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Acta Cryst. (2009). E65, m48-m49    [ doi:10.1107/S1600536808041391 ]

Aquabis(2,2'-bipyridine-[kappa]2N,N')(1H-indole-2-carboxylato-[kappa]O)nickel(II) 1H-indole-2-carboxylate dihydrate

B.-S. Zhang, Z.-X. Liu, L.-H. Liu, T. Pan and S.-F. Ye

Abstract top

The hydrothermal reaction of Ni2(OH)2CO3 with 2,2'-bipyridine and 2-indolyl-formic acid in CH3OH/H2O at 423 K for 7 d produced the novel NiII complex [Ni(C9H6NO2)(C10H8N2)2(H2O)](C9H6NO2)·2H2O. The asymmetric unit of the title compound consists of a monovalent [Ni(L)(bpy)2(H2O)]+ cation (bpy is 2,2'-bipyridine and L is 1H-indole-2-carboxylate), an L anion and two solvent water molecules. In the [Ni(L)(bpy)2(H2O)]+ cations, the Ni atom coordinates to four N atoms from the two bpy ligands and two O atoms, one from a L anion and the other from a water molecule to complete an significantly distorted NiN4O2 octahedron. The coordinated and solvate water molecules form an extensive series of O-H...O hydrogen bonds. N-H...O and C-H...O hydrogen bonds are also present and the molecules are interlinked, forming a three-dimensional network.

Comment top

We have prepared the title complex, [Ni(H2O)(bpy)2(L)].L.2H2O [bpy = 2,2'-bipyridine, HL = 2-indolyl-formic acid] (I), and report its crystal structure here, Fig. 1. The title compound has a structure similar to those of complexes of halobenzoate ligands, X—C6H4COO-, where X is F,Cl,Br and I, (Zhang, 2004, 2005, 2006a,b,c; Zhang et al., 2005).

The asymmetric unit of the title compound consists of a [Ni(H2O)(bpy)2(L)]+ cation, a 1H-indole-2-carboxylate anion and two solvent water molecules (Fig.1). In the cation, the Ni(1) atom is coordinated by four N atoms from two 2,2'-bipyridine ligands and two O atoms, one from a 1H-indole-2-carboxylate anion and the other from a water molecule to complete a significantly distorted NiN4O2 octahedron. The Ni—N bond lengths are in the range 2.066 (2) to 2.097 (2) Å, with Ni—O distances 2.075 (2)Å and 2.080 (2)Å, Table 1.

The coordinated and solvate water molecules show extensive hydrogen bonding to the carboxylate O atoms of 2-indolyl-formic acid anions, Table 2. An N6—HN6···O6 hydrogen bond also forms. In addition, weak C—H···O hydrogen bonds form between the O atoms of solvate water molecules and the H atoms of the 2,2'-bipyridine ligands. A combination of these strong and weak hydrogen bonding interactions link the molecules into a three-dimensional network, Fig 2.

Related literature top

For other complexes of the 1H-indole-2-carboxylate ligand, see: Lou & Zhang (2007); Zhang & Ying (2005). For related structures, see: Zhang (2004, 2005, 2006a,b,c); Zhang et al. (2005).

Experimental top

Ni2(OH)2CO3 (0.12 g 0.57 mmol), 2,2'-bpy (0.04 g 0.26 mmol),2-indolyl- formic acid (0.06 g 0.37 mmol),15 ml CH3OH/H2O (1:2, v/v) were mixed and stirred for ca3.5 h., the resulting suspension was heated in a 23 ml Teflon-lined stainless steel autoclave at 423 K for 7 days. After the autoclave cooled to room temperature, the solid was filtered off. The resulting pink filtrate was allowed to stand at room temperature and slow evaporation over two weeks gave brown block-like crystals suitable for X-ray analysis.

Refinement top

C-bound H atoms were placed in calculated positions, with C—H = 0.93Å and Uiso(H) = 1.2Ueq(C),and were refined using the riding-model approximation. The H atoms of the water molecule were located in a difference Fourier map and refined with O—H distance restraints of 0.82 (1) Å and Uiso(H) = 1.5Ueq(O). The highest residual electron density was 1.04Å and the deepest hole 0.89Å from atom Ni1.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); 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 asymmetric unit of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. A packing diagram of the title complex, viewed along the c axis (the H atoms have been omitted). Hydrogen bonds are drawn as dashed lines.
Aquabis(2,2'-bipyridine-k2N,N')(1H-indole-2-carboxylato-κO)nickel(II) 1H-indole-2-carboxylate dihydrate top
Crystal data top
[Ni(C9H6NO2)(C10H8N2)2(H2O)](C9H6NO2)·2H2OZ = 2
Mr = 745.42F(000) = 776
Triclinic, P1Dx = 1.483 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 12.499 (8) ÅCell parameters from 238 reflections
b = 13.128 (9) Åθ = 1.9–26.0°
c = 13.477 (9) ŵ = 0.64 mm−1
α = 95.389 (9)°T = 293 K
β = 114.166 (9)°Block, brown
γ = 117.804 (8)°0.40 × 0.21 × 0.13 mm
V = 1669.7 (19) Å3
Data collection top
Bruker SMART CCD area-detector
diffractometer		6750 independent reflections
Radiation source: fine-focus sealed tube5675 reflections with I > 2σ(I)
graphiteRint = 0.026
φ and ω scansθmax = 27.8°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −15→15
Tmin = 0.848, Tmax = 0.920k = −14→16
9411 measured reflectionsl = −16→16
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)] = 0.050H-atom parameters constrained
wR(F2) = 0.148 w = 1/[σ2(Fo2) + (0.1085P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.005
6750 reflectionsΔρmax = 1.23 e Å−3
470 parametersΔρmin = −0.88 e Å−3
0 restraintsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0027 (13)
Crystal data top
[Ni(C9H6NO2)(C10H8N2)2(H2O)](C9H6NO2)·2H2Oγ = 117.804 (8)°
Mr = 745.42V = 1669.7 (19) Å3
Triclinic, P1Z = 2
a = 12.499 (8) ÅMo Kα radiation
b = 13.128 (9) ŵ = 0.64 mm−1
c = 13.477 (9) ÅT = 293 K
α = 95.389 (9)°0.40 × 0.21 × 0.13 mm
β = 114.166 (9)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		6750 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		5675 reflections with I > 2σ(I)
Tmin = 0.848, Tmax = 0.920Rint = 0.026
9411 measured reflectionsθmax = 27.8°
Refinement top
R[F2 > 2σ(F2)] = 0.050H-atom parameters constrained
wR(F2) = 0.148Δρmax = 1.23 e Å−3
S = 1.07Δρmin = −0.88 e Å−3
6750 reflectionsAbsolute structure: ?
470 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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.

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 > 2sigma(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
Ni10.04771 (3)0.33215 (2)0.29047 (2)0.02858 (13)
N10.1702 (2)0.52501 (17)0.35544 (16)0.0333 (4)
N20.2419 (2)0.37219 (18)0.31901 (17)0.0336 (4)
N3−0.0299 (2)0.33007 (17)0.11931 (16)0.0322 (4)
N4−0.1395 (2)0.31369 (17)0.25242 (16)0.0321 (4)
N50.1344 (2)0.18354 (19)0.67095 (17)0.0420 (5)
HN50.10150.10870.63500.050*
N60.5831 (2)0.01927 (17)0.89144 (16)0.0326 (4)
HN60.58800.01820.95680.039*
O1−0.04967 (16)0.14307 (14)0.22692 (13)0.0349 (4)
H1A−0.03150.11990.28250.052*
H1B−0.13570.10100.19550.052*
O20.2771 (4)0.0847 (4)0.5299 (3)0.1255 (14)
H2A0.27980.07140.58890.188*
H2B0.23400.11780.51260.188*
O30.09785 (19)0.32891 (16)0.45695 (14)0.0403 (4)
O40.0692 (2)0.14428 (18)0.44129 (15)0.0512 (5)
O50.2852 (2)0.0358 (2)0.72467 (18)0.0577 (5)
O60.33868 (18)−0.01581 (16)0.88179 (15)0.0408 (4)
O70.4874 (3)0.3091 (2)0.8106 (3)0.0908 (9)
H7B0.53980.37700.80900.136*
H7A0.44390.24780.75420.136*
C10.1267 (3)0.5974 (2)0.3726 (2)0.0416 (6)
H10.03430.56050.35610.050*
C20.2134 (3)0.7250 (2)0.4139 (2)0.0479 (6)
H20.18040.77290.42550.058*
C30.3493 (3)0.7785 (2)0.4372 (2)0.0497 (7)
H30.40980.86380.46520.060*
C40.3965 (3)0.7059 (2)0.4189 (2)0.0456 (6)
H40.48830.74150.43430.055*
C50.3036 (2)0.5785 (2)0.37713 (19)0.0350 (5)
C60.3433 (2)0.4923 (2)0.35529 (19)0.0338 (5)
C70.4745 (3)0.5295 (3)0.3708 (2)0.0458 (6)
H70.54280.61260.39380.055*
C80.5028 (3)0.4418 (3)0.3517 (3)0.0520 (7)
H80.59070.46520.36260.062*
C90.3989 (3)0.3189 (3)0.3161 (2)0.0476 (6)
H90.41560.25830.30320.057*
C100.2701 (3)0.2880 (2)0.3001 (2)0.0415 (6)
H100.19970.20530.27520.050*
C110.0317 (3)0.3393 (2)0.0559 (2)0.0423 (6)
H110.11700.34560.08880.051*
C12−0.0259 (3)0.3397 (3)−0.0549 (2)0.0495 (7)
H120.01930.3458−0.09650.059*
C13−0.1513 (3)0.3311 (2)−0.1035 (2)0.0506 (7)
H13−0.19220.3313−0.17870.061*
C14−0.2165 (3)0.3221 (2)−0.0404 (2)0.0424 (6)
H14−0.30050.3181−0.07160.051*
C15−0.1548 (2)0.31915 (19)0.07050 (19)0.0328 (5)
C16−0.2200 (2)0.30411 (18)0.14345 (19)0.0313 (5)
C17−0.3542 (2)0.2789 (2)0.1037 (2)0.0399 (5)
H17−0.40960.26970.02750.048*
C18−0.4041 (3)0.2679 (2)0.1790 (3)0.0471 (6)
H18−0.49370.25130.15420.057*
C19−0.3208 (3)0.2816 (2)0.2905 (3)0.0443 (6)
H19−0.35180.27670.34290.053*
C20−0.1910 (3)0.3025 (2)0.3239 (2)0.0383 (5)
H20−0.13610.30940.39920.046*
C210.1409 (3)0.2719 (2)0.6209 (2)0.0379 (5)
C220.1981 (3)0.3790 (2)0.7048 (2)0.0408 (6)
H220.21280.45210.69360.049*
C230.2310 (3)0.3590 (2)0.8116 (2)0.0370 (5)
C240.1892 (3)0.2352 (2)0.7879 (2)0.0366 (5)
C250.2055 (3)0.1829 (2)0.8741 (2)0.0444 (6)
H250.17650.10080.85690.053*
C260.2667 (3)0.2583 (2)0.9862 (2)0.0446 (6)
H260.27800.22601.04550.054*
C270.3118 (3)0.3818 (3)1.0123 (2)0.0488 (7)
H270.35350.43021.08880.059*
C280.2961 (3)0.4334 (2)0.9277 (2)0.0502 (7)
H280.32790.51610.94660.060*
C290.0993 (2)0.2451 (2)0.4966 (2)0.0387 (5)
C300.4817 (2)0.0220 (2)0.8002 (2)0.0342 (5)
C310.5085 (3)0.0230 (2)0.7109 (2)0.0374 (5)
H310.45620.02530.63940.045*
C320.6304 (2)0.0198 (2)0.7472 (2)0.0336 (5)
C330.7085 (3)0.0185 (2)0.6963 (2)0.0384 (5)
H330.67910.01580.62000.046*
C340.8288 (3)0.0215 (2)0.7610 (2)0.0437 (6)
H340.88240.02340.72860.052*
C350.8722 (3)0.0216 (2)0.8743 (2)0.0443 (6)
H350.95350.02270.91550.053*
C360.7973 (3)0.0202 (2)0.9269 (2)0.0381 (5)
H360.82640.02031.00240.046*
C370.6758 (2)0.01867 (19)0.86157 (19)0.0328 (5)
C380.3603 (2)0.0142 (2)0.8030 (2)0.0356 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.02652 (19)0.03213 (19)0.02880 (18)0.01791 (14)0.01357 (14)0.01124 (12)
N10.0342 (10)0.0333 (10)0.0309 (10)0.0188 (8)0.0158 (8)0.0108 (7)
N20.0290 (10)0.0372 (10)0.0348 (10)0.0210 (8)0.0138 (8)0.0114 (8)
N30.0321 (10)0.0344 (10)0.0294 (9)0.0188 (8)0.0150 (8)0.0111 (7)
N40.0333 (10)0.0339 (10)0.0329 (10)0.0210 (8)0.0171 (8)0.0126 (8)
N50.0545 (13)0.0401 (11)0.0338 (10)0.0288 (10)0.0214 (10)0.0148 (8)
N60.0334 (10)0.0351 (10)0.0319 (10)0.0193 (8)0.0183 (8)0.0126 (8)
O10.0324 (8)0.0352 (8)0.0332 (8)0.0176 (7)0.0150 (7)0.0125 (7)
O20.133 (3)0.273 (5)0.095 (2)0.164 (3)0.087 (2)0.116 (3)
O30.0456 (10)0.0482 (10)0.0321 (9)0.0296 (8)0.0186 (8)0.0192 (7)
O40.0678 (13)0.0569 (12)0.0365 (9)0.0437 (10)0.0216 (9)0.0195 (8)
O50.0598 (13)0.0922 (15)0.0621 (13)0.0577 (12)0.0414 (11)0.0479 (12)
O60.0356 (9)0.0513 (10)0.0395 (9)0.0242 (8)0.0220 (8)0.0185 (8)
O70.0528 (14)0.0629 (15)0.121 (2)0.0271 (12)0.0237 (15)0.0274 (14)
C10.0440 (14)0.0406 (13)0.0456 (14)0.0257 (11)0.0250 (12)0.0146 (11)
C20.0625 (18)0.0416 (14)0.0484 (15)0.0330 (13)0.0306 (14)0.0159 (11)
C30.0553 (17)0.0321 (13)0.0458 (15)0.0180 (12)0.0213 (13)0.0111 (11)
C40.0391 (14)0.0378 (13)0.0452 (14)0.0158 (11)0.0168 (11)0.0137 (11)
C50.0334 (12)0.0370 (12)0.0298 (11)0.0178 (10)0.0141 (9)0.0130 (9)
C60.0273 (11)0.0415 (12)0.0303 (11)0.0186 (10)0.0133 (9)0.0140 (9)
C70.0333 (13)0.0511 (15)0.0488 (15)0.0204 (11)0.0215 (11)0.0173 (12)
C80.0372 (14)0.074 (2)0.0561 (17)0.0350 (14)0.0279 (13)0.0258 (14)
C90.0466 (15)0.0642 (18)0.0526 (16)0.0412 (14)0.0289 (13)0.0236 (13)
C100.0399 (14)0.0441 (14)0.0482 (14)0.0275 (11)0.0241 (12)0.0159 (11)
C110.0426 (14)0.0480 (14)0.0399 (13)0.0246 (11)0.0247 (11)0.0161 (11)
C120.0605 (18)0.0504 (15)0.0391 (14)0.0270 (14)0.0310 (13)0.0177 (11)
C130.0613 (18)0.0483 (15)0.0306 (13)0.0262 (13)0.0193 (12)0.0146 (11)
C140.0433 (14)0.0420 (13)0.0349 (12)0.0245 (11)0.0134 (11)0.0152 (10)
C150.0334 (12)0.0252 (10)0.0311 (11)0.0152 (9)0.0115 (9)0.0076 (8)
C160.0297 (11)0.0246 (10)0.0341 (11)0.0160 (9)0.0116 (9)0.0082 (8)
C170.0323 (12)0.0362 (12)0.0471 (14)0.0219 (10)0.0140 (10)0.0135 (10)
C180.0362 (13)0.0454 (14)0.0689 (18)0.0275 (12)0.0284 (13)0.0214 (13)
C190.0453 (15)0.0446 (14)0.0620 (17)0.0295 (12)0.0360 (13)0.0241 (12)
C200.0424 (14)0.0424 (13)0.0427 (13)0.0274 (11)0.0264 (11)0.0193 (10)
C210.0368 (13)0.0466 (14)0.0369 (12)0.0256 (11)0.0201 (10)0.0202 (10)
C220.0475 (14)0.0416 (13)0.0451 (14)0.0286 (12)0.0271 (12)0.0228 (11)
C230.0390 (13)0.0388 (12)0.0398 (13)0.0245 (10)0.0217 (11)0.0160 (10)
C240.0401 (13)0.0420 (13)0.0315 (11)0.0253 (11)0.0181 (10)0.0147 (9)
C250.0593 (17)0.0445 (14)0.0401 (13)0.0344 (13)0.0263 (12)0.0211 (11)
C260.0509 (16)0.0561 (16)0.0374 (13)0.0348 (13)0.0236 (12)0.0238 (11)
C270.0549 (17)0.0533 (16)0.0342 (13)0.0288 (13)0.0220 (12)0.0121 (11)
C280.0653 (18)0.0394 (14)0.0460 (15)0.0297 (13)0.0285 (14)0.0127 (11)
C290.0337 (12)0.0518 (15)0.0355 (12)0.0274 (11)0.0165 (10)0.0195 (11)
C300.0369 (12)0.0299 (11)0.0367 (12)0.0187 (9)0.0196 (10)0.0115 (9)
C310.0380 (13)0.0433 (13)0.0360 (12)0.0250 (11)0.0198 (10)0.0158 (10)
C320.0363 (12)0.0330 (11)0.0352 (12)0.0205 (10)0.0196 (10)0.0129 (9)
C330.0459 (14)0.0433 (13)0.0365 (12)0.0285 (11)0.0244 (11)0.0175 (10)
C340.0456 (14)0.0494 (15)0.0524 (15)0.0315 (12)0.0315 (13)0.0210 (12)
C350.0425 (14)0.0537 (15)0.0488 (15)0.0346 (12)0.0227 (12)0.0237 (12)
C360.0375 (13)0.0403 (13)0.0374 (12)0.0223 (11)0.0188 (10)0.0154 (10)
C370.0373 (12)0.0283 (11)0.0351 (11)0.0184 (9)0.0200 (10)0.0122 (9)
C380.0335 (12)0.0358 (12)0.0386 (12)0.0200 (10)0.0184 (10)0.0139 (9)
Geometric parameters (Å, °) top
Ni1—N42.064 (2)C10—H100.9300
Ni1—O12.075 (2)C11—C121.369 (4)
Ni1—O32.078 (2)C11—H110.9300
Ni1—N22.079 (2)C12—C131.371 (4)
Ni1—N12.095 (2)C12—H120.9300
Ni1—N32.096 (2)C13—C141.378 (4)
N1—C11.341 (3)C13—H130.9300
N1—C51.352 (3)C14—C151.387 (3)
N2—C101.339 (3)C14—H140.9300
N2—C61.347 (3)C15—C161.486 (3)
N3—C111.345 (3)C16—C171.388 (3)
N3—C151.350 (3)C17—C181.379 (4)
N4—C201.346 (3)C17—H170.9300
N4—C161.350 (3)C18—C191.367 (4)
N5—C241.377 (3)C18—H180.9300
N5—C211.382 (3)C19—C201.367 (4)
N5—HN50.8598C19—H190.9300
N6—C301.376 (3)C20—H200.9300
N6—C371.377 (3)C21—C221.367 (4)
N6—HN60.8591C21—C291.485 (3)
O1—H1A0.8201C22—C231.413 (3)
O1—H1B0.8190C22—H220.9300
O2—H2A0.8192C23—C241.410 (4)
O2—H2B0.8176C23—C281.412 (4)
O3—C291.272 (3)C24—C251.396 (3)
O4—C291.253 (3)C25—C261.384 (4)
O5—C381.253 (3)C25—H250.9300
O6—C381.253 (3)C26—C271.395 (4)
O7—H7B0.8336C26—H260.9300
O7—H7A0.8125C27—C281.372 (4)
C1—C21.389 (4)C27—H270.9300
C1—H10.9300C28—H280.9300
C2—C31.374 (4)C30—C311.375 (3)
C2—H20.9300C30—C381.489 (4)
C3—C41.385 (4)C31—C321.420 (4)
C3—H30.9300C31—H310.9300
C4—C51.392 (3)C32—C331.409 (3)
C4—H40.9300C32—C371.412 (3)
C5—C61.481 (3)C33—C341.375 (4)
C6—C71.388 (4)C33—H330.9300
C7—C81.385 (4)C34—C351.395 (4)
C7—H70.9300C34—H340.9300
C8—C91.382 (4)C35—C361.381 (4)
C8—H80.9300C35—H350.9300
C9—C101.376 (4)C36—C371.398 (4)
C9—H90.9300C36—H360.9300
N4—Ni1—O192.31 (7)C14—C13—H13120.2
N4—Ni1—O393.38 (7)C13—C14—C15118.9 (3)
O1—Ni1—O390.27 (7)C13—C14—H14120.5
N4—Ni1—N2171.38 (7)C15—C14—H14120.5
O1—Ni1—N294.06 (7)N3—C15—C14121.5 (2)
O3—Ni1—N292.40 (7)N3—C15—C16115.51 (19)
N4—Ni1—N195.40 (8)C14—C15—C16123.0 (2)
O1—Ni1—N1172.15 (7)N4—C16—C17121.6 (2)
O3—Ni1—N190.72 (7)N4—C16—C15114.8 (2)
N2—Ni1—N178.12 (8)C17—C16—C15123.6 (2)
N4—Ni1—N378.62 (7)C18—C17—C16119.0 (2)
O1—Ni1—N389.26 (7)C18—C17—H17120.5
O3—Ni1—N3171.96 (7)C16—C17—H17120.5
N2—Ni1—N395.64 (8)C19—C18—C17119.4 (2)
N1—Ni1—N390.84 (7)C19—C18—H18120.3
C1—N1—C5118.6 (2)C17—C18—H18120.3
C1—N1—Ni1126.13 (17)C20—C19—C18119.1 (2)
C5—N1—Ni1115.25 (16)C20—C19—H19120.4
C10—N2—C6119.1 (2)C18—C19—H19120.4
C10—N2—Ni1124.84 (16)N4—C20—C19122.8 (2)
C6—N2—Ni1116.03 (16)N4—C20—H20118.6
C11—N3—C15118.3 (2)C19—C20—H20118.6
C11—N3—Ni1127.00 (18)C22—C21—N5108.9 (2)
C15—N3—Ni1114.71 (14)C22—C21—C29130.2 (2)
C20—N4—C16118.0 (2)N5—C21—C29120.7 (2)
C20—N4—Ni1125.64 (16)C21—C22—C23108.0 (2)
C16—N4—Ni1116.17 (15)C21—C22—H22126.0
C24—N5—C21108.7 (2)C23—C22—H22126.0
C24—N5—HN5125.7C24—C23—C28118.4 (2)
C21—N5—HN5125.6C24—C23—C22106.7 (2)
C30—N6—C37109.19 (19)C28—C23—C22134.8 (2)
C30—N6—HN6125.5N5—C24—C25129.7 (2)
C37—N6—HN6125.3N5—C24—C23107.7 (2)
Ni1—O1—H1A108.1C25—C24—C23122.5 (2)
Ni1—O1—H1B116.3C26—C25—C24117.1 (2)
H1A—O1—H1B97.8C26—C25—H25121.4
H2A—O2—H2B106.3C24—C25—H25121.4
C29—O3—Ni1128.90 (17)C25—C26—C27121.5 (2)
H7B—O7—H7A118.6C25—C26—H26119.3
N1—C1—C2122.9 (3)C27—C26—H26119.3
N1—C1—H1118.5C28—C27—C26121.4 (2)
C2—C1—H1118.5C28—C27—H27119.3
C3—C2—C1118.1 (3)C26—C27—H27119.3
C3—C2—H2121.0C27—C28—C23119.0 (3)
C1—C2—H2121.0C27—C28—H28120.5
C2—C3—C4120.2 (2)C23—C28—H28120.5
C2—C3—H3119.9O4—C29—O3126.4 (2)
C4—C3—H3119.9O4—C29—C21118.1 (2)
C3—C4—C5118.6 (3)O3—C29—C21115.5 (2)
C3—C4—H4120.7C31—C30—N6108.7 (2)
C5—C4—H4120.7C31—C30—C38129.2 (2)
N1—C5—C4121.7 (2)N6—C30—C38121.8 (2)
N1—C5—C6115.3 (2)C30—C31—C32107.8 (2)
C4—C5—C6123.1 (2)C30—C31—H31126.1
N2—C6—C7121.1 (2)C32—C31—H31126.1
N2—C6—C5115.1 (2)C33—C32—C37118.5 (2)
C7—C6—C5123.8 (2)C33—C32—C31134.9 (2)
C8—C7—C6119.4 (2)C37—C32—C31106.6 (2)
C8—C7—H7120.3C34—C33—C32119.0 (2)
C6—C7—H7120.3C34—C33—H33120.5
C9—C8—C7119.1 (3)C32—C33—H33120.5
C9—C8—H8120.5C33—C34—C35121.3 (2)
C7—C8—H8120.5C33—C34—H34119.3
C10—C9—C8118.6 (3)C35—C34—H34119.3
C10—C9—H9120.7C36—C35—C34121.6 (2)
C8—C9—H9120.7C36—C35—H35119.2
N2—C10—C9122.7 (2)C34—C35—H35119.2
N2—C10—H10118.6C35—C36—C37117.1 (2)
C9—C10—H10118.6C35—C36—H36121.4
N3—C11—C12122.8 (3)C37—C36—H36121.4
N3—C11—H11118.6N6—C37—C36129.9 (2)
C12—C11—H11118.6N6—C37—C32107.7 (2)
C11—C12—C13118.8 (3)C36—C37—C32122.4 (2)
C11—C12—H12120.6O6—C38—O5124.6 (2)
C13—C12—H12120.6O6—C38—C30118.0 (2)
C12—C13—C14119.6 (2)O5—C38—C30117.4 (2)
C12—C13—H13120.2
N4—Ni1—N1—C16.3 (2)N3—C11—C12—C130.4 (4)
O1—Ni1—N1—C1175.6 (4)C11—C12—C13—C140.0 (4)
O3—Ni1—N1—C1−87.2 (2)C12—C13—C14—C15−1.5 (4)
N2—Ni1—N1—C1−179.5 (2)C11—N3—C15—C14−2.5 (3)
N3—Ni1—N1—C184.9 (2)Ni1—N3—C15—C14176.99 (17)
N4—Ni1—N1—C5−171.13 (16)C11—N3—C15—C16177.54 (19)
O1—Ni1—N1—C5−1.8 (5)Ni1—N3—C15—C16−3.0 (2)
O3—Ni1—N1—C595.41 (16)C13—C14—C15—N32.8 (3)
N2—Ni1—N1—C53.11 (15)C13—C14—C15—C16−177.2 (2)
N3—Ni1—N1—C5−92.48 (16)C20—N4—C16—C17−2.4 (3)
N4—Ni1—N2—C10−139.6 (4)Ni1—N4—C16—C17173.42 (16)
O1—Ni1—N2—C10−2.1 (2)C20—N4—C16—C15179.22 (19)
O3—Ni1—N2—C1088.3 (2)Ni1—N4—C16—C15−5.0 (2)
N1—Ni1—N2—C10178.5 (2)N3—C15—C16—N45.3 (3)
N3—Ni1—N2—C10−91.8 (2)C14—C15—C16—N4−174.7 (2)
N4—Ni1—N2—C637.9 (5)N3—C15—C16—C17−173.1 (2)
O1—Ni1—N2—C6175.46 (16)C14—C15—C16—C176.9 (3)
O3—Ni1—N2—C6−94.10 (17)N4—C16—C17—C182.3 (3)
N1—Ni1—N2—C6−3.88 (16)C15—C16—C17—C18−179.4 (2)
N3—Ni1—N2—C685.80 (17)C16—C17—C18—C19−0.2 (4)
N4—Ni1—N3—C11179.7 (2)C17—C18—C19—C20−1.8 (4)
O1—Ni1—N3—C11−87.7 (2)C16—N4—C20—C190.3 (3)
O3—Ni1—N3—C11−174.4 (4)Ni1—N4—C20—C19−175.07 (18)
N2—Ni1—N3—C116.3 (2)C18—C19—C20—N41.8 (4)
N1—Ni1—N3—C1184.4 (2)C24—N5—C21—C22−0.6 (3)
N4—Ni1—N3—C150.30 (14)C24—N5—C21—C29175.2 (2)
O1—Ni1—N3—C1592.81 (15)N5—C21—C22—C230.9 (3)
O3—Ni1—N3—C156.1 (6)C29—C21—C22—C23−174.3 (2)
N2—Ni1—N3—C15−173.19 (15)C21—C22—C23—C24−0.9 (3)
N1—Ni1—N3—C15−95.04 (16)C21—C22—C23—C28176.7 (3)
O1—Ni1—N4—C2089.34 (19)C21—N5—C24—C25−179.7 (3)
O3—Ni1—N4—C20−1.07 (19)C21—N5—C24—C230.0 (3)
N2—Ni1—N4—C20−133.1 (4)C28—C23—C24—N5−177.5 (2)
N1—Ni1—N4—C20−92.11 (19)C22—C23—C24—N50.6 (3)
N3—Ni1—N4—C20178.1 (2)C28—C23—C24—C252.1 (4)
O1—Ni1—N4—C16−86.09 (15)C22—C23—C24—C25−179.7 (2)
O3—Ni1—N4—C16−176.50 (15)N5—C24—C25—C26179.0 (3)
N2—Ni1—N4—C1651.5 (5)C23—C24—C25—C26−0.6 (4)
N1—Ni1—N4—C1692.46 (15)C24—C25—C26—C27−0.8 (4)
N3—Ni1—N4—C162.69 (14)C25—C26—C27—C280.7 (4)
N4—Ni1—O3—C29109.4 (2)C26—C27—C28—C230.9 (4)
O1—Ni1—O3—C2917.0 (2)C24—C23—C28—C27−2.2 (4)
N2—Ni1—O3—C29−77.1 (2)C22—C23—C28—C27−179.7 (3)
N1—Ni1—O3—C29−155.2 (2)Ni1—O3—C29—O4−0.3 (4)
N3—Ni1—O3—C29103.6 (5)Ni1—O3—C29—C21179.74 (15)
C5—N1—C1—C2−1.3 (4)C22—C21—C29—O4169.1 (3)
Ni1—N1—C1—C2−178.66 (19)N5—C21—C29—O4−5.6 (4)
N1—C1—C2—C30.5 (4)C22—C21—C29—O3−10.9 (4)
C1—C2—C3—C40.3 (4)N5—C21—C29—O3174.3 (2)
C2—C3—C4—C5−0.2 (4)C37—N6—C30—C310.1 (3)
C1—N1—C5—C41.4 (3)C37—N6—C30—C38175.52 (19)
Ni1—N1—C5—C4179.07 (18)N6—C30—C31—C320.5 (3)
C1—N1—C5—C6−179.6 (2)C38—C30—C31—C32−174.5 (2)
Ni1—N1—C5—C6−2.0 (2)C30—C31—C32—C33179.7 (3)
C3—C4—C5—N1−0.7 (4)C30—C31—C32—C37−0.8 (3)
C3—C4—C5—C6−179.6 (2)C37—C32—C33—C34−2.7 (3)
C10—N2—C6—C71.4 (3)C31—C32—C33—C34176.8 (3)
Ni1—N2—C6—C7−176.33 (18)C32—C33—C34—C352.1 (4)
C10—N2—C6—C5−178.3 (2)C33—C34—C35—C36−0.7 (4)
Ni1—N2—C6—C54.0 (2)C34—C35—C36—C370.0 (4)
N1—C5—C6—N2−1.3 (3)C30—N6—C37—C36177.7 (2)
C4—C5—C6—N2177.6 (2)C30—N6—C37—C32−0.6 (2)
N1—C5—C6—C7179.0 (2)C35—C36—C37—N6−178.7 (2)
C4—C5—C6—C7−2.0 (4)C35—C36—C37—C32−0.7 (3)
N2—C6—C7—C8−1.8 (4)C33—C32—C37—N6−179.6 (2)
C5—C6—C7—C8177.9 (2)C31—C32—C37—N60.9 (2)
C6—C7—C8—C90.8 (4)C33—C32—C37—C362.0 (3)
C7—C8—C9—C100.4 (4)C31—C32—C37—C36−177.6 (2)
C6—N2—C10—C9−0.1 (4)C31—C30—C38—O6162.5 (2)
Ni1—N2—C10—C9177.42 (19)N6—C30—C38—O6−11.8 (3)
C8—C9—C10—N2−0.8 (4)C31—C30—C38—O5−16.1 (4)
C15—N3—C11—C120.9 (4)N6—C30—C38—O5169.5 (2)
Ni1—N3—C11—C12−178.53 (19)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···O40.821.892.647 (3)154.0
O2—H2A···O50.821.912.732 (4)178.3
O2—H2B···O40.822.102.885 (4)161.7
O7—H7A···O50.812.422.994 (4)129.0
N6—HN6···O6i0.861.992.814 (3)159.0
O1—H1B···O6ii0.821.932.750 (3)174.2
O1—H1B···O5ii0.822.603.166 (3)127.6
C4—H4···O2iii0.932.543.400 (5)155
C14—H14···O7iv0.932.413.320 (4)167
Symmetry codes: (i) −x+1, −y, −z+2; (ii) −x, −y, −z+1; (iii) −x+1, −y+1, −z+1; (iv) x−1, y, z−1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···O40.821.892.647 (3)154.0
O2—H2A···O50.821.912.732 (4)178.3
O2—H2B···O40.822.102.885 (4)161.7
O7—H7A···O50.812.422.994 (4)129.0
N6—HN6···O6i0.861.992.814 (3)159.0
O1—H1B···O6ii0.821.932.750 (3)174.2
O1—H1B···O5ii0.822.603.166 (3)127.6
C4—H4···O2iii0.932.543.400 (5)155
C14—H14···O7iv0.932.413.320 (4)167
Symmetry codes: (i) −x+1, −y, −z+2; (ii) −x, −y, −z+1; (iii) −x+1, −y+1, −z+1; (iv) x−1, y, z−1.
Acknowledgements top

The authors gratefully acknowledge the financial support of the Education Office of Zhejiang Province (grant No. 20051316).

references
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