Crystal structure of the one-dimensional coordination polymer formed by the macrocyclic [Ni(cyclam)]2+ cation and the dianion of di-phenyl-silanediylbis(4-benzoic acid).

The asymmetric unit of the title compound, catena-poly[[[(1,4,8,11-tetra-aza-cyclo-tetra-decane-κ4 N 1,N 4,N 8,N 11)nickel(II)]-μ-4,4'-(di-phenyl-silanedi-yl)dibenz-o-ato-κ2 O:O'] sesquihydrate], {[Ni(C26H18O4Si)(C10H24N4)]·1.5H2O} n , consists of the halves of the centrosymmetric macrocyclic cation and the C 2-symmetric di-carboxyl-ate dianion and of the water mol-ecule of crystallization. The Ni2+ ion is coordinated by the four secondary N atoms of the macrocyclic ligand characterized by the most energetically favourable trans-III conformation and two mutually trans O atoms of the carboxyl-ate, forming a slightly tetra-gonally elongated trans-N4O2 octa-hedron. The crystals are composed of parallel polymeric chains of the macrocyclic cations linked by the anions of the acid running along the [101] direction. Each polymeric chain is bonded to four neighbouring ones via water mol-ecules providing O-H⋯O hydrogen bonds to the non-coordinated carboxyl O atoms to form a three-dimensional supra-molecular network. © Gavrish et al. 2020.

Chemical context

Aromatic carboxyl­ates are the most popular ligands employed as linkers joining n class="Chemical">metal-containing fragments (secondary building units, SBUs) in the construction of coordination polymers (Rao et al., 2004 ▸). This class of hybrid organic–inorganic materials possesses great potential for applications in gas storage, separation, catalysis, etc. (MacGillivray & Lukehart, 2014 ▸; Kaskel, 2016 ▸). At the same time, carboxyl­ate linkers containing a silicon core are still rare objects of investigation, although it is assumed that the presence of these heteroatoms may affect the topology and properties of the resulting coordination polymers, which are known to be rather sensitive to tiny structural variations in the constituting parts. Besides these structural aspects, carboxyl­ate ligands containing heteroatoms are of current inter­est as precursors for the preparation of structured heteroatom-doped carbonaceous materials possessing excellent electron conductivity, high porosity and diverse applications, including electrocatalysis and energy storage and conversion (Yang et al., 2019 ▸; Zhong et al., 2019 ▸).

Di­phenyl­silanediylbis(n class="Chemical">4-benzoic acid), a dicarboxylate possessing a characteristic bent shape, has been already utilized for the synthesis of coordination polymers with tetra­nuclear ZnII (Liu et al., 2009 ▸) and dinuclear ZnII and MnII (Turcan-Trofin et al., 2018 ▸) SBUs, as well as a copper(II) complex with 1,10-phenanthroline as co-ligand (Cazacu et al., 2014 ▸). However, no attempt has been made thus far to combine this linker with macrocyclic complexes, which provide pre-formed SBUs of another type (two vacant trans axial positions in the coordination sphere of the metal ion) with an additional benefit of extremely high thermodynamic stability and kinetic inertness (Melson, 1979 ▸; Yatsimirskii & Lampeka, 1985 ▸). At the same time, such SBUs have been used successfully for the assembly of a number of coordination polymers (Lampeka & Tsymbal, 2004 ▸; Suh & Moon, 2007 ▸; Suh et al., 2012 ▸; Stackhouse & Ma, 2018 ▸), including those with some other Si-containing carboxyl­ates (Gavrish et al., 2020a ▸; Gavrish et al., 2020b ▸).

As part of our research on such compounds, we report herein the synthesis and crystal structure of the coordination n class="Chemical">polymer built up from the nickel(II) complex of the 14-membered macrocyclic ligand 1,4,8,11-tetra­aza­cyclo­tetra­decane (cyclam, L), and the dianion of di­phenyl­silane­diylbis(4-benzoic acid) (H2A), viz., catena-poly[[[(1,4,8,11-tetra­aza­cyclo­tetra­decane-κ 4 N 1 N 4 N 8 N 11)nickel(II)]-μ-di­phen­yl­silanediylbis(4-benzoato)-κ 2 O:O′] sesquihydrate], [Ni(L)(A)·1.5H2O], (I).

Structural commentary

The mol­ecular structure of the title compound I is shown in Fig. 1 ▸. It represents a one-dimensional coordination n class="Chemical">polymer built of the centrosymmetric macrocyclic [Ni(L)]2+ cations coordinated in axial positions by the oxygen atoms of the carboxyl groups of the acid.

Figure 1

The extended asymmetric unit in I showing the coordination environment of the Ni atoms and the atom-labelling scheme (displacement ellipsoids are drawn at the 40% probability level). The atoms obtained by symmetry transformations are shown with 50% transparency. C-bound H atoms are omitted for clarity. Dashed lines represent hydrogen-bonding inter­actions. [Symmetry codes: (i) −x + , −y + , −z; (ii) −x + 1, y, −z + ].

The macrocyclic ligand in the complex cation adopts the most abundant energetically favourable trans-III (R,R,S,S) conformation (Bosnich et al., 1965 ▸) with almost equal Ni—n class="Chemical">N bond lengths (Table 1 ▸). The five-membered chelate rings are present in gauche and the six-membered in chair conformations. The geometric parameters observed are characteristic of high-spin nickel(II) complexes with 14-membered tetra­amine ligands (Lampeka & Tsymbal, 2004 ▸). The axial Ni—O bond lengths are somewhat longer than the Ni—N ones resulting in a slight tetra­gonal distortion of the trans-N4O2 nickel(II) coordination polyhedron. The location of the metal ion on the inversion centre enforces strict planarity of the equatorial Ni(N4) fragment.

Table 1

Selected bond lengths and angles (Å, °)

Distances		Bite angles
Ni1—N1	2.066 (3)	N1—Ni1—N2	86.05 (13)
Ni1—N2	2.068 (3)	N1—Ni1—N2i	93.95 (13)
Ni1—O1	2.128 (2)

Symmetry code: (i) −x + , −y + , −z.

The dianion of the acid in complex I possesses intrinn class="Chemical">sic twofold axial symmetry, with the Si atom lying on the rotation axis. An analogous C 2-symmetric conformation was found [Cambridge Structural Database (CSD, Version 5.40, last update February 2019; Groom et al., 2016 ▸)] for the mol­ecules/anions of the acid in the structures XOZVIT (Cazacu et al., 2014 ▸) and ZIGXEV (Turcan-Trofin et al., 2018 ▸). In two cases [XOZWAM (Cazacu et al., 2014 ▸) and ZIGXIZ (Turcan-Trofin et al., 2018 ▸)], the carboxyl­ate is present in an asymmetric conformation. At the same time, the coordination polymer XOQXIL (Liu et al., 2009 ▸) includes dianions of the acid in both C 2-symmetric and asymmetric conformations. All these data are summarized in Fig. 2 ▸, which clearly illustrates the capability of rotation of aromatic rings in the tetra­phenyl­silane moiety around the Si—Car­yl bonds by a wide range of angles. Another feature worth noting is that the symmetric and asymmetric species in fact refer to essentially different types with minor structural variations within each group, with the exception of anion XOQXIL-1.

Figure 2

Comparison of the conformations of di­phenyl­silanediylbis(4-benzoic acid) and its anions. (a) C2-symmetric structures. H: dark-green – XOZVIT; A: red – I (current work), blue – ZIGXEV-1, yellow – XOQXIL-1. (b) Asymmetric structures. HA: light-green – XOZWAM; A: lilac – ZIGXIZ-1, pink – ZIGXIZ-2, orange – XOQXIL-2. Numbers accompanying refcodes refer to two structurally non-equivalent anions in a given compound. The disordered symmetric anion in ZIGXEV-2 is not shown.

The carboxyl groups in I are coordinated in a monodentate fashion via the n class="Chemical">O1 atom. The non-coordinated O2 atom is involved as proton acceptor in strong hydrogen bonding with the NH group of the macrocycle (Fig. 1 ▸, Table 2 ▸), a situation that is frequently observed in carboxyl­ate complexes of cyclam-like ligands. Almost identical C—O bond lengths [C6—O1 = 1.254 (4) and C6—O2 = 1.260 (4) Å] support the model of essential electronic delocalization in the carboxyl­ate group. The carboxyl group is tilted with respect to the plane of benzene ring by 23.6 (2)°. In general, this angle is prone to large variations, e.g. for the structures presented in Fig. 2 ▸ it spans the range 4.1–30.1°.

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2	0.98	2.02	2.916 (4)	151
O1W—H1WA⋯O2i	0.85	2.05	2.850 (5)	156
O1W—H1WB⋯O2	0.85	1.89	2.744 (5)	177

Symmetry code: (i) .

Supra­molecular features

The crystals of I are composed of polymeric chains of n class="Chemical">[Ni(L)]2+ cations bridged by the carboxyl­ate ligands, which propagate along the [101] direction. These chains have a distinctive zigzag shape with a chain link length (Si⋯Si distance) of 17.854 (3) Å and an almost ideal tetra­hedral angle (Si⋯Si⋯Si) of 109.09 (2)°(Fig. 3 ▸). The nickel(II) cations in a chain are arranged in line with an Ni⋯Ni separation of 14.543 (2) Å.

Figure 3

The structure of the polymeric chain in I. C-bound H atoms are omitted for clarity.

In the crystal, each such chain is linked to four neighbouring ones due to formation of water-mediated n class="Chemical">hydrogen bonds between the non-coordinated O2 atoms of the carboxyl group: O2⋯HO1W—H⋯O2 (Table 2 ▸). In turn, each O2 atom is involved in hydrogen bonding with two H2O mol­ecules [symmetry codes: x, y, z; −x + , y − , −z + ], which in conjunction with the N1—H⋯O2 hydrogen bond makes it a triple proton acceptor, while the water mol­ecule serves as a proton donor only. Thus, the water mol­ecules of crystallization play a key role in assembling the one-dimensional polymeric chains into a three-dimensional supra­molecular network (Fig. 4 ▸).

Figure 4

The packing in I viewed down the [101] direction with polymeric chains cross-linked by O2⋯H—O1W—H⋯O2 hydrogen bonds (dotted lines) to form a three-dimensional supra­molecular network. C-bound H atoms are omitted for clarity.

Synthesis and crystallization

All chemicals and solvents used in this work were purchased from Sigma–Aldrich and were used without further purification. The macrocyclic n class="Chemical">nickel(II) complex Ni(L)(ClO4)2 (Barefield et al., 1976 ▸) and di­phenyl­silanediylbis(4-benzoic acid) (Cazacu et al., 2014 ▸) were prepared according to procedures described previously.

{Ni( )(A)·1.5H , (I). A solution of 100 mg (0.236 mmol) of n class="Chemical">the acid (H2A) in 24.5 ml of DMF containing 0.3 ml of tri­ethyl­amine was thoroughly layered on top of the solution of 120 mg (0.262 mmol) of [Ni(L)](ClO4)2 in 7.5 ml of water and the tightly closed system was left for two weeks at room temperature. The crystalline precipitate formed was filtered off, washed with DMF, methanol and dried in air. Yield 157 mg (94%). Analysis calculated for C72H90N8Ni2O11Si2: C, 61.03; H, 6.40; N, 7.91%. Found: C, 61.16; H, 6.36; N, 8.09%.

Single crystals of I in the form of light-yellow prisms suitable for X-ray diffraction analyn class="Chemical">sis were obtained analogously using ca 10 times lower concentration of reagents.

Safety note: Perchlorate salts of n class="Chemical">metal complexes are potentially explosive and should be handled with care.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3 ▸. All H atoms were placed in geometrically idealized pon class="Chemical">sitions and constrained to ride on their parent atoms, with C—H distances of 0.93 (ring H atoms) or 0.97 Å (open-chain H atoms), an N—H distance of 0.98 Å and an aqua O—H distance of 0.85 Å with U iso(H) values of 1.2 or 1.5U eq times that of the parent atoms. Since the water mol­ecule of crystallization at full occupancy exhibited unreasonably high displacement ellipsoids, its occupancy parameter was reduced to 75%.

Table 3

Experimental details

Crystal data
Chemical formula	[Ni(C26H18O4Si)(C10H24N4)]·1.5H2O
M r	1417.11
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	200
a, b, c (Å)	25.390 (4), 7.3865 (10), 18.2424 (16)
β (°)	98.161 (10)
V (Å3)	3386.6 (8)
Z	2
Radiation type	Mo Kα
μ (mm−1)	0.66
Crystal size (mm)	0.35 × 0.10 × 0.10
Data collection
Diffractometer	Agilent Xcalibur, Eos
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2014 ▸),
T min, T max	0.964, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	7999, 3926, 2512
R int	0.052
(sin θ/λ)max (Å−1)	0.693
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.066, 0.147, 1.03
No. of reflections	3926
No. of parameters	219
H-atom treatment	H-atom parameters constrained
Δρmax, Δρmin (e Å−3)	0.51, −0.51

Computer programs: CrysAlis PRO (Agilent, 2014 ▸), SHELXT (Sheldrick, 2015a ▸), SHELXL2018/3 (Sheldrick, 2015b ▸), OLEX2 (Dolomanov et al., 2009 ▸) and publCIF (Westrip, 2010 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020006544/hb7914sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989020006544/hb7914Isup2.hkl

CCDC reference: 2004084

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Ni(C26H18O4Si)(C10H24N4)]·1.5H2O	F(000) = 1500
Mr = 1417.11	Dx = 1.390 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 25.390 (4) Å	Cell parameters from 1577 reflections
b = 7.3865 (10) Å	θ = 2.6–29.5°
c = 18.2424 (16) Å	µ = 0.66 mm−1
β = 98.161 (10)°	T = 200 K
V = 3386.6 (8) Å3	Prism, clear light yellow
Z = 2	0.35 × 0.10 × 0.10 mm

Agilent Xcalibur, Eos diffractometer	3926 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2512 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.052
Detector resolution: 16.1593 pixels mm-1	θmax = 29.5°, θmin = 2.6°
ω scans	h = −31→21
Absorption correction: multi-scan (CrysAlisPro; Agilent, 2014),	k = −10→9
Tmin = 0.964, Tmax = 1.000	l = −21→23
7999 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.066	H-atom parameters constrained
wR(F2) = 0.147	w = 1/[σ2(Fo2) + (0.0427P)2 + 4.2041P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max < 0.001
3926 reflections	Δρmax = 0.51 e Å−3
219 parameters	Δρmin = −0.51 e Å−3
0 restraints

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ni1	0.250000	0.250000	0.000000	0.0273 (2)
Si1	0.500000	0.95105 (19)	0.250000	0.0256 (3)
O1	0.30989 (10)	0.3756 (4)	0.07669 (14)	0.0372 (7)
O2	0.27252 (11)	0.4301 (4)	0.17836 (15)	0.0514 (8)
N1	0.19897 (12)	0.2120 (5)	0.07732 (17)	0.0377 (8)
H1	0.214580	0.275668	0.122344	0.045*
N2	0.27921 (12)	−0.0047 (4)	0.03013 (18)	0.0381 (8)
H2	0.262042	−0.087426	−0.007954	0.046*
C1	0.20090 (17)	0.0146 (6)	0.0952 (2)	0.0464 (11)
H1A	0.177654	−0.051687	0.057721	0.056*
H1B	0.188941	−0.005714	0.142697	0.056*
C2	0.25790 (17)	−0.0508 (6)	0.0976 (2)	0.0480 (11)
H2A	0.279912	0.003615	0.139702	0.058*
H2B	0.259044	−0.181115	0.104319	0.058*
C3	0.33655 (17)	−0.0306 (6)	0.0316 (2)	0.0490 (12)
H3A	0.345186	−0.156556	0.042523	0.059*
H3B	0.355364	0.042076	0.071235	0.059*
C4	0.14439 (17)	0.4804 (6)	0.0397 (2)	0.0477 (11)
H4A	0.108246	0.524309	0.038067	0.057*
H4B	0.166204	0.543620	0.079585	0.057*
C5	0.14505 (15)	0.2795 (6)	0.0585 (2)	0.0435 (11)
H5A	0.125675	0.260021	0.100024	0.052*
H5B	0.127171	0.212343	0.016526	0.052*
C6	0.30912 (15)	0.4468 (5)	0.1389 (2)	0.0319 (9)
C7	0.35609 (14)	0.5657 (5)	0.16868 (18)	0.0247 (8)
C8	0.40442 (14)	0.5475 (5)	0.14241 (19)	0.0312 (9)
H8	0.408530	0.458487	0.107630	0.037*
C9	0.44678 (14)	0.6610 (5)	0.1675 (2)	0.0329 (9)
H9	0.479200	0.644164	0.150332	0.039*
C10	0.44174 (14)	0.8002 (5)	0.21810 (18)	0.0264 (8)
C11	0.39244 (14)	0.8183 (5)	0.24315 (18)	0.0296 (8)
H11	0.387380	0.911020	0.275947	0.035*
C12	0.35091 (14)	0.7001 (5)	0.21976 (19)	0.0309 (9)
H12	0.319013	0.711608	0.238874	0.037*
C13	0.51508 (14)	1.1037 (5)	0.1735 (2)	0.0285 (8)
C14	0.55319 (15)	1.2399 (5)	0.1896 (2)	0.0371 (9)
H14	0.571043	1.249604	0.237641	0.044*
C15	0.56512 (17)	1.3597 (6)	0.1370 (2)	0.0466 (11)
H15	0.590586	1.449113	0.149517	0.056*
C16	0.53943 (17)	1.3472 (6)	0.0658 (2)	0.0458 (11)
H16	0.547953	1.426763	0.029713	0.055*
C17	0.50098 (17)	1.2169 (6)	0.0477 (2)	0.0464 (11)
H17	0.483033	1.210014	−0.000366	0.056*
C18	0.48907 (15)	1.0964 (5)	0.1009 (2)	0.0361 (9)
H18	0.463175	1.008505	0.088027	0.043*
O1W	0.19429 (16)	0.6528 (6)	0.2165 (2)	0.0640 (12)	0.75
H1WA	0.205149	0.708674	0.256534	0.096*	0.75
H1WB	0.218579	0.582004	0.206074	0.096*	0.75

	U11	U22	U33	U12	U13	U23
Ni1	0.0236 (4)	0.0255 (4)	0.0312 (4)	−0.0020 (3)	−0.0015 (3)	−0.0022 (3)
Si1	0.0214 (7)	0.0242 (7)	0.0295 (7)	0.000	−0.0019 (6)	0.000
O1	0.0313 (15)	0.0442 (17)	0.0345 (14)	−0.0102 (13)	−0.0009 (11)	−0.0133 (14)
O2	0.0425 (19)	0.065 (2)	0.0492 (17)	−0.0234 (16)	0.0151 (14)	−0.0184 (16)
N1	0.0339 (19)	0.043 (2)	0.0352 (18)	−0.0042 (16)	0.0013 (14)	−0.0049 (16)
N2	0.035 (2)	0.0298 (18)	0.047 (2)	0.0013 (15)	−0.0039 (15)	0.0018 (17)
C1	0.046 (3)	0.039 (2)	0.054 (3)	−0.011 (2)	0.005 (2)	0.004 (2)
C2	0.052 (3)	0.041 (3)	0.051 (3)	0.008 (2)	0.006 (2)	0.016 (2)
C3	0.040 (3)	0.046 (3)	0.060 (3)	0.016 (2)	0.003 (2)	0.002 (2)
C4	0.037 (3)	0.050 (3)	0.053 (3)	0.004 (2)	−0.001 (2)	−0.004 (2)
C5	0.028 (2)	0.059 (3)	0.044 (2)	−0.002 (2)	0.0067 (18)	−0.009 (2)
C6	0.032 (2)	0.025 (2)	0.036 (2)	−0.0021 (17)	−0.0012 (17)	0.0018 (18)
C7	0.0252 (19)	0.0228 (18)	0.0245 (18)	−0.0011 (15)	−0.0023 (14)	0.0033 (16)
C8	0.033 (2)	0.028 (2)	0.031 (2)	0.0018 (17)	−0.0005 (16)	−0.0102 (17)
C9	0.021 (2)	0.033 (2)	0.043 (2)	−0.0005 (17)	0.0023 (16)	−0.0034 (19)
C10	0.0216 (19)	0.0271 (19)	0.0277 (18)	0.0005 (15)	−0.0060 (14)	0.0048 (16)
C11	0.030 (2)	0.034 (2)	0.0238 (18)	−0.0023 (17)	−0.0003 (15)	−0.0045 (17)
C12	0.0223 (19)	0.039 (2)	0.0311 (19)	−0.0028 (17)	0.0026 (15)	−0.0015 (18)
C13	0.024 (2)	0.0255 (19)	0.036 (2)	0.0017 (16)	0.0037 (15)	0.0035 (18)
C14	0.038 (2)	0.032 (2)	0.040 (2)	−0.0025 (19)	0.0004 (17)	0.002 (2)
C15	0.041 (3)	0.032 (2)	0.067 (3)	−0.005 (2)	0.008 (2)	0.004 (2)
C16	0.046 (3)	0.039 (3)	0.054 (3)	0.011 (2)	0.015 (2)	0.017 (2)
C17	0.049 (3)	0.053 (3)	0.036 (2)	0.010 (2)	0.0020 (19)	0.008 (2)
C18	0.028 (2)	0.038 (2)	0.040 (2)	−0.0006 (18)	−0.0031 (17)	0.003 (2)
O1W	0.050 (3)	0.070 (3)	0.072 (3)	0.000 (2)	0.009 (2)	−0.012 (3)

Ni1—O1i	2.128 (2)	C4—C5	1.523 (6)
Ni1—O1	2.128 (2)	C5—H5A	0.9700
Ni1—N1	2.066 (3)	C5—H5B	0.9700
Ni1—N1i	2.065 (3)	C6—C7	1.518 (5)
Ni1—N2i	2.068 (3)	C7—C8	1.386 (5)
Ni1—N2	2.068 (3)	C7—C12	1.381 (5)
Si1—C10ii	1.878 (4)	C8—H8	0.9300
Si1—C10	1.878 (4)	C8—C9	1.389 (5)
Si1—C13ii	1.875 (4)	C9—H9	0.9300
Si1—C13	1.875 (4)	C9—C10	1.399 (5)
O1—C6	1.254 (4)	C10—C11	1.399 (5)
O2—C6	1.260 (4)	C11—H11	0.9300
N1—H1	0.9800	C11—C12	1.389 (5)
N1—C1	1.493 (5)	C12—H12	0.9300
N1—C5	1.452 (5)	C13—C14	1.398 (5)
N2—H2	0.9800	C13—C18	1.395 (5)
N2—C2	1.455 (5)	C14—H14	0.9300
N2—C3	1.465 (5)	C14—C15	1.371 (5)
C1—H1A	0.9700	C15—H15	0.9300
C1—H1B	0.9700	C15—C16	1.372 (6)
C1—C2	1.520 (5)	C16—H16	0.9300
C2—H2A	0.9700	C16—C17	1.377 (6)
C2—H2B	0.9700	C17—H17	0.9300
C3—H3A	0.9700	C17—C18	1.382 (5)
C3—H3B	0.9700	C18—H18	0.9300
C3—C4i	1.497 (6)	O1W—H1WA	0.8499
C4—H4A	0.9700	O1W—H1WB	0.8504
C4—H4B	0.9700
O1—Ni1—O1i	180.0	C3i—C4—H4A	108.2
N1i—Ni1—O1i	93.98 (11)	C3i—C4—H4B	108.2
N1i—Ni1—O1	86.02 (11)	C3i—C4—C5	116.3 (4)
N1—Ni1—O1	93.98 (11)	H4A—C4—H4B	107.4
N1—Ni1—O1i	86.02 (11)	C5—C4—H4A	108.2
N1i—Ni1—N1	180.0	C5—C4—H4B	108.2
N1—Ni1—N2i	93.95 (13)	N1—C5—C4	111.6 (3)
N1—Ni1—N2	86.05 (13)	N1—C5—H5A	109.3
N1i—Ni1—N2	93.95 (13)	N1—C5—H5B	109.3
N1i—Ni1—N2i	86.05 (13)	C4—C5—H5A	109.3
N2—Ni1—O1i	88.51 (11)	C4—C5—H5B	109.3
N2—Ni1—O1	91.49 (11)	H5A—C5—H5B	108.0
N2i—Ni1—O1	88.51 (11)	O1—C6—O2	125.7 (3)
N2i—Ni1—O1i	91.49 (11)	O1—C6—C7	117.0 (3)
N2—Ni1—N2i	180.0	O2—C6—C7	117.3 (3)
C10—Si1—C10ii	107.2 (2)	C8—C7—C6	120.6 (3)
C13ii—Si1—C10ii	111.20 (15)	C12—C7—C6	120.8 (3)
C13—Si1—C10	111.20 (15)	C12—C7—C8	118.5 (3)
C13ii—Si1—C10	110.63 (16)	C7—C8—H8	119.7
C13—Si1—C10ii	110.63 (16)	C7—C8—C9	120.7 (3)
C13—Si1—C13ii	106.1 (2)	C9—C8—H8	119.7
C6—O1—Ni1	132.6 (2)	C8—C9—H9	119.3
Ni1—N1—H1	106.8	C8—C9—C10	121.4 (3)
C1—N1—Ni1	106.1 (2)	C10—C9—H9	119.3
C1—N1—H1	106.8	C9—C10—Si1	119.9 (3)
C5—N1—Ni1	117.0 (3)	C11—C10—Si1	123.0 (3)
C5—N1—H1	106.8	C11—C10—C9	117.1 (3)
C5—N1—C1	112.8 (3)	C10—C11—H11	119.5
Ni1—N2—H2	105.8	C12—C11—C10	121.0 (3)
C2—N2—Ni1	106.0 (2)	C12—C11—H11	119.5
C2—N2—H2	105.8	C7—C12—C11	121.2 (3)
C2—N2—C3	116.2 (3)	C7—C12—H12	119.4
C3—N2—Ni1	116.2 (3)	C11—C12—H12	119.4
C3—N2—H2	105.8	C14—C13—Si1	119.0 (3)
N1—C1—H1A	110.0	C18—C13—Si1	124.3 (3)
N1—C1—H1B	110.0	C18—C13—C14	116.6 (3)
N1—C1—C2	108.6 (3)	C13—C14—H14	118.9
H1A—C1—H1B	108.4	C15—C14—C13	122.2 (4)
C2—C1—H1A	110.0	C15—C14—H14	118.9
C2—C1—H1B	110.0	C14—C15—H15	120.1
N2—C2—C1	111.6 (3)	C14—C15—C16	119.8 (4)
N2—C2—H2A	109.3	C16—C15—H15	120.1
N2—C2—H2B	109.3	C15—C16—H16	120.0
C1—C2—H2A	109.3	C15—C16—C17	120.0 (4)
C1—C2—H2B	109.3	C17—C16—H16	120.0
H2A—C2—H2B	108.0	C16—C17—H17	120.0
N2—C3—H3A	108.9	C16—C17—C18	120.0 (4)
N2—C3—H3B	108.9	C18—C17—H17	120.0
N2—C3—C4i	113.2 (3)	C13—C18—H18	119.3
H3A—C3—H3B	107.7	C17—C18—C13	121.4 (4)
C4i—C3—H3A	108.9	C17—C18—H18	119.3
C4i—C3—H3B	108.9	H1WA—O1W—H1WB	109.5
Ni1—O1—C6—O2	14.6 (6)	C8—C9—C10—Si1	−179.6 (3)
Ni1—O1—C6—C7	−164.5 (2)	C8—C9—C10—C11	0.9 (5)
Ni1—N1—C1—C2	38.6 (4)	C9—C10—C11—C12	1.4 (5)
Ni1—N1—C5—C4	−55.8 (4)	C10ii—Si1—C10—C9	−51.0 (3)
Ni1—N2—C2—C1	38.2 (4)	C10ii—Si1—C10—C11	128.4 (3)
Ni1—N2—C3—C4i	−54.2 (4)	C10ii—Si1—C13—C14	−68.5 (3)
Si1—C10—C11—C12	−178.0 (3)	C10—Si1—C13—C14	172.6 (3)
Si1—C13—C14—C15	−178.1 (3)	C10ii—Si1—C13—C18	114.3 (3)
Si1—C13—C18—C17	177.9 (3)	C10—Si1—C13—C18	−4.6 (4)
O1—C6—C7—C8	−21.4 (5)	C10—C11—C12—C7	−2.8 (5)
O1—C6—C7—C12	155.4 (3)	C12—C7—C8—C9	0.6 (5)
O2—C6—C7—C8	159.4 (4)	C13ii—Si1—C10—C9	−172.4 (3)
O2—C6—C7—C12	−23.9 (5)	C13—Si1—C10—C9	70.0 (3)
N1—C1—C2—N2	−53.4 (4)	C13ii—Si1—C10—C11	7.0 (3)
C1—N1—C5—C4	−179.3 (3)	C13—Si1—C10—C11	−110.6 (3)
C2—N2—C3—C4i	180.0 (4)	C13ii—Si1—C13—C14	52.2 (3)
C3—N2—C2—C1	169.0 (3)	C13ii—Si1—C13—C18	−125.0 (4)
C3i—C4—C5—N1	70.1 (5)	C13—C14—C15—C16	−0.3 (6)
C5—N1—C1—C2	168.0 (3)	C14—C13—C18—C17	0.6 (6)
C6—C7—C8—C9	177.4 (3)	C14—C15—C16—C17	1.3 (6)
C6—C7—C12—C11	−175.1 (3)	C15—C16—C17—C18	−1.3 (6)
C7—C8—C9—C10	−2.0 (5)	C16—C17—C18—C13	0.3 (6)
C8—C7—C12—C11	1.8 (5)	C18—C13—C14—C15	−0.7 (6)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.98	2.02	2.916 (4)	151
O1W—H1WA···O2iii	0.85	2.05	2.850 (5)	156
O1W—H1WB···O2	0.85	1.89	2.744 (5)	177