(Acetonitrile-κN){2-[bis­(2-pyridylethyl)­amino]ethanol-κ⁴N,N′,N′′,O}zinc(II) bis­(perchlorate) monohydrate

In the title compound, [Zn(C₂H₃N)(C₁₆H₂₁N₃O)](ClO₄)₂·H₂O, the Zn^II ion is coordinated by two pyridyl N atoms, one amine N atom, and an ethanol O atom from the N,N′,N′′,O-tetra­dentate 2-[bis­(2-pyridylethyl)amino]­ethanol donor ligand. The fifth coordination site is filled by an acetonitrile N atom, and there is one solvent water mol­ecule in the asymmetric unit. The 2+ charge of the cationic portion of the complex is balanced by two perchlorate counter-anions.

S1. Comment

Zinc complexes of multidentate N-donor ligands with pendant alcohol or alkoxide O-donors have been useful for modelling alkaline phosphatase, a Zn^II-containing phosphomonoesterase that catalyzes the hydrolysis of phosphate monoesters at high pH (Kimura et al., 1994). Recently, we reported the crystal structure of a new Zn^II complex containing the 2-[bis(2-pyridin-2-ylethyl)amino]ethanol ligand, (I), in which the ethanol moiety was deprotonated upon coordinating to a Zn^II centre, to form a bridging alkoxide ligand in a dimeric Zn^II structure, (II), in the solid state (Zhang & Liang, 2004). The previous crystal structure was obtained by crystallizing the complex in an aqueous solution. Here, we report on a crystal structure of a similar complex, (III), crystallized from acetonitrile, in which the monomeric Zn^II complex of the ligand 2-[bis(2-pyridin-2-ylethyl)amino]ethanol is obtained and the ethanol H atom remains bound to the O atom of the ethanol unit.

As shown in Fig. 1, complex (III) has five donor atoms coordinated to the Zn^II centre. The calculated τ value for the Zn^II centre in (III) is 0.23, which shows that it is closer to square-pyramidal geometry [N2—Zn1—N4 159.35 (6)° and N1—Zn1—O1 145.36 (6)°; τ = 0 correlates to perfect square-pyramidal geometry and τ = 1 correlates to perfect trigonal–bipyramidal geometry (Addison et al., 1984)]. The structure of (III) can be viewed as having atoms N1, N2, N4, O1 and Zn1 as the basal atoms and N3 in the apical position of a pseudo square-pyramidal complex.

The Zn—ligand bond lengths in (III) (Table 1) are similar to those found in analogous Zn^II complexes. For example, the Zn—N_pyridyl bond lengths of 2.0418 (15) Å (Zn1—N1) and 2.0498 (14) Å (Zn1—N3) are similar to the analogous Zn—N_pyridyl bond lengths in (II) [2.049 (4) and 2.068 (4) Å; Zhang & Liang (2004)]. However, the amine N2—Zn1 bond of 2.1336 (14) Å in (III) is shorter than that found in the dimeric complex [2.231 (4) Å]. The longer Zn—N_amine bond in (II) can be explained by the fact that the Zn^II centre in (II) adopts a more trigonal–pyramidal shape than in (III), with a τ value of 0.46. Because the amine atom N3 of (II) can be considered as more of an axial ligand in a trigonal–bipyramidal geometry than the analogous amine atom N2 in (III), the Zn—N_amine bond in (II) is expected to be longer. Comparison of the Zn—O bonds in complexes (II) and (III) also reveals differences in bond lengths [1.959 (3) Å in (II) and 2.0552 (14) Å in (III)]. This observed lengthening of the Zn—O bond in (III) is consistent with a Zn^II metal centre bonded to a neutral ethanol O-atom donor, whereas the intramolecular Zn—O bond in (II) involves a monoanionic alkoxide O-atom donor. Several previous studies have shown that Zn^II–alcohol complexes with neutral coordinating O-atom donors have Zn—O bonds longer than 2 Å (Follner, 1972; Lutz & Bakker, 2003; Iranzo et al., 2003), while Zn^II alkoxide compounds typically exhibit Zn—O bonds shorter than 2 Å (Kimura et al., 1994; Hahn et al., 2003; Davies et al., 1998).

Inspection of the asymmetric unit of compound (III) (Fig. 1) reveals one complex cation, one uncoordinated water molecule and two perchlorate anions. The ethanolic OH group of (III) forms an intermolecular O1—H1A···O10 hydrogen bond with a water molecule, which further links two adjacent perchlorate anions via O10–H10A(H10B).·O2(O9) close contacts (Table 2). As can be seen in Fig. 2, the organization of this motif is influenced by a complex blend of weak C—H···perchlorate interactions that extend along the a axis. Although a structural feature of this organization is inversion-related face-to-face stacking of pyridyl fragments, only the pyridyl (N3) moiety adopts a favourable geometry for π–π stacking [interplanar distance 3.434 (3) Å and centroid···centroid distance 3.862 (3) Å].

S2. Experimental

Caution! Although no problems were encountered in this work, metal perchlorate complexes are potentially explosive and should be handled with proper precautions and in small amounts.

Complex (III) was synthesized by treating the ligand (I) (0.030 g, 0.11 mmol) with 1 equivalent of Zn(ClO₄)₂·6H₂O (0.041 g, 0.11 mmol) in CH₃CN (10 ml) with stirring for 1 h at room temperature. After 1 h, diethyl ether (25 ml) was layered onto the light-yellow acetonitrile solution of (III), and the mixture was set aside for crystallization. After 4 d, colourless crystals of (III) had formed (0.037 g, 0.058 mmol, 53% yield). A single-crystal from this procedure was used for X-ray analysis. Spectroscopic analysis: ¹H NMR (500 MHz, CD₃CN, δ, p.p.m.): 8.55 (d, py-6H), 8.19 (t, py-4H), 7.71 (d, py-5H), 7.60 (t, py-3H), 3.86 (t, NCH₂CH₂OZn), 3.28–3.04 (py-CH₂CH₂N), 2.97 (t, NCH₂CH₂OZn); ¹³C NMR (CD₃CN, δ, p.p.m.): 162.1 (py-2), 149.9 (py-6), 142.1 (py-4), 127.1 (py-3), 124.7 (py-5), 60.7 (NCH₂CH₂OZn), 58.5 (NCH₂CH₂OZn), 54.5 (py-CH₂CH₂N), 33.5 (py-CH₂CH₂N); FT–IR (KBr, ν, cm⁻¹): 3448 (O—H, str, br), 3073, 2948, 2926, 2871, 2809 (C–H, str), 1608, 1571, 1486, 1445 (pyridine ring), 1085, 622 (ClO₄⁻). Elemental analysis, calculated for C₁₈H₂₆Cl₂N₄O₁₀Zn: C 36.35, H 4.41, N 9.42%; found: C 35.98, H 4.67, N 9.05%. MS (ESI) m/z 334 ([L¹—H + M - CH₃CN]⁺).

S3. Refinement

Methyl H atoms were treated as riding, with C—H distances of 0.98 Å and U_iso(H) = 1.5U_eq(C), and were allowed to rotate freely during refinement using the AFIX 137 command of SHELXTL (Bruker, 2000). All other H atoms were located in a difference density map and refined isotropically.

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SMART; data reduction: SAINT (Bruker, 2002) and XPREP (Bruker, 2001); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: X-SEED; software used to prepare material for publication: X-SEED (Barbour, 2001).

Figures

	Fig. 1. The molecular structure of (III), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Dotted lines indicate what?
	Fig. 2. A view of the molecular packing of (III), projected down the a axis showing the hydrogen-bond network (dotted lines?). H atoms have been omitted for clarity. [Symmetry codes: (i) x, y − 1, z; (ii) 2 − x, 2 − y, 2 − z; (iii) 1 − x, 2 − y, 2 − z; (iv) 2 − x,1 − y, 2 − z; (v) 1 − x,1 − y, 2 − z.]

(Acetonitrile-κN){2-[bis(2-pyridethyl)amino]ethanol-κ⁴N,N',N'',O}zinc(II) bis(perchlorate) monohydrate

Crystal data

[Zn(C2H3N)(C16H21N3O)](ClO4)2·H2O	F(000) = 1224
Mr = 594.72	Dx = 1.637 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9361 reflections
a = 17.3792 (13) Å	θ = 2.3–28.3°
b = 7.8924 (6) Å	µ = 1.30 mm^−1
c = 18.6583 (14) Å	T = 193 K
β = 109.487 (1)°	Block, colourless
V = 2412.6 (3) Å^3	0.35 × 0.20 × 0.10 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	5502 independent reflections
Radiation source: fine-focus sealed tube	4695 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
ϕ and ω scans	θmax = 27.5°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −22→20
Tmin = 0.659, Tmax = 0.881	k = −10→10
16837 measured reflections	l = −24→23

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) = 0.098	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0503P)^2 + 1.2239P] where P = (Fo^2 + 2Fc^2)/3
5502 reflections	(Δ/σ)max = 0.002
409 parameters	Δρmax = 0.91 e Å^−3
0 restraints	Δρmin = −0.40 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	0.730424 (11)	0.63244 (3)	0.985731 (11)	0.02481 (5)
O1	0.70047 (8)	0.80338 (17)	1.05525 (7)	0.0301 (3)
N1	0.81947 (8)	0.55236 (19)	0.94474 (9)	0.0279 (3)
N2	0.68983 (8)	0.83863 (19)	0.90833 (8)	0.0258 (3)
N3	0.62484 (8)	0.49311 (19)	0.95215 (9)	0.0272 (3)
N4	0.78804 (9)	0.5013 (2)	1.08945 (9)	0.0332 (4)
C1	0.84356 (12)	0.3900 (2)	0.95692 (12)	0.0351 (5)
C2	0.90413 (13)	0.3235 (3)	0.93368 (13)	0.0417 (5)
C3	0.94193 (12)	0.4269 (3)	0.89649 (13)	0.0437 (5)
C4	0.91751 (11)	0.5927 (3)	0.88364 (12)	0.0394 (5)
C5	0.85618 (10)	0.6534 (2)	0.90817 (11)	0.0296 (4)
C6	0.83011 (11)	0.8349 (3)	0.89702 (12)	0.0351 (4)
C7	0.73912 (12)	0.8607 (3)	0.85710 (11)	0.0328 (4)
C8	0.60303 (11)	0.8128 (3)	0.86066 (11)	0.0324 (4)
C9	0.58665 (12)	0.6342 (3)	0.82901 (11)	0.0363 (5)
C10	0.56823 (11)	0.5115 (2)	0.88268 (10)	0.0302 (4)
C11	0.49605 (12)	0.4225 (3)	0.86301 (12)	0.0372 (5)
C12	0.48063 (12)	0.3136 (3)	0.91336 (13)	0.0389 (5)
C13	0.53755 (11)	0.2974 (2)	0.98477 (12)	0.0343 (4)
C14	0.60837 (11)	0.3892 (2)	1.00197 (11)	0.0299 (4)
C15	0.69742 (11)	0.9930 (2)	0.95501 (11)	0.0317 (4)
C16	0.66839 (11)	0.9608 (2)	1.02142 (11)	0.0327 (4)
C17	0.82307 (10)	0.4511 (2)	1.14735 (11)	0.0306 (4)
C18	0.86836 (14)	0.3869 (3)	1.22227 (13)	0.0506 (6)
H18A	0.8331	0.3127	1.2399	0.076*
H18B	0.8869	0.4820	1.2577	0.076*
H18C	0.9157	0.3227	1.2200	0.076*
H1	0.8187 (11)	0.326 (3)	0.9857 (11)	0.027 (5)*
H2	0.9166 (13)	0.215 (3)	0.9465 (12)	0.044 (6)*
H3	0.9862 (14)	0.381 (3)	0.8795 (13)	0.045 (7)*
H4	0.9424 (13)	0.676 (3)	0.8602 (13)	0.042 (6)*
H6A	0.8559 (15)	0.886 (3)	0.8696 (14)	0.051 (7)*
H6B	0.8503 (12)	0.896 (3)	0.9493 (12)	0.031 (5)*
H7A	0.7307 (11)	0.970 (3)	0.8395 (11)	0.030 (5)*
H7B	0.7202 (11)	0.780 (3)	0.8179 (11)	0.028 (5)*
H8A	0.5695 (12)	0.839 (2)	0.8916 (11)	0.027 (5)*
H8B	0.5859 (11)	0.897 (3)	0.8210 (11)	0.028 (5)*
H9A	0.6331 (14)	0.588 (3)	0.8139 (13)	0.044 (6)*
H9B	0.5453 (13)	0.637 (3)	0.7867 (13)	0.039 (6)*
H11	0.4625 (13)	0.436 (3)	0.8172 (13)	0.045 (6)*
H12	0.4309 (13)	0.252 (3)	0.9009 (12)	0.044 (6)*
H13	0.5291 (13)	0.223 (3)	1.0221 (13)	0.041 (6)*
H14	0.6486 (13)	0.387 (3)	1.0541 (13)	0.037 (6)*
H15A	0.7548 (12)	1.021 (3)	0.9759 (11)	0.032 (5)*
H15B	0.6707 (12)	1.084 (3)	0.9269 (12)	0.030 (5)*
H16A	0.6101 (12)	0.957 (3)	1.0093 (11)	0.029 (5)*
H16B	0.6874 (11)	1.044 (3)	1.0581 (11)	0.025 (5)*
H1A	0.7228 (15)	0.823 (3)	1.0949 (15)	0.052 (8)*
Cl1	0.92321 (3)	0.97603 (7)	1.12378 (3)	0.03805 (12)
O2	0.93152 (11)	0.9510 (4)	1.20099 (10)	0.0809 (7)
O3	0.99937 (10)	1.0086 (3)	1.11588 (12)	0.0713 (6)
O4	0.89125 (11)	0.8214 (2)	1.08408 (13)	0.0683 (6)
O5	0.86505 (12)	1.1040 (2)	1.09256 (11)	0.0682 (6)
Cl2	0.65077 (3)	1.20441 (7)	1.22309 (3)	0.03733 (11)
O6	0.59799 (11)	1.0986 (3)	1.16613 (11)	0.0660 (5)
O7	0.67617 (11)	1.3450 (3)	1.18870 (11)	0.0680 (5)
O8	0.60992 (10)	1.2649 (2)	1.27248 (10)	0.0560 (4)
O9	0.72074 (10)	1.1088 (2)	1.26714 (9)	0.0546 (5)
O10	0.77656 (10)	0.8372 (2)	1.20043 (9)	0.0438 (4)
H10A	0.8169 (19)	0.872 (4)	1.1985 (18)	0.070 (10)*
H10B	0.7573 (15)	0.908 (3)	1.2160 (15)	0.050 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.02616 (9)	0.02270 (10)	0.02630 (10)	0.00160 (7)	0.00971 (8)	0.00305 (8)
O1	0.0354 (6)	0.0282 (6)	0.0255 (6)	0.0030 (5)	0.0087 (5)	0.0001 (5)
N1	0.0277 (6)	0.0250 (7)	0.0312 (8)	0.0009 (6)	0.0099 (6)	0.0002 (6)
N2	0.0284 (6)	0.0250 (7)	0.0251 (7)	0.0026 (6)	0.0103 (6)	0.0032 (6)
N3	0.0288 (6)	0.0248 (7)	0.0290 (7)	−0.0008 (6)	0.0109 (6)	−0.0021 (6)
N4	0.0340 (7)	0.0330 (8)	0.0329 (8)	0.0034 (7)	0.0116 (6)	0.0034 (7)
C1	0.0393 (9)	0.0283 (9)	0.0377 (10)	0.0013 (8)	0.0130 (8)	−0.0004 (8)
C2	0.0445 (10)	0.0315 (10)	0.0489 (12)	0.0094 (9)	0.0152 (9)	−0.0021 (9)
C3	0.0366 (9)	0.0476 (12)	0.0507 (12)	0.0110 (9)	0.0197 (9)	−0.0017 (10)
C4	0.0340 (8)	0.0436 (11)	0.0452 (11)	0.0010 (8)	0.0194 (8)	0.0013 (9)
C5	0.0279 (7)	0.0311 (9)	0.0301 (9)	−0.0005 (7)	0.0099 (7)	−0.0002 (7)
C6	0.0370 (8)	0.0306 (9)	0.0443 (11)	−0.0003 (8)	0.0225 (8)	0.0095 (8)
C7	0.0400 (8)	0.0307 (10)	0.0327 (9)	0.0038 (8)	0.0187 (7)	0.0102 (8)
C8	0.0301 (8)	0.0358 (10)	0.0282 (9)	0.0030 (8)	0.0057 (7)	0.0072 (8)
C9	0.0382 (9)	0.0444 (11)	0.0230 (9)	−0.0065 (9)	0.0059 (8)	−0.0028 (8)
C10	0.0335 (8)	0.0306 (9)	0.0266 (9)	−0.0004 (7)	0.0101 (7)	−0.0058 (7)
C11	0.0345 (8)	0.0425 (11)	0.0323 (10)	−0.0047 (8)	0.0081 (8)	−0.0087 (9)
C12	0.0339 (8)	0.0347 (10)	0.0507 (12)	−0.0071 (8)	0.0175 (8)	−0.0073 (9)
C13	0.0363 (8)	0.0275 (9)	0.0447 (11)	0.0002 (8)	0.0208 (8)	0.0013 (8)
C14	0.0354 (8)	0.0224 (8)	0.0336 (9)	0.0019 (7)	0.0138 (7)	0.0011 (7)
C15	0.0385 (8)	0.0242 (9)	0.0336 (9)	0.0043 (7)	0.0136 (8)	0.0042 (8)
C16	0.0374 (8)	0.0283 (9)	0.0334 (9)	0.0061 (8)	0.0131 (7)	−0.0013 (8)
C17	0.0287 (7)	0.0311 (9)	0.0317 (9)	−0.0002 (7)	0.0099 (7)	−0.0023 (8)
C18	0.0451 (11)	0.0676 (16)	0.0299 (11)	0.0067 (11)	0.0001 (9)	0.0017 (11)
Cl1	0.03131 (19)	0.0432 (3)	0.0390 (2)	0.00640 (19)	0.01093 (18)	0.0074 (2)
O2	0.0477 (9)	0.148 (2)	0.0455 (10)	0.0170 (11)	0.0135 (8)	0.0286 (12)
O3	0.0480 (8)	0.0870 (14)	0.0833 (13)	−0.0125 (9)	0.0281 (9)	0.0105 (11)
O4	0.0596 (10)	0.0473 (10)	0.0895 (14)	−0.0037 (9)	0.0137 (10)	−0.0118 (10)
O5	0.0701 (11)	0.0498 (10)	0.0628 (12)	0.0255 (9)	−0.0070 (9)	−0.0032 (9)
Cl2	0.0361 (2)	0.0452 (3)	0.0322 (2)	0.0008 (2)	0.01346 (18)	0.0027 (2)
O6	0.0578 (10)	0.0774 (13)	0.0504 (10)	−0.0063 (9)	0.0015 (8)	−0.0168 (10)
O7	0.0605 (9)	0.0810 (13)	0.0664 (11)	−0.0064 (9)	0.0266 (9)	0.0309 (10)
O8	0.0700 (9)	0.0539 (10)	0.0574 (9)	0.0102 (8)	0.0390 (8)	0.0030 (8)
O9	0.0461 (8)	0.0707 (11)	0.0427 (9)	0.0164 (8)	0.0089 (7)	0.0063 (8)
O10	0.0507 (8)	0.0499 (9)	0.0323 (7)	−0.0004 (7)	0.0157 (6)	−0.0007 (7)

Geometric parameters (Å, º)

Zn1—N1	2.0418 (15)	C8—H8B	0.96 (2)
Zn1—N3	2.0498 (14)	C9—C10	1.502 (3)
Zn1—O1	2.0552 (14)	C9—H9A	1.01 (2)
Zn1—N4	2.1273 (16)	C9—H9B	0.87 (2)
Zn1—N2	2.1336 (14)	C10—C11	1.376 (3)
O1—C16	1.420 (2)	C11—C12	1.364 (3)
O1—H1A	0.73 (3)	C11—H11	0.87 (2)
N1—C5	1.341 (2)	C12—C13	1.375 (3)
N1—C1	1.344 (2)	C12—H12	0.95 (2)
N2—C15	1.478 (2)	C13—C14	1.371 (3)
N2—C8	1.488 (2)	C13—H13	0.96 (2)
N2—C7	1.491 (3)	C14—H14	0.99 (2)
N3—C14	1.340 (2)	C15—C16	1.507 (3)
N3—C10	1.348 (2)	C15—H15A	0.97 (2)
N4—C17	1.121 (2)	C15—H15B	0.92 (2)
C1—C2	1.370 (3)	C16—H16A	0.962 (19)
C1—H1	0.94 (2)	C16—H16B	0.93 (2)
C2—C3	1.372 (3)	C17—C18	1.448 (3)
C2—H2	0.90 (2)	C18—H18A	0.9800
C3—C4	1.372 (3)	C18—H18B	0.9800
C3—H3	0.99 (2)	C18—H18C	0.9800
C4—C5	1.378 (3)	Cl1—O3	1.4036 (18)
C4—H4	0.97 (2)	Cl1—O5	1.4098 (17)
C5—C6	1.496 (3)	Cl1—O2	1.4130 (19)
C6—C7	1.520 (3)	Cl1—O4	1.439 (2)
C6—H6A	0.88 (3)	Cl2—O6	1.4204 (19)
C6—H6B	1.04 (2)	Cl2—O8	1.4203 (17)
C7—H7A	0.92 (2)	Cl2—O7	1.4237 (19)
C7—H7B	0.94 (2)	Cl2—O9	1.4341 (16)
C8—C9	1.519 (3)	O10—H10A	0.76 (3)
C8—H8A	0.97 (2)	O10—H10B	0.76 (3)
N1—Zn1—N3	115.63 (6)	N2—C8—H8B	110.8 (12)
N1—Zn1—O1	145.36 (6)	C9—C8—H8B	111.8 (12)
N3—Zn1—O1	98.96 (6)	H8A—C8—H8B	102.6 (17)
N1—Zn1—N4	90.27 (6)	C10—C9—C8	113.16 (17)
N3—Zn1—N4	96.83 (6)	C10—C9—H9A	108.7 (14)
O1—Zn1—N4	83.49 (6)	C8—C9—H9A	112.5 (14)
N1—Zn1—N2	95.93 (6)	C10—C9—H9B	108.9 (16)
N3—Zn1—N2	98.17 (6)	C8—C9—H9B	108.8 (15)
O1—Zn1—N2	80.23 (6)	H9A—C9—H9B	104 (2)
N4—Zn1—N2	159.35 (6)	N3—C10—C11	120.61 (18)
C16—O1—Zn1	115.99 (11)	N3—C10—C9	117.43 (16)
C16—O1—H1A	105 (2)	C11—C10—C9	121.94 (17)
Zn1—O1—H1A	128 (2)	C12—C11—C10	120.59 (18)
C5—N1—C1	118.60 (17)	C12—C11—H11	122.5 (17)
C5—N1—Zn1	123.73 (13)	C10—C11—H11	116.9 (17)
C1—N1—Zn1	117.65 (13)	C11—C12—C13	118.88 (18)
C15—N2—C8	109.79 (14)	C11—C12—H12	121.8 (14)
C15—N2—C7	108.91 (15)	C13—C12—H12	119.3 (14)
C8—N2—C7	108.52 (14)	C14—C13—C12	118.49 (19)
C15—N2—Zn1	106.59 (11)	C14—C13—H13	119.8 (12)
C8—N2—Zn1	109.92 (11)	C12—C13—H13	121.7 (13)
C7—N2—Zn1	113.08 (11)	N3—C14—C13	122.95 (17)
C14—N3—C10	118.45 (15)	N3—C14—H14	116.7 (13)
C14—N3—Zn1	119.52 (12)	C13—C14—H14	120.2 (13)
C10—N3—Zn1	121.86 (13)	N2—C15—C16	110.92 (16)
C17—N4—Zn1	171.29 (16)	N2—C15—H15A	107.7 (13)
N1—C1—C2	122.7 (2)	C16—C15—H15A	106.9 (13)
N1—C1—H1	115.7 (12)	N2—C15—H15B	112.4 (13)
C2—C1—H1	121.4 (12)	C16—C15—H15B	110.9 (14)
C1—C2—C3	118.7 (2)	H15A—C15—H15B	107.9 (18)
C1—C2—H2	115.1 (15)	O1—C16—C15	108.87 (15)
C3—C2—H2	126.1 (15)	O1—C16—H16A	107.8 (13)
C2—C3—C4	118.9 (2)	C15—C16—H16A	115.3 (12)
C2—C3—H3	119.8 (14)	O1—C16—H16B	107.7 (12)
C4—C3—H3	121.3 (14)	C15—C16—H16B	110.6 (13)
C3—C4—C5	120.1 (2)	H16A—C16—H16B	106.3 (17)
C3—C4—H4	124.6 (14)	N4—C17—C18	179.7 (3)
C5—C4—H4	115.2 (14)	C17—C18—H18A	109.5
N1—C5—C4	120.97 (18)	C17—C18—H18B	109.5
N1—C5—C6	117.81 (17)	H18A—C18—H18B	109.5
C4—C5—C6	121.20 (18)	C17—C18—H18C	109.5
C5—C6—C7	114.46 (16)	H18A—C18—H18C	109.5
C5—C6—H6A	109.1 (16)	H18B—C18—H18C	109.5
C7—C6—H6A	107.6 (15)	O3—Cl1—O5	113.37 (13)
C5—C6—H6B	108.8 (11)	O3—Cl1—O2	110.70 (12)
C7—C6—H6B	111.6 (11)	O5—Cl1—O2	109.70 (14)
H6A—C6—H6B	105 (2)	O3—Cl1—O4	108.46 (13)
N2—C7—C6	113.36 (16)	O5—Cl1—O4	107.11 (11)
N2—C7—H7A	106.4 (13)	O2—Cl1—O4	107.26 (15)
C6—C7—H7A	108.5 (12)	O6—Cl2—O8	110.19 (12)
N2—C7—H7B	107.1 (13)	O6—Cl2—O7	109.92 (12)
C6—C7—H7B	109.1 (12)	O8—Cl2—O7	109.14 (12)
H7A—C7—H7B	112.5 (17)	O6—Cl2—O9	109.39 (12)
N2—C8—C9	112.38 (16)	O8—Cl2—O9	108.47 (10)
N2—C8—H8A	107.9 (11)	O7—Cl2—O9	109.71 (11)
C9—C8—H8A	110.9 (12)	H10A—O10—H10B	107 (3)
N1—Zn1—O1—C16	87.53 (15)	C2—C3—C4—C5	0.2 (3)
N3—Zn1—O1—C16	−95.58 (12)	C1—N1—C5—C4	−0.2 (3)
N4—Zn1—O1—C16	168.49 (13)	Zn1—N1—C5—C4	178.23 (14)
N2—Zn1—O1—C16	1.24 (12)	C1—N1—C5—C6	−178.38 (17)
N3—Zn1—N1—C5	127.12 (14)	Zn1—N1—C5—C6	0.0 (2)
O1—Zn1—N1—C5	−56.29 (18)	C3—C4—C5—N1	0.0 (3)
N4—Zn1—N1—C5	−135.17 (14)	C3—C4—C5—C6	178.12 (19)
N2—Zn1—N1—C5	25.10 (14)	N1—C5—C6—C7	−55.3 (2)
N3—Zn1—N1—C1	−54.48 (15)	C4—C5—C6—C7	126.5 (2)
O1—Zn1—N1—C1	122.12 (14)	C15—N2—C7—C6	78.02 (19)
N4—Zn1—N1—C1	43.23 (14)	C8—N2—C7—C6	−162.50 (16)
N2—Zn1—N1—C1	−156.50 (13)	Zn1—N2—C7—C6	−40.27 (19)
N1—Zn1—N2—C15	−122.82 (11)	C5—C6—C7—N2	79.4 (2)
N3—Zn1—N2—C15	120.16 (11)	C15—N2—C8—C9	−163.48 (16)
O1—Zn1—N2—C15	22.41 (11)	C7—N2—C8—C9	77.59 (19)
N4—Zn1—N2—C15	−16.0 (2)	Zn1—N2—C8—C9	−46.54 (18)
N1—Zn1—N2—C8	118.25 (12)	N2—C8—C9—C10	85.9 (2)
N3—Zn1—N2—C8	1.24 (13)	C14—N3—C10—C11	−1.4 (3)
O1—Zn1—N2—C8	−96.51 (12)	Zn1—N3—C10—C11	−176.70 (15)
N4—Zn1—N2—C8	−134.96 (17)	C14—N3—C10—C9	177.50 (17)
N1—Zn1—N2—C7	−3.19 (12)	Zn1—N3—C10—C9	2.2 (2)
N3—Zn1—N2—C7	−120.20 (12)	C8—C9—C10—N3	−57.6 (2)
O1—Zn1—N2—C7	142.05 (12)	C8—C9—C10—C11	121.3 (2)
N4—Zn1—N2—C7	103.60 (19)	N3—C10—C11—C12	−0.3 (3)
N1—Zn1—N3—C14	106.38 (14)	C9—C10—C11—C12	−179.1 (2)
O1—Zn1—N3—C14	−71.66 (14)	C10—C11—C12—C13	1.6 (3)
N4—Zn1—N3—C14	12.79 (14)	C11—C12—C13—C14	−1.2 (3)
N2—Zn1—N3—C14	−152.98 (14)	C10—N3—C14—C13	1.8 (3)
N1—Zn1—N3—C10	−78.41 (15)	Zn1—N3—C14—C13	177.21 (15)
O1—Zn1—N3—C10	103.55 (14)	C12—C13—C14—N3	−0.5 (3)
N4—Zn1—N3—C10	−172.00 (14)	C8—N2—C15—C16	76.63 (18)
N2—Zn1—N3—C10	22.23 (15)	C7—N2—C15—C16	−164.68 (14)
C5—N1—C1—C2	0.1 (3)	Zn1—N2—C15—C16	−42.38 (16)
Zn1—N1—C1—C2	−178.35 (16)	Zn1—O1—C16—C15	−24.41 (18)
N1—C1—C2—C3	0.1 (3)	N2—C15—C16—O1	44.55 (19)
C1—C2—C3—C4	−0.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O10	0.73 (3)	1.88 (3)	2.602 (2)	170 (3)
O10—H10A···O2	0.76 (3)	2.07 (3)	2.836 (3)	175 (3)
O10—H10B···O9	0.76 (3)	2.06 (3)	2.809 (3)	172 (3)
C1—H1···O5^i	0.94 (2)	2.57 (2)	3.318 (3)	136 (2)
C6—H6A···O3^ii	0.88 (3)	2.58 (2)	3.293 (3)	139 (2)
C8—H8A···O6^iii	0.97 (2)	2.79 (2)	3.432 (3)	124 (1)
C9—H9B···O8^iii	0.87 (2)	2.67 (2)	3.402 (3)	143 (2)
C14—H14···O7^i	0.99 (2)	2.42 (2)	3.303 (3)	149 (2)

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