Poly[[tris­(μ-4,4′-bipyridine-κ2N:N′)bis­(μ-l-lysinato-κ3N1,O1:O1′)dizinc(II)] tetra­nitrate 0.6-hydrate dimethyl­formamide disolvate]

Li, S.-Q.; Hu, N.-H.

doi:10.1107/S1600536812016121

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 5| May 2012| Pages m633-m634

doi:10.1107/S1600536812016121

Open

access

Poly[[tris(μ-4,4′-bipyridine-κ²N:N′)bis(μ-L-lysinato-κ³N¹,O¹:O^1′)dizinc(II)] tetranitrate 0.6-hydrate dimethylformamide disolvate]

Shu-Qiang Li ^a and Ning-Hai Hu ^b ^*

^aOrthopaedic Department, First Hospital, Jilin University, Changchun 130021, People's Republic of China, and ^bChangchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, People's Republic of China
^*Correspondence e-mail: hunh@ciac.jl.cn

(Received 25 February 2012; accepted 13 April 2012; online 21 April 2012)

In the title compound, {[Zn₂(C₆H₁₄N₂O₂)₂(C₁₀H₈N₂)₃](NO₃)₄·0.6H₂O·2C₃H₇NO}_n, the Zn^II ion is six-coordinated with a distorted octahedral geometry by two carboxylate O atoms and one amino N atom from two L-lysinate (L-lys) ligands, and three N atoms from three 4,4′-bipyridine (4,4′-bipy) ligands. The Zn^II ions are connected by the carboxylate groups of the L-lys ligands in the a-axis direction and the bridging 4,4′-bipy ligands in the b- and c-axis directions, forming a three-dimensional cationic framework with channels along [100]. The nitrate anions and solvent water and dimethylformamide (DMF) molecules are located in the channels and linked to the cationic framework by N—H⋯O and O—H⋯O hydrogen bonds. The occupancy of the water molecule was fixed at 0.6. One of the DMF molecules is disordered over two sets of sites, with an occupancy ratio of 0.632:0.368 (11).

Related literature

For general background to the structures and properties of chiral coordination polymers, see: Dai et al. (2005 ); Kesanli & Lin (2003 ); Vaidhyanathan et al. (2006 ); Zaworotko (2001 ). For the structures of metal complexes with 4,4′-bipy and L-tyrosinate ligands, see: Li & Hu (2011 ); Zhang & Hu (2009 ). For the structures of Cu^II complexes with 4,4′-bipy and L-valinate ligands, see: Lou et al. (2007 ); Lou & Hong (2008 ).

Experimental

Crystal data

[Zn₂(C₆H₁₄N₂O₂)₂(C₁₀H₈N₂)₃](NO₃)₄·0.6H₂O·2C₃H₇NO
M_r = 1296.76
Monoclinic, P 2₁
a = 10.3039 (4) Å
b = 24.9425 (10) Å
c = 11.5740 (4) Å
β = 93.197 (1)°
V = 2970.0 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.89 mm⁻¹
T = 187 K
0.26 × 0.23 × 0.13 mm

Data collection

Bruker APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.801, T_max = 0.893
16802 measured reflections
11087 independent reflections
10039 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.107
S = 1.00
11087 reflections
820 parameters
63 restraints
H-atom parameters constrained
Δρ_max = 0.81 e Å⁻³
Δρ_min = −0.33 e Å⁻³
Absolute structure: Flack (1983 ), 5102 Friedel pairs
Flack parameter: 0.003 (9)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1A⋯O15	0.95	1.91	2.823 (11)	159
O1W—H1B⋯O10ⁱ	0.90	2.48	3.182 (8)	136
N7—H7A⋯O3ⁱⁱ	0.92	2.54	3.066 (4)	117
N7—H7B⋯O18	0.92	2.03	2.940 (9)	167
N7—H7B⋯O18′	0.92	2.32	3.215 (17)	163
N8—H8A⋯O17ⁱⁱⁱ	0.91	1.86	2.755 (7)	166
N8—H8B⋯O8ⁱⁱⁱ	0.91	2.04	2.842 (6)	147
N8—H8B⋯O9ⁱⁱⁱ	0.91	2.39	3.057 (6)	130
N8—H8C⋯O5ⁱⁱⁱ	0.91	2.00	2.907 (7)	172
N9—H9A⋯O1^iv	0.92	2.44	2.999 (4)	119
N9—H9B⋯O10	0.92	2.16	3.075 (4)	174
N10—H10A⋯O14	0.91	2.00	2.869 (6)	160
N10—H10A⋯O16	0.91	2.44	3.183 (8)	139
N10—H10B⋯O11^v	0.91	2.00	2.844 (5)	154
N10—H10B⋯O12^v	0.91	2.48	3.066 (6)	123
N10—H10C⋯O7ⁱ	0.91	2.04	2.914 (7)	161
Symmetry codes: (i) x, y, z+1; (ii) $[-x+1, y-{\script{1\over 2}}, -z+1]$ ; (iii) x, y-1, z; (iv) $[-x+2, y+{\script{1\over 2}}, -z+1]$ ; (v) x, y+1, z.

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812016121/nk2149sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812016121/nk2149Isup2.hkl

checkCIF report

Comment top

Chiral coordination polymers have attracted much interest because they exhibit potential applications in asymmetric catalysis and chiral separation (Kesanli & Lin, 2003). Mixed-ligand systems containing both chiral and achiral ligands have been developed as an effective approach to construct chiral complexes (Dai et al., 2005; Vaidhyanathan et al., 2006; Zaworotko, 2001). Amino acids are a kind of candidate for chiral building blocks, with their amino and carboxylate groups binding to metal ions (Lou et al., 2007; Lou & Hong, 2008). We previously reported a chiral one-dimensional Zn(II) complex, [Zn(L-tyr)(4,4'-bipy)₂(H₂O)]NO₃.2H₂O, (II), (L-tyr = L-tyrosinate, 4,4'-bipy = 4,4'-bipyridine) (Li & Hu, 2011) and a chiral two-dimensional Cu(II) complex, [Cu₂(L-tyr)₂(4,4'-bipy)(NO₃)₂(H₂O)₂], (III), (Zhang & Hu, 2009). Herein, we present the title compound, (I), a three-dimensional Zn(II) complex with L-lysinate (L-lys) and 4,4'-bipy ligands.

In (I), the Zn(II) ion is six-coordinated by one N atom and two O atoms from two L-lys ligands, three N atoms from three 4,4'-bipy ligands in a distorted octahedral geometry (Fig. 1). The L-lys ligands bind to the Zn atoms in a µ-(κ³N,O:O') mode, the same as that observed in (II) and (III). The 4,4'-bipy ligands adopt a bridging mode, similar to that in (III) but different from the monodentate terminal mode in (II). The 4,4'-bipy ligands bridge the Zn atoms in the b and c directions, while the L-lys ligands bridge adjacent Zn atoms through the carboxylate groups in the a direction, forming a three-dimensional chiral cationic framework, which exhibits channels in the a direction (Fig. 2). The nitrate anions and the water and dimethylformamide (DMF) solvent molecules are located in the channels. The ammonium tails of the L-lys ligands extend into the channels and form N—H···O hydrogen bonds with the nitrate anions and DMF molecules (Table 1). Moreover, the water molecules and α-amino groups acting as donors form O—H···O and N—H···O hydrogen bonds with the nitrate anions, carboxylate groups and DMF molecules.

Related literature top

For general background to the structures and properties of chiral coordination polymers, see: Dai et al. (2005); Kesanli & Lin (2003); Vaidhyanathan et al. (2006); Zaworotko (2001). For the structures of metal complexes with 4,4'-bipy and L-tyrosinate ligands, see: Li & Hu (2011); Zhang & Hu (2009). For the structures of Cu^II complexes with 4,4'-bipy and L-valinate ligands, see: Lou et al. (2007); Lou & Hong (2008).

Experimental top

Zn(NO₃)₂.6H₂O (0.119 g, 0.4 mmol), L-lysine (0.058 g, 0.4 mmol) and 4,4'-bipy (0.062 g, 0.4 mmol) were dissolved in water/DMF (20 ml, v/v 1:1) under stirring. The resulting solution was allowed to stand at room temperature and colorless crystals suitable for X-ray diffraction analysis were obtained after two weeks.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of (I). Displacement ellipsoids are drawn at the 50% probability level. H atoms and the minor component of the disordered DMF molecule have been omitted for clarity. [Symmetry codes: (i) 1 - x, -1/2 + y, 1 - z; (ii) x, y, 1 + z; (iii) 2 - x, 1/2 + y, 1 - z; (iv) x, y, -1 + z; (v) 2 - x, -1/2 + y, 1 - z; (vi) 1 - x, 1/2 + y, 1 - z.]
	Fig. 2. A view of the crystal packing of (I). H atoms have been omitted for clarity. Dashed lines denote hydrogen bonds.

Poly[[tris(µ-4,4'-bipyridine-κ²N:N')bis(µ-L- lysinato-κ³N¹,O¹:O^1')dizinc(II)] tetranitrate 0.6-hydrate dimethylformamide disolvate] top

Crystal data top

[Zn₂(C₆H₁₄N₂O₂)₂(C₁₀H₈N₂)₃](NO₃)₄·0.6H₂O·2C₃H₇NO	F(000) = 1352
M_r = 1296.76	D_x = 1.450 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 7390 reflections
a = 10.3039 (4) Å	θ = 2.4–26.0°
b = 24.9425 (10) Å	µ = 0.89 mm⁻¹
c = 11.5740 (4) Å	T = 187 K
β = 93.197 (1)°	Block, colorless
V = 2970.0 (2) Å³	0.26 × 0.23 × 0.13 mm
Z = 2

Data collection top

Bruker APEX CCD diffractometer	11087 independent reflections
Radiation source: fine-focus sealed tube	10039 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
ϕ and ω scans	θ_max = 26.0°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→12
T_min = 0.801, T_max = 0.893	k = −29→30
16802 measured reflections	l = −13→14

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.041	H-atom parameters constrained
wR(F²) = 0.107	w = 1/[σ²(F_o²) + (0.0664P)²] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max = 0.013
11087 reflections	Δρ_max = 0.81 e Å⁻³
820 parameters	Δρ_min = −0.33 e Å⁻³
63 restraints	Absolute structure: Flack (1983), 5102 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.003 (9)

Crystal data top

[Zn₂(C₆H₁₄N₂O₂)₂(C₁₀H₈N₂)₃](NO₃)₄·0.6H₂O·2C₃H₇NO	V = 2970.0 (2) Å³
M_r = 1296.76	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 10.3039 (4) Å	µ = 0.89 mm⁻¹
b = 24.9425 (10) Å	T = 187 K
c = 11.5740 (4) Å	0.26 × 0.23 × 0.13 mm
β = 93.197 (1)°

Data collection top

Bruker APEX CCD diffractometer	11087 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	10039 reflections with I > 2σ(I)
T_min = 0.801, T_max = 0.893	R_int = 0.019
16802 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	H-atom parameters constrained
wR(F²) = 0.107	Δρ_max = 0.81 e Å⁻³
S = 1.00	Δρ_min = −0.33 e Å⁻³
11087 reflections	Absolute structure: Flack (1983), 5102 Friedel pairs
820 parameters	Absolute structure parameter: 0.003 (9)
63 restraints

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Zn1	0.56823 (4)	0.220094 (14)	0.41441 (3)	0.01985 (10)
Zn2	0.93007 (3)	0.646779 (14)	0.56498 (3)	0.01945 (10)
O1	0.7620 (2)	0.19164 (10)	0.4199 (2)	0.0224 (5)
O2	0.8839 (2)	0.11711 (10)	0.4272 (2)	0.0223 (5)
O3	0.7372 (2)	0.67874 (10)	0.5549 (2)	0.0214 (5)
O4	0.6204 (2)	0.75003 (10)	0.5995 (2)	0.0226 (6)
N1	0.6347 (3)	0.30147 (14)	0.4389 (3)	0.0247 (7)
N2	0.8485 (3)	0.56755 (12)	0.5548 (2)	0.0213 (6)
N3	0.5749 (3)	0.23036 (15)	0.2219 (3)	0.0285 (8)
N4	0.5693 (3)	0.21814 (15)	−0.3919 (2)	0.0232 (6)
N5	0.9354 (3)	0.63940 (14)	0.7606 (2)	0.0241 (7)
N6	0.9337 (3)	0.64466 (16)	1.3743 (2)	0.0234 (6)
N7	0.5354 (3)	0.13638 (14)	0.4023 (3)	0.0301 (8)
H7A	0.4746	0.1266	0.4537	0.036*
H7B	0.5024	0.1281	0.3290	0.036*
N8	0.7276 (5)	−0.09001 (18)	0.1681 (4)	0.0660 (13)
H8A	0.6545	−0.1075	0.1411	0.079*
H8B	0.7932	−0.1141	0.1809	0.079*
H8C	0.7509	−0.0655	0.1148	0.079*
N9	0.9625 (3)	0.73065 (13)	0.5758 (3)	0.0254 (7)
H9A	1.0364	0.7373	0.6219	0.030*
H9B	0.9750	0.7441	0.5032	0.030*
N10	0.8106 (4)	0.94545 (17)	0.7743 (4)	0.0570 (11)
H10A	0.8015	0.9123	0.8058	0.068*
H10B	0.7364	0.9646	0.7819	0.068*
H10C	0.8786	0.9627	0.8116	0.068*
C1	0.5721 (4)	0.34315 (16)	0.3901 (3)	0.0316 (9)
H1	0.5006	0.3366	0.3365	0.038*
C2	0.6079 (4)	0.39617 (16)	0.4148 (3)	0.0312 (9)
H2	0.5605	0.4249	0.3790	0.037*
C3	0.7122 (4)	0.40660 (15)	0.4913 (3)	0.0232 (8)
C4	0.7785 (4)	0.36297 (16)	0.5417 (3)	0.0286 (9)
H4	0.8515	0.3684	0.5942	0.034*
C5	0.7360 (3)	0.31163 (15)	0.5139 (3)	0.0255 (8)
H5	0.7807	0.2821	0.5496	0.031*
C6	0.7558 (4)	0.55603 (16)	0.4730 (3)	0.0274 (8)
H6	0.7195	0.5847	0.4280	0.033*
C7	0.7106 (4)	0.50566 (15)	0.4503 (3)	0.0274 (8)
H7	0.6470	0.4998	0.3890	0.033*
C8	0.7575 (3)	0.46277 (15)	0.5168 (3)	0.0237 (8)
C9	0.8495 (4)	0.47439 (16)	0.6051 (3)	0.0319 (9)
H9	0.8823	0.4467	0.6549	0.038*
C10	0.8935 (4)	0.52661 (17)	0.6205 (3)	0.0299 (9)
H10	0.9583	0.5337	0.6801	0.036*
C11	0.4679 (4)	0.24046 (18)	0.1545 (3)	0.0337 (10)
H11	0.3899	0.2483	0.1912	0.040*
C12	0.4639 (4)	0.24026 (17)	0.0350 (3)	0.0319 (9)
H12	0.3845	0.2469	−0.0084	0.038*
C13	0.5770 (4)	0.23018 (17)	−0.0211 (3)	0.0290 (10)
C14	0.6897 (4)	0.2229 (2)	0.0483 (3)	0.0358 (9)
H14	0.7709	0.2186	0.0143	0.043*
C15	0.6835 (4)	0.2221 (2)	0.1664 (3)	0.0365 (9)
H15	0.7615	0.2152	0.2117	0.044*
C16	0.4819 (4)	0.24829 (18)	−0.3386 (3)	0.0332 (10)
H16	0.4180	0.2670	−0.3851	0.040*
C17	0.4805 (4)	0.25351 (17)	−0.2188 (3)	0.0296 (9)
H17	0.4164	0.2748	−0.1848	0.035*
C18	0.5756 (4)	0.22671 (19)	−0.1495 (3)	0.0267 (9)
C19	0.6641 (4)	0.19624 (18)	−0.2039 (3)	0.0358 (10)
H19	0.7296	0.1772	−0.1599	0.043*
C20	0.6575 (4)	0.19326 (18)	−0.3237 (3)	0.0349 (10)
H20	0.7205	0.1720	−0.3592	0.042*
C21	0.8295 (4)	0.6508 (2)	0.8174 (3)	0.0362 (9)
H21	0.7514	0.6586	0.7731	0.043*
C22	0.8265 (4)	0.6521 (2)	0.9363 (3)	0.0351 (9)
H22	0.7488	0.6619	0.9714	0.042*
C23	0.9371 (4)	0.63896 (17)	1.0046 (3)	0.0270 (9)
C24	1.0445 (4)	0.62388 (17)	0.9460 (3)	0.0314 (9)
H24	1.1211	0.6121	0.9880	0.038*
C25	1.0411 (4)	0.62576 (17)	0.8277 (3)	0.0302 (9)
H25	1.1181	0.6169	0.7906	0.036*
C26	0.8586 (4)	0.67658 (18)	1.3066 (3)	0.0361 (10)
H26	0.8032	0.7011	1.3428	0.043*
C27	0.8563 (4)	0.67624 (19)	1.1882 (3)	0.0408 (11)
H27	0.8010	0.7001	1.1445	0.049*
C28	0.9368 (4)	0.64021 (18)	1.1321 (3)	0.0269 (8)
C29	1.0147 (4)	0.60713 (18)	1.2027 (3)	0.0296 (9)
H29	1.0700	0.5817	1.1694	0.035*
C30	1.0119 (4)	0.61110 (17)	1.3200 (3)	0.0275 (8)
H30	1.0687	0.5888	1.3661	0.033*
C31	0.7762 (3)	0.14177 (17)	0.4243 (3)	0.0212 (7)
C32	0.6570 (3)	0.10546 (16)	0.4278 (3)	0.0268 (8)
H32	0.6540	0.0922	0.5091	0.032*
C33	0.6704 (4)	0.05621 (17)	0.3512 (4)	0.0421 (11)
H33A	0.6645	0.0680	0.2694	0.051*
H33B	0.7583	0.0409	0.3670	0.051*
C34	0.5725 (5)	0.0125 (2)	0.3652 (5)	0.0540 (13)
H34A	0.4840	0.0281	0.3616	0.065*
H34B	0.5881	−0.0046	0.4419	0.065*
C35	0.5818 (6)	−0.0303 (2)	0.2692 (6)	0.0812 (19)
H35A	0.5065	−0.0548	0.2719	0.097*
H35B	0.5765	−0.0122	0.1929	0.097*
C36	0.7015 (6)	−0.0617 (3)	0.2801 (6)	0.0804 (18)
H36A	0.6945	−0.0886	0.3423	0.096*
H36B	0.7754	−0.0378	0.3021	0.096*
C37	0.7262 (3)	0.72627 (15)	0.5884 (2)	0.0175 (7)
C38	0.8500 (3)	0.75806 (14)	0.6249 (3)	0.0239 (8)
H38	0.8622	0.7542	0.7108	0.029*
C39	0.8394 (4)	0.81792 (16)	0.6008 (4)	0.0371 (10)
H39A	0.8387	0.8239	0.5162	0.045*
H39B	0.7559	0.8312	0.6279	0.045*
C40	0.9493 (5)	0.84975 (19)	0.6590 (5)	0.0478 (12)
H40A	1.0329	0.8332	0.6401	0.057*
H40B	0.9428	0.8475	0.7439	0.057*
C41	0.9503 (5)	0.90914 (19)	0.6232 (5)	0.0618 (15)
H41A	1.0274	0.9265	0.6620	0.074*
H41B	0.9606	0.9110	0.5387	0.074*
C42	0.8355 (6)	0.9400 (2)	0.6496 (5)	0.0609 (14)
H42A	0.7586	0.9230	0.6098	0.073*
H42B	0.8439	0.9764	0.6166	0.073*
O1W	1.0534 (7)	0.7542 (3)	1.0804 (7)	0.094 (2)	0.60
H1A	0.9869	0.7577	1.0201	0.141*	0.60
H1B	1.0386	0.7803	1.1317	0.141*	0.60
N11	0.9419 (6)	0.9875 (2)	0.0281 (5)	0.0771 (15)
O5	0.8211 (5)	0.9923 (2)	0.0153 (4)	0.0944 (15)
O6	0.9935 (6)	0.9850 (2)	0.1267 (4)	0.121 (2)
O7	1.0058 (5)	0.9887 (2)	−0.0591 (5)	0.0891 (14)
N12	0.9215 (4)	0.81777 (17)	0.3054 (3)	0.0471 (10)
O8	0.9535 (4)	0.86466 (16)	0.2816 (4)	0.0716 (12)
O9	0.8025 (4)	0.80580 (18)	0.2939 (4)	0.0813 (14)
O10	1.0025 (3)	0.78428 (14)	0.3412 (3)	0.0488 (8)
N13	0.5965 (4)	0.04442 (16)	0.7044 (3)	0.0408 (9)
O11	0.5668 (3)	−0.00369 (14)	0.7245 (3)	0.0572 (9)
O12	0.7113 (3)	0.05824 (15)	0.7120 (3)	0.0551 (10)
O13	0.5102 (3)	0.07704 (15)	0.6750 (3)	0.0550 (9)
N14	0.8082 (6)	0.8281 (2)	0.9323 (6)	0.0852 (16)
O14	0.7168 (5)	0.8458 (2)	0.8613 (5)	0.1016 (16)
O15	0.8287 (5)	0.7804 (2)	0.9411 (7)	0.136 (2)
O16	0.8814 (6)	0.8622 (2)	0.9766 (6)	0.136 (2)
O17	0.4854 (5)	0.8717 (2)	0.0970 (5)	0.115 (2)
N15	0.2865 (5)	0.8676 (2)	0.0072 (4)	0.0790 (15)
C43	0.4144 (5)	0.8691 (3)	0.0078 (6)	0.0826 (19)
H43	0.4541	0.8680	−0.0644	0.099*
C44	0.2217 (8)	0.8683 (4)	0.1147 (6)	0.136 (4)
H44A	0.2559	0.8392	0.1647	0.203*
H44B	0.1281	0.8632	0.0988	0.203*
H44C	0.2373	0.9027	0.1536	0.203*
C45	0.2102 (7)	0.8662 (3)	−0.1010 (5)	0.106 (3)
H45A	0.2651	0.8547	−0.1628	0.158*
H45B	0.1756	0.9020	−0.1187	0.158*
H45C	0.1381	0.8409	−0.0950	0.158*
O18	0.4301 (14)	0.0931 (6)	0.1802 (10)	0.132 (6)	0.632 (11)
N16	0.4160 (12)	0.0515 (5)	0.0087 (9)	0.073 (4)	0.632 (11)
C46	0.3757 (11)	0.0613 (4)	0.1123 (9)	0.097 (5)	0.632 (11)
H46	0.3009	0.0430	0.1359	0.117*	0.632 (11)
C47	0.5301 (11)	0.0789 (5)	−0.0281 (10)	0.099 (5)	0.632 (11)
H47A	0.5649	0.1022	0.0344	0.148*	0.632 (11)
H47B	0.5067	0.1007	−0.0967	0.148*	0.632 (11)
H47C	0.5960	0.0525	−0.0469	0.148*	0.632 (11)
C48	0.340 (2)	0.0177 (10)	−0.0733 (13)	0.120 (9)	0.632 (11)
H48A	0.2504	0.0154	−0.0499	0.180*	0.632 (11)
H48B	0.3784	−0.0183	−0.0739	0.180*	0.632 (11)
H48C	0.3411	0.0333	−0.1509	0.180*	0.632 (11)
O18'	0.484 (2)	0.1047 (8)	0.1345 (15)	0.095 (8)	0.368 (11)
N16'	0.367 (2)	0.0472 (9)	0.0221 (11)	0.054 (5)	0.368 (11)
C46'	0.4563 (13)	0.0842 (6)	0.0395 (14)	0.063 (5)	0.368 (11)
H46'	0.5023	0.0960	−0.0247	0.076*	0.368 (11)
C47'	0.3019 (16)	0.0244 (8)	0.1188 (13)	0.097 (9)	0.368 (11)
H47D	0.3278	0.0440	0.1897	0.146*	0.368 (11)
H47E	0.3262	−0.0134	0.1280	0.146*	0.368 (11)
H47F	0.2075	0.0272	0.1038	0.146*	0.368 (11)
C48'	0.331 (3)	0.0274 (14)	−0.0941 (14)	0.110 (15)	0.368 (11)
H48D	0.3640	0.0521	−0.1516	0.166*	0.368 (11)
H48E	0.2365	0.0249	−0.1045	0.166*	0.368 (11)
H48F	0.3696	−0.0082	−0.1042	0.166*	0.368 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0190 (2)	0.0191 (2)	0.02137 (18)	0.00000 (16)	0.00039 (14)	−0.00195 (16)
Zn2	0.0203 (2)	0.0185 (2)	0.01949 (18)	−0.00060 (16)	0.00063 (14)	−0.00140 (16)
O1	0.0200 (12)	0.0209 (15)	0.0260 (13)	0.0019 (11)	−0.0007 (10)	−0.0023 (10)
O2	0.0192 (12)	0.0240 (15)	0.0236 (13)	0.0035 (10)	−0.0004 (10)	0.0007 (10)
O3	0.0201 (13)	0.0190 (14)	0.0249 (12)	−0.0006 (10)	−0.0017 (10)	−0.0005 (10)
O4	0.0190 (13)	0.0241 (15)	0.0246 (13)	0.0031 (10)	−0.0006 (10)	−0.0003 (10)
N1	0.0204 (16)	0.0278 (19)	0.0260 (16)	−0.0033 (13)	0.0010 (12)	−0.0022 (13)
N2	0.0237 (16)	0.0138 (16)	0.0261 (15)	0.0000 (13)	0.0000 (12)	−0.0007 (12)
N3	0.0278 (17)	0.036 (2)	0.0211 (15)	−0.0023 (15)	−0.0012 (12)	−0.0013 (14)
N4	0.0307 (16)	0.0216 (16)	0.0173 (13)	0.0035 (15)	0.0003 (11)	0.0008 (14)
N5	0.0266 (15)	0.0259 (19)	0.0199 (14)	−0.0017 (14)	0.0021 (11)	−0.0010 (13)
N6	0.0241 (15)	0.0269 (17)	0.0192 (14)	0.0011 (15)	0.0021 (11)	−0.0018 (15)
N7	0.0282 (16)	0.026 (2)	0.0362 (17)	−0.0057 (15)	0.0034 (13)	−0.0080 (13)
N8	0.077 (3)	0.047 (3)	0.072 (3)	0.024 (2)	−0.012 (2)	−0.008 (2)
N9	0.0231 (15)	0.023 (2)	0.0301 (16)	0.0003 (14)	0.0015 (12)	−0.0009 (12)
N10	0.070 (3)	0.042 (3)	0.058 (3)	0.019 (2)	0.005 (2)	−0.001 (2)
C1	0.033 (2)	0.022 (2)	0.039 (2)	−0.0016 (16)	−0.0107 (16)	0.0016 (16)
C2	0.029 (2)	0.021 (2)	0.042 (2)	−0.0020 (16)	−0.0104 (16)	0.0003 (16)
C3	0.0217 (18)	0.0210 (19)	0.0267 (18)	0.0017 (14)	0.0010 (14)	0.0004 (14)
C4	0.026 (2)	0.026 (2)	0.033 (2)	−0.0053 (16)	−0.0038 (15)	−0.0021 (16)
C5	0.024 (2)	0.019 (2)	0.033 (2)	0.0008 (15)	−0.0032 (15)	−0.0016 (15)
C6	0.026 (2)	0.025 (2)	0.030 (2)	0.0019 (16)	−0.0066 (15)	0.0000 (15)
C7	0.027 (2)	0.020 (2)	0.034 (2)	0.0017 (16)	−0.0065 (15)	−0.0033 (15)
C8	0.0217 (18)	0.0211 (19)	0.0280 (19)	−0.0027 (14)	−0.0017 (14)	−0.0037 (14)
C9	0.038 (2)	0.021 (2)	0.035 (2)	−0.0032 (16)	−0.0142 (17)	0.0056 (16)
C10	0.033 (2)	0.025 (2)	0.031 (2)	−0.0040 (16)	−0.0110 (16)	−0.0011 (16)
C11	0.037 (2)	0.045 (3)	0.0198 (19)	0.0031 (19)	0.0057 (16)	−0.0015 (17)
C12	0.027 (2)	0.042 (3)	0.027 (2)	0.0018 (17)	−0.0035 (16)	−0.0009 (17)
C13	0.037 (2)	0.031 (3)	0.0192 (18)	0.0016 (18)	0.0038 (15)	0.0005 (16)
C14	0.0264 (19)	0.057 (3)	0.0240 (18)	0.006 (2)	0.0041 (14)	0.001 (2)
C15	0.0234 (19)	0.060 (3)	0.0255 (18)	0.003 (2)	−0.0005 (14)	0.001 (2)
C16	0.035 (2)	0.043 (3)	0.0220 (19)	−0.0008 (19)	−0.0001 (16)	0.0011 (17)
C17	0.035 (2)	0.033 (2)	0.0207 (19)	0.0098 (18)	−0.0020 (15)	−0.0057 (16)
C18	0.0277 (19)	0.030 (2)	0.0223 (18)	−0.0017 (18)	0.0018 (14)	0.0004 (17)
C19	0.043 (2)	0.042 (3)	0.0222 (19)	0.0166 (19)	0.0005 (17)	0.0058 (17)
C20	0.040 (2)	0.040 (3)	0.025 (2)	0.0165 (19)	0.0025 (17)	−0.0013 (17)
C21	0.036 (2)	0.051 (3)	0.0211 (17)	0.008 (2)	−0.0032 (15)	0.002 (2)
C22	0.035 (2)	0.050 (3)	0.0201 (17)	0.009 (2)	0.0038 (14)	0.0045 (19)
C23	0.033 (2)	0.026 (2)	0.0219 (18)	0.0010 (17)	−0.0020 (14)	0.0005 (16)
C24	0.032 (2)	0.039 (3)	0.0224 (19)	0.0048 (17)	0.0001 (16)	−0.0022 (16)
C25	0.025 (2)	0.038 (3)	0.027 (2)	0.0022 (16)	0.0021 (15)	−0.0036 (16)
C26	0.050 (3)	0.036 (3)	0.0226 (19)	0.015 (2)	0.0023 (18)	−0.0023 (17)
C27	0.050 (3)	0.048 (3)	0.024 (2)	0.024 (2)	−0.0003 (18)	0.0052 (18)
C28	0.032 (2)	0.028 (2)	0.0213 (18)	0.0037 (18)	0.0032 (14)	−0.0024 (17)
C29	0.025 (2)	0.038 (2)	0.026 (2)	0.0027 (17)	0.0045 (15)	−0.0027 (17)
C30	0.027 (2)	0.029 (2)	0.0256 (19)	0.0068 (16)	−0.0046 (15)	−0.0010 (16)
C31	0.0264 (18)	0.026 (2)	0.0113 (14)	0.0009 (16)	−0.0003 (12)	0.0009 (14)
C32	0.0261 (19)	0.027 (2)	0.0272 (19)	−0.0018 (15)	0.0038 (15)	−0.0013 (15)
C33	0.034 (2)	0.033 (3)	0.059 (3)	−0.0053 (18)	0.005 (2)	−0.016 (2)
C34	0.056 (3)	0.036 (3)	0.070 (3)	−0.005 (2)	0.007 (3)	−0.009 (2)
C35	0.074 (4)	0.048 (3)	0.121 (6)	−0.010 (3)	0.001 (4)	−0.038 (3)
C36	0.078 (4)	0.060 (4)	0.100 (5)	0.006 (3)	−0.016 (4)	−0.021 (3)
C37	0.0177 (16)	0.023 (2)	0.0120 (14)	−0.0003 (15)	0.0011 (11)	0.0007 (13)
C38	0.0243 (18)	0.0209 (18)	0.0264 (19)	0.0007 (14)	0.0028 (15)	−0.0009 (14)
C39	0.034 (2)	0.025 (2)	0.054 (3)	0.0025 (17)	0.012 (2)	0.0017 (19)
C40	0.040 (3)	0.031 (3)	0.074 (3)	−0.009 (2)	0.017 (2)	−0.018 (2)
C41	0.084 (4)	0.033 (3)	0.072 (4)	−0.016 (2)	0.032 (3)	−0.005 (2)
C42	0.078 (4)	0.045 (3)	0.060 (3)	0.000 (3)	0.011 (3)	0.007 (2)
O1W	0.099 (5)	0.091 (6)	0.097 (6)	−0.014 (4)	0.046 (5)	−0.018 (4)
N11	0.110 (5)	0.055 (3)	0.064 (3)	0.008 (3)	−0.026 (3)	0.005 (3)
O5	0.120 (4)	0.089 (4)	0.072 (3)	0.025 (3)	−0.010 (3)	−0.005 (2)
O6	0.184 (6)	0.091 (4)	0.079 (3)	0.021 (4)	−0.066 (4)	−0.001 (3)
O7	0.082 (3)	0.088 (4)	0.096 (4)	−0.007 (3)	−0.009 (3)	0.023 (3)
N12	0.042 (2)	0.050 (3)	0.049 (2)	−0.016 (2)	−0.0059 (18)	0.0044 (19)
O8	0.055 (2)	0.056 (3)	0.100 (3)	−0.0173 (19)	−0.027 (2)	0.031 (2)
O9	0.038 (2)	0.063 (3)	0.142 (4)	−0.013 (2)	−0.014 (2)	0.013 (3)
O10	0.0351 (17)	0.052 (2)	0.058 (2)	−0.0029 (16)	−0.0070 (15)	0.0159 (17)
N13	0.035 (2)	0.043 (2)	0.043 (2)	−0.0078 (18)	−0.0074 (16)	0.0057 (17)
O11	0.049 (2)	0.041 (2)	0.080 (2)	−0.0115 (16)	−0.0111 (18)	0.0115 (17)
O12	0.0346 (19)	0.048 (2)	0.081 (3)	−0.0100 (16)	−0.0079 (17)	0.0069 (19)
O13	0.042 (2)	0.052 (2)	0.070 (2)	0.0007 (17)	−0.0129 (16)	0.0124 (18)
N14	0.083 (4)	0.059 (4)	0.113 (5)	−0.013 (3)	−0.002 (4)	−0.010 (3)
O14	0.096 (4)	0.097 (4)	0.111 (4)	−0.025 (3)	0.003 (3)	0.022 (3)
O15	0.104 (4)	0.062 (4)	0.240 (8)	−0.005 (3)	0.009 (4)	0.019 (4)
O16	0.147 (5)	0.115 (5)	0.147 (5)	−0.045 (4)	0.002 (4)	−0.033 (4)
O17	0.124 (4)	0.083 (4)	0.131 (5)	−0.014 (3)	−0.059 (4)	−0.007 (3)
N15	0.082 (4)	0.062 (3)	0.090 (4)	0.016 (3)	−0.017 (3)	−0.016 (3)
C43	0.081 (5)	0.062 (4)	0.102 (5)	0.014 (3)	−0.021 (4)	−0.004 (4)
C44	0.183 (9)	0.110 (7)	0.120 (7)	0.011 (6)	0.068 (7)	0.010 (6)
C45	0.107 (6)	0.107 (7)	0.098 (5)	0.016 (5)	−0.045 (5)	−0.007 (5)
O18	0.159 (13)	0.141 (13)	0.085 (8)	0.078 (9)	−0.080 (8)	−0.072 (9)
N16	0.108 (12)	0.055 (6)	0.057 (6)	0.000 (7)	0.015 (6)	0.001 (5)
C46	0.098 (10)	0.074 (9)	0.124 (13)	0.030 (7)	0.036 (9)	0.023 (9)
C47	0.112 (10)	0.094 (9)	0.091 (9)	−0.051 (8)	0.027 (8)	−0.025 (7)
C48	0.16 (2)	0.099 (12)	0.107 (13)	−0.079 (13)	0.045 (13)	−0.044 (11)
O18'	0.082 (12)	0.058 (9)	0.137 (19)	−0.033 (9)	−0.067 (11)	0.020 (11)
N16'	0.061 (11)	0.082 (11)	0.019 (7)	−0.010 (8)	0.008 (6)	−0.019 (7)
C46'	0.053 (10)	0.049 (10)	0.090 (14)	−0.001 (8)	0.016 (10)	−0.004 (9)
C47'	0.106 (17)	0.12 (2)	0.065 (11)	0.070 (15)	0.019 (11)	0.034 (12)
C48'	0.068 (17)	0.17 (4)	0.094 (19)	0.007 (18)	0.011 (14)	−0.09 (2)

Geometric parameters (Å, º) top

Zn1—O4ⁱ	2.080 (2)	C24—C25	1.368 (5)
Zn1—N7	2.119 (3)	C24—H24	0.9500
Zn1—O1	2.117 (2)	C25—H25	0.9500
Zn1—N1	2.156 (3)	C26—C27	1.369 (5)
Zn1—N4ⁱⁱ	2.242 (3)	C26—H26	0.9500
Zn1—N3	2.248 (3)	C27—C28	1.406 (6)
Zn2—O2ⁱⁱⁱ	2.052 (2)	C27—H27	0.9500
Zn2—N9	2.121 (3)	C28—C29	1.385 (6)
Zn2—O3	2.139 (2)	C29—C30	1.363 (5)
Zn2—N2	2.148 (3)	C29—H29	0.9500
Zn2—N6^iv	2.210 (3)	C30—H30	0.9500
Zn2—N5	2.269 (3)	C31—C32	1.528 (5)
O1—C31	1.253 (5)	C32—C33	1.526 (5)
O2—C31	1.268 (4)	C32—H32	1.0000
O2—Zn2^v	2.052 (2)	C33—C34	1.500 (6)
O3—C37	1.254 (4)	C33—H33A	0.9900
O4—C37	1.254 (4)	C33—H33B	0.9900
O4—Zn1^vi	2.080 (2)	C34—C35	1.547 (7)
N1—C1	1.332 (5)	C34—H34A	0.9900
N1—C5	1.344 (5)	C34—H34B	0.9900
N2—C6	1.338 (5)	C35—C36	1.462 (8)
N2—C10	1.340 (5)	C35—H35A	0.9900
N3—C15	1.337 (5)	C35—H35B	0.9900
N3—C11	1.338 (5)	C36—H36A	0.9900
N4—C20	1.325 (5)	C36—H36B	0.9900
N4—C16	1.348 (5)	C37—C38	1.541 (5)
N4—Zn1^iv	2.242 (3)	C38—C39	1.522 (5)
N5—C21	1.335 (5)	C38—H38	1.0000
N5—C25	1.346 (5)	C39—C40	1.511 (6)
N6—C26	1.334 (5)	C39—H39A	0.9900
N6—C30	1.342 (5)	C39—H39B	0.9900
N6—Zn2ⁱⁱ	2.210 (3)	C40—C41	1.538 (7)
N7—C32	1.487 (5)	C40—H40A	0.9900
N7—H7A	0.9200	C40—H40B	0.9900
N7—H7B	0.9200	C41—C42	1.457 (7)
N8—C36	1.513 (7)	C41—H41A	0.9900
N8—H8A	0.9100	C41—H41B	0.9900
N8—H8B	0.9100	C42—H42A	0.9900
N8—H8C	0.9100	C42—H42B	0.9900
N9—C38	1.486 (4)	O1W—H1A	0.9547
N9—H9A	0.9200	O1W—H1B	0.8984
N9—H9B	0.9200	N11—O6	1.234 (6)
N10—C42	1.486 (6)	N11—O7	1.236 (6)
N10—H10A	0.9100	N11—O5	1.251 (6)
N10—H10B	0.9100	N12—O10	1.236 (5)
N10—H10C	0.9100	N12—O8	1.250 (5)
C1—C2	1.398 (6)	N12—O9	1.262 (5)
C1—H1	0.9500	N13—O12	1.230 (4)
C2—C3	1.379 (5)	N13—O13	1.239 (5)
C2—H2	0.9500	N13—O11	1.263 (5)
C3—C4	1.395 (5)	N14—O15	1.212 (6)
C3—C8	1.501 (4)	N14—O16	1.231 (6)
C4—C5	1.385 (5)	N14—O14	1.292 (6)
C4—H4	0.9500	O17—C43	1.233 (6)
C5—H5	0.9500	N15—C43	1.319 (6)
C6—C7	1.361 (5)	N15—C45	1.441 (6)
C6—H6	0.9500	N15—C44	1.444 (6)
C7—C8	1.389 (5)	C43—H43	0.9500
C7—H7	0.9500	C44—H44A	0.9800
C8—C9	1.385 (5)	C44—H44B	0.9800
C9—C10	1.387 (6)	C44—H44C	0.9800
C9—H9	0.9500	C45—H45A	0.9800
C10—H10	0.9500	C45—H45B	0.9800
C11—C12	1.382 (5)	C45—H45C	0.9800
C11—H11	0.9500	O18—C46	1.229 (9)
C12—C13	1.389 (5)	N16—C46	1.314 (7)
C12—H12	0.9500	N16—C47	1.444 (8)
C13—C14	1.387 (5)	N16—C48	1.463 (8)
C13—C18	1.488 (5)	C46—H46	0.9500
C14—C15	1.372 (5)	C47—H47A	0.9800
C14—H14	0.9500	C47—H47B	0.9800
C15—H15	0.9500	C47—H47C	0.9800
C16—C17	1.393 (5)	C48—H48A	0.9800
C16—H16	0.9500	C48—H48B	0.9800
C17—C18	1.401 (5)	C48—H48C	0.9800
C17—H17	0.9500	O18'—C46'	1.230 (9)
C18—C19	1.367 (5)	N16'—C46'	1.310 (8)
C19—C20	1.386 (5)	N16'—C47'	1.454 (9)
C19—H19	0.9500	N16'—C48'	1.461 (8)
C20—H20	0.9500	C46'—H46'	0.9500
C21—C22	1.378 (5)	C47'—H47D	0.9800
C21—H21	0.9500	C47'—H47E	0.9800
C22—C23	1.390 (5)	C47'—H47F	0.9800
C22—H22	0.9500	C48'—H48D	0.9800
C23—C24	1.383 (5)	C48'—H48E	0.9800
C23—C28	1.476 (5)	C48'—H48F	0.9800

O4ⁱ—Zn1—N7	101.75 (11)	C22—C23—C28	121.2 (3)
O4ⁱ—Zn1—O1	176.88 (10)	C25—C24—C23	120.3 (4)
N7—Zn1—O1	79.54 (11)	C25—C24—H24	119.8
O4ⁱ—Zn1—N1	87.76 (11)	C23—C24—H24	119.8
N7—Zn1—N1	170.06 (13)	N5—C25—C24	124.2 (4)
O1—Zn1—N1	91.12 (11)	N5—C25—H25	117.9
O4ⁱ—Zn1—N4ⁱⁱ	92.15 (10)	C24—C25—H25	117.9
N7—Zn1—N4ⁱⁱ	92.09 (13)	N6—C26—C27	124.2 (4)
O1—Zn1—N4ⁱⁱ	90.64 (10)	N6—C26—H26	117.9
N1—Zn1—N4ⁱⁱ	84.57 (12)	C27—C26—H26	117.9
O4ⁱ—Zn1—N3	87.85 (11)	C26—C27—C28	119.3 (4)
N7—Zn1—N3	93.47 (13)	C26—C27—H27	120.4
O1—Zn1—N3	89.23 (11)	C28—C27—H27	120.4
N1—Zn1—N3	89.76 (12)	C29—C28—C27	116.4 (3)
N4ⁱⁱ—Zn1—N3	174.33 (15)	C29—C28—C23	123.0 (3)
O2ⁱⁱⁱ—Zn2—N9	102.08 (11)	C27—C28—C23	120.6 (4)
O2ⁱⁱⁱ—Zn2—O3	179.04 (10)	C30—C29—C28	120.0 (4)
N9—Zn2—O3	77.21 (11)	C30—C29—H29	120.0
O2ⁱⁱⁱ—Zn2—N2	91.85 (11)	C28—C29—H29	120.0
N9—Zn2—N2	166.03 (12)	N6—C30—C29	123.9 (4)
O3—Zn2—N2	88.87 (11)	N6—C30—H30	118.0
O2ⁱⁱⁱ—Zn2—N6^iv	88.14 (10)	C29—C30—H30	118.0
N9—Zn2—N6^iv	94.08 (13)	O1—C31—O2	125.6 (3)
O3—Zn2—N6^iv	91.26 (10)	O1—C31—C32	119.8 (3)
N2—Zn2—N6^iv	87.23 (12)	O2—C31—C32	114.5 (4)
O2ⁱⁱⁱ—Zn2—N5	87.49 (10)	N7—C32—C33	113.9 (3)
N9—Zn2—N5	91.50 (12)	N7—C32—C31	110.9 (3)
O3—Zn2—N5	93.16 (10)	C33—C32—C31	111.3 (3)
N2—Zn2—N5	88.14 (12)	N7—C32—H32	106.8
N6^iv—Zn2—N5	173.53 (15)	C33—C32—H32	106.8
C31—O1—Zn1	116.2 (2)	C31—C32—H32	106.8
C31—O2—Zn2^v	129.8 (3)	C34—C33—C32	116.0 (4)
C37—O3—Zn2	115.8 (2)	C34—C33—H33A	108.3
C37—O4—Zn1^vi	129.5 (2)	C32—C33—H33A	108.3
C1—N1—C5	117.8 (3)	C34—C33—H33B	108.3
C1—N1—Zn1	122.4 (3)	C32—C33—H33B	108.3
C5—N1—Zn1	119.5 (3)	H33A—C33—H33B	107.4
C6—N2—C10	116.7 (3)	C33—C34—C35	110.8 (4)
C6—N2—Zn2	119.9 (2)	C33—C34—H34A	109.5
C10—N2—Zn2	123.2 (3)	C35—C34—H34A	109.5
C15—N3—C11	115.7 (3)	C33—C34—H34B	109.5
C15—N3—Zn1	122.1 (3)	C35—C34—H34B	109.5
C11—N3—Zn1	121.9 (2)	H34A—C34—H34B	108.1
C20—N4—C16	116.2 (3)	C36—C35—C34	113.2 (5)
C20—N4—Zn1^iv	124.8 (2)	C36—C35—H35A	108.9
C16—N4—Zn1^iv	118.7 (2)	C34—C35—H35A	108.9
C21—N5—C25	115.2 (3)	C36—C35—H35B	108.9
C21—N5—Zn2	120.0 (2)	C34—C35—H35B	108.9
C25—N5—Zn2	124.8 (2)	H35A—C35—H35B	107.7
C26—N6—C30	116.1 (3)	C35—C36—N8	111.5 (5)
C26—N6—Zn2ⁱⁱ	122.1 (3)	C35—C36—H36A	109.3
C30—N6—Zn2ⁱⁱ	121.8 (3)	N8—C36—H36A	109.3
C32—N7—Zn1	111.6 (2)	C35—C36—H36B	109.3
C32—N7—H7A	109.3	N8—C36—H36B	109.3
Zn1—N7—H7A	109.3	H36A—C36—H36B	108.0
C32—N7—H7B	109.3	O3—C37—O4	124.9 (3)
Zn1—N7—H7B	109.3	O3—C37—C38	118.9 (3)
H7A—N7—H7B	108.0	O4—C37—C38	116.1 (3)
C36—N8—H8A	109.5	N9—C38—C39	115.5 (3)
C36—N8—H8B	109.5	N9—C38—C37	108.1 (3)
H8A—N8—H8B	109.5	C39—C38—C37	113.9 (3)
C36—N8—H8C	109.5	N9—C38—H38	106.2
H8A—N8—H8C	109.5	C39—C38—H38	106.2
H8B—N8—H8C	109.5	C37—C38—H38	106.2
C38—N9—Zn2	110.6 (2)	C40—C39—C38	112.9 (4)
C38—N9—H9A	109.5	C40—C39—H39A	109.0
Zn2—N9—H9A	109.5	C38—C39—H39A	109.0
C38—N9—H9B	109.5	C40—C39—H39B	109.0
Zn2—N9—H9B	109.5	C38—C39—H39B	109.0
H9A—N9—H9B	108.1	H39A—C39—H39B	107.8
C42—N10—H10A	109.5	C39—C40—C41	113.7 (5)
C42—N10—H10B	109.5	C39—C40—H40A	108.8
H10A—N10—H10B	109.5	C41—C40—H40A	108.8
C42—N10—H10C	109.5	C39—C40—H40B	108.8
H10A—N10—H10C	109.5	C41—C40—H40B	108.8
H10B—N10—H10C	109.5	H40A—C40—H40B	107.7
N1—C1—C2	122.3 (4)	C42—C41—C40	115.8 (4)
N1—C1—H1	118.8	C42—C41—H41A	108.3
C2—C1—H1	118.8	C40—C41—H41A	108.3
C3—C2—C1	119.8 (4)	C42—C41—H41B	108.3
C3—C2—H2	120.1	C40—C41—H41B	108.3
C1—C2—H2	120.1	H41A—C41—H41B	107.4
C2—C3—C4	117.8 (4)	C41—C42—N10	116.0 (5)
C2—C3—C8	121.7 (3)	C41—C42—H42A	108.3
C4—C3—C8	120.5 (3)	N10—C42—H42A	108.3
C5—C4—C3	118.9 (4)	C41—C42—H42B	108.3
C5—C4—H4	120.5	N10—C42—H42B	108.3
C3—C4—H4	120.5	H42A—C42—H42B	107.4
N1—C5—C4	123.2 (4)	H1A—O1W—H1B	106.0
N1—C5—H5	118.4	O6—N11—O7	122.3 (7)
C4—C5—H5	118.4	O6—N11—O5	119.3 (7)
N2—C6—C7	123.9 (4)	O7—N11—O5	118.2 (5)
N2—C6—H6	118.0	O10—N12—O8	121.6 (4)
C7—C6—H6	118.0	O10—N12—O9	120.6 (4)
C6—C7—C8	120.0 (4)	O8—N12—O9	117.7 (4)
C6—C7—H7	120.0	O12—N13—O13	120.6 (4)
C8—C7—H7	120.0	O12—N13—O11	119.7 (4)
C9—C8—C7	116.8 (3)	O13—N13—O11	119.8 (4)
C9—C8—C3	122.2 (3)	O15—N14—O16	123.0 (7)
C7—C8—C3	121.0 (3)	O15—N14—O14	120.5 (6)
C10—C9—C8	119.8 (4)	O16—N14—O14	115.8 (6)
C10—C9—H9	120.1	C43—N15—C45	120.1 (5)
C8—C9—H9	120.1	C43—N15—C44	120.4 (5)
N2—C10—C9	122.8 (4)	C45—N15—C44	119.5 (5)
N2—C10—H10	118.6	O17—C43—N15	123.5 (6)
C9—C10—H10	118.6	O17—C43—H43	118.3
N3—C11—C12	124.1 (4)	N15—C43—H43	118.3
N3—C11—H11	118.0	N15—C44—H44A	109.5
C12—C11—H11	118.0	N15—C44—H44B	109.5
C11—C12—C13	119.3 (4)	H44A—C44—H44B	109.5
C11—C12—H12	120.3	N15—C44—H44C	109.5
C13—C12—H12	120.3	H44A—C44—H44C	109.5
C14—C13—C12	116.8 (3)	H44B—C44—H44C	109.5
C14—C13—C18	122.2 (3)	N15—C45—H45A	109.5
C12—C13—C18	121.0 (4)	N15—C45—H45B	109.5
C15—C14—C13	119.7 (3)	H45A—C45—H45B	109.5
C15—C14—H14	120.2	N15—C45—H45C	109.5
C13—C14—H14	120.2	H45A—C45—H45C	109.5
N3—C15—C14	124.2 (4)	H45B—C45—H45C	109.5
N3—C15—H15	117.9	C46—N16—C47	119.0 (7)
C14—C15—H15	117.9	C46—N16—C48	121.0 (8)
N4—C16—C17	123.5 (4)	C47—N16—C48	119.7 (7)
N4—C16—H16	118.2	O18—C46—N16	123.2 (10)
C17—C16—H16	118.2	O18—C46—H46	118.4
C16—C17—C18	118.6 (4)	N16—C46—H46	118.4
C16—C17—H17	120.7	C46'—N16'—C47'	120.5 (8)
C18—C17—H17	120.7	C46'—N16'—C48'	121.3 (9)
C19—C18—C17	117.7 (3)	C47'—N16'—C48'	118.2 (8)
C19—C18—C13	121.5 (4)	O18'—C46'—N16'	123.6 (11)
C17—C18—C13	120.8 (3)	O18'—C46'—H46'	118.2
C18—C19—C20	119.6 (4)	N16'—C46'—H46'	118.2
C18—C19—H19	120.2	N16'—C47'—H47D	109.5
C20—C19—H19	120.2	N16'—C47'—H47E	109.5
N4—C20—C19	124.3 (4)	H47D—C47'—H47E	109.5
N4—C20—H20	117.8	N16'—C47'—H47F	109.5
C19—C20—H20	117.8	H47D—C47'—H47F	109.5
N5—C21—C22	124.2 (4)	H47E—C47'—H47F	109.5
N5—C21—H21	117.9	N16'—C48'—H48D	109.5
C22—C21—H21	117.9	N16'—C48'—H48E	109.5
C21—C22—C23	120.0 (4)	H48D—C48'—H48E	109.5
C21—C22—H22	120.0	N16'—C48'—H48F	109.5
C23—C22—H22	120.0	H48D—C48'—H48F	109.5
C24—C23—C22	116.0 (3)	H48E—C48'—H48F	109.5
C24—C23—C28	122.9 (4)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1A···O15	0.95	1.91	2.823 (11)	159
O1W—H1B···O10ⁱⁱ	0.90	2.48	3.182 (8)	136
N7—H7A···O3ⁱ	0.92	2.54	3.066 (4)	117
N7—H7B···O18	0.92	2.03	2.940 (9)	167
N7—H7B···O18′	0.92	2.32	3.215 (17)	163
N8—H8A···O17^vii	0.91	1.86	2.755 (7)	166
N8—H8B···O8^vii	0.91	2.04	2.842 (6)	147
N8—H8B···O9^vii	0.91	2.39	3.057 (6)	130
N8—H8C···O5^vii	0.91	2.00	2.907 (7)	172
N9—H9A···O1ⁱⁱⁱ	0.92	2.44	2.999 (4)	119
N9—H9B···O10	0.92	2.16	3.075 (4)	174
N10—H10A···O14	0.91	2.00	2.869 (6)	160
N10—H10A···O16	0.91	2.44	3.183 (8)	139
N10—H10B···O11^viii	0.91	2.00	2.844 (5)	154
N10—H10B···O12^viii	0.91	2.48	3.066 (6)	123
N10—H10C···O7ⁱⁱ	0.91	2.04	2.914 (7)	161

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

Experimental details

Crystal data
Chemical formula	[Zn₂(C₆H₁₄N₂O₂)₂(C₁₀H₈N₂)₃](NO₃)₄·0.6H₂O·2C₃H₇NO
M_r	1296.76
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	187
a, b, c (Å)	10.3039 (4), 24.9425 (10), 11.5740 (4)
β (°)	93.197 (1)
V (Å³)	2970.0 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.89
Crystal size (mm)	0.26 × 0.23 × 0.13

Data collection
Diffractometer	Bruker APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.801, 0.893
No. of measured, independent and observed [I > 2σ(I)] reflections	16802, 11087, 10039
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.618

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.107, 1.00
No. of reflections	11087
No. of parameters	820
No. of restraints	63
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.81, −0.33
Absolute structure	Flack (1983), 5102 Friedel pairs
Absolute structure parameter	0.003 (9)

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1A···O15	0.95	1.91	2.823 (11)	159
O1W—H1B···O10ⁱ	0.90	2.48	3.182 (8)	136
N7—H7A···O3ⁱⁱ	0.92	2.54	3.066 (4)	117
N7—H7B···O18	0.92	2.03	2.940 (9)	167
N7—H7B···O18'	0.92	2.32	3.215 (17)	163
N8—H8A···O17ⁱⁱⁱ	0.91	1.86	2.755 (7)	166
N8—H8B···O8ⁱⁱⁱ	0.91	2.04	2.842 (6)	147
N8—H8B···O9ⁱⁱⁱ	0.91	2.39	3.057 (6)	130
N8—H8C···O5ⁱⁱⁱ	0.91	2.00	2.907 (7)	172
N9—H9A···O1^iv	0.92	2.44	2.999 (4)	119
N9—H9B···O10	0.92	2.16	3.075 (4)	174
N10—H10A···O14	0.91	2.00	2.869 (6)	160
N10—H10A···O16	0.91	2.44	3.183 (8)	139
N10—H10B···O11^v	0.91	2.00	2.844 (5)	154
N10—H10B···O12^v	0.91	2.48	3.066 (6)	123
N10—H10C···O7ⁱ	0.91	2.04	2.914 (7)	161

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

Acknowledgements

This work was supported by Changchun Institute of Applied Chemistry, Chinese Academy of Sciences.

References

Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dai, Y.-M., Ma, E., Tang, E., Zhang, J., Li, Z.-J., Huang, X.-D. & Yao, Y.-G. (2005). Cryst. Growth Des. 5, 1313–1315. Web of Science CSD CrossRef CAS Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Kesanli, B. & Lin, W. (2003). Coord. Chem. Rev. 246, 305–326. Web of Science CrossRef CAS Google Scholar
Li, S.-Q. & Hu, N.-H. (2011). Acta Cryst. E67, m884–m885. Web of Science CSD CrossRef IUCr Journals Google Scholar
Lou, B.-Y. & Hong, M.-C. (2008). Acta Cryst. E64, m405. Web of Science CSD CrossRef IUCr Journals Google Scholar
Lou, B.-Y., Huang, X.-D. & Lin, X.-C. (2007). Z. Anorg. Allg. Chem. 633, 372–374. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Vaidhyanathan, R., Bradshaw, D., Rebilly, J.-N., Barrio, J. P., Gould, J. A., Berry, N. G. & Rosseinsky, M. J. (2006). Angew. Chem. Int. Ed. 45, 6495–6499. Web of Science CSD CrossRef CAS Google Scholar
Zaworotko, M. J. (2001). Chem. Commun. pp. 1–9. Web of Science CrossRef Google Scholar
Zhang, S. & Hu, N.-H. (2009). Acta Cryst. C65, m7–m9. Web of Science CSD CrossRef IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.