Acetate and acetamide complexes of [Ni(Me₄[12]aneN₄)]PF₆: a tale of two ligands

Although there are many examples of acetate complexes, acetamide complexes are virtually unknown. A side-by-side comparison in (acetato-κ²O,O′)(1,4,7,10-tetra­methyl-1,4,7,10-tetra­aza­cyclo­dodecane-κ⁴N)nickel(II) hexafluoridophosphate, [Ni(C₂H₃O₂)(C₁₂H₂₈N₄)]PF₆, (1), and (acetamidato-κ²O,O′)(1,4,7,10-tetra­methyl-1,4,7,10-tetra­aza­cyclo­dodecane-κ⁴N)nickel(II) hexafluoridophosphate, [Ni(C₂H₄NO)(C₁₂H₂₈N₄)]PF₆, (2), shows the steric equivalence between these two ligands, suggesting that acetamide could be considered as a viable acetate replacement for electronic tuning.

Computing details

For both compounds, data collection: APEX2 (Bruker, 2007); cell refinement: APEX2 (Bruker, 2007); data reduction: APEX2 (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

(1) (Acetato-κ²O,O')(1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane-κ⁴N)nickel(II) hexafluoridophosphate

Crystal data

[Ni(C2H3O2)(C12H28N4)]PF6	F(000) = 1024
Mr = 491.11	Dx = 1.548 Mg m^−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
a = 10.5588 (10) Å	Cell parameters from 2513 reflections
b = 11.7643 (11) Å	θ = 2.4–20.9°
c = 17.2263 (16) Å	µ = 1.07 mm^−1
β = 99.929 (2)°	T = 200 K
V = 2107.7 (3) Å^3	Needle, blue
Z = 4	0.20 × 0.12 × 0.12 mm

Data collection

Bruker APEXII diffractometer	4725 independent reflections
Graphite monochromator	4117 reflections with I > 2σ(I)
Detector resolution: 8.33 pixels mm^-1	Rint = 0.041
φ and ω scans	θmax = 27.7°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −13→13
Tmin = 0.642, Tmax = 0.746	k = −15→15
11775 measured reflections	l = −22→22

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.041	w = 1/[σ^2(Fo^2) + (0.0446P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.091	(Δ/σ)max < 0.001
S = 1.02	Δρmax = 0.52 e Å^−3
4725 reflections	Δρmin = −0.30 e Å^−3
259 parameters	Absolute structure: Refined as an inversion twin
2 restraints	Absolute structure parameter: 0.143 (19)
0 constraints

Special details

Experimental. Data collection is performed with four batch runs at φ = 0.00 ° (600 frames), at φ = 90.00 ° (600 frames), at φ = 180 ° (600 frames) and at φ = 270 ° (600 frames). Frame width = 0.30 \& in ω.

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. Refined as a two-component inversion twin.

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

	x	y	z	Uiso*/Ueq
Ni1	0.50415 (4)	0.57477 (4)	0.24742 (3)	0.02109 (15)
O1	0.6177 (3)	0.4425 (3)	0.3014 (2)	0.0310 (8)
O2	0.4145 (4)	0.4484 (3)	0.3095 (2)	0.0317 (8)
N1	0.3346 (4)	0.6648 (4)	0.2049 (2)	0.0285 (10)
N2	0.4746 (4)	0.5075 (3)	0.1290 (2)	0.0282 (10)
N3	0.6602 (4)	0.6608 (3)	0.2126 (2)	0.0274 (9)
N4	0.5284 (4)	0.6994 (4)	0.3399 (2)	0.0286 (9)
C1	0.3311 (6)	0.6791 (5)	0.1191 (3)	0.0417 (14)
H1A	0.3945	0.7374	0.1100	0.050*
H1B	0.2447	0.7054	0.0939	0.050*
C2	0.3618 (6)	0.5673 (5)	0.0828 (4)	0.0430 (15)
H2A	0.2857	0.5170	0.0781	0.052*
H2B	0.3789	0.5818	0.0289	0.052*
C3	0.5945 (6)	0.5355 (5)	0.0997 (3)	0.0378 (13)
H3A	0.5783	0.5317	0.0414	0.045*
H3B	0.6609	0.4781	0.1195	0.045*
C4	0.6452 (6)	0.6529 (5)	0.1254 (3)	0.0345 (12)
H4A	0.7291	0.6657	0.1086	0.041*
H4B	0.5844	0.7118	0.1006	0.041*
C5	0.6534 (6)	0.7792 (5)	0.2404 (4)	0.0340 (14)
H5A	0.5820	0.8197	0.2068	0.041*
H5B	0.7346	0.8193	0.2368	0.041*
C6	0.6316 (6)	0.7784 (5)	0.3253 (3)	0.0375 (13)
H6A	0.7128	0.7568	0.3599	0.045*
H6B	0.6093	0.8563	0.3399	0.045*
C7	0.4016 (6)	0.7575 (5)	0.3324 (4)	0.0431 (15)
H7A	0.4131	0.8322	0.3592	0.052*
H7B	0.3431	0.7114	0.3588	0.052*
C8	0.3416 (6)	0.7747 (5)	0.2467 (4)	0.0377 (15)
H8A	0.2542	0.8069	0.2433	0.045*
H8B	0.3939	0.8290	0.2218	0.045*
C9	0.2194 (6)	0.6009 (6)	0.2195 (4)	0.0402 (15)
H9A	0.2233	0.5912	0.2764	0.060*
H9B	0.2175	0.5260	0.1943	0.060*
H9C	0.1415	0.6432	0.1975	0.060*
C10	0.4539 (6)	0.3836 (5)	0.1231 (4)	0.0411 (14)
H10A	0.4471	0.3599	0.0680	0.062*
H10B	0.3743	0.3642	0.1421	0.062*
H10C	0.5264	0.3445	0.1553	0.062*
C11	0.7841 (5)	0.6101 (6)	0.2487 (4)	0.0375 (14)
H11A	0.8547	0.6573	0.2367	0.056*
H11B	0.7912	0.5335	0.2274	0.056*
H11C	0.7888	0.6056	0.3059	0.056*
C12	0.5620 (6)	0.6527 (6)	0.4200 (3)	0.0431 (15)
H12A	0.5718	0.7150	0.4584	0.065*
H12B	0.6430	0.6105	0.4248	0.065*
H12C	0.4937	0.6014	0.4303	0.065*
C13	0.5251 (5)	0.4019 (5)	0.3285 (3)	0.0286 (11)
C14	0.5438 (6)	0.3008 (5)	0.3817 (3)	0.0407 (14)
H14A	0.5528	0.2325	0.3505	0.061*
H14B	0.4693	0.2924	0.4081	0.061*
H14C	0.6216	0.3112	0.4212	0.061*
P1	0.45346 (14)	0.01522 (13)	0.51715 (9)	0.0344 (3)
F1	0.4883 (5)	0.0116 (4)	0.4309 (3)	0.0858 (15)
F2	0.3829 (4)	0.1338 (4)	0.4933 (3)	0.0717 (12)
F3	0.5792 (4)	0.0863 (3)	0.5493 (3)	0.0792 (15)
F4	0.4172 (6)	0.0244 (4)	0.6019 (3)	0.0963 (18)
F5	0.5291 (5)	−0.0987 (4)	0.5378 (4)	0.100 (2)
F6	0.3272 (4)	−0.0550 (4)	0.4857 (3)	0.0704 (13)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0217 (3)	0.0185 (3)	0.0234 (3)	0.0004 (3)	0.0049 (2)	0.0002 (3)
O1	0.028 (2)	0.027 (2)	0.039 (2)	0.0045 (15)	0.0076 (16)	0.0086 (16)
O2	0.028 (2)	0.028 (2)	0.040 (2)	−0.0015 (15)	0.0070 (16)	0.0055 (16)
N1	0.027 (2)	0.024 (2)	0.033 (2)	0.0022 (18)	0.0025 (18)	−0.0003 (17)
N2	0.031 (2)	0.027 (2)	0.028 (2)	−0.0043 (19)	0.0069 (18)	−0.0023 (18)
N3	0.027 (2)	0.024 (2)	0.032 (2)	−0.0032 (18)	0.0075 (18)	−0.0010 (18)
N4	0.028 (2)	0.031 (2)	0.028 (2)	−0.0009 (19)	0.0075 (17)	−0.0062 (18)
C1	0.043 (4)	0.040 (3)	0.038 (3)	0.005 (3)	−0.007 (3)	0.009 (3)
C2	0.042 (4)	0.056 (4)	0.029 (3)	−0.001 (3)	0.001 (2)	−0.002 (3)
C3	0.043 (3)	0.040 (3)	0.035 (3)	−0.012 (3)	0.020 (3)	−0.012 (2)
C4	0.042 (3)	0.036 (3)	0.028 (3)	−0.010 (3)	0.014 (2)	0.000 (2)
C5	0.036 (3)	0.018 (3)	0.048 (4)	−0.007 (2)	0.009 (3)	−0.003 (3)
C6	0.042 (3)	0.034 (3)	0.037 (3)	−0.010 (3)	0.009 (2)	−0.015 (2)
C7	0.037 (3)	0.042 (3)	0.051 (4)	0.009 (3)	0.011 (3)	−0.020 (3)
C8	0.035 (4)	0.025 (3)	0.053 (4)	0.010 (3)	0.007 (3)	−0.002 (3)
C9	0.027 (3)	0.037 (3)	0.056 (4)	0.004 (3)	0.007 (3)	0.001 (3)
C10	0.053 (4)	0.032 (3)	0.041 (3)	−0.017 (3)	0.017 (3)	−0.011 (3)
C11	0.020 (3)	0.037 (3)	0.056 (4)	−0.003 (3)	0.008 (3)	0.001 (3)
C12	0.057 (4)	0.048 (4)	0.023 (3)	−0.005 (3)	0.003 (3)	−0.005 (2)
C13	0.032 (3)	0.027 (3)	0.027 (3)	0.003 (2)	0.003 (2)	−0.002 (2)
C14	0.051 (4)	0.031 (3)	0.039 (3)	−0.001 (3)	0.005 (3)	0.016 (3)
P1	0.0307 (7)	0.0369 (8)	0.0338 (8)	0.0035 (7)	0.0003 (6)	−0.0098 (6)
F1	0.119 (4)	0.082 (4)	0.067 (3)	−0.024 (3)	0.045 (3)	−0.027 (3)
F2	0.079 (3)	0.055 (3)	0.076 (3)	0.017 (2)	0.000 (2)	0.006 (2)
F3	0.055 (3)	0.056 (3)	0.117 (4)	−0.008 (2)	−0.013 (3)	−0.035 (3)
F4	0.160 (5)	0.091 (3)	0.049 (3)	−0.036 (4)	0.048 (3)	−0.018 (2)
F5	0.102 (4)	0.043 (2)	0.132 (5)	0.030 (3)	−0.047 (3)	−0.023 (3)
F6	0.047 (2)	0.081 (3)	0.081 (3)	−0.023 (2)	0.005 (2)	−0.018 (2)

Geometric parameters (Å, º)

Ni1—N1	2.100 (4)	C5—H5A	0.9900
Ni1—N2	2.160 (4)	C5—H5B	0.9900
Ni1—N3	2.107 (4)	C6—H6A	0.9900
Ni1—N4	2.148 (4)	C6—H6B	0.9900
Ni1—O1	2.083 (3)	C7—C8	1.517 (9)
Ni1—O2	2.145 (4)	C7—H7A	0.9900
Ni1—C13	2.456 (6)	C7—H7B	0.9900
O1—C13	1.250 (7)	C8—H8A	0.9900
O2—C13	1.280 (7)	C8—H8B	0.9900
N1—C8	1.477 (7)	C9—H9A	0.9800
N1—C1	1.480 (7)	C9—H9B	0.9800
N1—C9	1.488 (8)	C9—H9C	0.9800
N2—C10	1.475 (7)	C10—H10A	0.9800
N2—C3	1.479 (6)	C10—H10B	0.9800
N2—C2	1.490 (7)	C10—H10C	0.9800
N3—C11	1.475 (7)	C11—H11A	0.9800
N3—C5	1.478 (7)	C11—H11B	0.9800
N3—C4	1.486 (6)	C11—H11C	0.9800
N4—C12	1.471 (7)	C12—H12A	0.9800
N4—C6	1.486 (7)	C12—H12B	0.9800
N4—C7	1.488 (7)	C12—H12C	0.9800
C1—C2	1.516 (8)	C13—C14	1.493 (7)
C1—H1A	0.9900	C14—H14A	0.9800
C1—H1B	0.9900	C14—H14B	0.9800
C2—H2A	0.9900	C14—H14C	0.9800
C2—H2B	0.9900	P1—F5	1.570 (4)
C3—C4	1.519 (8)	P1—F4	1.576 (4)
C3—H3A	0.9900	P1—F6	1.582 (4)
C3—H3B	0.9900	P1—F3	1.586 (4)
C4—H4A	0.9900	P1—F1	1.592 (5)
C4—H4B	0.9900	P1—F2	1.602 (4)
C5—C6	1.519 (8)
O1—Ni1—N1	157.34 (15)	C6—C5—H5A	109.8
O1—Ni1—N3	93.89 (15)	N3—C5—H5B	109.8
N1—Ni1—N3	108.64 (17)	C6—C5—H5B	109.8
O1—Ni1—O2	61.92 (14)	H5A—C5—H5B	108.3
N1—Ni1—O2	95.77 (16)	N4—C6—C5	113.9 (4)
N3—Ni1—O2	155.39 (15)	N4—C6—H6A	108.8
O1—Ni1—N4	101.13 (16)	C5—C6—H6A	108.8
N1—Ni1—N4	84.28 (16)	N4—C6—H6B	108.8
N3—Ni1—N4	83.35 (16)	C5—C6—H6B	108.8
O2—Ni1—N4	96.30 (16)	H6A—C6—H6B	107.7
O1—Ni1—N2	97.25 (16)	N4—C7—C8	111.4 (4)
N1—Ni1—N2	83.07 (16)	N4—C7—H7A	109.4
N3—Ni1—N2	84.25 (16)	C8—C7—H7A	109.4
O2—Ni1—N2	102.28 (15)	N4—C7—H7B	109.4
N4—Ni1—N2	158.44 (16)	C8—C7—H7B	109.4
O1—Ni1—C13	30.58 (16)	H7A—C7—H7B	108.0
N1—Ni1—C13	127.13 (18)	N1—C8—C7	109.6 (5)
N3—Ni1—C13	124.20 (18)	N1—C8—H8A	109.7
O2—Ni1—C13	31.38 (16)	C7—C8—H8A	109.7
N4—Ni1—C13	98.97 (17)	N1—C8—H8B	109.7
N2—Ni1—C13	102.59 (17)	C7—C8—H8B	109.7
C13—O1—Ni1	91.4 (3)	H8A—C8—H8B	108.2
C13—O2—Ni1	87.8 (3)	N1—C9—H9A	109.5
C8—N1—C1	112.2 (4)	N1—C9—H9B	109.5
C8—N1—C9	109.5 (4)	H9A—C9—H9B	109.5
C1—N1—C9	110.3 (4)	N1—C9—H9C	109.5
C8—N1—Ni1	107.6 (3)	H9A—C9—H9C	109.5
C1—N1—Ni1	106.2 (3)	H9B—C9—H9C	109.5
C9—N1—Ni1	111.0 (3)	N2—C10—H10A	109.5
C10—N2—C3	108.8 (4)	N2—C10—H10B	109.5
C10—N2—C2	109.5 (4)	H10A—C10—H10B	109.5
C3—N2—C2	111.4 (5)	N2—C10—H10C	109.5
C10—N2—Ni1	115.0 (3)	H10A—C10—H10C	109.5
C3—N2—Ni1	104.3 (3)	H10B—C10—H10C	109.5
C2—N2—Ni1	107.7 (3)	N3—C11—H11A	109.5
C11—N3—C5	109.5 (5)	N3—C11—H11B	109.5
C11—N3—C4	109.5 (4)	H11A—C11—H11B	109.5
C5—N3—C4	112.6 (4)	N3—C11—H11C	109.5
C11—N3—Ni1	111.5 (3)	H11A—C11—H11C	109.5
C5—N3—Ni1	106.1 (3)	H11B—C11—H11C	109.5
C4—N3—Ni1	107.8 (3)	N4—C12—H12A	109.5
C12—N4—C6	109.1 (4)	N4—C12—H12B	109.5
C12—N4—C7	108.7 (4)	H12A—C12—H12B	109.5
C6—N4—C7	111.9 (4)	N4—C12—H12C	109.5
C12—N4—Ni1	114.8 (3)	H12A—C12—H12C	109.5
C6—N4—Ni1	107.3 (3)	H12B—C12—H12C	109.5
C7—N4—Ni1	105.0 (3)	O1—C13—O2	118.7 (5)
N1—C1—C2	110.0 (4)	O1—C13—C14	120.3 (5)
N1—C1—H1A	109.7	O2—C13—C14	121.0 (5)
C2—C1—H1A	109.7	O1—C13—Ni1	58.0 (3)
N1—C1—H1B	109.7	O2—C13—Ni1	60.8 (3)
C2—C1—H1B	109.7	C14—C13—Ni1	176.3 (4)
H1A—C1—H1B	108.2	C13—C14—H14A	109.5
N2—C2—C1	113.4 (5)	C13—C14—H14B	109.5
N2—C2—H2A	108.9	H14A—C14—H14B	109.5
C1—C2—H2A	108.9	C13—C14—H14C	109.5
N2—C2—H2B	108.9	H14A—C14—H14C	109.5
C1—C2—H2B	108.9	H14B—C14—H14C	109.5
H2A—C2—H2B	107.7	F5—P1—F4	92.5 (3)
N2—C3—C4	112.5 (4)	F5—P1—F6	89.9 (3)
N2—C3—H3A	109.1	F4—P1—F6	91.6 (3)
C4—C3—H3A	109.1	F5—P1—F3	90.5 (3)
N2—C3—H3B	109.1	F4—P1—F3	87.8 (3)
C4—C3—H3B	109.1	F6—P1—F3	179.4 (3)
H3A—C3—H3B	107.8	F5—P1—F1	89.9 (3)
N3—C4—C3	108.8 (4)	F4—P1—F1	177.5 (3)
N3—C4—H4A	109.9	F6—P1—F1	89.0 (3)
C3—C4—H4A	109.9	F3—P1—F1	91.5 (3)
N3—C4—H4B	109.9	F5—P1—F2	176.6 (3)
C3—C4—H4B	109.9	F4—P1—F2	90.1 (3)
H4A—C4—H4B	108.3	F6—P1—F2	92.3 (2)
N3—C5—C6	109.3 (4)	F3—P1—F2	87.4 (3)
N3—C5—H5A	109.8	F1—P1—F2	87.5 (3)
C8—N1—C1—C2	164.0 (5)	Ni1—N3—C5—C6	46.5 (5)
C9—N1—C1—C2	−73.7 (6)	C12—N4—C6—C5	146.5 (5)
Ni1—N1—C1—C2	46.7 (5)	C7—N4—C6—C5	−93.1 (6)
C10—N2—C2—C1	145.6 (5)	Ni1—N4—C6—C5	21.5 (6)
C3—N2—C2—C1	−94.0 (6)	N3—C5—C6—N4	−46.9 (6)
Ni1—N2—C2—C1	19.9 (6)	C12—N4—C7—C8	−162.1 (5)
N1—C1—C2—N2	−45.6 (7)	C6—N4—C7—C8	77.3 (6)
C10—N2—C3—C4	−162.9 (5)	Ni1—N4—C7—C8	−38.7 (5)
C2—N2—C3—C4	76.2 (6)	C1—N1—C8—C7	−155.5 (5)
Ni1—N2—C3—C4	−39.7 (5)	C9—N1—C8—C7	81.7 (6)
C11—N3—C4—C3	82.9 (6)	Ni1—N1—C8—C7	−39.1 (5)
C5—N3—C4—C3	−155.1 (5)	N4—C7—C8—N1	54.2 (6)
Ni1—N3—C4—C3	−38.5 (5)	Ni1—O1—C13—O2	4.1 (5)
N2—C3—C4—N3	54.7 (6)	Ni1—O1—C13—C14	−176.2 (5)
C11—N3—C5—C6	−73.8 (6)	Ni1—O2—C13—O1	−4.0 (5)
C4—N3—C5—C6	164.2 (4)	Ni1—O2—C13—C14	176.3 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···F2^i	0.99	2.50	3.202 (7)	127
C1—H1B···F5^ii	0.99	2.63	3.389 (8)	133
C2—H2A···F3^ii	0.99	2.47	3.451 (8)	170
C4—H4B···F3^i	0.99	2.53	3.362 (7)	141
C5—H5B···O2^iii	0.99	2.58	3.442 (7)	146
C7—H7A···F1^iv	0.99	2.50	3.480 (8)	169
C8—H8A···O1^v	0.99	2.47	3.337 (7)	146
C12—H12B···F2^iii	0.98	2.62	3.412 (7)	138
C14—H14B···F2	0.98	2.63	3.402 (7)	136

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

(2) (Acetamidato-κ²O,O')(1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane-κ⁴N)nickel(II) hexafluoridophosphate

Crystal data

[Ni(C2H4NO)(C12H28N4)]PF6	Z = 2
Mr = 490.12	F(000) = 512
Triclinic, P1	Dx = 1.541 Mg m^−3
a = 8.0392 (10) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.6289 (10) Å	Cell parameters from 4379 reflections
c = 15.8882 (19) Å	θ = 2.5–21.9°
α = 78.883 (2)°	µ = 1.06 mm^−1
β = 89.641 (2)°	T = 200 K
γ = 77.826 (2)°	Plate, blue
V = 1056.5 (2) Å^3	0.49 × 0.34 × 0.07 mm

Data collection

Bruker APEXII diffractometer	3720 reflections with I > 2σ(I)
Detector resolution: 8.33 pixels mm^-1	Rint = 0.064
φ and ω scans	θmax = 27.8°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −10→10
Tmin = 0.592, Tmax = 0.746	k = −11→11
26793 measured reflections	l = −20→20
4810 independent reflections

Refinement

Refinement on F^2	7 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.090	w = 1/[σ^2(Fo^2) + (0.0317P)^2 + 0.7758P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max = 0.001
4810 reflections	Δρmax = 0.80 e Å^−3
271 parameters	Δρmin = −0.56 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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ni1	0.35609 (4)	0.45003 (4)	0.23694 (2)	0.02149 (10)
N1	0.1327 (3)	0.3770 (2)	0.20368 (13)	0.0270 (5)
N2	0.1810 (3)	0.6008 (2)	0.30687 (14)	0.0305 (5)
N3	0.4362 (3)	0.3191 (3)	0.36320 (14)	0.0305 (5)
N4	0.4822 (3)	0.2269 (3)	0.20044 (14)	0.0300 (5)
N5	0.3676 (3)	0.6179 (3)	0.12767 (14)	0.0309 (5)
H5N	0.324 (4)	0.669 (3)	0.0827 (19)	0.037*
O1	0.5728 (2)	0.5622 (2)	0.22545 (11)	0.0326 (4)
C1	−0.0044 (3)	0.4356 (3)	0.25969 (19)	0.0355 (6)
H1A	0.0060	0.3596	0.3156	0.043*
H1B	−0.1168	0.4415	0.2327	0.043*
C2	0.0091 (3)	0.6015 (3)	0.2734 (2)	0.0383 (7)
H2A	−0.0157	0.6798	0.2182	0.046*
H2B	−0.0769	0.6371	0.3144	0.046*
C3	0.2052 (4)	0.5275 (4)	0.40008 (18)	0.0437 (7)
H3A	0.0931	0.5421	0.4271	0.052*
H3B	0.2771	0.5852	0.4275	0.052*
C4	0.2877 (4)	0.3487 (4)	0.41657 (17)	0.0398 (7)
H4A	0.3236	0.3113	0.4779	0.048*
H4B	0.2041	0.2866	0.4033	0.048*
C5	0.4942 (4)	0.1463 (3)	0.35932 (18)	0.0385 (7)
H5A	0.3951	0.0946	0.3611	0.046*
H5B	0.5713	0.0904	0.4093	0.046*
C6	0.5869 (4)	0.1323 (3)	0.27709 (19)	0.0434 (7)
H6A	0.6939	0.1713	0.2793	0.052*
H6B	0.6174	0.0172	0.2721	0.052*
C7	0.3485 (4)	0.1458 (3)	0.17720 (19)	0.0378 (7)
H7A	0.3882	0.0275	0.1961	0.045*
H7B	0.3326	0.1687	0.1139	0.045*
C8	0.1782 (3)	0.1982 (3)	0.21629 (19)	0.0340 (6)
H8A	0.0892	0.1590	0.1888	0.041*
H8B	0.1848	0.1506	0.2784	0.041*
C9	0.0800 (4)	0.4469 (4)	0.11289 (18)	0.0398 (7)
H9A	−0.0138	0.4011	0.0965	0.060*
H9B	0.1765	0.4214	0.0763	0.060*
H9C	0.0423	0.5644	0.1057	0.060*
C10	0.2029 (4)	0.7709 (3)	0.2921 (2)	0.0451 (8)
H10A	0.1889	0.8177	0.2306	0.068*
H10B	0.3170	0.7730	0.3125	0.068*
H10C	0.1172	0.8340	0.3234	0.068*
C11	0.5788 (4)	0.3768 (4)	0.39645 (18)	0.0432 (7)
H11A	0.5461	0.4940	0.3927	0.065*
H11B	0.6791	0.3514	0.3622	0.065*
H11C	0.6057	0.3232	0.4565	0.065*
C12	0.5965 (4)	0.2496 (4)	0.1273 (2)	0.0442 (7)
H12A	0.6838	0.3047	0.1421	0.066*
H12B	0.5298	0.3150	0.0765	0.066*
H12C	0.6513	0.1439	0.1151	0.066*
C13	0.5097 (3)	0.6448 (3)	0.15271 (16)	0.0268 (5)
C14	0.6060 (4)	0.7611 (3)	0.10163 (18)	0.0383 (7)
H14A	0.6582	0.8139	0.1406	0.057*
H14B	0.5273	0.8430	0.0608	0.057*
H14C	0.6950	0.7020	0.0703	0.057*
P1	0.0000	0.0000	0.0000	0.0250 (2)
P2	0.0000	0.0000	0.5000	0.0295 (2)
F1	0.1916 (2)	−0.0034 (2)	0.02653 (12)	0.0510 (5)
F2	−0.0553 (2)	0.18309 (19)	0.01107 (11)	0.0525 (5)
F3	−0.0372 (2)	−0.0592 (2)	0.09804 (10)	0.0501 (5)
F5	0.1877 (2)	−0.0281 (2)	0.46488 (12)	0.0550 (5)
F4	−0.0669 (4)	0.0535 (5)	0.40314 (17)	0.0837 (13)	0.768 (4)
F6	−0.0068 (5)	0.1836 (3)	0.5021 (3)	0.0833 (13)	0.768 (4)
F4'	−0.0555 (14)	0.1423 (17)	0.4245 (6)	0.0837 (13)	0.232 (4)
F6'	0.0794 (14)	0.1083 (13)	0.5479 (8)	0.0833 (13)	0.232 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.01885 (16)	0.02385 (17)	0.02261 (17)	−0.00717 (12)	0.00068 (12)	−0.00373 (12)
N1	0.0232 (11)	0.0270 (11)	0.0322 (12)	−0.0101 (9)	−0.0006 (9)	−0.0037 (9)
N2	0.0333 (12)	0.0274 (11)	0.0316 (12)	−0.0066 (10)	0.0054 (10)	−0.0079 (9)
N3	0.0281 (12)	0.0336 (12)	0.0291 (12)	−0.0086 (10)	−0.0011 (9)	−0.0020 (9)
N4	0.0272 (12)	0.0290 (11)	0.0353 (12)	−0.0064 (9)	0.0052 (10)	−0.0100 (10)
N5	0.0275 (12)	0.0351 (13)	0.0290 (12)	−0.0118 (10)	−0.0022 (10)	0.0023 (10)
O1	0.0242 (9)	0.0384 (10)	0.0353 (10)	−0.0124 (8)	−0.0029 (8)	−0.0009 (8)
C1	0.0188 (13)	0.0413 (16)	0.0465 (17)	−0.0086 (12)	0.0040 (12)	−0.0070 (13)
C2	0.0260 (14)	0.0366 (15)	0.0503 (18)	−0.0010 (12)	0.0071 (13)	−0.0095 (13)
C3	0.0502 (19)	0.0506 (18)	0.0285 (15)	−0.0040 (15)	0.0099 (13)	−0.0114 (13)
C4	0.0428 (17)	0.0485 (18)	0.0246 (14)	−0.0089 (14)	0.0041 (12)	0.0007 (12)
C5	0.0384 (16)	0.0322 (15)	0.0379 (16)	−0.0026 (13)	−0.0065 (13)	0.0048 (12)
C6	0.0386 (17)	0.0353 (16)	0.0503 (19)	0.0054 (13)	−0.0024 (14)	−0.0087 (14)
C7	0.0397 (16)	0.0309 (14)	0.0490 (18)	−0.0128 (13)	0.0052 (14)	−0.0173 (13)
C8	0.0324 (15)	0.0288 (14)	0.0443 (16)	−0.0143 (12)	−0.0005 (12)	−0.0067 (12)
C9	0.0372 (16)	0.0476 (17)	0.0369 (16)	−0.0196 (14)	−0.0113 (13)	−0.0016 (13)
C10	0.0541 (19)	0.0306 (15)	0.0554 (19)	−0.0114 (14)	0.0117 (15)	−0.0180 (14)
C11	0.0416 (18)	0.0558 (19)	0.0330 (16)	−0.0165 (15)	−0.0119 (13)	−0.0039 (14)
C12	0.0420 (18)	0.0470 (17)	0.0488 (18)	−0.0112 (14)	0.0224 (14)	−0.0213 (15)
C13	0.0236 (13)	0.0255 (13)	0.0319 (14)	−0.0063 (10)	0.0055 (11)	−0.0060 (11)
C14	0.0342 (16)	0.0371 (15)	0.0440 (17)	−0.0157 (13)	0.0084 (13)	−0.0005 (13)
P1	0.0247 (5)	0.0230 (4)	0.0275 (5)	−0.0072 (4)	−0.0016 (4)	−0.0029 (4)
P2	0.0267 (5)	0.0293 (5)	0.0290 (5)	−0.0038 (4)	0.0048 (4)	0.0002 (4)
F1	0.0301 (9)	0.0613 (12)	0.0611 (12)	−0.0167 (8)	−0.0103 (8)	−0.0023 (9)
F2	0.0700 (13)	0.0269 (8)	0.0594 (12)	−0.0036 (8)	−0.0076 (10)	−0.0127 (8)
F3	0.0555 (11)	0.0592 (11)	0.0308 (9)	−0.0113 (9)	0.0046 (8)	0.0021 (8)
F5	0.0328 (10)	0.0643 (12)	0.0615 (12)	−0.0037 (9)	0.0178 (8)	−0.0046 (10)
F4	0.0581 (15)	0.142 (4)	0.0265 (14)	0.036 (2)	−0.0048 (12)	−0.0184 (16)
F6	0.080 (2)	0.0326 (17)	0.148 (4)	−0.0216 (15)	0.072 (2)	−0.0359 (19)
F4'	0.0581 (15)	0.142 (4)	0.0265 (14)	0.036 (2)	−0.0048 (12)	−0.0184 (16)
F6'	0.080 (2)	0.0326 (17)	0.148 (4)	−0.0216 (15)	0.072 (2)	−0.0359 (19)

Geometric parameters (Å, º)

Ni1—N1	2.126 (2)	C1—C2	1.514 (4)
Ni1—N2	2.162 (2)	C3—C4	1.518 (4)
Ni1—N3	2.133 (2)	C5—C6	1.513 (4)
Ni1—N4	2.162 (2)	C7—C8	1.517 (4)
Ni1—O1	2.1550 (17)	C13—C14	1.506 (3)
Ni1—N5	2.051 (2)	P1—F3	1.5901 (16)
N5—C13	1.293 (3)	P1—F3^i	1.5901 (16)
O1—C13	1.280 (3)	P1—F2^i	1.5920 (15)
Ni1—C13	2.476 (2)	P1—F2	1.5920 (15)
N1—C9	1.479 (3)	P1—F1	1.5921 (16)
N1—C1	1.480 (3)	P1—F1^i	1.5921 (16)
N1—C8	1.482 (3)	P2—F4'^ii	1.534 (10)
N2—C2	1.483 (3)	P2—F4'	1.534 (10)
N2—C10	1.488 (3)	P2—F6'	1.546 (9)
N2—C3	1.491 (3)	P2—F6'^ii	1.546 (9)
N3—C4	1.467 (3)	P2—F6^ii	1.581 (2)
N3—C5	1.478 (3)	P2—F6	1.581 (2)
N3—C11	1.480 (3)	P2—F4	1.582 (3)
N4—C6	1.482 (3)	P2—F4^ii	1.582 (3)
N4—C7	1.484 (3)	P2—F5	1.5921 (16)
N4—C12	1.486 (3)	P2—F5^ii	1.5921 (16)
N5—Ni1—N1	98.45 (8)	N4—C7—C8	113.8 (2)
N5—Ni1—N3	154.59 (9)	N1—C8—C7	109.8 (2)
N1—Ni1—N3	106.87 (8)	O1—C13—N5	116.3 (2)
N5—Ni1—O1	62.55 (8)	O1—C13—C14	118.9 (2)
N1—Ni1—O1	160.58 (7)	N5—C13—C14	124.8 (2)
N3—Ni1—O1	92.31 (7)	O1—C13—Ni1	60.47 (12)
N5—Ni1—N4	102.31 (9)	N5—C13—Ni1	55.83 (13)
N1—Ni1—N4	82.96 (8)	C14—C13—Ni1	179.01 (19)
N3—Ni1—N4	83.10 (8)	F3—P1—F3^i	180.0
O1—Ni1—N4	96.65 (8)	F3—P1—F2^i	90.02 (9)
N5—Ni1—N2	98.93 (9)	F3^i—P1—F2^i	89.98 (9)
N1—Ni1—N2	83.27 (8)	F3—P1—F2	89.98 (9)
N3—Ni1—N2	82.37 (8)	F3^i—P1—F2	90.02 (9)
O1—Ni1—N2	102.76 (8)	F2^i—P1—F2	180.0
N4—Ni1—N2	156.13 (8)	F3—P1—F1	89.76 (9)
N5—Ni1—C13	31.43 (8)	F3^i—P1—F1	90.24 (9)
N1—Ni1—C13	129.80 (8)	F2^i—P1—F1	89.70 (10)
N3—Ni1—C13	123.32 (8)	F2—P1—F1	90.30 (10)
O1—Ni1—C13	31.12 (7)	F3—P1—F1^i	90.24 (9)
N4—Ni1—C13	101.36 (8)	F3^i—P1—F1^i	89.76 (9)
N2—Ni1—C13	102.44 (8)	F2^i—P1—F1^i	90.30 (10)
C9—N1—C1	109.4 (2)	F2—P1—F1^i	89.70 (10)
C9—N1—C8	109.8 (2)	F1—P1—F1^i	180.0
C1—N1—C8	112.9 (2)	F4'^ii—P2—F4'	180.0
C9—N1—Ni1	110.52 (15)	F4'^ii—P2—F6'	89.6 (6)
C1—N1—Ni1	108.13 (15)	F4'—P2—F6'	90.4 (6)
C8—N1—Ni1	106.11 (15)	F4'^ii—P2—F6'^ii	90.4 (6)
C2—N2—C10	108.1 (2)	F4'—P2—F6'^ii	89.6 (6)
C2—N2—C3	111.9 (2)	F6'—P2—F6'^ii	180.0
C10—N2—C3	109.9 (2)	F6^ii—P2—F6	180.0
C2—N2—Ni1	105.25 (15)	F6^ii—P2—F4	91.32 (19)
C10—N2—Ni1	113.30 (17)	F6—P2—F4	88.68 (19)
C3—N2—Ni1	108.34 (16)	F6^ii—P2—F4^ii	88.68 (19)
C4—N3—C5	112.6 (2)	F6—P2—F4^ii	91.32 (19)
C4—N3—C11	110.1 (2)	F4—P2—F4^ii	180.0 (3)
C5—N3—C11	108.9 (2)	F4'^ii—P2—F5	90.6 (4)
C4—N3—Ni1	106.05 (16)	F4'—P2—F5	89.4 (4)
C5—N3—Ni1	108.28 (16)	F6'—P2—F5	79.6 (4)
C11—N3—Ni1	110.87 (16)	F6'^ii—P2—F5	100.4 (4)
C6—N4—C7	112.4 (2)	F6^ii—P2—F5	86.56 (12)
C6—N4—C12	108.4 (2)	F6—P2—F5	93.44 (12)
C7—N4—C12	109.2 (2)	F4—P2—F5	87.30 (13)
C6—N4—Ni1	105.33 (16)	F4^ii—P2—F5	92.70 (13)
C7—N4—Ni1	107.69 (15)	F4'^ii—P2—F5^ii	89.4 (4)
C12—N4—Ni1	113.80 (16)	F4'—P2—F5^ii	90.6 (4)
C13—N5—Ni1	92.74 (16)	F6'—P2—F5^ii	100.4 (4)
C13—O1—Ni1	88.41 (14)	F6'^ii—P2—F5^ii	79.6 (4)
N1—C1—C2	109.4 (2)	F6^ii—P2—F5^ii	93.44 (12)
N2—C2—C1	111.5 (2)	F6—P2—F5^ii	86.56 (12)
N2—C3—C4	112.8 (2)	F4—P2—F5^ii	92.70 (13)
N3—C4—C3	110.4 (2)	F4^ii—P2—F5^ii	87.30 (13)
N3—C5—C6	109.2 (2)	F5—P2—F5^ii	180.0
N4—C6—C5	112.0 (2)
C9—N1—C1—C2	−82.4 (3)	Ni1—N3—C5—C6	37.7 (3)
C8—N1—C1—C2	155.0 (2)	C7—N4—C6—C5	−76.7 (3)
Ni1—N1—C1—C2	38.0 (2)	C12—N4—C6—C5	162.5 (2)
C10—N2—C2—C1	162.0 (2)	Ni1—N4—C6—C5	40.3 (3)
C3—N2—C2—C1	−76.9 (3)	N3—C5—C6—N4	−54.2 (3)
Ni1—N2—C2—C1	40.6 (3)	C6—N4—C7—C8	93.1 (3)
N1—C1—C2—N2	−54.6 (3)	C12—N4—C7—C8	−146.5 (2)
C2—N2—C3—C4	94.1 (3)	Ni1—N4—C7—C8	−22.5 (3)
C10—N2—C3—C4	−145.8 (3)	C9—N1—C8—C7	73.7 (3)
Ni1—N2—C3—C4	−21.5 (3)	C1—N1—C8—C7	−164.0 (2)
C5—N3—C4—C3	−165.0 (2)	Ni1—N1—C8—C7	−45.7 (2)
C11—N3—C4—C3	73.2 (3)	N4—C7—C8—N1	47.1 (3)
Ni1—N3—C4—C3	−46.8 (3)	Ni1—O1—C13—N5	−0.9 (2)
N2—C3—C4—N3	47.1 (3)	Ni1—O1—C13—C14	−179.1 (2)
C4—N3—C5—C6	154.6 (2)	Ni1—N5—C13—O1	0.9 (2)
C11—N3—C5—C6	−82.9 (3)	Ni1—N5—C13—C14	179.0 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5N···F2^iii	0.80 (3)	2.58 (3)	3.302 (3)	150 (3)
C1—H1A···F4′	0.99	2.43	3.362 (12)	158
C1—H1B···O1^iv	0.99	2.49	3.357 (3)	146
C2—H2A···F3^v	0.99	2.63	3.589 (3)	162
C4—H4B···F6	0.99	2.49	3.181 (4)	127
C4—H4B···F4′	0.99	2.64	3.576 (16)	159
C5—H5A···F5	0.99	2.58	3.419 (3)	143
C7—H7B···F1	0.99	2.64	3.301 (3)	125
C9—H9A···F2	0.98	2.60	3.386 (3)	138
C9—H9C···F2^iii	0.98	2.60	3.380 (3)	137
C10—H10C···F6′^vi	0.98	2.64	3.557 (10)	157
C11—H11B···F4′^vii	0.98	2.55	3.177 (10)	122

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