[μ-10,21-Dimethyl-3,6,14,17-tetra­aza­tricyclo­[17.3.1.1^8,12]tetra­cosa-1(23),8(24),9,11,19,21-hexa­ene-23,24-diolato-κ⁸ N ³,N ⁶,O ²³,O ²⁴:N ¹⁴,N ¹⁷,O ²³,O ²⁴]bis­[(nitrato-κ² O,O′)nickel(II)]

Abstract

In the title centrosymmetric dinuclear nickel complex, [Ni₂(C₂₂H₃₀N₄O₂)(NO₃)₂], each of the two Ni^II 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.

Related literature

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

Crystal data

• [Ni₂(C₂₂H₃₀N₄O₂)(NO₃)₂]

• M _r = 623.90

• Trigonal,

• a = 25.020 (5) Å

• c = 10.616 (5) Å

• V = 5755 (3) ų

• Z = 9

• Mo Kα radiation

• μ = 1.53 mm⁻¹

• T = 293 K

• 0.40 × 0.30 × 0.25 mm

Data collection

• Bruker APEX CCD diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.495, T _max = 0.609 (expected range = 0.554–0.682)

• 9432 measured reflections

• 2213 independent reflections

• 1745 reflections with I > 2σ(I)

• R _int = 0.107

Refinement

• R[F ² > 2σ(F ²)] = 0.043

• wR(F ²) = 0.117

• S = 1.03

• 2213 reflections

• 178 parameters

• 1 restraint

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

• Δρ_max = 1.06 e Å⁻³

• Δρ_min = −0.35 e Å⁻³

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

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected bond lengths (Å).

Ni1—O1	2.000 (2)
Ni1—O1i	2.006 (2)
Ni1—N2	2.038 (3)
Ni1—N1	2.054 (3)
Ni1—O3	2.134 (3)
Ni1—O2	2.183 (3)

Symmetry code: (i) .

supplementary crystallographic information

Comment

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 Ni^II 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).

Experimental

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

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 U_iso = 1.2(1.5 for methyl)U_eq(C). The imino H atoms were located in a difference Fourier map and refined with U_iso(H) = 0.128 Ų. The highest residual electron density was found 1.03Å from Ni1 and the deepest hole 0.76 Å from Ni1.

Figures

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.]

Crystal data

[Ni2(C22H30N4O2)(NO3)2]	Dx = 1.620 Mg m−3
Mr = 623.90	Mo Kα radiation, λ = 0.71069 Å
Trigonal, R3	Cell parameters from 3000 reflections
Hall symbol: -R 3	θ = 2.4–28.4°
a = 25.020 (5) Å	µ = 1.53 mm−1
c = 10.616 (5) Å	T = 293 K
V = 5755 (3) Å3	Block, green
Z = 9	0.40 × 0.30 × 0.25 mm
F(000) = 2916

Data collection

Bruker APEX CCD diffractometer	2213 independent reflections
Radiation source: fine-focus sealed tube	1745 reflections with I > 2σ(I)
graphite	Rint = 0.107
φ and ω scans	θmax = 24.9°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −15→29
Tmin = 0.495, Tmax = 0.609	k = −29→23
9432 measured reflections	l = −12→12

Refinement

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.117	H 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 parameters	Δρmax = 1.06 e Å−3
1 restraint	Δρmin = −0.35 e Å−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Ni1	0.355561 (19)	0.13534 (2)	0.25357 (4)	0.03150 (19)
C1	0.04882 (19)	−0.0620 (2)	0.3314 (4)	0.0658 (13)
H1A	0.0488	−0.0770	0.4147	0.099*
H1B	0.0372	−0.0948	0.2717	0.099*
H1C	0.0199	−0.0475	0.3276	0.099*
C2	0.11262 (17)	−0.00973 (17)	0.3005 (3)	0.0431 (9)
C3	0.12561 (16)	0.01995 (17)	0.1862 (3)	0.0410 (9)
H3	0.0947	0.0056	0.1255	0.049*
C4	0.18315 (15)	0.07079 (16)	0.1570 (3)	0.0353 (8)
C5	0.22847 (15)	0.09460 (15)	0.2510 (3)	0.0347 (8)
C6	0.16018 (17)	0.01062 (17)	0.3868 (3)	0.0446 (9)
H6	0.1536	−0.0111	0.4617	0.054*
C7	0.21738 (16)	0.06230 (16)	0.3656 (3)	0.0374 (8)
C8	0.26663 (17)	0.08766 (18)	0.4652 (3)	0.0443 (9)
H8A	0.2746	0.1284	0.4892	0.053*
H8B	0.2515	0.0614	0.5391	0.053*
C9	0.37778 (18)	0.13034 (17)	0.5104 (3)	0.0430 (9)
H9A	0.4112	0.1221	0.4949	0.052*
H9B	0.3646	0.1196	0.5972	0.052*
C10	0.40046 (18)	0.19842 (17)	0.4892 (3)	0.0421 (9)
H10A	0.3704	0.2085	0.5224	0.050*
H10B	0.4390	0.2230	0.5342	0.050*
C11	0.47350 (15)	0.23666 (16)	0.3077 (3)	0.0383 (8)
H11A	0.4824	0.2031	0.3091	0.046*
H11B	0.5022	0.2685	0.3644	0.046*
N1	0.32528 (14)	0.09201 (14)	0.4244 (3)	0.0377 (7)
N2	0.41009 (14)	0.21377 (13)	0.3532 (2)	0.0355 (7)
N3	0.37310 (14)	0.05216 (15)	0.1596 (3)	0.0479 (8)
O1	0.28230 (10)	0.14687 (10)	0.23716 (19)	0.0342 (5)
O2	0.41509 (12)	0.09599 (12)	0.2220 (2)	0.0455 (6)
O3	0.32302 (12)	0.05220 (12)	0.1480 (2)	0.0459 (6)
O4	0.38022 (15)	0.01126 (15)	0.1141 (4)	0.0853 (11)
HN1	0.320 (3)	0.055 (3)	0.423 (6)	0.128*
HN2	0.401 (3)	0.242 (2)	0.336 (6)	0.128*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Ni1	0.0299 (3)	0.0299 (3)	0.0353 (3)	0.0154 (2)	−0.00202 (16)	0.00065 (16)
C1	0.041 (3)	0.060 (3)	0.081 (3)	0.014 (2)	0.014 (2)	0.004 (2)
C2	0.037 (2)	0.035 (2)	0.052 (2)	0.0137 (17)	0.0119 (16)	−0.0027 (16)
C3	0.033 (2)	0.038 (2)	0.055 (2)	0.0200 (18)	−0.0023 (16)	−0.0069 (16)
C4	0.0299 (19)	0.0322 (19)	0.0451 (18)	0.0165 (16)	0.0011 (14)	−0.0002 (14)
C5	0.0322 (19)	0.033 (2)	0.0424 (18)	0.0193 (17)	0.0038 (14)	−0.0001 (14)
C6	0.044 (2)	0.042 (2)	0.049 (2)	0.022 (2)	0.0114 (17)	0.0067 (16)
C7	0.037 (2)	0.037 (2)	0.0402 (18)	0.0193 (17)	0.0053 (15)	0.0017 (14)
C8	0.043 (2)	0.051 (2)	0.0380 (18)	0.024 (2)	0.0040 (15)	0.0054 (16)
C9	0.047 (2)	0.045 (2)	0.0366 (18)	0.0226 (19)	−0.0053 (15)	0.0029 (15)
C10	0.048 (2)	0.043 (2)	0.0359 (18)	0.0227 (19)	−0.0046 (15)	−0.0049 (15)
C11	0.033 (2)	0.034 (2)	0.049 (2)	0.0181 (17)	−0.0105 (15)	−0.0059 (15)
N1	0.0404 (18)	0.0370 (18)	0.0381 (14)	0.0211 (16)	−0.0010 (12)	0.0024 (13)
N2	0.0366 (17)	0.0327 (17)	0.0383 (15)	0.0182 (15)	−0.0035 (12)	−0.0001 (12)
N3	0.0349 (19)	0.040 (2)	0.067 (2)	0.0180 (16)	−0.0012 (15)	−0.0111 (16)
O1	0.0289 (13)	0.0311 (13)	0.0408 (12)	0.0137 (11)	−0.0007 (10)	0.0025 (10)
O2	0.0341 (14)	0.0377 (15)	0.0634 (16)	0.0171 (13)	−0.0070 (12)	−0.0076 (12)
O3	0.0329 (15)	0.0434 (16)	0.0570 (15)	0.0159 (13)	−0.0059 (11)	−0.0075 (11)
O4	0.058 (2)	0.062 (2)	0.139 (3)	0.0324 (18)	−0.0003 (19)	−0.048 (2)

Geometric parameters (Å, °)

Ni1—O1	2.000 (2)	C7—C8	1.502 (5)
Ni1—O1i	2.006 (2)	C8—N1	1.481 (5)
Ni1—N2	2.038 (3)	C8—H8A	0.9700
Ni1—N1	2.054 (3)	C8—H8B	0.9700
Ni1—O3	2.134 (3)	C9—N1	1.489 (4)
Ni1—O2	2.183 (3)	C9—C10	1.519 (5)
Ni1—Ni1i	2.9737 (10)	C9—H9A	0.9700
C1—C2	1.510 (5)	C9—H9B	0.9700
C1—H1A	0.9600	C10—N2	1.483 (4)
C1—H1B	0.9600	C10—H10A	0.9700
C1—H1C	0.9600	C10—H10B	0.9700
C2—C3	1.374 (5)	C11—N2	1.473 (4)
C2—C6	1.382 (5)	C11—C4i	1.505 (5)
C3—C4	1.398 (5)	C11—H11A	0.9700
C3—H3	0.9300	C11—H11B	0.9700
C4—C5	1.400 (5)	N1—HN1	0.87 (6)
C4—C11i	1.505 (5)	N2—HN2	0.86 (6)
C5—O1	1.336 (4)	N3—O4	1.223 (4)
C5—C7	1.408 (5)	N3—O3	1.260 (4)
C6—C7	1.386 (5)	N3—O2	1.262 (4)
C6—H6	0.9300
O1—Ni1—O1i	84.17 (9)	N1—C8—C7	113.5 (3)
O1—Ni1—N2	97.29 (10)	N1—C8—H8A	108.9
O1i—Ni1—N2	87.95 (10)	C7—C8—H8A	108.9
O1—Ni1—N1	91.74 (10)	N1—C8—H8B	108.9
O1i—Ni1—N1	172.81 (10)	C7—C8—H8B	108.9
N2—Ni1—N1	86.72 (12)	H8A—C8—H8B	107.7
O1—Ni1—O3	99.46 (9)	N1—C9—C10	110.3 (3)
O1i—Ni1—O3	91.39 (10)	N1—C9—H9A	109.6
N2—Ni1—O3	163.09 (11)	C10—C9—H9A	109.6
N1—Ni1—O3	95.11 (11)	N1—C9—H9B	109.6
O1—Ni1—O2	158.83 (9)	C10—C9—H9B	109.6
O1i—Ni1—O2	92.93 (9)	H9A—C9—H9B	108.1
N2—Ni1—O2	103.57 (11)	N2—C10—C9	110.8 (3)
N1—Ni1—O2	92.99 (11)	N2—C10—H10A	109.5
O3—Ni1—O2	59.57 (10)	C9—C10—H10A	109.5
O1—Ni1—Ni1i	42.16 (6)	N2—C10—H10B	109.5
O1i—Ni1—Ni1i	42.01 (6)	C9—C10—H10B	109.5
N2—Ni1—Ni1i	93.51 (8)	H10A—C10—H10B	108.1
N1—Ni1—Ni1i	133.62 (9)	N2—C11—C4i	112.7 (3)
O3—Ni1—Ni1i	97.29 (7)	N2—C11—H11A	109.0
O2—Ni1—Ni1i	131.44 (7)	C4i—C11—H11A	109.0
C2—C1—H1A	109.5	N2—C11—H11B	109.0
C2—C1—H1B	109.5	C4i—C11—H11B	109.0
H1A—C1—H1B	109.5	H11A—C11—H11B	107.8
C2—C1—H1C	109.5	C8—N1—C9	113.0 (3)
H1A—C1—H1C	109.5	C8—N1—Ni1	112.8 (2)
H1B—C1—H1C	109.5	C9—N1—Ni1	103.2 (2)
C3—C2—C6	117.3 (3)	C8—N1—HN1	108 (4)
C3—C2—C1	121.5 (4)	C9—N1—HN1	108 (4)
C6—C2—C1	121.2 (4)	Ni1—N1—HN1	112 (4)
C2—C3—C4	123.0 (3)	C11—N2—C10	115.1 (3)
C2—C3—H3	118.5	C11—N2—Ni1	106.0 (2)
C4—C3—H3	118.5	C10—N2—Ni1	108.2 (2)
C3—C4—C5	118.4 (3)	C11—N2—HN2	107 (4)
C3—C4—C11i	118.1 (3)	C10—N2—HN2	110 (4)
C5—C4—C11i	123.5 (3)	Ni1—N2—HN2	110 (4)
O1—C5—C4	122.9 (3)	O4—N3—O3	121.5 (3)
O1—C5—C7	118.0 (3)	O4—N3—O2	121.9 (3)
C4—C5—C7	119.1 (3)	O3—N3—O2	116.6 (3)
C2—C6—C7	122.2 (3)	C5—O1—Ni1	113.40 (19)
C2—C6—H6	118.9	C5—O1—Ni1i	125.52 (19)
C7—C6—H6	118.9	Ni1—O1—Ni1i	95.83 (9)
C6—C7—C5	119.4 (3)	N3—O2—Ni1	90.8 (2)
C6—C7—C8	121.7 (3)	N3—O3—Ni1	93.11 (19)
C5—C7—C8	118.7 (3)
C6—C2—C3—C4	−3.1 (5)	O2—Ni1—N2—C11	32.8 (2)
C1—C2—C3—C4	176.2 (4)	Ni1i—Ni1—N2—C11	−101.34 (19)
C2—C3—C4—C5	−3.7 (5)	O1—Ni1—N2—C10	92.5 (2)
C2—C3—C4—C11i	175.9 (3)	O1i—Ni1—N2—C10	176.3 (2)
C3—C4—C5—O1	−172.4 (3)	N1—Ni1—N2—C10	1.1 (2)
C11i—C4—C5—O1	8.1 (5)	O3—Ni1—N2—C10	−95.6 (4)
C3—C4—C5—C7	7.8 (5)	O2—Ni1—N2—C10	−91.1 (2)
C11i—C4—C5—C7	−171.7 (3)	Ni1i—Ni1—N2—C10	134.7 (2)
C3—C2—C6—C7	5.8 (5)	C4—C5—O1—Ni1	−120.4 (3)
C1—C2—C6—C7	−173.5 (4)	C7—C5—O1—Ni1	59.4 (3)
C2—C6—C7—C5	−1.7 (5)	C4—C5—O1—Ni1i	−4.0 (4)
C2—C6—C7—C8	173.8 (3)	C7—C5—O1—Ni1i	175.8 (2)
O1—C5—C7—C6	174.9 (3)	O1i—Ni1—O1—C5	132.9 (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—C8	179.1 (3)	O3—Ni1—O1—C5	42.4 (2)
C6—C7—C8—N1	123.4 (4)	O2—Ni1—O1—C5	49.8 (3)
C5—C7—C8—N1	−61.0 (4)	Ni1i—Ni1—O1—C5	132.9 (2)
N1—C9—C10—N2	−48.9 (4)	O1i—Ni1—O1—Ni1i	0.0
C7—C8—N1—C9	166.4 (3)	N2—Ni1—O1—Ni1i	87.17 (11)
C7—C8—N1—Ni1	49.9 (4)	N1—Ni1—O1—Ni1i	174.08 (11)
C10—C9—N1—C8	−76.0 (4)	O3—Ni1—O1—Ni1i	−90.44 (10)
C10—C9—N1—Ni1	46.1 (3)	O2—Ni1—O1—Ni1i	−83.0 (3)
N2—Ni1—N1—C8	96.4 (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—C8	4.7 (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—C9	137.3 (2)	N1—Ni1—O2—N3	94.4 (2)
O2—Ni1—N1—C9	77.6 (2)	O3—Ni1—O2—N3	0.24 (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—Ni1	179.5 (4)
C4i—C11—N2—Ni1	71.2 (3)	O2—N3—O3—Ni1	0.4 (3)
C9—C10—N2—C11	−94.0 (4)	O1—Ni1—O3—N3	176.7 (2)
C9—C10—N2—Ni1	24.3 (4)	O1i—Ni1—O3—N3	92.3 (2)
O1—Ni1—N2—C11	−143.54 (19)	N2—Ni1—O3—N3	4.8 (5)
O1i—Ni1—N2—C11	−59.7 (2)	N1—Ni1—O3—N3	−90.7 (2)
N1—Ni1—N2—C11	125.1 (2)	O2—Ni1—O3—N3	−0.24 (19)
O3—Ni1—N2—C11	28.3 (5)	Ni1i—Ni1—O3—N3	134.08 (19)

Symmetry codes: (i) −x+2/3, −y+1/3, −z+1/3.