A cadmium(II) coordination polymer formed from a third generation tetra­topic tris­(pyrazol­yl)methane ligand

The reaction of a third generation tetra­topic tris­(pyrazol­yl)methane ligand, namely 1,2,4,5-{[2,2,2-tris­(1H-pyrazol-1-yl)eth­oxy]meth­yl}benzene {1,2,4,5-C₆H₂[CH₂OCH₂C(pz)₃]₄, L4}, and [Cd₂(thf)₅](BF₄)₄ (thf is tetra­hydro­furan) produces the coordination polymer catena-poly[[[bis­[aceto­nitrile­cadmium(II)]-μ₄-1,2,4,5-{[2,2,2-tris­(1H-pyrazol-1-yl)eth­oxy]meth­yl}benzene] tetra­kis­(tetra­fluoro­borate)]–diethyl ether–aceto­nitrile (1/2/2)], {[Cd₂(CH₃CN)₂(C₅₄H₅₄N₂₄O₄)](BF₄)₄·2C₄H₁₀O·2CH₃CN}_n. The Cd^II center is coordinated in a κ³-fashion by one tris­(pyrazol­yl)methane group and in a κ²–κ⁰ fashion by another, while the sixth coordination site on the Cd^II cation is occupied by an aceto­nitrile mol­ecule. This bonding mode of the ligand generates an infinite one-dimensional structure built upon 32-atom metallomacrocycles connected by the C₆H₂ spacer. This com­pound is isostructural with the silver(I) analogue of this ligand, i.e. {[Ag₂(L4)](BF₄)₂·4CH₃CN}_n, thus showing the tendency of this system to form metal-based macrocyclic architectures.

Computing details

Data collection: SMART-NT (Bruker, 2000); cell refinement: SAINT-Plus-NT (Bruker, 1998); data reduction: SAINT-Plus-NT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

catena-Poly[[[[bis[acetonitrilecadmium(II)]-µ-4-1,2,4,5-([2,2,2-tris(1H-pyrazol-1-yl)ethoxy]methyl}benzene] tetrakis(tetrafluoridoborate)]–diethyl ether–acetonitrile (1/2/2)],

Crystal data

[Cd2(C2H3N)2(C54H54N24O4)](BF4)4·2C4H10O·2C2H3N	F(000) = 2020
Mr = 1987.71	Dx = 1.557 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 14.4909 (6) Å	Cell parameters from 6781 reflections
b = 16.1418 (7) Å	θ = 2.3–22.4°
c = 18.2891 (8) Å	µ = 0.60 mm^−1
β = 97.687 (1)°	T = 150 K
V = 4239.5 (3) Å^3	Irregular, colorless
Z = 2	0.28 × 0.18 × 0.10 mm

Data collection

Bruker SMART APEX CCD diffractometer	3844 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.092
Graphite monochromator	θmax = 22.5°, θmin = 1.7°
ω scans	h = −15→15
23397 measured reflections	k = −15→17
5579 independent reflections	l = −19→19

Refinement

Refinement on F^2	38 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.078	H-atom parameters constrained
wR(F^2) = 0.178	w = 1/[σ^2(Fo^2) + (0.0634P)^2 + 11.2944P] where P = (Fo^2 + 2Fc^2)/3
S = 1.14	(Δ/σ)max < 0.001
5579 reflections	Δρmax = 0.98 e Å^−3
570 parameters	Δρmin = −0.63 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	Occ. (<1)
Cd	−0.04860 (4)	0.49666 (5)	0.22415 (4)	0.0455 (3)
C1	0.1697 (6)	0.4205 (6)	0.2810 (5)	0.050 (3)
C2	0.2669 (6)	0.3844 (6)	0.3036 (5)	0.048 (2)
H2A	0.2617	0.3279	0.3238	0.058*
H2B	0.3003	0.3805	0.2599	0.058*
C3	0.4080 (6)	0.4007 (7)	0.3813 (6)	0.060 (3)
H3A	0.4446	0.3978	0.3393	0.072*
H3B	0.4018	0.3439	0.4004	0.072*
C4	0.4564 (6)	0.4547 (7)	0.4405 (5)	0.047 (2)
C5	0.5053 (6)	0.5255 (6)	0.4274 (5)	0.043 (3)
C6	0.4506 (6)	0.4317 (7)	0.5138 (6)	0.054 (3)
H6	0.4146	0.3845	0.5227	0.065*
C7	0.5148 (7)	0.5528 (7)	0.3506 (5)	0.063 (3)
H7A	0.4687	0.5235	0.3149	0.076*
H7B	0.5029	0.6131	0.3456	0.076*
C8	0.6176 (6)	0.5554 (6)	0.2622 (5)	0.049 (3)
H8A	0.6038	0.6150	0.2537	0.058*
H8B	0.5727	0.5232	0.2277	0.058*
C9	0.7144 (6)	0.5377 (5)	0.2465 (5)	0.036 (2)
C11	0.2561 (7)	0.5415 (7)	0.2309 (5)	0.053 (3)
H11	0.3176	0.5199	0.2394	0.064*
C12	0.2310 (7)	0.6132 (7)	0.1989 (6)	0.057 (3)
H12	0.2709	0.6539	0.1823	0.068*
C13	0.1317 (7)	0.6171 (7)	0.1943 (5)	0.055 (3)
H13	0.0935	0.6607	0.1724	0.066*
C21	0.1567 (8)	0.3001 (7)	0.1893 (6)	0.061 (3)
H21	0.2180	0.2782	0.1979	0.074*
C22	0.0864 (9)	0.2727 (7)	0.1397 (6)	0.071 (3)
H22	0.0894	0.2291	0.1052	0.085*
C23	0.0089 (8)	0.3198 (7)	0.1482 (6)	0.065 (3)
H23	−0.0516	0.3116	0.1221	0.079*
C31	0.1440 (7)	0.3922 (6)	0.4126 (5)	0.052 (3)
H31	0.2013	0.3658	0.4299	0.062*
C32	0.0719 (7)	0.4050 (6)	0.4519 (5)	0.058 (3)
H32	0.0687	0.3900	0.5017	0.069*
C33	0.0044 (7)	0.4444 (7)	0.4039 (5)	0.059 (3)
H33	−0.0547	0.4607	0.4160	0.070*
C41	0.7675 (8)	0.6483 (6)	0.3415 (5)	0.051 (3)
H41	0.7105	0.6564	0.3608	0.061*
C42	0.8467 (8)	0.6917 (6)	0.3619 (5)	0.053 (3)
H42	0.8573	0.7346	0.3975	0.064*
C43	0.9092 (7)	0.6582 (6)	0.3182 (5)	0.055 (3)
H43	0.9718	0.6763	0.3199	0.067*
C51	0.6840 (7)	0.3892 (7)	0.2770 (6)	0.064 (3)
H51	0.6202	0.3934	0.2834	0.077*
C52	0.7372 (7)	0.3190 (6)	0.2828 (6)	0.058 (3)
H52	0.7185	0.2650	0.2954	0.069*
C53	0.8235 (7)	0.3428 (6)	0.2665 (5)	0.055 (3)
H53	0.8749	0.3063	0.2659	0.067*
C61	0.6869 (6)	0.5028 (7)	0.1122 (5)	0.052 (2)
H61	0.6786	0.4445	0.1154	0.062*
C62	0.6718 (6)	0.5498 (7)	0.0506 (5)	0.054 (3)
H62	0.6528	0.5310	0.0017	0.064*
C63	0.6895 (6)	0.6298 (6)	0.0728 (5)	0.049 (3)
H63	0.6841	0.6763	0.0406	0.059*
N11	0.1014 (5)	0.5496 (5)	0.2257 (4)	0.056 (2)
N12	0.1777 (5)	0.5042 (5)	0.2496 (4)	0.0459 (18)
N21	0.0318 (6)	0.3780 (5)	0.1980 (4)	0.051 (2)
N22	0.1231 (5)	0.3654 (5)	0.2250 (4)	0.0419 (19)
N31	0.0321 (5)	0.4564 (5)	0.3394 (4)	0.047 (2)
N32	0.1191 (5)	0.4242 (4)	0.3443 (4)	0.0409 (18)
N41	0.8719 (5)	0.5986 (4)	0.2740 (4)	0.0409 (19)
N42	0.7816 (5)	0.5920 (4)	0.2896 (4)	0.0389 (18)
N51	0.8258 (5)	0.4230 (4)	0.2517 (4)	0.0396 (18)
N52	0.7405 (5)	0.4520 (5)	0.2605 (4)	0.0424 (19)
N61	0.7155 (5)	0.6343 (4)	0.1458 (4)	0.0415 (18)
N62	0.7161 (5)	0.5551 (4)	0.1684 (4)	0.0358 (17)
O1	0.3165 (4)	0.4353 (4)	0.3569 (3)	0.0498 (16)
O2	0.6060 (4)	0.5346 (4)	0.3360 (3)	0.0448 (16)
C71	−0.1078 (7)	0.5319 (6)	0.0411 (7)	0.058 (3)
C72	−0.1382 (8)	0.5422 (8)	−0.0383 (5)	0.085 (4)
H72A	−0.1886	0.5832	−0.0458	0.127*
H72B	−0.1607	0.4891	−0.0596	0.127*
H72C	−0.0857	0.5614	−0.0625	0.127*
N71	−0.0834 (5)	0.5256 (5)	0.1021 (5)	0.053 (2)
B1	0.1796 (9)	0.7003 (9)	0.0062 (7)	0.056 (3)
F1	0.2259 (5)	0.7367 (4)	0.0670 (4)	0.107 (3)
F2	0.2287 (5)	0.6400 (6)	−0.0172 (5)	0.130 (3)
F3	0.1639 (6)	0.7577 (5)	−0.0485 (4)	0.118 (3)
F4	0.0970 (5)	0.6706 (5)	0.0203 (4)	0.099 (2)
B2	0.5712 (11)	0.6351 (10)	0.8446 (8)	0.073 (4)
F5	0.5462 (5)	0.5715 (6)	0.7997 (5)	0.133 (3)
F6	0.5771 (6)	0.7012 (6)	0.7957 (4)	0.136 (4)
F7	0.5117 (6)	0.6533 (6)	0.8898 (4)	0.141 (4)
F8	0.6572 (5)	0.6222 (5)	0.8772 (4)	0.109 (3)
C91A	0.6323 (15)	0.8558 (17)	−0.0442 (16)	0.126 (8)*	0.6
H91A	0.6332	0.8039	−0.0163	0.189*	0.6
H91B	0.5905	0.8500	−0.0907	0.189*	0.6
H91C	0.6100	0.9008	−0.0150	0.189*	0.6
C92A	0.7291 (17)	0.876 (2)	−0.060 (2)	0.172 (12)*	0.6
H92A	0.7300	0.8805	−0.1141	0.207*	0.6
H92B	0.7510	0.9284	−0.0365	0.207*	0.6
O3A	0.7873 (15)	0.8083 (15)	−0.0308 (12)	0.166 (7)*	0.6
C93A	0.836 (2)	0.8354 (15)	0.0342 (15)	0.123 (7)*	0.6
H93A	0.7918	0.8507	0.0690	0.148*	0.6
H93B	0.8726	0.8851	0.0251	0.148*	0.6
C94A	0.8997 (15)	0.7669 (14)	0.0669 (12)	0.078 (5)*	0.6
H94A	0.8682	0.7341	0.1012	0.116*	0.6
H94B	0.9566	0.7912	0.0933	0.116*	0.6
H94C	0.9159	0.7311	0.0272	0.116*	0.6
C91B	0.681 (3)	0.865 (3)	−0.0864 (19)	0.126 (8)*	0.4
H91D	0.7245	0.8402	−0.1172	0.189*	0.4
H91E	0.6559	0.9164	−0.1093	0.189*	0.4
H91F	0.6305	0.8261	−0.0818	0.189*	0.4
C92B	0.733 (3)	0.884 (3)	−0.010 (2)	0.172 (12)*	0.4
H92C	0.7767	0.9308	−0.0116	0.207*	0.4
H92D	0.6898	0.8953	0.0259	0.207*	0.4
O3B	0.782 (2)	0.807 (2)	0.0050 (19)	0.166 (7)*	0.4
C93B	0.857 (3)	0.820 (2)	0.058 (3)	0.123 (7)*	0.4
H93C	0.8342	0.8505	0.0986	0.148*	0.4
H93D	0.9000	0.8569	0.0359	0.148*	0.4
C94B	0.913 (2)	0.748 (2)	0.0912 (18)	0.078 (5)*	0.4
H94D	0.8717	0.7082	0.1110	0.116*	0.4
H94E	0.9594	0.7681	0.1312	0.116*	0.4
H94F	0.9444	0.7211	0.0535	0.116*	0.4
N81A	0.485 (5)	0.710 (4)	0.183 (2)	0.063 (6)	0.4
C81A	0.462 (6)	0.692 (4)	0.1236 (19)	0.070 (6)	0.4
C82A	0.451 (3)	0.670 (2)	0.0463 (16)	0.082 (7)	0.4
H82A	0.3886	0.6853	0.0232	0.123*	0.4
H82B	0.4602	0.6103	0.0411	0.123*	0.4
H82C	0.4976	0.6999	0.0221	0.123*	0.4
N81B	0.461 (3)	0.721 (3)	0.1831 (15)	0.063 (6)	0.6
C81B	0.458 (4)	0.681 (3)	0.1322 (16)	0.070 (6)	0.6
C82B	0.4417 (19)	0.6251 (13)	0.0703 (11)	0.082 (7)	0.6
H82D	0.3790	0.6342	0.0441	0.123*	0.6
H82E	0.4473	0.5677	0.0878	0.123*	0.6
H82F	0.4877	0.6354	0.0367	0.123*	0.6

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd	0.0370 (4)	0.0541 (5)	0.0461 (4)	0.0037 (4)	0.0082 (3)	0.0051 (4)
C1	0.044 (6)	0.055 (7)	0.052 (6)	0.001 (5)	0.012 (5)	0.008 (5)
C2	0.053 (6)	0.039 (6)	0.053 (6)	0.003 (5)	0.009 (5)	0.008 (5)
C3	0.045 (6)	0.072 (8)	0.063 (7)	0.019 (5)	0.012 (5)	0.001 (6)
C4	0.024 (5)	0.065 (7)	0.053 (6)	0.012 (5)	0.011 (4)	−0.002 (5)
C5	0.035 (5)	0.052 (7)	0.046 (6)	0.023 (4)	0.018 (5)	0.016 (5)
C6	0.041 (6)	0.066 (8)	0.062 (7)	0.012 (5)	0.028 (5)	0.019 (6)
C7	0.057 (7)	0.084 (8)	0.055 (6)	0.026 (6)	0.029 (5)	0.016 (6)
C8	0.062 (6)	0.049 (6)	0.040 (5)	0.020 (5)	0.025 (5)	0.014 (5)
C9	0.036 (5)	0.033 (5)	0.040 (5)	0.002 (4)	0.012 (4)	0.004 (4)
C11	0.038 (6)	0.062 (7)	0.061 (6)	−0.003 (5)	0.010 (5)	0.014 (6)
C12	0.050 (7)	0.049 (7)	0.075 (7)	−0.012 (5)	0.023 (5)	0.007 (6)
C13	0.067 (8)	0.054 (7)	0.047 (6)	0.006 (5)	0.017 (5)	0.018 (5)
C21	0.082 (8)	0.049 (7)	0.057 (7)	0.002 (6)	0.022 (6)	0.011 (6)
C22	0.108 (10)	0.057 (8)	0.051 (7)	−0.007 (7)	0.021 (7)	−0.010 (6)
C23	0.070 (8)	0.057 (8)	0.067 (7)	−0.011 (6)	−0.001 (6)	−0.007 (6)
C31	0.058 (7)	0.045 (7)	0.053 (6)	0.013 (5)	0.007 (5)	0.009 (5)
C32	0.064 (7)	0.076 (8)	0.036 (5)	0.004 (6)	0.015 (5)	0.004 (5)
C33	0.051 (6)	0.087 (8)	0.041 (6)	0.018 (6)	0.017 (5)	0.008 (6)
C41	0.086 (8)	0.038 (6)	0.030 (5)	0.006 (6)	0.016 (5)	−0.004 (5)
C42	0.082 (8)	0.038 (6)	0.038 (6)	−0.001 (6)	0.000 (5)	−0.012 (5)
C43	0.053 (6)	0.047 (7)	0.066 (7)	−0.011 (5)	0.007 (6)	0.005 (6)
C51	0.050 (7)	0.052 (8)	0.093 (8)	0.006 (6)	0.022 (6)	0.011 (6)
C52	0.068 (7)	0.035 (6)	0.074 (7)	−0.001 (5)	0.022 (6)	0.016 (5)
C53	0.066 (7)	0.035 (7)	0.067 (7)	0.001 (5)	0.017 (6)	0.000 (5)
C61	0.067 (6)	0.043 (6)	0.048 (6)	0.004 (6)	0.015 (5)	−0.009 (6)
C62	0.046 (6)	0.065 (8)	0.049 (6)	−0.009 (5)	0.005 (5)	−0.006 (6)
C63	0.049 (6)	0.053 (7)	0.047 (6)	0.007 (5)	0.009 (5)	0.014 (5)
N11	0.039 (5)	0.057 (6)	0.069 (6)	0.017 (4)	0.000 (4)	0.023 (5)
N12	0.041 (4)	0.040 (5)	0.057 (5)	−0.002 (4)	0.008 (4)	0.005 (4)
N21	0.058 (6)	0.048 (5)	0.044 (5)	0.012 (4)	−0.005 (4)	−0.006 (4)
N22	0.053 (5)	0.040 (5)	0.035 (4)	0.007 (4)	0.014 (4)	0.001 (4)
N31	0.038 (5)	0.068 (6)	0.037 (4)	0.022 (4)	0.009 (4)	0.015 (4)
N32	0.045 (5)	0.045 (5)	0.031 (4)	0.007 (4)	0.000 (3)	0.003 (4)
N41	0.044 (5)	0.033 (5)	0.041 (4)	−0.020 (4)	−0.009 (4)	−0.002 (4)
N42	0.044 (5)	0.034 (5)	0.041 (4)	−0.004 (4)	0.013 (4)	−0.001 (4)
N51	0.031 (4)	0.028 (5)	0.059 (5)	0.014 (3)	0.005 (4)	0.014 (4)
N52	0.039 (5)	0.035 (5)	0.054 (5)	0.008 (4)	0.009 (4)	0.008 (4)
N61	0.050 (5)	0.027 (5)	0.050 (5)	−0.002 (3)	0.015 (4)	0.004 (4)
N62	0.042 (4)	0.029 (5)	0.039 (4)	−0.002 (3)	0.014 (3)	−0.001 (4)
O1	0.041 (4)	0.053 (4)	0.056 (4)	0.009 (3)	0.009 (3)	−0.004 (3)
O2	0.048 (4)	0.051 (4)	0.040 (3)	0.010 (3)	0.023 (3)	0.011 (3)
C71	0.037 (6)	0.062 (8)	0.076 (8)	0.014 (5)	0.014 (6)	0.006 (6)
C72	0.090 (9)	0.129 (11)	0.039 (6)	0.029 (8)	0.020 (6)	0.015 (7)
N71	0.041 (5)	0.069 (7)	0.048 (5)	0.021 (4)	0.000 (4)	0.007 (4)
B1	0.054 (8)	0.062 (9)	0.051 (7)	−0.005 (7)	0.006 (6)	0.009 (7)
F1	0.140 (7)	0.073 (5)	0.099 (5)	−0.044 (4)	−0.017 (5)	−0.027 (4)
F2	0.106 (6)	0.124 (7)	0.156 (8)	0.028 (5)	0.010 (5)	−0.069 (6)
F3	0.134 (7)	0.107 (6)	0.113 (6)	−0.017 (5)	0.017 (5)	0.051 (5)
F4	0.090 (5)	0.132 (7)	0.073 (4)	−0.026 (5)	0.009 (4)	0.023 (4)
B2	0.079 (11)	0.079 (12)	0.064 (9)	0.003 (8)	0.024 (8)	0.003 (9)
F5	0.092 (6)	0.160 (9)	0.153 (8)	−0.043 (6)	0.036 (5)	−0.062 (7)
F6	0.179 (9)	0.139 (8)	0.103 (6)	0.087 (7)	0.070 (6)	0.030 (6)
F7	0.134 (7)	0.195 (10)	0.113 (6)	0.060 (7)	0.087 (6)	0.016 (6)
F8	0.067 (5)	0.167 (8)	0.089 (5)	0.011 (5)	−0.007 (4)	0.021 (5)
N81A	0.04 (2)	0.073 (11)	0.076 (6)	0.022 (9)	0.016 (7)	0.002 (5)
C81A	0.046 (8)	0.089 (12)	0.077 (7)	0.021 (9)	0.012 (7)	−0.007 (8)
C82A	0.062 (10)	0.101 (16)	0.082 (9)	0.027 (14)	0.005 (9)	−0.013 (9)
N81B	0.04 (2)	0.073 (11)	0.076 (6)	0.022 (9)	0.016 (7)	0.002 (5)
C81B	0.046 (8)	0.089 (12)	0.077 (7)	0.021 (9)	0.012 (7)	−0.007 (8)
C82B	0.062 (10)	0.101 (16)	0.082 (9)	0.027 (14)	0.005 (9)	−0.013 (9)

Geometric parameters (Å, º)

Cd—N41^i	2.269 (8)	C53—H53	0.9500
Cd—N71	2.270 (8)	C61—C62	1.352 (13)
Cd—N51^i	2.286 (7)	C61—N62	1.354 (11)
Cd—N21	2.324 (8)	C61—H61	0.9500
Cd—N11	2.332 (8)	C62—C63	1.368 (13)
Cd—N31	2.360 (7)	C62—H62	0.9500
C1—N32	1.451 (11)	C63—N61	1.339 (11)
C1—N22	1.453 (12)	C63—H63	0.9500
C1—N12	1.478 (11)	N11—N12	1.351 (9)
C1—C2	1.530 (12)	N21—N22	1.364 (10)
C2—O1	1.398 (10)	N31—N32	1.356 (9)
C2—H2A	0.9900	N41—N42	1.381 (9)
C2—H2B	0.9900	N41—Cd^iii	2.269 (8)
C3—O1	1.453 (10)	N51—N52	1.351 (9)
C3—C4	1.490 (13)	N51—Cd^iii	2.286 (7)
C3—H3A	0.9900	N61—N62	1.344 (9)
C3—H3B	0.9900	C71—N71	1.130 (12)
C4—C5	1.383 (13)	C71—C72	1.469 (15)
C4—C6	1.404 (12)	C72—H72A	0.9800
C5—C6^ii	1.363 (13)	C72—H72B	0.9800
C5—C7	1.495 (12)	C72—H72C	0.9800
C6—C5^ii	1.363 (13)	B1—F2	1.311 (14)
C6—H6	0.9500	B1—F4	1.345 (13)
C7—O2	1.414 (10)	B1—F1	1.354 (13)
C7—H7A	0.9900	B1—F3	1.360 (13)
C7—H7B	0.9900	B2—F7	1.305 (14)
C8—O2	1.422 (9)	B2—F8	1.324 (16)
C8—C9	1.497 (11)	B2—F5	1.335 (16)
C8—H8A	0.9900	B2—F6	1.402 (16)
C8—H8B	0.9900	C91A—C92A	1.505 (15)
C9—N52	1.448 (11)	C91A—H91A	0.9800
C9—N62	1.459 (10)	C91A—H91B	0.9800
C9—N42	1.459 (11)	C91A—H91C	0.9800
C11—C12	1.326 (13)	C92A—O3A	1.434 (14)
C11—N12	1.369 (11)	C92A—H92A	0.9900
C11—H11	0.9500	C92A—H92B	0.9900
C12—C13	1.432 (13)	O3A—C93A	1.368 (14)
C12—H12	0.9500	C93A—C94A	1.514 (14)
C13—N11	1.332 (12)	C93A—H93A	0.9900
C13—H13	0.9500	C93A—H93B	0.9900
C21—C22	1.346 (14)	C94A—H94A	0.9800
C21—N22	1.363 (12)	C94A—H94B	0.9800
C21—H21	0.9500	C94A—H94C	0.9800
C22—C23	1.382 (15)	C91B—C92B	1.519 (15)
C22—H22	0.9500	C91B—H91D	0.9800
C23—N21	1.320 (12)	C91B—H91E	0.9800
C23—H23	0.9500	C91B—H91F	0.9800
C31—N32	1.356 (11)	C92B—O3B	1.432 (15)
C31—C32	1.360 (12)	C92B—H92C	0.9900
C31—H31	0.9500	C92B—H92D	0.9900
C32—C33	1.380 (13)	O3B—C93B	1.370 (15)
C32—H32	0.9500	C93B—C94B	1.496 (15)
C33—N31	1.310 (11)	C93B—H93C	0.9900
C33—H33	0.9500	C93B—H93D	0.9900
C41—N42	1.349 (10)	C94B—H94D	0.9800
C41—C42	1.354 (13)	C94B—H94E	0.9800
C41—H41	0.9500	C94B—H94F	0.9800
C42—C43	1.394 (13)	N81A—C81A	1.132 (10)
C42—H42	0.9500	C81A—C82A	1.444 (10)
C43—N41	1.324 (11)	C82A—H82A	0.9800
C43—H43	0.9500	C82A—H82B	0.9800
C51—N52	1.362 (12)	C82A—H82C	0.9800
C51—C52	1.367 (13)	N81B—C81B	1.129 (9)
C51—H51	0.9500	C81B—C82B	1.440 (9)
C52—C53	1.379 (13)	C82B—H82D	0.9800
C52—H52	0.9500	C82B—H82E	0.9800
C53—N51	1.324 (11)	C82B—H82F	0.9800
N41^i—Cd—N71	100.8 (3)	N11—N12—C11	110.5 (8)
N41^i—Cd—N51^i	80.0 (3)	N11—N12—C1	121.2 (7)
N71—Cd—N51^i	104.2 (3)	C11—N12—C1	127.7 (8)
N41^i—Cd—N21	167.3 (3)	C23—N21—N22	106.6 (8)
N71—Cd—N21	91.1 (3)	C23—N21—Cd	129.9 (7)
N51^i—Cd—N21	93.0 (3)	N22—N21—Cd	122.5 (6)
N41^i—Cd—N11	104.6 (3)	C21—N22—N21	109.5 (8)
N71—Cd—N11	91.2 (3)	C21—N22—C1	130.5 (9)
N51^i—Cd—N11	163.0 (2)	N21—N22—C1	120.0 (7)
N21—Cd—N11	79.2 (3)	C33—N31—N32	106.1 (7)
N41^i—Cd—N31	93.3 (2)	C33—N31—Cd	132.0 (6)
N71—Cd—N31	162.4 (2)	N32—N31—Cd	120.7 (5)
N51^i—Cd—N31	88.5 (3)	C31—N32—N31	109.7 (7)
N21—Cd—N31	75.8 (3)	C31—N32—C1	128.2 (8)
N11—Cd—N31	75.0 (3)	N31—N32—C1	121.8 (7)
N32—C1—N22	110.5 (7)	C43—N41—N42	104.5 (7)
N32—C1—N12	110.3 (8)	C43—N41—Cd^iii	125.8 (7)
N22—C1—N12	109.8 (7)	N42—N41—Cd^iii	125.0 (5)
N32—C1—C2	110.2 (7)	C41—N42—N41	109.3 (7)
N22—C1—C2	106.3 (8)	C41—N42—C9	129.2 (8)
N12—C1—C2	109.6 (7)	N41—N42—C9	121.1 (7)
O1—C2—C1	109.4 (8)	C53—N51—N52	105.5 (7)
O1—C2—H2A	109.8	C53—N51—Cd^iii	126.5 (6)
C1—C2—H2A	109.8	N52—N51—Cd^iii	127.9 (5)
O1—C2—H2B	109.8	N51—N52—C51	110.8 (7)
C1—C2—H2B	109.8	N51—N52—C9	122.1 (7)
H2A—C2—H2B	108.2	C51—N52—C9	126.9 (8)
O1—C3—C4	108.6 (8)	C63—N61—N62	104.2 (7)
O1—C3—H3A	110.0	N61—N62—C61	111.7 (7)
C4—C3—H3A	110.0	N61—N62—C9	119.0 (7)
O1—C3—H3B	110.0	C61—N62—C9	125.4 (8)
C4—C3—H3B	110.0	C2—O1—C3	110.5 (7)
H3A—C3—H3B	108.4	C7—O2—C8	111.3 (6)
C5—C4—C6	118.7 (9)	N71—C71—C72	178.4 (13)
C5—C4—C3	124.1 (9)	C71—C72—H72A	109.5
C6—C4—C3	117.2 (10)	C71—C72—H72B	109.5
C6^ii—C5—C4	118.6 (8)	H72A—C72—H72B	109.5
C6^ii—C5—C7	120.0 (10)	C71—C72—H72C	109.5
C4—C5—C7	121.3 (10)	H72A—C72—H72C	109.5
C5^ii—C6—C4	122.6 (9)	H72B—C72—H72C	109.5
C5^ii—C6—H6	118.7	C71—N71—Cd	171.6 (9)
C4—C6—H6	118.7	F2—B1—F4	109.5 (11)
O2—C7—C5	108.8 (7)	F2—B1—F1	111.1 (10)
O2—C7—H7A	109.9	F4—B1—F1	110.7 (10)
C5—C7—H7A	109.9	F2—B1—F3	108.1 (11)
O2—C7—H7B	109.9	F4—B1—F3	108.5 (10)
C5—C7—H7B	109.9	F1—B1—F3	108.9 (11)
H7A—C7—H7B	108.3	F7—B2—F8	114.3 (13)
O2—C8—C9	111.7 (7)	F7—B2—F5	114.5 (14)
O2—C8—H8A	109.3	F8—B2—F5	108.5 (13)
C9—C8—H8A	109.3	F7—B2—F6	109.6 (12)
O2—C8—H8B	109.3	F8—B2—F6	105.8 (12)
C9—C8—H8B	109.3	F5—B2—F6	103.2 (12)
H8A—C8—H8B	107.9	C92A—C91A—H91A	109.5
N52—C9—N62	108.5 (7)	C92A—C91A—H91B	109.5
N52—C9—N42	109.8 (7)	H91A—C91A—H91B	109.5
N62—C9—N42	108.4 (7)	C92A—C91A—H91C	109.5
N52—C9—C8	112.2 (7)	H91A—C91A—H91C	109.5
N62—C9—C8	106.8 (7)	H91B—C91A—H91C	109.5
N42—C9—C8	110.9 (7)	O3A—C92A—C91A	106.4 (19)
C12—C11—N12	107.9 (9)	O3A—C92A—H92A	110.4
C12—C11—H11	126.0	C91A—C92A—H92A	110.4
N12—C11—H11	126.0	O3A—C92A—H92B	110.4
C11—C12—C13	106.1 (9)	C91A—C92A—H92B	110.4
C11—C12—H12	126.9	H92A—C92A—H92B	108.6
C13—C12—H12	126.9	C93A—O3A—C92A	107 (2)
N11—C13—C12	109.0 (9)	O3A—C93A—C94A	109.0 (18)
N11—C13—H13	125.5	O3A—C93A—H93A	109.9
C12—C13—H13	125.5	C94A—C93A—H93A	109.9
C22—C21—N22	106.9 (10)	O3A—C93A—H93B	109.9
C22—C21—H21	126.5	C94A—C93A—H93B	109.9
N22—C21—H21	126.5	H93A—C93A—H93B	108.3
C21—C22—C23	107.2 (10)	C93A—C94A—H94A	109.5
C21—C22—H22	126.4	C93A—C94A—H94B	109.5
C23—C22—H22	126.4	H94A—C94A—H94B	109.5
N21—C23—C22	109.7 (10)	C93A—C94A—H94C	109.5
N21—C23—H23	125.2	H94A—C94A—H94C	109.5
C22—C23—H23	125.2	H94B—C94A—H94C	109.5
N32—C31—C32	107.5 (8)	C92B—C91B—H91D	109.5
N32—C31—H31	126.3	C92B—C91B—H91E	109.5
C32—C31—H31	126.3	H91D—C91B—H91E	109.5
C31—C32—C33	105.2 (8)	C92B—C91B—H91F	109.5
C31—C32—H32	127.4	H91D—C91B—H91F	109.5
C33—C32—H32	127.4	H91E—C91B—H91F	109.5
N31—C33—C32	111.4 (9)	O3B—C92B—C91B	100 (2)
N31—C33—H33	124.3	O3B—C92B—H92C	111.8
C32—C33—H33	124.3	C91B—C92B—H92C	111.8
N42—C41—C42	109.9 (9)	O3B—C92B—H92D	111.8
N42—C41—H41	125.1	C91B—C92B—H92D	111.8
C42—C41—H41	125.1	H92C—C92B—H92D	109.5
C41—C42—C43	103.5 (8)	C93B—O3B—C92B	109 (2)
C41—C42—H42	128.3	O3B—C93B—C94B	121 (3)
C43—C42—H42	128.3	O3B—C93B—H93C	107.1
N41—C43—C42	112.8 (9)	C94B—C93B—H93C	107.1
N41—C43—H43	123.6	O3B—C93B—H93D	107.1
C42—C43—H43	123.6	C94B—C93B—H93D	107.1
N52—C51—C52	106.5 (9)	H93C—C93B—H93D	106.8
N52—C51—H51	126.7	C93B—C94B—H94D	109.5
C52—C51—H51	126.7	C93B—C94B—H94E	109.5
C51—C52—C53	105.7 (9)	H94D—C94B—H94E	109.5
C51—C52—H52	127.1	C93B—C94B—H94F	109.5
C53—C52—H52	127.1	H94D—C94B—H94F	109.5
N51—C53—C52	111.4 (9)	H94E—C94B—H94F	109.5
N51—C53—H53	124.3	N81A—C81A—C82A	169 (8)
C52—C53—H53	124.3	C81A—C82A—H82A	109.5
C62—C61—N62	106.4 (9)	C81A—C82A—H82B	109.5
C62—C61—H61	126.8	H82A—C82A—H82B	109.5
N62—C61—H61	126.8	C81A—C82A—H82C	109.5
C61—C62—C63	106.3 (9)	H82A—C82A—H82C	109.5
C61—C62—H62	126.9	H82B—C82A—H82C	109.5
C63—C62—H62	126.9	N81B—C81B—C82B	172 (5)
N61—C63—C62	111.3 (8)	C81B—C82B—H82D	109.5
N61—C63—H63	124.4	C81B—C82B—H82E	109.5
C62—C63—H63	124.4	H82D—C82B—H82E	109.5
C13—N11—N12	106.3 (8)	C81B—C82B—H82F	109.5
C13—N11—Cd	130.9 (6)	H82D—C82B—H82F	109.5
N12—N11—Cd	121.8 (6)	H82E—C82B—H82F	109.5
N32—C1—C2—O1	−61.1 (10)	C32—C31—N32—C1	−175.2 (9)
N22—C1—C2—O1	179.1 (7)	C33—N31—N32—C31	0.1 (11)
N12—C1—C2—O1	60.5 (10)	Cd—N31—N32—C31	−169.0 (6)
O1—C3—C4—C5	−84.0 (10)	C33—N31—N32—C1	175.2 (9)
O1—C3—C4—C6	95.5 (10)	Cd—N31—N32—C1	6.1 (11)
C6—C4—C5—C6^ii	2.7 (14)	N22—C1—N32—C31	109.1 (10)
C3—C4—C5—C6^ii	−177.7 (8)	N12—C1—N32—C31	−129.3 (9)
C6—C4—C5—C7	179.4 (8)	C2—C1—N32—C31	−8.1 (13)
C3—C4—C5—C7	−1.1 (13)	N22—C1—N32—N31	−65.0 (11)
C5—C4—C6—C5^ii	−2.9 (15)	N12—C1—N32—N31	56.7 (11)
C3—C4—C6—C5^ii	177.6 (8)	C2—C1—N32—N31	177.8 (8)
C6^ii—C5—C7—O2	71.7 (11)	C42—C43—N41—N42	−0.5 (10)
C4—C5—C7—O2	−104.9 (10)	C42—C43—N41—Cd^iii	−157.0 (6)
O2—C8—C9—N52	56.8 (10)	C42—C41—N42—N41	−1.0 (10)
O2—C8—C9—N62	175.6 (7)	C42—C41—N42—C9	−173.3 (8)
O2—C8—C9—N42	−66.4 (10)	C43—N41—N42—C41	0.8 (9)
N12—C11—C12—C13	−3.4 (11)	Cd^iii—N41—N42—C41	157.6 (6)
C11—C12—C13—N11	2.1 (12)	C43—N41—N42—C9	173.9 (8)
N22—C21—C22—C23	−2.6 (12)	Cd^iii—N41—N42—C9	−29.3 (10)
C21—C22—C23—N21	3.9 (13)	N52—C9—N42—C41	−120.2 (9)
N32—C31—C32—C33	0.7 (12)	N62—C9—N42—C41	121.4 (9)
C31—C32—C33—N31	−0.6 (13)	C8—C9—N42—C41	4.4 (12)
N42—C41—C42—C43	0.6 (11)	N52—C9—N42—N41	68.3 (9)
C41—C42—C43—N41	−0.1 (11)	N62—C9—N42—N41	−50.1 (10)
N52—C51—C52—C53	−2.2 (12)	C8—C9—N42—N41	−167.1 (7)
C51—C52—C53—N51	0.4 (12)	C52—C53—N51—N52	1.6 (11)
N62—C61—C62—C63	−2.2 (10)	C52—C53—N51—Cd^iii	178.3 (6)
C61—C62—C63—N61	0.4 (11)	C53—N51—N52—C51	−3.0 (10)
C12—C13—N11—N12	0.1 (11)	Cd^iii—N51—N52—C51	−179.7 (6)
C12—C13—N11—Cd	−168.1 (7)	C53—N51—N52—C9	−177.7 (8)
C13—N11—N12—C11	−2.2 (10)	Cd^iii—N51—N52—C9	5.6 (11)
Cd—N11—N12—C11	167.3 (6)	C52—C51—N52—N51	3.3 (11)
C13—N11—N12—C1	−173.9 (8)	C52—C51—N52—C9	177.7 (8)
Cd—N11—N12—C1	−4.4 (11)	N62—C9—N52—N51	63.8 (9)
C12—C11—N12—N11	3.6 (11)	N42—C9—N52—N51	−54.5 (10)
C12—C11—N12—C1	174.6 (9)	C8—C9—N52—N51	−178.4 (7)
N32—C1—N12—N11	−58.2 (10)	N62—C9—N52—C51	−110.0 (10)
N22—C1—N12—N11	63.9 (10)	N42—C9—N52—C51	131.7 (9)
C2—C1—N12—N11	−179.8 (8)	C8—C9—N52—C51	7.8 (13)
N32—C1—N12—C11	131.6 (9)	C62—C63—N61—N62	1.6 (10)
N22—C1—N12—C11	−106.3 (10)	C63—N61—N62—C61	−3.0 (9)
C2—C1—N12—C11	10.1 (12)	C63—N61—N62—C9	−162.1 (7)
C22—C23—N21—N22	−3.5 (11)	C62—C61—N62—N61	3.4 (10)
C22—C23—N21—Cd	165.0 (7)	C62—C61—N62—C9	160.8 (8)
C22—C21—N22—N21	0.5 (10)	N52—C9—N62—N61	−164.8 (7)
C22—C21—N22—C1	−176.6 (9)	N42—C9—N62—N61	−45.5 (9)
C23—N21—N22—C21	1.9 (10)	C8—C9—N62—N61	74.0 (9)
Cd—N21—N22—C21	−167.7 (6)	N52—C9—N62—C61	39.3 (11)
C23—N21—N22—C1	179.3 (8)	N42—C9—N62—C61	158.5 (8)
Cd—N21—N22—C1	9.7 (10)	C8—C9—N62—C61	−81.9 (10)
N32—C1—N22—C21	−127.8 (9)	C1—C2—O1—C3	177.9 (7)
N12—C1—N22—C21	110.2 (10)	C4—C3—O1—C2	−177.3 (8)
C2—C1—N22—C21	−8.2 (12)	C5—C7—O2—C8	177.0 (8)
N32—C1—N22—N21	55.3 (10)	C9—C8—O2—C7	179.0 (8)
N12—C1—N22—N21	−66.6 (10)	C91A—C92A—O3A—C93A	−102 (3)
C2—C1—N22—N21	175.0 (7)	C92A—O3A—C93A—C94A	−179 (2)
C32—C33—N31—N32	0.3 (12)	C91B—C92B—O3B—C93B	158 (4)
C32—C33—N31—Cd	167.7 (7)	C92B—O3B—C93B—C94B	172 (4)
C32—C31—N32—N31	−0.5 (11)

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