metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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μ-Acetato-aqua-μ-(5-bromo-2-{1,3-bis­­[2-(5-bromo-2-oxido­benzyl­­idene­amino)­eth­yl]imidazolidin-2-yl}phenolato)methano­ldinickel(II) methanol disolvate monohydrate

aDepartment of Chemistry, Howard University, 525 College Street NW, Washington, DC 20059, USA
*Correspondence e-mail: rbutcher99@yahoo.com

(Received 10 August 2011; accepted 30 August 2011; online 14 September 2011)

The crystal structure of the title compound, [Ni2(C27H24Br3N4O3)(CH3CO2)(CH3OH)(H2O)]·2CH3OH·H2O contains [L(OAc){(CH3OH)Ni}{(H2O)Ni}] mol­ecules {H3L = 2-(5-bromo-2-hy­droxy­phen­yl)-1,3-bis­[4-(5-bromo-2-hy­droxy­phen­yl)-3-aza­but-3-en­yl]-1,3-imidazolidine} with additional water and two methanol solvent mol­ecules. In this instance, one of the two Ni atoms is coordinated to a water and the other to a methanol mol­ecule. The Ni—O and Ni—N distances, as well as the angles about the metal atoms, show quite regular octa­hedra around the central ions. The Ni—Ophenol—Ni and Ni—Oacetate—Ni angles are not similar [95.26 (13) and 97.34 (13)°, respectively], indicating that this subtle solvate exchange induces significant differences in the conformation adopted. The coordinated methanol ligand is involved in an intra­molecular hydrogen bond to the uncoordinated O atom of the bridging acetate ligand, while the coordinated water mol­ecule forms a hydrogen bond with the one of the methanol solvent mol­ecules. The water solvent mol­ecule forms strong hydrogen bonds to both phenolate O atoms. The remaining methanol solvent mol­ecule also forms a hydrogen bond with this solvent water mol­ecule.

Related literature

For nickel complexes of similar ligands, see: Fondo et al. (2005[Fondo, M., Garcia-Deibe, A. M., Corbella, M., Ruiz, E., Tercero, J., Sanmartin, J. & Bermejo, M. R. (2005). Inorg. Chem. 44, 5011-5020.], 2006a[Fondo, M., Garcia-Deibe, A. M., Ocampo, N., Sanmartin, J., Bermejo, M. R. & Llamas-Saiz, A. L. (2006a). Dalton Trans. pp. 4260-4270.],b[Fondo, M., Ocampo, N., Garcia-Deibe, A. M., Vicente, R., Corbella, M., Bermejo, M. R. & Sanmartin, J. (2006b). Inorg. Chem. 45, 255-262.], 2007[Fondo, M., Garcia-Deibe, A. M., Ocampo, N., Sanmartin, J. & Bermejo, M. R. (2007). Dalton Trans. pp. 414-416.], 2009[Fondo, M., Ocampo, N., Garcia-Deibe, A. M., Ruiz, E., Tercero, J. & Sanmartin, J. (2009). Inorg. Chem. 48, 9861-9873.]); Khan et al. (2011[Khan, A. R., Tesema, Y., Butcher, R. J. & Gultneh, Y. (2011). Acta Cryst. E67, m1264-m1265.]); Lu et al. (2007[Lu, L.-P., Lu, X.-P. & Zhu, M.-L. (2007). Acta Cryst. C63, m374-m376.]); Paital et al. (2007[Paital, A. R., Wong, W. T., Aromi, G. & Ray, D. (2007). Inorg. Chem. 46, 5727-5733.], 2009[Paital, A. R., Ribas, J., Barrios, L. A., Aromi, G. & Ray, D. (2009). Dalton Trans. pp. 256-258.]).

[Scheme 1]

Experimental

Crystal data
  • [Ni2(C27H24Br3N4O3)(C2H3O2)(CH4O)(H2O)]·2CH4O·H2O

  • Mr = 1000.85

  • Orthorhombic, P n a 21

  • a = 14.7385 (16) Å

  • b = 18.552 (2) Å

  • c = 14.2504 (15) Å

  • V = 3896.4 (7) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 4.10 mm−1

  • T = 168 K

  • 0.49 × 0.12 × 0.06 mm

Data collection
  • Bruker SMART 1000 CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2000[Bruker (2000). SADABS, SMART and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.676, Tmax = 1.000

  • 25239 measured reflections

  • 8737 independent reflections

  • 6627 reflections with I > 2σ(I)

  • Rint = 0.054

Refinement
  • R[F2 > 2σ(F2)] = 0.041

  • wR(F2) = 0.092

  • S = 0.96

  • 8737 reflections

  • 479 parameters

  • 7 restraints

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.71 e Å−3

  • Δρmin = −0.73 e Å−3

  • Absolute structure: Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), 3686 Friedel pairs

  • Flack parameter: 0.007 (8)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O1W—H1W1⋯O2Wi 0.80 (2) 2.01 (2) 2.810 (5) 174 (5)
O1W—H1W2⋯O3M 0.82 (2) 1.97 (3) 2.770 (5) 164 (5)
O2W—H2W1⋯O1B 0.80 (2) 1.86 (3) 2.631 (5) 160 (6)
O2W—H2W2⋯O1A 0.83 (2) 1.91 (2) 2.744 (5) 177 (6)
O1M—H1M⋯O2AA 0.84 1.77 2.602 (5) 174
O2M—H2M⋯O2W 0.84 1.89 2.725 (5) 172
O3M—H3M⋯O2Mi 0.84 1.96 2.753 (6) 158
Symmetry code: (i) [x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z].

Data collection: SMART (Bruker, 2000[Bruker (2000). SADABS, SMART and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT-Plus (Bruker, 2000[Bruker (2000). SADABS, SMART and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

Nickel complexes of the compartmental triprotic heptadentate ligand, 2-hydroxyphenyl-1,3-bis[4-(2-hydroxyphenyl)-3-azabut- 3-enyl]-1,3-imidazolidine and its derivatives have been of interest for their ability to give rise to dinuclear compounds with a predefined ground state (Fondo et al., 2005, 2006a,b, 2007, 2009; Lu et al., 2007; Paital, et al., 2007, 2009). Density functional theory (DFT) calculations demonstrated that the Schiff base provides an NCN bridge between the metal ions that helps to mediate the ferromagnetic exchange (Fondo, et al., 2005). Consequently, the use of suitable cross-linking ligands between the dinuclear units could be a route to produce complexes of higher nuclearity, with all of the unpaired electrons aligned parallel to each other. The type of complex obtained depends on the synthesis conditions as the coordination environment about the metals is usually completed by coordinating solvent molecules.

The crystal structure shows that the title compound, [Ni2(CH3CO2)(C27H24Br3N4O3) (H2O)(CH3OH)].2CH3OH.H2O, (I), contains [L(OAc){(CH3OH)Ni}{(H2O)Ni}] molecules (H3L = 2-(5-bromo-2-hydroxyphenyl)-1,3-bis[4-(5-bromo-2- hydroxyphenyl)-3-azabut-3-enyl]-1,3-imidazolidine) with water and two methanol molecules as solvates. In this instance one of the two nickel atoms is coordinated to a water and the other to a methanol molecule. This is in contrast to its related complex involving the ligand 2-(5-chloro-2-hydroxyphenyl)-1,3-bis[4-(5-chloro-2-hydroxyphenyl)-3-azabut-3- enyl]-1,3-imidazolidine, which was synthesized under similar conditions. In this case both nickel atoms contain coordinated methanol molecules (Khan et al., 2011). It has previous been observed that nickel complexes involving this type of ligand are prone to solvate exchange (Fondo et al., 2009).

(I) is a neutral dinuclear compound, where the L3- Schiff base acts as a trianionic heptadentate ligand, using each one of its N2O compartments to coordinate a nickel atom. Thus, the metal atoms are joined to one terminal phenol oxygen (O1A, O1B), an iminic nitrogen (N1A, N1B), and an aminic nitrogen atom (N1, N2), with the aminic NCN group (N2—C7—N2) acting as a bridge between both nickel ions. In addition, the nickel atoms are linked by the endogenous phenolate oxygen atom (O1) of the central ligand arm and by an exogenous bridging monodentate acetate group (O11A). This gives rise to a nearly planar Ni2O2 metallacycle, with an intramolecular Ni—Ni distance of 3.0927 (9) Å. The coordination spheres of the nickel atoms are completed by solvent molecules. In the case of Ni1A by water and in the case of Ni1B by methanol molecules. Therefore, the metal atoms are hexacoordinated in a N2O4 environment, with an octahedral geometry. The Ni—O and Ni—N distances, as well as the angles about the metal atoms, show quite regular polyhedra around the central ions. However, unlike the analogous complex formed with 2-(5-chloro-2-hydroxyphenyl)-1,3-bis[4-(5-chloro-2- hydroxyphenyl)-3-azabut-3-enyl]-1,3-imidazolidine (Khan et al., 2011) the Ni—Ophenol—Ni and Ni—Oacetate—Ni angles are not similar [95.26 (13)° and 97.34 (13)°, respectively] and more closely related to a similar complex (Fondo et al., 2009) with a similar coordination environment about the two Ni atoms (one with water and the other with methanol coordinated). Thus this subtle solvate exchange induces significant differences in the conformation adopted. There are structures of Ni complexes involving similar ligands reported in the literature which differ only in the nature of the coordinating solvent (H2O) and solvate molecules (H2O, CH3CN) in the lattice (Fondo et al., 2006b) and similar differences are observed.

The coordinated methanol ligand is involved in an intramolecular hydrogen bond to the uncoordinated O atom (O2AA) of the bridging acetate ligand while the coordinated water molecule forms a hydrogen bond with the one of the methanol solvate molecules. The solvate water molecule forms strong hydrogen bonds to both O1A and O1B. The remaining methanol solvate molecule also forms a hydrogen bond with this water solvate molecule.

Related literature top

For nickel complexes of similar ligands, see: Fondo et al. (2005, 2006a,b, 2007, 2009); Khan et al. (2011); Lu et al. (2007); Paital et al. (2007, 2009).

Experimental top

For the synthesis of the ligand (H3L) methanol solutions of triethylenetetramine and 5-bromosalicylaldehyde were mixed in a 1:3 molar ratio. After heating at 333 K for a few minutes, diethylether was added to this mixture, and yellow crystals were separated, filtered and recrystallized from methanol solution: Mp 376 K. For synthesis of the complex, to a stirred methanol solution (25 ml) of [Ni(OAc)2].4H2O (1.5 g, 2.67 mmol) was added 1.33 g (5.35 mmol) of the ligand H3L. Slow evaporation of the green filtrate overnight yielded green to brownish cystal suitable for X-ray analysis in 70% yield.

Refinement top

H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms with an O—H distance of 0.84 and C—H distances of 0.95 - 0.99 Å [Uiso(H) = 1.2Ueq(OH, CH, CH2) [Uiso(H) = 1.5Ueq(CH3)]. Water H atoms were refined isotropically with O—H distances restrained to 0.82 Å and H—O—H angle to 104.5° with [Uiso(H) = 1.5Ueq(O)].

Structure description top

Nickel complexes of the compartmental triprotic heptadentate ligand, 2-hydroxyphenyl-1,3-bis[4-(2-hydroxyphenyl)-3-azabut- 3-enyl]-1,3-imidazolidine and its derivatives have been of interest for their ability to give rise to dinuclear compounds with a predefined ground state (Fondo et al., 2005, 2006a,b, 2007, 2009; Lu et al., 2007; Paital, et al., 2007, 2009). Density functional theory (DFT) calculations demonstrated that the Schiff base provides an NCN bridge between the metal ions that helps to mediate the ferromagnetic exchange (Fondo, et al., 2005). Consequently, the use of suitable cross-linking ligands between the dinuclear units could be a route to produce complexes of higher nuclearity, with all of the unpaired electrons aligned parallel to each other. The type of complex obtained depends on the synthesis conditions as the coordination environment about the metals is usually completed by coordinating solvent molecules.

The crystal structure shows that the title compound, [Ni2(CH3CO2)(C27H24Br3N4O3) (H2O)(CH3OH)].2CH3OH.H2O, (I), contains [L(OAc){(CH3OH)Ni}{(H2O)Ni}] molecules (H3L = 2-(5-bromo-2-hydroxyphenyl)-1,3-bis[4-(5-bromo-2- hydroxyphenyl)-3-azabut-3-enyl]-1,3-imidazolidine) with water and two methanol molecules as solvates. In this instance one of the two nickel atoms is coordinated to a water and the other to a methanol molecule. This is in contrast to its related complex involving the ligand 2-(5-chloro-2-hydroxyphenyl)-1,3-bis[4-(5-chloro-2-hydroxyphenyl)-3-azabut-3- enyl]-1,3-imidazolidine, which was synthesized under similar conditions. In this case both nickel atoms contain coordinated methanol molecules (Khan et al., 2011). It has previous been observed that nickel complexes involving this type of ligand are prone to solvate exchange (Fondo et al., 2009).

(I) is a neutral dinuclear compound, where the L3- Schiff base acts as a trianionic heptadentate ligand, using each one of its N2O compartments to coordinate a nickel atom. Thus, the metal atoms are joined to one terminal phenol oxygen (O1A, O1B), an iminic nitrogen (N1A, N1B), and an aminic nitrogen atom (N1, N2), with the aminic NCN group (N2—C7—N2) acting as a bridge between both nickel ions. In addition, the nickel atoms are linked by the endogenous phenolate oxygen atom (O1) of the central ligand arm and by an exogenous bridging monodentate acetate group (O11A). This gives rise to a nearly planar Ni2O2 metallacycle, with an intramolecular Ni—Ni distance of 3.0927 (9) Å. The coordination spheres of the nickel atoms are completed by solvent molecules. In the case of Ni1A by water and in the case of Ni1B by methanol molecules. Therefore, the metal atoms are hexacoordinated in a N2O4 environment, with an octahedral geometry. The Ni—O and Ni—N distances, as well as the angles about the metal atoms, show quite regular polyhedra around the central ions. However, unlike the analogous complex formed with 2-(5-chloro-2-hydroxyphenyl)-1,3-bis[4-(5-chloro-2- hydroxyphenyl)-3-azabut-3-enyl]-1,3-imidazolidine (Khan et al., 2011) the Ni—Ophenol—Ni and Ni—Oacetate—Ni angles are not similar [95.26 (13)° and 97.34 (13)°, respectively] and more closely related to a similar complex (Fondo et al., 2009) with a similar coordination environment about the two Ni atoms (one with water and the other with methanol coordinated). Thus this subtle solvate exchange induces significant differences in the conformation adopted. There are structures of Ni complexes involving similar ligands reported in the literature which differ only in the nature of the coordinating solvent (H2O) and solvate molecules (H2O, CH3CN) in the lattice (Fondo et al., 2006b) and similar differences are observed.

The coordinated methanol ligand is involved in an intramolecular hydrogen bond to the uncoordinated O atom (O2AA) of the bridging acetate ligand while the coordinated water molecule forms a hydrogen bond with the one of the methanol solvate molecules. The solvate water molecule forms strong hydrogen bonds to both O1A and O1B. The remaining methanol solvate molecule also forms a hydrogen bond with this water solvate molecule.

For nickel complexes of similar ligands, see: Fondo et al. (2005, 2006a,b, 2007, 2009); Khan et al. (2011); Lu et al. (2007); Paital et al. (2007, 2009).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT-Plus (Bruker, 2000); data reduction: SAINT-Plus (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of compound (I), C32H43Br3N4Ni2O10, showing the atom labeling with displacement ellipsoids at the 30% probability level. All H atoms except those involved in the hydrogen bonding were removed for clarity. Hydrogen bonds are shown by dashed lines.
[Figure 2] Fig. 2. The molecular packing for C32H43Br3N4Ni2O10 viewed down the c axis. Hydrogen bonds are shown by dashed lines.
µ-Acetato-aqua-µ-(5-bromo-2-{1,3-bis[2-(5-bromo-2- oxidobenzylideneamino)ethyl]imidazolidin-2-yl}phenolato)methanoldinickel(II) methanol disolvate monohydrate top
Crystal data top
[Ni2(C27H24Br3N4O3)(C2H3O2)(CH4O)(H2O)]·2CH4O·H2OF(000) = 2016
Mr = 1000.85Dx = 1.706 Mg m3
Orthorhombic, Pna21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2nCell parameters from 7492 reflections
a = 14.7385 (16) Åθ = 2.3–26.7°
b = 18.552 (2) ŵ = 4.10 mm1
c = 14.2504 (15) ÅT = 168 K
V = 3896.4 (7) Å3Needle, brown
Z = 40.49 × 0.12 × 0.06 mm
Data collection top
Bruker SMART 1000 CCD
diffractometer
8737 independent reflections
Radiation source: fine-focus sealed tube6627 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.054
φ and ω scansθmax = 28.3°, θmin = 1.8°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
h = 1916
Tmin = 0.676, Tmax = 1.000k = 2419
25239 measured reflectionsl = 1814
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.041H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.092 w = 1/[σ2(Fo2) + (0.0457P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.96(Δ/σ)max = 0.001
8737 reflectionsΔρmax = 0.71 e Å3
479 parametersΔρmin = 0.73 e Å3
7 restraintsAbsolute structure: Flack (1983), 3686 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.007 (8)
Crystal data top
[Ni2(C27H24Br3N4O3)(C2H3O2)(CH4O)(H2O)]·2CH4O·H2OV = 3896.4 (7) Å3
Mr = 1000.85Z = 4
Orthorhombic, Pna21Mo Kα radiation
a = 14.7385 (16) ŵ = 4.10 mm1
b = 18.552 (2) ÅT = 168 K
c = 14.2504 (15) Å0.49 × 0.12 × 0.06 mm
Data collection top
Bruker SMART 1000 CCD
diffractometer
8737 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
6627 reflections with I > 2σ(I)
Tmin = 0.676, Tmax = 1.000Rint = 0.054
25239 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.041H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.092Δρmax = 0.71 e Å3
S = 0.96Δρmin = 0.73 e Å3
8737 reflectionsAbsolute structure: Flack (1983), 3686 Friedel pairs
479 parametersAbsolute structure parameter: 0.007 (8)
7 restraints
Special details top

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 (Å2) top
xyzUiso*/Ueq
Ni1A0.91124 (4)0.76904 (3)0.22387 (4)0.02018 (13)
Ni1B0.94953 (4)0.60931 (3)0.27176 (4)0.02102 (13)
Br0.94521 (4)0.74287 (4)0.73692 (4)0.04501 (16)
Br1A1.18571 (4)1.09747 (3)0.11852 (4)0.04143 (15)
Br1B1.35626 (4)0.37081 (3)0.29322 (5)0.04296 (16)
O10.9917 (2)0.71201 (17)0.3177 (2)0.0215 (7)
O1A1.0148 (2)0.80326 (17)0.1449 (2)0.0242 (7)
O1B1.0661 (2)0.58968 (18)0.2059 (2)0.0270 (8)
O11A0.9104 (2)0.67067 (18)0.1578 (2)0.0223 (7)
O2AA0.8697 (3)0.5877 (2)0.0550 (3)0.0340 (9)
O1W0.8185 (2)0.8101 (2)0.1226 (3)0.0331 (8)
H1W10.7642 (13)0.808 (3)0.119 (4)0.050*
H1W20.835 (3)0.844 (2)0.089 (4)0.050*
O2W1.1295 (2)0.69264 (18)0.0972 (2)0.0261 (8)
H2W11.106 (3)0.6574 (16)0.119 (4)0.039*
H2W21.096 (3)0.7270 (17)0.113 (4)0.039*
O1M0.8879 (2)0.51575 (18)0.2106 (3)0.0320 (9)
H1M0.88060.53610.15850.038*
O2M1.1750 (3)0.6277 (2)0.0678 (3)0.0433 (10)
H2M1.15570.64740.01850.052*
O3M0.8398 (3)0.9221 (3)0.0041 (3)0.0471 (11)
H3M0.79810.89720.02780.057*
N10.7953 (2)0.7411 (2)0.3129 (3)0.0208 (9)
N20.8242 (3)0.6225 (2)0.3479 (3)0.0212 (9)
N1A0.9061 (2)0.8629 (2)0.2906 (3)0.0227 (9)
N1B0.9873 (3)0.5495 (2)0.3811 (3)0.0237 (9)
C10.9803 (3)0.7248 (3)0.4090 (3)0.0230 (11)
C21.0506 (3)0.7471 (3)0.4670 (4)0.0336 (13)
H2A1.10750.75820.43920.040*
C31.0418 (4)0.7540 (3)0.5630 (4)0.0380 (14)
H3A1.09200.76890.60010.046*
C40.9591 (4)0.7391 (3)0.6046 (4)0.0309 (12)
C50.8851 (3)0.7210 (3)0.5493 (3)0.0255 (11)
H5A0.82750.71320.57750.031*
C60.8950 (3)0.7144 (3)0.4532 (3)0.0219 (11)
C70.8156 (3)0.6939 (3)0.3951 (3)0.0233 (11)
H7A0.76080.69270.43640.028*
C80.7254 (3)0.6988 (3)0.2607 (3)0.0239 (11)
H8A0.73360.70400.19210.029*
H8B0.66350.71490.27770.029*
C90.7410 (3)0.6207 (3)0.2912 (4)0.0267 (11)
H9A0.68920.60290.32880.032*
H9B0.74890.58910.23590.032*
C1A0.7612 (4)0.8134 (3)0.3400 (4)0.0293 (12)
H1AA0.72030.80850.39470.035*
H1AB0.72530.83370.28740.035*
C2A0.8367 (4)0.8651 (3)0.3643 (4)0.0286 (12)
H2AA0.81230.91460.37000.034*
H2AB0.86400.85150.42530.034*
C3A0.9487 (3)0.9210 (2)0.2692 (4)0.0243 (10)
H3AA0.93350.96340.30310.029*
C4A1.0182 (3)0.9272 (3)0.1972 (3)0.0235 (11)
C5A1.0590 (3)0.9946 (3)0.1885 (3)0.0276 (12)
H5AA1.03961.03310.22750.033*
C6A1.1270 (3)1.0062 (3)0.1243 (4)0.0311 (12)
C7A1.1550 (4)0.9513 (3)0.0658 (4)0.0302 (12)
H7AA1.20140.95970.02080.036*
C8A1.1158 (3)0.8849 (3)0.0731 (4)0.0259 (11)
H8AA1.13480.84780.03150.031*
C9A1.0476 (3)0.8692 (3)0.1405 (3)0.0211 (10)
C1B0.8263 (3)0.5603 (3)0.4150 (3)0.0266 (12)
H1BA0.80700.51610.38160.032*
H1BB0.78230.56930.46610.032*
C2B0.9192 (3)0.5476 (3)0.4575 (3)0.0268 (12)
H2BA0.93280.58550.50440.032*
H2BB0.92080.50030.48940.032*
C3B1.0569 (3)0.5090 (3)0.3867 (4)0.0258 (11)
H3BA1.06400.48100.44210.031*
C4B1.1270 (3)0.5023 (3)0.3140 (3)0.0220 (10)
C5B1.1949 (3)0.4516 (3)0.3329 (4)0.0284 (12)
H5BA1.19350.42480.38970.034*
C6B1.2640 (3)0.4404 (2)0.2688 (4)0.0255 (11)
C7B1.2655 (3)0.4783 (3)0.1860 (4)0.0267 (11)
H7BA1.31280.47010.14200.032*
C8B1.1996 (3)0.5278 (3)0.1668 (4)0.0254 (11)
H8BA1.20230.55380.10950.030*
C9B1.1275 (3)0.5415 (2)0.2293 (4)0.0221 (10)
C1AA0.8968 (3)0.6495 (3)0.0734 (4)0.0246 (11)
C2AA0.9144 (4)0.7004 (3)0.0069 (4)0.0354 (14)
H2AC0.95380.67690.05310.053*
H2AD0.94410.74400.01680.053*
H2AE0.85670.71340.03660.053*
C1M0.9324 (4)0.4483 (3)0.1970 (5)0.0475 (17)
H1MA0.89510.41750.15650.071*
H1MB0.94110.42460.25780.071*
H1MC0.99150.45640.16730.071*
C2M1.1886 (5)0.6806 (4)0.1371 (5)0.067 (2)
H2MA1.21290.65790.19390.101*
H2MB1.23170.71670.11410.101*
H2MC1.13060.70390.15170.101*
C3M0.9083 (6)0.9318 (7)0.0695 (6)0.119 (5)
H3M10.93580.88510.08440.178*
H3M20.95460.96400.04360.178*
H3M30.88290.95310.12670.178*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni1A0.0220 (3)0.0193 (3)0.0192 (3)0.0021 (2)0.0017 (3)0.0004 (3)
Ni1B0.0247 (3)0.0203 (3)0.0181 (3)0.0015 (2)0.0013 (3)0.0023 (3)
Br0.0482 (3)0.0678 (4)0.0190 (3)0.0032 (3)0.0009 (3)0.0048 (3)
Br1A0.0510 (4)0.0299 (3)0.0434 (3)0.0129 (3)0.0024 (3)0.0073 (3)
Br1B0.0395 (3)0.0385 (3)0.0509 (4)0.0175 (2)0.0036 (3)0.0121 (3)
O10.0211 (17)0.0257 (18)0.0178 (17)0.0023 (13)0.0012 (13)0.0022 (14)
O1A0.0263 (18)0.0211 (19)0.0253 (19)0.0010 (14)0.0037 (14)0.0027 (15)
O1B0.0300 (19)0.0273 (19)0.0239 (19)0.0065 (14)0.0047 (14)0.0101 (15)
O11A0.0271 (18)0.0228 (19)0.0169 (17)0.0012 (14)0.0042 (14)0.0006 (14)
O2AA0.046 (2)0.031 (2)0.025 (2)0.0039 (17)0.0010 (17)0.0087 (17)
O1W0.0222 (17)0.036 (2)0.041 (2)0.0025 (17)0.0027 (17)0.016 (2)
O2W0.0271 (19)0.0209 (19)0.030 (2)0.0018 (15)0.0038 (15)0.0039 (16)
O1M0.038 (2)0.026 (2)0.032 (2)0.0018 (16)0.0003 (17)0.0011 (17)
O2M0.065 (3)0.034 (2)0.032 (2)0.007 (2)0.003 (2)0.0002 (19)
O3M0.043 (3)0.057 (3)0.042 (3)0.008 (2)0.0026 (19)0.019 (2)
N10.0168 (19)0.025 (2)0.021 (2)0.0044 (16)0.0005 (15)0.0000 (18)
N20.026 (2)0.020 (2)0.018 (2)0.0001 (17)0.0020 (16)0.0008 (17)
N1A0.0210 (19)0.020 (2)0.027 (2)0.0050 (16)0.0055 (19)0.0004 (18)
N1B0.030 (2)0.026 (2)0.015 (2)0.0004 (18)0.0009 (17)0.0049 (18)
C10.025 (3)0.023 (3)0.020 (2)0.007 (2)0.000 (2)0.005 (2)
C20.023 (3)0.050 (4)0.028 (3)0.002 (3)0.001 (2)0.010 (3)
C30.031 (3)0.056 (4)0.027 (3)0.003 (3)0.008 (2)0.011 (3)
C40.035 (3)0.036 (3)0.021 (3)0.008 (2)0.001 (2)0.001 (2)
C50.025 (3)0.030 (3)0.021 (3)0.001 (2)0.003 (2)0.000 (2)
C60.024 (3)0.022 (3)0.019 (2)0.005 (2)0.002 (2)0.000 (2)
C70.023 (3)0.025 (3)0.023 (3)0.001 (2)0.004 (2)0.000 (2)
C80.023 (2)0.026 (3)0.023 (3)0.0025 (19)0.0003 (19)0.001 (2)
C90.024 (2)0.029 (3)0.027 (3)0.006 (2)0.001 (2)0.003 (2)
C1A0.032 (3)0.030 (3)0.026 (3)0.003 (2)0.003 (2)0.001 (2)
C2A0.036 (3)0.023 (3)0.027 (3)0.006 (2)0.014 (2)0.002 (2)
C3A0.029 (2)0.017 (2)0.027 (3)0.002 (2)0.001 (2)0.006 (2)
C4A0.026 (2)0.021 (3)0.024 (3)0.001 (2)0.002 (2)0.005 (2)
C5A0.029 (3)0.029 (3)0.025 (3)0.002 (2)0.002 (2)0.001 (2)
C6A0.031 (3)0.029 (3)0.034 (3)0.003 (2)0.004 (2)0.007 (3)
C7A0.032 (3)0.031 (3)0.028 (3)0.002 (2)0.004 (2)0.010 (2)
C8A0.029 (3)0.025 (3)0.025 (3)0.004 (2)0.002 (2)0.005 (2)
C9A0.021 (2)0.022 (3)0.021 (2)0.0049 (19)0.0039 (19)0.003 (2)
C1B0.030 (3)0.028 (3)0.021 (3)0.002 (2)0.009 (2)0.008 (2)
C2B0.031 (3)0.027 (3)0.022 (3)0.003 (2)0.010 (2)0.008 (2)
C3B0.029 (3)0.024 (3)0.024 (3)0.002 (2)0.003 (2)0.009 (2)
C4B0.022 (2)0.022 (3)0.021 (3)0.0018 (19)0.0024 (19)0.007 (2)
C5B0.032 (3)0.021 (3)0.032 (3)0.001 (2)0.002 (2)0.005 (2)
C6B0.027 (3)0.019 (2)0.031 (3)0.0052 (19)0.001 (2)0.004 (2)
C7B0.027 (3)0.024 (3)0.029 (3)0.006 (2)0.007 (2)0.004 (2)
C8B0.029 (3)0.023 (3)0.024 (3)0.002 (2)0.003 (2)0.004 (2)
C9B0.028 (2)0.018 (2)0.021 (2)0.0002 (19)0.000 (2)0.000 (2)
C1AA0.023 (3)0.028 (3)0.022 (3)0.004 (2)0.000 (2)0.001 (2)
C2AA0.040 (3)0.043 (4)0.023 (3)0.005 (3)0.005 (2)0.006 (3)
C1M0.049 (4)0.029 (3)0.064 (5)0.001 (3)0.007 (3)0.009 (3)
C2M0.082 (6)0.065 (5)0.055 (5)0.010 (4)0.001 (4)0.014 (4)
C3M0.048 (5)0.231 (13)0.077 (7)0.013 (7)0.019 (4)0.088 (8)
Geometric parameters (Å, º) top
Ni1A—N1A1.986 (4)C7—H7A1.0000
Ni1A—O1A2.000 (3)C8—C91.529 (7)
Ni1A—O11A2.053 (3)C8—H8A0.9900
Ni1A—O12.077 (3)C8—H8B0.9900
Ni1A—O1W2.129 (3)C9—H9A0.9900
Ni1A—N12.190 (4)C9—H9B0.9900
Ni1A—Ni1B3.0927 (9)C1A—C2A1.510 (7)
Ni1B—O1B1.991 (3)C1A—H1AA0.9900
Ni1B—N1B1.992 (4)C1A—H1AB0.9900
Ni1B—O11A2.065 (3)C2A—H2AA0.9900
Ni1B—O12.109 (3)C2A—H2AB0.9900
Ni1B—O1M2.144 (3)C3A—C4A1.455 (7)
Ni1B—N22.157 (4)C3A—H3AA0.9500
Br—C41.898 (5)C4A—C5A1.392 (7)
Br1A—C6A1.904 (5)C4A—C9A1.413 (7)
Br1B—C6B1.907 (5)C5A—C6A1.373 (7)
O1—C11.333 (5)C5A—H5AA0.9500
O1A—C9A1.317 (6)C6A—C7A1.378 (8)
O1B—C9B1.315 (5)C7A—C8A1.365 (7)
O11A—C1AA1.282 (6)C7A—H7AA0.9500
O2AA—C1AA1.243 (6)C8A—C9A1.421 (7)
O1W—H1W10.802 (19)C8A—H8AA0.9500
O1W—H1W20.823 (19)C1B—C2B1.515 (7)
O2W—H2W10.803 (19)C1B—H1BA0.9900
O2W—H2W20.832 (19)C1B—H1BB0.9900
O1M—C1M1.426 (6)C2B—H2BA0.9900
O1M—H1M0.8400C2B—H2BB0.9900
O2M—C2M1.406 (8)C3B—C4B1.469 (7)
O2M—H2M0.8400C3B—H3BA0.9500
O3M—C3M1.385 (8)C4B—C5B1.400 (7)
O3M—H3M0.8400C4B—C9B1.409 (6)
N1—C1A1.485 (6)C5B—C6B1.383 (7)
N1—C71.493 (6)C5B—H5BA0.9500
N1—C81.493 (6)C6B—C7B1.374 (7)
N2—C91.469 (6)C7B—C8B1.365 (7)
N2—C71.490 (6)C7B—H7BA0.9500
N2—C1B1.499 (6)C8B—C9B1.409 (7)
N1A—C3A1.284 (6)C8B—H8BA0.9500
N1A—C2A1.466 (6)C1AA—C2AA1.505 (7)
N1B—C3B1.274 (6)C2AA—H2AC0.9800
N1B—C2B1.481 (6)C2AA—H2AD0.9800
C1—C21.388 (7)C2AA—H2AE0.9800
C1—C61.419 (7)C1M—H1MA0.9800
C2—C31.380 (7)C1M—H1MB0.9800
C2—H2A0.9500C1M—H1MC0.9800
C3—C41.383 (8)C2M—H2MA0.9800
C3—H3A0.9500C2M—H2MB0.9800
C4—C51.387 (7)C2M—H2MC0.9800
C5—C61.383 (7)C3M—H3M10.9800
C5—H5A0.9500C3M—H3M20.9800
C6—C71.484 (7)C3M—H3M30.9800
N1A—Ni1A—O1A91.15 (14)C9—C8—H8A110.8
N1A—Ni1A—O11A177.16 (14)N1—C8—H8B110.8
O1A—Ni1A—O11A91.63 (13)C9—C8—H8B110.8
N1A—Ni1A—O199.20 (15)H8A—C8—H8B108.9
O1A—Ni1A—O195.07 (13)N2—C9—C8105.1 (4)
O11A—Ni1A—O181.13 (13)N2—C9—H9A110.7
N1A—Ni1A—O1W89.21 (16)C8—C9—H9A110.7
O1A—Ni1A—O1W89.69 (14)N2—C9—H9B110.7
O11A—Ni1A—O1W90.22 (14)C8—C9—H9B110.7
O1—Ni1A—O1W170.23 (14)H9A—C9—H9B108.8
N1A—Ni1A—N184.31 (15)N1—C1A—C2A112.6 (4)
O1A—Ni1A—N1175.19 (14)N1—C1A—H1AA109.1
O11A—Ni1A—N192.89 (14)C2A—C1A—H1AA109.1
O1—Ni1A—N187.26 (13)N1—C1A—H1AB109.1
O1W—Ni1A—N188.65 (14)C2A—C1A—H1AB109.1
N1A—Ni1A—Ni1B137.86 (12)H1AA—C1A—H1AB107.8
O1A—Ni1A—Ni1B106.81 (9)N1A—C2A—C1A109.4 (4)
O11A—Ni1A—Ni1B41.47 (9)N1A—C2A—H2AA109.8
O1—Ni1A—Ni1B42.76 (9)C1A—C2A—H2AA109.8
O1W—Ni1A—Ni1B127.59 (11)N1A—C2A—H2AB109.8
N1—Ni1A—Ni1B77.74 (10)C1A—C2A—H2AB109.8
O1B—Ni1B—N1B91.46 (15)H2AA—C2A—H2AB108.2
O1B—Ni1B—O11A88.35 (13)N1A—C3A—C4A125.3 (4)
N1B—Ni1B—O11A179.59 (16)N1A—C3A—H3AA117.3
O1B—Ni1B—O193.27 (14)C4A—C3A—H3AA117.3
N1B—Ni1B—O1100.24 (15)C5A—C4A—C9A120.0 (4)
O11A—Ni1B—O180.13 (13)C5A—C4A—C3A116.0 (4)
O1B—Ni1B—O1M91.50 (14)C9A—C4A—C3A123.9 (4)
N1B—Ni1B—O1M89.16 (16)C6A—C5A—C4A121.0 (5)
O11A—Ni1B—O1M90.49 (13)C6A—C5A—H5AA119.5
O1—Ni1B—O1M169.33 (13)C4A—C5A—H5AA119.5
O1B—Ni1B—N2175.60 (14)C5A—C6A—C7A120.4 (5)
N1B—Ni1B—N284.77 (16)C5A—C6A—Br1A120.0 (4)
O11A—Ni1B—N295.40 (14)C7A—C6A—Br1A119.6 (4)
O1—Ni1B—N289.65 (13)C8A—C7A—C6A119.6 (5)
O1M—Ni1B—N286.18 (14)C8A—C7A—H7AA120.2
O1B—Ni1B—Ni1A103.23 (10)C6A—C7A—H7AA120.2
N1B—Ni1B—Ni1A139.22 (12)C7A—C8A—C9A122.4 (5)
O11A—Ni1B—Ni1A41.19 (9)C7A—C8A—H8AA118.8
O1—Ni1B—Ni1A41.98 (8)C9A—C8A—H8AA118.8
O1M—Ni1B—Ni1A127.49 (10)O1A—C9A—C4A124.6 (4)
N2—Ni1B—Ni1A81.14 (11)O1A—C9A—C8A118.8 (4)
C1—O1—Ni1A117.8 (3)C4A—C9A—C8A116.6 (4)
C1—O1—Ni1B115.3 (3)N2—C1B—C2B113.2 (4)
Ni1A—O1—Ni1B95.26 (13)N2—C1B—H1BA108.9
C9A—O1A—Ni1A127.0 (3)C2B—C1B—H1BA108.9
C9B—O1B—Ni1B126.8 (3)N2—C1B—H1BB108.9
C1AA—O11A—Ni1A134.7 (3)C2B—C1B—H1BB108.9
C1AA—O11A—Ni1B127.8 (3)H1BA—C1B—H1BB107.8
Ni1A—O11A—Ni1B97.34 (13)N1B—C2B—C1B108.3 (4)
Ni1A—O1W—H1W1132 (4)N1B—C2B—H2BA110.0
Ni1A—O1W—H1W2119 (4)C1B—C2B—H2BA110.0
H1W1—O1W—H1W2107 (3)N1B—C2B—H2BB110.0
H2W1—O2W—H2W2105 (3)C1B—C2B—H2BB110.0
C1M—O1M—Ni1B124.8 (3)H2BA—C2B—H2BB108.4
C1M—O1M—H1M109.5N1B—C3B—C4B124.9 (5)
Ni1B—O1M—H1M92.8N1B—C3B—H3BA117.6
C2M—O2M—H2M109.5C4B—C3B—H3BA117.6
C3M—O3M—H3M109.5C5B—C4B—C9B120.5 (4)
C1A—N1—C7113.2 (4)C5B—C4B—C3B115.0 (4)
C1A—N1—C8111.8 (4)C9B—C4B—C3B124.4 (4)
C7—N1—C8102.7 (4)C6B—C5B—C4B120.0 (5)
C1A—N1—Ni1A101.6 (3)C6B—C5B—H5BA120.0
C7—N1—Ni1A115.9 (3)C4B—C5B—H5BA120.0
C8—N1—Ni1A112.0 (3)C7B—C6B—C5B120.1 (4)
C9—N2—C7101.4 (4)C7B—C6B—Br1B119.4 (4)
C9—N2—C1B110.6 (4)C5B—C6B—Br1B120.4 (4)
C7—N2—C1B113.5 (4)C8B—C7B—C6B120.3 (5)
C9—N2—Ni1B115.8 (3)C8B—C7B—H7BA119.8
C7—N2—Ni1B113.6 (3)C6B—C7B—H7BA119.8
C1B—N2—Ni1B102.4 (3)C7B—C8B—C9B122.1 (5)
C3A—N1A—C2A119.2 (4)C7B—C8B—H8BA119.0
C3A—N1A—Ni1A127.1 (3)C9B—C8B—H8BA119.0
C2A—N1A—Ni1A113.2 (3)O1B—C9B—C4B124.3 (4)
C3B—N1B—C2B119.1 (4)O1B—C9B—C8B118.8 (4)
C3B—N1B—Ni1B127.1 (3)C4B—C9B—C8B116.9 (4)
C2B—N1B—Ni1B113.5 (3)O2AA—C1AA—O11A122.1 (5)
O1—C1—C2122.7 (5)O2AA—C1AA—C2AA118.3 (5)
O1—C1—C6121.4 (4)O11A—C1AA—C2AA119.6 (5)
C2—C1—C6115.9 (5)C1AA—C2AA—H2AC109.5
C3—C2—C1123.2 (5)C1AA—C2AA—H2AD109.5
C3—C2—H2A118.4H2AC—C2AA—H2AD109.5
C1—C2—H2A118.4C1AA—C2AA—H2AE109.5
C2—C3—C4119.3 (5)H2AC—C2AA—H2AE109.5
C2—C3—H3A120.4H2AD—C2AA—H2AE109.5
C4—C3—H3A120.4O1M—C1M—H1MA109.5
C3—C4—C5119.9 (5)O1M—C1M—H1MB109.5
C3—C4—Br120.9 (4)H1MA—C1M—H1MB109.5
C5—C4—Br119.2 (4)O1M—C1M—H1MC109.5
C6—C5—C4120.0 (5)H1MA—C1M—H1MC109.5
C6—C5—H5A120.0H1MB—C1M—H1MC109.5
C4—C5—H5A120.0O2M—C2M—H2MA109.5
C5—C6—C1121.4 (5)O2M—C2M—H2MB109.5
C5—C6—C7119.5 (4)H2MA—C2M—H2MB109.5
C1—C6—C7119.1 (4)O2M—C2M—H2MC109.5
C6—C7—N2114.4 (4)H2MA—C2M—H2MC109.5
C6—C7—N1116.5 (4)H2MB—C2M—H2MC109.5
N2—C7—N1100.6 (4)O3M—C3M—H3M1109.5
C6—C7—H7A108.3O3M—C3M—H3M2109.5
N2—C7—H7A108.3H3M1—C3M—H3M2109.5
N1—C7—H7A108.3O3M—C3M—H3M3109.5
N1—C8—C9104.6 (4)H3M1—C3M—H3M3109.5
N1—C8—H8A110.8H3M2—C3M—H3M3109.5
N1A—Ni1A—Ni1B—O1B112.42 (19)O1M—Ni1B—N2—C1B69.5 (3)
O1A—Ni1A—Ni1B—O1B1.01 (14)Ni1A—Ni1B—N2—C1B161.6 (3)
O11A—Ni1A—Ni1B—O1B71.72 (18)O1A—Ni1A—N1A—C3A9.8 (4)
O1—Ni1A—Ni1B—O1B80.01 (16)O1—Ni1A—N1A—C3A105.1 (4)
O1W—Ni1A—Ni1B—O1B102.02 (17)O1W—Ni1A—N1A—C3A79.9 (4)
N1—Ni1A—Ni1B—O1B179.38 (15)N1—Ni1A—N1A—C3A168.6 (4)
N1A—Ni1A—Ni1B—N1B4.2 (2)Ni1B—Ni1A—N1A—C3A126.8 (4)
O1A—Ni1A—Ni1B—N1B107.2 (2)O1A—Ni1A—N1A—C2A178.3 (3)
O11A—Ni1A—Ni1B—N1B179.9 (2)O1—Ni1A—N1A—C2A82.9 (3)
O1—Ni1A—Ni1B—N1B28.2 (2)O1W—Ni1A—N1A—C2A92.1 (3)
O1W—Ni1A—Ni1B—N1B149.8 (2)N1—Ni1A—N1A—C2A3.3 (3)
N1—Ni1A—Ni1B—N1B71.2 (2)Ni1B—Ni1A—N1A—C2A61.3 (4)
N1A—Ni1A—Ni1B—O11A175.9 (2)O1B—Ni1B—N1B—C3B8.8 (5)
O1A—Ni1A—Ni1B—O11A72.73 (17)O1—Ni1B—N1B—C3B102.4 (4)
O1—Ni1A—Ni1B—O11A151.73 (19)O1M—Ni1B—N1B—C3B82.7 (5)
O1W—Ni1A—Ni1B—O11A30.3 (2)N2—Ni1B—N1B—C3B168.9 (5)
N1—Ni1A—Ni1B—O11A108.89 (18)Ni1A—Ni1B—N1B—C3B121.1 (4)
N1A—Ni1A—Ni1B—O132.4 (2)O1B—Ni1B—N1B—C2B178.6 (3)
O1A—Ni1A—Ni1B—O179.00 (16)O1—Ni1B—N1B—C2B85.0 (3)
O11A—Ni1A—Ni1B—O1151.73 (19)O1M—Ni1B—N1B—C2B89.9 (3)
O1W—Ni1A—Ni1B—O1177.97 (19)N2—Ni1B—N1B—C2B3.7 (3)
N1—Ni1A—Ni1B—O199.37 (16)Ni1A—Ni1B—N1B—C2B66.3 (4)
N1A—Ni1A—Ni1B—O1M145.2 (2)Ni1A—O1—C1—C2123.0 (5)
O1A—Ni1A—Ni1B—O1M103.37 (16)Ni1B—O1—C1—C2125.7 (5)
O11A—Ni1A—Ni1B—O1M30.64 (18)Ni1A—O1—C1—C658.6 (5)
O1—Ni1A—Ni1B—O1M177.62 (18)Ni1B—O1—C1—C652.7 (5)
O1W—Ni1A—Ni1B—O1M0.34 (18)O1—C1—C2—C3173.7 (5)
N1—Ni1A—Ni1B—O1M78.25 (16)C6—C1—C2—C34.7 (8)
N1A—Ni1A—Ni1B—N267.03 (19)C1—C2—C3—C40.9 (9)
O1A—Ni1A—Ni1B—N2178.43 (15)C2—C3—C4—C53.3 (9)
O11A—Ni1A—Ni1B—N2108.83 (18)C2—C3—C4—Br176.7 (5)
O1—Ni1A—Ni1B—N299.43 (16)C3—C4—C5—C63.2 (8)
O1W—Ni1A—Ni1B—N278.53 (17)Br—C4—C5—C6176.7 (4)
N1—Ni1A—Ni1B—N20.06 (15)C4—C5—C6—C10.9 (8)
N1A—Ni1A—O1—C136.4 (3)C4—C5—C6—C7179.0 (5)
O1A—Ni1A—O1—C1128.4 (3)O1—C1—C6—C5173.8 (5)
O11A—Ni1A—O1—C1140.7 (3)C2—C1—C6—C54.7 (7)
N1—Ni1A—O1—C147.3 (3)O1—C1—C6—C74.4 (7)
Ni1B—Ni1A—O1—C1122.2 (4)C2—C1—C6—C7177.1 (5)
N1A—Ni1A—O1—Ni1B158.64 (13)C5—C6—C7—N2114.7 (5)
O1A—Ni1A—O1—Ni1B109.37 (13)C1—C6—C7—N263.5 (6)
O11A—Ni1A—O1—Ni1B18.51 (12)C5—C6—C7—N1128.4 (5)
N1—Ni1A—O1—Ni1B74.85 (14)C1—C6—C7—N153.3 (6)
O1B—Ni1B—O1—C1129.7 (3)C9—N2—C7—C6175.4 (4)
N1B—Ni1B—O1—C137.6 (3)C1B—N2—C7—C666.0 (5)
O11A—Ni1B—O1—C1142.6 (3)Ni1B—N2—C7—C650.5 (5)
O1M—Ni1B—O1—C1113.9 (7)C9—N2—C7—N149.7 (4)
N2—Ni1B—O1—C147.0 (3)C1B—N2—C7—N1168.4 (4)
Ni1A—Ni1B—O1—C1124.1 (3)Ni1B—N2—C7—N175.2 (3)
O1B—Ni1B—O1—Ni1A106.20 (13)C1A—N1—C7—C669.7 (5)
N1B—Ni1B—O1—Ni1A161.72 (14)C8—N1—C7—C6169.6 (4)
O11A—Ni1B—O1—Ni1A18.45 (12)Ni1A—N1—C7—C647.1 (5)
O1M—Ni1B—O1—Ni1A10.2 (8)C1A—N1—C7—N2166.1 (4)
N2—Ni1B—O1—Ni1A77.09 (14)C8—N1—C7—N245.4 (4)
N1A—Ni1A—O1A—C9A8.3 (4)Ni1A—N1—C7—N277.1 (4)
O11A—Ni1A—O1A—C9A171.1 (4)C1A—N1—C8—C9145.4 (4)
O1—Ni1A—O1A—C9A107.6 (4)C7—N1—C8—C923.7 (4)
O1W—Ni1A—O1A—C9A80.9 (4)Ni1A—N1—C8—C9101.4 (4)
Ni1B—Ni1A—O1A—C9A149.6 (3)C7—N2—C9—C834.7 (5)
N1B—Ni1B—O1B—C9B11.5 (4)C1B—N2—C9—C8155.4 (4)
O11A—Ni1B—O1B—C9B168.1 (4)Ni1B—N2—C9—C888.7 (4)
O1—Ni1B—O1B—C9B111.9 (4)N1—C8—C9—N26.9 (5)
O1M—Ni1B—O1B—C9B77.7 (4)C7—N1—C1A—C2A82.8 (5)
Ni1A—Ni1B—O1B—C9B153.2 (4)C8—N1—C1A—C2A161.8 (4)
O1A—Ni1A—O11A—C1AA62.1 (4)Ni1A—N1—C1A—C2A42.2 (4)
O1—Ni1A—O11A—C1AA157.0 (4)C3A—N1A—C2A—C1A145.2 (5)
O1W—Ni1A—O11A—C1AA27.6 (4)Ni1A—N1A—C2A—C1A27.4 (5)
N1—Ni1A—O11A—C1AA116.2 (4)N1—C1A—C2A—N1A48.7 (6)
Ni1B—Ni1A—O11A—C1AA176.0 (5)C2A—N1A—C3A—C4A179.3 (5)
O1A—Ni1A—O11A—Ni1B113.87 (14)Ni1A—N1A—C3A—C4A7.8 (7)
O1—Ni1A—O11A—Ni1B18.99 (13)N1A—C3A—C4A—C5A176.9 (5)
O1W—Ni1A—O11A—Ni1B156.43 (15)N1A—C3A—C4A—C9A0.5 (8)
N1—Ni1A—O11A—Ni1B67.78 (15)C9A—C4A—C5A—C6A1.0 (7)
O1B—Ni1B—O11A—C1AA64.0 (4)C3A—C4A—C5A—C6A178.5 (5)
O1—Ni1B—O11A—C1AA157.6 (4)C4A—C5A—C6A—C7A1.1 (8)
O1M—Ni1B—O11A—C1AA27.4 (4)C4A—C5A—C6A—Br1A176.8 (4)
N2—Ni1B—O11A—C1AA113.7 (4)C5A—C6A—C7A—C8A1.0 (8)
Ni1A—Ni1B—O11A—C1AA176.4 (5)Br1A—C6A—C7A—C8A176.9 (4)
O1B—Ni1B—O11A—Ni1A112.37 (15)C6A—C7A—C8A—C9A1.3 (8)
O1—Ni1B—O11A—Ni1A18.76 (13)Ni1A—O1A—C9A—C4A4.7 (7)
O1M—Ni1B—O11A—Ni1A156.15 (14)Ni1A—O1A—C9A—C8A173.8 (3)
N2—Ni1B—O11A—Ni1A69.94 (15)C5A—C4A—C9A—O1A178.4 (4)
O1B—Ni1B—O1M—C1M39.2 (4)C3A—C4A—C9A—O1A1.1 (8)
N1B—Ni1B—O1M—C1M52.3 (4)C5A—C4A—C9A—C8A3.1 (7)
O11A—Ni1B—O1M—C1M127.5 (4)C3A—C4A—C9A—C8A179.6 (5)
O1—Ni1B—O1M—C1M155.8 (6)C7A—C8A—C9A—O1A178.1 (5)
N2—Ni1B—O1M—C1M137.1 (4)C7A—C8A—C9A—C4A3.3 (7)
Ni1A—Ni1B—O1M—C1M147.2 (4)C9—N2—C1B—C2B165.2 (4)
N1A—Ni1A—N1—C1A20.9 (3)C7—N2—C1B—C2B81.6 (5)
O11A—Ni1A—N1—C1A158.6 (3)Ni1B—N2—C1B—C2B41.2 (4)
O1—Ni1A—N1—C1A120.5 (3)C3B—N1B—C2B—C1B146.4 (5)
O1W—Ni1A—N1—C1A68.4 (3)Ni1B—N1B—C2B—C1B26.8 (5)
Ni1B—Ni1A—N1—C1A162.6 (3)N2—C1B—C2B—N1B46.9 (6)
N1A—Ni1A—N1—C7102.2 (3)C2B—N1B—C3B—C4B176.4 (5)
O11A—Ni1A—N1—C778.3 (3)Ni1B—N1B—C3B—C4B4.2 (8)
O1—Ni1A—N1—C72.7 (3)N1B—C3B—C4B—C5B176.6 (5)
O1W—Ni1A—N1—C7168.4 (3)N1B—C3B—C4B—C9B1.8 (8)
Ni1B—Ni1A—N1—C739.4 (3)C9B—C4B—C5B—C6B1.1 (7)
N1A—Ni1A—N1—C8140.3 (3)C3B—C4B—C5B—C6B179.5 (5)
O11A—Ni1A—N1—C839.2 (3)C4B—C5B—C6B—C7B0.9 (8)
O1—Ni1A—N1—C8120.1 (3)C4B—C5B—C6B—Br1B179.4 (4)
O1W—Ni1A—N1—C851.0 (3)C5B—C6B—C7B—C8B0.7 (8)
Ni1B—Ni1A—N1—C878.0 (3)Br1B—C6B—C7B—C8B179.3 (4)
N1B—Ni1B—N2—C9140.4 (3)C6B—C7B—C8B—C9B0.7 (8)
O11A—Ni1B—N2—C939.2 (3)Ni1B—O1B—C9B—C4B9.8 (7)
O1—Ni1B—N2—C9119.3 (3)Ni1B—O1B—C9B—C8B170.7 (3)
O1M—Ni1B—N2—C950.9 (3)C5B—C4B—C9B—O1B179.5 (5)
Ni1A—Ni1B—N2—C978.0 (3)C3B—C4B—C9B—O1B1.2 (7)
N1B—Ni1B—N2—C7102.8 (3)C5B—C4B—C9B—C8B1.0 (7)
O11A—Ni1B—N2—C777.5 (3)C3B—C4B—C9B—C8B179.3 (5)
O1—Ni1B—N2—C72.5 (3)C7B—C8B—C9B—O1B179.6 (5)
O1M—Ni1B—N2—C7167.7 (3)C7B—C8B—C9B—C4B0.8 (7)
Ni1A—Ni1B—N2—C738.8 (3)Ni1A—O11A—C1AA—O2AA154.8 (4)
N1B—Ni1B—N2—C1B20.0 (3)Ni1B—O11A—C1AA—O2AA30.2 (7)
O11A—Ni1B—N2—C1B159.6 (3)Ni1A—O11A—C1AA—C2AA25.4 (7)
O1—Ni1B—N2—C1B120.3 (3)Ni1B—O11A—C1AA—C2AA149.6 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W1···O2Wi0.80 (2)2.01 (2)2.810 (5)174 (5)
O1W—H1W2···O3M0.82 (2)1.97 (3)2.770 (5)164 (5)
O2W—H2W1···O1B0.80 (2)1.86 (3)2.631 (5)160 (6)
O2W—H2W2···O1A0.83 (2)1.91 (2)2.744 (5)177 (6)
O1M—H1M···O2AA0.841.772.602 (5)174
O2M—H2M···O2W0.841.892.725 (5)172
O3M—H3M···O2Mi0.841.962.753 (6)158
Symmetry code: (i) x1/2, y+3/2, z.

Experimental details

Crystal data
Chemical formula[Ni2(C27H24Br3N4O3)(C2H3O2)(CH4O)(H2O)]·2CH4O·H2O
Mr1000.85
Crystal system, space groupOrthorhombic, Pna21
Temperature (K)168
a, b, c (Å)14.7385 (16), 18.552 (2), 14.2504 (15)
V3)3896.4 (7)
Z4
Radiation typeMo Kα
µ (mm1)4.10
Crystal size (mm)0.49 × 0.12 × 0.06
Data collection
DiffractometerBruker SMART 1000 CCD
Absorption correctionMulti-scan
(SADABS; Bruker, 2000)
Tmin, Tmax0.676, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
25239, 8737, 6627
Rint0.054
(sin θ/λ)max1)0.668
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.092, 0.96
No. of reflections8737
No. of parameters479
No. of restraints7
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.71, 0.73
Absolute structureFlack (1983), 3686 Friedel pairs
Absolute structure parameter0.007 (8)

Computer programs: SMART (Bruker, 2000), SAINT-Plus (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W1···O2Wi0.802 (19)2.01 (2)2.810 (5)174 (5)
O1W—H1W2···O3M0.823 (19)1.97 (3)2.770 (5)164 (5)
O2W—H2W1···O1B0.803 (19)1.86 (3)2.631 (5)160 (6)
O2W—H2W2···O1A0.832 (19)1.91 (2)2.744 (5)177 (6)
O1M—H1M···O2AA0.841.772.602 (5)173.7
O2M—H2M···O2W0.841.892.725 (5)171.9
O3M—H3M···O2Mi0.841.962.753 (6)157.7
Symmetry code: (i) x1/2, y+3/2, z.
 

Acknowledgements

RJB wishes to acknowledge the NSF–MRI program (grant CHE-0619278) for funds to purchase the diffractometer. ARK and YT wish to acknowledge the Howard University Graduate School of Arts & Sciences for the award of Teaching Assistanceships.

References

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