[N,N,N′,N′-Tetra­kis(benzimidazol-2-yl­meth­yl)cyclo­hexane-1,2-diamine]­nickel(II) dinitrate dihydrate

In the title compound, [Ni(C₃₈H₃₈N₁₀)](NO₃)₂·2H₂O, the Ni^II ion is located on a crystallographic twofold rotation axis and is in a distorted octa­hedral coordination environment. The crystal structure is stablized by inter­molecular N—H...O and C—H...O hydrogen bonds, and weak C—H...π inter­actions. The O atoms of the unique nitrate ion are disordered over two sites with occupancies of 0.63 (1) and 0.37 (1). In addition, the O atom of the unique solvent water mol­ecule is disorded over two sites with equal occupancies.

Key indicators

• Single-crystal X-ray study
• T = 292 K
• Mean [sigma](C-C) = 0.005 Å
• H-atom completeness 91%
• Disorder in solvent or counterion
• R factor = 0.056
• wR factor = 0.133
• Data-to-parameter ratio = 12.7

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT432_ALERT_2_B Short Inter X...Y Contact  C9     ..  O3'     ..       2.91 Ang.

Author Response: O3' is a minor component of disorder. Short C...O distances of this sort are not unusual.

PLAT221_ALERT_4_B Large Solvent/Anion  O     Ueq(max)/Ueq(min) ...       5.00 Ratio

Author Response: This is owing to the disoder of the O atoms of the nitrate ion

Alert level C
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.56
PLAT410_ALERT_2_C Short Intra H...H Contact  H2B    ..  H4B     ..       1.90 Ang.
PLAT432_ALERT_2_C Short Inter X...Y Contact  C5     ..  O3'     ..       2.95 Ang.

Author Response: O3' is a minor component of disorder. Short C...O distances of this sort are not unusual.

PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?

Author Response: H atoms of water molecules were not located or included in the refinement but are included in the formula

PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)...          ?
PLAT164_ALERT_4_C Nr. of Refined C-H H-Atoms in Heavy-At Struct...          1
PLAT166_ALERT_4_C S.U's Given on Coordinates for calc-flagged ....        H3A
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for         N6

Alert level G
FORMU01_ALERT_2_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and the formula from the _atom_site* data.
            Atom count from _chemical_formula_sum:C38 H42 N12 Ni1 O8
            Atom count from the _atom_site data:  C38 H38 N12 Ni1 O8
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G WARNING: H atoms missing from atom site list. Is this intentional?
           From the CIF: _cell_formula_units_Z    4
           From the CIF: _chemical_formula_sum  C38 H42 N12 Ni O8
           TEST: Compare cell contents of formula and atom_site data

           atom    Z*formula  cif sites diff
           C        152.00    152.00    0.00
           H        168.00    152.00   16.00
           N         48.00     48.00    0.00
           Ni         4.00      4.00    0.00
           O         32.00     32.00    0.00
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         65
PLAT302_ALERT_4_G Anion/Solvent Disorder .........................      44.00 Perc.
PLAT793_ALERT_4_G Check the Absolute Configuration of C3     .....          R

   0 ALERT level A = In general: serious problem
   2 ALERT level B = Potentially serious problem
   9 ALERT level C = Check and explain
   6 ALERT level G = General alerts; check

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

---

S1. Comment

N,N,N',N'-Tetrakis(2-benzimidazolymethyl) cyclohexane-1,2-diamine (CTB) is a polybenzimidazole ligand, which has the advantage that the basicity of the coordinating group approximates that of histidine (pKb: histidine = 7.96 and benzimidazole = 8.47; Main, 1992). Recently, studies of ligand CTB and its metal coordination compounds have been widely carried out (Li et al.,2005; Zhao et al., 2005). In a continuation of this work, the title compound, (I), was prepared as part of a series of syntheses to produce new benzimidazole derivatives. We report the crystal stucture of the title compound herein.

In the molecule structure of (I), the Ni^II ion is located on a crystallographic twofold rotation axis and is is coordinated by four benzimidazolyl(bzim) N atoms and two amino N atoms of the ligand CTB, in a distorted octahedral environment (Fig.1). The amino N atoms are slightly further away from the Ni^II ion than the benzimidazolyl N atoms. The Ni-N bond lengths are similar to the values reported in a related structure (Oki et al.,1996). As shown in Fig. 2, the crystal structure is stablized by intermolecular N—H···O, C—H···O hydrogen bonds and weak C—H···π interactions.

Related literature

For background information, see: Oki et al. (1996); Hendriks et al. (1982); Main (1992); Zhao et al. (2005). For the structure of the free ligand of the title compound, see: Li et al. (2005).

S2. Experimental

All reagents and solvents were used as obtained without further purification. The ligand CTB was prepared according to literature methods (Hendriks et al., 1982). Compound (I) was synthesized by refluxing stoichiometric quantities (1:1 molar ratio) of CTB (0.64 g, 1 mmol) and nickel(II) dinitrate hexahydrate (0.29 g, 1 mmol) in 95% ethanol (30 ml) at 333 K for 6 h. The solution was cooled to room temperature, filtered and evaporated to obtain the product (yield 72%). Crystals of (I) were grown from an ethanol solution by slow evaporation.

S3. Refinement

In (I), the nitrate O atoms are disordered over two positions with the final refined occupancies of 0.63 (1):0.37 (1). Water atom O4 is also disordered over two positions with both the occupancies being set to 0.5. H atoms bonded to water molecules were not located and were not included in the refinement but are included in the molecular formula. All H atoms (except for H3A) were included in geometrical positions with C—H=0.97 Å (methylene), 0.93Å (aromatic), 0.86Å (imine) and all the U_isovalues were set 1.2 times of their carrier atoms. The positional parameters of atom H3A were refined.

Computing details

Data collection: SMART (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. The nitrate anions, water molecules and H atoms are omitted for clarity [symmetry code: (a) -x, y, -z+3/2].
	Fig. 2. Part of the crystal structure showing the linking of molecules by H-bonding and weak C—H···π interactions as dashed lines.

[N,N,N',N'-Tetrakis(benzimidazol-2- ylmethyl)cyclohexane-1,2-diamine]nickel(II) dinitrate dihydrate

Crystal data

[Ni(C38H38N10)](NO3)2·2H2O	F(000) = 1784
Mr = 853.55	Dx = 1.447 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2061 reflections
a = 15.3395 (16) Å	θ = 2.4–22.1°
b = 13.1695 (14) Å	µ = 0.57 mm^−1
c = 19.606 (2) Å	T = 292 K
β = 98.501 (2)°	Plate, purple
V = 3917.2 (7) Å^3	0.32 × 0.20 × 0.10 mm
Z = 4

Data collection

Bruker SMART APEX CCD diffractometer	3847 independent reflections
Radiation source: fine-focus sealed tube	2618 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.074
ϕ and ω scans	θmax = 26.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −18→17
Tmin = 0.840, Tmax = 0.946	k = −10→16
10917 measured reflections	l = −24→24

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.133	H atoms treated by a mixture of independent and constrained refinement
S = 0.95	w = 1/[σ^2(Fo^2) + (0.0618P)^2] where P = (Fo^2 + 2Fc^2)/3
3847 reflections	(Δ/σ)max = 0.001
303 parameters	Δρmax = 0.43 e Å^−3
65 restraints	Δρmin = −0.34 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.

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	0.0000	0.06922 (5)	0.7500	0.0383 (2)
N1	0.08499 (16)	0.1952 (2)	0.79130 (13)	0.0411 (7)
N2	0.03564 (16)	0.0758 (2)	0.65276 (12)	0.0420 (7)
N3	0.01367 (17)	0.1461 (2)	0.54912 (12)	0.0461 (7)
H3	−0.0083	0.1852	0.5158	0.055*
N4	−0.11459 (17)	−0.0078 (2)	0.71196 (12)	0.0419 (7)
N5	−0.25584 (18)	0.0113 (3)	0.66910 (14)	0.0552 (8)
H5	−0.3063	0.0401	0.6586	0.066*
N6	0.8994 (3)	0.3077 (5)	0.4093 (3)	0.139 (2)
O1	0.9736 (6)	0.2879 (13)	0.4445 (5)	0.268 (8)	0.630 (9)
O2	0.8880 (3)	0.3273 (6)	0.3471 (3)	0.119 (3)	0.630 (9)
O3	0.8392 (5)	0.3165 (5)	0.4456 (4)	0.142 (3)	0.630 (9)
O1'	0.9621 (5)	0.2465 (7)	0.4281 (4)	0.058 (3)	0.370 (9)
O2'	0.9055 (8)	0.4029 (8)	0.4173 (8)	0.161 (7)	0.370 (9)
O3'	0.8270 (19)	0.2712 (14)	0.377 (3)	0.29 (12)*	0.370 (9)
O4	0.0215 (8)	0.4055 (10)	0.9433 (5)	0.169 (6)	0.50 (2)
O4'	0.0237 (12)	0.491 (2)	0.9646 (10)	0.279 (12)	0.50 (2)
C1	0.0479 (3)	0.4797 (3)	0.7444 (2)	0.0738 (12)
H1A	0.0765	0.5412	0.7635	0.089*
H1B	0.0512	0.4784	0.6954	0.089*
C2	0.0954 (2)	0.3874 (3)	0.7790 (2)	0.0609 (10)
H2A	0.1560	0.3873	0.7704	0.073*
H2B	0.0958	0.3916	0.8284	0.073*
C3	0.0508 (2)	0.2889 (3)	0.75205 (18)	0.0454 (8)
H3A	0.063 (2)	0.280 (2)	0.7048 (16)	0.054*
C4	0.0837 (2)	0.2029 (3)	0.86709 (16)	0.0494 (9)
H4A	0.1394	0.1790	0.8917	0.059*
H4B	0.0767	0.2734	0.8795	0.059*
C5	0.1735 (2)	0.1638 (3)	0.77788 (18)	0.0492 (9)
H5A	0.2189	0.2039	0.8052	0.059*
H5B	0.1787	0.1722	0.7295	0.059*
C6	−0.0106 (2)	0.1420 (3)	0.61190 (15)	0.0412 (8)
C7	0.0944 (2)	0.0319 (3)	0.61274 (15)	0.0412 (8)
C8	0.1581 (2)	−0.0419 (3)	0.62782 (19)	0.0570 (10)
H8	0.1678	−0.0735	0.6707	0.068*
C9	0.2069 (3)	−0.0668 (3)	0.5766 (2)	0.0644 (11)
H9	0.2502	−0.1165	0.5852	0.077*
C10	0.1936 (3)	−0.0204 (3)	0.51282 (19)	0.0658 (11)
H10	0.2289	−0.0386	0.4801	0.079*
C11	0.1299 (2)	0.0515 (3)	0.49675 (17)	0.0561 (10)
H11	0.1204	0.0823	0.4536	0.067*
C12	0.0804 (2)	0.0764 (3)	0.54747 (15)	0.0441 (8)
C13	−0.1819 (2)	0.0548 (3)	0.70208 (16)	0.0453 (8)
C14	−0.2356 (2)	−0.0880 (3)	0.65533 (18)	0.0546 (10)
C15	−0.2841 (3)	−0.1652 (4)	0.6196 (2)	0.0793 (14)
H15	−0.3432	−0.1566	0.6015	0.095*
C16	−0.2408 (3)	−0.2551 (4)	0.6122 (2)	0.0862 (15)
H16	−0.2710	−0.3084	0.5883	0.103*
C17	−0.1518 (3)	−0.2677 (3)	0.6401 (2)	0.0800 (14)
H17	−0.1248	−0.3298	0.6346	0.096*
C18	−0.1031 (3)	−0.1913 (3)	0.67524 (18)	0.0601 (10)
H18	−0.0439	−0.2002	0.6931	0.072*
C19	−0.1463 (2)	−0.1002 (3)	0.68280 (16)	0.0468 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0387 (4)	0.0453 (4)	0.0307 (3)	0.000	0.0044 (2)	0.000
N1	0.0380 (15)	0.0490 (17)	0.0366 (14)	−0.0011 (13)	0.0062 (11)	0.0024 (13)
N2	0.0414 (15)	0.0507 (17)	0.0342 (14)	0.0041 (14)	0.0066 (11)	0.0015 (14)
N3	0.0536 (17)	0.0550 (18)	0.0292 (14)	0.0030 (15)	0.0044 (12)	0.0085 (13)
N4	0.0433 (16)	0.0469 (17)	0.0347 (15)	−0.0039 (14)	0.0028 (12)	−0.0051 (13)
N5	0.0393 (17)	0.071 (2)	0.0544 (19)	−0.0096 (16)	0.0027 (14)	0.0030 (17)
N6	0.087 (4)	0.119 (5)	0.203 (8)	0.000 (4)	−0.007 (5)	0.038 (5)
O1	0.179 (10)	0.317 (15)	0.290 (14)	0.021 (10)	−0.025 (9)	0.206 (12)
O2	0.079 (4)	0.176 (7)	0.097 (4)	0.031 (4)	−0.003 (3)	0.091 (5)
O3	0.127 (6)	0.125 (6)	0.191 (7)	0.023 (5)	0.082 (5)	−0.025 (5)
O1'	0.052 (5)	0.076 (6)	0.044 (4)	0.027 (4)	0.005 (3)	0.023 (4)
O2'	0.115 (9)	0.170 (13)	0.184 (13)	0.027 (9)	−0.025 (8)	0.000 (10)
O4	0.239 (11)	0.123 (10)	0.149 (8)	0.023 (7)	0.043 (7)	−0.076 (6)
O4'	0.311 (17)	0.28 (2)	0.247 (17)	0.064 (15)	0.042 (12)	0.007 (16)
C1	0.084 (3)	0.050 (2)	0.088 (3)	−0.011 (2)	0.013 (3)	−0.001 (2)
C2	0.061 (2)	0.053 (2)	0.069 (3)	−0.011 (2)	0.012 (2)	−0.003 (2)
C3	0.0481 (19)	0.045 (2)	0.0440 (19)	−0.0006 (17)	0.0101 (16)	0.0002 (17)
C4	0.047 (2)	0.059 (2)	0.0403 (19)	−0.0071 (18)	0.0007 (15)	−0.0039 (17)
C5	0.0388 (19)	0.058 (2)	0.050 (2)	−0.0037 (17)	0.0064 (15)	0.0022 (18)
C6	0.0418 (18)	0.047 (2)	0.0339 (17)	−0.0018 (16)	0.0043 (14)	−0.0007 (16)
C7	0.0434 (18)	0.047 (2)	0.0335 (17)	−0.0016 (16)	0.0075 (14)	−0.0021 (15)
C8	0.060 (2)	0.063 (3)	0.049 (2)	0.013 (2)	0.0106 (18)	0.0008 (19)
C9	0.063 (2)	0.073 (3)	0.059 (2)	0.017 (2)	0.0133 (19)	−0.008 (2)
C10	0.060 (3)	0.094 (3)	0.047 (2)	−0.002 (2)	0.0188 (19)	−0.017 (2)
C11	0.059 (2)	0.075 (3)	0.0358 (18)	−0.004 (2)	0.0118 (17)	−0.0019 (19)
C12	0.0461 (19)	0.051 (2)	0.0345 (17)	−0.0066 (18)	0.0051 (14)	−0.0027 (16)
C13	0.0402 (19)	0.059 (2)	0.0372 (18)	−0.0065 (18)	0.0069 (14)	0.0005 (17)
C14	0.052 (2)	0.068 (3)	0.044 (2)	−0.016 (2)	0.0081 (17)	0.0011 (19)
C15	0.073 (3)	0.094 (4)	0.069 (3)	−0.042 (3)	0.005 (2)	−0.005 (3)
C16	0.105 (4)	0.079 (4)	0.073 (3)	−0.048 (3)	0.010 (3)	−0.014 (3)
C17	0.121 (4)	0.055 (3)	0.067 (3)	−0.024 (3)	0.023 (3)	−0.009 (2)
C18	0.076 (3)	0.058 (3)	0.046 (2)	−0.008 (2)	0.0063 (19)	−0.0029 (19)
C19	0.057 (2)	0.053 (2)	0.0319 (17)	−0.0085 (18)	0.0091 (15)	0.0018 (16)

Geometric parameters (Å, º)

Ni1—N2	2.061 (2)	C2—H2B	0.9700
Ni1—N2^i	2.062 (2)	C3—C3^i	1.549 (6)
Ni1—N4	2.071 (3)	C3—H3A	0.98 (3)
Ni1—N4^i	2.071 (3)	C4—C6^i	1.485 (4)
Ni1—N1^i	2.190 (3)	C4—H4A	0.9700
Ni1—N1	2.190 (3)	C4—H4B	0.9700
N1—C5	1.479 (4)	C5—C13^i	1.489 (5)
N1—C4	1.493 (4)	C5—H5A	0.9700
N1—C3	1.506 (4)	C5—H5B	0.9700
N2—C6	1.318 (4)	C6—C4^i	1.485 (4)
N2—C7	1.404 (4)	C7—C8	1.379 (5)
N3—C6	1.339 (4)	C7—C12	1.395 (4)
N3—C12	1.378 (4)	C8—C9	1.378 (5)
N3—H3	0.8600	C8—H8	0.9300
N4—C13	1.313 (4)	C9—C10	1.378 (5)
N4—C19	1.400 (4)	C9—H9	0.9300
N5—C13	1.348 (4)	C10—C11	1.364 (5)
N5—C14	1.379 (5)	C10—H10	0.9300
N5—H5	0.8600	C11—C12	1.378 (4)
N6—O2	1.233 (6)	C11—H11	0.9300
N6—O3	1.252 (6)	C13—C5^i	1.489 (5)
N6—O2'	1.265 (8)	C14—C15	1.387 (5)
N6—O1'	1.267 (7)	C14—C19	1.405 (5)
N6—O1	1.268 (7)	C15—C16	1.375 (7)
N6—O3'	1.286 (9)	C15—H15	0.9300
O4'—O4'^ii	1.68 (4)	C16—C17	1.403 (6)
C1—C1^i	1.519 (8)	C16—H16	0.9300
C1—C2	1.524 (5)	C17—C18	1.376 (5)
C1—H1A	0.9700	C17—H17	0.9300
C1—H1B	0.9700	C18—C19	1.389 (5)
C2—C3	1.524 (5)	C18—H18	0.9300
C2—H2A	0.9700
N2—Ni1—N2^i	175.20 (15)	C2—C3—C3^i	114.5 (2)
N2—Ni1—N4	90.83 (10)	N1—C3—H3A	106.6 (19)
N2^i—Ni1—N4	91.53 (10)	C2—C3—H3A	106.6 (19)
N2—Ni1—N4^i	91.53 (10)	C3^i—C3—H3A	106.6 (19)
N2^i—Ni1—N4^i	90.82 (10)	C6^i—C4—N1	111.2 (3)
N4—Ni1—N4^i	121.31 (16)	C6^i—C4—H4A	109.4
N2—Ni1—N1^i	81.44 (10)	N1—C4—H4A	109.4
N2^i—Ni1—N1^i	94.90 (10)	C6^i—C4—H4B	109.4
N4—Ni1—N1^i	79.11 (10)	N1—C4—H4B	109.4
N4^i—Ni1—N1^i	158.69 (11)	H4A—C4—H4B	108.0
N2—Ni1—N1	94.90 (10)	N1—C5—C13^i	105.6 (3)
N2^i—Ni1—N1	81.43 (10)	N1—C5—H5A	110.6
N4—Ni1—N1	158.69 (10)	C13^i—C5—H5A	110.6
N4^i—Ni1—N1	79.11 (10)	N1—C5—H5B	110.6
N1^i—Ni1—N1	81.47 (14)	C13^i—C5—H5B	110.6
C5—N1—C4	110.1 (2)	H5A—C5—H5B	108.8
C5—N1—C3	113.4 (2)	N2—C6—N3	112.8 (3)
C4—N1—C3	113.5 (3)	N2—C6—C4^i	123.3 (3)
C5—N1—Ni1	103.5 (2)	N3—C6—C4^i	123.8 (3)
C4—N1—Ni1	108.93 (19)	C8—C7—C12	120.1 (3)
C3—N1—Ni1	106.76 (18)	C8—C7—N2	131.6 (3)
C6—N2—C7	105.4 (3)	C12—C7—N2	108.3 (3)
C6—N2—Ni1	113.4 (2)	C9—C8—C7	117.1 (3)
C7—N2—Ni1	141.2 (2)	C9—C8—H8	121.5
C6—N3—C12	107.6 (3)	C7—C8—H8	121.5
C6—N3—H3	126.2	C8—C9—C10	122.2 (4)
C12—N3—H3	126.2	C8—C9—H9	118.9
C13—N4—C19	105.5 (3)	C10—C9—H9	118.9
C13—N4—Ni1	110.6 (2)	C11—C10—C9	121.4 (3)
C19—N4—Ni1	142.9 (2)	C11—C10—H10	119.3
C13—N5—C14	107.4 (3)	C9—C10—H10	119.3
C13—N5—H5	126.3	C10—C11—C12	116.8 (3)
C14—N5—H5	126.3	C10—C11—H11	121.6
O2—N6—O3	122.3 (5)	C12—C11—H11	121.6
O2—N6—O2'	85.0 (9)	C11—C12—N3	131.8 (3)
O3—N6—O2'	83.4 (9)	C11—C12—C7	122.4 (3)
O2—N6—O1'	114.3 (7)	N3—C12—C7	105.8 (3)
O3—N6—O1'	119.1 (7)	N4—C13—N5	113.0 (3)
O2'—N6—O1'	123.7 (6)	N4—C13—C5^i	122.1 (3)
O2—N6—O1	124.5 (6)	N5—C13—C5^i	124.8 (3)
O3—N6—O1	112.8 (6)	N5—C14—C15	132.4 (4)
O2'—N6—O1	95.3 (11)	N5—C14—C19	105.5 (3)
O2'—N6—O3'	118.3 (7)	C15—C14—C19	122.0 (4)
O1'—N6—O3'	117.9 (7)	C16—C15—C14	116.9 (4)
O1—N6—O3'	146.2 (13)	C16—C15—H15	121.5
C1^i—C1—C2	110.1 (3)	C14—C15—H15	121.5
C1^i—C1—H1A	109.6	C15—C16—C17	121.2 (5)
C2—C1—H1A	109.6	C15—C16—H16	119.4
C1^i—C1—H1B	109.6	C17—C16—H16	119.4
C2—C1—H1B	109.6	C18—C17—C16	122.3 (5)
H1A—C1—H1B	108.1	C18—C17—H17	118.9
C3—C2—C1	111.4 (3)	C16—C17—H17	118.9
C3—C2—H2A	109.4	C17—C18—C19	116.9 (4)
C1—C2—H2A	109.4	C17—C18—H18	121.6
C3—C2—H2B	109.4	C19—C18—H18	121.6
C1—C2—H2B	109.4	C18—C19—N4	130.6 (3)
H2A—C2—H2B	108.0	C18—C19—C14	120.8 (4)
N1—C3—C2	114.5 (3)	N4—C19—C14	108.5 (3)
N1—C3—C3^i	107.3 (2)
N2—Ni1—N1—C5	−55.5 (2)	Ni1—N1—C5—C13^i	−44.1 (3)
N2^i—Ni1—N1—C5	127.6 (2)	C7—N2—C6—N3	−0.9 (4)
N4—Ni1—N1—C5	−160.6 (2)	Ni1—N2—C6—N3	179.5 (2)
N4^i—Ni1—N1—C5	35.10 (19)	C7—N2—C6—C4^i	177.3 (3)
N1^i—Ni1—N1—C5	−136.1 (2)	Ni1—N2—C6—C4^i	−2.3 (4)
N2—Ni1—N1—C4	−172.7 (2)	C12—N3—C6—N2	0.9 (4)
N2^i—Ni1—N1—C4	10.5 (2)	C12—N3—C6—C4^i	−177.3 (3)
N4—Ni1—N1—C4	82.3 (3)	C6—N2—C7—C8	−179.7 (4)
N4^i—Ni1—N1—C4	−82.0 (2)	Ni1—N2—C7—C8	−0.2 (6)
N1^i—Ni1—N1—C4	106.8 (2)	C6—N2—C7—C12	0.5 (4)
N2—Ni1—N1—C3	64.4 (2)	Ni1—N2—C7—C12	180.0 (3)
N2^i—Ni1—N1—C3	−112.4 (2)	C12—C7—C8—C9	1.3 (5)
N4—Ni1—N1—C3	−40.6 (3)	N2—C7—C8—C9	−178.5 (3)
N4^i—Ni1—N1—C3	155.1 (2)	C7—C8—C9—C10	0.3 (6)
N1^i—Ni1—N1—C3	−16.12 (14)	C8—C9—C10—C11	−1.3 (6)
N4—Ni1—N2—C6	74.0 (2)	C9—C10—C11—C12	0.8 (6)
N4^i—Ni1—N2—C6	−164.6 (2)	C10—C11—C12—N3	178.2 (4)
N1^i—Ni1—N2—C6	−4.9 (2)	C10—C11—C12—C7	0.8 (5)
N1—Ni1—N2—C6	−85.4 (2)	C6—N3—C12—C11	−178.2 (4)
N4—Ni1—N2—C7	−105.4 (3)	C6—N3—C12—C7	−0.5 (4)
N4^i—Ni1—N2—C7	15.9 (3)	C8—C7—C12—C11	−1.9 (5)
N1^i—Ni1—N2—C7	175.7 (4)	N2—C7—C12—C11	178.0 (3)
N1—Ni1—N2—C7	95.1 (3)	C8—C7—C12—N3	−179.8 (3)
N2—Ni1—N4—C13	−98.7 (2)	N2—C7—C12—N3	0.0 (4)
N2^i—Ni1—N4—C13	77.1 (2)	C19—N4—C13—N5	0.4 (4)
N4^i—Ni1—N4—C13	169.0 (2)	Ni1—N4—C13—N5	171.9 (2)
N1^i—Ni1—N4—C13	−17.6 (2)	C19—N4—C13—C5^i	−176.2 (3)
N1—Ni1—N4—C13	7.0 (4)	Ni1—N4—C13—C5^i	−4.6 (4)
N2—Ni1—N4—C19	67.7 (3)	C14—N5—C13—N4	−0.7 (4)
N2^i—Ni1—N4—C19	−116.5 (3)	C14—N5—C13—C5^i	175.7 (3)
N4^i—Ni1—N4—C19	−24.6 (3)	C13—N5—C14—C15	−175.8 (4)
N1^i—Ni1—N4—C19	148.8 (3)	C13—N5—C14—C19	0.7 (4)
N1—Ni1—N4—C19	173.5 (3)	N5—C14—C15—C16	176.1 (4)
C1^i—C1—C2—C3	57.5 (5)	C19—C14—C15—C16	0.1 (6)
C5—N1—C3—C2	−73.2 (4)	C14—C15—C16—C17	0.4 (6)
C4—N1—C3—C2	53.5 (4)	C15—C16—C17—C18	−0.8 (7)
Ni1—N1—C3—C2	173.5 (2)	C16—C17—C18—C19	0.7 (6)
C5—N1—C3—C3^i	158.5 (3)	C17—C18—C19—N4	−176.0 (3)
C4—N1—C3—C3^i	−74.8 (3)	C17—C18—C19—C14	−0.1 (5)
Ni1—N1—C3—C3^i	45.2 (3)	C13—N4—C19—C18	176.4 (3)
C1—C2—C3—N1	−171.0 (3)	Ni1—N4—C19—C18	9.6 (6)
C1—C2—C3—C3^i	−46.4 (5)	C13—N4—C19—C14	0.1 (3)
C5—N1—C4—C6^i	−126.7 (3)	Ni1—N4—C19—C14	−166.7 (3)
C3—N1—C4—C6^i	104.9 (3)	N5—C14—C19—C18	−177.2 (3)
Ni1—N1—C4—C6^i	−13.8 (3)	C15—C14—C19—C18	−0.3 (5)
C4—N1—C5—C13^i	72.2 (3)	N5—C14—C19—N4	−0.5 (4)
C3—N1—C5—C13^i	−159.4 (3)	C15—C14—C19—N4	176.5 (3)

Symmetry codes: (i) −x, y, −z+3/2; (ii) −x, −y+1, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O1^iii	0.86	1.94	2.774 (10)	165
N5—H5···O2^iv	0.86	2.14	2.923 (7)	151
C4—H4B···O4	0.97	2.37	3.268 (12)	154
C11—H11···Cg1^v	0.93	2.73	3.542	147
C16—H16···Cg2^vi	0.93	2.79	3.680	160

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