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Acta Cryst. (2008). E64, m1588    [ doi:10.1107/S1600536808038051 ]

(Benzoato-[kappa]2O,O')(5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane-[kappa]4N,N',N'',N''')nickel(II) perchlorate benzoic acid solvate

G.-C. Ou, M. Zhang, X.-Y. Yuan and Y.-Q. Dai

Abstract top

In the title compound, [Ni(C7H5O2)(C16H36N4)]ClO4·C7H6O2, the Ni atom displays a distorted octahedral coordination geometry with four N atoms of the ligand rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane (L) in a folded configuration and two benzoate (bz) O atoms. The [Ni(rac-L)(bz)]+ complex cation, perchlorate anion and benzoic acid molecules engage in hydrogen bonding, with N...O distances between 2.970 (3) and 3.123 (3) Å and an O...O distance of 2.691 (3) Å.

Comment top

It is important to control the geometries of ML2+ [M = Ni(II), Co(II), Cu(II)] with cis- or trans-conformation, since they form different structures and show different properties (Tait & Busch, 1976; Curtis, 1965). Continuing our research (Ou et al., 2008), we have synthesized the title compound, (I), which is presented in this paper.

The asymmetric unit of the title compouind, (I), contains one [Ni(rac-L)(bz)]+ cation, one [ClO4]- anion and one benzoic acid molecule (Fig. 1). The six-coordinated Ni2+ of the complex [Ni(rac-L)(bz)]+ cation displays a distorted octahedral geometry by coordination with four nitrogen atoms of the macrocyclic ligand L in a folded configuration, and two carboxylate oxygen atoms of benzoic acid in cis-position. The Ni—N distances range between 2.082 (2) to 2.134 (2) Å, and are slightly shorter than the Ni—O distance (2.116 (2) and 2.212 (2) Å). The neighbouring cations, anions and benzoic acid are connected to each other through intermolecular hydrogen bond of the types N—H···O and O—H···O (Table 1, Fig. 2). The crystal structures of a few compound closely related to (I) have been reported (Ou et al., 2008a,b; Basiuk et al. 2001; Jiang et al., 2005).

Related literature top

For related background, see: Tait & Busch (1976); Curtis (1965). For related structures, see: Ou et al. (2008); Basiuk et al. (2001); Jiang et al. (2005).

Experimental top

Benzoic acid (0.36 g, 3 mmol) and NaOH (0.08 g, 2 mmol) were dissolved in 15 ml of water. To this solution was added [Ni(rac-L)](ClO4)2 (0.54 g, 1 mmol) dissolved in 2 ml of CH3CN. The solution was left to stand at room temperature and blue crystals formed after several weeks.

Refinement top

H atoms bound to C, O and N atoms were positioned geometrically and refined using the riding model, and with C—H = 0.93, 0.96, 0.97 and 0.98 Å, for aryl, methyl, methylene and methine H-atoms, O—H = 0.82 Å and N—H = 0.91 Å, and with Uiso(H) set to 1.5Ueq(methyl C) and 1.2Ueq(the rest of the parent atoms).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SMART (Bruker, 1997); data reduction: SAINT (Bruker, 2003; 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 (I), showing displacement ellipsoids at the 30% probability level; H-atoms have been excluded for clarity.
[Figure 2] Fig. 2. A view of the packing of the title compound along a axis.
(Benzoato-κ2O,O')(5,5,7,12,12,14-hexamethyl-1,4,8,11- tetraazacyclotetradecane- κ4N,N',N'',N''')nickel(II) perchlorate benzoic acid solvate top
Crystal data top
[Ni(C7H5O2)(C16H36N4)]ClO4·C7H6O2F(000) = 1456
Mr = 685.88Dx = 1.367 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 8.8035 (11) ÅCell parameters from 7647 reflections
b = 18.138 (2) Åθ = 2.3–26.9°
c = 20.966 (3) ŵ = 0.72 mm−1
β = 95.512 (2)°T = 293 K
V = 3332.4 (7) Å3Prism, light-blue
Z = 40.48 × 0.26 × 0.15 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		7304 independent reflections
Radiation source: fine-focus sealed tube5272 reflections with I > 2σ(I)
graphiteRint = 0.037
φ and ω scansθmax = 27.1°, θmin = 1.5°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −10→11
Tmin = 0.725, Tmax = 0.900k = −20→23
22312 measured reflectionsl = −26→26
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.126H-atom parameters constrained
S = 1.11 w = 1/[σ2(Fo2) + (0.0643P)2 + 0.7856P]
where P = (Fo2 + 2Fc2)/3
7304 reflections(Δ/σ)max = 0.001
404 parametersΔρmax = 0.58 e Å−3
0 restraintsΔρmin = −0.42 e Å−3
Crystal data top
[Ni(C7H5O2)(C16H36N4)]ClO4·C7H6O2V = 3332.4 (7) Å3
Mr = 685.88Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.8035 (11) ŵ = 0.72 mm−1
b = 18.138 (2) ÅT = 293 K
c = 20.966 (3) Å0.48 × 0.26 × 0.15 mm
β = 95.512 (2)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		7304 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		5272 reflections with I > 2σ(I)
Tmin = 0.725, Tmax = 0.900Rint = 0.037
22312 measured reflectionsθmax = 27.1°
Refinement top
R[F2 > 2σ(F2)] = 0.042H-atom parameters constrained
wR(F2) = 0.126Δρmax = 0.58 e Å−3
S = 1.11Δρmin = −0.42 e Å−3
7304 reflectionsAbsolute structure: ?
404 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
Ni10.64844 (4)0.771339 (17)0.564296 (14)0.01920 (11)
Cl10.08075 (7)0.70176 (4)0.44238 (3)0.02611 (16)
N30.5075 (2)0.77519 (11)0.47565 (9)0.0208 (5)
H3C0.40980.77160.48610.025*
N10.8063 (2)0.76085 (12)0.64759 (9)0.0219 (5)
H1C0.78380.79830.67400.026*
O10.5623 (2)0.87209 (10)0.60812 (8)0.0226 (4)
O20.4528 (2)0.76422 (10)0.61520 (8)0.0253 (4)
N40.6736 (2)0.65959 (12)0.54328 (10)0.0220 (5)
H4D0.76380.65400.52600.026*
O6−0.0503 (3)0.67518 (13)0.47084 (12)0.0527 (6)
O50.1734 (3)0.64124 (12)0.42671 (10)0.0428 (6)
N20.8262 (2)0.82271 (12)0.52275 (10)0.0233 (5)
H2C0.87280.78760.50050.028*
O80.1626 (3)0.74917 (15)0.48804 (11)0.0530 (6)
C60.5101 (3)0.84150 (15)0.43238 (12)0.0258 (6)
C140.8130 (3)0.69224 (14)0.68843 (12)0.0244 (6)
C90.5394 (3)0.70458 (14)0.44370 (12)0.0257 (6)
H9A0.63510.70810.42450.031*
H9B0.45890.69430.41000.031*
C180.3568 (3)0.86310 (14)0.67420 (11)0.0229 (6)
C170.4615 (3)0.83124 (14)0.62995 (11)0.0217 (5)
O70.0320 (4)0.74181 (15)0.38604 (11)0.0672 (8)
C70.4224 (3)0.82719 (17)0.36663 (12)0.0326 (7)
H7A0.47330.78940.34470.049*
H7B0.41870.87170.34180.049*
H7C0.32040.81150.37240.049*
C30.7870 (3)0.88481 (15)0.47783 (12)0.0278 (6)
H3A0.73780.92350.50110.033*
C50.6758 (3)0.86021 (15)0.42156 (12)0.0268 (6)
H5A0.71930.81700.40300.032*
H5B0.67270.89890.38950.032*
C230.3032 (4)0.93478 (16)0.66577 (14)0.0359 (7)
H230.33290.96340.63230.043*
C150.6751 (3)0.69292 (16)0.72747 (13)0.0317 (7)
H15A0.67860.73620.75400.048*
H15B0.67700.64970.75400.048*
H15C0.58300.69330.69890.048*
C100.5483 (3)0.64341 (15)0.49227 (12)0.0265 (6)
H10A0.45210.63930.51100.032*
H10B0.56790.59690.47170.032*
C10.9551 (3)0.78073 (16)0.62444 (13)0.0289 (6)
H1A0.99630.73850.60350.035*
H1B1.02690.79440.66050.035*
C20.9351 (3)0.84413 (16)0.57805 (12)0.0286 (6)
H2A0.89650.88680.59920.034*
H2B1.03270.85710.56320.034*
C130.8127 (3)0.62333 (15)0.64645 (12)0.0280 (6)
H13A0.90160.62570.62250.034*
H13B0.82610.58090.67460.034*
C80.4328 (4)0.90494 (16)0.46373 (13)0.0334 (7)
H8A0.32760.89290.46690.050*
H8B0.43900.94860.43830.050*
H8C0.48300.91340.50580.050*
C190.3146 (3)0.82170 (16)0.72532 (12)0.0298 (6)
H190.34950.77350.73110.036*
C40.9287 (4)0.91798 (16)0.45124 (14)0.0373 (7)
H4A1.00070.93290.48610.056*
H4B0.89920.96000.42510.056*
H4C0.97470.88170.42580.056*
C160.9575 (3)0.69124 (16)0.73619 (13)0.0346 (7)
H16A1.04630.68810.71310.052*
H16B0.95430.64930.76400.052*
H16C0.96190.73560.76130.052*
C110.6742 (3)0.60875 (14)0.59886 (12)0.0260 (6)
H110.58260.61890.62050.031*
C120.6712 (4)0.52789 (16)0.58023 (15)0.0436 (8)
H12A0.58210.51810.55130.065*
H12B0.66850.49810.61790.065*
H12C0.76100.51630.55960.065*
C200.2205 (3)0.85191 (18)0.76787 (13)0.0365 (7)
H200.19380.82440.80250.044*
C220.2050 (4)0.96368 (19)0.70754 (15)0.0443 (8)
H220.16511.01080.70080.053*
C210.1668 (4)0.92287 (19)0.75872 (15)0.0423 (8)
H210.10430.94320.78740.051*
O30.3369 (3)0.47611 (10)0.80658 (9)0.0360 (5)
H3B0.37300.44650.83340.054*
O40.2469 (3)0.37507 (12)0.75552 (10)0.0530 (7)
C300.2927 (3)0.55960 (15)0.69518 (13)0.0303 (6)
H300.33930.58190.73190.036*
C290.2669 (3)0.59937 (16)0.63842 (14)0.0342 (7)
H290.29660.64850.63700.041*
C240.2768 (3)0.44005 (16)0.75521 (13)0.0308 (6)
C250.2481 (3)0.48619 (15)0.69640 (12)0.0264 (6)
C260.1793 (3)0.45290 (16)0.64188 (13)0.0320 (7)
H260.15090.40360.64290.038*
C270.1524 (4)0.49276 (18)0.58565 (13)0.0362 (7)
H270.10460.47060.54910.043*
C280.1971 (4)0.56580 (17)0.58414 (14)0.0365 (7)
H280.18010.59250.54630.044*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.02147 (19)0.01929 (18)0.01704 (16)−0.00093 (13)0.00287 (12)−0.00228 (13)
Cl10.0256 (4)0.0316 (4)0.0216 (3)0.0031 (3)0.0049 (3)0.0003 (3)
N30.0188 (11)0.0249 (12)0.0193 (10)−0.0003 (9)0.0048 (8)0.0003 (9)
N10.0241 (12)0.0218 (12)0.0198 (10)0.0002 (9)0.0028 (9)−0.0028 (9)
O10.0251 (10)0.0244 (10)0.0187 (8)−0.0022 (8)0.0044 (7)−0.0002 (7)
O20.0289 (11)0.0240 (10)0.0233 (9)−0.0022 (8)0.0044 (8)−0.0030 (8)
N40.0210 (12)0.0240 (12)0.0214 (10)−0.0026 (9)0.0035 (9)−0.0034 (9)
O60.0437 (14)0.0526 (15)0.0674 (16)−0.0160 (11)0.0336 (12)−0.0186 (12)
O50.0486 (14)0.0445 (13)0.0372 (11)0.0199 (11)0.0146 (10)0.0008 (10)
N20.0251 (12)0.0221 (12)0.0231 (11)−0.0010 (9)0.0038 (9)−0.0029 (9)
O80.0355 (14)0.0714 (17)0.0527 (14)−0.0149 (12)0.0072 (11)−0.0293 (12)
C60.0291 (15)0.0268 (15)0.0212 (12)−0.0008 (11)0.0008 (11)0.0031 (11)
C140.0281 (15)0.0251 (14)0.0199 (12)0.0029 (11)0.0015 (11)0.0002 (11)
C90.0325 (16)0.0257 (14)0.0185 (12)−0.0047 (12)−0.0003 (11)−0.0047 (10)
C180.0221 (14)0.0271 (14)0.0195 (12)−0.0008 (11)0.0013 (10)−0.0017 (10)
C170.0244 (14)0.0240 (14)0.0157 (11)0.0014 (11)−0.0024 (10)0.0012 (10)
O70.107 (2)0.0608 (17)0.0328 (12)0.0366 (16)−0.0002 (14)0.0145 (12)
C70.0348 (17)0.0392 (17)0.0230 (13)−0.0028 (13)−0.0018 (12)0.0060 (12)
C30.0344 (16)0.0204 (14)0.0288 (14)−0.0024 (12)0.0044 (12)−0.0001 (11)
C50.0337 (16)0.0236 (14)0.0234 (13)−0.0027 (12)0.0049 (11)0.0051 (11)
C230.0443 (19)0.0305 (17)0.0345 (15)0.0063 (14)0.0118 (14)−0.0006 (13)
C150.0438 (18)0.0303 (16)0.0222 (13)0.0037 (13)0.0090 (12)0.0011 (12)
C100.0269 (15)0.0271 (15)0.0247 (13)−0.0062 (11)−0.0011 (11)−0.0037 (11)
C10.0210 (14)0.0395 (17)0.0258 (13)−0.0041 (12)0.0006 (11)0.0002 (12)
C20.0248 (15)0.0353 (16)0.0251 (13)−0.0086 (12)0.0001 (11)−0.0050 (12)
C130.0324 (16)0.0252 (15)0.0261 (13)0.0028 (12)0.0016 (11)−0.0012 (11)
C80.0375 (18)0.0328 (16)0.0293 (14)0.0075 (13)0.0000 (12)0.0042 (12)
C190.0336 (17)0.0337 (16)0.0222 (13)−0.0015 (13)0.0037 (12)−0.0006 (12)
C40.0380 (18)0.0305 (17)0.0433 (17)−0.0106 (13)0.0030 (14)0.0065 (14)
C160.0395 (18)0.0364 (17)0.0259 (14)0.0026 (14)−0.0071 (12)−0.0011 (12)
C110.0326 (16)0.0211 (14)0.0246 (13)−0.0028 (11)0.0040 (11)0.0009 (11)
C120.069 (2)0.0228 (16)0.0367 (16)−0.0051 (15)−0.0085 (16)0.0017 (13)
C200.0347 (17)0.050 (2)0.0263 (14)−0.0108 (14)0.0100 (12)−0.0080 (13)
C220.045 (2)0.0380 (19)0.0514 (19)0.0114 (15)0.0147 (16)−0.0105 (15)
C210.0358 (18)0.056 (2)0.0379 (17)−0.0041 (16)0.0158 (14)−0.0217 (15)
O30.0535 (14)0.0279 (11)0.0243 (10)0.0026 (10)−0.0078 (9)0.0011 (8)
O40.093 (2)0.0331 (13)0.0289 (11)−0.0227 (12)−0.0128 (12)0.0130 (9)
C300.0327 (16)0.0280 (15)0.0297 (14)−0.0047 (12)0.0005 (12)0.0028 (12)
C290.0327 (17)0.0253 (15)0.0455 (17)0.0006 (12)0.0085 (13)0.0099 (13)
C240.0365 (17)0.0299 (16)0.0255 (14)−0.0018 (13)0.0010 (12)0.0037 (12)
C250.0286 (16)0.0257 (15)0.0250 (13)−0.0016 (11)0.0028 (11)0.0038 (11)
C260.0370 (18)0.0307 (16)0.0283 (14)−0.0033 (13)0.0032 (12)0.0034 (12)
C270.0414 (19)0.0423 (18)0.0244 (13)−0.0005 (14)0.0005 (12)0.0038 (13)
C280.0374 (18)0.0431 (19)0.0297 (15)0.0064 (14)0.0068 (13)0.0152 (13)
Geometric parameters (Å, °) top
Ni1—N22.082 (2)C15—H15C0.9600
Ni1—N42.091 (2)C10—H10A0.9700
Ni1—O22.116 (2)C10—H10B0.9700
Ni1—N12.133 (2)C1—C21.506 (4)
Ni1—N32.134 (2)C1—H1A0.9700
Ni1—O12.212 (2)C1—H1B0.9700
Cl1—O71.418 (2)C2—H2A0.9700
Cl1—O51.425 (2)C2—H2B0.9700
Cl1—O81.429 (2)C13—C111.523 (4)
Cl1—O61.433 (2)C13—H13A0.9700
N3—C91.484 (3)C13—H13B0.9700
N3—C61.508 (3)C8—H8A0.9600
N3—H3C0.9100C8—H8B0.9600
N1—C11.485 (3)C8—H8C0.9600
N1—C141.508 (3)C19—C201.387 (4)
N1—H1C0.9100C19—H190.9300
O1—C171.274 (3)C4—H4A0.9600
O2—C171.255 (3)C4—H4B0.9600
N4—C111.485 (3)C4—H4C0.9600
N4—C101.490 (3)C16—H16A0.9600
N4—H4D0.9100C16—H16B0.9600
N2—C21.484 (3)C16—H16C0.9600
N2—C31.487 (3)C11—C121.517 (4)
N2—H2C0.9100C11—H110.9800
C6—C81.518 (4)C12—H12A0.9600
C6—C51.536 (4)C12—H12B0.9600
C6—C71.536 (3)C12—H12C0.9600
C14—C131.529 (4)C20—C211.378 (5)
C14—C151.529 (4)C20—H200.9300
C14—C161.541 (4)C22—C211.372 (5)
C9—C101.503 (4)C22—H220.9300
C9—H9A0.9700C21—H210.9300
C9—H9B0.9700O3—C241.326 (3)
C18—C191.388 (4)O3—H3B0.8200
C18—C231.389 (4)O4—C241.208 (3)
C18—C171.486 (4)C30—C251.389 (4)
C7—H7A0.9600C30—C291.392 (4)
C7—H7B0.9600C30—H300.9300
C7—H7C0.9600C29—C281.382 (4)
C3—C51.526 (4)C29—H290.9300
C3—C41.537 (4)C24—C251.492 (4)
C3—H3A0.9800C25—C261.380 (4)
C5—H5A0.9700C26—C271.384 (4)
C5—H5B0.9700C26—H260.9300
C23—C221.391 (4)C27—C281.383 (4)
C23—H230.9300C27—H270.9300
C15—H15A0.9600C28—H280.9300
C15—H15B0.9600
N2—Ni1—N4104.28 (8)C14—C15—H15B109.5
N2—Ni1—O2156.80 (8)H15A—C15—H15B109.5
N4—Ni1—O298.91 (8)C14—C15—H15C109.5
N2—Ni1—N185.74 (8)H15A—C15—H15C109.5
N4—Ni1—N190.70 (8)H15B—C15—H15C109.5
O2—Ni1—N194.56 (8)N4—C10—C9109.1 (2)
N2—Ni1—N391.05 (8)N4—C10—H10A109.9
N4—Ni1—N384.99 (8)C9—C10—H10A109.9
O2—Ni1—N390.46 (8)N4—C10—H10B109.9
N1—Ni1—N3173.84 (8)C9—C10—H10B109.9
N2—Ni1—O196.06 (8)H10A—C10—H10B108.3
N4—Ni1—O1159.39 (8)N1—C1—C2110.1 (2)
O2—Ni1—O160.82 (7)N1—C1—H1A109.6
N1—Ni1—O187.49 (7)C2—C1—H1A109.6
N3—Ni1—O198.09 (7)N1—C1—H1B109.6
O7—Cl1—O5109.69 (14)C2—C1—H1B109.6
O7—Cl1—O8110.04 (18)H1A—C1—H1B108.1
O5—Cl1—O8110.78 (15)N2—C2—C1109.4 (2)
O7—Cl1—O6109.14 (18)N2—C2—H2A109.8
O5—Cl1—O6109.81 (14)C1—C2—H2A109.8
O8—Cl1—O6107.34 (14)N2—C2—H2B109.8
C9—N3—C6113.71 (19)C1—C2—H2B109.8
C9—N3—Ni1104.21 (14)H2A—C2—H2B108.2
C6—N3—Ni1120.59 (15)C11—C13—C14118.4 (2)
C9—N3—H3C105.7C11—C13—H13A107.7
C6—N3—H3C105.7C14—C13—H13A107.7
Ni1—N3—H3C105.7C11—C13—H13B107.7
C1—N1—C14113.5 (2)C14—C13—H13B107.7
C1—N1—Ni1103.69 (15)H13A—C13—H13B107.1
C14—N1—Ni1121.68 (15)C6—C8—H8A109.5
C1—N1—H1C105.6C6—C8—H8B109.5
C14—N1—H1C105.6H8A—C8—H8B109.5
Ni1—N1—H1C105.6C6—C8—H8C109.5
C17—O1—Ni186.98 (15)H8A—C8—H8C109.5
C17—O2—Ni191.82 (16)H8B—C8—H8C109.5
C11—N4—C10112.8 (2)C20—C19—C18120.2 (3)
C11—N4—Ni1115.40 (15)C20—C19—H19119.9
C10—N4—Ni1104.85 (15)C18—C19—H19119.9
C11—N4—H4D107.8C3—C4—H4A109.5
C10—N4—H4D107.8C3—C4—H4B109.5
Ni1—N4—H4D107.8H4A—C4—H4B109.5
C2—N2—C3112.9 (2)C3—C4—H4C109.5
C2—N2—Ni1104.20 (15)H4A—C4—H4C109.5
C3—N2—Ni1117.77 (16)H4B—C4—H4C109.5
C2—N2—H2C107.1C14—C16—H16A109.5
C3—N2—H2C107.1C14—C16—H16B109.5
Ni1—N2—H2C107.1H16A—C16—H16B109.5
N3—C6—C8108.1 (2)C14—C16—H16C109.5
N3—C6—C5109.5 (2)H16A—C16—H16C109.5
C8—C6—C5111.6 (2)H16B—C16—H16C109.5
N3—C6—C7111.7 (2)N4—C11—C12113.5 (2)
C8—C6—C7108.0 (2)N4—C11—C13110.4 (2)
C5—C6—C7107.9 (2)C12—C11—C13109.2 (2)
N1—C14—C13110.5 (2)N4—C11—H11107.8
N1—C14—C15107.9 (2)C12—C11—H11107.8
C13—C14—C15110.9 (2)C13—C11—H11107.8
N1—C14—C16111.3 (2)C11—C12—H12A109.5
C13—C14—C16108.7 (2)C11—C12—H12B109.5
C15—C14—C16107.5 (2)H12A—C12—H12B109.5
N3—C9—C10109.3 (2)C11—C12—H12C109.5
N3—C9—H9A109.8H12A—C12—H12C109.5
C10—C9—H9A109.8H12B—C12—H12C109.5
N3—C9—H9B109.8C21—C20—C19119.8 (3)
C10—C9—H9B109.8C21—C20—H20120.1
H9A—C9—H9B108.3C19—C20—H20120.1
C19—C18—C23119.5 (3)C21—C22—C23120.2 (3)
C19—C18—C17120.0 (2)C21—C22—H22119.9
C23—C18—C17120.5 (2)C23—C22—H22119.9
O2—C17—O1120.2 (2)C22—C21—C20120.4 (3)
O2—C17—C18120.2 (2)C22—C21—H21119.8
O1—C17—C18119.6 (2)C20—C21—H21119.8
C6—C7—H7A109.5C24—O3—H3B109.5
C6—C7—H7B109.5C25—C30—C29119.3 (3)
H7A—C7—H7B109.5C25—C30—H30120.3
C6—C7—H7C109.5C29—C30—H30120.3
H7A—C7—H7C109.5C28—C29—C30119.9 (3)
H7B—C7—H7C109.5C28—C29—H29120.0
N2—C3—C5111.1 (2)C30—C29—H29120.0
N2—C3—C4112.3 (2)O4—C24—O3123.2 (2)
C5—C3—C4108.5 (2)O4—C24—C25122.2 (2)
N2—C3—H3A108.3O3—C24—C25114.7 (2)
C5—C3—H3A108.3C26—C25—C30120.4 (2)
C4—C3—H3A108.3C26—C25—C24117.7 (2)
C3—C5—C6119.9 (2)C30—C25—C24121.8 (2)
C3—C5—H5A107.3C25—C26—C27120.2 (3)
C6—C5—H5A107.3C25—C26—H26119.9
C3—C5—H5B107.3C27—C26—H26119.9
C6—C5—H5B107.3C28—C27—C26119.6 (3)
H5A—C5—H5B106.9C28—C27—H27120.2
C18—C23—C22119.8 (3)C26—C27—H27120.2
C18—C23—H23120.1C29—C28—C27120.5 (3)
C22—C23—H23120.1C29—C28—H28119.7
C14—C15—H15A109.5C27—C28—H28119.7
N2—Ni1—N3—C990.62 (16)Ni1—N1—C14—C15−74.8 (2)
N4—Ni1—N3—C9−13.62 (16)C1—N1—C14—C1642.7 (3)
O2—Ni1—N3—C9−112.53 (16)Ni1—N1—C14—C16167.49 (17)
N1—Ni1—N3—C932.1 (8)C6—N3—C9—C10174.9 (2)
O1—Ni1—N3—C9−173.10 (15)Ni1—N3—C9—C1041.7 (2)
N2—Ni1—N3—C6−38.55 (19)Ni1—O2—C17—O14.4 (2)
N4—Ni1—N3—C6−142.79 (19)Ni1—O2—C17—C18−174.22 (19)
O2—Ni1—N3—C6118.30 (18)Ni1—O1—C17—O2−4.2 (2)
N1—Ni1—N3—C6−97.1 (8)Ni1—O1—C17—C18174.4 (2)
O1—Ni1—N3—C657.73 (19)C19—C18—C17—O236.7 (4)
N2—Ni1—N1—C1−11.37 (16)C23—C18—C17—O2−144.8 (3)
N4—Ni1—N1—C192.90 (16)C19—C18—C17—O1−141.9 (2)
O2—Ni1—N1—C1−168.10 (16)C23—C18—C17—O136.6 (4)
N3—Ni1—N1—C147.4 (8)C2—N2—C3—C5179.6 (2)
O1—Ni1—N1—C1−107.64 (16)Ni1—N2—C3—C5−58.8 (3)
N2—Ni1—N1—C14−140.56 (19)C2—N2—C3—C457.9 (3)
N4—Ni1—N1—C14−36.29 (19)Ni1—N2—C3—C4179.49 (17)
O2—Ni1—N1—C1462.71 (19)N2—C3—C5—C670.1 (3)
N3—Ni1—N1—C14−81.8 (8)C4—C3—C5—C6−166.0 (2)
O1—Ni1—N1—C14123.17 (18)N3—C6—C5—C3−64.4 (3)
N2—Ni1—O1—C17−179.64 (13)C8—C6—C5—C355.3 (3)
N4—Ni1—O1—C17−8.9 (3)C7—C6—C5—C3173.8 (2)
O2—Ni1—O1—C172.45 (13)C19—C18—C23—C22−1.6 (4)
N1—Ni1—O1—C17−94.19 (14)C17—C18—C23—C22179.9 (3)
N3—Ni1—O1—C1788.43 (14)C11—N4—C10—C9170.4 (2)
N2—Ni1—O2—C17−7.8 (3)Ni1—N4—C10—C944.0 (2)
N4—Ni1—O2—C17173.50 (14)N3—C9—C10—N4−60.2 (3)
N1—Ni1—O2—C1782.07 (15)C14—N1—C1—C2173.4 (2)
N3—Ni1—O2—C17−101.50 (14)Ni1—N1—C1—C239.4 (2)
O1—Ni1—O2—C17−2.48 (13)C3—N2—C2—C1173.9 (2)
N2—Ni1—N4—C11129.24 (18)Ni1—N2—C2—C145.0 (2)
O2—Ni1—N4—C11−51.27 (18)N1—C1—C2—N2−59.7 (3)
N1—Ni1—N4—C1143.46 (18)N1—C14—C13—C11−62.5 (3)
N3—Ni1—N4—C11−140.95 (18)C15—C14—C13—C1157.1 (3)
O1—Ni1—N4—C11−41.3 (3)C16—C14—C13—C11175.1 (2)
N2—Ni1—N4—C10−106.03 (16)C23—C18—C19—C20−0.4 (4)
O2—Ni1—N4—C1073.46 (16)C17—C18—C19—C20178.1 (2)
N1—Ni1—N4—C10168.18 (16)C10—N4—C11—C1251.8 (3)
N3—Ni1—N4—C10−16.22 (16)Ni1—N4—C11—C12172.2 (2)
O1—Ni1—N4—C1083.5 (3)C10—N4—C11—C13174.8 (2)
N4—Ni1—N2—C2−107.64 (16)Ni1—N4—C11—C13−64.7 (2)
O2—Ni1—N2—C273.6 (3)C14—C13—C11—N474.4 (3)
N1—Ni1—N2—C2−18.00 (16)C14—C13—C11—C12−160.1 (2)
N3—Ni1—N2—C2167.26 (16)C18—C19—C20—C211.1 (4)
O1—Ni1—N2—C269.01 (16)C18—C23—C22—C213.1 (5)
N4—Ni1—N2—C3126.38 (17)C23—C22—C21—C20−2.5 (5)
O2—Ni1—N2—C3−52.3 (3)C19—C20—C21—C220.4 (5)
N1—Ni1—N2—C3−143.98 (18)C25—C30—C29—C280.2 (4)
N3—Ni1—N2—C341.29 (18)C29—C30—C25—C260.2 (4)
O1—Ni1—N2—C3−56.96 (18)C29—C30—C25—C24178.1 (3)
C9—N3—C6—C8163.9 (2)O4—C24—C25—C262.7 (5)
Ni1—N3—C6—C8−71.2 (2)O3—C24—C25—C26−177.2 (3)
C9—N3—C6—C5−74.3 (3)O4—C24—C25—C30−175.3 (3)
Ni1—N3—C6—C550.6 (3)O3—C24—C25—C304.8 (4)
C9—N3—C6—C745.2 (3)C30—C25—C26—C27−0.8 (4)
Ni1—N3—C6—C7170.07 (17)C24—C25—C26—C27−178.8 (3)
C1—N1—C14—C13−78.2 (3)C25—C26—C27—C281.0 (5)
Ni1—N1—C14—C1346.7 (3)C30—C29—C28—C270.0 (5)
C1—N1—C14—C15160.4 (2)C26—C27—C28—C29−0.6 (5)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1C···O4i0.912.072.970 (3)171
N4—H4D···O6ii0.912.133.001 (3)161
O3—H3B···O1iii0.821.872.691 (3)174
N3—H3C···O80.912.223.108 (3)166
N2—H2C···O6ii0.912.253.123 (3)160
Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) x+1, y, z; (iii) −x+1, y−1/2, −z+3/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1C···O4i0.912.072.970 (3)171
N4—H4D···O6ii0.912.133.001 (3)161
O3—H3B···O1iii0.821.872.691 (3)174
N3—H3C···O80.912.223.108 (3)166
N2—H2C···O6ii0.912.253.123 (3)160
Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) x+1, y, z; (iii) −x+1, y−1/2, −z+3/2.
Acknowledgements top

The authors thank the Key Subject Construction Project of Hunan Province (grant No. 2006-180), the Scientific Research Project of the Hunan Provincial Finance Bureau and Education Department (grant No. 08C366), and the Foundation for University Key Teachers of the Education Department of Hunan Province for supporting this study.

references
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