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Acta Cryst. (2009). E65, m522    [ doi:10.1107/S1600536809010174 ]

[[mu]-10,21-Dimethyl-3,6,14,17-tetraazatricyclo[17.3.1.18,12]tetracosa-1(23),8(24),9,11,19,21-hexaene-23,24-diolato-[kappa]8N3,N6,O23,O24:N14,N17,O23,O24]bis[(nitrato-[kappa]2O,O')nickel(II)]

Q.-J. Li, J.-F. Ma, J. Liu and T.-T. Han

Abstract top

In the title centrosymmetric dinuclear nickel complex, [Ni2(C22H30N4O2)(NO3)2], each of the two NiII atoms has a distorted octahedral geometry, defined by two N atoms and two O atoms from the macrocyclic ligand and two O atoms from a chelating nitrate anion. The two Ni atoms are bridged by two phenolate O atoms, forming a four-membered Ni2O2 ring.

Comment top

Crown ether compounds have attracted much interest as a result of their significance in biological transport systems (Caldwell & Crumbliss, 1998). In addition, crown ether compounds are found to have functions in selective molecular recognition (Rosa et al., 1998). To further widen the scope of applications of crown ether, there is a need to prepare new series of crown ether compounds. In this work, a new dinuclear nickel(II) compound has been synthesized and its struture is reported here.

As shown in Fig. 1, the title compound is a centrosymmetric dinuclear nickel complex. The coordination environment around each NiII atom is distorted octahedral, with one N atom and one O atom from the macrocyclic ligand and two O atoms from the nitrate anion occupying the equatorial plane, and the other N atom and O atom from the ligand occupying the axial positions. In the complex molecule, two Ni atoms are bridged by two phenolate O atoms, generating a four-membered Ni2O2 ring, with a Ni···Ni distance of 2.9737 (10) Å. The Ni—O and Ni—N distances are normal (Aromi et al., 2002).

Related literature top

For general background, see: Caldwell & Crumbliss (1998); Rosa et al. (1998). For related structures, see: Aromi et al. (2002). For the ligand synthesis, see: Mandal & Nag (1986).

Experimental top

The macrocyclic ligand, C22H32N4O2 (H2L), was prepared by the reported procedure (Mandal & Nag, 1986). A mixture of H2L (0.10 g, 0.26 mmol) and Ni(NO3)2.6H2O (0.15 g, 0.52 mmol) in methanol (20 ml) was stirred for 10 min. The resulting solution was filtered. Green single crystals were obtained by slow evaporation of the filtrate at room temperature (yield 56%).

Refinement top

H atoms bound to C atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 (aromatic), 0.97 (CH2) and 0.96 (CH3) Å and with Uiso = 1.2(1.5 for methyl)Ueq(C). The imino H atoms were located in a difference Fourier map and refined with Uiso(H) = 0.128 Å2. The highest residual electron density was found 1.03Å from Ni1 and the deepest hole 0.76 Å from Ni1.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound. Displacement ellipsoids are draw at the 30% probability level. H atoms have been omitted for clarity. [Symmetry code: (i) -x + 2/3, -y + 1/3, -z + 1/3.]
[µ-10,21-Dimethyl-3,6,14,17-tetraazatricyclo[17.3.1.18,12]tetracosa- 1(23),8(24),9,11,19,21-hexaene-23,24-diolato- κ8N3,N6,O23,O24:N14, N17,O23,O24]bis[(nitrato- κ2O,O')nickel(II)] top
Crystal data top
[Ni2(C22H30N4O2)(NO3)2]Dx = 1.620 Mg m−3
Mr = 623.90Mo Kα radiation, λ = 0.71069 Å
Trigonal, R3Cell parameters from 3000 reflections
Hall symbol: -R 3θ = 2.4–28.4°
a = 25.020 (5) ŵ = 1.53 mm−1
c = 10.616 (5) ÅT = 293 K
V = 5755 (3) Å3Block, green
Z = 90.40 × 0.30 × 0.25 mm
F(000) = 2916
Data collection top
Bruker APEX CCD
diffractometer		2213 independent reflections
Radiation source: fine-focus sealed tube1745 reflections with I > 2σ(I)
graphiteRint = 0.107
φ and ω scansθmax = 24.9°, θmin = 1.6°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −15→29
Tmin = 0.495, Tmax = 0.609k = −29→23
9432 measured reflectionsl = −12→12
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)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.117H atoms treated by a mixture of independent and constrained refinement
S = 1.03 w = 1/[σ2(Fo2) + (0.066P)2]
where P = (Fo2 + 2Fc2)/3
2213 reflections(Δ/σ)max = 0.007
178 parametersΔρmax = 1.06 e Å−3
1 restraintΔρmin = −0.35 e Å−3
Crystal data top
[Ni2(C22H30N4O2)(NO3)2]Z = 9
Mr = 623.90Mo Kα radiation
Trigonal, R3µ = 1.53 mm−1
a = 25.020 (5) ÅT = 293 K
c = 10.616 (5) Å0.40 × 0.30 × 0.25 mm
V = 5755 (3) Å3
Data collection top
Bruker APEX CCD
diffractometer		2213 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1745 reflections with I > 2σ(I)
Tmin = 0.495, Tmax = 0.609Rint = 0.107
9432 measured reflectionsθmax = 24.9°
Refinement top
R[F2 > 2σ(F2)] = 0.043H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.117Δρmax = 1.06 e Å−3
S = 1.03Δρmin = −0.35 e Å−3
2213 reflectionsAbsolute structure: ?
178 parametersFlack parameter: ?
1 restraintRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ni10.355561 (19)0.13534 (2)0.25357 (4)0.03150 (19)
C10.04882 (19)−0.0620 (2)0.3314 (4)0.0658 (13)
H1A0.0488−0.07700.41470.099*
H1B0.0372−0.09480.27170.099*
H1C0.0199−0.04750.32760.099*
C20.11262 (17)−0.00973 (17)0.3005 (3)0.0431 (9)
C30.12561 (16)0.01995 (17)0.1862 (3)0.0410 (9)
H30.09470.00560.12550.049*
C40.18315 (15)0.07079 (16)0.1570 (3)0.0353 (8)
C50.22847 (15)0.09460 (15)0.2510 (3)0.0347 (8)
C60.16018 (17)0.01062 (17)0.3868 (3)0.0446 (9)
H60.1536−0.01110.46170.054*
C70.21738 (16)0.06230 (16)0.3656 (3)0.0374 (8)
C80.26663 (17)0.08766 (18)0.4652 (3)0.0443 (9)
H8A0.27460.12840.48920.053*
H8B0.25150.06140.53910.053*
C90.37778 (18)0.13034 (17)0.5104 (3)0.0430 (9)
H9A0.41120.12210.49490.052*
H9B0.36460.11960.59720.052*
C100.40046 (18)0.19842 (17)0.4892 (3)0.0421 (9)
H10A0.37040.20850.52240.050*
H10B0.43900.22300.53420.050*
C110.47350 (15)0.23666 (16)0.3077 (3)0.0383 (8)
H11A0.48240.20310.30910.046*
H11B0.50220.26850.36440.046*
N10.32528 (14)0.09201 (14)0.4244 (3)0.0377 (7)
N20.41009 (14)0.21377 (13)0.3532 (2)0.0355 (7)
N30.37310 (14)0.05216 (15)0.1596 (3)0.0479 (8)
O10.28230 (10)0.14687 (10)0.23716 (19)0.0342 (5)
O20.41509 (12)0.09599 (12)0.2220 (2)0.0455 (6)
O30.32302 (12)0.05220 (12)0.1480 (2)0.0459 (6)
O40.38022 (15)0.01126 (15)0.1141 (4)0.0853 (11)
HN10.320 (3)0.055 (3)0.423 (6)0.128*
HN20.401 (3)0.242 (2)0.336 (6)0.128*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0299 (3)0.0299 (3)0.0353 (3)0.0154 (2)−0.00202 (16)0.00065 (16)
C10.041 (3)0.060 (3)0.081 (3)0.014 (2)0.014 (2)0.004 (2)
C20.037 (2)0.035 (2)0.052 (2)0.0137 (17)0.0119 (16)−0.0027 (16)
C30.033 (2)0.038 (2)0.055 (2)0.0200 (18)−0.0023 (16)−0.0069 (16)
C40.0299 (19)0.0322 (19)0.0451 (18)0.0165 (16)0.0011 (14)−0.0002 (14)
C50.0322 (19)0.033 (2)0.0424 (18)0.0193 (17)0.0038 (14)−0.0001 (14)
C60.044 (2)0.042 (2)0.049 (2)0.022 (2)0.0114 (17)0.0067 (16)
C70.037 (2)0.037 (2)0.0402 (18)0.0193 (17)0.0053 (15)0.0017 (14)
C80.043 (2)0.051 (2)0.0380 (18)0.024 (2)0.0040 (15)0.0054 (16)
C90.047 (2)0.045 (2)0.0366 (18)0.0226 (19)−0.0053 (15)0.0029 (15)
C100.048 (2)0.043 (2)0.0359 (18)0.0227 (19)−0.0046 (15)−0.0049 (15)
C110.033 (2)0.034 (2)0.049 (2)0.0181 (17)−0.0105 (15)−0.0059 (15)
N10.0404 (18)0.0370 (18)0.0381 (14)0.0211 (16)−0.0010 (12)0.0024 (13)
N20.0366 (17)0.0327 (17)0.0383 (15)0.0182 (15)−0.0035 (12)−0.0001 (12)
N30.0349 (19)0.040 (2)0.067 (2)0.0180 (16)−0.0012 (15)−0.0111 (16)
O10.0289 (13)0.0311 (13)0.0408 (12)0.0137 (11)−0.0007 (10)0.0025 (10)
O20.0341 (14)0.0377 (15)0.0634 (16)0.0171 (13)−0.0070 (12)−0.0076 (12)
O30.0329 (15)0.0434 (16)0.0570 (15)0.0159 (13)−0.0059 (11)−0.0075 (11)
O40.058 (2)0.062 (2)0.139 (3)0.0324 (18)−0.0003 (19)−0.048 (2)
Geometric parameters (Å, °) top
Ni1—O12.000 (2)C7—C81.502 (5)
Ni1—O1i2.006 (2)C8—N11.481 (5)
Ni1—N22.038 (3)C8—H8A0.9700
Ni1—N12.054 (3)C8—H8B0.9700
Ni1—O32.134 (3)C9—N11.489 (4)
Ni1—O22.183 (3)C9—C101.519 (5)
Ni1—Ni1i2.9737 (10)C9—H9A0.9700
C1—C21.510 (5)C9—H9B0.9700
C1—H1A0.9600C10—N21.483 (4)
C1—H1B0.9600C10—H10A0.9700
C1—H1C0.9600C10—H10B0.9700
C2—C31.374 (5)C11—N21.473 (4)
C2—C61.382 (5)C11—C4i1.505 (5)
C3—C41.398 (5)C11—H11A0.9700
C3—H30.9300C11—H11B0.9700
C4—C51.400 (5)N1—HN10.87 (6)
C4—C11i1.505 (5)N2—HN20.86 (6)
C5—O11.336 (4)N3—O41.223 (4)
C5—C71.408 (5)N3—O31.260 (4)
C6—C71.386 (5)N3—O21.262 (4)
C6—H60.9300
O1—Ni1—O1i84.17 (9)N1—C8—C7113.5 (3)
O1—Ni1—N297.29 (10)N1—C8—H8A108.9
O1i—Ni1—N287.95 (10)C7—C8—H8A108.9
O1—Ni1—N191.74 (10)N1—C8—H8B108.9
O1i—Ni1—N1172.81 (10)C7—C8—H8B108.9
N2—Ni1—N186.72 (12)H8A—C8—H8B107.7
O1—Ni1—O399.46 (9)N1—C9—C10110.3 (3)
O1i—Ni1—O391.39 (10)N1—C9—H9A109.6
N2—Ni1—O3163.09 (11)C10—C9—H9A109.6
N1—Ni1—O395.11 (11)N1—C9—H9B109.6
O1—Ni1—O2158.83 (9)C10—C9—H9B109.6
O1i—Ni1—O292.93 (9)H9A—C9—H9B108.1
N2—Ni1—O2103.57 (11)N2—C10—C9110.8 (3)
N1—Ni1—O292.99 (11)N2—C10—H10A109.5
O3—Ni1—O259.57 (10)C9—C10—H10A109.5
O1—Ni1—Ni1i42.16 (6)N2—C10—H10B109.5
O1i—Ni1—Ni1i42.01 (6)C9—C10—H10B109.5
N2—Ni1—Ni1i93.51 (8)H10A—C10—H10B108.1
N1—Ni1—Ni1i133.62 (9)N2—C11—C4i112.7 (3)
O3—Ni1—Ni1i97.29 (7)N2—C11—H11A109.0
O2—Ni1—Ni1i131.44 (7)C4i—C11—H11A109.0
C2—C1—H1A109.5N2—C11—H11B109.0
C2—C1—H1B109.5C4i—C11—H11B109.0
H1A—C1—H1B109.5H11A—C11—H11B107.8
C2—C1—H1C109.5C8—N1—C9113.0 (3)
H1A—C1—H1C109.5C8—N1—Ni1112.8 (2)
H1B—C1—H1C109.5C9—N1—Ni1103.2 (2)
C3—C2—C6117.3 (3)C8—N1—HN1108 (4)
C3—C2—C1121.5 (4)C9—N1—HN1108 (4)
C6—C2—C1121.2 (4)Ni1—N1—HN1112 (4)
C2—C3—C4123.0 (3)C11—N2—C10115.1 (3)
C2—C3—H3118.5C11—N2—Ni1106.0 (2)
C4—C3—H3118.5C10—N2—Ni1108.2 (2)
C3—C4—C5118.4 (3)C11—N2—HN2107 (4)
C3—C4—C11i118.1 (3)C10—N2—HN2110 (4)
C5—C4—C11i123.5 (3)Ni1—N2—HN2110 (4)
O1—C5—C4122.9 (3)O4—N3—O3121.5 (3)
O1—C5—C7118.0 (3)O4—N3—O2121.9 (3)
C4—C5—C7119.1 (3)O3—N3—O2116.6 (3)
C2—C6—C7122.2 (3)C5—O1—Ni1113.40 (19)
C2—C6—H6118.9C5—O1—Ni1i125.52 (19)
C7—C6—H6118.9Ni1—O1—Ni1i95.83 (9)
C6—C7—C5119.4 (3)N3—O2—Ni190.8 (2)
C6—C7—C8121.7 (3)N3—O3—Ni193.11 (19)
C5—C7—C8118.7 (3)
C6—C2—C3—C4−3.1 (5)O2—Ni1—N2—C1132.8 (2)
C1—C2—C3—C4176.2 (4)Ni1i—Ni1—N2—C11−101.34 (19)
C2—C3—C4—C5−3.7 (5)O1—Ni1—N2—C1092.5 (2)
C2—C3—C4—C11i175.9 (3)O1i—Ni1—N2—C10176.3 (2)
C3—C4—C5—O1−172.4 (3)N1—Ni1—N2—C101.1 (2)
C11i—C4—C5—O18.1 (5)O3—Ni1—N2—C10−95.6 (4)
C3—C4—C5—C77.8 (5)O2—Ni1—N2—C10−91.1 (2)
C11i—C4—C5—C7−171.7 (3)Ni1i—Ni1—N2—C10134.7 (2)
C3—C2—C6—C75.8 (5)C4—C5—O1—Ni1−120.4 (3)
C1—C2—C6—C7−173.5 (4)C7—C5—O1—Ni159.4 (3)
C2—C6—C7—C5−1.7 (5)C4—C5—O1—Ni1i−4.0 (4)
C2—C6—C7—C8173.8 (3)C7—C5—O1—Ni1i175.8 (2)
O1—C5—C7—C6174.9 (3)O1i—Ni1—O1—C5132.9 (2)
C4—C5—C7—C6−5.2 (5)N2—Ni1—O1—C5−139.9 (2)
O1—C5—C7—C8−0.7 (5)N1—Ni1—O1—C5−53.0 (2)
C4—C5—C7—C8179.1 (3)O3—Ni1—O1—C542.4 (2)
C6—C7—C8—N1123.4 (4)O2—Ni1—O1—C549.8 (3)
C5—C7—C8—N1−61.0 (4)Ni1i—Ni1—O1—C5132.9 (2)
N1—C9—C10—N2−48.9 (4)O1i—Ni1—O1—Ni1i0.0
C7—C8—N1—C9166.4 (3)N2—Ni1—O1—Ni1i87.17 (11)
C7—C8—N1—Ni149.9 (4)N1—Ni1—O1—Ni1i174.08 (11)
C10—C9—N1—C8−76.0 (4)O3—Ni1—O1—Ni1i−90.44 (10)
C10—C9—N1—Ni146.1 (3)O2—Ni1—O1—Ni1i−83.0 (3)
N2—Ni1—N1—C896.4 (2)O4—N3—O2—Ni1−179.5 (4)
O3—Ni1—N1—C8−100.4 (2)O3—N3—O2—Ni1−0.4 (3)
O2—Ni1—N1—C8−160.1 (2)O1—Ni1—O2—N3−8.2 (4)
Ni1i—Ni1—N1—C84.7 (3)O1i—Ni1—O2—N3−89.6 (2)
N2—Ni1—N1—C9−25.8 (2)N2—Ni1—O2—N3−178.2 (2)
O3—Ni1—N1—C9137.3 (2)N1—Ni1—O2—N394.4 (2)
O2—Ni1—N1—C977.6 (2)O3—Ni1—O2—N30.24 (19)
Ni1i—Ni1—N1—C9−117.5 (2)Ni1i—Ni1—O2—N3−71.0 (2)
C4i—C11—N2—C10−169.3 (3)O4—N3—O3—Ni1179.5 (4)
C4i—C11—N2—Ni171.2 (3)O2—N3—O3—Ni10.4 (3)
C9—C10—N2—C11−94.0 (4)O1—Ni1—O3—N3176.7 (2)
C9—C10—N2—Ni124.3 (4)O1i—Ni1—O3—N392.3 (2)
O1—Ni1—N2—C11−143.54 (19)N2—Ni1—O3—N34.8 (5)
O1i—Ni1—N2—C11−59.7 (2)N1—Ni1—O3—N3−90.7 (2)
N1—Ni1—N2—C11125.1 (2)O2—Ni1—O3—N3−0.24 (19)
O3—Ni1—N2—C1128.3 (5)Ni1i—Ni1—O3—N3134.08 (19)
Symmetry codes: (i) −x+2/3, −y+1/3, −z+1/3.
Table 1
Selected geometric parameters (Å) top
Ni1—O12.000 (2)Ni1—N12.054 (3)
Ni1—O1i2.006 (2)Ni1—O32.134 (3)
Ni1—N22.038 (3)Ni1—O22.183 (3)
Symmetry codes: (i) −x+2/3, −y+1/3, −z+1/3.
Acknowledgements top

We thank the National Natural Science Foundation of China (grant No. 20471014), the Program for New Century Excellent Talents in Chinese Universities (grant No. NCET-05–0320), the Fok Ying Tung Education Foundation and the Analysis and Testing Foundation of Northeast Normal University for support.

references
References top

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