Bis{2,6-bis­[(E)-(4-fluoro­benzyl­imino)­meth­yl]pyridine}­nickel(II) dinitrate dihydrate

In the title hydrated salt, [Ni(C₂₁H₁₇F₂N₃)₂](NO₃)₂·2H₂O, the central Ni^II ion is coordinated by six N atoms from two tridentate chelating 2,6-bis­[(E)-(4-fluoro­benzyl­imino)­meth­yl]pyridine ligands. While the central Ni^II ion is six-coordinate, its environment is distorted from an octa­hedral structure because of the unequal Ni—N distances. The Ni—N bond lengths vary from 1.8642 (14) to 2.2131 (15) Å, while the N—Ni—N angles range from 79.98 (6) to 104.44 (6)°. Three coordinating sites of each chelating agent are almost coplanar with respect to the pyridine ring, and two pyridine moieties are perpendicular to each other. Two non-coordinating nitrate anions within the asymmetric unit balance the charges of the central metal ion, and are linked with two crystal water mol­ecules, forming a water–nitrate cyclic tetra­meric unit [O...O = 2.813 (2) to 3.062 (2) Å]. In an isolated mol­ecule, the fluoro­phenyl rings of one ligand are stacked with the central ring of the other ligand via π–π inter­actions, with the closest centroid-to-plane distances being 3.359 (6), 3.408 (5), 3.757 (6) and 3.659 (5) Å.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.035
• wR factor = 0.109
• Data-to-parameter ratio = 15.0

checkCIF/PLATON results

No syntax errors found



Alert level C
CRYSC01_ALERT_1_C The word below has not been recognised as a standard
            identifier.
            bluish
PLAT244_ALERT_4_C Low    'Solvent' Ueq as Compared to Neighbors of        N1D Check

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          6 Note
PLAT083_ALERT_2_G SHELXL Second Parameter in WGHT  Unusually Large       7.10 Why ?
PLAT172_ALERT_4_G The CIF-Embedded .res File Contains DFIX Records          1 Report
PLAT432_ALERT_2_G Short Inter X...Y Contact  O1C      ..C35              3.01 Ang.
                                                      x,y,z  =      1_555 Check
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          1 Note
PLAT794_ALERT_5_G Tentative Bond Valency for Ni1       (III)     .       2.79 Info
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          4 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         18 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.         17 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   2 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   9 ALERT level G = General information/check it is not something unexpected

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 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
   4 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

---

Computing details

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2020); software used to prepare material for publication: SHELXL2018 (Sheldrick, 2015b).

Bis{2,6-bis[(E)-(4-fluorobenzylimino)methyl]pyridine}nickel(II) dinitrate dihydrate

Crystal data

[Ni(C21H17F2N3)2](NO3)2·2H2O	Dx = 1.496 Mg m^−3
Mr = 917.51	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 9364 reflections
a = 17.0353 (13) Å	θ = 2.3–26.7°
b = 18.7759 (14) Å	µ = 0.56 mm^−1
c = 25.4659 (18) Å	T = 100 K
V = 8145.3 (10) Å^3	Block, bluish_black
Z = 8	0.52 × 0.40 × 0.24 mm
F(000) = 3792

Data collection

Bruker APEX CCD diffractometer	7462 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.032
Absorption correction: multi-scan (SADABS; Bruker, 2007)	θmax = 26.8°, θmin = 1.6°
Tmin = 0.685, Tmax = 0.745	h = −21→21
161343 measured reflections	k = −23→23
8675 independent reflections	l = −32→32

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)] = 0.035	Hydrogen site location: mixed
wR(F^2) = 0.109	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.064P)^2 + 7.1P] where P = (Fo^2 + 2Fc^2)/3
8675 reflections	(Δ/σ)max = 0.003
580 parameters	Δρmax = 0.56 e Å^−3
4 restraints	Δρmin = −0.69 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. The H atoms of the water molecules were located from a difference Fourier map and were refined with distance restraints (O—H = 0.85 (2) Å) and with U_iso(H) = 1.2U_eq(O).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Ni1	0.56405 (2)	0.28869 (2)	0.64363 (2)	0.01841 (8)
F1	0.63434 (12)	0.22324 (10)	0.89733 (6)	0.0683 (5)
F2	0.36925 (9)	−0.03240 (7)	0.57727 (6)	0.0470 (4)
F3	0.89670 (8)	0.41647 (8)	0.50480 (5)	0.0438 (3)
F4	0.31167 (8)	0.55522 (6)	0.61596 (5)	0.0392 (3)
N1	0.52019 (8)	0.34183 (7)	0.69806 (5)	0.0170 (3)
N2	0.55829 (8)	0.38380 (8)	0.60935 (6)	0.0187 (3)
N3	0.55104 (9)	0.21275 (7)	0.69753 (6)	0.0184 (3)
N4	0.61183 (9)	0.23418 (8)	0.58681 (6)	0.0190 (3)
N5	0.69087 (9)	0.29623 (8)	0.66063 (6)	0.0212 (3)
N6	0.46197 (9)	0.25163 (8)	0.59733 (6)	0.0201 (3)
C1	0.49857 (10)	0.30917 (9)	0.74283 (7)	0.0194 (3)
C2	0.46540 (11)	0.34686 (10)	0.78416 (7)	0.0232 (4)
H2	0.449286	0.323263	0.815346	0.028*
C3	0.45641 (11)	0.42011 (10)	0.77864 (8)	0.0254 (4)
H3	0.434032	0.447191	0.806363	0.030*
C4	0.48008 (11)	0.45384 (10)	0.73265 (7)	0.0231 (4)
H4	0.475052	0.503976	0.728884	0.028*
C5	0.51122 (10)	0.41274 (9)	0.69232 (7)	0.0191 (3)
C6	0.53341 (10)	0.43430 (9)	0.63923 (7)	0.0206 (3)
H6	0.529733	0.482243	0.627570	0.025*
C7	0.57583 (11)	0.40007 (10)	0.55444 (7)	0.0234 (4)
H7A	0.554387	0.447612	0.545665	0.028*
H7AB	0.549607	0.364625	0.531617	0.028*
C8	0.66288 (11)	0.39936 (9)	0.54347 (7)	0.0227 (4)
C9	0.71632 (12)	0.42861 (10)	0.57875 (7)	0.0260 (4)
H9	0.698114	0.446061	0.611577	0.031*
C10	0.79573 (12)	0.43276 (11)	0.56685 (8)	0.0302 (4)
H10	0.832377	0.451112	0.591503	0.036*
C11	0.81964 (13)	0.40936 (11)	0.51810 (8)	0.0321 (4)
C12	0.76922 (13)	0.38008 (11)	0.48242 (8)	0.0338 (5)
H12	0.787768	0.364129	0.449264	0.041*
C13	0.69037 (13)	0.37403 (10)	0.49549 (7)	0.0288 (4)
H13	0.654907	0.352446	0.471504	0.035*
C14	0.51882 (10)	0.23369 (9)	0.74059 (7)	0.0203 (3)
H14	0.508897	0.202136	0.768985	0.024*
C15	0.57673 (11)	0.13819 (9)	0.69424 (7)	0.0218 (4)
H15A	0.580371	0.117940	0.730054	0.026*
H15B	0.629590	0.136110	0.678154	0.026*
C16	0.52024 (11)	0.09422 (9)	0.66190 (7)	0.0213 (4)
C17	0.54625 (12)	0.05882 (10)	0.61703 (7)	0.0254 (4)
H17	0.599182	0.064108	0.605950	0.030*
C18	0.49532 (14)	0.01572 (11)	0.58828 (8)	0.0326 (5)
H18	0.512802	−0.008752	0.557796	0.039*
C19	0.41938 (14)	0.00969 (11)	0.60527 (8)	0.0330 (5)
C20	0.39085 (13)	0.04347 (11)	0.64916 (8)	0.0318 (4)
H20	0.337693	0.037982	0.659681	0.038*
C21	0.44252 (11)	0.08608 (10)	0.67776 (8)	0.0253 (4)
H21	0.424493	0.109822	0.708410	0.030*
C22	0.56689 (11)	0.20617 (9)	0.54884 (7)	0.0206 (4)
C23	0.59935 (13)	0.16824 (10)	0.50687 (7)	0.0278 (4)
H23	0.566872	0.149833	0.479749	0.033*
C24	0.67990 (13)	0.15809 (11)	0.50567 (8)	0.0327 (4)
H24	0.703320	0.131766	0.477934	0.039*
C25	0.72610 (12)	0.18666 (11)	0.54530 (8)	0.0297 (4)
H25	0.781380	0.180018	0.545100	0.036*
C26	0.69029 (11)	0.22510 (10)	0.58523 (7)	0.0229 (4)
C27	0.73211 (11)	0.26043 (10)	0.62806 (7)	0.0245 (4)
H27	0.787498	0.256930	0.631529	0.029*
C28	0.73112 (11)	0.33406 (11)	0.70322 (8)	0.0283 (4)
H28A	0.718569	0.385485	0.701435	0.034*
H28B	0.788617	0.328482	0.699332	0.034*
C29	0.70543 (11)	0.30453 (11)	0.75535 (7)	0.0264 (4)
C30	0.66522 (11)	0.34672 (11)	0.79102 (8)	0.0285 (4)
H30	0.654053	0.394904	0.782425	0.034*
C31	0.64102 (13)	0.31965 (13)	0.83910 (8)	0.0368 (5)
H31	0.613410	0.348573	0.863511	0.044*
C32	0.65816 (16)	0.24988 (15)	0.85031 (8)	0.0434 (6)
C33	0.69808 (16)	0.20601 (12)	0.81624 (9)	0.0423 (6)
H33	0.708871	0.157882	0.825219	0.051*
C34	0.72215 (13)	0.23395 (11)	0.76841 (8)	0.0339 (5)
H34	0.750222	0.204811	0.744382	0.041*
C35	0.48277 (11)	0.21748 (9)	0.55641 (7)	0.0218 (4)
H35	0.445293	0.200148	0.531924	0.026*
C36	0.37800 (11)	0.26274 (10)	0.60653 (8)	0.0272 (4)
H36A	0.362563	0.239761	0.639955	0.033*
H36B	0.347472	0.240427	0.577827	0.033*
C37	0.35948 (10)	0.34148 (10)	0.60900 (7)	0.0217 (4)
C38	0.36431 (11)	0.38280 (10)	0.56371 (7)	0.0238 (4)
H38	0.378772	0.361272	0.531371	0.029*
C39	0.34813 (12)	0.45525 (11)	0.56546 (8)	0.0278 (4)
H39	0.351257	0.483902	0.534786	0.033*
C40	0.32736 (11)	0.48422 (10)	0.61331 (8)	0.0265 (4)
C41	0.32144 (11)	0.44549 (11)	0.65888 (7)	0.0257 (4)
H41	0.306529	0.467281	0.691036	0.031*
C42	0.33817 (10)	0.37303 (10)	0.65607 (7)	0.0242 (4)
H42	0.334916	0.344751	0.686930	0.029*
N1C	0.44870 (10)	0.25225 (9)	0.41568 (6)	0.0270 (3)
O1C	0.45857 (12)	0.29359 (9)	0.45374 (6)	0.0453 (4)
O2C	0.46221 (11)	0.18737 (8)	0.41992 (7)	0.0447 (4)
O3C	0.42413 (9)	0.27623 (8)	0.37264 (6)	0.0321 (3)
N1D	0.26557 (10)	0.46087 (9)	0.30779 (7)	0.0300 (4)
O1D	0.26571 (9)	0.41323 (8)	0.34230 (6)	0.0378 (4)
O2D	0.33011 (10)	0.48588 (9)	0.29188 (8)	0.0479 (4)
O3D	0.20287 (10)	0.48652 (9)	0.29197 (8)	0.0516 (5)
O1S	0.45995 (11)	0.39752 (8)	0.31231 (6)	0.0382 (4)
H1S	0.4519 (16)	0.3656 (12)	0.3342 (10)	0.046*
H2S	0.4180 (12)	0.4219 (14)	0.3062 (11)	0.046*
O1T	0.38587 (10)	0.42834 (8)	0.43101 (6)	0.0362 (3)
H1T	0.4134 (15)	0.3897 (11)	0.4336 (11)	0.043*
H2T	0.3526 (14)	0.4229 (15)	0.4063 (9)	0.043*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.01987 (13)	0.01626 (13)	0.01908 (13)	−0.00008 (8)	−0.00018 (8)	−0.00037 (8)
F1	0.0980 (14)	0.0766 (12)	0.0303 (8)	0.0026 (10)	−0.0023 (8)	0.0246 (7)
F2	0.0559 (9)	0.0391 (7)	0.0459 (8)	−0.0122 (6)	−0.0231 (7)	−0.0091 (6)
F3	0.0330 (7)	0.0560 (8)	0.0424 (7)	0.0115 (6)	0.0156 (6)	0.0121 (6)
F4	0.0540 (8)	0.0238 (6)	0.0398 (7)	0.0121 (6)	0.0005 (6)	−0.0013 (5)
N1	0.0158 (7)	0.0162 (7)	0.0192 (7)	−0.0009 (5)	−0.0010 (5)	−0.0005 (5)
N2	0.0188 (7)	0.0176 (7)	0.0198 (7)	−0.0030 (5)	−0.0022 (5)	0.0023 (6)
N3	0.0191 (7)	0.0154 (7)	0.0208 (7)	−0.0018 (5)	−0.0031 (6)	0.0006 (5)
N4	0.0214 (7)	0.0168 (7)	0.0188 (7)	0.0015 (6)	0.0001 (6)	0.0017 (5)
N5	0.0210 (7)	0.0206 (7)	0.0221 (7)	−0.0027 (6)	−0.0023 (6)	0.0023 (6)
N6	0.0208 (7)	0.0149 (7)	0.0245 (7)	−0.0001 (5)	−0.0021 (6)	0.0017 (6)
C1	0.0174 (8)	0.0209 (8)	0.0197 (8)	−0.0033 (6)	−0.0016 (6)	−0.0002 (6)
C2	0.0212 (9)	0.0267 (9)	0.0216 (8)	−0.0028 (7)	0.0011 (7)	−0.0017 (7)
C3	0.0236 (9)	0.0262 (9)	0.0264 (9)	0.0005 (7)	0.0022 (7)	−0.0083 (7)
C4	0.0224 (9)	0.0175 (8)	0.0295 (9)	0.0001 (7)	0.0006 (7)	−0.0037 (7)
C5	0.0174 (8)	0.0159 (8)	0.0241 (8)	−0.0011 (6)	−0.0015 (6)	−0.0017 (6)
C6	0.0199 (8)	0.0163 (8)	0.0256 (9)	−0.0015 (6)	−0.0031 (7)	0.0015 (6)
C7	0.0296 (9)	0.0220 (9)	0.0185 (8)	−0.0037 (7)	−0.0023 (7)	0.0025 (7)
C8	0.0307 (10)	0.0177 (8)	0.0197 (8)	−0.0009 (7)	0.0020 (7)	0.0034 (6)
C9	0.0314 (10)	0.0268 (9)	0.0200 (8)	−0.0045 (8)	0.0051 (7)	−0.0020 (7)
C10	0.0301 (10)	0.0312 (10)	0.0293 (10)	−0.0035 (8)	0.0029 (8)	0.0008 (8)
C11	0.0322 (10)	0.0316 (10)	0.0325 (10)	0.0078 (8)	0.0103 (8)	0.0100 (8)
C12	0.0449 (12)	0.0317 (10)	0.0249 (9)	0.0152 (9)	0.0068 (9)	0.0010 (8)
C13	0.0428 (11)	0.0220 (9)	0.0215 (9)	0.0071 (8)	−0.0025 (8)	−0.0014 (7)
C14	0.0209 (8)	0.0202 (8)	0.0199 (8)	−0.0031 (7)	−0.0015 (7)	0.0029 (6)
C15	0.0240 (9)	0.0159 (8)	0.0256 (9)	0.0006 (7)	−0.0048 (7)	0.0014 (7)
C16	0.0274 (9)	0.0139 (8)	0.0225 (8)	0.0019 (7)	−0.0052 (7)	0.0033 (6)
C17	0.0339 (10)	0.0184 (8)	0.0238 (9)	0.0022 (7)	−0.0019 (8)	0.0018 (7)
C18	0.0483 (13)	0.0261 (10)	0.0235 (9)	0.0021 (9)	−0.0068 (9)	−0.0030 (8)
C19	0.0446 (12)	0.0232 (9)	0.0311 (10)	−0.0057 (9)	−0.0172 (9)	−0.0006 (8)
C20	0.0286 (10)	0.0280 (10)	0.0386 (11)	−0.0048 (8)	−0.0073 (8)	0.0019 (8)
C21	0.0287 (10)	0.0217 (9)	0.0255 (9)	0.0001 (7)	−0.0026 (7)	−0.0009 (7)
C22	0.0271 (9)	0.0160 (8)	0.0187 (8)	0.0015 (6)	−0.0014 (7)	0.0018 (6)
C23	0.0390 (11)	0.0251 (9)	0.0193 (8)	0.0039 (8)	−0.0010 (8)	−0.0027 (7)
C24	0.0405 (11)	0.0324 (10)	0.0252 (9)	0.0093 (9)	0.0063 (8)	−0.0041 (8)
C25	0.0279 (10)	0.0318 (10)	0.0295 (10)	0.0097 (8)	0.0056 (8)	0.0018 (8)
C26	0.0236 (9)	0.0221 (9)	0.0230 (9)	0.0038 (7)	0.0017 (7)	0.0034 (7)
C27	0.0186 (8)	0.0268 (9)	0.0282 (9)	−0.0003 (7)	−0.0002 (7)	0.0037 (8)
C28	0.0251 (9)	0.0291 (10)	0.0305 (10)	−0.0076 (8)	−0.0063 (8)	−0.0007 (8)
C29	0.0240 (9)	0.0286 (9)	0.0266 (9)	−0.0048 (8)	−0.0109 (7)	0.0004 (7)
C30	0.0259 (9)	0.0308 (10)	0.0288 (9)	−0.0017 (8)	−0.0106 (8)	−0.0005 (8)
C31	0.0357 (11)	0.0479 (13)	0.0267 (10)	0.0013 (10)	−0.0089 (9)	0.0008 (9)
C32	0.0529 (14)	0.0521 (14)	0.0251 (10)	−0.0053 (12)	−0.0098 (10)	0.0112 (10)
C33	0.0570 (15)	0.0335 (11)	0.0364 (12)	0.0013 (10)	−0.0194 (11)	0.0101 (9)
C34	0.0395 (12)	0.0301 (11)	0.0320 (10)	0.0000 (9)	−0.0144 (9)	−0.0023 (8)
C35	0.0266 (9)	0.0171 (8)	0.0218 (8)	−0.0007 (7)	−0.0055 (7)	0.0007 (6)
C36	0.0203 (9)	0.0218 (9)	0.0396 (11)	−0.0035 (7)	0.0007 (8)	−0.0007 (8)
C37	0.0135 (8)	0.0225 (9)	0.0292 (9)	−0.0017 (6)	−0.0029 (7)	−0.0005 (7)
C38	0.0230 (9)	0.0253 (9)	0.0232 (8)	0.0023 (7)	−0.0039 (7)	−0.0031 (7)
C39	0.0313 (10)	0.0284 (10)	0.0238 (9)	0.0047 (8)	−0.0032 (8)	0.0039 (7)
C40	0.0252 (9)	0.0221 (9)	0.0322 (10)	0.0053 (7)	−0.0030 (8)	−0.0024 (7)
C41	0.0209 (9)	0.0313 (10)	0.0249 (9)	0.0057 (7)	0.0002 (7)	−0.0028 (7)
C42	0.0176 (8)	0.0291 (9)	0.0259 (9)	0.0006 (7)	0.0022 (7)	0.0045 (7)
N1C	0.0274 (8)	0.0300 (9)	0.0235 (8)	0.0027 (7)	−0.0005 (6)	0.0046 (6)
O1C	0.0702 (12)	0.0405 (9)	0.0253 (8)	0.0120 (8)	−0.0079 (8)	−0.0044 (6)
O2C	0.0649 (11)	0.0270 (8)	0.0423 (9)	0.0016 (8)	−0.0131 (8)	0.0090 (7)
O3C	0.0400 (8)	0.0296 (7)	0.0268 (7)	0.0021 (6)	−0.0073 (6)	0.0058 (6)
N1D	0.0323 (9)	0.0223 (8)	0.0354 (9)	−0.0052 (7)	−0.0031 (7)	0.0030 (7)
O1D	0.0388 (9)	0.0341 (8)	0.0406 (8)	−0.0086 (7)	−0.0068 (7)	0.0143 (7)
O2D	0.0354 (9)	0.0420 (9)	0.0664 (12)	0.0028 (7)	0.0134 (8)	0.0209 (8)
O3D	0.0333 (9)	0.0421 (9)	0.0795 (13)	−0.0073 (7)	−0.0176 (9)	0.0244 (9)
O1S	0.0492 (10)	0.0299 (8)	0.0353 (8)	0.0083 (7)	0.0144 (7)	0.0072 (6)
O1T	0.0434 (9)	0.0305 (8)	0.0346 (8)	0.0024 (7)	−0.0015 (7)	−0.0018 (6)

Geometric parameters (Å, º)

Ni1—N1	1.8642 (14)	C18—C19	1.369 (3)
Ni1—N4	1.9503 (15)	C18—H18	0.9500
Ni1—N2	1.9901 (15)	C19—C20	1.374 (3)
Ni1—N3	1.9916 (15)	C20—C21	1.395 (3)
Ni1—N5	2.2079 (16)	C20—H20	0.9500
Ni1—N6	2.2131 (15)	C21—H21	0.9500
F1—C32	1.360 (3)	C22—C23	1.398 (3)
F2—C19	1.365 (2)	C22—C35	1.461 (3)
F3—C11	1.362 (2)	C23—C24	1.386 (3)
F4—C40	1.361 (2)	C23—H23	0.9500
N1—C1	1.346 (2)	C24—C25	1.388 (3)
N1—C5	1.348 (2)	C24—H24	0.9500
N2—C6	1.287 (2)	C25—C26	1.388 (3)
N2—C7	1.462 (2)	C25—H25	0.9500
N3—C14	1.288 (2)	C26—C27	1.462 (3)
N3—C15	1.469 (2)	C27—H27	0.9500
N4—C22	1.341 (2)	C28—C29	1.504 (3)
N4—C26	1.348 (2)	C28—H28A	0.9900
N5—C27	1.278 (3)	C28—H28B	0.9900
N5—C28	1.467 (2)	C29—C30	1.386 (3)
N6—C35	1.274 (2)	C29—C34	1.396 (3)
N6—C36	1.464 (2)	C30—C31	1.388 (3)
C1—C2	1.388 (2)	C30—H30	0.9500
C1—C14	1.460 (2)	C31—C32	1.372 (4)
C2—C3	1.391 (3)	C31—H31	0.9500
C2—H2	0.9500	C32—C33	1.376 (4)
C3—C4	1.391 (3)	C33—C34	1.388 (3)
C3—H3	0.9500	C33—H33	0.9500
C4—C5	1.390 (2)	C34—H34	0.9500
C4—H4	0.9500	C35—H35	0.9500
C5—C6	1.461 (2)	C36—C37	1.513 (3)
C6—H6	0.9500	C36—H36A	0.9900
C7—C8	1.509 (3)	C36—H36B	0.9900
C7—H7A	0.9900	C37—C42	1.386 (3)
C7—H7AB	0.9900	C37—C38	1.392 (3)
C8—C9	1.392 (3)	C38—C39	1.389 (3)
C8—C13	1.392 (3)	C38—H38	0.9500
C9—C10	1.388 (3)	C39—C40	1.380 (3)
C9—H9	0.9500	C39—H39	0.9500
C10—C11	1.379 (3)	C40—C41	1.373 (3)
C10—H10	0.9500	C41—C42	1.392 (3)
C11—C12	1.366 (3)	C41—H41	0.9500
C12—C13	1.388 (3)	C42—H42	0.9500
C12—H12	0.9500	N1C—O2C	1.244 (2)
C13—H13	0.9500	N1C—O1C	1.253 (2)
C14—H14	0.9500	N1C—O3C	1.257 (2)
C15—C16	1.512 (2)	N1D—O3D	1.239 (2)
C15—H15A	0.9900	N1D—O1D	1.254 (2)
C15—H15B	0.9900	N1D—O2D	1.262 (2)
C16—C21	1.392 (3)	O1S—H1S	0.830 (17)
C16—C17	1.394 (3)	O1S—H2S	0.862 (17)
C17—C18	1.394 (3)	O1T—H1T	0.867 (17)
C17—H17	0.9500	O1T—H2T	0.853 (17)
N1—Ni1—N4	178.87 (6)	C19—C18—C17	118.05 (19)
N1—Ni1—N2	79.98 (6)	C19—C18—H18	121.0
N4—Ni1—N2	99.56 (6)	C17—C18—H18	121.0
N1—Ni1—N3	79.99 (6)	F2—C19—C18	118.3 (2)
N4—Ni1—N3	100.49 (6)	F2—C19—C20	118.1 (2)
N2—Ni1—N3	159.92 (6)	C18—C19—C20	123.59 (19)
N1—Ni1—N5	102.24 (6)	C19—C20—C21	117.8 (2)
N4—Ni1—N5	76.75 (6)	C19—C20—H20	121.1
N2—Ni1—N5	94.40 (6)	C21—C20—H20	121.1
N3—Ni1—N5	91.12 (6)	C16—C21—C20	120.77 (19)
N1—Ni1—N6	104.44 (6)	C16—C21—H21	119.6
N4—Ni1—N6	76.57 (6)	C20—C21—H21	119.6
N2—Ni1—N6	90.56 (6)	N4—C22—C23	121.68 (17)
N3—Ni1—N6	93.13 (6)	N4—C22—C35	114.07 (16)
N5—Ni1—N6	153.31 (6)	C23—C22—C35	124.23 (17)
C1—N1—C5	120.71 (15)	C24—C23—C22	118.58 (18)
C1—N1—Ni1	119.71 (12)	C24—C23—H23	120.7
C5—N1—Ni1	119.58 (12)	C22—C23—H23	120.7
C6—N2—C7	118.60 (15)	C23—C24—C25	119.51 (18)
C6—N2—Ni1	114.70 (12)	C23—C24—H24	120.2
C7—N2—Ni1	126.64 (12)	C25—C24—H24	120.2
C14—N3—C15	117.80 (15)	C24—C25—C26	118.98 (19)
C14—N3—Ni1	114.56 (12)	C24—C25—H25	120.5
C15—N3—Ni1	127.58 (12)	C26—C25—H25	120.5
C22—N4—C26	119.67 (15)	N4—C26—C25	121.55 (18)
C22—N4—Ni1	120.17 (12)	N4—C26—C27	113.79 (16)
C26—N4—Ni1	120.16 (12)	C25—C26—C27	124.64 (18)
C27—N5—C28	118.53 (16)	N5—C27—C26	117.07 (17)
C27—N5—Ni1	112.14 (12)	N5—C27—H27	121.5
C28—N5—Ni1	129.31 (12)	C26—C27—H27	121.5
C35—N6—C36	118.31 (16)	N5—C28—C29	109.76 (15)
C35—N6—Ni1	112.05 (12)	N5—C28—H28A	109.7
C36—N6—Ni1	129.61 (12)	C29—C28—H28A	109.7
N1—C1—C2	121.42 (16)	N5—C28—H28B	109.7
N1—C1—C14	110.15 (15)	C29—C28—H28B	109.7
C2—C1—C14	128.36 (16)	H28A—C28—H28B	108.2
C1—C2—C3	118.17 (17)	C30—C29—C34	119.16 (19)
C1—C2—H2	120.9	C30—C29—C28	120.77 (18)
C3—C2—H2	120.9	C34—C29—C28	120.07 (19)
C2—C3—C4	120.22 (17)	C29—C30—C31	121.0 (2)
C2—C3—H3	119.9	C29—C30—H30	119.5
C4—C3—H3	119.9	C31—C30—H30	119.5
C5—C4—C3	118.67 (17)	C32—C31—C30	118.0 (2)
C5—C4—H4	120.7	C32—C31—H31	121.0
C3—C4—H4	120.7	C30—C31—H31	121.0
N1—C5—C4	120.77 (16)	F1—C32—C31	118.1 (2)
N1—C5—C6	110.15 (15)	F1—C32—C33	118.8 (2)
C4—C5—C6	128.96 (16)	C31—C32—C33	123.1 (2)
N2—C6—C5	115.35 (15)	C32—C33—C34	118.2 (2)
N2—C6—H6	122.3	C32—C33—H33	120.9
C5—C6—H6	122.3	C34—C33—H33	120.9
N2—C7—C8	112.08 (15)	C33—C34—C29	120.5 (2)
N2—C7—H7A	109.2	C33—C34—H34	119.7
C8—C7—H7A	109.2	C29—C34—H34	119.7
N2—C7—H7AB	109.2	N6—C35—C22	116.99 (16)
C8—C7—H7AB	109.2	N6—C35—H35	121.5
H7A—C7—H7AB	107.9	C22—C35—H35	121.5
C9—C8—C13	118.76 (18)	N6—C36—C37	110.46 (14)
C9—C8—C7	121.31 (16)	N6—C36—H36A	109.6
C13—C8—C7	119.74 (17)	C37—C36—H36A	109.6
C10—C9—C8	121.23 (18)	N6—C36—H36B	109.6
C10—C9—H9	119.4	C37—C36—H36B	109.6
C8—C9—H9	119.4	H36A—C36—H36B	108.1
C11—C10—C9	117.80 (19)	C42—C37—C38	119.60 (17)
C11—C10—H10	121.1	C42—C37—C36	120.55 (17)
C9—C10—H10	121.1	C38—C37—C36	119.85 (17)
F3—C11—C12	118.69 (19)	C39—C38—C37	120.50 (17)
F3—C11—C10	118.5 (2)	C39—C38—H38	119.8
C12—C11—C10	122.8 (2)	C37—C38—H38	119.8
C11—C12—C13	118.80 (18)	C40—C39—C38	117.72 (18)
C11—C12—H12	120.6	C40—C39—H39	121.1
C13—C12—H12	120.6	C38—C39—H39	121.1
C12—C13—C8	120.53 (19)	F4—C40—C41	117.54 (17)
C12—C13—H13	119.7	F4—C40—C39	118.68 (17)
C8—C13—H13	119.7	C41—C40—C39	123.78 (18)
N3—C14—C1	115.50 (15)	C40—C41—C42	117.34 (17)
N3—C14—H14	122.3	C40—C41—H41	121.3
C1—C14—H14	122.3	C42—C41—H41	121.3
N3—C15—C16	111.20 (14)	C37—C42—C41	121.06 (17)
N3—C15—H15A	109.4	C37—C42—H42	119.5
C16—C15—H15A	109.4	C41—C42—H42	119.5
N3—C15—H15B	109.4	O2C—N1C—O1C	120.96 (16)
C16—C15—H15B	109.4	O2C—N1C—O3C	119.22 (17)
H15A—C15—H15B	108.0	O1C—N1C—O3C	119.82 (17)
C21—C16—C17	119.18 (17)	O3D—N1D—O1D	120.45 (18)
C21—C16—C15	120.47 (17)	O3D—N1D—O2D	120.13 (17)
C17—C16—C15	120.29 (17)	O1D—N1D—O2D	119.25 (17)
C16—C17—C18	120.61 (19)	H1S—O1S—H2S	112 (3)
C16—C17—H17	119.7	H1T—O1T—H2T	108 (3)
C18—C17—H17	119.7
N2—Ni1—N1—C1	175.88 (14)	C18—C19—C20—C21	−0.1 (3)
N3—Ni1—N1—C1	−2.77 (13)	C17—C16—C21—C20	−0.4 (3)
N5—Ni1—N1—C1	−91.74 (13)	C15—C16—C21—C20	−177.62 (17)
N6—Ni1—N1—C1	87.91 (13)	C19—C20—C21—C16	0.4 (3)
N2—Ni1—N1—C5	−4.79 (13)	C26—N4—C22—C23	−0.9 (3)
N3—Ni1—N1—C5	176.56 (14)	Ni1—N4—C22—C23	178.46 (13)
N5—Ni1—N1—C5	87.59 (13)	C26—N4—C22—C35	177.66 (15)
N6—Ni1—N1—C5	−92.76 (13)	Ni1—N4—C22—C35	−3.0 (2)
C5—N1—C1—C2	1.0 (3)	N4—C22—C23—C24	1.7 (3)
Ni1—N1—C1—C2	−179.72 (13)	C35—C22—C23—C24	−176.63 (18)
C5—N1—C1—C14	−176.35 (15)	C22—C23—C24—C25	−1.2 (3)
Ni1—N1—C1—C14	2.98 (19)	C23—C24—C25—C26	−0.2 (3)
N1—C1—C2—C3	−1.3 (3)	C22—N4—C26—C25	−0.6 (3)
C14—C1—C2—C3	175.45 (17)	Ni1—N4—C26—C25	−179.93 (14)
C1—C2—C3—C4	0.2 (3)	C22—N4—C26—C27	178.07 (15)
C2—C3—C4—C5	1.2 (3)	Ni1—N4—C26—C27	−1.3 (2)
C1—N1—C5—C4	0.6 (2)	C24—C25—C26—N4	1.2 (3)
Ni1—N1—C5—C4	−178.77 (13)	C24—C25—C26—C27	−177.37 (18)
C1—N1—C5—C6	−175.78 (15)	C28—N5—C27—C26	−178.27 (16)
Ni1—N1—C5—C6	4.90 (19)	Ni1—N5—C27—C26	3.0 (2)
C3—C4—C5—N1	−1.6 (3)	N4—C26—C27—N5	−1.4 (2)
C3—C4—C5—C6	173.93 (18)	C25—C26—C27—N5	177.20 (18)
C7—N2—C6—C5	175.30 (15)	C27—N5—C28—C29	−117.17 (19)
Ni1—N2—C6—C5	−2.03 (19)	Ni1—N5—C28—C29	61.3 (2)
N1—C5—C6—N2	−1.6 (2)	N5—C28—C29—C30	−116.22 (19)
C4—C5—C6—N2	−177.54 (17)	N5—C28—C29—C34	64.0 (2)
C6—N2—C7—C8	108.60 (18)	C34—C29—C30—C31	−0.5 (3)
Ni1—N2—C7—C8	−74.43 (18)	C28—C29—C30—C31	179.69 (18)
N2—C7—C8—C9	−41.1 (2)	C29—C30—C31—C32	0.1 (3)
N2—C7—C8—C13	143.91 (17)	C30—C31—C32—F1	−179.8 (2)
C13—C8—C9—C10	0.0 (3)	C30—C31—C32—C33	0.1 (4)
C7—C8—C9—C10	−175.08 (18)	F1—C32—C33—C34	−179.9 (2)
C8—C9—C10—C11	2.4 (3)	C31—C32—C33—C34	0.2 (4)
C9—C10—C11—F3	176.66 (18)	C32—C33—C34—C29	−0.6 (3)
C9—C10—C11—C12	−2.6 (3)	C30—C29—C34—C33	0.7 (3)
F3—C11—C12—C13	−178.77 (18)	C28—C29—C34—C33	−179.43 (19)
C10—C11—C12—C13	0.5 (3)	C36—N6—C35—C22	−178.93 (15)
C11—C12—C13—C8	1.9 (3)	Ni1—N6—C35—C22	2.81 (19)
C9—C8—C13—C12	−2.2 (3)	N4—C22—C35—N6	−0.2 (2)
C7—C8—C13—C12	172.98 (17)	C23—C22—C35—N6	178.24 (17)
C15—N3—C14—C1	176.60 (14)	C35—N6—C36—C37	−120.46 (18)
Ni1—N3—C14—C1	−0.9 (2)	Ni1—N6—C36—C37	57.4 (2)
N1—C1—C14—N3	−1.2 (2)	N6—C36—C37—C42	−110.12 (19)
C2—C1—C14—N3	−178.26 (17)	N6—C36—C37—C38	69.5 (2)
C14—N3—C15—C16	103.36 (19)	C42—C37—C38—C39	0.2 (3)
Ni1—N3—C15—C16	−79.53 (18)	C36—C37—C38—C39	−179.45 (17)
N3—C15—C16—C21	−61.9 (2)	C37—C38—C39—C40	0.0 (3)
N3—C15—C16—C17	120.90 (18)	C38—C39—C40—F4	179.65 (17)
C21—C16—C17—C18	0.0 (3)	C38—C39—C40—C41	−0.4 (3)
C15—C16—C17—C18	177.22 (17)	F4—C40—C41—C42	−179.48 (17)
C16—C17—C18—C19	0.4 (3)	C39—C40—C41—C42	0.5 (3)
C17—C18—C19—F2	179.97 (17)	C38—C37—C42—C41	0.0 (3)
C17—C18—C19—C20	−0.3 (3)	C36—C37—C42—C41	179.63 (17)
F2—C19—C20—C21	179.65 (18)	C40—C41—C42—C37	−0.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1S—H1S···O3C	0.83 (2)	2.00 (2)	2.814 (2)	167 (3)
O1S—H2S···O2D	0.86 (2)	1.96 (2)	2.813 (2)	174 (3)
O1T—H1T···O1C	0.87 (2)	2.03 (2)	2.876 (2)	166 (3)
O1T—H2T···O1D	0.85 (2)	2.21 (2)	3.062 (2)	178 (3)
C2—H2···O3C^i	0.95	2.41	3.303 (2)	157
C4—H4···O1S^ii	0.95	2.40	3.185 (2)	140
C13—H13···F1^iii	0.95	2.39	3.240 (3)	149
C14—H14···O1S^i	0.95	2.33	3.227 (2)	158
C15—H15B···O1D^iv	0.99	2.55	3.487 (2)	158
C18—H18···F3^v	0.95	2.48	3.373 (3)	156
C23—H23···O2C	0.95	2.45	3.239 (3)	140
C27—H27···O3C^iv	0.95	2.41	3.343 (2)	166
C28—H28A···O2D^ii	0.99	2.56	3.540 (3)	171
C33—H33···F4^vi	0.95	2.47	3.320 (3)	150
C35—H35···F3^vii	0.95	2.52	3.302 (2)	140

Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+1, −y+1, −z+1; (iii) x, −y+1/2, z−1/2; (iv) x+1/2, −y+1/2, −z+1; (v) −x+3/2, y−1/2, z; (vi) −x+1, y−1/2, −z+3/2; (vii) x−1/2, −y+1/2, −z+1.