Crystal and molecular structure of [Ni{2-H₂NC(=O)C₅H₄N}₂(H₂O)₂][Ni{2,6-(O₂C)₂C₅H₃N}₂]·4.67H₂O; DFT studies on hydrogen bonding energies in the crystal

[Ni{2-H₂NC(=O)C₅H₄N}₂(H₂O)₂][Ni{2,6-(O₂C)₂C₅H₃N}₂]·4.67H₂O, a new complex salt containing a bis(2,6-di­carb­oxy­pyridine)­nickel(II) anion and a bis(2-amido­pyridine)­diaqua­nickel(II) cation, was synthesized and characterized. The crystal is stabilized by an extensive network of hydrogen bonds. Alternate layers of anions and cations/water molecules parallel to (010) can be distinguished. Computational studies of the network packing of the title compound by high-level DFT-D/B3LYP calculations indicate stabilization of the networks with conventional and non-conventional intermolecular O—H...O, N—H...O and C—H...O hydrogen bonds along with π-stacking contacts. Due to the presence of water molecules and the importance of forming hydrogen bonds with the involvement of water clusters to the stability of the crystal packing, the importance and role of these water clusters, and the quantitative stability resulting from the formation of hydrogen bonds and possibly other noncovalent bonds such as π-stacking are examined. The binding energies obtained by DFT-D calculations for these contacts indicate that hydrogen bonds, especially O—H...O and N—H...O, control the construction of the crystalline packing. Additionally, the results of Bader's theory of AIM for these interactions agree reasonably well with the calculated energies.

Computing details

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/6 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Diaqua-bis(pyridine-2-carboxamide-N,O)-nickel(ii) bis(2,6-pyridinedicarboxylato)-nickel(ii) 4.67-hydrate

Crystal data

C26H31.34N6Ni2O16.67	Z = 2
Mr = 813.49	F(000) = 839
Triclinic, P1	Dx = 1.627 Mg m^−3
a = 10.1294 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.2011 (9) Å	Cell parameters from 5643 reflections
c = 14.2430 (11) Å	θ = 2.2–27.5°
α = 82.035 (4)°	µ = 1.22 mm^−1
β = 74.232 (3)°	T = 296 K
γ = 79.373 (3)°	Prism, blue
V = 1657.7 (2) Å^3	0.38 × 0.20 × 0.18 mm

Data collection

Bruker Kappa APEXII CCD diffractometer	7584 independent reflections
Radiation source: fine-focus sealed tube	5642 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.047
Detector resolution: 0.76 pixels mm^-1	θmax = 27.5°, θmin = 2.2°
ω scans	h = −13→11
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −15→15
Tmin = 0.640, Tmax = 0.840	l = −18→18
20962 measured reflections

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.113	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.054P)^2 + 0.0685P] where P = (Fo^2 + 2Fc^2)/3
7584 reflections	(Δ/σ)max = 0.001
515 parameters	Δρmax = 0.64 e Å^−3
18 restraints	Δρmin = −0.34 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ni1	0.26869 (3)	0.49927 (3)	0.25271 (2)	0.02749 (10)
O1	0.15048 (19)	0.36721 (16)	0.32202 (14)	0.0360 (4)
O2	0.0623 (2)	0.28291 (17)	0.46869 (14)	0.0427 (5)
O3	0.36664 (19)	0.64061 (16)	0.24888 (14)	0.0382 (5)
O4	0.3919 (2)	0.75572 (18)	0.35097 (16)	0.0519 (6)
O5	0.45482 (19)	0.38287 (17)	0.21684 (15)	0.0414 (5)
O6	0.5781 (2)	0.27569 (19)	0.09867 (18)	0.0541 (6)
O7	0.09136 (18)	0.61167 (15)	0.22332 (13)	0.0344 (4)
O8	−0.0027 (2)	0.68393 (18)	0.09874 (15)	0.0453 (5)
N1	0.2475 (2)	0.50913 (17)	0.39231 (15)	0.0281 (5)
N2	0.2832 (2)	0.47969 (17)	0.11548 (15)	0.0279 (5)
C1	0.1276 (3)	0.3538 (2)	0.4139 (2)	0.0316 (6)
C2	0.1858 (3)	0.4340 (2)	0.45899 (18)	0.0293 (6)
C3	0.1804 (3)	0.4343 (3)	0.5567 (2)	0.0445 (7)
H3	0.1372	0.3820	0.6031	0.053*
C4	0.2403 (4)	0.5138 (3)	0.5845 (2)	0.0535 (9)
H4	0.2392	0.5146	0.6499	0.064*
C5	0.3016 (3)	0.5917 (3)	0.5144 (2)	0.0439 (7)
H5	0.3420	0.6457	0.5319	0.053*
C6	0.3021 (3)	0.5883 (2)	0.4189 (2)	0.0315 (6)
C7	0.3592 (3)	0.6686 (2)	0.3325 (2)	0.0365 (6)
C8	0.4823 (3)	0.3496 (2)	0.1330 (2)	0.0372 (6)
C9	0.3845 (3)	0.4048 (2)	0.0699 (2)	0.0331 (6)
C10	0.3945 (3)	0.3837 (3)	−0.0244 (2)	0.0476 (8)
H10	0.4662	0.3318	−0.0562	0.057*
C11	0.2948 (3)	0.4421 (3)	−0.0708 (2)	0.0530 (8)
H11	0.2995	0.4298	−0.1347	0.064*
C12	0.1884 (3)	0.5184 (3)	−0.0218 (2)	0.0436 (7)
H12	0.1199	0.5568	−0.0515	0.052*
C13	0.1866 (3)	0.5360 (2)	0.07185 (19)	0.0293 (5)
C14	0.0821 (3)	0.6173 (2)	0.1356 (2)	0.0328 (6)
Ni2	0.09828 (3)	0.07788 (3)	0.71413 (2)	0.02964 (10)
O9	0.1893 (2)	−0.06232 (17)	0.78693 (16)	0.0446 (5)
O10	0.04663 (18)	−0.03287 (16)	0.63522 (15)	0.0395 (5)
O11	0.1795 (2)	0.1826 (2)	0.77421 (17)	0.0455 (5)
H11A	0.2523 (19)	0.166 (3)	0.790 (2)	0.055*
H11B	0.130 (3)	0.223 (2)	0.814 (2)	0.055*
O12	−0.02329 (19)	0.21512 (16)	0.66076 (15)	0.0340 (4)
H12A	−0.034 (3)	0.2682 (17)	0.691 (2)	0.041*
H12B	0.007 (3)	0.239 (2)	0.6049 (10)	0.041*
N3	−0.0662 (2)	0.05063 (18)	0.83220 (16)	0.0313 (5)
N4	0.2550 (2)	0.08274 (18)	0.58697 (16)	0.0302 (5)
N5	0.1445 (3)	−0.1874 (2)	0.9188 (2)	0.0483 (7)
H5A	0.2309 (14)	−0.218 (3)	0.905 (2)	0.058*
H5B	0.079 (2)	−0.213 (3)	0.9649 (18)	0.058*
N6	0.1393 (3)	−0.1384 (2)	0.5094 (2)	0.0451 (6)
H6A	0.074 (2)	−0.178 (2)	0.528 (2)	0.054*
H6B	0.210 (2)	−0.151 (3)	0.4611 (17)	0.054*
C15	0.1056 (3)	−0.0996 (2)	0.8623 (2)	0.0370 (6)
C16	−0.0417 (3)	−0.0418 (2)	0.8900 (2)	0.0344 (6)
C17	−0.1426 (3)	−0.0800 (3)	0.9671 (2)	0.0503 (8)
H17	−0.1223	−0.1454	1.0061	0.060*
C18	−0.2759 (3)	−0.0187 (3)	0.9856 (2)	0.0562 (9)
H18	−0.3465	−0.0425	1.0370	0.067*
C19	−0.3013 (3)	0.0774 (3)	0.9264 (2)	0.0495 (8)
H19	−0.3890	0.1206	0.9381	0.059*
C20	−0.1964 (3)	0.1089 (3)	0.8504 (2)	0.0424 (7)
H20	−0.2150	0.1729	0.8095	0.051*
C21	0.1374 (3)	−0.0550 (2)	0.5581 (2)	0.0326 (6)
C22	0.2481 (3)	0.0183 (2)	0.5200 (2)	0.0325 (6)
C23	0.3319 (3)	0.0229 (3)	0.4265 (2)	0.0457 (7)
H23	0.3247	−0.0229	0.3817	0.055*
C24	0.4278 (3)	0.0969 (3)	0.3997 (2)	0.0526 (8)
H24	0.4853	0.1021	0.3365	0.063*
C25	0.4358 (3)	0.1621 (3)	0.4682 (2)	0.0482 (8)
H25	0.4994	0.2121	0.4522	0.058*
C26	0.3492 (3)	0.1532 (2)	0.5608 (2)	0.0392 (7)
H26	0.3559	0.1974	0.6070	0.047*
O13	0.6818 (3)	0.2837 (3)	0.3017 (2)	0.0702 (8)
H13A	0.610 (2)	0.305 (4)	0.285 (3)	0.084*
H13B	0.700 (4)	0.229 (2)	0.271 (3)	0.070*
O14	0.4502 (3)	0.0784 (3)	0.1621 (3)	0.0875 (9)
H14A	0.3648 (13)	0.095 (4)	0.184 (3)	0.105*
H14B	0.494 (4)	0.129 (3)	0.135 (3)	0.105*
O15	0.9395 (6)	0.3782 (6)	0.2050 (4)	0.107 (3)	0.670 (8)
H15A	0.984 (8)	0.332 (6)	0.235 (6)	0.129*	0.670 (8)
H15B	0.864 (4)	0.358 (7)	0.224 (6)	0.129*	0.670 (8)
O16	0.4325 (2)	0.1375 (2)	0.8005 (2)	0.0620 (7)
H16A	0.468 (4)	0.0721 (13)	0.804 (3)	0.074*
H16B	0.493 (3)	0.166 (3)	0.760 (2)	0.074*
O17	0.1736 (3)	0.1601 (3)	0.2442 (3)	0.0897 (10)
H17A	0.122 (4)	0.121 (4)	0.283 (3)	0.108*
H17B	0.172 (5)	0.2251 (16)	0.254 (4)	0.108*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.03361 (18)	0.02521 (18)	0.02208 (19)	−0.00571 (13)	−0.00441 (13)	−0.00071 (14)
O1	0.0510 (11)	0.0350 (11)	0.0254 (11)	−0.0189 (9)	−0.0093 (8)	0.0012 (8)
O2	0.0596 (12)	0.0419 (12)	0.0317 (12)	−0.0311 (10)	−0.0079 (9)	0.0037 (9)
O3	0.0475 (11)	0.0365 (11)	0.0293 (11)	−0.0189 (9)	−0.0006 (9)	0.0000 (9)
O4	0.0717 (14)	0.0432 (13)	0.0443 (14)	−0.0363 (11)	−0.0018 (11)	−0.0052 (10)
O5	0.0415 (11)	0.0408 (12)	0.0399 (13)	0.0034 (9)	−0.0138 (9)	−0.0034 (10)
O6	0.0409 (11)	0.0495 (14)	0.0645 (16)	0.0137 (10)	−0.0096 (10)	−0.0162 (12)
O7	0.0431 (10)	0.0309 (10)	0.0251 (11)	0.0030 (8)	−0.0071 (8)	−0.0040 (8)
O8	0.0485 (12)	0.0450 (12)	0.0356 (12)	0.0149 (10)	−0.0143 (9)	−0.0034 (10)
N1	0.0341 (11)	0.0250 (11)	0.0254 (12)	−0.0095 (9)	−0.0063 (9)	0.0009 (9)
N2	0.0307 (11)	0.0261 (11)	0.0237 (12)	−0.0028 (9)	−0.0025 (9)	−0.0023 (9)
C1	0.0362 (14)	0.0294 (14)	0.0318 (16)	−0.0116 (11)	−0.0110 (12)	0.0015 (12)
C2	0.0369 (13)	0.0305 (14)	0.0208 (14)	−0.0129 (11)	−0.0060 (11)	0.0044 (11)
C3	0.067 (2)	0.0457 (18)	0.0264 (16)	−0.0303 (15)	−0.0111 (14)	0.0062 (13)
C4	0.090 (2)	0.055 (2)	0.0260 (17)	−0.0344 (18)	−0.0202 (16)	0.0032 (15)
C5	0.0604 (18)	0.0438 (18)	0.0354 (17)	−0.0264 (15)	−0.0135 (14)	−0.0032 (14)
C6	0.0363 (14)	0.0285 (14)	0.0309 (15)	−0.0126 (11)	−0.0053 (11)	−0.0031 (11)
C7	0.0383 (15)	0.0368 (16)	0.0346 (17)	−0.0163 (12)	−0.0040 (12)	0.0000 (13)
C8	0.0331 (14)	0.0299 (15)	0.0454 (19)	−0.0034 (11)	−0.0059 (12)	−0.0029 (13)
C9	0.0324 (13)	0.0325 (15)	0.0302 (15)	−0.0025 (11)	−0.0012 (11)	−0.0054 (12)
C10	0.0478 (17)	0.0485 (19)	0.0405 (19)	0.0048 (14)	−0.0016 (14)	−0.0189 (15)
C11	0.067 (2)	0.061 (2)	0.0290 (17)	0.0042 (17)	−0.0123 (15)	−0.0175 (15)
C12	0.0488 (17)	0.0463 (18)	0.0348 (18)	0.0023 (14)	−0.0148 (13)	−0.0054 (14)
C13	0.0342 (13)	0.0254 (13)	0.0264 (14)	−0.0024 (10)	−0.0065 (11)	−0.0016 (11)
C14	0.0361 (14)	0.0292 (14)	0.0292 (16)	−0.0016 (11)	−0.0046 (11)	−0.0016 (12)
Ni2	0.02957 (18)	0.02692 (19)	0.0272 (2)	−0.00476 (13)	0.00123 (14)	−0.00129 (14)
O9	0.0405 (11)	0.0428 (12)	0.0401 (13)	0.0003 (9)	−0.0019 (9)	0.0053 (10)
O10	0.0371 (10)	0.0350 (11)	0.0418 (13)	−0.0117 (8)	0.0037 (9)	−0.0078 (9)
O11	0.0358 (11)	0.0552 (14)	0.0480 (14)	0.0013 (10)	−0.0105 (10)	−0.0248 (11)
O12	0.0393 (10)	0.0287 (11)	0.0289 (11)	−0.0039 (8)	−0.0017 (9)	−0.0014 (8)
N3	0.0289 (11)	0.0283 (12)	0.0305 (13)	−0.0004 (9)	−0.0020 (9)	0.0014 (10)
N4	0.0290 (10)	0.0291 (12)	0.0299 (13)	−0.0062 (9)	−0.0017 (9)	−0.0032 (9)
N5	0.0419 (14)	0.0443 (16)	0.0493 (18)	0.0042 (12)	−0.0093 (13)	0.0083 (13)
N6	0.0535 (16)	0.0394 (15)	0.0428 (17)	−0.0185 (12)	−0.0012 (12)	−0.0121 (12)
C15	0.0387 (15)	0.0346 (16)	0.0370 (17)	−0.0021 (12)	−0.0121 (13)	−0.0013 (13)
C16	0.0352 (14)	0.0391 (16)	0.0278 (15)	−0.0056 (12)	−0.0072 (11)	−0.0004 (12)
C17	0.0458 (17)	0.060 (2)	0.0373 (19)	−0.0081 (15)	−0.0061 (14)	0.0136 (16)
C18	0.0390 (16)	0.076 (3)	0.041 (2)	−0.0089 (16)	0.0054 (14)	0.0070 (18)
C19	0.0335 (15)	0.060 (2)	0.047 (2)	0.0027 (14)	−0.0050 (14)	−0.0032 (17)
C20	0.0399 (16)	0.0419 (17)	0.0393 (18)	−0.0034 (13)	−0.0048 (13)	0.0022 (14)
C21	0.0346 (14)	0.0280 (14)	0.0355 (16)	−0.0054 (11)	−0.0095 (12)	−0.0022 (12)
C22	0.0342 (14)	0.0276 (14)	0.0329 (16)	−0.0051 (11)	−0.0038 (11)	−0.0023 (12)
C23	0.0522 (17)	0.0468 (19)	0.0345 (18)	−0.0143 (14)	0.0026 (13)	−0.0101 (14)
C24	0.0554 (19)	0.061 (2)	0.0336 (18)	−0.0212 (16)	0.0099 (14)	−0.0036 (16)
C25	0.0441 (17)	0.053 (2)	0.045 (2)	−0.0257 (15)	0.0014 (14)	0.0001 (16)
C26	0.0388 (15)	0.0372 (16)	0.0406 (18)	−0.0145 (12)	−0.0019 (13)	−0.0051 (13)
O13	0.0625 (16)	0.102 (2)	0.0541 (18)	−0.0089 (16)	−0.0245 (14)	−0.0200 (15)
O14	0.0760 (19)	0.0583 (19)	0.116 (3)	−0.0137 (16)	0.0012 (19)	−0.0142 (18)
O15	0.103 (4)	0.169 (6)	0.068 (4)	−0.060 (4)	−0.041 (3)	0.017 (3)
O16	0.0388 (13)	0.0720 (18)	0.0656 (18)	−0.0178 (12)	−0.0053 (11)	0.0228 (15)
O17	0.095 (2)	0.085 (2)	0.087 (2)	−0.0407 (18)	0.0138 (17)	−0.041 (2)

Geometric parameters (Å, º)

Ni1—N1	1.959 (2)	O10—C21	1.251 (3)
Ni1—N2	1.964 (2)	O11—H11A	0.807 (10)
Ni1—O5	2.1266 (19)	O11—H11B	0.805 (10)
Ni1—O3	2.1301 (18)	O12—H12A	0.806 (10)
Ni1—O7	2.1502 (17)	O12—H12B	0.805 (10)
Ni1—O1	2.1524 (17)	N3—C16	1.327 (3)
O1—C1	1.257 (3)	N3—C20	1.353 (3)
O2—C1	1.240 (3)	N4—C22	1.340 (3)
O3—C7	1.263 (3)	N4—C26	1.345 (3)
O4—C7	1.250 (3)	N5—C15	1.314 (4)
O5—C8	1.257 (4)	N5—H5A	0.866 (10)
O6—C8	1.239 (3)	N5—H5B	0.867 (10)
O7—C14	1.269 (3)	N6—C21	1.304 (4)
O8—C14	1.243 (3)	N6—H6A	0.850 (10)
N1—C2	1.334 (3)	N6—H6B	0.853 (10)
N1—C6	1.340 (3)	C15—C16	1.500 (4)
N2—C9	1.328 (3)	C16—C17	1.376 (4)
N2—C13	1.335 (3)	C17—C18	1.393 (4)
C1—C2	1.521 (3)	C17—H17	0.9300
C2—C3	1.377 (4)	C18—C19	1.373 (5)
C3—C4	1.386 (4)	C18—H18	0.9300
C3—H3	0.9300	C19—C20	1.363 (4)
C4—C5	1.380 (4)	C19—H19	0.9300
C4—H4	0.9300	C20—H20	0.9300
C5—C6	1.365 (4)	C21—C22	1.501 (4)
C5—H5	0.9300	C22—C23	1.371 (4)
C6—C7	1.516 (4)	C23—C24	1.390 (4)
C8—C9	1.520 (4)	C23—H23	0.9300
C9—C10	1.376 (4)	C24—C25	1.369 (5)
C10—C11	1.390 (4)	C24—H24	0.9300
C10—H10	0.9300	C25—C26	1.373 (4)
C11—C12	1.385 (4)	C25—H25	0.9300
C11—H11	0.9300	C26—H26	0.9300
C12—C13	1.375 (4)	O13—H13A	0.810 (10)
C12—H12	0.9300	O13—H13B	0.810 (10)
C13—C14	1.507 (4)	O14—H14A	0.831 (10)
Ni2—O11	2.029 (2)	O14—H14B	0.821 (10)
Ni2—N3	2.059 (2)	O15—H15A	0.813 (10)
Ni2—N4	2.061 (2)	O15—H15B	0.812 (10)
Ni2—O12	2.0721 (19)	O16—H16A	0.814 (10)
Ni2—O9	2.073 (2)	O16—H16B	0.809 (10)
Ni2—O10	2.089 (2)	O17—H17A	0.821 (10)
O9—C15	1.261 (3)	O17—H17B	0.819 (10)
N1—Ni1—N2	175.84 (8)	N4—Ni2—O12	92.02 (8)
N1—Ni1—O5	101.70 (8)	O11—Ni2—O9	92.10 (9)
N2—Ni1—O5	77.93 (8)	N3—Ni2—O9	79.87 (8)
N1—Ni1—O3	78.20 (8)	N4—Ni2—O9	97.73 (8)
N2—Ni1—O3	105.96 (8)	O12—Ni2—O9	170.09 (8)
O5—Ni1—O3	96.18 (8)	O11—Ni2—O10	170.45 (8)
N1—Ni1—O7	103.04 (8)	N3—Ni2—O10	91.54 (8)
N2—Ni1—O7	77.40 (8)	N4—Ni2—O10	78.94 (8)
O5—Ni1—O7	155.26 (8)	O12—Ni2—O10	93.35 (8)
O3—Ni1—O7	88.89 (7)	O9—Ni2—O10	86.80 (8)
N1—Ni1—O1	77.24 (8)	C15—O9—Ni2	112.71 (17)
N2—Ni1—O1	98.61 (8)	C21—O10—Ni2	113.37 (16)
O5—Ni1—O1	91.61 (8)	Ni2—O11—H11A	124 (2)
O3—Ni1—O1	155.27 (7)	Ni2—O11—H11B	120 (2)
O7—Ni1—O1	93.79 (7)	H11A—O11—H11B	106 (3)
C1—O1—Ni1	114.82 (16)	Ni2—O12—H12A	112 (2)
C7—O3—Ni1	113.96 (16)	Ni2—O12—H12B	116 (2)
C8—O5—Ni1	114.53 (17)	H12A—O12—H12B	104 (3)
C14—O7—Ni1	114.18 (16)	C16—N3—C20	118.0 (2)
C2—N1—C6	120.9 (2)	C16—N3—Ni2	114.15 (17)
C2—N1—Ni1	119.94 (17)	C20—N3—Ni2	127.43 (18)
C6—N1—Ni1	119.04 (17)	C22—N4—C26	118.1 (2)
C9—N2—C13	121.2 (2)	C22—N4—Ni2	114.60 (16)
C9—N2—Ni1	119.00 (18)	C26—N4—Ni2	126.64 (19)
C13—N2—Ni1	119.67 (17)	C15—N5—H5A	119 (2)
O2—C1—O1	125.9 (2)	C15—N5—H5B	116 (2)
O2—C1—C2	118.8 (2)	H5A—N5—H5B	125 (3)
O1—C1—C2	115.2 (2)	C21—N6—H6A	120 (2)
N1—C2—C3	120.6 (2)	C21—N6—H6B	116 (2)
N1—C2—C1	112.5 (2)	H6A—N6—H6B	124 (3)
C3—C2—C1	126.9 (2)	O9—C15—N5	121.7 (3)
C2—C3—C4	118.9 (3)	O9—C15—C16	119.7 (2)
C2—C3—H3	120.6	N5—C15—C16	118.6 (3)
C4—C3—H3	120.6	N3—C16—C17	122.8 (3)
C5—C4—C3	119.5 (3)	N3—C16—C15	113.3 (2)
C5—C4—H4	120.2	C17—C16—C15	123.9 (3)
C3—C4—H4	120.2	C16—C17—C18	118.5 (3)
C6—C5—C4	119.0 (3)	C16—C17—H17	120.7
C6—C5—H5	120.5	C18—C17—H17	120.7
C4—C5—H5	120.5	C19—C18—C17	118.8 (3)
N1—C6—C5	121.1 (2)	C19—C18—H18	120.6
N1—C6—C7	112.1 (2)	C17—C18—H18	120.6
C5—C6—C7	126.8 (2)	C20—C19—C18	119.2 (3)
O4—C7—O3	126.9 (3)	C20—C19—H19	120.4
O4—C7—C6	117.2 (3)	C18—C19—H19	120.4
O3—C7—C6	115.9 (2)	N3—C20—C19	122.6 (3)
O6—C8—O5	126.5 (3)	N3—C20—H20	118.7
O6—C8—C9	117.9 (3)	C19—C20—H20	118.7
O5—C8—C9	115.6 (2)	O10—C21—N6	122.8 (2)
N2—C9—C10	121.1 (3)	O10—C21—C22	118.5 (2)
N2—C9—C8	112.6 (2)	N6—C21—C22	118.8 (3)
C10—C9—C8	126.2 (3)	N4—C22—C23	122.4 (2)
C9—C10—C11	118.3 (3)	N4—C22—C21	112.7 (2)
C9—C10—H10	120.9	C23—C22—C21	124.8 (3)
C11—C10—H10	120.9	C22—C23—C24	119.1 (3)
C12—C11—C10	120.0 (3)	C22—C23—H23	120.4
C12—C11—H11	120.0	C24—C23—H23	120.4
C10—C11—H11	120.0	C25—C24—C23	118.5 (3)
C13—C12—C11	118.3 (3)	C25—C24—H24	120.7
C13—C12—H12	120.8	C23—C24—H24	120.7
C11—C12—H12	120.8	C24—C25—C26	119.5 (3)
N2—C13—C12	121.1 (2)	C24—C25—H25	120.2
N2—C13—C14	112.8 (2)	C26—C25—H25	120.2
C12—C13—C14	126.1 (2)	N4—C26—C25	122.3 (3)
O8—C14—O7	126.0 (3)	N4—C26—H26	118.8
O8—C14—C13	118.4 (2)	C25—C26—H26	118.8
O7—C14—C13	115.6 (2)	H13A—O13—H13B	92 (4)
O11—Ni2—N3	97.61 (9)	H14A—O14—H14B	118 (5)
O11—Ni2—N4	91.83 (9)	H15A—O15—H15B	101 (8)
N3—Ni2—N4	170.32 (9)	H16A—O16—H16B	102 (4)
O11—Ni2—O12	89.37 (9)	H17A—O17—H17B	120 (5)
N3—Ni2—O12	90.22 (8)
Ni1—O1—C1—O2	−179.8 (2)	Ni1—N2—C13—C14	5.0 (3)
Ni1—O1—C1—C2	0.8 (3)	C11—C12—C13—N2	−1.2 (4)
C6—N1—C2—C3	−1.8 (4)	C11—C12—C13—C14	178.3 (3)
Ni1—N1—C2—C3	174.6 (2)	Ni1—O7—C14—O8	−172.5 (2)
C6—N1—C2—C1	178.4 (2)	Ni1—O7—C14—C13	6.4 (3)
Ni1—N1—C2—C1	−5.1 (3)	N2—C13—C14—O8	171.4 (2)
O2—C1—C2—N1	−176.9 (2)	C12—C13—C14—O8	−8.1 (4)
O1—C1—C2—N1	2.6 (3)	N2—C13—C14—O7	−7.6 (3)
O2—C1—C2—C3	3.4 (4)	C12—C13—C14—O7	172.9 (3)
O1—C1—C2—C3	−177.1 (3)	Ni2—O9—C15—N5	−179.3 (2)
N1—C2—C3—C4	−0.2 (5)	Ni2—O9—C15—C16	−0.3 (3)
C1—C2—C3—C4	179.5 (3)	C20—N3—C16—C17	−0.2 (4)
C2—C3—C4—C5	1.2 (5)	Ni2—N3—C16—C17	−173.7 (2)
C3—C4—C5—C6	−0.2 (5)	C20—N3—C16—C15	179.6 (2)
C2—N1—C6—C5	2.8 (4)	Ni2—N3—C16—C15	6.1 (3)
Ni1—N1—C6—C5	−173.6 (2)	O9—C15—C16—N3	−4.0 (4)
C2—N1—C6—C7	−176.7 (2)	N5—C15—C16—N3	175.0 (3)
Ni1—N1—C6—C7	6.9 (3)	O9—C15—C16—C17	175.8 (3)
C4—C5—C6—N1	−1.8 (5)	N5—C15—C16—C17	−5.2 (4)
C4—C5—C6—C7	177.6 (3)	N3—C16—C17—C18	−0.3 (5)
Ni1—O3—C7—O4	−170.3 (2)	C15—C16—C17—C18	179.9 (3)
Ni1—O3—C7—C6	8.6 (3)	C16—C17—C18—C19	−0.2 (5)
N1—C6—C7—O4	168.7 (2)	C17—C18—C19—C20	1.3 (5)
C5—C6—C7—O4	−10.7 (4)	C16—N3—C20—C19	1.3 (5)
N1—C6—C7—O3	−10.3 (3)	Ni2—N3—C20—C19	173.8 (2)
C5—C6—C7—O3	170.3 (3)	C18—C19—C20—N3	−1.9 (5)
Ni1—O5—C8—O6	−173.8 (2)	Ni2—O10—C21—N6	165.6 (2)
Ni1—O5—C8—C9	4.5 (3)	Ni2—O10—C21—C22	−14.9 (3)
C13—N2—C9—C10	0.9 (4)	C26—N4—C22—C23	−0.8 (4)
Ni1—N2—C9—C10	176.4 (2)	Ni2—N4—C22—C23	170.8 (2)
C13—N2—C9—C8	−179.4 (2)	C26—N4—C22—C21	−179.1 (2)
Ni1—N2—C9—C8	−3.9 (3)	Ni2—N4—C22—C21	−7.5 (3)
O6—C8—C9—N2	177.7 (2)	O10—C21—C22—N4	15.4 (4)
O5—C8—C9—N2	−0.8 (4)	N6—C21—C22—N4	−165.0 (3)
O6—C8—C9—C10	−2.6 (4)	O10—C21—C22—C23	−162.9 (3)
O5—C8—C9—C10	178.9 (3)	N6—C21—C22—C23	16.6 (4)
N2—C9—C10—C11	−0.7 (5)	N4—C22—C23—C24	0.0 (5)
C8—C9—C10—C11	179.7 (3)	C21—C22—C23—C24	178.1 (3)
C9—C10—C11—C12	−0.5 (5)	C22—C23—C24—C25	0.6 (5)
C10—C11—C12—C13	1.4 (5)	C23—C24—C25—C26	−0.3 (5)
C9—N2—C13—C12	0.0 (4)	C22—N4—C26—C25	1.0 (4)
Ni1—N2—C13—C12	−175.5 (2)	Ni2—N4—C26—C25	−169.4 (2)
C9—N2—C13—C14	−179.5 (2)	C24—C25—C26—N4	−0.5 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O13^i	0.93	2.57	3.261 (4)	132
C12—H12···O15^ii	0.93	2.41	3.225 (6)	146
O11—H11A···O16	0.81 (1)	1.84 (1)	2.637 (3)	169 (3)
O11—H11B···O8^iii	0.81 (1)	1.87 (1)	2.667 (3)	175 (3)
O12—H12A···O7^iii	0.81 (1)	1.94 (1)	2.735 (3)	170 (3)
O12—H12B···O2	0.81 (1)	1.90 (1)	2.696 (3)	172 (3)
N5—H5A···O6^iv	0.87 (1)	1.92 (1)	2.775 (3)	168 (3)
N5—H5B···O8^v	0.87 (1)	2.18 (2)	2.988 (3)	155 (3)
N6—H6A···O2^vi	0.85 (1)	2.04 (1)	2.864 (3)	164 (3)
N6—H6B···O4^vii	0.85 (1)	2.30 (2)	3.123 (4)	161 (3)
C17—H17···O8^v	0.93	2.59	3.501 (4)	166
C20—H20···O12	0.93	2.52	3.057 (3)	117
C25—H25···O13	0.93	2.59	3.348 (4)	139
C26—H26···O11	0.93	2.57	3.092 (4)	116
O13—H13A···O5	0.81 (1)	2.09 (2)	2.879 (3)	166 (4)
O13—H13B···O9^iv	0.81 (1)	2.28 (2)	3.057 (4)	161 (4)
O14—H14A···O17	0.83 (1)	1.96 (2)	2.779 (4)	168 (5)
O14—H14B···O6	0.82 (1)	2.06 (2)	2.864 (4)	166 (5)
O15—H15A···O1^viii	0.81 (1)	2.46 (7)	3.022 (5)	127 (8)
O15—H15A···O17^viii	0.81 (1)	2.58 (5)	3.316 (8)	152 (9)
O15—H15B···O13	0.81 (1)	2.16 (2)	2.959 (6)	167 (8)
O16—H16A···O14^iv	0.81 (1)	1.92 (1)	2.726 (4)	169 (4)
O16—H16B···O4^i	0.81 (1)	1.94 (1)	2.740 (3)	168 (4)
O17—H17A···O10^vi	0.82 (1)	2.16 (2)	2.965 (3)	167 (5)
O17—H17B···O1	0.82 (1)	2.05 (2)	2.844 (4)	162 (5)

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