—N3—C8—C7	171.8 (3)	C25—C26—C28—O8	−2.0 (4)
C6—C7—C8—N3	−1.0 (4)	C21—C26—C28—O8	−178.3 (3)
C8—N3—C9—C10	103.8 (4)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O10—H10A···O11	0.85	1.93	2.715 (4)	153
O10—H10B···O5	0.85	1.95	2.802 (4)	178
O11—H11A···O10^iii	0.85	1.98	2.828 (4)	179
O11—H11B···O3^iii	0.85	2.09	2.821 (4)	144

Symmetry code: (iii) −x+1, −y+1, −z+1.