A cationic zinc(II) complex of a new ligand based on N,N,N′,N′-tetramethylstreptamine 2,4,6-orthoformate as the trichloro(pyridine)zincate(II) salt

In the title compound, rac-Bis­[μ-(1R,2S,12R,13s,15s,17S,18r)-14,16,19-trioxa-3,7,11-tri­aza­tetra­cyclo[13.3.1.0^2,13.0^12,17]­nonadecan-18-olato-1κ³N³,N⁷,N¹¹:2κ²O¹⁸]­dizinc(II) bis­[tri­chloro­(pyridine)­zincate(II)], [Zn₂(C₁₃H₂₂N₃O₄)₂][ZnCl₃(C₅H₄N)]₂, the cation displays crystallographic inversion symmetry. The geometry at zinc is trigonal bipyramidal. Three hydrogen bonds N—H...Cl—Zn lead to the formation of columns parallel to the a axis.

Key indicators

• Single-crystal X-ray study
• T = 143 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.029
• wR factor = 0.068
• Data-to-parameter ratio = 13.8

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level B:



ABSTM_02  Alert B The ratio of expected to reported Tmax/Tmin(RR) is > 1.50
          Tmin and Tmax reported:      0.670     0.984
          Tmin and Tmax expected:      0.302     0.688
          RR =      1.553
          Please check that your absorption correction is appropriate.

General Notes



ABSTM_02  When printed, the submitted absorption T values will be replaced
          by the scaled T values. Since the ratio of scaled T's is
          identical to the ratio of reported T values, the scaling does
          not imply a change to the absorption corrections used in the
          study.
          Ratio of Tmax expected/reported      0.700
          Tmax scaled      0.688 Tmin scaled      0.469


 0 Alert Level A = Potentially serious problem

 1 Alert Level B = Potential problem

 0 Alert Level C = Please check

---

S1. Comment

The previous communication (Jones et al., 2003) described the crystal and molecular structure of a cationic zinc complex, of interest as a potential leaving group in models for certain aspects of catalysis in metalloenzymes. Crystal structures also contain a wealth of potential information about reactivity, but evidence from a single structure (which may be `basically anecdotal'; Kirby, 1994) should be regarded with caution. We report here a second structure, (2), containing the same dication (but with a different counter-ion). The structure was determined because it was thought that a different, possibly monomeric form of the zinc complex might have been formed (see Experimental). However, the structure solution (Fig. 1) revealed the same dimeric dication, again with inversion symmetry, but with the complex anion [Zn(py)Cl<sub>3</sub>]<sup>-</sup> replacing chloride as counter-ion. The formation of the dimeric complex in two different structures with distinctly different counter-ions, and in the presence of a potentially competing ligand (pyridine), suggests that the species is relatively stable and not just the `accidental' result of a compromise between packing forces in a specific structure.

The cations of both compounds are structurally similar, as would be expected; the general comments of the previous paper are thus valid for the current structure (e.g. the inversion symmetry and the trigonal-bipyramidal geometry at zinc; however, some differences are presented below). We also have good spectroscopic evidence that the structures are similar in solution (Beckmann, 1998). A least-squares fit of the asymmetric unit of both cations (Fig. 2) shows that the ZnNC₃N rings differ in conformation between the two compounds; except for these three C atoms; however, the r.m.s. displacement is only 0.09 Å. Bond lengths and angles at zinc (see Table 1 for exact values and s.u.'s) differ appreciably for Zn—O4_ax (here 2.09, previously 2.16 Å) and O4_eq—Zn—N3 (here 124°, previously 107°).

The anion has distorted tetrahedral geometry at the central Zn atom. Three classical N—H···Cl—Zn hydrogen bonds (Table 2) are observed between anion and cation, the net effect of which is to form columns of anions and cations parallel to the x axis in the regions x,y ≈ 1/2 (Fig. 3) and x,y ≈ 0. However, these interactions are appreciably longer than the N—H···Cl^- of the previous structure, and are supplemented by a series of `weak' C—H···X hydrogen bonds (X = Cl and O; Table 2) of comparable lengths.

S2. Experimental

Crystals of (2) were obtained fortuitously on adding pyridine to the combined `waste' solutions from completed kinetic experiments (which had been retained for recycling) (Beckmann, 1998). Crystals began to grow from an aqueous solution (also containing N-ethylmorpholine buffer and KCl) some days after

adding pyridine.

S3. Refinement

H atoms of NH groups were identified in difference syntheses and refined freely, but with a common N—H distance restraint. Other H atoms were included using a riding model with fixed C—H bond lengths of 1.00 (CH) or 0.99 Å (CH₂); U_iso(H) values were fixed at 1.2U_eq of the parent atom. One curious feature of the structure is the very short bond C5—C6, which at 1.442 (5) Å is much shorter than the corresponding bond in the previous paper, 1.524 (3) Å. We attribute this to libration effects arising from the appreciably higher U values of C5 and C6, or to a slight disorder of these atoms.

Computing details

Data collection: DIF4 (Stoe & Cie, 1992); cell refinement: DIF4; data reduction: REDU4 (Stoe & Cie, 1992); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The structure of the title compound in the crystal. Ellipsoids represent 30% probability levels. H-atom radii are arbitrary.
	Fig. 2. Least-squares fit of the chemically identical cations (asymmetric unit only, H atoms have been omitted) of the title compound (dashed bonds) and that of the previous paper (full bonds; Jones et al., 2003).
	Fig. 3. Packing diagram of the title compound, showing one column (see text). Hydrogen bonds are indicated by dashed lines. H atoms not involved in classical hydrogen bonds have been omitted.

rac-Bis[µ-(1R,2S,12R,13S,15S,17S,18R)-14,16,19-trioxa-3,7,11- triazatetracyclo[13.3.1.0^2,13.0^12,17]nonadecan-18-olato- 1κ³N³,N⁷,N¹¹:2κ²O¹⁸]dizinc(II) bis[trichloro(pyridine)zincate(II)]

Crystal data

[Zn2(C13H22N3O4)2][ZnCl3(C5H4N)]2	F(000) = 1224
Mr = 1201.05	Dx = 1.750 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 54 reflections
a = 9.5416 (15) Å	θ = 10–11.5°
b = 17.491 (2) Å	µ = 2.49 mm^−1
c = 14.098 (3) Å	T = 143 K
β = 104.366 (10)°	Tablet, colourless
V = 2279.2 (7) Å^3	0.5 × 0.45 × 0.15 mm
Z = 2

Data collection

Stoe STADI-4 diffractometer	3390 reflections with I > 2s(I)
Radiation source: fine-focus sealed tube	Rint = 0.035
Graphite monochromator	θmax = 25.0°, θmin = 3.2°
ω/θ–scans	h = −11→11
Absorption correction: ψ scans (XEMP; Siemens, 1994)	k = −20→20
Tmin = 0.670, Tmax = 0.984	l = 0→16
8250 measured reflections	3 standard reflections every 60 min
4031 independent reflections	intensity decay: 4%

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.069	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0268P)^2 + 1.2592P] where P = (Fo^2 + 2Fc^2)/3
4031 reflections	(Δ/σ)max < 0.001
292 parameters	Δρmax = 0.47 e Å^−3
3 restraints	Δρmin = −0.38 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	0.91734 (4)	0.571013 (18)	0.44236 (2)	0.02080 (10)
N1	1.0368 (3)	0.62766 (14)	0.35878 (18)	0.0228 (5)
H01	1.117 (3)	0.6281 (17)	0.396 (2)	0.024 (9)*
N2	0.8144 (3)	0.67003 (15)	0.4767 (2)	0.0299 (6)
H02	0.798 (3)	0.6616 (18)	0.5288 (18)	0.025 (9)*
N3	0.7508 (3)	0.53112 (15)	0.32799 (18)	0.0236 (5)
H03	0.733 (3)	0.4924 (14)	0.355 (2)	0.021 (9)*
O1	0.9238 (2)	0.41052 (12)	0.17158 (15)	0.0318 (5)
O2	1.1323 (2)	0.48262 (13)	0.19182 (16)	0.0340 (5)
O3	0.9116 (2)	0.53528 (12)	0.11301 (15)	0.0326 (5)
O4	1.0343 (2)	0.47328 (11)	0.42589 (14)	0.0241 (4)
C1	0.8035 (3)	0.50532 (16)	0.2431 (2)	0.0235 (6)
H1	0.7170	0.4914	0.1897	0.028*
C2	0.8874 (3)	0.56684 (17)	0.2026 (2)	0.0226 (6)
H2	0.8278	0.6144	0.1877	0.027*
C3	1.0378 (3)	0.58641 (17)	0.2671 (2)	0.0245 (7)
H3	1.0871	0.6200	0.2278	0.029*
C4	0.9922 (4)	0.70875 (18)	0.3387 (2)	0.0362 (8)
H4A	0.8920	0.7102	0.2971	0.043*
H4B	1.0559	0.7330	0.3017	0.043*
C5	0.9989 (5)	0.7544 (2)	0.4308 (3)	0.0610 (12)
H5A	1.1020	0.7567	0.4668	0.073*
H5B	0.9699	0.8073	0.4096	0.073*
C6	0.9187 (5)	0.7337 (2)	0.5012 (3)	0.0583 (11)
H6A	0.8653	0.7795	0.5139	0.070*
H6B	0.9894	0.7207	0.5633	0.070*
C7	0.6733 (4)	0.69055 (19)	0.4128 (2)	0.0357 (8)
H7A	0.6882	0.7178	0.3545	0.043*
H7B	0.6228	0.7258	0.4482	0.043*
C8	0.5795 (4)	0.6211 (2)	0.3800 (3)	0.0404 (9)
H8A	0.4773	0.6378	0.3590	0.049*
H8B	0.5884	0.5865	0.4367	0.049*
C9	0.6165 (3)	0.57671 (19)	0.2968 (2)	0.0339 (8)
H9A	0.5352	0.5420	0.2677	0.041*
H9B	0.6274	0.6131	0.2453	0.041*
C10	0.9947 (4)	0.4676 (2)	0.1319 (2)	0.0350 (8)
H10	1.0076	0.4483	0.0679	0.042*
C11	0.9011 (3)	0.43465 (17)	0.2645 (2)	0.0261 (7)
H11	0.8506	0.3932	0.2919	0.031*
C12	1.0487 (3)	0.45019 (17)	0.3346 (2)	0.0240 (6)
H12	1.1077	0.4023	0.3423	0.029*
C13	1.1229 (3)	0.51127 (18)	0.2867 (2)	0.0269 (7)
H13	1.2222	0.5213	0.3285	0.032*
Zn2	0.55898 (4)	0.29695 (2)	0.33708 (2)	0.02471 (10)
Cl1	0.70807 (10)	0.19961 (5)	0.33195 (6)	0.0420 (2)
Cl2	0.33240 (8)	0.26753 (5)	0.34444 (6)	0.03215 (19)
Cl3	0.65690 (9)	0.38564 (5)	0.45101 (6)	0.0352 (2)
N4	0.5270 (3)	0.34672 (14)	0.20015 (17)	0.0255 (6)
C20	0.4145 (3)	0.39309 (19)	0.1681 (2)	0.0336 (8)
H20	0.3556	0.4060	0.2110	0.040*
C21	0.3809 (4)	0.4229 (2)	0.0750 (3)	0.0437 (9)
H21	0.3009	0.4566	0.0544	0.052*
C22	0.4643 (4)	0.4036 (2)	0.0123 (3)	0.0455 (10)
H22	0.4410	0.4224	−0.0530	0.055*
C23	0.5817 (4)	0.3568 (2)	0.0449 (2)	0.0396 (9)
H23	0.6431	0.3439	0.0036	0.048*
C24	0.6084 (3)	0.32891 (18)	0.1391 (2)	0.0292 (7)
H24	0.6884	0.2955	0.1614	0.035*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.02457 (18)	0.02292 (18)	0.01495 (17)	0.00391 (14)	0.00496 (13)	0.00259 (14)
N1	0.0199 (13)	0.0264 (13)	0.0203 (13)	−0.0012 (11)	0.0018 (11)	0.0009 (11)
N2	0.0402 (16)	0.0307 (15)	0.0198 (14)	0.0073 (12)	0.0094 (12)	0.0010 (12)
N3	0.0254 (13)	0.0222 (14)	0.0236 (14)	0.0009 (11)	0.0072 (11)	0.0029 (11)
O1	0.0483 (14)	0.0280 (12)	0.0192 (11)	0.0035 (10)	0.0086 (10)	−0.0046 (9)
O2	0.0387 (13)	0.0427 (14)	0.0268 (12)	0.0102 (11)	0.0201 (11)	0.0020 (10)
O3	0.0472 (14)	0.0363 (13)	0.0145 (11)	0.0083 (11)	0.0082 (10)	0.0024 (9)
O4	0.0328 (11)	0.0254 (11)	0.0137 (10)	0.0086 (9)	0.0052 (9)	0.0012 (8)
C1	0.0240 (15)	0.0257 (16)	0.0188 (15)	0.0001 (12)	0.0014 (12)	−0.0014 (12)
C2	0.0270 (15)	0.0268 (16)	0.0148 (14)	0.0056 (12)	0.0067 (12)	0.0019 (12)
C3	0.0253 (16)	0.0289 (16)	0.0217 (16)	−0.0009 (12)	0.0102 (13)	0.0047 (13)
C4	0.056 (2)	0.0265 (17)	0.0311 (19)	0.0026 (16)	0.0210 (17)	0.0090 (14)
C5	0.098 (3)	0.035 (2)	0.061 (3)	−0.021 (2)	0.038 (3)	−0.016 (2)
C6	0.069 (3)	0.063 (3)	0.050 (3)	−0.019 (2)	0.026 (2)	−0.024 (2)
C7	0.048 (2)	0.0378 (19)	0.0242 (17)	0.0248 (16)	0.0137 (15)	0.0047 (15)
C8	0.0270 (17)	0.064 (2)	0.0321 (19)	0.0152 (17)	0.0110 (15)	0.0016 (17)
C9	0.0201 (15)	0.045 (2)	0.0333 (19)	0.0054 (14)	0.0003 (14)	−0.0026 (15)
C10	0.046 (2)	0.043 (2)	0.0178 (16)	0.0126 (16)	0.0106 (15)	0.0002 (15)
C11	0.0346 (17)	0.0249 (16)	0.0198 (15)	0.0012 (13)	0.0089 (13)	−0.0011 (13)
C12	0.0280 (16)	0.0255 (16)	0.0190 (15)	0.0103 (13)	0.0069 (13)	0.0013 (12)
C13	0.0242 (16)	0.0380 (18)	0.0192 (16)	0.0071 (13)	0.0063 (13)	−0.0010 (13)
Zn2	0.02293 (19)	0.0324 (2)	0.01939 (19)	0.00034 (15)	0.00636 (14)	0.00079 (15)
Cl1	0.0425 (5)	0.0506 (5)	0.0359 (5)	0.0195 (4)	0.0154 (4)	0.0044 (4)
Cl2	0.0265 (4)	0.0461 (5)	0.0262 (4)	−0.0075 (3)	0.0109 (3)	−0.0082 (3)
Cl3	0.0405 (5)	0.0406 (5)	0.0234 (4)	−0.0131 (4)	0.0057 (3)	−0.0024 (3)
N4	0.0228 (13)	0.0323 (14)	0.0205 (13)	−0.0033 (11)	0.0037 (11)	−0.0010 (11)
C20	0.0283 (17)	0.0392 (19)	0.0321 (19)	0.0021 (14)	0.0054 (14)	0.0017 (15)
C21	0.037 (2)	0.048 (2)	0.041 (2)	0.0027 (17)	−0.0013 (17)	0.0141 (18)
C22	0.057 (2)	0.053 (2)	0.0203 (18)	−0.0144 (19)	−0.0016 (17)	0.0081 (16)
C23	0.050 (2)	0.049 (2)	0.0248 (18)	−0.0166 (18)	0.0179 (16)	−0.0060 (16)
C24	0.0292 (17)	0.0340 (17)	0.0265 (17)	−0.0041 (14)	0.0109 (14)	−0.0046 (14)

Geometric parameters (Å, º)

Zn1—O4^i	1.9590 (19)	C5—H5A	0.9900
Zn1—N1	2.082 (2)	C5—H5B	0.9900
Zn1—N3	2.083 (3)	C6—H6A	0.9900
Zn1—O4	2.0860 (19)	C6—H6B	0.9900
Zn1—N2	2.106 (3)	C7—C8	1.511 (5)
N1—C3	1.483 (4)	C7—H7A	0.9900
N1—C4	1.488 (4)	C7—H7B	0.9900
N1—H01	0.81 (2)	C8—C9	1.520 (4)
N2—C7	1.467 (4)	C8—H8A	0.9900
N2—C6	1.477 (5)	C8—H8B	0.9900
N2—H02	0.80 (2)	C9—H9A	0.9900
N3—C1	1.479 (4)	C9—H9B	0.9900
N3—C9	1.480 (4)	C10—H10	1.0000
N3—H03	0.82 (2)	C11—C12	1.531 (4)
O1—C10	1.398 (4)	C11—H11	1.0000
O1—C11	1.443 (3)	C12—C13	1.528 (4)
O2—C10	1.399 (4)	C12—H12	1.0000
O2—C13	1.452 (4)	C13—H13	1.0000
O3—C10	1.414 (4)	Zn2—N4	2.070 (2)
O3—C2	1.449 (3)	Zn2—Cl1	2.2314 (9)
O4—C12	1.388 (3)	Zn2—Cl2	2.2496 (9)
O4—Zn1^i	1.9590 (19)	Zn2—Cl3	2.2615 (9)
C1—C11	1.532 (4)	N4—C20	1.332 (4)
C1—C2	1.533 (4)	N4—C24	1.332 (4)
C1—H1	1.0000	C20—C21	1.375 (5)
C2—C3	1.534 (4)	C20—H20	0.9500
C2—H2	1.0000	C21—C22	1.371 (5)
C3—C13	1.533 (4)	C21—H21	0.9500
C3—H3	1.0000	C22—C23	1.372 (5)
C4—C5	1.512 (5)	C22—H22	0.9500
C4—H4A	0.9900	C23—C24	1.377 (4)
C4—H4B	0.9900	C23—H23	0.9500
C5—C6	1.442 (5)	C24—H24	0.9500
O4^i—Zn1—N1	133.76 (9)	N2—C6—H6B	107.8
O4^i—Zn1—N3	123.80 (10)	H6A—C6—H6B	107.1
N1—Zn1—N3	98.10 (10)	N2—C7—C8	112.0 (3)
O4^i—Zn1—O4	76.99 (8)	N2—C7—H7A	109.2
N1—Zn1—O4	86.78 (9)	C8—C7—H7A	109.2
N3—Zn1—O4	88.04 (9)	N2—C7—H7B	109.2
O4^i—Zn1—N2	96.93 (9)	C8—C7—H7B	109.2
N1—Zn1—N2	95.22 (10)	H7A—C7—H7B	107.9
N3—Zn1—N2	98.26 (10)	C7—C8—C9	114.4 (3)
O4—Zn1—N2	173.04 (9)	C7—C8—H8A	108.7
C3—N1—C4	111.2 (2)	C9—C8—H8A	108.7
C3—N1—Zn1	112.64 (18)	C7—C8—H8B	108.7
C4—N1—Zn1	112.96 (19)	C9—C8—H8B	108.7
C3—N1—H01	111 (2)	H8A—C8—H8B	107.6
C4—N1—H01	107 (2)	N3—C9—C8	113.3 (3)
Zn1—N1—H01	102 (2)	N3—C9—H9A	108.9
C7—N2—C6	115.0 (3)	C8—C9—H9A	108.9
C7—N2—Zn1	118.0 (2)	N3—C9—H9B	108.9
C6—N2—Zn1	110.3 (2)	C8—C9—H9B	108.9
C7—N2—H02	105 (2)	H9A—C9—H9B	107.7
C6—N2—H02	101 (2)	O1—C10—O2	111.6 (2)
Zn1—N2—H02	105 (2)	O1—C10—O3	111.6 (3)
C1—N3—C9	111.5 (2)	O2—C10—O3	110.8 (3)
C1—N3—Zn1	112.41 (18)	O1—C10—H10	107.5
C9—N3—Zn1	119.17 (19)	O2—C10—H10	107.5
C1—N3—H03	106 (2)	O3—C10—H10	107.5
C9—N3—H03	109 (2)	O1—C11—C12	108.5 (2)
Zn1—N3—H03	97 (2)	O1—C11—C1	106.1 (2)
C10—O1—C11	110.5 (2)	C12—C11—C1	113.6 (2)
C10—O2—C13	111.0 (2)	O1—C11—H11	109.5
C10—O3—C2	111.0 (2)	C12—C11—H11	109.5
C12—O4—Zn1^i	135.25 (17)	C1—C11—H11	109.5
C12—O4—Zn1	121.35 (16)	O4—C12—C13	111.7 (2)
Zn1^i—O4—Zn1	103.01 (8)	O4—C12—C11	111.3 (2)
N3—C1—C11	113.5 (2)	C13—C12—C11	107.0 (2)
N3—C1—C2	113.6 (2)	O4—C12—H12	108.9
C11—C1—C2	107.0 (2)	C13—C12—H12	108.9
N3—C1—H1	107.5	C11—C12—H12	108.9
C11—C1—H1	107.5	O2—C13—C12	107.9 (2)
C2—C1—H1	107.5	O2—C13—C3	106.3 (2)
O3—C2—C1	105.5 (2)	C12—C13—C3	113.4 (2)
O3—C2—C3	105.9 (2)	O2—C13—H13	109.7
C1—C2—C3	115.8 (2)	C12—C13—H13	109.7
O3—C2—H2	109.8	C3—C13—H13	109.7
C1—C2—H2	109.8	N4—Zn2—Cl1	103.78 (7)
C3—C2—H2	109.8	N4—Zn2—Cl2	102.62 (7)
N1—C3—C13	112.2 (2)	Cl1—Zn2—Cl2	117.04 (4)
N1—C3—C2	114.6 (2)	N4—Zn2—Cl3	108.25 (7)
C13—C3—C2	106.9 (2)	Cl1—Zn2—Cl3	113.08 (4)
N1—C3—H3	107.6	Cl2—Zn2—Cl3	110.89 (3)
C13—C3—H3	107.6	C20—N4—C24	118.3 (3)
C2—C3—H3	107.6	C20—N4—Zn2	119.5 (2)
N1—C4—C5	113.1 (3)	C24—N4—Zn2	122.0 (2)
N1—C4—H4A	109.0	N4—C20—C21	122.2 (3)
C5—C4—H4A	109.0	N4—C20—H20	118.9
N1—C4—H4B	109.0	C21—C20—H20	118.9
C5—C4—H4B	109.0	C22—C21—C20	119.2 (3)
H4A—C4—H4B	107.8	C22—C21—H21	120.4
C6—C5—C4	122.8 (3)	C20—C21—H21	120.4
C6—C5—H5A	106.6	C21—C22—C23	119.2 (3)
C4—C5—H5A	106.6	C21—C22—H22	120.4
C6—C5—H5B	106.6	C23—C22—H22	120.4
C4—C5—H5B	106.6	C22—C23—C24	118.3 (3)
H5A—C5—H5B	106.6	C22—C23—H23	120.8
C5—C6—N2	118.1 (3)	C24—C23—H23	120.8
C5—C6—H6A	107.8	N4—C24—C23	122.8 (3)
N2—C6—H6A	107.8	N4—C24—H24	118.6
C5—C6—H6B	107.8	C23—C24—H24	118.6
O4^i—Zn1—N1—C3	118.42 (19)	Zn1—N2—C6—C5	55.2 (5)
N3—Zn1—N1—C3	−37.7 (2)	C6—N2—C7—C8	172.4 (3)
O4—Zn1—N1—C3	49.89 (19)	Zn1—N2—C7—C8	39.5 (3)
N2—Zn1—N1—C3	−136.80 (19)	N2—C7—C8—C9	−79.1 (4)
O4^i—Zn1—N1—C4	−114.5 (2)	C1—N3—C9—C8	−165.2 (3)
N3—Zn1—N1—C4	89.4 (2)	Zn1—N3—C9—C8	−31.7 (4)
O4—Zn1—N1—C4	176.9 (2)	C7—C8—C9—N3	74.4 (4)
N2—Zn1—N1—C4	−9.8 (2)	C11—O1—C10—O2	62.5 (3)
O4^i—Zn1—N2—C7	−132.1 (2)	C11—O1—C10—O3	−62.1 (3)
N1—Zn1—N2—C7	92.6 (2)	C13—O2—C10—O1	−62.5 (3)
N3—Zn1—N2—C7	−6.3 (2)	C13—O2—C10—O3	62.6 (3)
O4^i—Zn1—N2—C6	93.0 (2)	C2—O3—C10—O1	62.1 (3)
N1—Zn1—N2—C6	−42.3 (2)	C2—O3—C10—O2	−63.0 (3)
N3—Zn1—N2—C6	−141.3 (2)	C10—O1—C11—C12	−60.4 (3)
O4^i—Zn1—N3—C1	−120.27 (18)	C10—O1—C11—C1	62.1 (3)
N1—Zn1—N3—C1	39.1 (2)	N3—C1—C11—O1	171.3 (2)
O4—Zn1—N3—C1	−47.36 (19)	C2—C1—C11—O1	−62.6 (3)
N2—Zn1—N3—C1	135.62 (19)	N3—C1—C11—C12	−69.6 (3)
O4^i—Zn1—N3—C9	106.5 (2)	C2—C1—C11—C12	56.5 (3)
N1—Zn1—N3—C9	−94.1 (2)	Zn1^i—O4—C12—C13	−128.5 (2)
O4—Zn1—N3—C9	179.4 (2)	Zn1—O4—C12—C13	60.0 (3)
N2—Zn1—N3—C9	2.4 (2)	Zn1^i—O4—C12—C11	112.0 (3)
O4^i—Zn1—O4—C12	173.9 (3)	Zn1—O4—C12—C11	−59.5 (3)
N1—Zn1—O4—C12	−49.7 (2)	O1—C11—C12—O4	−179.6 (2)
N3—Zn1—O4—C12	48.5 (2)	C1—C11—C12—O4	62.6 (3)
O4^i—Zn1—O4—Zn1^i	0.0	O1—C11—C12—C13	58.1 (3)
N1—Zn1—O4—Zn1^i	136.38 (10)	C1—C11—C12—C13	−59.6 (3)
N3—Zn1—O4—Zn1^i	−125.39 (11)	C10—O2—C13—C12	60.1 (3)
C9—N3—C1—C11	−157.1 (3)	C10—O2—C13—C3	−61.8 (3)
Zn1—N3—C1—C11	66.1 (3)	O4—C12—C13—O2	−179.6 (2)
C9—N3—C1—C2	80.4 (3)	C11—C12—C13—O2	−57.6 (3)
Zn1—N3—C1—C2	−56.4 (3)	O4—C12—C13—C3	−62.2 (3)
C10—O3—C2—C1	−61.2 (3)	C11—C12—C13—C3	59.8 (3)
C10—O3—C2—C3	62.0 (3)	N1—C3—C13—O2	−172.2 (2)
N3—C1—C2—O3	−172.1 (2)	C2—C3—C13—O2	61.3 (3)
C11—C1—C2—O3	61.9 (3)	N1—C3—C13—C12	69.4 (3)
N3—C1—C2—C3	71.3 (3)	C2—C3—C13—C12	−57.0 (3)
C11—C1—C2—C3	−54.8 (3)	Cl1—Zn2—N4—C20	161.8 (2)
C4—N1—C3—C13	163.7 (3)	Cl2—Zn2—N4—C20	39.5 (2)
Zn1—N1—C3—C13	−68.3 (3)	Cl3—Zn2—N4—C20	−77.8 (2)
C4—N1—C3—C2	−74.1 (3)	Cl1—Zn2—N4—C24	−12.4 (2)
Zn1—N1—C3—C2	53.9 (3)	Cl2—Zn2—N4—C24	−134.7 (2)
O3—C2—C3—N1	173.6 (2)	Cl3—Zn2—N4—C24	108.0 (2)
C1—C2—C3—N1	−69.9 (3)	C24—N4—C20—C21	−0.3 (5)
O3—C2—C3—C13	−61.4 (3)	Zn2—N4—C20—C21	−174.7 (3)
C1—C2—C3—C13	55.1 (3)	N4—C20—C21—C22	1.0 (5)
C3—N1—C4—C5	−176.3 (3)	C20—C21—C22—C23	−2.0 (5)
Zn1—N1—C4—C5	55.9 (4)	C21—C22—C23—C24	2.1 (5)
N1—C4—C5—C6	−58.2 (6)	C20—N4—C24—C23	0.5 (5)
C4—C5—C6—N2	−6.7 (7)	Zn2—N4—C24—C23	174.7 (2)
C7—N2—C6—C5	−81.3 (5)	C22—C23—C24—N4	−1.4 (5)

Symmetry code: (i) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H01···Cl3^i	0.81 (2)	2.66 (2)	3.449 (3)	165 (3)
N2—H02···Cl2^ii	0.80 (2)	2.72 (3)	3.356 (3)	138 (3)
N3—H03···Cl3	0.82 (2)	2.52 (2)	3.325 (3)	172 (3)
C3—H3···Cl1^iii	1.00	2.70	3.664 (3)	162
C23—H23···Cl1^iv	0.95	2.75	3.638 (3)	156
C24—H24···Cl1	0.95	2.90	3.483 (3)	121
C4—H4A···Cl2^v	0.99	2.73	3.653 (4)	155
C7—H7A···Cl2^v	0.99	2.90	3.856 (3)	164
C7—H7B···Cl2^ii	0.99	2.85	3.514 (3)	125
C5—H5B···O1^iii	0.99	2.48	3.257 (4)	135
C20—H20···O2^vi	0.95	2.47	3.203 (4)	134

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