A hybrid imidazolyl­idene/imidazolium nickel NHC complex: an isolated inter­mediate

Macrocyclic ligand systems with a variety of (different) donor sites oftentimes give rise to very exciting and unexpected multinuclear metal complexes. We report herein the structure of a trinuclear mixed imidazolyl­idene/imidazolium nickel N-heterocyclic carbene (NHC) complex, namely di-μ-chlorido-bis{μ-calix[2]imidazolium[2]imidazolylidene[2]pyrazolate}trinickel(II) tetrakis(hexafluoridophosphate) acetonitrile tetrasolvate, [Ni₃(C₂₄H₂₄N₁₂)₂Cl₂](PF₆)₄·4CH₃CN or [Ni₃(L^Me)₂Cl₂](PF₆)₄·4CH₃CN, that can be understood as a trapped reaction inter­mediate during the synthesis of the respective [Ni₂L^Me](PF₆)₂ product. The structure not only contains protonated next to deprotonated imidazole heterocycles, but also Ni²⁺ ions with fundamentally different coordination modes within one mol­ecule. Two of the three metal atoms are coordinated in a square-pyramidal fashion by half a ligand mol­ecule and one chloride ligand, whereas the third Ni²⁺ ion is bound octa­hedrally by four pyrazolate moieties and two chloride anions.

Computing details

Data collection: APEX3 (Bruker, 2015); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXT (Sheldrick, 2015); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015), SHELXLE (Hübschle et al., 2011); molecular graphics: PLATON (Spek, 2009), Mercury (Macrae et al., 2008); software used to prepare material for publication: PLATON (Spek, 2009), enCIFer (Allen et al., 2004).

Di-µ-chlorido-bis{µ-calix[2]imidazolium[2]imidazolylidene[2]pyrazolate}trinickel(II) tetrakis(hexafluoridophosphate) acetonitrile tetrasolvate

Crystal data

[Ni3(C24H24N12)2Cl2](PF6)4·4C2H3N	Z = 1
Mr = 1952.17	F(000) = 986
Triclinic, P1	Dx = 1.778 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 11.8775 (9) Å	Cell parameters from 9868 reflections
b = 13.3374 (9) Å	θ = 2.3–32.0°
c = 13.9741 (9) Å	µ = 1.05 mm^−1
α = 66.056 (3)°	T = 100 K
β = 73.926 (3)°	Fragment, clear yellow
γ = 65.297 (3)°	0.20 × 0.13 × 0.08 mm
V = 1822.7 (2) Å^3

Data collection

Bruker Photon CMOS diffractometer	9819 independent reflections
Radiation source: IMS microsource	7472 reflections with I > 2σ(I)
Helios optic monochromator	Rint = 0.061
Detector resolution: 16 pixels mm^-1	θmax = 29.1°, θmin = 2.3°
phi– and ω–rotation scans	h = −16→16
Absorption correction: multi-scan SADABS 2014/5, Bruker, 2014	k = −18→18
Tmin = 0.673, Tmax = 0.746	l = −19→19
51283 measured reflections

Refinement

Refinement on F^2	12 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.041	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.094	W = 1/[Σ^2(FO^2) + (0.0381P)^2 + 2.3353P] WHERE P = (FO^2 + 2FC^2)/3
S = 1.02	(Δ/σ)max < 0.001
9819 reflections	Δρmax = 1.67 e Å^−3
539 parameters	Δρmin = −0.77 e Å^−3

Special details

Experimental. Diffractometer operator Philipp J. Altmann scanspeed 60 s per frame dx 34 mm 6428 frames measured in 23 data sets phi-scans with delta_phi = 0.5 omega-scans with delta_omega = 0.5

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 on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > 2sigma(F²) is used only for calculating -R-factor-obs 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
Ni1	0.18222 (3)	0.27876 (2)	0.68985 (2)	0.00985 (7)
Ni2	0.0000	0.5000	0.5000	0.00856 (9)
Cl1	−0.04051 (5)	0.42980 (5)	0.69365 (4)	0.01104 (11)
N1	0.25435 (18)	0.39455 (17)	0.16855 (15)	0.0134 (4)
N2	0.09296 (18)	0.34947 (17)	0.26072 (15)	0.0124 (4)
N3	0.07904 (17)	0.32379 (16)	0.50325 (14)	0.0096 (4)
N4	0.14200 (17)	0.24252 (16)	0.58621 (14)	0.0107 (4)
N5	0.17948 (19)	0.04291 (17)	0.77712 (15)	0.0145 (4)
N6	0.12259 (18)	0.12316 (17)	0.89528 (15)	0.0139 (4)
N7	0.19490 (19)	0.25883 (17)	0.90073 (15)	0.0148 (4)
N8	0.33596 (19)	0.31899 (17)	0.78935 (16)	0.0145 (4)
N9	0.23851 (17)	0.40452 (16)	0.59363 (14)	0.0106 (4)
N10	0.17849 (17)	0.49036 (16)	0.51056 (14)	0.0098 (4)
N11	0.27539 (18)	0.63160 (17)	0.27492 (15)	0.0127 (4)
N12	0.34110 (18)	0.52256 (17)	0.17706 (15)	0.0133 (4)
C1	0.3689 (2)	0.4192 (2)	0.14945 (19)	0.0148 (5)
H1A	0.4042	0.4332	0.0741	0.018*
H1B	0.4314	0.3512	0.1926	0.018*
C2	0.2079 (2)	0.3379 (2)	0.26376 (19)	0.0129 (4)
C3	0.1633 (2)	0.4470 (2)	0.10200 (19)	0.0164 (5)
H3	0.1702	0.4941	0.0298	0.020*
C4	0.0632 (2)	0.4182 (2)	0.15988 (18)	0.0161 (5)
H4	−0.0140	0.4409	0.1357	0.019*
C5	0.0014 (2)	0.3201 (2)	0.35500 (17)	0.0129 (4)
H5A	−0.0314	0.2663	0.3485	0.015*
H5B	−0.0697	0.3923	0.3586	0.015*
C6	0.0612 (2)	0.2636 (2)	0.45378 (18)	0.0123 (4)
C7	0.1098 (2)	0.1443 (2)	0.50590 (19)	0.0151 (5)
H7	0.1092	0.0828	0.4884	0.018*
C8	0.1592 (2)	0.1350 (2)	0.58914 (19)	0.0146 (5)
C9	0.2220 (3)	0.0272 (2)	0.67348 (19)	0.0192 (5)
H9A	0.2035	−0.0394	0.6753	0.023*
H9B	0.3136	0.0085	0.6571	0.023*
C10	0.1554 (2)	0.1445 (2)	0.79008 (18)	0.0134 (4)
C11	0.1660 (2)	−0.0428 (2)	0.87331 (19)	0.0182 (5)
H11	0.1788	−0.1217	0.8843	0.022*
C12	0.1312 (2)	0.0077 (2)	0.9480 (2)	0.0178 (5)
H12	0.1156	−0.0287	1.0221	0.021*
C13	0.0920 (2)	0.2148 (2)	0.93958 (19)	0.0170 (5)
H13A	0.0131	0.2784	0.9169	0.020*
H13B	0.0817	0.1827	1.0177	0.020*
C14	0.2382 (2)	0.28962 (19)	0.79639 (18)	0.0135 (4)
C15	0.2678 (3)	0.2655 (2)	0.9583 (2)	0.0191 (5)
H15	0.2575	0.2466	1.0327	0.023*
C16	0.3560 (3)	0.3041 (2)	0.8881 (2)	0.0200 (5)
H16	0.4200	0.3185	0.9031	0.024*
C17	0.4114 (2)	0.3571 (2)	0.68931 (19)	0.0159 (5)
H17A	0.4747	0.2878	0.6718	0.019*
H17B	0.4561	0.4017	0.6960	0.019*
C18	0.3314 (2)	0.4322 (2)	0.60247 (18)	0.0119 (4)
C19	0.3354 (2)	0.5352 (2)	0.52378 (18)	0.0133 (4)
H19	0.3916	0.5744	0.5110	0.016*
C20	0.2386 (2)	0.56861 (19)	0.46741 (17)	0.0111 (4)
C21	0.2088 (2)	0.6697 (2)	0.36821 (17)	0.0129 (4)
H21A	0.1176	0.7020	0.3657	0.016*
H21B	0.2345	0.7320	0.3668	0.016*
C22	0.3116 (2)	0.5231 (2)	0.27621 (18)	0.0123 (4)
C23	0.2803 (2)	0.7043 (2)	0.17070 (19)	0.0184 (5)
H23	0.2589	0.7868	0.1467	0.022*
C24	0.3213 (2)	0.6360 (2)	0.10939 (19)	0.0181 (5)
H24	0.3340	0.6612	0.0344	0.022*
H2	0.248 (2)	0.298 (2)	0.322 (2)	0.010 (6)*
H22	0.316 (2)	0.459 (2)	0.336 (2)	0.015 (7)*
P1	0.80480 (7)	−0.00924 (6)	0.76308 (5)	0.02291 (15)
F1	0.88392 (16)	0.05572 (15)	0.77728 (14)	0.0315 (4)
F2	0.72555 (18)	−0.07490 (16)	0.75257 (15)	0.0378 (4)
F3	0.69023 (15)	0.11300 (13)	0.73112 (13)	0.0287 (4)
F4	0.8644 (2)	0.01359 (18)	0.64277 (14)	0.0434 (5)
F5	0.91719 (18)	−0.13127 (15)	0.79802 (15)	0.0410 (5)
F6	0.74400 (15)	−0.02860 (15)	0.88527 (12)	0.0299 (4)
P2	0.71199 (6)	0.35070 (6)	0.19854 (5)	0.01652 (13)
F7	0.77596 (15)	0.43748 (14)	0.19221 (15)	0.0308 (4)
F8	0.64811 (14)	0.26367 (14)	0.20333 (14)	0.0275 (4)
F9	0.82073 (15)	0.30684 (14)	0.11073 (13)	0.0292 (4)
F10	0.79073 (15)	0.24998 (14)	0.29032 (14)	0.0307 (4)
F11	0.60129 (15)	0.39598 (15)	0.28365 (13)	0.0292 (4)
F12	0.63129 (14)	0.45153 (14)	0.10512 (12)	0.0256 (3)
N13	0.4955 (2)	−0.2079 (2)	0.9165 (2)	0.0289 (5)
C25	0.4749 (3)	−0.1115 (2)	0.8972 (2)	0.0239 (6)
C26	0.4477 (3)	0.0122 (3)	0.8749 (3)	0.0360 (7)
H26A	0.5248	0.0250	0.8702	0.054*
H26B	0.3868	0.0373	0.9317	0.054*
H26C	0.4130	0.0577	0.8078	0.054*
N14	0.4185 (3)	0.2205 (3)	0.4152 (2)	0.0551 (8)
C27	0.5005 (3)	0.1757 (4)	0.4612 (3)	0.0503 (8)
C28	0.6071 (4)	0.1257 (4)	0.5191 (3)	0.0611 (9)
H28A	0.6487	0.0426	0.5263	0.092*
H28B	0.5781	0.1336	0.5894	0.092*
H28C	0.6661	0.1671	0.4806	0.092*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.01309 (14)	0.00777 (14)	0.00867 (13)	−0.00374 (11)	−0.00414 (10)	−0.00081 (11)
Ni2	0.00964 (19)	0.00759 (19)	0.00830 (18)	−0.00324 (15)	−0.00262 (14)	−0.00133 (15)
Cl1	0.0112 (2)	0.0110 (2)	0.0101 (2)	−0.00318 (19)	−0.00209 (19)	−0.0030 (2)
N1	0.0128 (9)	0.0129 (9)	0.0144 (9)	−0.0035 (8)	−0.0003 (7)	−0.0064 (8)
N2	0.0141 (9)	0.0126 (9)	0.0120 (9)	−0.0044 (8)	−0.0010 (7)	−0.0061 (8)
N3	0.0110 (9)	0.0092 (9)	0.0076 (8)	−0.0026 (7)	−0.0028 (7)	−0.0016 (7)
N4	0.0118 (9)	0.0087 (9)	0.0098 (9)	−0.0022 (7)	−0.0040 (7)	−0.0010 (7)
N5	0.0195 (10)	0.0102 (9)	0.0128 (9)	−0.0053 (8)	−0.0050 (8)	−0.0007 (8)
N6	0.0170 (10)	0.0105 (9)	0.0108 (9)	−0.0040 (8)	−0.0040 (7)	0.0004 (8)
N7	0.0203 (10)	0.0117 (9)	0.0106 (9)	−0.0034 (8)	−0.0059 (8)	−0.0018 (8)
N8	0.0202 (10)	0.0113 (9)	0.0135 (9)	−0.0056 (8)	−0.0096 (8)	−0.0007 (8)
N9	0.0126 (9)	0.0091 (9)	0.0098 (9)	−0.0030 (7)	−0.0048 (7)	−0.0015 (7)
N10	0.0110 (9)	0.0087 (9)	0.0081 (8)	−0.0024 (7)	−0.0020 (7)	−0.0017 (7)
N11	0.0144 (9)	0.0126 (9)	0.0102 (9)	−0.0058 (8)	−0.0019 (7)	−0.0015 (8)
N12	0.0117 (9)	0.0156 (10)	0.0125 (9)	−0.0057 (8)	−0.0001 (7)	−0.0043 (8)
C1	0.0110 (11)	0.0171 (12)	0.0174 (11)	−0.0047 (9)	0.0019 (9)	−0.0094 (10)
C2	0.0138 (11)	0.0117 (11)	0.0134 (11)	−0.0031 (9)	−0.0025 (9)	−0.0052 (9)
C3	0.0183 (12)	0.0218 (12)	0.0109 (11)	−0.0080 (10)	−0.0024 (9)	−0.0058 (10)
C4	0.0179 (12)	0.0217 (12)	0.0113 (11)	−0.0080 (10)	−0.0030 (9)	−0.0059 (10)
C5	0.0141 (11)	0.0166 (11)	0.0107 (10)	−0.0086 (9)	−0.0008 (8)	−0.0044 (9)
C6	0.0132 (11)	0.0141 (11)	0.0111 (10)	−0.0072 (9)	−0.0001 (8)	−0.0042 (9)
C7	0.0210 (12)	0.0131 (11)	0.0156 (11)	−0.0086 (9)	−0.0022 (9)	−0.0063 (9)
C8	0.0191 (12)	0.0099 (11)	0.0144 (11)	−0.0055 (9)	−0.0024 (9)	−0.0029 (9)
C9	0.0296 (14)	0.0114 (11)	0.0166 (12)	−0.0049 (10)	−0.0074 (10)	−0.0040 (10)
C10	0.0137 (11)	0.0110 (11)	0.0144 (11)	−0.0035 (9)	−0.0053 (9)	−0.0017 (9)
C11	0.0223 (12)	0.0095 (11)	0.0177 (12)	−0.0063 (10)	−0.0065 (10)	0.0038 (9)
C12	0.0187 (12)	0.0150 (12)	0.0159 (11)	−0.0074 (10)	−0.0050 (9)	0.0019 (9)
C13	0.0201 (12)	0.0147 (11)	0.0130 (11)	−0.0035 (10)	−0.0037 (9)	−0.0033 (9)
C14	0.0172 (11)	0.0070 (10)	0.0136 (11)	−0.0005 (9)	−0.0070 (9)	−0.0015 (9)
C15	0.0327 (14)	0.0127 (11)	0.0144 (11)	−0.0062 (10)	−0.0114 (10)	−0.0033 (9)
C16	0.0325 (14)	0.0133 (12)	0.0182 (12)	−0.0073 (10)	−0.0164 (11)	−0.0012 (10)
C17	0.0142 (11)	0.0163 (12)	0.0172 (12)	−0.0057 (9)	−0.0068 (9)	−0.0019 (10)
C18	0.0100 (10)	0.0128 (11)	0.0138 (11)	−0.0028 (8)	−0.0034 (8)	−0.0054 (9)
C19	0.0128 (11)	0.0130 (11)	0.0145 (11)	−0.0060 (9)	−0.0033 (9)	−0.0025 (9)
C20	0.0127 (10)	0.0108 (10)	0.0109 (10)	−0.0046 (8)	−0.0010 (8)	−0.0043 (9)
C21	0.0156 (11)	0.0127 (11)	0.0111 (10)	−0.0067 (9)	−0.0008 (9)	−0.0034 (9)
C22	0.0106 (10)	0.0133 (11)	0.0123 (11)	−0.0044 (9)	−0.0008 (8)	−0.0038 (9)
C23	0.0249 (13)	0.0164 (12)	0.0119 (11)	−0.0099 (10)	−0.0040 (9)	0.0010 (9)
C24	0.0217 (12)	0.0193 (12)	0.0122 (11)	−0.0098 (10)	−0.0022 (9)	−0.0012 (10)
P1	0.0367 (4)	0.0157 (3)	0.0175 (3)	−0.0094 (3)	−0.0092 (3)	−0.0027 (3)
F1	0.0342 (9)	0.0317 (9)	0.0373 (10)	−0.0121 (8)	−0.0119 (8)	−0.0142 (8)
F2	0.0467 (11)	0.0312 (10)	0.0490 (11)	−0.0215 (8)	−0.0083 (9)	−0.0165 (9)
F3	0.0321 (9)	0.0175 (8)	0.0331 (9)	−0.0090 (7)	−0.0149 (7)	0.0021 (7)
F4	0.0637 (13)	0.0552 (13)	0.0200 (9)	−0.0312 (11)	−0.0007 (8)	−0.0131 (9)
F5	0.0466 (11)	0.0230 (9)	0.0413 (11)	0.0023 (8)	−0.0068 (9)	−0.0134 (8)
F6	0.0306 (9)	0.0313 (9)	0.0177 (8)	−0.0069 (7)	−0.0042 (7)	−0.0018 (7)
P2	0.0147 (3)	0.0152 (3)	0.0211 (3)	−0.0047 (2)	−0.0062 (2)	−0.0054 (3)
F7	0.0246 (8)	0.0186 (8)	0.0545 (11)	−0.0081 (7)	−0.0145 (8)	−0.0104 (8)
F8	0.0229 (8)	0.0231 (8)	0.0436 (10)	−0.0100 (7)	−0.0084 (7)	−0.0131 (8)
F9	0.0221 (8)	0.0272 (9)	0.0308 (9)	−0.0050 (7)	0.0042 (7)	−0.0112 (7)
F10	0.0308 (9)	0.0224 (8)	0.0363 (10)	−0.0044 (7)	−0.0197 (7)	−0.0021 (7)
F11	0.0261 (8)	0.0325 (9)	0.0294 (9)	−0.0053 (7)	−0.0017 (7)	−0.0170 (8)
F12	0.0247 (8)	0.0224 (8)	0.0220 (8)	−0.0035 (7)	−0.0106 (6)	0.0002 (6)
N13	0.0326 (13)	0.0243 (13)	0.0325 (13)	−0.0062 (10)	−0.0128 (11)	−0.0100 (11)
C25	0.0228 (13)	0.0228 (14)	0.0266 (14)	−0.0046 (11)	−0.0102 (11)	−0.0077 (12)
C26	0.0252 (15)	0.0189 (14)	0.059 (2)	−0.0036 (12)	−0.0078 (14)	−0.0111 (14)
N14	0.0364 (14)	0.0775 (19)	0.0378 (14)	−0.0161 (13)	−0.0158 (11)	−0.0030 (14)
C27	0.0385 (14)	0.0704 (17)	0.0355 (13)	−0.0061 (13)	−0.0142 (11)	−0.0187 (13)
C28	0.0464 (17)	0.080 (2)	0.0433 (16)	0.0062 (16)	−0.0205 (14)	−0.0269 (16)

Geometric parameters (Å, º)

Ni1—C10	1.861 (2)	C6—C7	1.386 (3)
Ni1—C14	1.866 (2)	C7—C8	1.383 (3)
Ni1—N9	1.9176 (19)	C7—H7	0.9500
Ni1—N4	1.9245 (19)	C8—C9	1.492 (3)
Ni1—Cl1	2.5718 (6)	C9—H9A	0.9900
Ni2—N10^i	2.1126 (18)	C9—H9B	0.9900
Ni2—N10	2.1126 (18)	C11—C12	1.346 (4)
Ni2—N3^i	2.1213 (18)	C11—H11	0.9500
Ni2—N3	2.1213 (18)	C12—H12	0.9500
Ni2—Cl1	2.4556 (5)	C13—H13A	0.9900
Ni2—Cl1^i	2.4556 (5)	C13—H13B	0.9900
N1—C2	1.331 (3)	C15—C16	1.340 (4)
N1—C3	1.386 (3)	C15—H15	0.9500
N1—C1	1.460 (3)	C16—H16	0.9500
N2—C2	1.319 (3)	C17—C18	1.496 (3)
N2—C4	1.381 (3)	C17—H17A	0.9900
N2—C5	1.488 (3)	C17—H17B	0.9900
N3—C6	1.356 (3)	C18—C19	1.377 (3)
N3—N4	1.364 (2)	C19—C20	1.389 (3)
N4—C8	1.347 (3)	C19—H19	0.9500
N5—C10	1.341 (3)	C20—C21	1.490 (3)
N5—C11	1.388 (3)	C21—H21A	0.9900
N5—C9	1.466 (3)	C21—H21B	0.9900
N6—C10	1.353 (3)	C22—H22	0.92 (3)
N6—C12	1.384 (3)	C23—C24	1.354 (4)
N6—C13	1.458 (3)	C23—H23	0.9500
N7—C14	1.354 (3)	C24—H24	0.9500
N7—C15	1.384 (3)	P1—F4	1.5895 (19)
N7—C13	1.452 (3)	P1—F2	1.5951 (18)
N8—C14	1.341 (3)	P1—F5	1.6030 (19)
N8—C16	1.385 (3)	P1—F1	1.6114 (17)
N8—C17	1.458 (3)	P1—F3	1.6126 (17)
N9—C18	1.350 (3)	P1—F6	1.6184 (17)
N9—N10	1.365 (2)	P2—F7	1.5936 (16)
N10—C20	1.355 (3)	P2—F10	1.5937 (17)
N11—C22	1.320 (3)	P2—F11	1.6005 (17)
N11—C23	1.385 (3)	P2—F8	1.6038 (16)
N11—C21	1.488 (3)	P2—F9	1.6092 (17)
N12—C22	1.334 (3)	P2—F12	1.6193 (16)
N12—C24	1.379 (3)	N13—C25	1.131 (4)
N12—C1	1.463 (3)	C25—C26	1.455 (4)
C1—H1A	0.9900	C26—H26A	0.9800
C1—H1B	0.9900	C26—H26B	0.9800
C2—H2	0.91 (3)	C26—H26C	0.9800
C3—C4	1.347 (3)	N14—C27	1.125 (4)
C3—H3	0.9500	C27—C28	1.458 (5)
C4—H4	0.9500	C28—H28A	0.9800
C5—C6	1.493 (3)	C28—H28B	0.9800
C5—H5A	0.9900	C28—H28C	0.9800
C5—H5B	0.9900
C10—Ni1—C14	86.29 (10)	N5—C10—N6	104.57 (19)
C10—Ni1—N9	170.02 (9)	N5—C10—Ni1	128.00 (18)
C14—Ni1—N9	87.53 (9)	N6—C10—Ni1	126.93 (18)
C10—Ni1—N4	87.91 (9)	C12—C11—N5	106.6 (2)
C14—Ni1—N4	171.02 (9)	C12—C11—H11	126.7
N9—Ni1—N4	97.24 (8)	N5—C11—H11	126.7
C10—Ni1—Cl1	100.88 (7)	C11—C12—N6	106.2 (2)
C14—Ni1—Cl1	100.19 (7)	C11—C12—H12	126.9
N9—Ni1—Cl1	87.92 (6)	N6—C12—H12	126.9
N4—Ni1—Cl1	87.63 (6)	N7—C13—N6	106.87 (19)
N10^i—Ni2—N10	180.00 (10)	N7—C13—H13A	110.3
N10^i—Ni2—N3^i	88.87 (7)	N6—C13—H13A	110.3
N10—Ni2—N3^i	91.13 (7)	N7—C13—H13B	110.3
N10^i—Ni2—N3	91.13 (7)	N6—C13—H13B	110.3
N10—Ni2—N3	88.87 (7)	H13A—C13—H13B	108.6
N3^i—Ni2—N3	180.00 (10)	N8—C14—N7	104.5 (2)
N10^i—Ni2—Cl1	90.74 (5)	N8—C14—Ni1	128.36 (18)
N10—Ni2—Cl1	89.26 (5)	N7—C14—Ni1	126.92 (18)
N3^i—Ni2—Cl1	90.83 (5)	C16—C15—N7	106.3 (2)
N3—Ni2—Cl1	89.17 (5)	C16—C15—H15	126.9
N10^i—Ni2—Cl1^i	89.26 (5)	N7—C15—H15	126.9
N10—Ni2—Cl1^i	90.74 (5)	C15—C16—N8	106.9 (2)
N3^i—Ni2—Cl1^i	89.17 (5)	C15—C16—H16	126.5
N3—Ni2—Cl1^i	90.83 (5)	N8—C16—H16	126.5
Cl1—Ni2—Cl1^i	180.0	N8—C17—C18	110.79 (19)
Ni2—Cl1—Ni1	86.701 (18)	N8—C17—H17A	109.5
C2—N1—C3	108.40 (19)	C18—C17—H17A	109.5
C2—N1—C1	123.0 (2)	N8—C17—H17B	109.5
C3—N1—C1	126.9 (2)	C18—C17—H17B	109.5
C2—N2—C4	108.3 (2)	H17A—C17—H17B	108.1
C2—N2—C5	124.97 (19)	N9—C18—C19	109.94 (19)
C4—N2—C5	125.05 (19)	N9—C18—C17	121.3 (2)
C6—N3—N4	106.63 (18)	C19—C18—C17	128.8 (2)
C6—N3—Ni2	134.34 (15)	C18—C19—C20	104.4 (2)
N4—N3—Ni2	117.30 (13)	C18—C19—H19	127.8
C8—N4—N3	108.90 (18)	C20—C19—H19	127.8
C8—N4—Ni1	126.18 (15)	N10—C20—C19	110.4 (2)
N3—N4—Ni1	124.60 (14)	N10—C20—C21	123.21 (19)
C10—N5—C11	111.2 (2)	C19—C20—C21	126.2 (2)
C10—N5—C9	122.3 (2)	N11—C21—C20	110.05 (18)
C11—N5—C9	126.3 (2)	N11—C21—H21A	109.7
C10—N6—C12	111.3 (2)	C20—C21—H21A	109.7
C10—N6—C13	120.13 (19)	N11—C21—H21B	109.7
C12—N6—C13	128.5 (2)	C20—C21—H21B	109.7
C14—N7—C15	111.2 (2)	H21A—C21—H21B	108.2
C14—N7—C13	120.2 (2)	N11—C22—N12	109.0 (2)
C15—N7—C13	128.4 (2)	N11—C22—H22	124.8 (17)
C14—N8—C16	111.1 (2)	N12—C22—H22	126.2 (17)
C14—N8—C17	122.66 (19)	C24—C23—N11	107.3 (2)
C16—N8—C17	126.2 (2)	C24—C23—H23	126.3
C18—N9—N10	108.49 (18)	N11—C23—H23	126.3
C18—N9—Ni1	127.13 (15)	C23—C24—N12	106.6 (2)
N10—N9—Ni1	123.91 (14)	C23—C24—H24	126.7
C20—N10—N9	106.79 (17)	N12—C24—H24	126.7
C20—N10—Ni2	132.83 (15)	F4—P1—F2	91.74 (11)
N9—N10—Ni2	118.10 (14)	F4—P1—F5	90.84 (11)
C22—N11—C23	108.4 (2)	F2—P1—F5	90.21 (11)
C22—N11—C21	123.80 (19)	F4—P1—F1	89.84 (10)
C23—N11—C21	125.9 (2)	F2—P1—F1	178.38 (11)
C22—N12—C24	108.7 (2)	F5—P1—F1	89.41 (10)
C22—N12—C1	123.2 (2)	F4—P1—F3	90.65 (11)
C24—N12—C1	127.3 (2)	F2—P1—F3	89.81 (10)
N1—C1—N12	109.47 (18)	F5—P1—F3	178.50 (11)
N1—C1—H1A	109.8	F1—P1—F3	90.53 (9)
N12—C1—H1A	109.8	F4—P1—F6	178.24 (11)
N1—C1—H1B	109.8	F2—P1—F6	89.69 (10)
N12—C1—H1B	109.8	F5—P1—F6	90.18 (10)
H1A—C1—H1B	108.2	F1—P1—F6	88.73 (10)
N2—C2—N1	109.1 (2)	F3—P1—F6	88.32 (9)
N2—C2—H2	124.9 (16)	F7—P2—F10	90.77 (9)
N1—C2—H2	125.9 (16)	F7—P2—F11	90.67 (10)
C4—C3—N1	106.5 (2)	F10—P2—F11	90.77 (9)
C4—C3—H3	126.8	F7—P2—F8	179.28 (10)
N1—C3—H3	126.8	F10—P2—F8	89.66 (9)
C3—C4—N2	107.7 (2)	F11—P2—F8	89.90 (9)
C3—C4—H4	126.2	F7—P2—F9	89.85 (10)
N2—C4—H4	126.2	F10—P2—F9	90.64 (9)
N2—C5—C6	110.78 (18)	F11—P2—F9	178.49 (9)
N2—C5—H5A	109.5	F8—P2—F9	89.56 (9)
C6—C5—H5A	109.5	F7—P2—F12	90.12 (9)
N2—C5—H5B	109.5	F10—P2—F12	179.09 (9)
C6—C5—H5B	109.5	F11—P2—F12	89.39 (9)
H5A—C5—H5B	108.1	F8—P2—F12	89.44 (9)
N3—C6—C7	110.4 (2)	F9—P2—F12	89.20 (9)
N3—C6—C5	123.8 (2)	N13—C25—C26	178.8 (3)
C7—C6—C5	125.7 (2)	C25—C26—H26A	109.5
C8—C7—C6	104.5 (2)	C25—C26—H26B	109.5
C8—C7—H7	127.8	H26A—C26—H26B	109.5
C6—C7—H7	127.8	C25—C26—H26C	109.5
N4—C8—C7	109.5 (2)	H26A—C26—H26C	109.5
N4—C8—C9	121.7 (2)	H26B—C26—H26C	109.5
C7—C8—C9	128.7 (2)	N14—C27—C28	176.0 (5)
N5—C9—C8	111.1 (2)	C27—C28—H28A	109.5
N5—C9—H9A	109.4	C27—C28—H28B	109.5
C8—C9—H9A	109.4	H28A—C28—H28B	109.5
N5—C9—H9B	109.4	C27—C28—H28C	109.5
C8—C9—H9B	109.4	H28A—C28—H28C	109.5
H9A—C9—H9B	108.0	H28B—C28—H28C	109.5
C6—N3—N4—C8	−1.7 (2)	C9—N5—C11—C12	176.9 (2)
Ni2—N3—N4—C8	165.49 (15)	N5—C11—C12—N6	0.9 (3)
C6—N3—N4—Ni1	−175.50 (15)	C10—N6—C12—C11	−2.1 (3)
Ni2—N3—N4—Ni1	−8.3 (2)	C13—N6—C12—C11	−178.0 (2)
C18—N9—N10—C20	1.7 (2)	C14—N7—C13—N6	49.5 (3)
Ni1—N9—N10—C20	174.35 (15)	C15—N7—C13—N6	−124.0 (2)
C18—N9—N10—Ni2	−163.28 (14)	C10—N6—C13—N7	−52.0 (3)
Ni1—N9—N10—Ni2	9.3 (2)	C12—N6—C13—N7	123.5 (2)
C2—N1—C1—N12	−81.1 (3)	C16—N8—C14—N7	1.5 (3)
C3—N1—C1—N12	82.2 (3)	C17—N8—C14—N7	179.4 (2)
C22—N12—C1—N1	70.5 (3)	C16—N8—C14—Ni1	−173.07 (17)
C24—N12—C1—N1	−98.4 (3)	C17—N8—C14—Ni1	4.8 (3)
C4—N2—C2—N1	−1.1 (3)	C15—N7—C14—N8	−1.9 (3)
C5—N2—C2—N1	−166.8 (2)	C13—N7—C14—N8	−176.4 (2)
C3—N1—C2—N2	1.3 (3)	C15—N7—C14—Ni1	172.79 (17)
C1—N1—C2—N2	167.3 (2)	C13—N7—C14—Ni1	−1.8 (3)
C2—N1—C3—C4	−1.1 (3)	C10—Ni1—C14—N8	139.2 (2)
C1—N1—C3—C4	−166.3 (2)	N9—Ni1—C14—N8	−33.0 (2)
N1—C3—C4—N2	0.4 (3)	Cl1—Ni1—C14—N8	−120.4 (2)
C2—N2—C4—C3	0.4 (3)	C10—Ni1—C14—N7	−34.3 (2)
C5—N2—C4—C3	166.1 (2)	N9—Ni1—C14—N7	153.6 (2)
C2—N2—C5—C6	−6.0 (3)	Cl1—Ni1—C14—N7	66.1 (2)
C4—N2—C5—C6	−169.3 (2)	C14—N7—C15—C16	1.6 (3)
N4—N3—C6—C7	1.4 (2)	C13—N7—C15—C16	175.6 (2)
Ni2—N3—C6—C7	−162.60 (17)	N7—C15—C16—N8	−0.6 (3)
N4—N3—C6—C5	−176.6 (2)	C14—N8—C16—C15	−0.6 (3)
Ni2—N3—C6—C5	19.4 (3)	C17—N8—C16—C15	−178.4 (2)
N2—C5—C6—N3	81.1 (3)	C14—N8—C17—C18	38.0 (3)
N2—C5—C6—C7	−96.7 (3)	C16—N8—C17—C18	−144.4 (2)
N3—C6—C7—C8	−0.6 (3)	N10—N9—C18—C19	−1.4 (3)
C5—C6—C7—C8	177.4 (2)	Ni1—N9—C18—C19	−173.75 (16)
N3—N4—C8—C7	1.4 (3)	N10—N9—C18—C17	177.6 (2)
Ni1—N4—C8—C7	175.06 (16)	Ni1—N9—C18—C17	5.3 (3)
N3—N4—C8—C9	−178.0 (2)	N8—C17—C18—N9	−42.5 (3)
Ni1—N4—C8—C9	−4.3 (3)	N8—C17—C18—C19	136.3 (2)
C6—C7—C8—N4	−0.5 (3)	N9—C18—C19—C20	0.5 (3)
C6—C7—C8—C9	178.9 (2)	C17—C18—C19—C20	−178.4 (2)
C10—N5—C9—C8	−37.5 (3)	N9—N10—C20—C19	−1.4 (2)
C11—N5—C9—C8	146.6 (2)	Ni2—N10—C20—C19	160.46 (16)
N4—C8—C9—N5	42.2 (3)	N9—N10—C20—C21	173.9 (2)
C7—C8—C9—N5	−137.1 (3)	Ni2—N10—C20—C21	−24.2 (3)
C11—N5—C10—N6	−1.9 (3)	C18—C19—C20—N10	0.6 (3)
C9—N5—C10—N6	−178.4 (2)	C18—C19—C20—C21	−174.6 (2)
C11—N5—C10—Ni1	170.33 (18)	C22—N11—C21—C20	25.2 (3)
C9—N5—C10—Ni1	−6.1 (3)	C23—N11—C21—C20	−172.6 (2)
C12—N6—C10—N5	2.5 (3)	N10—C20—C21—N11	−83.4 (3)
C13—N6—C10—N5	178.7 (2)	C19—C20—C21—N11	91.2 (3)
C12—N6—C10—Ni1	−169.87 (17)	C23—N11—C22—N12	0.7 (3)
C13—N6—C10—Ni1	6.3 (3)	C21—N11—C22—N12	165.59 (19)
C14—Ni1—C10—N5	−138.8 (2)	C24—N12—C22—N11	−0.8 (3)
N4—Ni1—C10—N5	34.4 (2)	C1—N12—C22—N11	−171.56 (19)
Cl1—Ni1—C10—N5	121.6 (2)	C22—N11—C23—C24	−0.3 (3)
C14—Ni1—C10—N6	31.8 (2)	C21—N11—C23—C24	−164.8 (2)
N4—Ni1—C10—N6	−155.0 (2)	N11—C23—C24—N12	−0.2 (3)
Cl1—Ni1—C10—N6	−67.8 (2)	C22—N12—C24—C23	0.6 (3)
C10—N5—C11—C12	0.7 (3)	C1—N12—C24—C23	170.9 (2)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···F12^ii	0.99	2.39	3.263 (3)	146
C1—H1B···F8	0.99	2.36	3.199 (3)	142
C4—H4···F7^iii	0.95	2.41	3.227 (3)	144
C5—H5B···N10^i	0.99	2.61	3.407 (3)	138
C7—H7···F4^iv	0.95	2.52	3.392 (3)	152
C11—H11···F9^iv	0.95	2.44	3.375 (3)	168
C13—H13B···F5^v	0.99	2.38	3.356 (3)	167
C13—H13B···F6^v	0.99	2.47	3.101 (3)	122
C16—H16···N13^v	0.95	2.59	3.186 (3)	122
C21—H21A···Cl1^i	0.99	2.75	3.257 (2)	112
C21—H21A···N3^i	0.99	2.59	3.376 (3)	136
C21—H21B···F3^vi	0.99	2.35	3.238 (3)	149
C23—H23···F1^vi	0.95	2.50	3.235 (3)	134
C2—H2···N14	0.91 (3)	2.34 (3)	3.188 (4)	155 (2)
C22—H22···N10	0.92 (3)	2.62 (3)	3.156 (3)	119 (2)
C26—H26A···F6	0.98	2.44	3.365 (4)	157
C28—H28B···F3	0.98	2.55	3.295 (4)	133

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