(Acetato-κO)[tris(3,5-dimethyl­pyra­zol-1-yl-κN²)hydro­borato]zinc(II)

The title complex, [Zn(C₁₅H₂₂BN₆)(C₂H₃O₂)] or (Tp^Me,Me)Zn(OAc), contains a tripodal tris(pyrazolyl)hydro­borate ligand, a monodentate acetate ligand and a Zn^II centre in a distorted tetra­hedral coordination environment capped on one triangular face by a secondary Zn...O inter­action with the second O atom of the acetate ligand. The four-coordination of Zn^II and the essentially monodentate character of the acetate ligand are due to the high steric demands of the ligand set, which prevent chelate formation and five-coordination and lead to relatively long Zn—O and Zn—N bonds compared with related complexes of Zn^II and other metals.

S1. Comment

Metal complexes containing hydrotris(pyrazolyl)borate ligands, Tp^R,R' or [HB(3-R,5-R'Pz)₃]^- (R, R' = H, alkyl or aryl), have been investigated widely by inorganic, organometallic and bioinorganic chemists (Trofimenko, 1993, 1999; Kitajima & Tolman, 1995). This popularity has resulted from their ease of preparation and wide variation of their steric and electronic properties by the use of different substituents on the pyrazole rings. Numerous studies have been performed to synthesize stable tetrahedral metal complexes MX(Tp^R,R') (M = Zn, Cd, Cu; X = Cl, OAc) by the use of these sterically demanding tridentate N-donor ligands to model the structure and function of the active site of the carbonic anhydrase enzyme (Guo et al., 1998; Vahrenkamp, 1999; Looney et al., 1993). The title complex, (I), has been prepared as one such model, and its structure has been determined to confirm the tetrahedral coordination and monomeric formulation. The molecular structure of (I) is shown in Fig. 1, and selected bond lengths and angles are given in Table 1.

Zn^II, as a d¹⁰ ion without a crystal field-stabilization energy preference for any particular coordination geometry, exhibits a very flexible and varied coordination chemistry. The most common coordination numbers are 4, 5 and 6, represented by structures in the approximate ratio 2:1:1 in the Cambridge Structural Database (CSD, Version 5.30 with updates to May 2009; Allen, 2002). Tetrahedral coordination (regular or distorted) is promoted by bulky ligands, including substituted Tp^R,R' ligands, as in the case of complex (I). Here the primary coordination is distorted tetrahedral, with an essentially regular tripodal arrangement for Tp^Me,Me and a monodentate acetate ligand; the Zn1—O1 bond length is 1.9217 (17) Å, while the non-bonded Zn1···O2 distance is 2.6033 (18) Å.

Complex (I) is almost isostructural with the corresponding Ni^II complex (Hikichi et al., 2002), and there is an r.m.s. deviation of only 0.028 Å for a least-squares overlay of the two MN₆B units. However, the nickel complex is clearly five-coordinate, with a more nearly symmetrically chelating acetate ligand, giving Ni—O bond lengths of 2.013 and 2.131 Å, a difference of only 0.118 Å, compared with 0.681 Å for the title zinc complex. Of the 25 (Tp^R,R')Zn(carboxylate) complexes in the CSD, 19 have a monodentate carboxylate ligand, five are chelate complexes and one contains both geometries.

As an alternative description, if the weaker but not insignificant secondary Zn1···O2 interaction is included, the coordination of Zn1 is monocapped tetrahedral, this interaction capping the N2/N4/O1 triangular face. The distortion of the tetrahedral geometry by the capping atom O2 is towards trigonal–bipyramidal, with atoms N2, N4 and O1 in the equatorial plane, and atoms N6 and O2 in axial sites. It might be expected that strengthening of the secondary Zn···O interaction relative to the primary Zn—O bond would tend to equalize the two carboxylate C—O bond lengths, the carboxylate group being delocalized as a symmetrical chelate ligand and having essentially localized single (coordinated O) and double (uncoordinated O) C—O bonds in monodentate mode, but an analysis of relevant four- and five-coordinate zinc complexes with acetate ligands in the CSD (of which there are approximately 100), using the CSD VISTA tool, shows only weak correlation. Indeed, there are numerous cases in which the C—O bonds have relative lengths opposite to the expected pattern, with what appears on this criterion to be the carbonyl O atom coordinated to Zn1. In the title zinc complex, which we prefer to describe as primarily tetrahedral with significant distortion through a secondary capping interaction, the difference in C—O bond lengths, 0.070 Å, is not much greater than in the corresponding nickel complex (0.056 Å), which is certainly better described as five-coordinate with two Ni—O bonds of similar strength. Irregular and intermediate coordination geometries are, of course, very much a matter of interpretation.

Although there are over 3000 known structures of metal complexes with Tp^R,R' ligands, of which almost 300 are zinc complexes, and nearly one-third of the metal complexes contain specifically the Tp^Me,Me ligand featured here, only four zinc complexes of Tp^Me,Me have previously been reported. Of these, two are octahedral Zn(Tp^Me,Me)₂, one of them unsolvated and the other a toluene solvate, and the other two are (Tp^Me,Me)ZnCl and (Tp^Me,Me)ZnMe, both tetrahedral. There are 189 four-coordinate (Tp^R,R')ZnL structures in the CSD (L = any monodentate ligand), in 69 of which L coordinates to Zn through an O atom. The range of Zn—O bond lengths in these 69 structures is 1.793–1.977 Å, with a mean of 1.879 Å. The Zn1—O1 bond in the title complex is one of the longest of these, at 1.9217 (17) Å, while complexes with the shortest Zn—O bonds include hydroxy complexes (Tp^R,R')ZnOH (Alsfasser et al., 1991; Ruf & Vahrenkamp, 1996). This, together with the fact that the Zn—N bonds here are marginally longer than the corresponding Ni—N bonds in the nickel(II) analogue (Hikichi et al., 2002), despite the smaller normal covalent radius of Zn^II compared with Ni^II, is a clear indication of the steric hindrance of the ligands in the title complex, which we have suggested as being responsible for the four- rather than five-coordination in this case.

S2. Experimental

Zinc acetate dihydrate (0.1 g, 0.45 mmol) and potassium hydrotris(3,5-dimethylpyrazolyl)borate (0.153 g, 0.45 mmol) (Trofimenko, 1967) were added to acetone (30 ml). The mixture was stirred for 6 h and then evaporated to dryness in vacuo. The residue was washed with diethyl ether (2 × 5 ml) and n-pentane (2 × 5 ml) and air-dried to give a white powder (0.123 g, 72% based on Zn). Colourless single crystals of the title complex, (I), were obtained from an acetone solution by slow evaporation of the solvent at room temperature. The air-stable crystals of (I) are slightly soluble in common organic solvents such as acetone, acetonitrile, dimethylformamide and dimethyl sulfoxide.

The FT–IR spectrum of (I) exhibits a medium-intensity feature at 2532.85 cm^-1, characteristic of the stretching vibration of the B—H bond in the Tp^Me,Me ligand. It is difficult to identify features due to the asymmetric and symmetric vibrations of the coordinated acetate, because the Tp^Me,Me ligand gives vibrational bands in the same regions.

S3. Refinement

H atoms were located in a difference map. The H atom bonded to B was refined freely. The remaining H atoms were idealized and refined with a riding model, including free rotation about C—C bonds, with C—H = 0.95–0.98 Å, and with U_iso = 1.5U_eq(C), or 1.2U_eq(C) for ring C atoms. [Please check added text.]

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and local programs.

Figures

Fig. 1. The molecular structure of (I), with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.

(Acetato-κO)[hydrotris(3,5-dimethylpyrazol-1-yl- κN²)borato]zinc(II)

Crystal data

[Zn(C15H22BN6)(C2H3O2)]	F(000) = 880
Mr = 421.61	Dx = 1.431 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5354 reflections
a = 13.766 (4) Å	θ = 2.4–28.3°
b = 7.721 (2) Å	µ = 1.28 mm^−1
c = 19.031 (5) Å	T = 150 K
β = 104.630 (4)°	Block, colourless
V = 1957.2 (9) Å^3	0.40 × 0.30 × 0.14 mm
Z = 4

Data collection

Bruker SMART 1K CCD area-detector diffractometer	3835 independent reflections
Radiation source: sealed tube	3441 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
Detector resolution: 8.192 pixels mm^-1	θmax = 26.0°, θmin = 1.5°
thin–slice ω scans	h = −16→16
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	k = −9→9
Tmin = 0.630, Tmax = 0.845	l = −23→23
14905 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.033	Hydrogen site location: difference Fourier map
wR(F^2) = 0.081	H atoms treated by a mixture of independent and constrained refinement
S = 1.16	w = 1/[σ^2(Fo^2) + (0.0313P)^2 + 1.8707P] where P = (Fo^2 + 2Fc^2)/3
3835 reflections	(Δ/σ)max = 0.001
255 parameters	Δρmax = 0.38 e Å^−3
0 restraints	Δρmin = −0.62 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Zn1	0.213815 (18)	0.41072 (3)	0.196958 (13)	0.01450 (9)
B1	0.31247 (18)	0.4142 (3)	0.35647 (14)	0.0157 (5)
H1	0.347 (2)	0.418 (4)	0.4155 (16)	0.035 (8)*
N1	0.37970 (13)	0.5071 (2)	0.31362 (10)	0.0153 (4)
N2	0.34894 (13)	0.5201 (2)	0.23930 (10)	0.0160 (4)
C1	0.47087 (16)	0.5817 (3)	0.33704 (13)	0.0197 (5)
C2	0.49941 (17)	0.6423 (3)	0.27725 (14)	0.0236 (5)
H2	0.5601	0.7003	0.2769	0.028*
C3	0.42162 (17)	0.6015 (3)	0.21751 (13)	0.0216 (5)
C4	0.52528 (19)	0.5957 (3)	0.41526 (14)	0.0284 (6)
H4A	0.4856	0.6656	0.4408	0.043*
H4B	0.5906	0.6511	0.4195	0.043*
H4C	0.5354	0.4798	0.4368	0.043*
C5	0.4124 (2)	0.6329 (4)	0.13851 (14)	0.0324 (6)
H5A	0.4067	0.5217	0.1129	0.049*
H5B	0.4720	0.6947	0.1326	0.049*
H5C	0.3524	0.7027	0.1183	0.049*
N3	0.29307 (13)	0.2249 (2)	0.32822 (10)	0.0153 (4)
N4	0.24954 (13)	0.1937 (2)	0.25624 (10)	0.0155 (4)
C6	0.31547 (16)	0.0717 (3)	0.36321 (12)	0.0181 (5)
C7	0.28612 (17)	−0.0587 (3)	0.31304 (13)	0.0208 (5)
H7	0.2923	−0.1799	0.3218	0.025*
C8	0.24553 (16)	0.0226 (3)	0.24676 (12)	0.0189 (5)
C9	0.36402 (19)	0.0587 (3)	0.44246 (13)	0.0251 (5)
H9A	0.4302	0.1142	0.4530	0.038*
H9B	0.3718	−0.0635	0.4567	0.038*
H9C	0.3220	0.1170	0.4698	0.038*
C10	0.2017 (2)	−0.0550 (3)	0.17372 (14)	0.0285 (6)
H10A	0.1295	−0.0307	0.1589	0.043*
H10B	0.2125	−0.1805	0.1761	0.043*
H10C	0.2343	−0.0046	0.1383	0.043*
N5	0.21046 (13)	0.5108 (2)	0.34247 (9)	0.0151 (4)
N6	0.15237 (13)	0.5259 (2)	0.27282 (10)	0.0151 (4)
C11	0.16486 (17)	0.5925 (3)	0.38832 (13)	0.0204 (5)
C12	0.07519 (17)	0.6601 (3)	0.34711 (13)	0.0214 (5)
H12	0.0268	0.7236	0.3644	0.026*
C13	0.07026 (16)	0.6160 (3)	0.27535 (13)	0.0177 (5)
C14	0.2099 (2)	0.6059 (3)	0.46821 (13)	0.0284 (6)
H14A	0.2238	0.4896	0.4889	0.043*
H14B	0.1628	0.6650	0.4911	0.043*
H14C	0.2726	0.6721	0.4771	0.043*
C15	−0.00933 (17)	0.6502 (3)	0.20762 (13)	0.0234 (5)
H15A	0.0156	0.6191	0.1654	0.035*
H15B	−0.0271	0.7733	0.2052	0.035*
H15C	−0.0688	0.5806	0.2077	0.035*
O1	0.12130 (13)	0.4304 (2)	0.10299 (9)	0.0305 (4)
O2	0.24834 (13)	0.2953 (2)	0.07702 (9)	0.0307 (4)
C16	0.16404 (19)	0.3569 (3)	0.05775 (13)	0.0259 (5)
C17	0.1052 (2)	0.3523 (5)	−0.02001 (15)	0.0532 (10)
H17A	0.1458	0.2983	−0.0496	0.080*
H17B	0.0877	0.4707	−0.0372	0.080*
H17C	0.0437	0.2848	−0.0242	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.01310 (14)	0.01482 (14)	0.01556 (14)	0.00145 (10)	0.00357 (9)	0.00122 (10)
B1	0.0151 (11)	0.0125 (11)	0.0205 (12)	−0.0009 (9)	0.0060 (10)	0.0004 (10)
N1	0.0132 (9)	0.0147 (9)	0.0172 (9)	−0.0008 (7)	0.0024 (7)	−0.0010 (7)
N2	0.0146 (9)	0.0171 (9)	0.0165 (9)	−0.0003 (7)	0.0045 (7)	0.0019 (7)
C1	0.0148 (10)	0.0152 (11)	0.0288 (12)	−0.0009 (9)	0.0049 (9)	−0.0025 (9)
C2	0.0168 (11)	0.0207 (12)	0.0358 (14)	−0.0038 (9)	0.0111 (10)	0.0000 (10)
C3	0.0209 (11)	0.0183 (12)	0.0280 (13)	0.0001 (9)	0.0111 (10)	0.0035 (9)
C4	0.0213 (12)	0.0317 (14)	0.0297 (13)	−0.0067 (11)	0.0019 (10)	−0.0057 (11)
C5	0.0300 (14)	0.0406 (16)	0.0309 (14)	−0.0076 (12)	0.0158 (11)	0.0065 (12)
N3	0.0147 (9)	0.0147 (9)	0.0161 (9)	0.0007 (7)	0.0033 (7)	0.0022 (7)
N4	0.0144 (9)	0.0150 (9)	0.0171 (9)	0.0001 (7)	0.0037 (7)	−0.0002 (7)
C6	0.0170 (10)	0.0155 (11)	0.0236 (12)	0.0032 (9)	0.0086 (9)	0.0056 (9)
C7	0.0245 (12)	0.0129 (11)	0.0267 (12)	0.0020 (9)	0.0097 (10)	0.0029 (9)
C8	0.0181 (11)	0.0152 (11)	0.0251 (12)	−0.0016 (9)	0.0087 (9)	0.0001 (9)
C9	0.0279 (13)	0.0222 (13)	0.0250 (13)	0.0024 (10)	0.0062 (10)	0.0074 (10)
C10	0.0380 (14)	0.0171 (12)	0.0284 (13)	−0.0008 (10)	0.0048 (11)	−0.0050 (10)
N5	0.0161 (9)	0.0147 (9)	0.0147 (9)	0.0000 (7)	0.0042 (7)	0.0001 (7)
N6	0.0135 (9)	0.0151 (9)	0.0167 (9)	0.0010 (7)	0.0042 (7)	0.0003 (7)
C11	0.0244 (12)	0.0170 (11)	0.0221 (12)	−0.0019 (9)	0.0105 (9)	−0.0009 (9)
C12	0.0214 (12)	0.0198 (12)	0.0262 (12)	0.0030 (9)	0.0123 (10)	−0.0032 (10)
C13	0.0163 (11)	0.0140 (11)	0.0245 (12)	0.0010 (8)	0.0083 (9)	0.0011 (9)
C14	0.0323 (14)	0.0316 (14)	0.0225 (13)	0.0023 (11)	0.0088 (11)	−0.0034 (10)
C15	0.0172 (11)	0.0255 (13)	0.0272 (13)	0.0066 (9)	0.0052 (10)	0.0004 (10)
O1	0.0268 (9)	0.0443 (11)	0.0180 (9)	0.0138 (8)	0.0011 (7)	−0.0031 (8)
O2	0.0225 (9)	0.0415 (11)	0.0275 (9)	0.0089 (8)	0.0053 (7)	0.0025 (8)
C16	0.0246 (13)	0.0304 (13)	0.0221 (12)	0.0051 (10)	0.0046 (10)	0.0004 (10)
C17	0.0439 (18)	0.086 (3)	0.0233 (15)	0.0313 (18)	−0.0029 (13)	−0.0118 (15)

Geometric parameters (Å, º)

Zn1—N2	2.0165 (19)	C7—C8	1.393 (3)
Zn1—N4	2.0104 (19)	C8—C10	1.494 (3)
Zn1—N6	2.0511 (18)	C9—H9A	0.980
Zn1—O1	1.9217 (17)	C9—H9B	0.980
B1—H1	1.10 (3)	C9—H9C	0.980
B1—N1	1.555 (3)	C10—H10A	0.980
B1—N3	1.557 (3)	C10—H10B	0.980
B1—N5	1.553 (3)	C10—H10C	0.980
N1—N2	1.374 (3)	N5—N6	1.369 (2)
N1—C1	1.350 (3)	N5—C11	1.352 (3)
N2—C3	1.333 (3)	N6—C13	1.339 (3)
C1—C2	1.376 (3)	C11—C12	1.386 (3)
C1—C4	1.492 (3)	C11—C14	1.493 (3)
C2—H2	0.950	C12—H12	0.950
C2—C3	1.387 (3)	C12—C13	1.392 (3)
C3—C5	1.496 (3)	C13—C15	1.489 (3)
C4—H4A	0.980	C14—H14A	0.980
C4—H4B	0.980	C14—H14B	0.980
C4—H4C	0.980	C14—H14C	0.980
C5—H5A	0.980	C15—H15A	0.980
C5—H5B	0.980	C15—H15B	0.980
C5—H5C	0.980	C15—H15C	0.980
N3—N4	1.371 (3)	O1—C16	1.291 (3)
N3—C6	1.355 (3)	O2—C16	1.221 (3)
N4—C8	1.333 (3)	C16—C17	1.497 (4)
C6—C7	1.376 (3)	C17—H17A	0.980
C6—C9	1.491 (3)	C17—H17B	0.980
C7—H7	0.950	C17—H17C	0.980
N2—Zn1—N4	93.14 (7)	N4—C8—C10	121.1 (2)
N2—Zn1—N6	92.29 (7)	C7—C8—C10	129.6 (2)
N4—Zn1—N6	92.99 (7)	C6—C9—H9A	109.5
N2—Zn1—O1	131.78 (8)	C6—C9—H9B	109.5
N4—Zn1—O1	126.80 (8)	C6—C9—H9C	109.5
N6—Zn1—O1	109.06 (7)	H9A—C9—H9B	109.5
H1—B1—N1	111.3 (15)	H9A—C9—H9C	109.5
H1—B1—N3	111.8 (15)	H9B—C9—H9C	109.5
H1—B1—N5	107.1 (15)	C8—C10—H10A	109.5
N1—B1—N3	108.94 (17)	C8—C10—H10B	109.5
N1—B1—N5	108.73 (18)	C8—C10—H10C	109.5
N3—B1—N5	108.84 (17)	H10A—C10—H10B	109.5
B1—N1—N2	120.29 (17)	H10A—C10—H10C	109.5
B1—N1—C1	130.58 (19)	H10B—C10—H10C	109.5
N2—N1—C1	109.12 (18)	B1—N5—N6	119.25 (17)
Zn1—N2—N1	113.20 (13)	B1—N5—C11	131.32 (19)
Zn1—N2—C3	139.65 (16)	N6—N5—C11	109.41 (17)
N1—N2—C3	107.13 (18)	Zn1—N6—N5	113.64 (13)
N1—C1—C2	107.9 (2)	Zn1—N6—C13	138.83 (16)
N1—C1—C4	123.4 (2)	N5—N6—C13	107.53 (17)
C2—C1—C4	128.6 (2)	N5—C11—C12	107.6 (2)
C1—C2—H2	126.9	N5—C11—C14	123.2 (2)
C1—C2—C3	106.1 (2)	C12—C11—C14	129.1 (2)
H2—C2—C3	126.9	C11—C12—H12	126.9
N2—C3—C2	109.7 (2)	C11—C12—C13	106.2 (2)
N2—C3—C5	120.6 (2)	H12—C12—C13	126.9
C2—C3—C5	129.7 (2)	N6—C13—C12	109.3 (2)
C1—C4—H4A	109.5	N6—C13—C15	120.3 (2)
C1—C4—H4B	109.5	C12—C13—C15	130.4 (2)
C1—C4—H4C	109.5	C11—C14—H14A	109.5
H4A—C4—H4B	109.5	C11—C14—H14B	109.5
H4A—C4—H4C	109.5	C11—C14—H14C	109.5
H4B—C4—H4C	109.5	H14A—C14—H14B	109.5
C3—C5—H5A	109.5	H14A—C14—H14C	109.5
C3—C5—H5B	109.5	H14B—C14—H14C	109.5
C3—C5—H5C	109.5	C13—C15—H15A	109.5
H5A—C5—H5B	109.5	C13—C15—H15B	109.5
H5A—C5—H5C	109.5	C13—C15—H15C	109.5
H5B—C5—H5C	109.5	H15A—C15—H15B	109.5
B1—N3—N4	120.25 (17)	H15A—C15—H15C	109.5
B1—N3—C6	130.72 (18)	H15B—C15—H15C	109.5
N4—N3—C6	109.00 (17)	Zn1—O1—C16	106.21 (15)
Zn1—N4—N3	113.42 (13)	O1—C16—O2	122.0 (2)
Zn1—N4—C8	138.97 (16)	O1—C16—C17	116.5 (2)
N3—N4—C8	107.60 (18)	O2—C16—C17	121.5 (2)
N3—C6—C7	107.9 (2)	C16—C17—H17A	109.5
N3—C6—C9	123.0 (2)	C16—C17—H17B	109.5
C7—C6—C9	129.1 (2)	C16—C17—H17C	109.5
C6—C7—H7	126.9	H17A—C17—H17B	109.5
C6—C7—C8	106.2 (2)	H17A—C17—H17C	109.5
H7—C7—C8	126.9	H17B—C17—H17C	109.5
N4—C8—C7	109.3 (2)
N3—B1—N1—N2	58.1 (2)	N4—N3—C6—C7	0.1 (2)
N3—B1—N1—C1	−120.8 (2)	N4—N3—C6—C9	179.8 (2)
N5—B1—N1—N2	−60.4 (2)	N3—C6—C7—C8	0.1 (2)
N5—B1—N1—C1	120.8 (2)	C9—C6—C7—C8	−179.6 (2)
B1—N1—N2—Zn1	0.2 (2)	Zn1—N4—C8—C7	178.83 (17)
B1—N1—N2—C3	−178.64 (18)	Zn1—N4—C8—C10	−1.6 (4)
C1—N1—N2—Zn1	179.33 (14)	N3—N4—C8—C7	0.4 (2)
C1—N1—N2—C3	0.4 (2)	N3—N4—C8—C10	179.9 (2)
N4—Zn1—N2—N1	−46.77 (14)	C6—C7—C8—N4	−0.3 (3)
N4—Zn1—N2—C3	131.6 (2)	C6—C7—C8—C10	−179.8 (2)
N6—Zn—N2—N1	46.35 (14)	N1—B1—N5—N6	59.1 (2)
N6—Zn1—N2—C3	−135.3 (2)	N1—B1—N5—C11	−119.1 (2)
O1—Zn1—N2—N1	164.64 (12)	N3—B1—N5—N6	−59.4 (2)
O1—Zn1—N2—C3	−17.0 (3)	N3—B1—N5—C11	122.3 (2)
B1—N1—C1—C2	178.5 (2)	B1—N5—N6—Zn1	0.5 (2)
B1—N1—C1—C4	−3.1 (4)	B1—N5—N6—C13	−178.97 (18)
N2—N1—C1—C2	−0.4 (2)	C11—N5—N6—Zn1	179.07 (14)
N2—N1—C1—C4	178.0 (2)	C11—N5—N6—C13	−0.4 (2)
N1—C1—C2—C3	0.2 (3)	N2—Zn1—N6—N5	−47.22 (14)
C4—C1—C2—C3	−178.1 (2)	N2—Zn1—N6—C13	132.0 (2)
Zn1—N2—C3—C2	−178.71 (18)	N4—Zn1—N6—N5	46.04 (14)
Zn1—N2—C3—C5	0.1 (4)	N4—Zn1—N6—C13	−134.8 (2)
N1—N2—C3—C2	−0.3 (3)	O1—Zn1—N6—N5	176.78 (13)
N1—N2—C3—C5	178.6 (2)	O1—Zn1—N6—C13	−4.0 (2)
C1—C2—C3—N2	0.0 (3)	B1—N5—C11—C12	178.9 (2)
C1—C2—C3—C5	−178.7 (2)	B1—N5—C11—C14	0.5 (4)
N1—B1—N3—N4	−57.5 (2)	N6—N5—C11—C12	0.5 (2)
N1—B1—N3—C6	119.9 (2)	N6—N5—C11—C14	−177.9 (2)
N5—B1—N3—N4	60.9 (2)	N5—C11—C12—C13	−0.4 (3)
N5—B1—N3—C6	−121.7 (2)	C14—C11—C12—C13	177.8 (2)
B1—N3—N4—Zn1	−1.3 (2)	Zn1—N6—C13—C12	−179.11 (17)
B1—N3—N4—C8	177.62 (18)	Zn1—N6—C13—C15	2.4 (4)
C6—N3—N4—Zn1	−179.20 (13)	N5—N6—C13—C12	0.1 (2)
C6—N3—N4—C8	−0.3 (2)	N5—N6—C13—C15	−178.44 (19)
N2—Zn1—N4—N3	47.33 (14)	C11—C12—C13—N6	0.2 (3)
N2—Zn1—N4—C8	−131.1 (2)	C11—C12—C13—C15	178.5 (2)
N6—Zn1—N4—N3	−45.13 (14)	N2—Zn1—O1—C16	68.3 (2)
N6—Zn1—N4—C8	136.5 (2)	N4—Zn1—O1—C16	−71.20 (19)
O1—Zn1—N4—N3	−161.71 (12)	N6—Zn1—O1—C16	179.70 (16)
O1—Zn1—N4—C8	19.9 (3)	Zn1—O1—C16—O2	−1.7 (3)
B1—N3—C6—C7	−177.5 (2)	Zn1—O1—C16—C17	178.8 (2)
B1—N3—C6—C9	2.2 (3)