Crystal structures of two nickel(II) macrocyclic salts: (5,7,7,12,12,14-hexa­methyl-1,4,8,11-tetra­aza­cyclo­tetra­deca­ne)nickel(II) bis­(perchlorate) monohydrate and (5,7,7,12,12,14-hexa­methyl-1,4,8,11-tetra­aza­cyclo­tetra­deca­ne)nickel(II) dibromide trihydrate

Corfield, P.W.R.; Goedken, V.L.

doi:10.1107/S2056989019002056

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 75| Part 3| March 2019| Pages 332-337

https://doi.org/10.1107/S2056989019002056

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Crystal structures of two nickel(II) macrocyclic salts: (5,7,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane)nickel(II) bis(perchlorate) monohydrate and (5,7,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane)nickel(II) dibromide trihydrate

Peter W. R. Corfield ^a ^* and Virgil L. Goedken ^b ‡

^aDepartment of Chemistry, Fordham University, 441 East Fordham Road, Bronx, NY 10458, USA, and ^bDepartment of Chemistry, The Ohio State University, Columbus, OH 43210, USA
^*Correspondence e-mail: pcorfield@fordham.edu

Edited by S. Parkin, University of Kentucky, USA (Received 17 January 2019; accepted 5 February 2019; online 8 February 2019)

The crystal structure of the Ni-14 macrocycle salt, (5,7,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane)nickel(II) bis(perchlorate) hemihydrate, [Ni(C₁₆H₃₆N₄)]₂(ClO₄)₄·H₂O, contains two different diasteriomeric macrocyclic cations in the asymmetric unit, one with two NH protons on each side of the cation (Ia), and the other with all four NH protons on the same side (Ib). The crystal structure of the bromide trihydrate salt of the same Ni-14 macrocyclic cation, namely (5,7,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane)nickel(II) dibromide trihydrate, [Ni(C₁₆H₃₆N₄)]Br₂·3H₂O (II), contains only the same diastereomer as Ib, with the four N—H bonds on the same side. The geometry around the Ni atom differs slightly between the two diastereomeric cations, as the mean Ni—N distance in Ia is 1.952 (2) Å, while that for Ib and II is 1.928 (2) Å. The hexamethyl substitution in all three macrocyclic cations has the two dimethyl-substituted C atoms cis to one another, different from the trans 5,5,7,12,12,14-hexamethyl Ni-14 cations found in all but one of the many published crystal structures of hexamethyl Ni-14 macrocycles. In each of the two crystal structures, the anions, water molecules, and N—H protons of the macrocyclic cations form extensive hydrogen-bonded zigzag chains propagating along [001] in I and [010] in II.

Keywords: crystal structure; nickel; macrocycle; cyclam; diasteriomers.

CCDC references: 1895686; 1895685

1. Chemical context

Reports of the formation of cyclic Schiff base–amine complexes of Ni by condensation of acetone with tris(ethylenediamine)nickel(II) salts and their reduction to 14-membered macrocyclic tetraamine complexes (Curtis, 1960 , 1964 ) led to extensive research on these and similar complexes in the 1960s and 1970s in the hope of using such metal-template reactions in chemical synthesis and of understanding the role of macrocyclic ligands in metalloproteins such as hemoglobin. Their chemical inertness enables chemical reactions of the ligand without losing stereochemistry of the N atoms (Busch, 1978 ) and allows characterization of numerous possible isomers (Warner & Busch, 1969 ). Crystal structures of isomers of the macrocyclic nickel complexes continue to appear (e.g. Shi et al., 2010 ; Curtis et al., 2016 ). The major product of the condensation referred to above is a 5,5,7,12,12,14-hexamethyl-1,4,8,11,tetraazacyclotetradeca-4,14-dienenickel(II) ion, where the dimethyl-substituted C atoms are trans to each other, and most chemical and structural studies have been concerned with these compounds and their oxidized or reduced species. The 5,7,7,12,12,14-hexamethyl-1,4,8,11,tetraazacyclotetradecanenickel(II) compounds presented here, abbreviated as cis-[Nime₆cyclam]²⁺, where the dimethyl-substituted C atoms are cis to one another, are derived from the minor product of the condensation, which has received less attention.

2. Structural commentary

Compound I crystallizes as a double salt, containing two independent cis-[Nime₆cyclam]²⁺ cations, with structures Ia and Ib in the scheme, four ClO₄⁻ anions, and one water of hydration in the asymmetric unit. Compound II crystallizes as a trihydrate built from cis-[Nime₆cyclam]²⁺ cations, with structure II in the scheme, two Br⁻ anions and three water molecules. The configurations of cations Ib and II are the same. Figs. 1–3 display the cations, anions, and packing diagram for compound I, while Figs. 4–6 give the cation, packing diagram and proposed hydrogen-bonding network for II.

Figure 1
The [Nime₆cyclam]²⁺ cations in the asymmetric unit of the double salt I. Displacement ellipsoids are drawn at the 50% probability level. The cation centered on Ni1 is structure Ia in the text, and the other cation is Ib.

Figure 2
The perchlorate anions and water molecule in the asymmetric unit of double salt I, showing their relationship with the cations, and hydrogen bonds formed. The disordered ClO₄⁻(2) anion does not appear to form any hydrogen bonds. Displacement ellipsoids are drawn at the 50% probability level.

Figure 3
Projection down the a axis for the double salt, I, showing the hydrogen-bonded network extending along the c-axis direction. Ions and the water molecule in the asymmetric unit are in bold.

Figure 4
The [Nime₆cyclam]²⁺cation in the macrocycle bromide salt II. Displacement ellipsoids are at the 50% probability level.

Figure 5
Projection down the c axis for the macrocycle bromide salt II. The asymmetric unit is in bold. Bromide ions are green, and water molecules red.

Figure 6
Details of the proposed hydrogen-bond network for the macrocycle bromide salt II. Displacement ellipsoids are at the 50% probability level, with anions and solvent in the asymmetric unit drawn in bold. Bromide ions are green, and water O atoms red. Putative hydrogen bonds involving water molecules for which protons were not found are in cyan while other hydrogen bonds are black. Water O atoms and Br1 at the top of the figure are related to the corresponding atoms at the bottom via the translation vector (0, ½, −½).

In each cation, the nickel atom is in square-planar coordination to the macrocycle, with the Ni and four N atoms in a close to planar arrangement. All six-membered chelate rings are in the chair form, and all singly substituted methyl groups are in the equatorial position. In the reference molecule for Ia there are two NH atoms above and two below the N₄ plane, designated as uudd, in an RRSS configuration, whereas cations Ib and II are diastereomers of Ia, with all four NH atoms lying on the same side of the molecule, uuuu, and the N atoms in an RSRS configuration. Cation Ia is roughly planar in overall shape, whereas the N—H geometry in Ib and II makes the cations in these structures more bowl shaped. The configurational differences at N appear to affect the Ni—N bond lengths slightly: the mean Ni—N distance in Ia is 1.952 (2) Å while that for Ib and II is 1.928 (2) Å.

The conformations of the five-membered chelate rings in the reference cations shown in the scheme are λ on the left and δ on the right for Ia, and λ on the right and δ on the left for Ib and II. (Mirror-related cations are present in both crystals.) The twists of these five-membered rings necessarily differentiate between the top and bottom six-membered chelate rings in Ib and II, whereas this is not the case in Ia. In diastereomers Ib and II, the top plane (N4, C5, C7, N8) is bent at a less steep angle to the NiN₄ coordination plane than the bottom plane (N11, C12, C14, N1) (add 20 to atom numbers for structure Ib) and the outer C atoms C6 and C13 are at widely different distances from the NiN₄ plane. Thus in Ib and II, the angles between the NiN₄ plane and the N₂C₂ plane of the top chelate ring are 29.6 (1) and 31.7 (3)°, respectively, while corresponding angles for the bottom rings are 52.7 (2) and 57.1 (2)°. The top outer carbon C6 is 0.317 (6) Å from the N₄ plane in Ib and 0.407 (10) Å in II, while the corresponding distances for the bottom outer atom C13 are respectively 1.176 (5) and 1.314 (11) Å. The Ni coordination geometry reflects this difference between the top and bottom of the molecule, with the top N4—Ni—N8 angle opened out to 94.58 (12)° in Ib and 94.79 (19)° in II, compared with bottom angles N1—Ni—N11 of 88.72 (12) and 87.73 (19)°, respectively. The five-membered chelate ring angles at the Ni atom, N1—Ni—N4 and N8—Ni—N11, average 88.48 (16)° in these two structures.

Molecule Ia is less-buckled, with angles between the N₄ plane and central planes of the chelate chairs more nearly equal, at 27.6 (2)° for the top chair and 31.9 (2)° for the bottom, and outer C atom distances from the N₄ plane of 0.250 (6) Å for C6 at the top, and −0.389 (6) for C13 at the bottom. The Ni coordination plane is more nearly symmetrical, with six-membered chelate angles N4—Ni1—N8 of 93.49 (14)° (top) and N1—Ni1—N11 of 92.88 (13)° (bottom), and five-membered chelate angles averaging 86.87 (13)°, somewhat smaller than for Ib and II.

In both of the Ib and II cations, hydrogen bonding of an anion or of a solvent molecule brings an O atom close to the axial direction of the Ni atom on the same side of the cation as the four NH bonds, though at distances too long to be regarded as due to Ni—O bonding. In Ib, perchlorate atom O31 is at 2.799 (3) Å from atom Ni2, while in II, water molecule O1 is at 2.863 (10) Å from the Ni atom.

3. Supramolecular features

Details of hydrogen bonding are given in Tables 1 and 2. The N—H bonds in all three cations form hydrogen bonds; to water or perchlorate O atoms in I, and to water O atoms or Br⁻ ions in II.

Table 1
Hydrogen-bond geometry (Å, °) for I

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O44	0.98	2.61	3.279 (9)	126
N4—H4⋯O14	0.98	2.02	2.941 (4)	157
N8—H8⋯OW	0.98	1.99	2.965 (5)	175
N11—H11⋯O43	0.98	2.11	3.028 (10)	155
N11—H11⋯O46	0.98	2.45	3.36 (3)	155
N21—H21⋯O13	0.98	2.14	3.093 (4)	165
N24—H24⋯O33	0.98	2.12	3.033 (5)	154
N28—H28⋯O45ⁱ	0.98	2.30	3.146 (16)	144
N31—H31⋯O12	0.98	2.16	3.083 (4)	156
OW—HW1⋯O41ⁱ	0.82 (1)	2.38 (2)	3.162 (11)	162 (5)
OW—HW1⋯O47ⁱ	0.82 (1)	2.37 (3)	3.139 (18)	157 (5)
OW—HW2⋯O12	0.82 (1)	2.45 (3)	3.181 (6)	149 (6)
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Table 2
Hydrogen-bond geometry (Å, °) for II

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯Br2	0.81 (6)	2.66 (6)	3.461 (5)	169 (6)
N4—H4⋯O1	0.80 (6)	2.80 (7)	3.283 (11)	121 (5)
N4—H4⋯O3	0.80 (6)	2.25 (6)	3.008 (13)	159 (6)
N8—H8⋯Br1	0.83 (6)	2.63 (6)	3.444 (5)	164 (5)
N11—H11⋯Br2	0.89 (6)	2.63 (6)	3.466 (4)	159 (5)

In the double salt I, hydrogen bonding between the cations, the four perchlorate ions ClO₄⁻(1)–ClO₄⁻(4) and the water molecule form a one-dimensional network extending along the c-axis direction, as shown in Fig. 3. Three of the four O atoms in the relatively ordered ClO₄⁻(1) anion link the two reference molecules together by N—H⋯O hydrogen bonds. Neither of the alternative orientations for ClO₄⁻(2) form any N—H⋯O or O—H⋯O H bonds. These disordered ions lie in a hydrophobic cavity in the crystal structure, and may be held in position by C—H⋯O bonds. The relatively ordered ion ClO₄⁻(3) is tethered by only one hydrogen bond, while each orientation for disordered ClO₄⁻(4) is hydrogen bonded to the water molecule and to either one or two N—H groups of the cations. The water molecule is well stabilized in its position by three separate hydrogen bonds.

The cyclam cation in II forms hydrogen bonds to the Br⁻ ions via N1—H1, N8—H8 and N11—H11, while N4—H4 hydrogen-bonds to water molecule O3. O3 appears to form rather short hydrogen bonds with water molecules O1 and O2, as well as with O3 rotated by the crystallographic twofold axis at x = y = $[1\over4]$ , with respective O⋯O distances of 2.671 (11), 2.635 (10) and 2.638 (12) Å. Exact details of the hydrogen-bonding network are not clear, as none of the water H atoms could be located with assurance (see Refinement section) However, distances O1⋯Br2 = 3.341 (9) Å, O2 ⋯ Br1 = 3.347 (9) Å, and O2 ⋯ Br2(x, y − $[{1\over 2}]$ , z + $[{1\over 2}]$ ) = 3.332 (8) Å are consistent with water–bromide ion hydrogen bonding, which would give rise to the hydrogen-bonding network suggested in Fig. 6. Short ribbons along the (0, $[{1\over 2}]$ , − $[{1\over 2}]$ ) direction linked to each other via presumed O3⋯O3 hydrogen bonds across the twofold axes lead to the formation of extended zigzag chains along the b-axis direction.

The shortest (C)H⋯(C)H distances are 2.61 Å in I, between H27F and H32B(x, $[{1\over 2}]$ − y, $[{1\over 2}]$ + z), with just four other contacts less than 2.70, and 2.47 Å in II, between H9B and H12E( $[{1\over 4}]$ − x, − $[{1\over 4}]$ + y, − $[{1\over 4}]$ + z), with five other contacts less than 2.70 Å.

4. Database survey

A search in the Cambridge Structural Database (CSD, Version of 2017; Groom et al., 2016 ) for cis-[Nime₆cyclam]²⁺ structures produced only one hit (TICCOX; Wang et al., 1996 ). This structure has a configuration with all NH atoms on the same side of the molecule, or uuuu, with a configuration the same as that of the structures Ib and II in the present work. The sole other cis-cyclam structure of any kind has Cu as the chelated metal ion (HMTZCP; Ochiai et al., 1978 ), with a configuration the same as that of structure Ia.

Of 38 3D trans-[Nime₆cyclam]²⁺structures found in the CSD, 26 have the NH configuration uudd of cation Ia in the present work, five have a udud configuration, and five have the NH configuration uuuu (or equivalently dddd), but with λλ or δδ conformations for the five-membered chelate rings, different from the conformations of Ib and II in the present work. In these 36 structures, there need be no difference between the geometries of the six-membered chelate rings, and indeed, minus a few exceptions, both N—Ni—N six-membered ring chelate angles are identical, with a mean of 93.2 (4)°. The last two trans structures [LIFYEG (Ou et al., 2013 ), NIBTET (Curtis et al., 1973 )] have cations with the same conformation as in Ib and II, and with the same differentiation in six-membered ring N—Ni—N chelate angles as in the present work.

A search for structures where Ni²⁺ is coordinated solely by the unsubstituted cyclam ligand gave 20 hits. Of these, one had the RRRR configuration, or udud, with alternate NH atoms pointing upwards and downwards, while 19 had the RRSS configuration, or uudd, as in the present Ia structure, the more stable isomer according to Bosnich et al. (1965 ). None of these unsubstituted Ni-cyclam structures had the RSRS configuration, or uuuu, with all NH atoms on the same side of the molecule, as in the present Ib and II structures. Presumably this particular configuration is stabilized by the methyl substituent groups.

5. Synthesis and crystallization

The double salt I was prepared in Daryle H. Busch's laboratories by methods described in Curtis (1967 ). The bromide salt II was prepared by a solution of I in methanol/KBr/HBr, precipitation with ether, and recrystallization from hot aqueous HBr.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3.

Table 3
Experimental details

	I	II
Crystal data
Chemical formula	[Ni(C₁₆H₃₆N₄)]₂(ClO₄)₄·H₂O	[Ni(C₁₆H₃₆N₄)]Br₂·3H₂O
M_r	1102.21	557.06
Crystal system, space group	Monoclinic, P2₁/c	Orthorhombic, Fdd2
Temperature (K)	295	295
a, b, c (Å)	8.906 (4), 29.412 (11), 19.505 (9)	60.3649 (18), 19.8364 (9), 7.9773 (3)
α, β, γ (°)	90, 107.030 (19), 90	90, 90, 90
V (Å³)	4885 (4)	9552.2 (6)
Z	4	16
Radiation type	Cu Kα	Mo Kα
μ (mm⁻¹)	3.60	4.17
Colour	Orange	Yellow
Crystal size (mm)	0.52 × 0.25 × 0.11	0.37 × 0.15 × 0.10

Data collection
Diffractometer	Picker 4-circle	Enraf–Nonius KappaCCD
Radiation source	sealed X-ray tube	fine-focus sealed tube
Absorption correction	Gaussian (Busing & Levy, 1957 )	Part of the refinement model (ΔF) (SCALEPACK; Otwinowski & Minor, 1997 )
T_min, T_max	0.454, 0.686	0.34, 0.67
No. of measured, independent and observed [I > 2σ(I)] reflections	7450, 6870, 4899	41142, 5382, 4897
R_int	0.060	0.096
θ_max (°)	58.4	27.5
(sin θ/λ)_max (Å⁻¹)	0.552	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.109, 1.04	0.035, 0.085, 1.04
No. of reflections	6870	5382
No. of parameters	686	253
No. of restraints	184	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.31	0.88, −0.56
Data reduction followed procedures in Corfield et al. (1973 ). Structure solution was by the heavy-atom method with local programs. Computer programs: Corfield & Gainsford (1972 ), KappaCCD Server Software (Nonius, 1997 ), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SHELXL2017 (Sheldrick, 2015 ), ORTEPIII (Burnett & Johnson, 1996 ), ORTEP-3 for Windows (Farrugia, 2012 ) and publCIF (Westrip, 2010 ).

Data for I were collected at The Ohio State University many years ago. As was the custom then, reflection data were stored as F values, so that those reflections for which F² values were negative were stored with values of zero. During the preparation of this manuscript, we found that the original absorption correction had been carried out with an incorrect value for the absorption coefficient, μ. While correcting this problem, we converted the reflection data into the F² values used in the final refinements. Thermal parameters for the perchlorate O atoms in I are all large, indicating probable positional disorder, common for these anions. After extensive modeling attempts, ClO₄⁻ ions 1 and 3 were refined with an ordered model, while ClO₄⁻ ions 2 and 4 were refined in two alternative orientations, with 50% occupancy each and a common Cl atom in ClO₄⁻(2), and occupancies of 65.0 (8)% and 35.0 (8)% and separate sites for the disordered Cl atoms in ClO₄⁻(4). Initially, tight restraints on the ClO₄ geometry were imposed, but these were relaxed during the final refinements. However, it proved useful to impose restraints on the thermal parameters for the O atoms with the Shelx RIGU command, and a DFIX command was used to prevent the too close approach of two O atoms from different perchlorate groups.

Crystal data for compound II, the bromide salt, were originally obtained with the same Picker four-circle diffractometer as used for compound I. (Three octants merged to give 1916 observations; Gaussian absorption correction applied; R₁ = 0.026 for 1780 observed > 2σ, R₂ = 0.078, NV = 241, GOOF = 0.876, Δρ = −0.42 to +0.60 e Å⁻³.) We recollected data on the same crystal much later with the KappaCCD system at Fordham University to expand the data set and because some of the previous processing details had been lost. Refinements with the two sets of data gave very similar results, with no bond length or interior bond angle differing by more than 2.0σ and average difference 0.7σ. Twinning by reflection about the (001) plane, perpendicular to the polar twofold axis in Fdd2, was indicated by the Flack parameter of 0.57 (2) as well as by the low value of 0.030 found for R_merg if the observed I(hkl) and I(hk $[\overline l]$ ) intensities were merged, compared with 0.070 if the calculated intensities for an untwinned crystal were merged.

As noted in the section on Supramolecular features, the water molecules refined to positions rather close to one another. It was necessary to introduce anti-bumping restraints in the SHELXL refinements to avoid unreasonably short O⋯O contacts. Difference maps at the end of the least-squares refinements were dominated by features associated with the Br⁻ ions, and were uninformative regarding the positions of H atoms, even when calculated with only low-angle data. Thus, none of the H atoms on the water molecules were located. Potential positions for some water H atoms could be derived from the presumed hydrogen-bonding pattern, but refinements including these atoms were inconclusive. We tried refining the SHELXL BASF factor to see if this improved the difference maps, obtaining BASF = 0.58 (2), with negligible changes in the difference map or R factors. Hence our final refinements assume equal contributions from each twin component. The close proximity of O3 to the crystallographic twofold axis suggests disorder of at least the H atoms on O3, and the large U_eq value for O3 suggests probable disorder of the O3 atoms themselves. It was possible to generate two closely positioned sites for O3, but extensive efforts to refine a suitable disordered model for O3 did not improve the R factors, nor give more reasonable U_eq values for the disordered O3 atoms, while difference maps from these refinements did not give any useful information either on water H atoms. In light of these factors, we have not reported a model with a disordered O3 atom.

In both compounds, H atoms on the cation were constrained to idealized positions, with C—H distances of 0.97 Å for the methylene groups, 0.98 Å for the methine CH groups, and 0.96 Å for the methyl groups, while the U_eq factors for these H atoms were set at 1.2 times the U_iso of the bonded atoms for methylene and methine groups, and 1.5 times for the methyl groups. All NH atoms were refined, with U_eq values set at 1.2 times the U_iso for their bonded N atom in I and 1.0 times U_iso for II.

Supporting information

CCDC references: 1895686; 1895685

Crystal structure: contains datablocks I, II. DOI: https://doi.org/10.1107/S2056989019002056/pk2613sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019002056/pk2613Isup2.hkl

Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989019002056/pk2613IIsup3.hkl

checkCIF report

Computing details top

Data collection: Corfield & Gainsford (1972) for (I); KappaCCD Server Software (Nonius, 1997) for (II). Cell refinement: Corfield & Gainsford (1972) for (I); SCALEPACK (Otwinowski & Minor, 1997) for (II). Data reduction: Data reduction followed procedures in Corfield et al. (1973) with p = 0.05 for (I); DENZO and SCALEPACK (Otwinowski & Minor, 1997) for (II). Program(s) used to solve structure: heavy atom method with local programs for (I); Corfield & Gainsford (1972) for (II). For both structures, program(s) used to refine structure: SHELXL2017 (Sheldrick, 2015); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: publCIF (Westrip, 2010).

(5,7,7,12,12,14-Hexamethyl-1,4,8,11-tetraazacyclotetradecane)nickel(II) bis(perchlorate) hemihydrate (I) top

Crystal data top

[Ni(C₁₆H₃₆N₄)]₂(ClO₄)₄·H₂O	F(000) = 2328
M_r = 1102.21	D_x = 1.499 Mg m⁻³ D_m = 1.49 Mg m⁻³ D_m measured by flotation in chloroform/carbon tetrachloride mixtures
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.5418 Å
a = 8.906 (4) Å	Cell parameters from 28 reflections
b = 29.412 (11) Å	θ = 5.2–28.2°
c = 19.505 (9) Å	µ = 3.60 mm⁻¹
β = 107.030 (19)°	T = 295 K
V = 4885 (4) Å³	Needle, orange
Z = 4	0.52 × 0.25 × 0.11 mm

Data collection top

Picker 4-circle diffractometer	4899 reflections with I > 2σ(I)
Radiation source: sealed X-ray tube	R_int = 0.060
Oriented graphite 200 reflection monochromator	θ_max = 58.4°, θ_min = 2.8°
θ/2θ scans	h = 0→9
Absorption correction: gaussian (Busing & Levy, 1957)	k = 0→32
T_min = 0.454, T_max = 0.686	l = −21→21
7450 measured reflections	3 standard reflections every 200 reflections
6870 independent reflections	intensity decay: +2(5)

Refinement top

Refinement on F²	Primary atom site location: heavy-atom method
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.043	Hydrogen site location: mixed
wR(F²) = 0.109	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.016P)² + 2.P] where P = (F_o² + 2F_c²)/3
6870 reflections	(Δ/σ)_max = 0.001
686 parameters	Δρ_max = 0.30 e Å⁻³
184 restraints	Δρ_min = −0.30 e Å⁻³

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ni1	0.33013 (7)	0.23109 (2)	−0.03275 (3)	0.04565 (18)
N1	0.1761 (4)	0.22148 (10)	−0.12620 (15)	0.0485 (8)
H1	0.197135	0.244899	−0.157932	0.058*
C2	0.0171 (5)	0.23125 (15)	−0.1204 (2)	0.0625 (11)
H2A	−0.025056	0.204666	−0.103052	0.075*
H2B	−0.053194	0.239506	−0.166885	0.075*
C3	0.0328 (5)	0.26965 (15)	−0.0690 (2)	0.0666 (12)
H3A	0.058301	0.297432	−0.090027	0.080*
H3B	−0.065282	0.274219	−0.057861	0.080*
N4	0.1597 (4)	0.25839 (10)	−0.00289 (15)	0.0486 (8)
H4	0.117301	0.233348	0.018922	0.058*
C5	0.1831 (5)	0.29636 (14)	0.0503 (2)	0.0633 (12)
H5	0.204365	0.324159	0.027016	0.076*
C6	0.3218 (5)	0.28734 (14)	0.1143 (2)	0.0664 (12)
H6A	0.304739	0.258561	0.135098	0.080*
H6B	0.324884	0.310785	0.149625	0.080*
C7	0.4812 (5)	0.28563 (15)	0.1010 (2)	0.0683 (12)
N8	0.4865 (4)	0.24318 (11)	0.05883 (16)	0.0550 (8)
H8	0.474060	0.218272	0.090082	0.066*
C9	0.6423 (5)	0.23559 (19)	0.0486 (2)	0.0823 (15)
H9A	0.720540	0.231303	0.094621	0.099*
H9B	0.672292	0.261661	0.025142	0.099*
C10	0.6320 (6)	0.19438 (18)	0.0036 (3)	0.0879 (16)
H10A	0.614938	0.167630	0.029429	0.105*
H10B	0.728654	0.190295	−0.009098	0.105*
N11	0.4978 (4)	0.20118 (10)	−0.06199 (16)	0.0533 (8)
H11	0.534956	0.224885	−0.088376	0.064*
C12	0.4711 (5)	0.16056 (14)	−0.1118 (2)	0.0636 (11)
C13	0.3333 (5)	0.17096 (15)	−0.1773 (2)	0.0690 (12)
H13A	0.356791	0.198604	−0.199267	0.083*
H13B	0.324394	0.146555	−0.211698	0.083*
C14	0.1776 (5)	0.17674 (13)	−0.1638 (2)	0.0592 (11)
H14	0.165234	0.152268	−0.131766	0.071*
C5A	0.0356 (6)	0.30423 (17)	0.0732 (3)	0.0869 (15)
H5A1	−0.049541	0.312685	0.032148	0.130*
H5A2	0.054457	0.328153	0.108138	0.130*
H5A3	0.008990	0.276807	0.093638	0.130*
C7A	0.5102 (7)	0.32751 (16)	0.0600 (3)	0.0999 (18)
H7A1	0.618224	0.328121	0.060308	0.150*
H7A2	0.486747	0.354513	0.082492	0.150*
H7A3	0.443885	0.326135	0.011349	0.150*
C7B	0.6055 (6)	0.2824 (2)	0.1752 (3)	0.110 (2)
H7B1	0.708755	0.283359	0.169304	0.164*
H7B2	0.592127	0.254428	0.198026	0.164*
H7B3	0.592894	0.307561	0.204499	0.164*
C12A	0.6159 (6)	0.15410 (19)	−0.1381 (3)	0.0979 (17)
H12A	0.702796	0.144134	−0.098918	0.147*
H12B	0.641932	0.182432	−0.156237	0.147*
H12C	0.593787	0.131693	−0.175486	0.147*
C12B	0.4445 (7)	0.11789 (15)	−0.0729 (3)	0.0946 (17)
H12D	0.543013	0.107441	−0.041676	0.142*
H12E	0.399218	0.094643	−0.107233	0.142*
H12F	0.374442	0.124680	−0.045039	0.142*
C14A	0.0443 (5)	0.17299 (15)	−0.2336 (2)	0.0746 (13)
H14A	−0.054456	0.172069	−0.223149	0.112*
H14B	0.056985	0.145700	−0.258362	0.112*
H14C	0.046527	0.198861	−0.263348	0.112*
Ni2	0.05959 (6)	0.05839 (2)	0.25539 (3)	0.03924 (17)
N21	−0.1278 (3)	0.05912 (10)	0.17423 (15)	0.0458 (7)
H21	−0.104191	0.078124	0.137427	0.055*
C22	−0.2528 (5)	0.08287 (15)	0.1966 (2)	0.0635 (11)
H22A	−0.355426	0.073191	0.166936	0.076*
H22B	−0.244200	0.115468	0.191214	0.076*
C23	−0.2330 (4)	0.07126 (14)	0.2733 (2)	0.0600 (11)
H23A	−0.302809	0.089655	0.291809	0.072*
H23B	−0.257880	0.039484	0.277655	0.072*
N24	−0.0664 (3)	0.08048 (10)	0.31420 (15)	0.0470 (8)
H24	−0.055655	0.113641	0.314496	0.056*
C25	−0.0287 (5)	0.06706 (14)	0.3911 (2)	0.0573 (10)
H25	−0.045248	0.034216	0.393331	0.069*
C26	0.1421 (5)	0.07703 (14)	0.42877 (19)	0.0578 (11)
H26A	0.159090	0.073180	0.479875	0.069*
H26B	0.161403	0.108758	0.420735	0.069*
C27	0.2636 (5)	0.04865 (13)	0.40731 (19)	0.0531 (10)
N28	0.2554 (3)	0.06168 (10)	0.33122 (14)	0.0441 (7)
H28	0.283461	0.093988	0.334118	0.053*
C29	0.3799 (4)	0.03908 (15)	0.3064 (2)	0.0588 (11)
H29A	0.481942	0.051537	0.331708	0.071*
H29B	0.381236	0.006718	0.316162	0.071*
C30	0.3462 (4)	0.04692 (14)	0.2288 (2)	0.0557 (10)
H30A	0.409650	0.026684	0.209428	0.067*
H30B	0.372762	0.077978	0.220239	0.067*
N31	0.1765 (3)	0.03858 (9)	0.19211 (14)	0.0421 (7)
H31	0.148791	0.060096	0.151995	0.050*
C32	0.1288 (5)	−0.00772 (12)	0.15832 (19)	0.0483 (9)
C33	−0.0400 (4)	−0.00298 (13)	0.11006 (19)	0.0515 (10)
H33A	−0.038622	0.018142	0.072057	0.062*
H33B	−0.071470	−0.032286	0.087650	0.062*
C34	−0.1677 (4)	0.01252 (13)	0.1419 (2)	0.0518 (10)
H34	−0.173451	−0.008818	0.179632	0.062*
C25A	−0.1327 (6)	0.09093 (19)	0.4291 (2)	0.0884 (16)
H25A	−0.238226	0.079776	0.410899	0.133*
H25B	−0.131361	0.123076	0.420719	0.133*
H25C	−0.094300	0.085053	0.479626	0.133*
C27A	0.4261 (5)	0.06038 (16)	0.4582 (2)	0.0758 (13)
H27A	0.503880	0.041184	0.447818	0.114*
H27B	0.425999	0.055662	0.506881	0.114*
H27C	0.450018	0.091620	0.451699	0.114*
C27B	0.2314 (5)	−0.00229 (13)	0.4118 (2)	0.0705 (13)
H27D	0.317339	−0.019414	0.404701	0.106*
H27E	0.136392	−0.010190	0.375432	0.106*
H27F	0.220133	−0.009180	0.458190	0.106*
C32A	0.1411 (5)	−0.04402 (13)	0.2156 (2)	0.0653 (12)
H32A	0.248832	−0.047298	0.243634	0.098*
H32B	0.103155	−0.072465	0.192932	0.098*
H32C	0.079130	−0.035147	0.246139	0.098*
C32B	0.2321 (5)	−0.02093 (15)	0.1112 (2)	0.0683 (12)
H32D	0.238820	0.004179	0.080827	0.102*
H32E	0.186955	−0.046664	0.082207	0.102*
H32F	0.335303	−0.028603	0.141077	0.102*
C34A	−0.3247 (5)	0.01198 (16)	0.0823 (2)	0.0732 (13)
H34A	−0.409332	0.015369	0.103082	0.110*
H34B	−0.335778	−0.016353	0.056878	0.110*
H34C	−0.327140	0.036600	0.049674	0.110*
Cl1	0.04648 (14)	0.12152 (3)	0.02020 (5)	0.0627 (3)
O11	0.0208 (4)	0.11563 (11)	−0.05487 (15)	0.0871 (10)
O12	0.1777 (4)	0.09572 (13)	0.05975 (19)	0.1046 (12)
O13	−0.0888 (4)	0.10628 (11)	0.03875 (16)	0.0824 (9)
O14	0.0730 (6)	0.16810 (10)	0.03803 (18)	0.1168 (15)
Cl2	−0.30063 (16)	−0.05995 (4)	0.32668 (7)	0.0744 (3)
O21	−0.317 (2)	−0.0287 (6)	0.3798 (9)	0.108 (5)	0.5
O22	−0.4040 (14)	−0.0460 (6)	0.2612 (7)	0.136 (6)	0.5
O23	−0.305 (3)	−0.1036 (4)	0.3459 (11)	0.167 (7)	0.5
O24	−0.1491 (10)	−0.0529 (4)	0.3129 (7)	0.125 (3)	0.5
O25	−0.279 (3)	−0.0260 (6)	0.3745 (12)	0.149 (8)	0.5
O26	−0.319 (3)	−0.0460 (6)	0.2625 (9)	0.224 (10)	0.5
O27	−0.204 (3)	−0.0931 (8)	0.3517 (16)	0.261 (11)	0.5
O28	−0.4420 (17)	−0.0831 (5)	0.3231 (8)	0.194 (6)	0.5
Cl3	0.06049 (14)	0.18122 (3)	0.22458 (6)	0.0676 (3)
O31	0.1373 (4)	0.14274 (10)	0.20864 (17)	0.0921 (11)
O32	0.1437 (6)	0.22121 (11)	0.2232 (2)	0.1241 (15)
O33	0.0440 (6)	0.17559 (12)	0.2931 (2)	0.1381 (18)
O34	−0.0876 (5)	0.18279 (19)	0.1739 (3)	0.169 (2)
Cl4A	0.5256 (7)	0.3146 (2)	−0.1429 (3)	0.0736 (9)	0.650 (8)
O41	0.5146 (12)	0.3523 (3)	−0.1872 (5)	0.132 (5)	0.650 (8)
O42	0.6606 (14)	0.3181 (5)	−0.0781 (5)	0.126 (4)	0.650 (8)
O43	0.5089 (18)	0.2745 (4)	−0.1693 (6)	0.192 (5)	0.650 (8)
O44	0.3937 (8)	0.3124 (3)	−0.1183 (3)	0.138 (3)	0.650 (8)
Cl4B	0.5700 (13)	0.3152 (4)	−0.1545 (7)	0.0736 (9)	0.350 (8)
O45	0.489 (2)	0.3555 (6)	−0.1438 (10)	0.142 (9)	0.350 (8)
O46	0.661 (3)	0.2972 (9)	−0.1007 (12)	0.136 (8)	0.350 (8)
O47	0.657 (2)	0.3202 (5)	−0.1969 (8)	0.164 (7)	0.350 (8)
O48	0.4912 (13)	0.2824 (8)	−0.2072 (9)	0.148 (7)	0.350 (8)
OW	0.4397 (5)	0.16490 (14)	0.1461 (2)	0.0980 (11)
HW1	0.475 (6)	0.165 (2)	0.1897 (7)	0.147*
HW2	0.354 (4)	0.152 (2)	0.134 (3)	0.147*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0521 (4)	0.0436 (4)	0.0405 (3)	0.0037 (3)	0.0125 (3)	0.0048 (3)
N1	0.059 (2)	0.0434 (18)	0.0428 (17)	−0.0001 (15)	0.0138 (15)	0.0058 (14)
C2	0.060 (3)	0.073 (3)	0.051 (2)	0.010 (2)	0.011 (2)	0.005 (2)
C3	0.067 (3)	0.076 (3)	0.056 (3)	0.020 (2)	0.016 (2)	0.005 (2)
N4	0.056 (2)	0.0442 (18)	0.0462 (18)	0.0025 (15)	0.0161 (16)	0.0039 (14)
C5	0.087 (3)	0.052 (2)	0.056 (3)	0.000 (2)	0.029 (2)	−0.003 (2)
C6	0.093 (4)	0.059 (3)	0.052 (3)	−0.006 (2)	0.029 (3)	−0.006 (2)
C7	0.075 (3)	0.070 (3)	0.061 (3)	−0.017 (2)	0.023 (2)	−0.011 (2)
N8	0.061 (2)	0.054 (2)	0.0459 (19)	−0.0004 (17)	0.0093 (16)	0.0042 (15)
C9	0.054 (3)	0.110 (4)	0.068 (3)	0.011 (3)	−0.005 (2)	−0.003 (3)
C10	0.072 (3)	0.104 (4)	0.077 (3)	0.037 (3)	0.006 (3)	−0.005 (3)
N11	0.056 (2)	0.0523 (19)	0.0514 (19)	0.0105 (16)	0.0159 (16)	0.0073 (15)
C12	0.072 (3)	0.052 (3)	0.071 (3)	0.008 (2)	0.028 (2)	−0.004 (2)
C13	0.090 (4)	0.064 (3)	0.057 (3)	−0.012 (3)	0.028 (3)	−0.011 (2)
C14	0.078 (3)	0.047 (2)	0.053 (2)	−0.004 (2)	0.020 (2)	−0.0026 (19)
C5A	0.106 (4)	0.095 (4)	0.072 (3)	0.024 (3)	0.043 (3)	−0.006 (3)
C7A	0.138 (5)	0.068 (3)	0.113 (4)	−0.029 (3)	0.067 (4)	−0.008 (3)
C7B	0.094 (4)	0.152 (6)	0.072 (3)	−0.035 (4)	0.008 (3)	−0.036 (4)
C12A	0.101 (4)	0.101 (4)	0.104 (4)	0.023 (3)	0.051 (3)	−0.015 (3)
C12B	0.120 (5)	0.057 (3)	0.107 (4)	0.014 (3)	0.034 (4)	0.021 (3)
C14A	0.087 (4)	0.070 (3)	0.058 (3)	−0.011 (3)	0.008 (3)	−0.010 (2)
Ni2	0.0378 (3)	0.0382 (3)	0.0413 (3)	0.0012 (3)	0.0109 (3)	0.0022 (3)
N21	0.0398 (17)	0.0485 (18)	0.0473 (17)	0.0015 (15)	0.0096 (14)	0.0041 (14)
C22	0.049 (3)	0.066 (3)	0.070 (3)	0.008 (2)	0.009 (2)	−0.005 (2)
C23	0.041 (2)	0.067 (3)	0.075 (3)	0.004 (2)	0.022 (2)	−0.011 (2)
N24	0.0465 (19)	0.0460 (18)	0.0502 (18)	0.0002 (15)	0.0169 (15)	−0.0003 (14)
C25	0.060 (3)	0.065 (3)	0.053 (2)	0.000 (2)	0.027 (2)	0.005 (2)
C26	0.071 (3)	0.062 (3)	0.041 (2)	−0.001 (2)	0.016 (2)	0.0021 (19)
C27	0.052 (2)	0.058 (3)	0.045 (2)	0.003 (2)	0.0084 (19)	0.0082 (19)
N28	0.0449 (18)	0.0434 (17)	0.0436 (17)	0.0034 (14)	0.0122 (14)	0.0014 (14)
C29	0.043 (2)	0.071 (3)	0.060 (3)	0.002 (2)	0.011 (2)	−0.005 (2)
C30	0.042 (2)	0.065 (3)	0.062 (3)	−0.004 (2)	0.018 (2)	−0.008 (2)
N31	0.0437 (18)	0.0418 (17)	0.0420 (16)	−0.0031 (14)	0.0145 (14)	−0.0004 (13)
C32	0.059 (3)	0.040 (2)	0.049 (2)	−0.0022 (19)	0.0186 (19)	−0.0043 (17)
C33	0.059 (3)	0.047 (2)	0.047 (2)	−0.008 (2)	0.013 (2)	−0.0030 (18)
C34	0.052 (2)	0.050 (2)	0.051 (2)	−0.0119 (19)	0.0110 (19)	0.0015 (18)
C25A	0.084 (4)	0.122 (4)	0.072 (3)	0.006 (3)	0.042 (3)	−0.011 (3)
C27A	0.068 (3)	0.097 (4)	0.050 (2)	0.003 (3)	−0.001 (2)	0.002 (2)
C27B	0.080 (3)	0.059 (3)	0.069 (3)	0.008 (2)	0.015 (2)	0.021 (2)
C32A	0.079 (3)	0.045 (2)	0.069 (3)	0.002 (2)	0.016 (2)	0.009 (2)
C32B	0.072 (3)	0.066 (3)	0.071 (3)	0.004 (2)	0.027 (2)	−0.020 (2)
C34A	0.053 (3)	0.084 (3)	0.072 (3)	−0.013 (2)	0.003 (2)	−0.012 (2)
Cl1	0.0884 (8)	0.0480 (6)	0.0518 (6)	−0.0145 (6)	0.0208 (6)	0.0056 (5)
O11	0.126 (3)	0.090 (2)	0.0525 (17)	−0.024 (2)	0.0374 (19)	−0.0008 (16)
O12	0.091 (2)	0.116 (3)	0.103 (3)	0.017 (2)	0.022 (2)	0.039 (2)
O13	0.099 (2)	0.083 (2)	0.075 (2)	−0.0148 (19)	0.0415 (19)	0.0139 (17)
O14	0.209 (4)	0.0520 (19)	0.088 (2)	−0.046 (2)	0.041 (3)	−0.0035 (17)
Cl2	0.0928 (9)	0.0517 (7)	0.0814 (8)	0.0066 (7)	0.0297 (7)	0.0028 (6)
O21	0.154 (11)	0.102 (8)	0.083 (6)	0.065 (9)	0.056 (7)	0.011 (5)
O22	0.101 (7)	0.162 (12)	0.103 (7)	0.053 (7)	−0.035 (6)	−0.021 (7)
O23	0.27 (2)	0.037 (4)	0.242 (16)	0.018 (9)	0.153 (17)	0.054 (6)
O24	0.068 (5)	0.160 (9)	0.166 (9)	0.007 (5)	0.061 (5)	0.016 (7)
O25	0.235 (18)	0.099 (8)	0.138 (10)	−0.069 (9)	0.094 (10)	−0.055 (7)
O26	0.47 (3)	0.128 (12)	0.122 (9)	−0.061 (18)	0.161 (15)	0.026 (8)
O27	0.250 (18)	0.193 (19)	0.33 (2)	0.157 (17)	0.07 (2)	0.041 (16)
O28	0.169 (10)	0.165 (12)	0.228 (14)	−0.083 (9)	0.027 (10)	0.033 (11)
Cl3	0.0846 (8)	0.0481 (6)	0.0707 (7)	0.0035 (6)	0.0235 (6)	0.0008 (5)
O31	0.133 (3)	0.0535 (18)	0.097 (2)	0.0242 (19)	0.045 (2)	0.0007 (17)
O32	0.192 (4)	0.053 (2)	0.142 (3)	−0.033 (2)	0.072 (3)	0.006 (2)
O33	0.263 (6)	0.084 (3)	0.106 (3)	−0.037 (3)	0.113 (3)	−0.024 (2)
O34	0.092 (3)	0.207 (5)	0.178 (5)	0.035 (3)	−0.005 (3)	0.019 (4)
Cl4A	0.083 (3)	0.0633 (8)	0.074 (2)	−0.008 (2)	0.0223 (15)	0.0158 (12)
O41	0.118 (7)	0.092 (6)	0.149 (8)	−0.043 (5)	−0.015 (6)	0.073 (6)
O42	0.086 (5)	0.210 (13)	0.075 (6)	0.005 (7)	0.010 (4)	0.020 (5)
O43	0.393 (16)	0.079 (5)	0.116 (8)	−0.050 (7)	0.094 (8)	−0.006 (6)
O44	0.093 (5)	0.223 (9)	0.097 (5)	−0.045 (5)	0.024 (4)	0.011 (5)
Cl4B	0.083 (3)	0.0633 (8)	0.074 (2)	−0.008 (2)	0.0223 (15)	0.0158 (12)
O45	0.140 (14)	0.098 (11)	0.158 (17)	0.061 (10)	−0.003 (12)	−0.026 (11)
O46	0.123 (12)	0.18 (2)	0.092 (11)	0.071 (13)	0.016 (9)	0.031 (11)
O47	0.273 (17)	0.138 (12)	0.129 (10)	−0.023 (11)	0.136 (12)	−0.011 (9)
O48	0.214 (15)	0.125 (14)	0.105 (12)	0.006 (9)	0.045 (10)	−0.055 (11)
OW	0.098 (3)	0.099 (3)	0.089 (2)	−0.011 (2)	0.015 (2)	0.019 (2)

Geometric parameters (Å, º) top

Ni1—N1	1.954 (3)	N24—C25	1.491 (5)
Ni1—N4	1.950 (3)	N24—H24	0.9800
Ni1—N8	1.949 (3)	C25—C26	1.511 (5)
Ni1—N11	1.956 (3)	C25—C25A	1.517 (5)
N1—C2	1.481 (5)	C25—H25	0.9800
N1—C14	1.508 (5)	C26—C27	1.520 (5)
N1—H1	0.9800	C26—H26A	0.9700
C2—C3	1.489 (5)	C26—H26B	0.9700
C2—H2A	0.9700	C27—N28	1.514 (4)
C2—H2B	0.9700	C27—C27B	1.533 (5)
C3—N4	1.482 (5)	C27—C27A	1.535 (5)
C3—H3A	0.9700	N28—C29	1.489 (5)
C3—H3B	0.9700	N28—H28	0.9800
N4—C5	1.496 (5)	C29—C30	1.474 (5)
N4—H4	0.9800	C29—H29A	0.9700
C5—C6	1.500 (6)	C29—H29B	0.9700
C5—C5A	1.524 (6)	C30—N31	1.490 (4)
C5—H5	0.9800	C30—H30A	0.9700
C6—C7	1.517 (6)	C30—H30B	0.9700
C6—H6A	0.9700	N31—C32	1.518 (4)
C6—H6B	0.9700	N31—H31	0.9800
C7—N8	1.504 (5)	C32—C32A	1.525 (5)
C7—C7A	1.532 (6)	C32—C32B	1.528 (5)
C7—C7B	1.547 (6)	C32—C33	1.529 (5)
N8—C9	1.475 (5)	C33—C34	1.517 (5)
N8—H8	0.9800	C33—H33A	0.9700
C9—C10	1.484 (6)	C33—H33B	0.9700
C9—H9A	0.9700	C34—C34A	1.534 (5)
C9—H9B	0.9700	C34—H34	0.9800
C10—N11	1.487 (5)	C25A—H25A	0.9600
C10—H10A	0.9700	C25A—H25B	0.9600
C10—H10B	0.9700	C25A—H25C	0.9600
N11—C12	1.515 (5)	C27A—H27A	0.9600
N11—H11	0.9800	C27A—H27B	0.9600
C12—C13	1.521 (6)	C27A—H27C	0.9600
C12—C12B	1.522 (6)	C27B—H27D	0.9600
C12—C12A	1.532 (6)	C27B—H27E	0.9600
C13—C14	1.495 (6)	C27B—H27F	0.9600
C13—H13A	0.9700	C32A—H32A	0.9600
C13—H13B	0.9700	C32A—H32B	0.9600
C14—C14A	1.527 (5)	C32A—H32C	0.9600
C14—H14	0.9800	C32B—H32D	0.9600
C5A—H5A1	0.9600	C32B—H32E	0.9600
C5A—H5A2	0.9600	C32B—H32F	0.9600
C5A—H5A3	0.9600	C34A—H34A	0.9600
C7A—H7A1	0.9600	C34A—H34B	0.9600
C7A—H7A2	0.9600	C34A—H34C	0.9600
C7A—H7A3	0.9600	Cl1—O14	1.416 (3)
C7B—H7B1	0.9600	Cl1—O12	1.417 (3)
C7B—H7B2	0.9600	Cl1—O11	1.425 (3)
C7B—H7B3	0.9600	Cl1—O13	1.428 (3)
C12A—H12A	0.9600	Cl2—O26	1.281 (13)
C12A—H12B	0.9600	Cl2—O27	1.299 (17)
C12A—H12C	0.9600	Cl2—O23	1.341 (10)
C12B—H12D	0.9600	Cl2—O25	1.342 (17)
C12B—H12E	0.9600	Cl2—O22	1.399 (11)
C12B—H12F	0.9600	Cl2—O28	1.414 (11)
C14A—H14A	0.9600	Cl2—O21	1.424 (17)
C14A—H14B	0.9600	Cl2—O24	1.466 (7)
C14A—H14C	0.9600	Cl3—O32	1.395 (3)
Ni2—N21	1.935 (3)	Cl3—O33	1.397 (4)
Ni2—N24	1.937 (3)	Cl3—O34	1.398 (4)
Ni2—N28	1.931 (3)	Cl3—O31	1.403 (3)
Ni2—N31	1.924 (3)	Cl4A—O43	1.279 (12)
Ni2—O31	2.799 (3)	Cl4A—O41	1.391 (9)
N21—C22	1.484 (5)	Cl4A—O44	1.394 (8)
N21—C34	1.507 (4)	Cl4A—O42	1.471 (11)
N21—H21	0.9800	Cl4B—O46	1.24 (3)
C22—C23	1.494 (5)	Cl4B—O47	1.300 (15)
C22—H22A	0.9700	Cl4B—O48	1.434 (19)
C22—H22B	0.9700	Cl4B—O45	1.44 (2)
C23—N24	1.489 (4)	O47—O48	1.82 (2)
C23—H23A	0.9700	OW—HW1	0.815 (10)
C23—H23B	0.9700	OW—HW2	0.821 (10)

N8—Ni1—N4	93.49 (14)	N24—C23—C22	107.6 (3)
N8—Ni1—N1	177.45 (13)	N24—C23—H23A	110.2
N4—Ni1—N1	86.74 (13)	C22—C23—H23A	110.2
N8—Ni1—N11	87.00 (14)	N24—C23—H23B	110.2
N4—Ni1—N11	177.59 (13)	C22—C23—H23B	110.2
N1—Ni1—N11	92.88 (13)	H23A—C23—H23B	108.5
C2—N1—C14	110.6 (3)	C23—N24—C25	112.7 (3)
C2—N1—Ni1	109.0 (2)	C23—N24—Ni2	106.3 (2)
C14—N1—Ni1	118.4 (2)	C25—N24—Ni2	120.5 (2)
C2—N1—H1	106.0	C23—N24—H24	105.3
C14—N1—H1	106.0	C25—N24—H24	105.3
Ni1—N1—H1	106.0	Ni2—N24—H24	105.3
N1—C2—C3	107.1 (3)	N24—C25—C26	109.6 (3)
N1—C2—H2A	110.3	N24—C25—C25A	112.2 (3)
C3—C2—H2A	110.3	C26—C25—C25A	110.1 (3)
N1—C2—H2B	110.3	N24—C25—H25	108.2
C3—C2—H2B	110.3	C26—C25—H25	108.2
H2A—C2—H2B	108.5	C25A—C25—H25	108.2
N4—C3—C2	108.3 (3)	C25—C26—C27	117.1 (3)
N4—C3—H3A	110.0	C25—C26—H26A	108.0
C2—C3—H3A	110.0	C27—C26—H26A	108.0
N4—C3—H3B	110.0	C25—C26—H26B	108.0
C2—C3—H3B	110.0	C27—C26—H26B	108.0
H3A—C3—H3B	108.4	H26A—C26—H26B	107.3
C3—N4—C5	110.6 (3)	N28—C27—C26	107.3 (3)
C3—N4—Ni1	107.1 (2)	N28—C27—C27B	110.3 (3)
C5—N4—Ni1	123.5 (3)	C26—C27—C27B	111.1 (3)
C3—N4—H4	104.7	N28—C27—C27A	110.0 (3)
C5—N4—H4	104.7	C26—C27—C27A	108.1 (3)
Ni1—N4—H4	104.7	C27B—C27—C27A	109.8 (3)
N4—C5—C6	111.0 (3)	C29—N28—C27	112.3 (3)
N4—C5—C5A	111.1 (4)	C29—N28—Ni2	108.7 (2)
C6—C5—C5A	110.7 (4)	C27—N28—Ni2	120.8 (2)
N4—C5—H5	108.0	C29—N28—H28	104.5
C6—C5—H5	108.0	C27—N28—H28	104.5
C5A—C5—H5	108.0	Ni2—N28—H28	104.5
C5—C6—C7	116.6 (4)	C30—C29—N28	108.5 (3)
C5—C6—H6A	108.1	C30—C29—H29A	110.0
C7—C6—H6A	108.1	N28—C29—H29A	110.0
C5—C6—H6B	108.1	C30—C29—H29B	110.0
C7—C6—H6B	108.1	N28—C29—H29B	110.0
H6A—C6—H6B	107.3	H29A—C29—H29B	108.4
N8—C7—C6	107.6 (3)	C29—C30—N31	109.9 (3)
N8—C7—C7A	110.2 (4)	C29—C30—H30A	109.7
C6—C7—C7A	111.8 (4)	N31—C30—H30A	109.7
N8—C7—C7B	109.5 (4)	C29—C30—H30B	109.7
C6—C7—C7B	107.0 (4)	N31—C30—H30B	109.7
C7A—C7—C7B	110.7 (4)	H30A—C30—H30B	108.2
C9—N8—C7	112.4 (3)	C30—N31—C32	118.1 (3)
C9—N8—Ni1	107.2 (2)	C30—N31—Ni2	107.8 (2)
C7—N8—Ni1	121.6 (3)	C32—N31—Ni2	114.5 (2)
C9—N8—H8	104.7	C30—N31—H31	105.0
C7—N8—H8	104.7	C32—N31—H31	105.0
Ni1—N8—H8	104.7	Ni2—N31—H31	105.0
N8—C9—C10	107.9 (4)	N31—C32—C32A	111.0 (3)
N8—C9—H9A	110.1	N31—C32—C32B	110.4 (3)
C10—C9—H9A	110.1	C32A—C32—C32B	109.6 (3)
N8—C9—H9B	110.1	N31—C32—C33	106.6 (3)
C10—C9—H9B	110.1	C32A—C32—C33	111.2 (3)
H9A—C9—H9B	108.4	C32B—C32—C33	108.0 (3)
C9—C10—N11	107.1 (4)	C34—C33—C32	119.7 (3)
C9—C10—H10A	110.3	C34—C33—H33A	107.4
N11—C10—H10A	110.3	C32—C33—H33A	107.4
C9—C10—H10B	110.3	C34—C33—H33B	107.4
N11—C10—H10B	110.3	C32—C33—H33B	107.4
H10A—C10—H10B	108.6	H33A—C33—H33B	106.9
C10—N11—C12	112.4 (3)	N21—C34—C33	109.4 (3)
C10—N11—Ni1	107.5 (3)	N21—C34—C34A	112.2 (3)
C12—N11—Ni1	123.5 (3)	C33—C34—C34A	108.2 (3)
C10—N11—H11	103.7	N21—C34—H34	109.0
C12—N11—H11	103.7	C33—C34—H34	109.0
Ni1—N11—H11	103.7	C34A—C34—H34	109.0
N11—C12—C13	108.4 (3)	C25—C25A—H25A	109.5
N11—C12—C12B	110.3 (4)	C25—C25A—H25B	109.5
C13—C12—C12B	112.3 (4)	H25A—C25A—H25B	109.5
N11—C12—C12A	108.9 (4)	C25—C25A—H25C	109.5
C13—C12—C12A	107.2 (4)	H25A—C25A—H25C	109.5
C12B—C12—C12A	109.5 (4)	H25B—C25A—H25C	109.5
C14—C13—C12	115.9 (4)	C27—C27A—H27A	109.5
C14—C13—H13A	108.3	C27—C27A—H27B	109.5
C12—C13—H13A	108.3	H27A—C27A—H27B	109.5
C14—C13—H13B	108.3	C27—C27A—H27C	109.5
C12—C13—H13B	108.3	H27A—C27A—H27C	109.5
H13A—C13—H13B	107.4	H27B—C27A—H27C	109.5
C13—C14—N1	109.0 (3)	C27—C27B—H27D	109.5
C13—C14—C14A	110.7 (3)	C27—C27B—H27E	109.5
N1—C14—C14A	112.4 (3)	H27D—C27B—H27E	109.5
C13—C14—H14	108.2	C27—C27B—H27F	109.5
N1—C14—H14	108.2	H27D—C27B—H27F	109.5
C14A—C14—H14	108.2	H27E—C27B—H27F	109.5
C5—C5A—H5A1	109.5	C32—C32A—H32A	109.5
C5—C5A—H5A2	109.5	C32—C32A—H32B	109.5
H5A1—C5A—H5A2	109.5	H32A—C32A—H32B	109.5
C5—C5A—H5A3	109.5	C32—C32A—H32C	109.5
H5A1—C5A—H5A3	109.5	H32A—C32A—H32C	109.5
H5A2—C5A—H5A3	109.5	H32B—C32A—H32C	109.5
C7—C7A—H7A1	109.5	C32—C32B—H32D	109.5
C7—C7A—H7A2	109.5	C32—C32B—H32E	109.5
H7A1—C7A—H7A2	109.5	H32D—C32B—H32E	109.5
C7—C7A—H7A3	109.5	C32—C32B—H32F	109.5
H7A1—C7A—H7A3	109.5	H32D—C32B—H32F	109.5
H7A2—C7A—H7A3	109.5	H32E—C32B—H32F	109.5
C7—C7B—H7B1	109.5	C34—C34A—H34A	109.5
C7—C7B—H7B2	109.5	C34—C34A—H34B	109.5
H7B1—C7B—H7B2	109.5	H34A—C34A—H34B	109.5
C7—C7B—H7B3	109.5	C34—C34A—H34C	109.5
H7B1—C7B—H7B3	109.5	H34A—C34A—H34C	109.5
H7B2—C7B—H7B3	109.5	H34B—C34A—H34C	109.5
C12—C12A—H12A	109.5	O14—Cl1—O12	109.4 (3)
C12—C12A—H12B	109.5	O14—Cl1—O11	109.59 (19)
H12A—C12A—H12B	109.5	O12—Cl1—O11	110.7 (2)
C12—C12A—H12C	109.5	O14—Cl1—O13	109.5 (2)
H12A—C12A—H12C	109.5	O12—Cl1—O13	108.4 (2)
H12B—C12A—H12C	109.5	O11—Cl1—O13	109.2 (2)
C12—C12B—H12D	109.5	O26—Cl2—O27	119.2 (16)
C12—C12B—H12E	109.5	O26—Cl2—O25	113.0 (13)
H12D—C12B—H12E	109.5	O27—Cl2—O25	110.6 (16)
C12—C12B—H12F	109.5	O23—Cl2—O22	118.0 (12)
H12D—C12B—H12F	109.5	O26—Cl2—O28	104.5 (12)
H12E—C12B—H12F	109.5	O27—Cl2—O28	98.1 (12)
C14—C14A—H14A	109.5	O25—Cl2—O28	109.8 (12)
C14—C14A—H14B	109.5	O23—Cl2—O21	113.5 (11)
H14A—C14A—H14B	109.5	O22—Cl2—O21	107.2 (9)
C14—C14A—H14C	109.5	O23—Cl2—O24	106.9 (8)
H14A—C14A—H14C	109.5	O22—Cl2—O24	100.8 (7)
H14B—C14A—H14C	109.5	O21—Cl2—O24	109.7 (10)
N31—Ni2—N28	88.24 (12)	O32—Cl3—O33	108.9 (2)
N31—Ni2—N21	88.72 (12)	O32—Cl3—O34	110.8 (3)
N28—Ni2—N21	174.45 (13)	O33—Cl3—O34	109.8 (3)
N31—Ni2—N24	176.44 (12)	O32—Cl3—O31	112.3 (3)
N28—Ni2—N24	94.58 (12)	O33—Cl3—O31	108.1 (2)
N21—Ni2—N24	88.30 (13)	O34—Cl3—O31	106.8 (3)
N31—Ni2—O31	80.07 (11)	Cl3—O31—Ni2	117.4 (2)
N28—Ni2—O31	87.20 (12)	O43—Cl4A—O41	120.3 (7)
N21—Ni2—O31	87.70 (12)	O43—Cl4A—O44	94.8 (8)
N24—Ni2—O31	97.88 (11)	O41—Cl4A—O44	109.8 (7)
C22—N21—C34	116.5 (3)	O43—Cl4A—O42	112.3 (9)
C22—N21—Ni2	107.8 (2)	O41—Cl4A—O42	111.7 (8)
C34—N21—Ni2	111.9 (2)	O44—Cl4A—O42	105.5 (6)
C22—N21—H21	106.7	O46—Cl4B—O47	102.8 (18)
C34—N21—H21	106.7	O46—Cl4B—O48	112.5 (17)
Ni2—N21—H21	106.7	O47—Cl4B—O48	83.1 (11)
N21—C22—C23	107.9 (3)	O46—Cl4B—O45	117.4 (15)
N21—C22—H22A	110.1	O47—Cl4B—O45	114.7 (14)
C23—C22—H22A	110.1	O48—Cl4B—O45	119.9 (13)
N21—C22—H22B	110.1	Cl4B—O47—O48	51.6 (9)
C23—C22—H22B	110.1	Cl4B—O48—O47	45.3 (6)
H22A—C22—H22B	108.4	HW1—OW—HW2	110 (2)

C14—N1—C2—C3	167.3 (3)	C22—C23—N24—Ni2	−41.8 (3)
Ni1—N1—C2—C3	35.5 (4)	C23—N24—C25—C26	179.5 (3)
N1—C2—C3—N4	−51.0 (4)	Ni2—N24—C25—C26	52.6 (4)
C2—C3—N4—C5	178.8 (3)	C23—N24—C25—C25A	−57.8 (4)
C2—C3—N4—Ni1	41.8 (4)	Ni2—N24—C25—C25A	175.3 (3)
C3—N4—C5—C6	−174.3 (3)	N24—C25—C26—C27	−67.9 (4)
Ni1—N4—C5—C6	−45.6 (4)	C25A—C25—C26—C27	168.2 (4)
C3—N4—C5—C5A	62.1 (4)	C25—C26—C27—N28	68.2 (4)
Ni1—N4—C5—C5A	−169.2 (3)	C25—C26—C27—C27B	−52.5 (5)
N4—C5—C6—C7	64.8 (5)	C25—C26—C27—C27A	−173.2 (3)
C5A—C5—C6—C7	−171.4 (4)	C26—C27—N28—C29	174.7 (3)
C5—C6—C7—N8	−69.8 (5)	C27B—C27—N28—C29	−64.1 (4)
C5—C6—C7—C7A	51.2 (5)	C27A—C27—N28—C29	57.3 (4)
C5—C6—C7—C7B	172.6 (4)	C26—C27—N28—Ni2	−55.0 (4)
C6—C7—N8—C9	−174.5 (4)	C27B—C27—N28—Ni2	66.2 (4)
C7A—C7—N8—C9	63.4 (5)	C27A—C27—N28—Ni2	−172.4 (3)
C7B—C7—N8—C9	−58.7 (5)	C27—N28—C29—C30	169.9 (3)
C6—C7—N8—Ni1	56.4 (4)	Ni2—N28—C29—C30	33.7 (4)
C7A—C7—N8—Ni1	−65.7 (5)	N28—C29—C30—N31	−45.5 (4)
C7B—C7—N8—Ni1	172.3 (3)	C29—C30—N31—C32	−96.4 (4)
C7—N8—C9—C10	−177.3 (4)	C29—C30—N31—Ni2	35.3 (4)
Ni1—N8—C9—C10	−41.0 (4)	C30—N31—C32—C32A	72.3 (4)
N8—C9—C10—N11	53.2 (5)	Ni2—N31—C32—C32A	−56.4 (4)
C9—C10—N11—C12	−178.2 (4)	C30—N31—C32—C32B	−49.4 (4)
C9—C10—N11—Ni1	−39.1 (5)	Ni2—N31—C32—C32B	−178.1 (2)
C10—N11—C12—C13	−179.4 (4)	C30—N31—C32—C33	−166.5 (3)
Ni1—N11—C12—C13	49.1 (4)	Ni2—N31—C32—C33	64.9 (3)
C10—N11—C12—C12B	57.2 (5)	N31—C32—C33—C34	−58.1 (4)
Ni1—N11—C12—C12B	−74.3 (4)	C32A—C32—C33—C34	63.1 (4)
C10—N11—C12—C12A	−63.1 (5)	C32B—C32—C33—C34	−176.6 (3)
Ni1—N11—C12—C12A	165.4 (3)	C22—N21—C34—C33	169.8 (3)
N11—C12—C13—C14	−64.9 (5)	Ni2—N21—C34—C33	−65.5 (3)
C12B—C12—C13—C14	57.3 (5)	C22—N21—C34—C34A	49.7 (4)
C12A—C12—C13—C14	177.7 (4)	Ni2—N21—C34—C34A	174.4 (3)
C12—C13—C14—N1	72.6 (4)	C32—C33—C34—N21	60.2 (4)
C12—C13—C14—C14A	−163.3 (4)	C32—C33—C34—C34A	−177.4 (3)
C2—N1—C14—C13	172.6 (3)	O32—Cl3—O31—Ni2	158.2 (2)
Ni1—N1—C14—C13	−60.6 (4)	O33—Cl3—O31—Ni2	38.0 (3)
C2—N1—C14—C14A	49.5 (4)	O34—Cl3—O31—Ni2	−80.2 (3)
Ni1—N1—C14—C14A	176.2 (3)	O46—Cl4B—O47—O48	111.6 (17)
C34—N21—C22—C23	91.2 (4)	O45—Cl4B—O47—O48	−119.9 (16)
Ni2—N21—C22—C23	−35.6 (4)	O46—Cl4B—O48—O47	−101.1 (19)
N21—C22—C23—N24	51.4 (4)	O45—Cl4B—O48—O47	114.6 (17)
C22—C23—N24—C25	−175.9 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O44	0.98	2.61	3.279 (9)	126
N4—H4···O14	0.98	2.02	2.941 (4)	157
N8—H8···OW	0.98	1.99	2.965 (5)	175
N11—H11···O43	0.98	2.11	3.028 (10)	155
N11—H11···O46	0.98	2.45	3.36 (3)	155
N21—H21···O13	0.98	2.14	3.093 (4)	165
N24—H24···O33	0.98	2.12	3.033 (5)	154
N28—H28···O45ⁱ	0.98	2.30	3.146 (16)	144
N31—H31···O12	0.98	2.16	3.083 (4)	156
OW—HW1···O41ⁱ	0.82 (1)	2.38 (2)	3.162 (11)	162 (5)
OW—HW1···O47ⁱ	0.82 (1)	2.37 (3)	3.139 (18)	157 (5)
OW—HW2···O12	0.82 (1)	2.45 (3)	3.181 (6)	149 (6)

Symmetry code: (i) x, −y+1/2, z+1/2.

(5,7,7,12,12,14-Hexamethyl-1,4,8,11-tetraazacyclotetradecane)nickel(II) dibromide trihydrate (II) top

Crystal data top

[Ni(C₁₆H₃₆N₄)]Br₂·3H₂O	D_x = 1.549 Mg m⁻³ D_m = 1.530 (3) Mg m⁻³ D_m measured by Flotation in chloroform/carbon tetrachloride mixtures
M_r = 557.06	Mo Kα radiation, λ = 0.7107 Å
Orthorhombic, Fdd2	Cell parameters from 6096 reflections
a = 60.3649 (18) Å	θ = 0.4–27.5°
b = 19.8364 (9) Å	µ = 4.17 mm⁻¹
c = 7.9773 (3) Å	T = 295 K
V = 9552.2 (6) Å³	Rod, yellow
Z = 16	0.37 × 0.15 × 0.10 mm
F(000) = 4608

Data collection top

Enraf–Nonius KappaCCD diffractometer	5382 independent reflections
Radiation source: fine-focus sealed tube	4897 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.096
Detector resolution: 9 pixels mm^-1	θ_max = 27.5°, θ_min = 2.2°
combination of ω and φ scans	h = −78→+78
Absorption correction: part of the refinement model (ΔF) (SCALEPACK; Otwinowski & Minor, 1997)	k = −25→+25
T_min = 0.34, T_max = 0.67	l = −10→+10
41142 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.035	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.085	w = 1/[σ²(F_o²) + (0.040P)² + 35.P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
5382 reflections	Δρ_max = 0.88 e Å⁻³
253 parameters	Δρ_min = −0.56 e Å⁻³
4 restraints	Absolute structure: Twinning involves inversion,with Flack parameter corresponding to twin-fraction occupancies
Primary atom site location: heavy-atom method

Special details top

Refinement. Refined as a 2-component perfect inversion twin.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Br1	0.15971 (2)	0.23829 (3)	0.64516 (9)	0.0645 (2)
Br2	0.20453 (2)	0.49097 (4)	0.45452 (7)	0.05935 (18)
Ni	0.18885 (2)	0.41205 (3)	0.92870 (8)	0.03245 (13)
N1	0.21367 (7)	0.4693 (2)	0.8794 (6)	0.0407 (10)
H1	0.2135 (10)	0.476 (3)	0.779 (8)	0.041*
C2	0.23414 (8)	0.4296 (3)	0.9187 (10)	0.0532 (14)
H2A	0.237732	0.400071	0.825597	0.064*
H2B	0.246536	0.459778	0.936969	0.064*
C3	0.22999 (9)	0.3892 (3)	1.0713 (9)	0.0547 (15)
H3A	0.228730	0.418374	1.168391	0.066*
H3B	0.242077	0.357842	1.090118	0.066*
N4	0.20894 (8)	0.3519 (2)	1.0439 (7)	0.0457 (11)
H4	0.2107 (10)	0.322 (3)	0.979 (8)	0.046*
C5	0.20145 (9)	0.3155 (3)	1.1970 (9)	0.0554 (14)
H5	0.198881	0.348705	1.285962	0.067*
C6	0.17993 (9)	0.2782 (3)	1.1644 (9)	0.0497 (13)
H6A	0.176834	0.250079	1.261144	0.060*
H6B	0.182237	0.248293	1.069725	0.060*
C7	0.15935 (9)	0.3206 (3)	1.1287 (7)	0.0405 (11)
N8	0.16302 (6)	0.3557 (2)	0.9622 (6)	0.0359 (9)
H8	0.1650 (9)	0.328 (3)	0.884 (8)	0.036*
C9	0.14319 (7)	0.3923 (2)	0.8992 (7)	0.0397 (11)
H9A	0.136777	0.419087	0.988532	0.048*
H9B	0.132137	0.360243	0.861173	0.048*
C10	0.15002 (9)	0.4369 (3)	0.7573 (7)	0.0434 (12)
H10A	0.152516	0.410081	0.657488	0.052*
H10B	0.138332	0.469111	0.733394	0.052*
N11	0.17079 (7)	0.4736 (2)	0.8034 (6)	0.0353 (8)
H11	0.1758 (9)	0.480 (2)	0.700 (8)	0.035*
C12	0.16868 (8)	0.5426 (2)	0.8824 (7)	0.0405 (11)
C13	0.19218 (9)	0.5742 (3)	0.8846 (7)	0.0442 (12)
H13A	0.196503	0.582262	0.769260	0.053*
H13B	0.191057	0.617843	0.938697	0.053*
C14	0.21089 (8)	0.5358 (3)	0.9689 (7)	0.0426 (11)
H14	0.206878	0.527186	1.085942	0.051*
C5A	0.21918 (13)	0.2649 (4)	1.2584 (14)	0.098 (4)
H5A1	0.231669	0.289119	1.302265	0.147*
H5A2	0.223883	0.237223	1.166271	0.147*
H5A3	0.213000	0.236900	1.344699	0.147*
C7A	0.13939 (11)	0.2730 (3)	1.1164 (9)	0.0587 (16)
H7A1	0.140979	0.244693	1.019498	0.088*
H7A2	0.126039	0.299016	1.106629	0.088*
H7A3	0.138659	0.245500	1.215218	0.088*
C7B	0.15541 (11)	0.3721 (3)	1.2670 (8)	0.0520 (14)
H7B1	0.141211	0.392963	1.251117	0.078*
H7B2	0.166781	0.405897	1.263101	0.078*
H7B3	0.155744	0.349927	1.373886	0.078*
C12A	0.15366 (12)	0.5887 (3)	0.7761 (10)	0.0657 (19)
H12A	0.158590	0.588079	0.661714	0.098*
H12B	0.154366	0.633877	0.818647	0.098*
H12C	0.138661	0.572708	0.781776	0.098*
C12B	0.15975 (10)	0.5374 (3)	1.0602 (8)	0.0493 (13)
H12D	0.169109	0.508202	1.124882	0.074*
H12E	0.144991	0.519431	1.057561	0.074*
H12F	0.159513	0.581408	1.110415	0.074*
C14A	0.23179 (10)	0.5796 (4)	0.9644 (12)	0.072 (2)
H14A	0.243228	0.558536	1.029552	0.109*
H14B	0.228530	0.623221	1.010142	0.109*
H14C	0.236705	0.584401	0.850538	0.109*
O1	0.20252 (16)	0.3394 (5)	0.6365 (12)	0.148 (3)
O2	0.19992 (17)	0.1516 (4)	0.8373 (16)	0.167 (4)
O3	0.22816 (10)	0.2518 (5)	0.801 (2)	0.248 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0804 (4)	0.0507 (3)	0.0625 (4)	−0.0051 (3)	−0.0021 (3)	−0.0088 (3)
Br2	0.0611 (3)	0.0760 (4)	0.0409 (3)	−0.0070 (3)	0.0056 (3)	0.0004 (3)
Ni	0.0272 (2)	0.0338 (3)	0.0364 (3)	−0.0001 (2)	−0.0010 (2)	−0.0003 (2)
N1	0.032 (2)	0.046 (2)	0.044 (3)	−0.0035 (17)	0.0034 (18)	0.001 (2)
C2	0.027 (2)	0.060 (3)	0.072 (4)	0.000 (2)	0.003 (3)	−0.002 (3)
C3	0.030 (2)	0.060 (3)	0.075 (4)	0.007 (2)	−0.010 (3)	0.001 (3)
N4	0.033 (2)	0.044 (3)	0.060 (3)	0.0056 (19)	−0.002 (2)	−0.004 (2)
C5	0.050 (3)	0.058 (3)	0.059 (4)	0.009 (2)	−0.008 (3)	0.018 (3)
C6	0.049 (3)	0.037 (3)	0.063 (4)	0.005 (2)	−0.002 (3)	0.010 (3)
C7	0.040 (3)	0.042 (3)	0.040 (3)	−0.003 (2)	−0.002 (2)	0.004 (2)
N8	0.0347 (19)	0.033 (2)	0.040 (2)	−0.0016 (15)	−0.0019 (18)	−0.0017 (17)
C9	0.030 (2)	0.041 (2)	0.048 (3)	−0.0043 (18)	−0.007 (2)	0.003 (2)
C10	0.044 (3)	0.043 (3)	0.044 (3)	−0.001 (2)	−0.014 (2)	0.002 (2)
N11	0.033 (2)	0.039 (2)	0.035 (2)	−0.0016 (16)	−0.0002 (17)	0.0037 (17)
C12	0.037 (2)	0.033 (2)	0.052 (3)	0.0020 (19)	−0.003 (2)	0.000 (2)
C13	0.046 (3)	0.036 (2)	0.051 (3)	−0.006 (2)	0.003 (2)	0.006 (2)
C14	0.039 (2)	0.045 (3)	0.043 (3)	−0.006 (2)	0.003 (2)	−0.005 (2)
C5A	0.067 (5)	0.088 (6)	0.140 (10)	0.017 (4)	−0.015 (5)	0.063 (6)
C7A	0.055 (3)	0.057 (4)	0.064 (4)	−0.018 (3)	0.002 (3)	0.012 (3)
C7B	0.059 (4)	0.058 (4)	0.040 (3)	0.006 (3)	0.004 (3)	0.002 (3)
C12A	0.063 (4)	0.045 (3)	0.089 (5)	0.005 (3)	−0.013 (4)	0.014 (3)
C12B	0.046 (3)	0.043 (3)	0.060 (4)	−0.003 (2)	0.016 (3)	−0.010 (3)
C14A	0.050 (3)	0.064 (4)	0.104 (6)	−0.017 (3)	−0.001 (4)	−0.015 (4)
O1	0.173 (8)	0.150 (8)	0.121 (8)	−0.029 (6)	0.007 (6)	−0.015 (6)
O2	0.192 (9)	0.094 (5)	0.216 (12)	0.025 (6)	−0.060 (8)	−0.008 (7)
O3	0.246 (15)	0.156 (9)	0.34 (2)	−0.014 (10)	0.074 (15)	−0.093 (12)

Geometric parameters (Å, º) top

Br1—O2	3.346 (9)	C10—H10A	0.9700
Br2—O1	3.341 (9)	C10—H10B	0.9700
Ni—N11	1.918 (4)	N11—C12	1.512 (6)
Ni—N1	1.921 (4)	N11—H11	0.89 (6)
Ni—N4	1.934 (5)	C12—C12B	1.521 (8)
Ni—N8	1.937 (4)	C12—C12A	1.541 (8)
Ni—O1	2.863 (10)	C12—C13	1.551 (7)
N1—C2	1.499 (7)	C13—C14	1.519 (7)
N1—C14	1.509 (7)	C13—H13A	0.9700
N1—H1	0.81 (6)	C13—H13B	0.9700
C2—C3	1.479 (10)	C14—C14A	1.531 (7)
C2—H2A	0.9700	C14—H14	0.9800
C2—H2B	0.9700	C5A—H5A1	0.9600
C3—N4	1.486 (7)	C5A—H5A2	0.9600
C3—H3A	0.9700	C5A—H5A3	0.9600
C3—H3B	0.9700	C7A—H7A1	0.9600
N4—C5	1.489 (8)	C7A—H7A2	0.9600
N4—H4	0.80 (6)	C7A—H7A3	0.9600
C5—C6	1.518 (8)	C7B—H7B1	0.9600
C5—C5A	1.548 (8)	C7B—H7B2	0.9600
C5—H5	0.9800	C7B—H7B3	0.9600
C6—C7	1.528 (7)	C12A—H12A	0.9600
C6—H6A	0.9700	C12A—H12B	0.9600
C6—H6B	0.9700	C12A—H12C	0.9600
C7—N8	1.515 (7)	C12B—H12D	0.9600
C7—C7B	1.522 (8)	C12B—H12E	0.9600
C7—C7A	1.535 (7)	C12B—H12F	0.9600
N8—C9	1.487 (6)	C14A—H14A	0.9600
N8—H8	0.83 (6)	C14A—H14B	0.9600
C9—C10	1.496 (7)	C14A—H14C	0.9600
C9—H9A	0.9700	O1—O3	2.671 (11)
C9—H9B	0.9700	O2—O3	2.635 (10)
C10—N11	1.495 (6)	O3—O3ⁱ	2.637 (12)

N11—Ni—N1	87.73 (19)	C10—N11—C12	118.1 (4)
N11—Ni—N4	175.6 (2)	C10—N11—Ni	107.2 (3)
N1—Ni—N4	88.5 (2)	C12—N11—Ni	114.0 (3)
N11—Ni—N8	88.93 (18)	C10—N11—H11	97 (3)
N1—Ni—N8	175.8 (2)	C12—N11—H11	107 (3)
N4—Ni—N8	94.79 (19)	Ni—N11—H11	112 (3)
N11—Ni—O1	93.4 (2)	N11—C12—C12B	110.9 (4)
N1—Ni—O1	84.6 (2)	N11—C12—C12A	110.9 (5)
N4—Ni—O1	84.0 (2)	C12B—C12—C12A	110.1 (5)
N8—Ni—O1	93.1 (2)	N11—C12—C13	107.1 (4)
C2—N1—C14	116.9 (5)	C12B—C12—C13	109.9 (4)
C2—N1—Ni	106.8 (3)	C12A—C12—C13	107.7 (4)
C14—N1—Ni	109.5 (3)	C14—C13—C12	118.9 (4)
C2—N1—H1	108 (4)	C14—C13—H13A	107.6
C14—N1—H1	108 (4)	C12—C13—H13A	107.6
Ni—N1—H1	107 (4)	C14—C13—H13B	107.6
C3—C2—N1	108.5 (5)	C12—C13—H13B	107.6
C3—C2—H2A	110.0	H13A—C13—H13B	107.0
N1—C2—H2A	110.0	N1—C14—C13	108.1 (4)
C3—C2—H2B	110.0	N1—C14—C14A	113.1 (5)
N1—C2—H2B	110.0	C13—C14—C14A	108.6 (5)
H2A—C2—H2B	108.4	N1—C14—H14	109.0
C2—C3—N4	107.0 (5)	C13—C14—H14	109.0
C2—C3—H3A	110.3	C14A—C14—H14	109.0
N4—C3—H3A	110.3	C5—C5A—H5A1	109.5
C2—C3—H3B	110.3	C5—C5A—H5A2	109.5
N4—C3—H3B	110.3	H5A1—C5A—H5A2	109.5
H3A—C3—H3B	108.6	C5—C5A—H5A3	109.5
C5—N4—C3	112.3 (5)	H5A1—C5A—H5A3	109.5
C5—N4—Ni	119.9 (3)	H5A2—C5A—H5A3	109.5
C3—N4—Ni	107.4 (4)	C7—C7A—H7A1	109.5
C5—N4—H4	102 (5)	C7—C7A—H7A2	109.5
C3—N4—H4	111 (4)	H7A1—C7A—H7A2	109.5
Ni—N4—H4	104 (5)	C7—C7A—H7A3	109.5
N4—C5—C6	110.9 (5)	H7A1—C7A—H7A3	109.5
N4—C5—C5A	111.4 (6)	H7A2—C7A—H7A3	109.5
C6—C5—C5A	109.2 (5)	C7—C7B—H7B1	109.5
N4—C5—H5	108.4	C7—C7B—H7B2	109.5
C6—C5—H5	108.4	H7B1—C7B—H7B2	109.5
C5A—C5—H5	108.4	C7—C7B—H7B3	109.5
C5—C6—C7	117.3 (4)	H7B1—C7B—H7B3	109.5
C5—C6—H6A	108.0	H7B2—C7B—H7B3	109.5
C7—C6—H6A	108.0	C12—C12A—H12A	109.5
C5—C6—H6B	108.0	C12—C12A—H12B	109.5
C7—C6—H6B	108.0	H12A—C12A—H12B	109.5
H6A—C6—H6B	107.2	C12—C12A—H12C	109.5
N8—C7—C7B	110.5 (4)	H12A—C12A—H12C	109.5
N8—C7—C6	107.3 (4)	H12B—C12A—H12C	109.5
C7B—C7—C6	111.2 (5)	C12—C12B—H12D	109.5
N8—C7—C7A	110.0 (4)	C12—C12B—H12E	109.5
C7B—C7—C7A	109.7 (5)	H12D—C12B—H12E	109.5
C6—C7—C7A	108.1 (4)	C12—C12B—H12F	109.5
C9—N8—C7	113.7 (4)	H12D—C12B—H12F	109.5
C9—N8—Ni	108.7 (3)	H12E—C12B—H12F	109.5
C7—N8—Ni	120.2 (3)	C14—C14A—H14A	109.5
C9—N8—H8	101 (4)	C14—C14A—H14B	109.5
C7—N8—H8	112 (4)	H14A—C14A—H14B	109.5
Ni—N8—H8	99 (4)	C14—C14A—H14C	109.5
N8—C9—C10	108.9 (4)	H14A—C14A—H14C	109.5
N8—C9—H9A	109.9	H14B—C14A—H14C	109.5
C10—C9—H9A	109.9	O3—O1—Ni	95.4 (4)
N8—C9—H9B	109.9	O3—O1—Br2	141.1 (4)
C10—C9—H9B	109.9	Ni—O1—Br2	84.9 (2)
H9A—C9—H9B	108.3	O3—O2—Br1	91.8 (3)
N11—C10—C9	109.4 (4)	O3—O2—Br2ⁱⁱ	134.3 (4)
N11—C10—H10A	109.8	Br1—O2—Br2ⁱⁱ	132.9 (3)
C9—C10—H10A	109.8	O3ⁱ—O3—O2	128.8 (6)
N11—C10—H10B	109.8	O3ⁱ—O3—O1	126.6 (5)
C9—C10—H10B	109.8	O2—O3—O1	99.8 (4)
H10A—C10—H10B	108.2

C14—N1—C2—C3	84.7 (6)	C7—N8—C9—C10	167.4 (4)
Ni—N1—C2—C3	−38.3 (6)	Ni—N8—C9—C10	30.6 (5)
N1—C2—C3—N4	51.3 (6)	N8—C9—C10—N11	−45.2 (6)
C2—C3—N4—C5	−173.1 (5)	C9—C10—N11—C12	−92.8 (5)
C2—C3—N4—Ni	−39.2 (6)	C9—C10—N11—Ni	37.6 (5)
C3—N4—C5—C6	180.0 (5)	C10—N11—C12—C12B	70.9 (6)
Ni—N4—C5—C6	52.4 (6)	Ni—N11—C12—C12B	−56.3 (5)
C3—N4—C5—C5A	−58.2 (8)	C10—N11—C12—C12A	−51.8 (6)
Ni—N4—C5—C5A	174.2 (5)	Ni—N11—C12—C12A	−179.1 (4)
N4—C5—C6—C7	−66.1 (7)	C10—N11—C12—C13	−169.1 (4)
C5A—C5—C6—C7	170.9 (7)	Ni—N11—C12—C13	63.6 (5)
C5—C6—C7—N8	66.7 (7)	N11—C12—C13—C14	−55.5 (6)
C5—C6—C7—C7B	−54.3 (7)	C12B—C12—C13—C14	65.0 (6)
C5—C6—C7—C7A	−174.7 (6)	C12A—C12—C13—C14	−174.9 (5)
C7B—C7—N8—C9	−66.0 (5)	C2—N1—C14—C13	167.8 (4)
C6—C7—N8—C9	172.6 (4)	Ni—N1—C14—C13	−70.6 (5)
C7A—C7—N8—C9	55.2 (6)	C2—N1—C14—C14A	47.6 (8)
C7B—C7—N8—Ni	65.4 (5)	Ni—N1—C14—C14A	169.1 (5)
C6—C7—N8—Ni	−56.1 (5)	C12—C13—C14—N1	60.7 (6)
C7A—C7—N8—Ni	−173.4 (4)	C12—C13—C14—C14A	−176.2 (5)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Br2	0.81 (6)	2.66 (6)	3.461 (5)	169 (6)
N4—H4···O1	0.80 (6)	2.80 (7)	3.283 (11)	121 (5)
N4—H4···O3	0.80 (6)	2.25 (6)	3.008 (13)	159 (6)
N8—H8···Br1	0.83 (6)	2.63 (6)	3.444 (5)	164 (5)
N11—H11···Br2	0.89 (6)	2.63 (6)	3.466 (4)	159 (5)

Footnotes

‡Deceased.

Acknowledgements

We are extremely grateful for the support and encouragement of Daryle H. Busch and for the assistance of Graeme J. Gainsford at The Ohio State University, where much of the experimental work was carried out. We are also grateful to the Office of the Dean at Fordham University for its generous financial support.

Funding information

Funding for this research was provided by: US National Science Foundation Equipment Grant (grant No. GP8534).

References

Bosnich, B., Poon, C. K. & Tobe, M. L. (1965). Inorg. Chem. 4, 1102–1108. CrossRef CAS Web of Science Google Scholar
Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL6895. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
Busch, D. H. (1978). Acc. Chem. Res. 11, 392–400. CrossRef CAS Google Scholar
Busing, W. R. & Levy, H. A. (1957). Acta Cryst. 10, 180–182. CrossRef CAS IUCr Journals Web of Science Google Scholar
Corfield, P. W. R., Dabrowiak, J. C. & Gore, E. S. (1973). Inorg. Chem. 12, 1734–1740. CrossRef CAS Web of Science Google Scholar
Corfield, P. W. R. & Gainsford, G. J. (1972). Local versions of standard programs, written at Ohio State University. Google Scholar
Curtis, N. F. (1960). J. Chem. Soc. pp. 4409–4413. CrossRef Google Scholar
Curtis, N. F. (1964). J. Chem. Soc. pp. 2644–2650. CrossRef Web of Science Google Scholar
Curtis, N. F. (1967). J. Chem. Soc. C, pp. 1979–1980. Google Scholar
Curtis, N. F., Coles, M. P. & Wikaira, J. (2016). Polyhedron, 110, 282–290. CrossRef CAS Google Scholar
Curtis, N. F., Swann, D. A. & Waters, T. N. (1973). J. Chem. Soc. Dalton Trans. pp. 1963–1974. CrossRef Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Nonius (1997). KappaCCD Server Software. Nonius BV, Delft, The Netherlands. Google Scholar
Ochiai, E., Rettig, S. J. & Trotter, J. (1978). Can. J. Chem. 56, 267–272. CrossRef CAS Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Ou, G.-C., Yuan, X.-Y. & Li, Z.-Z. (2013). Chin. J. Struct. Chem. 32, 375–380. CAS Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Shi, F., Chen, X., Rong, R. & Bao, Q. (2010). Acta Cryst. E66, m665–m666. CrossRef IUCr Journals Google Scholar
Wang, A., Lee, T.-J., Chen, B.-H., Yuan, Y.-Z. & Chung, C.-S. (1996). Acta Cryst. C52, 3033–3035. CrossRef CAS IUCr Journals Google Scholar
Warner, L. G. & Busch, D. H. (1969). J. Am. Chem. Soc. 91, 4092–4101. CrossRef CAS Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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