Unsolvated (dimethyl­formamide)(tetra­phenyl­porphyrinato)zinc(II)

The title compound, [Zn(C₄₄H₂₈N₄)(C₃H₇NO)], is a square-pyramidal five-coordinate zinc-porphyrin complex with N,N'-dimethyl­formamide as an apical ligand. The crystal structure is characterized by a layered organization of the porphyrin species with tight stacking of the corrugated layers along the b axis.

Key indicators

• Single-crystal X-ray study
• T = 110 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.052
• wR factor = 0.132
• Data-to-parameter ratio = 17.8

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT230_ALERT_2_B Hirshfeld Test Diff for    N51    -   C50     ..      14.65 su

Author Response: While the main axis of atomic displacement of C50 is along b, that of N51 is along a. This may be due to the smaller size of the N-atom and thus a less restricted motion perpendicular to the ligand's main axis, as well as to the tendency of the pyramidal N-atom to invert its conformation. O49 is also free to move sideways parallel to the porphyrin plane (with a significant component along a).

PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Zn     -   O49     ..      11.60 su

Author Response: The Zn-ion is tightly held near the porphyrin centre, and has a thermal motion ellipsoid of nearly spherical shape. On the other hand O49 is free to move sideways parallel to the porphyrin plane (with a significant component along a). Atom C50 reveals expected displacement mainly along b (the main axis of the axial ligand).

Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.97
PLAT230_ALERT_2_C Hirshfeld Test Diff for    O49    -   C50     ..       5.73 su

Author Response: While the main axis of atomic displacement of C50 is along b, that of N51 is along a. This may be due to the smaller size of the N-atom and thus a less restricted motion perpendicular to the ligand's main axis, as well as to the tendency of the pyramidal N-atom to invert its conformation. O49 is also free to move sideways parallel to the porphyrin plane (with a significant component along a).

   0 ALERT level A = In general: serious problem
   2 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion

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S1. Comment

Numerous four-coordinate, five-coordinate and six-coordinate complexes of metallo-tetraphenylporphyrin have been reported with a wide variety of crystallization solvents (many of these compounds form clathrates) and axial ligands coordinated to the metal centre (Byrn, et al., 1991; Byrn et al., 1993). Porphyrin complexes with dimethylformamide as an axial ligand include Zn^II-tetra(4-hydroxyphenyl)porphyrin (Goldberg et al., 1995), Mn^III-tetraphenylporphyrin perchlorate (Hill & Williamson, 1985), Zr^IV-tetraphenylporphyrin dichloride (Tutass et al., 2002), and Zn^II-tetraphenylporphyrin (Droege et al., 1994). The latter crystallized as a dichloromethane solvate. The present report provides information on the five-coordinate complex of the title compound, (I) (Fig. 1), determined at low temperature (ca 110 K).

In the crystal structure, the porphyrin core is slightly saddled with the inner pyrrole N atoms deviating ±0.023 (1) Å from their mean plane. The zinc ion is shifted by 0.329 (1) Å from this N₄ plane towards the axial ligand, imparting to the metalloporphyrin entity a domed structure (Fig. 2), which is typical of many five-coordinate complexes of metallated tetraarylporphyrins (Allen, 2002).

Efficient crystal packing of the molecular units of (I) (Fig. 3) is realised by waved layers of the metalloporphyrin species running perpendicular to the b axis. Adjacent inversion-related layers fit tightly into one another; the axial ligands of one layer are inserted between the porphyrin frameworks of neighbouring layers. The parallel offset of these layers allows a close van der Waals contact between the concave surface of a given metalloporphyrin core and a phenyl ring from another layer. The corresponding shortest non-bonding distances include: C4···C35(1 − x, −y, 2 − z) = 3.583 (2) Å, N22···C36(1 − x, −y, 2 − z) = 3.459 (2) Å, and C6···C36(1 − x, −y, 2 − z) = 3.463 (2) Å. This concave surface is in van der Waals contact with one of the methyl residues from the nearest layer translated along b. The axial ligand from one layer penetrates through the nearest layer approaching the porphyrin core [N24···C52(x, 1 + y, z) =3.776 (3) Å]. The geometry of the coordination around the zinc ion (Table 1) shows already known values (Allen, 2002, Vinodu & Goldberg, 2004).

S2. Experimental

The crystals of the title compound were obtained as a side product by dissolving zinc-tetraphenylporphyrin in N,N'-dimethylformamide in the presence of tris(acetoneperoxide) while attempting to formulate new porphyrin complexes.

S3. Refinement

H atoms were placeded in calculated positions and were constrained to ride on their parent atoms, with C—H distances in the range 0.95–0.98 Å and with U_iso(H) = 1.2 or 1.5 times U_eq(C).

Computing details

Data collection: COLLECT (Nonius, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-III (Burnett & Johnson, 1996) and Mercury (Bruno et al., 2002); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

	Fig. 1. Molecular structure of the title compound, with the atom-labelling scheme. Displacement parameters are drawn at the 50% probablity level.
	Fig. 2. Stick illustration of the domed molecular structure. The Zn atom is represented by a small sphere. Colour code: C dark grey, H white, N blue, O red, Zn violet.
	Fig. 3. Crystal packing of the title compound, illustrating the tight layered intermolecular organization. Hatoms are omitted for clarity. Zn atoms are represented by small spheres. Colour code: C dark grey, N blue, O red, Zn violet.

(dimethylformamide)(tetraphenylporphyrinato)zinc(II)

Crystal data

[Zn(C44H28N4)(C3H7NO)]	F(000) = 1560
Mr = 751.17	Dx = 1.371 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8468 reflections
a = 13.7419 (3) Å	θ = 2.3–28.2°
b = 9.2278 (2) Å	µ = 0.72 mm^−1
c = 29.3016 (7) Å	T = 110 K
β = 101.7186 (13)°	Prism, red
V = 3638.22 (14) Å^3	0.20 × 0.15 × 0.15 mm
Z = 4

Data collection

Nonius KappaCCD diffractometer	5627 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.059
Graphite monochromator	θmax = 28.2°, θmin = 2.3°
Detector resolution: 56 microns pixels mm^-1	h = −18→18
ϕ and ω scans	k = −12→12
29748 measured reflections	l = −38→37
8697 independent 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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.132	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.058P)^2 + 1.2438P] where P = (Fo^2 + 2Fc^2)/3
8697 reflections	(Δ/σ)max = 0.003
489 parameters	Δρmax = 0.85 e Å^−3
0 restraints	Δρmin = −0.64 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
Zn	0.27658 (2)	0.24348 (3)	0.894088 (10)	0.02084 (10)
C1	0.04751 (18)	0.2034 (3)	0.88257 (9)	0.0231 (6)
C2	−0.0296 (2)	0.1944 (3)	0.90945 (9)	0.0300 (7)
H2	−0.0977	0.1731	0.8977	0.036*
C3	0.0130 (2)	0.2218 (3)	0.95413 (9)	0.0293 (7)
H3	−0.0195	0.2233	0.9798	0.035*
C4	0.11684 (19)	0.2483 (3)	0.95587 (9)	0.0232 (6)
C5	0.18809 (19)	0.2700 (3)	0.99681 (9)	0.0238 (6)
C6	0.29151 (19)	0.2725 (3)	1.00014 (9)	0.0230 (6)
C7	0.3634 (2)	0.2901 (3)	1.04308 (9)	0.0285 (7)
H7	0.3495	0.3074	1.0731	0.034*
C8	0.4543 (2)	0.2772 (3)	1.03261 (9)	0.0281 (7)
H8	0.5163	0.2837	1.0539	0.034*
C9	0.43969 (18)	0.2517 (3)	0.98299 (8)	0.0221 (6)
C10	0.51630 (18)	0.2214 (3)	0.95946 (9)	0.0222 (6)
C11	0.50308 (18)	0.1851 (3)	0.91205 (9)	0.0227 (6)
C12	0.58215 (19)	0.1554 (3)	0.88778 (9)	0.0271 (6)
H12	0.6512	0.1535	0.9011	0.033*
C13	0.54055 (18)	0.1309 (3)	0.84283 (9)	0.0257 (6)
H13	0.5746	0.1089	0.8185	0.031*
C14	0.43358 (18)	0.1444 (3)	0.83833 (9)	0.0218 (6)
C15	0.36284 (18)	0.1337 (3)	0.79652 (9)	0.0219 (6)
C16	0.25902 (18)	0.1433 (3)	0.79266 (8)	0.0216 (6)
C17	0.18718 (18)	0.1212 (3)	0.74991 (9)	0.0239 (6)
H17	0.2012	0.1014	0.7201	0.029*
C18	0.09645 (18)	0.1340 (3)	0.76037 (8)	0.0234 (6)
H18	0.0345	0.1256	0.7391	0.028*
C19	0.11052 (18)	0.1624 (3)	0.80944 (8)	0.0221 (6)
C20	0.03357 (17)	0.1770 (3)	0.83449 (8)	0.0215 (6)
N21	0.13662 (15)	0.2360 (2)	0.91168 (7)	0.0224 (5)
N22	0.33965 (15)	0.2524 (2)	0.96387 (7)	0.0214 (5)
N23	0.41256 (15)	0.1766 (2)	0.88132 (7)	0.0218 (5)
N24	0.21054 (14)	0.1700 (3)	0.82855 (7)	0.0221 (5)
C25	0.1518 (2)	0.2820 (3)	1.04185 (9)	0.0274 (7)
C26	0.1004 (2)	0.4026 (4)	1.05195 (10)	0.0342 (7)
H26	0.0869	0.4795	1.0300	0.041*
C27	0.0680 (2)	0.4127 (4)	1.09381 (11)	0.0427 (8)
H27	0.0321	0.4955	1.1003	0.051*
C28	0.0883 (2)	0.3026 (4)	1.12576 (11)	0.0463 (9)
H28	0.0672	0.3103	1.1546	0.056*
C29	0.1386 (2)	0.1820 (4)	1.11649 (11)	0.0475 (9)
H29	0.1520	0.1059	1.1387	0.057*
C30	0.1705 (2)	0.1706 (4)	1.07419 (10)	0.0411 (8)
H30	0.2050	0.0864	1.0676	0.049*
C31	0.62109 (19)	0.2259 (3)	0.98724 (9)	0.0237 (6)
C32	0.6652 (2)	0.3566 (3)	1.00331 (10)	0.0318 (7)
H32	0.6284	0.4441	0.9975	0.038*
C33	0.76340 (19)	0.3599 (3)	1.02803 (10)	0.0315 (7)
H33	0.7934	0.4499	1.0385	0.038*
C34	0.8170 (2)	0.2336 (3)	1.03736 (9)	0.0288 (7)
H34	0.8841	0.2363	1.0537	0.035*
C35	0.7725 (2)	0.1032 (4)	1.02281 (10)	0.0375 (7)
H35	0.8084	0.0154	1.0301	0.045*
C36	0.6752 (2)	0.0996 (3)	0.99752 (10)	0.0344 (7)
H36	0.6455	0.0092	0.9872	0.041*
C37	0.39887 (17)	0.1146 (3)	0.75206 (9)	0.0227 (6)
C38	0.45292 (17)	−0.0066 (3)	0.74393 (9)	0.0255 (6)
H38	0.4690	−0.0788	0.7674	0.031*
C39	0.48369 (18)	−0.0235 (3)	0.70193 (10)	0.0306 (7)
H39	0.5218	−0.1059	0.6972	0.037*
C40	0.45926 (19)	0.0787 (4)	0.66696 (10)	0.0330 (7)
H40	0.4785	0.0650	0.6379	0.040*
C41	0.4069 (2)	0.2004 (4)	0.67459 (10)	0.0317 (7)
H41	0.3915	0.2721	0.6510	0.038*
C42	0.37632 (19)	0.2189 (3)	0.71677 (9)	0.0262 (6)
H42	0.3399	0.3030	0.7216	0.031*
C43	−0.07116 (17)	0.1582 (3)	0.80790 (8)	0.0217 (6)
C44	−0.10151 (18)	0.0328 (3)	0.78242 (9)	0.0250 (6)
H44	−0.0553	−0.0435	0.7820	0.030*
C45	−0.19850 (19)	0.0183 (3)	0.75757 (9)	0.0288 (6)
H45	−0.2179	−0.0669	0.7399	0.035*
C46	−0.2667 (2)	0.1274 (4)	0.75856 (10)	0.0329 (7)
H46	−0.3331	0.1171	0.7417	0.040*
C47	−0.2383 (2)	0.2517 (3)	0.78414 (10)	0.0325 (7)
H47	−0.2853	0.3265	0.7851	0.039*
C48	−0.14061 (19)	0.2674 (3)	0.80847 (10)	0.0283 (6)
H48	−0.1213	0.3537	0.8256	0.034*
O49	0.29027 (15)	0.4680 (2)	0.87671 (7)	0.0377 (5)
C50	0.2233 (2)	0.5474 (4)	0.86032 (10)	0.0376 (8)
H50	0.1587	0.5066	0.8519	0.045*
N51	0.23272 (17)	0.6899 (3)	0.85300 (8)	0.0305 (5)
C52	0.1458 (2)	0.7731 (4)	0.83234 (12)	0.0443 (9)
H52A	0.0877	0.7092	0.8259	0.066*
H52B	0.1559	0.8169	0.8032	0.066*
H52C	0.1350	0.8496	0.8540	0.066*
C53	0.3246 (2)	0.7675 (4)	0.86449 (12)	0.0428 (8)
H53A	0.3795	0.6987	0.8733	0.064*
H53B	0.3229	0.8331	0.8906	0.064*
H53C	0.3343	0.8238	0.8374	0.064*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn	0.02044 (16)	0.02527 (19)	0.01600 (16)	0.00285 (13)	0.00177 (12)	0.00048 (13)
C1	0.0214 (13)	0.0271 (16)	0.0203 (14)	0.0037 (11)	0.0035 (11)	0.0024 (11)
C2	0.0235 (13)	0.0405 (19)	0.0257 (15)	−0.0013 (13)	0.0047 (12)	−0.0011 (13)
C3	0.0255 (13)	0.041 (2)	0.0225 (14)	0.0003 (12)	0.0073 (12)	−0.0018 (13)
C4	0.0256 (13)	0.0235 (15)	0.0210 (13)	0.0033 (11)	0.0056 (11)	0.0015 (12)
C5	0.0287 (13)	0.0254 (16)	0.0181 (13)	0.0007 (11)	0.0064 (11)	0.0015 (11)
C6	0.0266 (13)	0.0235 (16)	0.0186 (13)	0.0010 (11)	0.0034 (11)	0.0006 (11)
C7	0.0306 (14)	0.0365 (18)	0.0175 (14)	−0.0012 (12)	0.0024 (12)	−0.0010 (12)
C8	0.0262 (14)	0.0359 (19)	0.0191 (14)	0.0000 (12)	−0.0027 (11)	−0.0007 (12)
C9	0.0239 (12)	0.0244 (15)	0.0155 (12)	−0.0007 (11)	−0.0019 (10)	0.0006 (11)
C10	0.0230 (13)	0.0221 (16)	0.0188 (13)	0.0001 (11)	−0.0020 (11)	0.0015 (11)
C11	0.0222 (12)	0.0217 (15)	0.0225 (14)	0.0014 (11)	0.0007 (11)	0.0028 (11)
C12	0.0208 (13)	0.0329 (18)	0.0263 (15)	0.0002 (12)	0.0016 (11)	0.0005 (13)
C13	0.0200 (12)	0.0325 (17)	0.0241 (14)	0.0031 (11)	0.0033 (11)	0.0014 (12)
C14	0.0207 (12)	0.0222 (15)	0.0232 (14)	0.0007 (11)	0.0061 (11)	−0.0016 (11)
C15	0.0233 (12)	0.0229 (15)	0.0195 (13)	0.0010 (11)	0.0046 (11)	0.0002 (11)
C16	0.0219 (12)	0.0229 (15)	0.0194 (13)	0.0015 (11)	0.0024 (11)	0.0020 (11)
C17	0.0239 (13)	0.0292 (16)	0.0189 (13)	0.0010 (11)	0.0052 (11)	0.0004 (12)
C18	0.0199 (12)	0.0316 (17)	0.0169 (13)	0.0002 (11)	−0.0005 (10)	0.0011 (12)
C19	0.0213 (12)	0.0246 (16)	0.0191 (13)	0.0029 (11)	0.0015 (11)	0.0014 (11)
C20	0.0190 (12)	0.0268 (16)	0.0184 (13)	0.0031 (11)	0.0030 (10)	0.0000 (11)
N21	0.0194 (10)	0.0303 (14)	0.0163 (11)	0.0035 (9)	0.0010 (9)	0.0007 (10)
N22	0.0221 (10)	0.0241 (13)	0.0172 (11)	0.0005 (9)	0.0020 (9)	0.0009 (10)
N23	0.0218 (10)	0.0260 (13)	0.0162 (11)	0.0023 (9)	0.0009 (9)	−0.0003 (10)
N24	0.0201 (10)	0.0281 (14)	0.0182 (11)	0.0034 (9)	0.0046 (9)	−0.0014 (10)
C25	0.0285 (14)	0.0363 (19)	0.0170 (13)	−0.0061 (12)	0.0036 (11)	−0.0038 (12)
C26	0.0305 (15)	0.045 (2)	0.0277 (16)	−0.0031 (14)	0.0068 (13)	−0.0075 (14)
C27	0.0361 (17)	0.060 (2)	0.0352 (18)	−0.0090 (16)	0.0134 (14)	−0.0187 (17)
C28	0.0391 (17)	0.081 (3)	0.0226 (16)	−0.0206 (18)	0.0147 (14)	−0.0158 (18)
C29	0.053 (2)	0.068 (3)	0.0222 (16)	−0.0129 (19)	0.0106 (15)	0.0085 (17)
C30	0.0495 (18)	0.047 (2)	0.0291 (17)	−0.0015 (16)	0.0131 (15)	0.0019 (15)
C31	0.0218 (12)	0.0295 (17)	0.0190 (13)	−0.0022 (11)	0.0026 (11)	−0.0009 (11)
C32	0.0323 (15)	0.0258 (17)	0.0334 (16)	0.0019 (13)	−0.0024 (13)	0.0022 (13)
C33	0.0274 (14)	0.0323 (18)	0.0318 (16)	−0.0055 (13)	−0.0012 (12)	−0.0012 (13)
C34	0.0225 (13)	0.0388 (19)	0.0237 (14)	−0.0001 (13)	0.0013 (11)	−0.0021 (13)
C35	0.0335 (15)	0.0307 (19)	0.0421 (18)	0.0043 (14)	−0.0072 (14)	−0.0016 (15)
C36	0.0317 (15)	0.0270 (18)	0.0373 (17)	−0.0013 (13)	−0.0098 (13)	−0.0023 (14)
C37	0.0168 (12)	0.0294 (16)	0.0207 (14)	−0.0036 (11)	0.0010 (10)	−0.0041 (12)
C38	0.0164 (12)	0.0334 (17)	0.0253 (14)	−0.0013 (11)	0.0011 (11)	−0.0036 (12)
C39	0.0201 (13)	0.0369 (19)	0.0349 (17)	0.0015 (12)	0.0060 (12)	−0.0108 (14)
C40	0.0280 (14)	0.049 (2)	0.0227 (15)	−0.0069 (14)	0.0076 (12)	−0.0090 (14)
C41	0.0319 (15)	0.0414 (19)	0.0218 (15)	−0.0058 (14)	0.0052 (12)	−0.0023 (13)
C42	0.0234 (13)	0.0348 (18)	0.0200 (14)	−0.0007 (12)	0.0037 (11)	−0.0035 (12)
C43	0.0197 (12)	0.0301 (17)	0.0156 (13)	−0.0004 (11)	0.0040 (10)	0.0033 (11)
C44	0.0256 (13)	0.0305 (17)	0.0195 (13)	0.0002 (12)	0.0057 (11)	0.0028 (12)
C45	0.0322 (14)	0.0340 (18)	0.0200 (14)	−0.0105 (13)	0.0049 (12)	0.0001 (12)
C46	0.0225 (13)	0.046 (2)	0.0284 (15)	−0.0091 (13)	0.0005 (12)	0.0043 (14)
C47	0.0203 (13)	0.042 (2)	0.0341 (16)	0.0052 (13)	0.0032 (12)	−0.0002 (15)
C48	0.0231 (13)	0.0314 (18)	0.0297 (15)	0.0024 (12)	0.0035 (12)	−0.0017 (13)
O49	0.0475 (12)	0.0383 (14)	0.0270 (11)	0.0116 (11)	0.0073 (10)	0.0032 (10)
C50	0.0302 (15)	0.054 (2)	0.0288 (17)	−0.0022 (15)	0.0059 (13)	−0.0073 (15)
N51	0.0428 (14)	0.0229 (14)	0.0255 (13)	0.0003 (11)	0.0062 (11)	0.0015 (11)
C52	0.0319 (16)	0.056 (2)	0.044 (2)	0.0019 (15)	0.0048 (14)	−0.0003 (17)
C53	0.0323 (16)	0.049 (2)	0.0438 (19)	0.0049 (15)	0.0003 (14)	−0.0047 (16)

Geometric parameters (Å, º)

Zn—N22	2.054 (2)	C27—H27	0.9500
Zn—N24	2.065 (2)	C28—C29	1.367 (5)
Zn—N23	2.073 (2)	C28—H28	0.9500
Zn—N21	2.091 (2)	C29—C30	1.400 (4)
Zn—O49	2.150 (2)	C29—H29	0.9500
C1—N21	1.376 (3)	C30—H30	0.9500
C1—C20	1.404 (3)	C31—C36	1.383 (4)
C1—C2	1.445 (4)	C31—C32	1.388 (4)
C2—C3	1.345 (4)	C32—C33	1.396 (4)
C2—H2	0.9500	C32—H32	0.9500
C3—C4	1.438 (4)	C33—C34	1.376 (4)
C3—H3	0.9500	C33—H33	0.9500
C4—N21	1.381 (3)	C34—C35	1.378 (4)
C4—C5	1.400 (4)	C34—H34	0.9500
C5—C6	1.405 (4)	C35—C36	1.391 (4)
C5—C25	1.506 (3)	C35—H35	0.9500
C6—N22	1.374 (3)	C36—H36	0.9500
C6—C7	1.442 (4)	C37—C38	1.389 (4)
C7—C8	1.350 (4)	C37—C42	1.401 (4)
C7—H7	0.9500	C38—C39	1.389 (4)
C8—C9	1.446 (4)	C38—H38	0.9500
C8—H8	0.9500	C39—C40	1.383 (4)
C9—N22	1.375 (3)	C39—H39	0.9500
C9—C10	1.399 (4)	C40—C41	1.376 (4)
C10—C11	1.404 (4)	C40—H40	0.9500
C10—C31	1.504 (3)	C41—C42	1.395 (4)
C11—N23	1.382 (3)	C41—H41	0.9500
C11—C12	1.441 (4)	C42—H42	0.9500
C12—C13	1.344 (4)	C43—C48	1.390 (4)
C12—H12	0.9500	C43—C44	1.394 (4)
C13—C14	1.454 (3)	C44—C45	1.389 (4)
C13—H13	0.9500	C44—H44	0.9500
C14—N23	1.381 (3)	C45—C46	1.380 (4)
C14—C15	1.404 (3)	C45—H45	0.9500
C15—C16	1.411 (3)	C46—C47	1.383 (4)
C15—C37	1.495 (3)	C46—H46	0.9500
C16—N24	1.377 (3)	C47—C48	1.393 (4)
C16—C17	1.443 (4)	C47—H47	0.9500
C17—C18	1.348 (3)	C48—H48	0.9500
C17—H17	0.9500	O49—C50	1.199 (3)
C18—C19	1.435 (3)	C50—N51	1.342 (4)
C18—H18	0.9500	C50—H50	0.9500
C19—N24	1.377 (3)	N51—C53	1.431 (4)
C19—C20	1.411 (3)	N51—C52	1.445 (4)
C20—C43	1.501 (3)	C52—H52A	0.9800
C25—C26	1.383 (4)	C52—H52B	0.9800
C25—C30	1.386 (4)	C52—H52C	0.9800
C26—C27	1.390 (4)	C53—H53A	0.9800
C26—H26	0.9500	C53—H53B	0.9800
C27—C28	1.371 (5)	C53—H53C	0.9800
N22—Zn—N24	162.90 (9)	C27—C26—H26	119.6
N22—Zn—N23	88.74 (8)	C28—C27—C26	119.7 (3)
N24—Zn—N23	88.64 (8)	C28—C27—H27	120.1
N22—Zn—N21	88.81 (8)	C26—C27—H27	120.1
N24—Zn—N21	88.04 (8)	C29—C28—C27	120.6 (3)
N23—Zn—N21	160.51 (9)	C29—C28—H28	119.7
N22—Zn—O49	99.08 (8)	C27—C28—H28	119.7
N24—Zn—O49	98.01 (8)	C28—C29—C30	119.9 (3)
N23—Zn—O49	96.81 (8)	C28—C29—H29	120.0
N21—Zn—O49	102.67 (8)	C30—C29—H29	120.0
N21—C1—C20	125.6 (2)	C25—C30—C29	120.2 (3)
N21—C1—C2	109.5 (2)	C25—C30—H30	119.9
C20—C1—C2	124.8 (2)	C29—C30—H30	119.9
C3—C2—C1	107.3 (2)	C36—C31—C32	118.7 (2)
C3—C2—H2	126.3	C36—C31—C10	120.5 (2)
C1—C2—H2	126.3	C32—C31—C10	120.8 (2)
C2—C3—C4	107.4 (2)	C31—C32—C33	120.3 (3)
C2—C3—H3	126.3	C31—C32—H32	119.8
C4—C3—H3	126.3	C33—C32—H32	119.8
N21—C4—C5	125.4 (2)	C34—C33—C32	120.4 (3)
N21—C4—C3	109.6 (2)	C34—C33—H33	119.8
C5—C4—C3	124.8 (2)	C32—C33—H33	119.8
C4—C5—C6	125.7 (2)	C33—C34—C35	119.5 (3)
C4—C5—C25	117.6 (2)	C33—C34—H34	120.3
C6—C5—C25	116.6 (2)	C35—C34—H34	120.3
N22—C6—C5	125.7 (2)	C34—C35—C36	120.3 (3)
N22—C6—C7	109.7 (2)	C34—C35—H35	119.9
C5—C6—C7	124.5 (2)	C36—C35—H35	119.9
C8—C7—C6	107.0 (2)	C31—C36—C35	120.8 (3)
C8—C7—H7	126.5	C31—C36—H36	119.6
C6—C7—H7	126.5	C35—C36—H36	119.6
C7—C8—C9	107.3 (2)	C38—C37—C42	118.2 (2)
C7—C8—H8	126.4	C38—C37—C15	121.8 (2)
C9—C8—H8	126.4	C42—C37—C15	120.0 (2)
N22—C9—C10	126.2 (2)	C39—C38—C37	120.8 (3)
N22—C9—C8	109.4 (2)	C39—C38—H38	119.6
C10—C9—C8	124.3 (2)	C37—C38—H38	119.6
C9—C10—C11	125.2 (2)	C40—C39—C38	120.6 (3)
C9—C10—C31	117.5 (2)	C40—C39—H39	119.7
C11—C10—C31	117.3 (2)	C38—C39—H39	119.7
N23—C11—C10	125.2 (2)	C41—C40—C39	119.5 (3)
N23—C11—C12	109.7 (2)	C41—C40—H40	120.3
C10—C11—C12	125.1 (2)	C39—C40—H40	120.3
C13—C12—C11	107.6 (2)	C40—C41—C42	120.4 (3)
C13—C12—H12	126.2	C40—C41—H41	119.8
C11—C12—H12	126.2	C42—C41—H41	119.8
C12—C13—C14	107.2 (2)	C41—C42—C37	120.6 (3)
C12—C13—H13	126.4	C41—C42—H42	119.7
C14—C13—H13	126.4	C37—C42—H42	119.7
N23—C14—C15	125.1 (2)	C48—C43—C44	118.5 (2)
N23—C14—C13	109.3 (2)	C48—C43—C20	119.9 (2)
C15—C14—C13	125.5 (2)	C44—C43—C20	121.7 (2)
C14—C15—C16	125.1 (2)	C45—C44—C43	120.8 (3)
C14—C15—C37	118.4 (2)	C45—C44—H44	119.6
C16—C15—C37	116.5 (2)	C43—C44—H44	119.6
N24—C16—C15	126.0 (2)	C46—C45—C44	120.1 (3)
N24—C16—C17	109.7 (2)	C46—C45—H45	119.9
C15—C16—C17	124.3 (2)	C44—C45—H45	119.9
C18—C17—C16	107.0 (2)	C45—C46—C47	119.9 (3)
C18—C17—H17	126.5	C45—C46—H46	120.0
C16—C17—H17	126.5	C47—C46—H46	120.0
C17—C18—C19	107.5 (2)	C46—C47—C48	120.0 (3)
C17—C18—H18	126.2	C46—C47—H47	120.0
C19—C18—H18	126.2	C48—C47—H47	120.0
N24—C19—C20	125.1 (2)	C43—C48—C47	120.7 (3)
N24—C19—C18	109.7 (2)	C43—C48—H48	119.6
C20—C19—C18	125.2 (2)	C47—C48—H48	119.6
C1—C20—C19	125.1 (2)	C50—O49—Zn	126.0 (2)
C1—C20—C43	117.5 (2)	O49—C50—N51	124.9 (3)
C19—C20—C43	117.4 (2)	O49—C50—H50	117.6
C1—N21—C4	106.2 (2)	N51—C50—H50	117.6
C1—N21—Zn	127.01 (16)	C50—N51—C53	124.2 (3)
C4—N21—Zn	126.48 (17)	C50—N51—C52	119.3 (3)
C6—N22—C9	106.5 (2)	C53—N51—C52	116.5 (3)
C6—N22—Zn	127.12 (17)	N51—C52—H52A	109.5
C9—N22—Zn	126.17 (16)	N51—C52—H52B	109.5
C14—N23—C11	106.22 (19)	H52A—C52—H52B	109.5
C14—N23—Zn	126.31 (16)	N51—C52—H52C	109.5
C11—N23—Zn	126.21 (17)	H52A—C52—H52C	109.5
C19—N24—C16	106.2 (2)	H52B—C52—H52C	109.5
C19—N24—Zn	127.51 (16)	N51—C53—H53A	109.5
C16—N24—Zn	125.43 (16)	N51—C53—H53B	109.5
C26—C25—C30	118.8 (3)	H53A—C53—H53B	109.5
C26—C25—C5	121.4 (3)	N51—C53—H53C	109.5
C30—C25—C5	119.7 (3)	H53A—C53—H53C	109.5
C25—C26—C27	120.8 (3)	H53B—C53—H53C	109.5
C25—C26—H26	119.6