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The title compounds, bis­(di­methyl­form­amide)-1κO,3κO-bis{μ-2,2′-[2,2′-di­methyl­propane-1,3-diyl­bis­(nitrilo­methylidyne)]­diphenolato}-1κ4N,N′,O,O′:2κ2O,O′;2κ2O,O′:3κ4N,N′,O,O′-di-μ-nitrito-1:2κ2N:O;2:3κ2O:N-dinickel(II)­cobalt(II), [CoNi2(NO2)2(C19H22N2O2)2(C3H7NO)2], (I), -copper(II), [CuNi2(NO2)2(C19H22N2O2)2(C3H7NO)2], (II), and -manganese(II), [MnNi2(NO2)2(C19H22N2O2)2(C3H7NO)2], (III), consist of centrosymmetric linear heterotrinuclear metal complexes. The three complexes are isostructural. There are three bridges across the Ni–M atom pairs (M is Co2+, Cu2+ or Mn2+) in each complex, involving two O atoms of a μ-N,N′-bis­(salicyl­idene)-2,2′di­methyl-1,3-propane­diaminate ligand and an N—O moiety of a μ-nitrito group. The coordination sphere around each metal atom, whether Co2+, Cu2+, Mn2+ or Ni2+, can be described as distorted octahedral. The Ni...M distances are 2.9988 (5) Å in (I), 2.9872 (5) Å in (II) and 3.0624 (8) Å in (III).

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102001609/ob1055sup1.cif
Contains datablocks global, I, II, III

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102001609/ob1055Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102001609/ob1055IIsup3.hkl
Contains datablock II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102001609/ob1055IIIsup4.hkl
Contains datablock III

CCDC references: 182987; 182988; 182989

Comment top

The investigation of metal-metal multiple bonds in transition metal complexes is an important and interesting subject in inorganic chemistry. The synthesis and analysis of octahedrally coordinated tribridged Ni···M···Ni linear or nonlinear homo- or hetero- di- and trinuclear complexes have been the focus of several studies (Fukuhara et al., 1990; Gerli et al., 1991).

The study of the intramolecular magnetic interactions in this type of complex helps to improve the understanding of the magnetic exchange mechanism on a structural basis, using molecular orbital considerations. Therefore, the magnetic properties of such complexes are under investigation.

We have recently reported the structures of several dimers and trimers with SALPD2- ligands [SALPD2- is N,N'-bis(salicylidene)-1,3-propanediaminato] (Ülkü, Ercan et al., 1997; Ülkü, Tahir et al., 1997; Ercan & Atakol, 1998; Tahir et al., 1998; Arıcı et al., 1999; Atakol et al., 1999; Ercan et al., 1999). We report here the structures of three new linear heterotrinuclear Ni2+ complexes, (I), (II) and (III). \sch

The unit cells of the three title complexes contain two centrosymmetric trinuclear [M{Ni(NO2)(dmSALPD2-)(dmf)}2] molecules ((M is Co2+, Cu2+ or Mn2+, dm is dimethyl and dmf is dimethylformamide), with the central M2+ ions located on an inversion centre.

The Ni···M pairs in these complexes are linked by two O atoms of a dmSALPD2- ligand, and by an N and an O atom of a nitrite group. The coordination sphere around each of the Ni, Co, Cu and Mn atoms can be described as a polyhedron. The distortions of the coordination polyhedra around Ni and M from octahedral to trigonal prismatic have been calculated using the τ models of Muetterties & Guggenberger (1974) and Addison et al. (1984). The resulting values of τNi are 0.013 in (I), 0.017 in (II) and 0.020 in (III), indicating that the polyhedra are close to octahedral. The central M ions in the three complexes have octahedral coordination environments, with a total of six O atoms in their coordination spheres, four from the dmSALPD2- ligands in the equatorial planes [atoms O2, O3, O2i and O3i; symmetry code: (i) -x, -y, -z] and two from the bridging nitrito groups in the apical positions. The M—O bond distances range from 2.0537 (16) to 2.160 (2) Å in (I), from 2.040 (3) to 2.107 (3) Å in (II) and from 2.1274 (16) to 2.270 (3) Å in (III).

The two terminal Ni2+ ions in the complexes, linked by the inversion centre, also have distorted octahedral coordination environments, each involving two O and two N atoms from a dmSALPD2- ligand, with the apical positions of the octahedron occupied by the N and O atoms from a nitrito group and a dmf ligand, respectively. The Ni—N and Ni—O bond distance ranges are 2.007 (2)–2.113 (3) and 2.0008 (18)–2.169 (2) Å, respectively, in (I), 2.011 (3)–2.131 (4) and 2.004 (3)–2.186 (3) Å, respectively, in (II) and 2.017 (2)–2.125 (3) and 2.0167 (18)–2.169 (2) Å, respectively, in (III).

The Ni2+ ions lie only 0.024 (2) Å in (I), 0.031 (2) Å in (II) and 0.0383 (18) Å in (III) out of the equatorial plane defined by O2/O3/N1/N2. The dihedral angles between this equatorial plane around the Ni2+ ions and the equatorial plane defined by O2/O3/O2i/O3i around the M2+ ions are 30.88 (8)° in (I), 31.40 (2)° in (II) and 31.83 (2)° in (III). The Ni—O—M—O four-membered bridging ring is not planar but is roof-shaped. The chelate rings formed by Ni/N1/C8—C10/N2 in all three compounds have a boat conformation. The distances of the two para positioned boat atoms, Ni and C9, from the best plane of the other four atoms (N1/C8/C10/N2) are -0.066 (2) and -0.201 (2) Å, respectively, in (I), -0.075 (2) and -0.181 (15) Å, respectively, in (II), and -0.0768 (18) and -0.167 (16) Å, respectively, in (III).

Table 4 compares the structural data for seven similar complexes, the dihedral angles between the two equatorial planes of neighbouring polyhedra (ϕ), and between the Ni—O—M—O bridging plane and the coordination plane (O2/O3/O2i/O3i) around the central atom (κ), along with the related distance ranges and bridging angles.

The stereochemistry of the bridging groups around the metal atoms is very important for Ni···M distances. If the µ bridging group across Ni···M is an acetato group, the µ bridge consists of coordination through three atoms. In this instance, the Ni···M distance is usually greater than 3.0 Å, as seen in Table 4, compounds (IV)-(VI). If the bridging group is a nitrito group, the µ bridge consists of coordination through two atoms. In this instance, the N atom of a µ nitrito group can be directly coordinated to the metal atom and the Ni···M distance is less than that of the µ acetato complex. This is seen in Table 4 for compounds (I), (II), (III) and (VII), which have µ-nitrito groups instead of µ-acetato bridges, and the Ni···M distances are similar.

We conclude that the bridging angles and Ni···M distances seem to play a significant role in determining the strength and sign of the exchange coupling constant in distorted octahedrally coordinated Ni···M dimers and trimers.

Experimental top

N,N'-bis(salicylidene)-2,2'-dimethyl-1,3-propanediamine (1.410 g, 5 mmol) was dissolved in hot ethanol (50 ml). To this solution were added 20% ammonia solution (10 ml) and a solution of NiCl2·6H2O (1.185 g, 5 mmol) in hot water (30 ml). The resulting mixture was set aside for 2 h. The light-green nickel complex which formed was filtered and dried in an oven at 423 K for 3 h. This complex (0.367 g, 1 mmol) was dissolved in hot dimethylformamide (50 ml) and the temperature of the solution was increased to 383 K. A solution of CoCl2·6H2O (0.120 g, 0.5 mmol) for the Co complex, (I), CuCl2·2H2O (0.085 g, 0.5 mmol) for the Cu complex, (II), or MnCl2·4H2O (0.99 g, 0.5 mmol) for the Mn complex, (III), in hot MeOH (20 ml), and a solution of NaNO2 (0.069 g, 1 mmol) in hot water (5 ml), were added slowly to this solution. The resulting mixture was set aside for 1 d. The crystals formed were filtered and dried in air.

Refinement top

H atoms were placed geometrically from their parent atoms for H8A—H10B and H19A—H20C in (I), all H atoms in (II), and H19A—H20C in (III), and they were refined with a riding model, with Ueq(H) = 1.2Ueq(C). The positional parameters of the remaining H atoms were taken from difference maps and refined. The C—H bond lengths were 0.81 (3)–0.98 (3) Å in (I) and 0.86 (4)–1.02 (3) Å in (II).

Computing details top

For all compounds, data collection: CAD-4 EXPRESS (Enraf-Nonius, 1993); cell refinement: SHELXL97 (Sheldrick, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97; molecular graphics: PLATON (Spek, 2000); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. A view of the molecule of (I) with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii [symmetry code: (i) 2 - x, -y, -z]. Please check this is the correct symmetry code.
[Figure 2] Fig. 2. A view of the molecule of (II) with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii [symmetry code: (i) 2 - x, -y, -z]. Please check this is the correct symmetry code.
[Figure 3] Fig. 3. A view of the molecule of (III) with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii [symmetry code: (i) 2 - x, -y, -z]. Please check this is the correct symmetry code.
(I) [bis(dimethylformamide)-1κO,3κO-bis{µ-2,2'-[2,2'-dimethylpropane- 1,3-diylbis(nitrilomethylidyne)]diphenolato- 1κ4N,N',O,O':2κ2O,O';2κ2O,O':3κ4N,N',O,O'-di-µ-nitrito- 1:2κ2N:O;2:3κ2O:N-dinickel(II)]cobalt(II) top
Crystal data top
[CoNi2(NO2)2(C19H22N2O2)2(C3H7NO)2]F(000) = 1074
Mr = 1031.30Dx = 1.480 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 25 reflections
a = 10.942 (2) Åθ = 2.3–26.0°
b = 10.223 (1) ŵ = 1.23 mm1
c = 21.092 (2) ÅT = 299 K
β = 101.24 (1)°Prism, dark brown
V = 2314.1 (5) Å30.25 × 0.18 × 0.13 mm
Z = 2
Data collection top
Enraf-Nonius CAD-4
diffractometer
Rint = 0.030
ω/2θ scansθmax = 26.0°
Absorption correction: ψ-scan
empirical (using intensity measurements) (Fair, 1990)
h = 139
Tmin = 0.812, Tmax = 0.865k = 120
8277 measured reflectionsl = 2525
4548 independent reflections3 standard reflections every 120 min
3019 reflections with I > 2σ(I) intensity decay: 0.9%
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)] = 0.031Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.085H atoms treated by a mixture of independent and constrained refinement
S = 1.02 w = 1/[σ2(Fo2) + (0.0429P)2 + 0.4521P]
where P = (Fo2 + 2Fc2)/3
4548 reflections(Δ/σ)max = 0.049
346 parametersΔρmax = 0.30 e Å3
0 restraintsΔρmin = 0.27 e Å3
Crystal data top
[CoNi2(NO2)2(C19H22N2O2)2(C3H7NO)2]V = 2314.1 (5) Å3
Mr = 1031.30Z = 2
Monoclinic, P21/nMo Kα radiation
a = 10.942 (2) ŵ = 1.23 mm1
b = 10.223 (1) ÅT = 299 K
c = 21.092 (2) Å0.25 × 0.18 × 0.13 mm
β = 101.24 (1)°
Data collection top
Enraf-Nonius CAD-4
diffractometer
3019 reflections with I > 2σ(I)
Absorption correction: ψ-scan
empirical (using intensity measurements) (Fair, 1990)
Rint = 0.030
Tmin = 0.812, Tmax = 0.8653 standard reflections every 120 min
8277 measured reflections intensity decay: 0.9%
4548 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0310 restraints
wR(F2) = 0.085H atoms treated by a mixture of independent and constrained refinement
S = 1.02Δρmax = 0.30 e Å3
4548 reflectionsΔρmin = 0.27 e Å3
346 parameters
Special details top

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
C10.7374 (2)0.1165 (3)0.01305 (11)0.0343 (6)
C20.7751 (3)0.1600 (3)0.07677 (13)0.0443 (7)
C30.6927 (3)0.2168 (4)0.10956 (14)0.0554 (8)
C40.5679 (3)0.2306 (4)0.08127 (15)0.0572 (9)
C50.5292 (3)0.1865 (3)0.01973 (15)0.0497 (8)
C60.6103 (2)0.1310 (3)0.01640 (12)0.0380 (6)
C70.5561 (3)0.0868 (3)0.08138 (12)0.0393 (6)
C80.5366 (3)0.0090 (3)0.18772 (12)0.0470 (7)
H8A0.45020.02940.18750.056*
H8B0.54360.08520.19100.056*
C90.5729 (3)0.0722 (3)0.24754 (12)0.0448 (7)
C100.6976 (3)0.0194 (3)0.25826 (13)0.0509 (8)
H10A0.69410.07540.25840.061*
H10B0.70950.04720.30060.061*
C110.9018 (3)0.0987 (3)0.23105 (13)0.0457 (8)
C121.0210 (3)0.1407 (3)0.19433 (12)0.0431 (7)
C131.1045 (3)0.1944 (4)0.22998 (15)0.0621 (10)
C141.2170 (3)0.2442 (4)0.20059 (17)0.0698 (11)
C151.2502 (3)0.2411 (4)0.13426 (17)0.0578 (9)
C161.1732 (3)0.1851 (3)0.09762 (14)0.0465 (7)
C171.0578 (2)0.1329 (3)0.12626 (12)0.0376 (6)
C180.8330 (3)0.3322 (3)0.06480 (15)0.0522 (8)
C190.6636 (4)0.4792 (4)0.0707 (2)0.0912 (14)
H19A0.64200.55330.04720.109*
H19B0.60350.41090.07050.109*
H19C0.66410.50460.11450.109*
C200.8439 (6)0.4947 (5)0.0188 (2)0.117 (2)
H20A0.79370.56640.02830.140*
H20B0.92450.52650.01460.140*
H20C0.85320.43190.05330.140*
C210.5712 (3)0.2185 (4)0.24332 (17)0.0535 (9)
C220.4770 (4)0.0283 (5)0.30661 (17)0.0656 (11)
N10.6139 (2)0.0524 (2)0.12601 (10)0.0382 (5)
N20.8068 (2)0.0611 (2)0.20985 (10)0.0392 (5)
N30.8293 (2)0.1412 (3)0.09816 (11)0.0447 (6)
N40.7841 (3)0.4331 (3)0.04106 (12)0.0630 (8)
O10.78600 (19)0.2727 (2)0.11392 (9)0.0476 (5)
O20.81824 (16)0.06480 (19)0.01796 (8)0.0392 (4)
O30.98536 (16)0.07896 (19)0.09073 (8)0.0395 (4)
O41.08137 (19)0.17210 (19)0.05094 (8)0.0467 (5)
O50.7680 (2)0.2304 (3)0.12502 (11)0.0718 (7)
Ni0.80003 (3)0.06113 (4)0.115005 (14)0.03394 (11)
Co1.00000.00000.00000.03373 (14)
H20.858 (3)0.148 (3)0.0946 (12)0.040*
H30.719 (3)0.245 (3)0.1482 (14)0.040*
H40.510 (3)0.263 (3)0.1017 (13)0.040*
H50.456 (3)0.193 (3)0.0048 (13)0.040*
H70.465 (3)0.082 (3)0.0890 (12)0.040*
H110.903 (2)0.103 (3)0.2747 (13)0.040*
H131.081 (2)0.197 (3)0.2742 (13)0.040*
H141.271 (3)0.291 (3)0.2226 (13)0.040*
H151.318 (3)0.285 (3)0.1157 (12)0.040*
H161.196 (2)0.183 (3)0.0544 (13)0.040*
H180.908 (3)0.302 (3)0.0419 (13)0.040*
H21A0.624 (3)0.254 (3)0.2095 (14)0.040*
H21B0.501 (3)0.251 (3)0.2394 (13)0.040*
H21C0.592 (3)0.258 (3)0.2784 (14)0.040*
H22A0.495 (3)0.074 (3)0.3413 (14)0.040*
H22B0.479 (3)0.066 (3)0.3126 (13)0.040*
H22C0.409 (3)0.051 (3)0.3012 (14)0.040*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0386 (15)0.0370 (15)0.0289 (12)0.0009 (11)0.0102 (11)0.0030 (12)
C20.0400 (17)0.060 (2)0.0334 (14)0.0014 (13)0.0078 (12)0.0095 (15)
C30.058 (2)0.075 (2)0.0347 (15)0.0117 (16)0.0134 (14)0.0074 (18)
C40.056 (2)0.072 (2)0.0496 (18)0.0017 (16)0.0268 (16)0.0199 (18)
C50.0371 (17)0.069 (2)0.0448 (16)0.0061 (15)0.0114 (13)0.0128 (16)
C60.0354 (15)0.0433 (16)0.0368 (13)0.0048 (12)0.0106 (11)0.0045 (13)
C70.0298 (14)0.0478 (18)0.0397 (14)0.0039 (12)0.0052 (12)0.0027 (13)
C80.0412 (17)0.0590 (19)0.0372 (14)0.0014 (14)0.0013 (12)0.0091 (15)
C90.0398 (16)0.061 (2)0.0299 (13)0.0013 (13)0.0029 (11)0.0033 (14)
C100.0551 (19)0.065 (2)0.0289 (13)0.0075 (13)0.0003 (13)0.0024 (16)
C110.0490 (18)0.063 (2)0.0257 (13)0.0039 (13)0.0099 (12)0.0086 (15)
C120.0393 (16)0.0584 (19)0.0334 (13)0.0073 (13)0.0111 (12)0.0084 (14)
C130.047 (2)0.103 (3)0.0381 (15)0.0144 (18)0.0145 (14)0.0034 (19)
C140.045 (2)0.109 (3)0.061 (2)0.032 (2)0.0217 (16)0.001 (2)
C150.0370 (18)0.071 (2)0.065 (2)0.0129 (18)0.0084 (16)0.0014 (17)
C160.0393 (17)0.059 (2)0.0397 (15)0.0082 (14)0.0050 (13)0.0033 (14)
C170.0336 (15)0.0444 (16)0.0359 (13)0.0065 (12)0.0100 (11)0.0099 (13)
C180.059 (2)0.0450 (19)0.0472 (17)0.0041 (15)0.0015 (15)0.0006 (16)
C190.107 (4)0.067 (3)0.112 (4)0.010 (2)0.051 (3)0.023 (3)
C200.196 (6)0.074 (3)0.075 (3)0.032 (3)0.016 (3)0.026 (3)
C210.045 (2)0.068 (2)0.0433 (17)0.0102 (17)0.0005 (15)0.0032 (17)
C220.061 (2)0.085 (3)0.0427 (18)0.0005 (18)0.0102 (17)0.008 (2)
N10.0358 (12)0.0467 (14)0.0302 (11)0.0019 (10)0.0016 (9)0.0021 (11)
N20.0418 (13)0.0479 (14)0.0266 (10)0.0015 (10)0.0036 (9)0.0049 (12)
N30.0508 (15)0.0462 (15)0.0390 (12)0.0043 (11)0.0137 (11)0.0005 (13)
N40.096 (2)0.0452 (16)0.0489 (15)0.0044 (13)0.0162 (15)0.0021 (16)
O10.0540 (13)0.0444 (12)0.0402 (10)0.0011 (9)0.0009 (9)0.0023 (10)
O20.0348 (10)0.0573 (12)0.0258 (8)0.0003 (8)0.0068 (7)0.0118 (9)
O30.0337 (10)0.0568 (12)0.0284 (8)0.0075 (8)0.0068 (7)0.0010 (9)
O40.0531 (13)0.0476 (12)0.0381 (10)0.0034 (9)0.0056 (9)0.0095 (10)
O50.0822 (19)0.0621 (16)0.0659 (15)0.0120 (13)0.0012 (13)0.0080 (14)
Ni0.03378 (19)0.0428 (2)0.02447 (16)0.00079 (15)0.00383 (12)0.00312 (16)
Co0.0333 (3)0.0436 (3)0.0240 (2)0.0037 (2)0.00486 (19)0.0083 (2)
Geometric parameters (Å, º) top
C1—O21.310 (3)C15—H150.89 (3)
C1—C21.399 (4)C16—C171.395 (4)
C1—C61.416 (4)C16—H160.90 (3)
C2—C31.368 (4)C17—O31.314 (3)
C2—H20.92 (3)C18—O11.225 (3)
C3—C41.387 (5)C18—N41.306 (4)
C3—H30.86 (3)C18—H180.92 (3)
C4—C51.361 (4)C19—N41.425 (5)
C4—H40.89 (3)C19—H19A0.9600
C5—C61.398 (4)C19—H19B0.9600
C5—H50.81 (3)C19—H19C0.9600
C6—C71.455 (4)C20—N41.449 (5)
C7—N11.282 (3)C20—H20A0.9600
C7—H70.98 (3)C20—H20B0.9600
C8—N11.475 (3)C20—H20C0.9600
C8—C91.537 (4)C21—H21A0.90 (3)
C8—H8A0.9700C21—H21B0.86 (3)
C8—H8B0.9700C21—H21C0.91 (3)
C9—C211.499 (5)C22—H22A0.92 (3)
C9—C101.525 (4)C22—H22B0.98 (3)
C9—C221.532 (4)C22—H22C0.81 (3)
C10—N21.475 (3)N1—Ni2.006 (2)
C10—H10A0.9700N2—Ni2.016 (2)
C10—H10B0.9700N3—O51.206 (3)
C11—N21.269 (4)N3—O4i1.292 (3)
C11—C121.446 (4)N3—Ni2.113 (3)
C11—H110.92 (3)O1—Ni2.169 (2)
C12—C131.404 (4)O2—Ni2.0178 (16)
C12—C171.416 (3)O2—Co2.0601 (18)
C13—C141.364 (5)O3—Ni2.0007 (18)
C13—H130.92 (3)O3—Co2.0542 (16)
C14—C151.376 (5)O4—Co2.161 (2)
C14—H140.95 (3)Ni—Co2.9988 (5)
C15—C161.375 (4)
O2—C1—C2120.4 (2)N4—C19—H19C109.5
O2—C1—C6121.6 (2)H19A—C19—H19C109.5
C2—C1—C6118.0 (2)H19B—C19—H19C109.5
C3—C2—C1121.4 (3)N4—C20—H20A109.5
C3—C2—H2122.8 (17)N4—C20—H20B109.5
C1—C2—H2115.8 (17)H20A—C20—H20B109.5
C2—C3—C4121.1 (3)N4—C20—H20C109.5
C2—C3—H3119.7 (19)H20A—C20—H20C109.5
C4—C3—H3119.2 (19)H20B—C20—H20C109.5
C5—C4—C3118.3 (3)C9—C21—H21A115.8 (18)
C5—C4—H4117.7 (18)C9—C21—H21B115 (2)
C3—C4—H4123.9 (18)H21A—C21—H21B102 (3)
C4—C5—C6122.8 (3)C9—C21—H21C112.8 (18)
C4—C5—H5117 (2)H21A—C21—H21C104 (3)
C6—C5—H5120 (2)H21B—C21—H21C106 (3)
C5—C6—C1118.5 (2)C9—C22—H22A106.3 (18)
C5—C6—C7117.0 (3)C9—C22—H22B111.6 (17)
C1—C6—C7124.5 (2)H22A—C22—H22B113 (2)
N1—C7—C6127.4 (3)C9—C22—H22C108 (2)
N1—C7—H7120.0 (15)H22A—C22—H22C108 (3)
C6—C7—H7112.6 (15)H22B—C22—H22C110 (3)
N1—C8—C9113.7 (2)C7—N1—C8116.8 (2)
N1—C8—H8A108.8C7—N1—Ni122.56 (18)
C9—C8—H8A108.8C8—N1—Ni120.64 (18)
N1—C8—H8B108.8C11—N2—C10116.9 (2)
C9—C8—H8B108.8C11—N2—Ni122.73 (19)
H8A—C8—H8B107.7C10—N2—Ni120.36 (19)
C21—C9—C10112.6 (3)O5—N3—Ni127.5 (2)
C21—C9—C22109.1 (3)C18—N4—C19120.4 (3)
C10—C9—C22105.5 (3)C18—N4—C20121.9 (4)
C21—C9—C8111.3 (3)C19—N4—C20117.5 (4)
C10—C9—C8110.8 (2)C18—O1—Ni119.04 (19)
C22—C9—C8107.4 (3)C1—O2—Ni124.84 (15)
N2—C10—C9115.0 (2)C1—O2—Co139.44 (15)
N2—C10—H10A108.5Ni—O2—Co94.67 (7)
C9—C10—H10A108.5C17—O3—Ni125.90 (15)
N2—C10—H10B108.5C17—O3—Co138.62 (16)
C9—C10—H10B108.5Ni—O3—Co95.38 (7)
H10A—C10—H10B107.5O3—Ni—N1171.51 (8)
N2—C11—C12128.1 (2)O3—Ni—N291.28 (8)
N2—C11—H11122.6 (17)N1—Ni—N296.78 (9)
C12—C11—H11109.4 (17)O3—Ni—O281.02 (7)
C13—C12—C17118.6 (3)N1—Ni—O290.89 (8)
C13—C12—C11116.3 (3)N2—Ni—O2172.30 (8)
C17—C12—C11125.1 (3)O3—Ni—N386.18 (9)
C14—C13—C12121.8 (3)N1—Ni—N395.33 (10)
C14—C13—H13119.8 (17)N2—Ni—N397.64 (9)
C12—C13—H13118.4 (17)O2—Ni—N382.29 (8)
C13—C14—C15119.3 (3)O3—Ni—O188.67 (8)
C13—C14—H14124.1 (16)N1—Ni—O188.46 (9)
C15—C14—H14116.2 (17)N2—Ni—O191.56 (8)
C16—C15—C14120.8 (3)O2—Ni—O187.93 (8)
C16—C15—H15120.8 (18)N3—Ni—O1169.55 (8)
C14—C15—H15117.9 (18)O3—Ni—Co43.00 (5)
C15—C16—C17121.2 (3)N1—Ni—Co130.43 (6)
C15—C16—H16120.4 (18)N2—Ni—Co129.81 (7)
C17—C16—H16118.4 (18)O2—Ni—Co43.21 (5)
O3—C17—C16120.6 (2)N3—Ni—Co66.25 (7)
O3—C17—C12121.2 (2)O1—Ni—Co103.96 (5)
C16—C17—C12118.2 (3)O3i—Co—O2101.24 (7)
O1—C18—N4125.5 (3)O3—Co—O278.76 (7)
O1—C18—H18117.7 (17)O3—Co—O495.34 (7)
N4—C18—H18116.8 (17)O2—Co—O496.84 (7)
N4—C19—H19A109.5O3—Co—Ni41.62 (5)
N4—C19—H19B109.5O2—Co—Ni42.12 (4)
H19A—C19—H19B109.5O4—Co—Ni113.42 (5)
O2—C1—C2—C3178.6 (3)C7—N1—Ni—N3102.1 (2)
C6—C1—C2—C31.0 (4)C8—N1—Ni—N379.8 (2)
C1—C2—C3—C41.5 (5)C7—N1—Ni—O168.2 (2)
C2—C3—C4—C50.2 (5)C8—N1—Ni—O1109.9 (2)
C3—C4—C5—C61.5 (5)C7—N1—Ni—Co38.9 (3)
C4—C5—C6—C12.0 (5)C8—N1—Ni—Co142.95 (18)
C4—C5—C6—C7179.4 (3)C11—N2—Ni—O315.9 (3)
O2—C1—C6—C5179.7 (3)C10—N2—Ni—O3165.7 (2)
C2—C1—C6—C50.7 (4)C11—N2—Ni—N1161.4 (2)
O2—C1—C6—C72.5 (4)C10—N2—Ni—N117.0 (2)
C2—C1—C6—C7177.9 (3)C11—N2—Ni—N3102.2 (3)
C5—C6—C7—N1168.3 (3)C10—N2—Ni—N379.4 (2)
C1—C6—C7—N114.4 (5)C11—N2—Ni—O172.8 (2)
N1—C8—C9—C2155.2 (3)C10—N2—Ni—O1105.6 (2)
N1—C8—C9—C1070.8 (3)C11—N2—Ni—Co36.9 (3)
N1—C8—C9—C22174.5 (3)C10—N2—Ni—Co144.72 (19)
C21—C9—C10—N255.5 (3)C1—O2—Ni—O3146.3 (2)
C22—C9—C10—N2174.4 (3)Co—O2—Ni—O324.04 (8)
C8—C9—C10—N269.8 (3)C1—O2—Ni—N131.1 (2)
N2—C11—C12—C13171.5 (3)Co—O2—Ni—N1158.55 (9)
N2—C11—C12—C177.7 (5)C1—O2—Ni—N3126.4 (2)
C17—C12—C13—C143.0 (6)Co—O2—Ni—N363.29 (9)
C11—C12—C13—C14176.3 (4)C1—O2—Ni—O157.3 (2)
C12—C13—C14—C150.5 (6)Co—O2—Ni—O1113.02 (8)
C13—C14—C15—C161.9 (6)C1—O2—Ni—Co170.3 (3)
C14—C15—C16—C171.7 (5)O5—N3—Ni—O3148.2 (3)
C15—C16—C17—O3179.6 (3)O5—N3—Ni—N140.1 (3)
C15—C16—C17—C120.9 (5)O5—N3—Ni—N257.4 (3)
C13—C12—C17—O3177.3 (3)O5—N3—Ni—O2130.3 (3)
C11—C12—C17—O33.4 (5)O5—N3—Ni—O1151.1 (4)
C13—C12—C17—C163.1 (5)O5—N3—Ni—Co172.3 (3)
C11—C12—C17—C16176.1 (3)C18—O1—Ni—O356.1 (2)
C6—C7—N1—C8178.9 (3)C18—O1—Ni—N1115.9 (3)
C6—C7—N1—Ni2.9 (4)C18—O1—Ni—N2147.3 (3)
C9—C8—N1—C7132.3 (3)C18—O1—Ni—O225.0 (2)
C9—C8—N1—Ni46.0 (3)C18—O1—Ni—N34.4 (6)
C12—C11—N2—C10178.2 (3)C18—O1—Ni—Co15.5 (3)
C12—C11—N2—Ni3.4 (5)C17—O3—Co—O2152.4 (3)
C9—C10—N2—C11135.1 (3)Ni—O3—Co—O223.79 (8)
C9—C10—N2—Ni43.4 (3)C17—O3—Co—O456.4 (3)
O1—C18—N4—C193.1 (5)Ni—O3—Co—O4119.73 (8)
O1—C18—N4—C20177.5 (4)C17—O3—Co—Ni176.2 (3)
N4—C18—O1—Ni140.0 (3)C1—O2—Co—O3144.2 (3)
C2—C1—O2—Ni155.3 (2)Ni—O2—Co—O323.55 (8)
C6—C1—O2—Ni24.3 (4)C1—O2—Co—O450.1 (3)
C2—C1—O2—Co9.7 (4)Ni—O2—Co—O4117.66 (8)
C6—C1—O2—Co170.67 (19)C1—O2—Co—Ni167.7 (3)
C16—C17—O3—Ni155.4 (2)N1—Ni—Co—O3172.55 (12)
C12—C17—O3—Ni24.2 (4)N2—Ni—Co—O331.67 (12)
C16—C17—O3—Co19.9 (4)O2—Ni—Co—O3143.84 (12)
C12—C17—O3—Co160.6 (2)N3—Ni—Co—O3111.43 (11)
C17—O3—Ni—N226.9 (2)O1—Ni—Co—O372.44 (10)
Co—O3—Ni—N2156.21 (9)O3—Ni—Co—O2143.84 (12)
C17—O3—Ni—O2152.7 (2)N1—Ni—Co—O228.71 (12)
Co—O3—Ni—O224.14 (8)N2—Ni—Co—O2175.51 (12)
C17—O3—Ni—N3124.5 (2)N3—Ni—Co—O2104.73 (11)
Co—O3—Ni—N358.64 (8)O1—Ni—Co—O271.40 (10)
C17—O3—Ni—O164.6 (2)O3—Ni—Co—O470.44 (10)
Co—O3—Ni—O1112.26 (8)N1—Ni—Co—O4102.11 (11)
C17—O3—Ni—Co176.9 (3)N2—Ni—Co—O4102.10 (11)
C7—N1—Ni—N2159.6 (2)O2—Ni—Co—O473.40 (10)
C8—N1—Ni—N218.6 (2)N3—Ni—Co—O4178.14 (9)
C7—N1—Ni—O219.7 (2)O1—Ni—Co—O42.01 (8)
C8—N1—Ni—O2162.2 (2)
Symmetry code: (i) x+2, y, z.
(II) [bis(dimethylformamide)-1κO,3κO-bis{µ-2,2'-[2,2'-dimethylpropane- 1,3-diylbis(nitrilomethylidyne)]diphenolato- 1κ4N,N',O,O':2κ2O,O';2κ2O,O':3κ4N,N',O,O'-di-µ-nitrito- 1:2κ2N:O;2:3κ2O:N-dinickel(II)]copper(II) top
Crystal data top
[CuNi2(NO2)2(C19H22N2O2)2(C3H7NO)2]F(000) = 1078
Mr = 1035.91Dx = 1.483 Mg m3
Monoclinic, P21/nCu Kα radiation, λ = 1.54180 Å
Hall symbol: -P 2ynCell parameters from 25 reflections
a = 10.9520 (12) Åθ = 4.3–74.2°
b = 10.2387 (13) ŵ = 2.02 mm1
c = 21.0884 (12) ÅT = 293 K
β = 101.252 (3)°Prism, blue green
V = 2319.3 (4) Å30.25 × 0.20 × 0.15 mm
Z = 2
Data collection top
Enraf-Nonius CAD-4
diffractometer
Rint = 0.046
ω/2θ scansθmax = 74.2°
Absorption correction: ψ-scan
empirical (using intensity measurements) (Fair, 1990)
h = 130
Tmin = 0.632, Tmax = 0.752k = 120
4867 measured reflectionsl = 2526
4626 independent reflections3 standard reflections every 120 min
3644 reflections with I > 2σ(I) intensity decay: 1.1%
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) = 0.159 w = 1/[σ2(Fo2) + (0.0962P)2 + 1.439P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
4626 reflectionsΔρmax = 0.44 e Å3
296 parametersΔρmin = 1.06 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997)
Primary atom site location: structure-invariant direct methodsExtinction coefficient: none
Crystal data top
[CuNi2(NO2)2(C19H22N2O2)2(C3H7NO)2]V = 2319.3 (4) Å3
Mr = 1035.91Z = 2
Monoclinic, P21/nCu Kα radiation
a = 10.9520 (12) ŵ = 2.02 mm1
b = 10.2387 (13) ÅT = 293 K
c = 21.0884 (12) Å0.25 × 0.20 × 0.15 mm
β = 101.252 (3)°
Data collection top
Enraf-Nonius CAD-4
diffractometer
3644 reflections with I > 2σ(I)
Absorption correction: ψ-scan
empirical (using intensity measurements) (Fair, 1990)
Rint = 0.046
Tmin = 0.632, Tmax = 0.7523 standard reflections every 120 min
4867 measured reflections intensity decay: 1.1%
4626 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0500 restraints
wR(F2) = 0.159H-atom parameters constrained
S = 1.04Δρmax = 0.44 e Å3
4626 reflectionsΔρmin = 1.06 e Å3
296 parameters
Special details top

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
C10.0592 (3)0.1320 (3)0.12558 (15)0.0380 (7)
C20.1750 (3)0.1842 (4)0.09629 (17)0.0471 (8)
H20.19960.18100.05150.057*
C30.2529 (3)0.2402 (4)0.1327 (2)0.0571 (10)
H30.32830.27610.11220.069*
C40.2199 (4)0.2434 (5)0.1996 (2)0.0667 (12)
H40.27350.27930.22410.080*
C50.1064 (4)0.1927 (5)0.22928 (19)0.0637 (11)
H50.08440.19430.27420.076*
C60.0229 (3)0.1385 (4)0.19334 (15)0.0451 (8)
C70.0960 (3)0.0965 (4)0.23058 (15)0.0477 (8)
H70.10330.09660.27530.057*
C80.3012 (3)0.0181 (4)0.25837 (16)0.0514 (9)
H8A0.30450.07660.25910.062*
H8B0.28970.04690.30060.062*
C90.4259 (3)0.0699 (4)0.24708 (16)0.0460 (8)
C100.4619 (3)0.0067 (4)0.18770 (16)0.0476 (8)
H10A0.54850.02660.18750.057*
H10B0.45460.08740.19110.057*
C110.4422 (3)0.0854 (3)0.08119 (16)0.0427 (7)
H110.52870.08260.09160.051*
C120.3875 (3)0.1297 (3)0.01584 (15)0.0384 (7)
C130.4696 (3)0.1855 (4)0.01981 (17)0.0499 (8)
H130.55360.19200.00090.060*
C140.4301 (4)0.2310 (4)0.08171 (18)0.0573 (10)
H140.48570.27020.10400.069*
C150.3050 (4)0.2172 (4)0.11039 (17)0.0553 (10)
H150.27730.24660.15250.066*
C160.2213 (3)0.1603 (4)0.07730 (15)0.0466 (8)
H160.13840.15110.09750.056*
C170.2606 (3)0.1164 (3)0.01341 (14)0.0357 (6)
C180.1666 (4)0.3322 (4)0.06460 (17)0.0517 (9)
H180.08980.30290.04230.062*
C190.1536 (7)0.4940 (6)0.0197 (3)0.108 (2)
H19A0.20280.56590.02980.162*
H19B0.07320.52520.01500.162*
H19C0.14390.43100.05410.162*
C200.3380 (5)0.4782 (5)0.0709 (3)0.0862 (16)
H20A0.35960.55250.04760.129*
H20B0.39770.40990.07020.129*
H20C0.33800.50280.11480.129*
C210.4273 (4)0.2176 (4)0.24303 (18)0.0526 (9)
H21A0.50690.24630.23580.079*
H21B0.41250.25410.28280.079*
H21C0.36330.24620.20790.079*
C220.5226 (4)0.0256 (5)0.30663 (18)0.0639 (11)
H22A0.52220.06800.30950.096*
H22B0.50200.06240.34510.096*
H22C0.60390.05480.30230.096*
Cu0.00000.00000.00000.0454 (2)
N10.1917 (3)0.0595 (3)0.20952 (12)0.0406 (6)
N20.3849 (3)0.0502 (3)0.12563 (13)0.0403 (6)
N30.1662 (3)0.1423 (3)0.09601 (14)0.0472 (7)
N40.2161 (4)0.4326 (3)0.04097 (16)0.0631 (9)
Ni0.19866 (5)0.06010 (5)0.11486 (2)0.03483 (18)
O10.2139 (2)0.2733 (3)0.11420 (11)0.0509 (6)
O20.0135 (2)0.0785 (2)0.08992 (10)0.0410 (5)
O30.1798 (2)0.0642 (2)0.01788 (10)0.0397 (5)
O40.0764 (2)0.1700 (2)0.04788 (11)0.0467 (6)
O50.2252 (3)0.2355 (3)0.12251 (15)0.0725 (9)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0344 (14)0.0459 (17)0.0346 (15)0.0076 (13)0.0091 (12)0.0098 (13)
C20.0413 (17)0.059 (2)0.0402 (17)0.0046 (15)0.0057 (14)0.0047 (15)
C30.0365 (17)0.074 (3)0.061 (2)0.018 (2)0.0095 (16)0.0040 (18)
C40.046 (2)0.100 (4)0.058 (2)0.026 (2)0.0205 (17)0.002 (2)
C50.049 (2)0.102 (3)0.0427 (19)0.019 (2)0.0154 (16)0.007 (2)
C60.0429 (17)0.061 (2)0.0330 (15)0.0054 (14)0.0103 (13)0.0071 (15)
C70.0497 (19)0.069 (2)0.0243 (14)0.0028 (14)0.0070 (13)0.0092 (17)
C80.052 (2)0.070 (2)0.0281 (15)0.0084 (15)0.0024 (14)0.0005 (18)
C90.0450 (17)0.059 (2)0.0294 (15)0.0011 (14)0.0053 (13)0.0016 (16)
C100.0450 (18)0.058 (2)0.0353 (17)0.0034 (15)0.0028 (14)0.0107 (16)
C110.0346 (15)0.053 (2)0.0382 (16)0.0026 (14)0.0026 (12)0.0021 (14)
C120.0361 (15)0.0468 (18)0.0325 (14)0.0040 (13)0.0072 (12)0.0051 (13)
C130.0414 (17)0.067 (2)0.0424 (17)0.0046 (16)0.0100 (14)0.0111 (16)
C140.056 (2)0.072 (3)0.048 (2)0.0030 (18)0.0216 (17)0.0175 (19)
C150.059 (2)0.074 (3)0.0334 (17)0.0063 (16)0.0099 (15)0.0080 (19)
C160.0444 (17)0.063 (2)0.0313 (15)0.0035 (15)0.0052 (13)0.0069 (16)
C170.0362 (15)0.0423 (16)0.0294 (14)0.0024 (12)0.0083 (11)0.0045 (13)
C180.060 (2)0.046 (2)0.0438 (19)0.0058 (15)0.0013 (16)0.0008 (17)
C190.169 (7)0.081 (4)0.068 (3)0.032 (3)0.007 (4)0.018 (4)
C200.096 (4)0.065 (3)0.105 (4)0.010 (3)0.039 (3)0.020 (3)
C210.0483 (19)0.060 (2)0.0444 (19)0.0058 (17)0.0028 (15)0.0021 (17)
C220.059 (2)0.084 (3)0.0380 (19)0.0033 (19)0.0161 (17)0.008 (2)
Cu0.0453 (4)0.0565 (5)0.0332 (4)0.0036 (3)0.0049 (3)0.0079 (3)
N10.0425 (14)0.0495 (16)0.0275 (12)0.0019 (11)0.0009 (10)0.0056 (12)
N20.0392 (13)0.0474 (16)0.0321 (13)0.0020 (11)0.0013 (10)0.0025 (12)
N30.0505 (16)0.0555 (18)0.0359 (14)0.0066 (13)0.0094 (12)0.0012 (14)
N40.095 (3)0.0467 (18)0.0472 (18)0.0022 (14)0.0115 (18)0.0017 (18)
Ni0.0350 (3)0.0447 (3)0.0236 (3)0.0007 (2)0.00273 (19)0.0031 (2)
O10.0596 (15)0.0497 (14)0.0376 (12)0.0020 (10)0.0047 (11)0.0041 (12)
O20.0374 (11)0.0581 (14)0.0269 (10)0.0083 (9)0.0052 (8)0.0029 (10)
O30.0350 (11)0.0566 (14)0.0270 (10)0.0001 (9)0.0048 (8)0.0117 (10)
O40.0506 (13)0.0489 (13)0.0389 (12)0.0014 (10)0.0047 (10)0.0066 (11)
O50.083 (2)0.0641 (19)0.0651 (18)0.0155 (15)0.0006 (16)0.0129 (16)
Geometric parameters (Å, º) top
C1—O21.316 (4)C15—H150.9300
C1—C21.404 (5)C16—C171.406 (4)
C1—C61.408 (4)C16—H160.9300
C2—C31.379 (5)C17—O31.316 (4)
C2—H20.9300C18—O11.230 (4)
C3—C41.386 (6)C18—N41.305 (5)
C3—H30.9300C18—H180.9300
C4—C51.379 (6)C19—N41.470 (6)
C4—H40.9300C19—H19A0.9600
C5—C61.410 (5)C19—H19B0.9600
C5—H50.9300C19—H19C0.9600
C6—C71.449 (5)C20—N41.439 (7)
C7—N11.273 (5)C20—H20A0.9600
C7—H70.9300C20—H20B0.9600
C8—N11.482 (4)C20—H20C0.9600
C8—C91.526 (5)C21—H21A0.9600
C8—H8A0.9700C21—H21B0.9600
C8—H8B0.9700C21—H21C0.9600
C9—C211.515 (6)C22—H22A0.9600
C9—C101.528 (5)C22—H22B0.9600
C9—C221.545 (4)C22—H22C0.9600
C10—N21.481 (4)Cu—O22.038 (2)
C10—H10A0.9700Cu—O32.040 (2)
C10—H10B0.9700Cu—O42.103 (2)
C11—N21.277 (4)Cu—Ni2.9872 (5)
C11—C121.463 (4)N1—Ni2.012 (3)
C11—H110.9300N2—Ni2.010 (3)
C12—C131.402 (5)N3—O51.224 (4)
C12—C171.413 (4)N3—O41.299 (4)
C13—C141.374 (5)N3—Ni2.127 (3)
C13—H130.9300Ni—O22.002 (2)
C14—C151.392 (5)Ni—O32.016 (2)
C14—H140.9300Ni—O12.190 (3)
C15—C161.384 (5)
O2—C1—C2120.2 (3)H19A—C19—H19C109.5
O2—C1—C6121.2 (3)H19B—C19—H19C109.5
C2—C1—C6118.7 (3)N4—C20—H20A109.5
C3—C2—C1121.1 (3)N4—C20—H20B109.5
C3—C2—H2119.4H20A—C20—H20B109.5
C1—C2—H2119.4N4—C20—H20C109.5
C2—C3—C4120.7 (4)H20A—C20—H20C109.5
C2—C3—H3119.7H20B—C20—H20C109.5
C4—C3—H3119.7C9—C21—H21A109.5
C5—C4—C3119.1 (4)C9—C21—H21B109.5
C5—C4—H4120.5H21A—C21—H21B109.5
C3—C4—H4120.5C9—C21—H21C109.5
C4—C5—C6121.7 (4)H21A—C21—H21C109.5
C4—C5—H5119.2H21B—C21—H21C109.5
C6—C5—H5119.2C9—C22—H22A109.5
C1—C6—C5118.7 (3)C9—C22—H22B109.5
C1—C6—C7125.6 (3)H22A—C22—H22B109.5
C5—C6—C7115.7 (3)C9—C22—H22C109.5
N1—C7—C6127.8 (3)H22A—C22—H22C109.5
N1—C7—H7116.1H22B—C22—H22C109.5
C6—C7—H7116.1O2—Cu—O379.00 (9)
N1—C8—C9114.8 (3)O2—Cu—O485.98 (9)
N1—C8—H8A108.6O3—Cu—O484.17 (9)
C9—C8—H8A108.6O2—Cu—Ni41.87 (6)
N1—C8—H8B108.6O3—Cu—Ni42.25 (6)
C9—C8—H8B108.6O4—Cu—Ni67.82 (6)
H8A—C8—H8B107.5C7—N1—C8116.9 (3)
C21—C9—C8112.0 (3)C7—N1—Ni122.6 (2)
C21—C9—C10111.7 (3)C8—N1—Ni120.5 (2)
C8—C9—C10111.3 (3)C11—N2—C10117.2 (3)
C21—C9—C22109.0 (3)C11—N2—Ni122.4 (2)
C8—C9—C22105.3 (3)C10—N2—Ni120.4 (2)
C10—C9—C22107.2 (3)O5—N3—O4116.0 (3)
N2—C10—C9113.8 (3)O5—N3—Ni128.3 (3)
N2—C10—H10A108.8O4—N3—Ni115.6 (2)
C9—C10—H10A108.8C18—N4—C20120.5 (4)
N2—C10—H10B108.8C18—N4—C19120.8 (4)
C9—C10—H10B108.8C20—N4—C19118.5 (5)
H10A—C10—H10B107.7O2—Ni—N2171.03 (10)
N2—C11—C12127.5 (3)O2—Ni—N191.63 (10)
N2—C11—H11116.2N2—Ni—N196.99 (11)
C12—C11—H11116.2O2—Ni—O380.43 (9)
C13—C12—C17119.0 (3)N2—Ni—O390.93 (10)
C13—C12—C11116.3 (3)N1—Ni—O3172.06 (10)
C17—C12—C11124.7 (3)O2—Ni—N385.34 (11)
C14—C13—C12122.1 (3)N2—Ni—N395.79 (12)
C14—C13—H13118.9N1—Ni—N398.35 (11)
C12—C13—H13118.9O3—Ni—N381.38 (10)
C13—C14—C15118.6 (3)O2—Ni—O188.81 (10)
C13—C14—H14120.7N2—Ni—O188.51 (11)
C15—C14—H14120.7N1—Ni—O191.55 (11)
C16—C15—C14121.1 (3)O3—Ni—O188.04 (9)
C16—C15—H15119.5N3—Ni—O1168.62 (10)
C14—C15—H15119.5O2—Ni—Cu42.79 (6)
C15—C16—C17120.6 (3)N2—Ni—Cu130.06 (8)
C15—C16—H16119.7N1—Ni—Cu129.88 (8)
C17—C16—H16119.7O3—Ni—Cu42.89 (6)
O3—C17—C16120.0 (3)N3—Ni—Cu65.11 (8)
O3—C17—C12121.3 (3)O1—Ni—Cu104.15 (6)
C16—C17—C12118.6 (3)C18—O1—Ni118.3 (2)
O1—C18—N4124.9 (4)C1—O2—Ni125.67 (19)
O1—C18—H18117.5C1—O2—Cu138.92 (19)
N4—C18—H18117.5Ni—O2—Cu95.34 (9)
N4—C19—H19A109.5C17—O3—Ni124.86 (18)
N4—C19—H19B109.5C17—O3—Cu139.22 (19)
H19A—C19—H19B109.5Ni—O3—Cu94.86 (9)
N4—C19—H19C109.5N3—O4—Cu111.3 (2)
O2—C1—C2—C3179.6 (3)O2i—Cu—Ni—O2180.0
C6—C1—C2—C30.4 (5)O3—Cu—Ni—O2143.44 (15)
C1—C2—C3—C41.6 (6)O4—Cu—Ni—O2109.97 (13)
C2—C3—C4—C51.6 (7)O2—Cu—Ni—N2172.49 (15)
C3—C4—C5—C60.4 (7)O3—Cu—Ni—N229.06 (15)
O2—C1—C6—C5177.7 (3)O4—Cu—Ni—N277.54 (13)
C2—C1—C6—C52.4 (5)O2—Cu—Ni—N132.01 (15)
O2—C1—C6—C73.8 (6)O3—Cu—Ni—N1175.45 (16)
C2—C1—C6—C7176.1 (4)O4—Cu—Ni—N177.96 (13)
C4—C5—C6—C12.4 (7)O2—Cu—Ni—O3143.44 (15)
C4—C5—C6—C7176.2 (4)O4—Cu—Ni—O3106.60 (13)
C1—C6—C7—N17.7 (7)O2—Cu—Ni—N3111.69 (14)
C5—C6—C7—N1170.9 (4)O3—Cu—Ni—N3104.88 (13)
N1—C8—C9—C2156.4 (4)O4—Cu—Ni—N31.72 (11)
N1—C8—C9—C1069.5 (4)O2—Cu—Ni—O172.30 (13)
N1—C8—C9—C22174.8 (3)O3—Cu—Ni—O171.14 (13)
C21—C9—C10—N254.9 (4)O4—Cu—Ni—O1177.73 (10)
C8—C9—C10—N271.1 (4)N4—C18—O1—Ni140.1 (3)
C22—C9—C10—N2174.3 (3)O2—Ni—O1—C1855.7 (3)
N2—C11—C12—C13168.6 (4)N2—Ni—O1—C18115.7 (3)
N2—C11—C12—C1713.2 (6)N1—Ni—O1—C18147.3 (3)
C11—C12—C13—C14180.0 (4)O3—Ni—O1—C1824.8 (3)
C15—C16—C17—O3179.1 (3)N3—Ni—O1—C183.3 (7)
C13—C12—C17—O3179.7 (3)Cu—Ni—O1—C1815.4 (3)
C11—C12—C17—C16178.3 (3)C2—C1—O2—Ni155.8 (3)
C6—C7—N1—C8178.5 (4)C6—C1—O2—Ni24.1 (4)
C6—C7—N1—Ni3.0 (6)C2—C1—O2—Cu20.3 (5)
C9—C8—N1—C7136.1 (4)C6—C1—O2—Cu159.8 (3)
C9—C8—N1—Ni42.4 (4)N1—Ni—O2—C126.6 (3)
C12—C11—N2—C10178.8 (3)O3—Ni—O2—C1153.1 (3)
C12—C11—N2—Ni4.0 (5)N3—Ni—O2—C1124.9 (3)
C9—C10—N2—C11131.5 (4)O1—Ni—O2—C164.9 (3)
C9—C10—N2—Ni45.7 (4)Cu—Ni—O2—C1177.4 (3)
O1—C18—N4—C203.7 (7)N1—Ni—O2—Cu155.99 (11)
O1—C18—N4—C19178.3 (5)O3—Ni—O2—Cu24.28 (10)
C11—N2—Ni—N1159.0 (3)N3—Ni—O2—Cu57.74 (11)
C10—N2—Ni—N118.1 (3)O1—Ni—O2—Cu112.49 (10)
C11—N2—Ni—O320.4 (3)O3—Cu—O2—C1152.7 (3)
C10—N2—Ni—O3162.5 (3)O4—Cu—O2—C1122.5 (3)
C11—N2—Ni—N3101.8 (3)O4i—Cu—O2—C157.5 (3)
C10—N2—Ni—N381.1 (3)Ni—Cu—O2—C1176.8 (4)
C11—N2—Ni—O167.6 (3)O3—Cu—O2—Ni24.08 (10)
C10—N2—Ni—O1109.5 (3)O4—Cu—O2—Ni60.75 (10)
C11—N2—Ni—Cu39.7 (3)C16—C17—O3—Ni155.2 (3)
C10—N2—Ni—Cu143.2 (2)C12—C17—O3—Ni24.9 (4)
C7—N1—Ni—O215.4 (3)C16—C17—O3—Cu9.8 (5)
C8—N1—Ni—O2166.1 (3)C12—C17—O3—Cu170.1 (2)
C7—N1—Ni—N2162.1 (3)O2—Ni—O3—C17146.0 (3)
C8—N1—Ni—N216.4 (3)N2—Ni—O3—C1731.6 (3)
C7—N1—Ni—N3100.9 (3)N3—Ni—O3—C17127.4 (3)
C8—N1—Ni—N380.6 (3)O1—Ni—O3—C1756.8 (3)
C7—N1—Ni—O173.4 (3)Cu—Ni—O3—C17170.2 (3)
C8—N1—Ni—O1105.0 (3)O2—Ni—O3—Cu24.23 (10)
C7—N1—Ni—Cu36.5 (3)N2—Ni—O3—Cu158.18 (11)
C8—N1—Ni—Cu145.0 (2)N3—Ni—O3—Cu62.46 (11)
O5—N3—Ni—O2147.6 (3)O1—Ni—O3—Cu113.35 (10)
O4—N3—Ni—O236.4 (2)O2i—Cu—O3—C1736.3 (3)
O5—N3—Ni—N241.3 (3)O2—Cu—O3—C17143.7 (3)
O4—N3—Ni—N2134.6 (2)O4—Cu—O3—C17129.2 (3)
O5—N3—Ni—N156.7 (3)Ni—Cu—O3—C17167.6 (4)
O4—N3—Ni—N1127.4 (2)O2—Cu—O3—Ni23.89 (10)
O5—N3—Ni—O3131.4 (3)O4—Cu—O3—Ni63.13 (10)
O4—N3—Ni—O344.6 (2)O5—N3—O4—Cu172.5 (2)
O5—N3—Ni—O1153.1 (5)Ni—N3—O4—Cu4.0 (3)
O4—N3—Ni—O122.8 (7)O2—Cu—O4—N341.7 (2)
O5—N3—Ni—Cu173.1 (3)O3—Cu—O4—N337.6 (2)
O4—N3—Ni—Cu2.86 (19)Ni—Cu—O4—N32.74 (18)
Symmetry code: (i) x, y, z.
(III) [bis(dimethylformamide)-1κO,3κO-bis{µ-2,2'-[2,2'-dimethylpropane- 1,3-diylbis(nitrilomethylidyne)]diphenolato- 1κ4N,N',O,O':2κ2O,O';2κ2O,O':3κ4N,N',O,O'-di-µ-nitrito- 1:2κ2N:O;2:3κ2O:N-dinickel(II)]manganese(II) top
Crystal data top
[MnNi2(NO2)2(C19H22N2O2)2(C3H7NO)2]F(000) = 1070
Mr = 1027.42Dx = 1.459 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 25 reflections
a = 11.009 (2) Åθ = 2.3–26.0°
b = 10.2060 (8) ŵ = 1.13 mm1
c = 21.216 (2) ÅT = 298 K
β = 101.247 (7)°Prism, light brown
V = 2338.0 (5) Å30.33 × 0.33 × 0.13 mm
Z = 2
Data collection top
Enraf-Nonius CAD-4
diffractometer
Rint = 0.019
ω/2θ scansθmax = 26.0°
Absorption correction: ψ-scan
empirical (using intensity measurements) (Fair, 1990)
h = 131
Tmin = 0.724, Tmax = 0.879k = 120
5026 measured reflectionsl = 2526
4589 independent reflections3 standard reflections every 120 min
3436 reflections with I > 2σ(I) intensity decay: 1.3%
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)] = 0.033Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.099H atoms treated by a mixture of independent and constrained refinement
S = 1.02 w = 1/[σ2(Fo2) + (0.0597P)2 + 0.7438P]
where P = (Fo2 + 2Fc2)/3
4589 reflections(Δ/σ)max = 0.004
359 parametersΔρmax = 0.41 e Å3
0 restraintsΔρmin = 0.54 e Å3
Crystal data top
[MnNi2(NO2)2(C19H22N2O2)2(C3H7NO)2]V = 2338.0 (5) Å3
Mr = 1027.42Z = 2
Monoclinic, P21/nMo Kα radiation
a = 11.009 (2) ŵ = 1.13 mm1
b = 10.2060 (8) ÅT = 298 K
c = 21.216 (2) Å0.33 × 0.33 × 0.13 mm
β = 101.247 (7)°
Data collection top
Enraf-Nonius CAD-4
diffractometer
3436 reflections with I > 2σ(I)
Absorption correction: ψ-scan
empirical (using intensity measurements) (Fair, 1990)
Rint = 0.019
Tmin = 0.724, Tmax = 0.8793 standard reflections every 120 min
5026 measured reflections intensity decay: 1.3%
4589 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0330 restraints
wR(F2) = 0.099H atoms treated by a mixture of independent and constrained refinement
S = 1.02Δρmax = 0.41 e Å3
4589 reflectionsΔρmin = 0.54 e Å3
359 parameters
Special details top

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
C10.0537 (2)0.1361 (3)0.12894 (12)0.0377 (5)
C20.1696 (3)0.1873 (3)0.10123 (14)0.0477 (7)
H20.189 (3)0.189 (3)0.0571 (15)0.057*
C30.2468 (3)0.2419 (4)0.13784 (16)0.0577 (8)
H30.323 (3)0.288 (3)0.1146 (13)0.049 (8)*
C40.2129 (3)0.2445 (4)0.20438 (17)0.0700 (10)
H40.271 (4)0.282 (4)0.2283 (18)0.084*
C50.1000 (3)0.1952 (4)0.23257 (15)0.0645 (9)
H50.077 (3)0.202 (4)0.2790 (17)0.077*
C60.0167 (2)0.1435 (3)0.19667 (12)0.0431 (6)
C70.1031 (3)0.1016 (3)0.23273 (12)0.0458 (7)
H70.106 (3)0.105 (3)0.2740 (15)0.055*
C80.3056 (3)0.0240 (4)0.25926 (13)0.0487 (7)
H8A0.294 (3)0.048 (3)0.3002 (17)0.058*
H8B0.310 (3)0.075 (3)0.2566 (15)0.058*
C90.4289 (3)0.0767 (3)0.24806 (12)0.0450 (6)
C100.4652 (3)0.0136 (3)0.18901 (13)0.0479 (7)
H10A0.451 (3)0.078 (3)0.1915 (15)0.057*
H10B0.549 (3)0.032 (3)0.1876 (15)0.057*
C110.4470 (2)0.0891 (3)0.08319 (13)0.0415 (6)
H110.538 (3)0.083 (3)0.0898 (14)0.050*
C120.3942 (2)0.1324 (3)0.01821 (12)0.0388 (5)
C130.4766 (3)0.1853 (3)0.01760 (14)0.0495 (7)
H130.560 (3)0.192 (3)0.0018 (14)0.059*
C140.4388 (3)0.2277 (3)0.07933 (15)0.0572 (8)
H140.500 (3)0.256 (3)0.1034 (16)0.069*
C150.3145 (3)0.2153 (4)0.10770 (14)0.0577 (8)
H150.288 (3)0.248 (3)0.1510 (17)0.069*
C160.2315 (3)0.1611 (3)0.07459 (13)0.0472 (7)
H160.146 (3)0.152 (3)0.0935 (14)0.057*
C170.2678 (2)0.1192 (3)0.01126 (11)0.0354 (5)
C180.1683 (3)0.3350 (3)0.06544 (15)0.0529 (7)
H180.092 (3)0.305 (3)0.0453 (16)0.063*
C190.3363 (5)0.4816 (4)0.0698 (2)0.0976 (15)
H19A0.35730.55550.04610.117*
H19B0.39580.41300.06940.117*
H19C0.33670.50730.11340.117*
C200.1559 (6)0.4952 (5)0.0187 (2)0.127 (2)
H20A0.20510.56710.02870.153*
H20B0.07570.52670.01440.153*
H20C0.14680.43140.05250.153*
C210.4306 (3)0.2252 (4)0.24425 (16)0.0551 (8)
H21A0.378 (3)0.253 (3)0.2115 (17)0.066*
H21B0.414 (3)0.265 (3)0.2812 (17)0.066*
H21C0.512 (3)0.261 (3)0.2405 (16)0.066*
C220.5263 (4)0.0339 (5)0.30714 (17)0.0660 (9)
H22A0.508 (4)0.087 (4)0.3416 (19)0.079*
H22B0.519 (4)0.053 (4)0.3123 (19)0.079*
H22C0.607 (4)0.064 (4)0.3034 (19)0.079*
N10.1969 (2)0.0648 (2)0.21077 (9)0.0385 (5)
N20.38940 (19)0.0566 (2)0.12700 (10)0.0372 (5)
N30.1776 (2)0.1397 (2)0.10145 (11)0.0478 (6)
N40.2163 (3)0.4355 (3)0.04107 (14)0.0658 (8)
O10.21634 (18)0.27722 (19)0.11464 (9)0.0493 (5)
O20.01728 (16)0.08439 (19)0.09301 (8)0.0420 (4)
O30.18599 (16)0.06902 (18)0.01938 (8)0.0404 (4)
O40.08938 (19)0.17680 (19)0.05540 (9)0.0530 (5)
O50.2423 (3)0.2243 (2)0.12945 (12)0.0741 (7)
Ni0.20295 (3)0.06525 (3)0.116356 (14)0.03349 (11)
Mn0.00000.00000.00000.03603 (15)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0315 (12)0.0452 (14)0.0379 (13)0.0053 (11)0.0107 (10)0.0108 (11)
C20.0379 (14)0.0614 (18)0.0438 (15)0.0059 (14)0.0078 (12)0.0078 (13)
C30.0355 (15)0.074 (2)0.0638 (19)0.0156 (17)0.0108 (14)0.0033 (15)
C40.0432 (17)0.109 (3)0.062 (2)0.027 (2)0.0214 (15)0.0004 (18)
C50.0479 (17)0.106 (3)0.0431 (16)0.0173 (18)0.0176 (13)0.0084 (18)
C60.0384 (13)0.0585 (17)0.0342 (13)0.0073 (12)0.0116 (11)0.0078 (13)
C70.0489 (16)0.0640 (19)0.0259 (12)0.0041 (12)0.0103 (11)0.0083 (14)
C80.0489 (16)0.0641 (19)0.0301 (13)0.0068 (13)0.0004 (12)0.0009 (14)
C90.0406 (14)0.0596 (17)0.0304 (13)0.0004 (12)0.0039 (11)0.0020 (13)
C100.0414 (15)0.0590 (18)0.0396 (14)0.0049 (14)0.0013 (12)0.0078 (14)
C110.0312 (13)0.0494 (16)0.0428 (14)0.0054 (12)0.0048 (11)0.0030 (11)
C120.0361 (13)0.0440 (14)0.0373 (13)0.0045 (12)0.0095 (10)0.0043 (11)
C130.0389 (15)0.0637 (19)0.0478 (16)0.0062 (14)0.0134 (12)0.0121 (13)
C140.0556 (18)0.072 (2)0.0504 (17)0.0008 (16)0.0262 (14)0.0195 (16)
C150.0561 (18)0.080 (2)0.0396 (15)0.0091 (15)0.0151 (13)0.0077 (16)
C160.0420 (15)0.0646 (19)0.0350 (13)0.0028 (13)0.0077 (11)0.0081 (14)
C170.0357 (13)0.0404 (13)0.0313 (12)0.0046 (11)0.0100 (10)0.0064 (11)
C180.0606 (19)0.0424 (16)0.0508 (17)0.0031 (13)0.0009 (14)0.0029 (14)
C190.117 (4)0.067 (3)0.121 (4)0.012 (3)0.053 (3)0.025 (3)
C200.210 (7)0.085 (3)0.080 (3)0.038 (3)0.012 (4)0.027 (4)
C210.0477 (18)0.064 (2)0.0483 (17)0.0057 (15)0.0030 (14)0.0061 (15)
C220.058 (2)0.090 (3)0.0418 (17)0.0014 (18)0.0110 (15)0.009 (2)
N10.0405 (12)0.0476 (13)0.0265 (10)0.0019 (9)0.0041 (9)0.0060 (10)
N20.0345 (11)0.0444 (12)0.0308 (10)0.0037 (9)0.0022 (8)0.0004 (9)
N30.0568 (14)0.0453 (14)0.0449 (13)0.0039 (11)0.0187 (11)0.0006 (12)
N40.098 (2)0.0442 (15)0.0553 (16)0.0053 (12)0.0159 (15)0.0022 (15)
O10.0561 (12)0.0447 (11)0.0426 (10)0.0006 (9)0.0017 (9)0.0024 (9)
O20.0337 (9)0.0605 (12)0.0317 (9)0.0097 (8)0.0064 (7)0.0019 (8)
O30.0350 (9)0.0585 (12)0.0277 (8)0.0014 (8)0.0059 (7)0.0133 (8)
O40.0602 (13)0.0479 (11)0.0495 (11)0.0040 (9)0.0072 (10)0.0116 (10)
O50.0841 (17)0.0610 (15)0.0716 (15)0.0091 (13)0.0013 (13)0.0055 (13)
Ni0.03218 (17)0.04194 (19)0.02571 (16)0.00051 (13)0.00412 (12)0.00366 (14)
Mn0.0326 (3)0.0489 (3)0.0261 (3)0.0056 (2)0.0046 (2)0.0109 (2)
Geometric parameters (Å, º) top
Ni—Mn3.0624 (8)C15—H150.97 (3)
C1—O21.304 (3)C16—C171.392 (3)
C1—C21.398 (4)C16—H160.95 (3)
C1—C61.417 (3)C17—O31.313 (3)
C2—C31.376 (4)C18—O11.225 (3)
C2—H20.92 (3)C18—N41.306 (4)
C3—C41.388 (5)C18—H180.91 (3)
C3—H31.00 (3)C19—N41.422 (5)
C4—C51.366 (5)C19—H19A0.9600
C4—H40.97 (4)C19—H19B0.9600
C5—C61.404 (4)C19—H19C0.9600
C5—H50.97 (4)C20—N41.446 (5)
C6—C71.453 (4)C20—H20A0.9600
C7—N11.270 (4)C20—H20B0.9600
C7—H70.87 (3)C20—H20C0.9600
C8—N11.478 (3)C21—H21A0.86 (4)
C8—C91.521 (4)C21—H21B0.93 (4)
C8—H8A0.93 (3)C21—H21C0.99 (4)
C8—H8B1.02 (3)C22—H22A0.96 (4)
C9—C211.518 (5)C22—H22B0.90 (4)
C9—C101.529 (4)C22—H22C0.95 (4)
C9—C221.545 (4)N1—Ni2.017 (2)
C10—N21.480 (3)N2—Ni2.023 (2)
C10—H10A0.95 (3)N3—O51.200 (3)
C10—H10B0.95 (3)N3—O41.293 (3)
C11—N21.267 (3)N3—Ni2.125 (3)
C11—C121.457 (4)O1—Ni2.169 (2)
C11—H110.99 (3)O2—Ni2.0167 (18)
C12—C131.400 (4)O2—Mn2.1274 (16)
C12—C171.416 (3)O3—Ni2.0296 (16)
C13—C141.365 (4)O3—Mn2.1283 (17)
C13—H130.93 (3)Mn—O2i2.1274 (16)
C14—C151.389 (4)Mn—O3i2.1283 (17)
C14—H140.97 (3)Mn—O42.270 (3)
C15—C161.373 (4)
O2—C1—C2120.5 (2)H19A—C19—H19B109.5
O2—C1—C6121.8 (2)N4—C19—H19C109.5
C2—C1—C6117.7 (2)H19A—C19—H19C109.5
C3—C2—C1121.8 (3)H19B—C19—H19C109.5
C3—C2—H2121 (2)N4—C20—H20A109.5
C1—C2—H2117 (2)N4—C20—H20B109.5
C2—C3—C4120.6 (3)H20A—C20—H20B109.5
C2—C3—H3117.5 (16)N4—C20—H20C109.5
C4—C3—H3121.6 (16)H20A—C20—H20C109.5
C5—C4—C3118.6 (3)H20B—C20—H20C109.5
C5—C4—H4123 (2)C9—C21—H21A111 (2)
C3—C4—H4118 (2)C9—C21—H21B112 (2)
C4—C5—C6122.4 (3)H21A—C21—H21B109 (3)
C4—C5—H5117 (2)C9—C21—H21C113 (2)
C6—C5—H5120 (2)H21A—C21—H21C107 (3)
C5—C6—C1118.7 (3)H21B—C21—H21C104 (3)
C5—C6—C7116.5 (2)C9—C22—H22A104 (2)
C1—C6—C7124.8 (2)C9—C22—H22B108 (3)
N1—C7—C6127.8 (2)H22A—C22—H22B115 (4)
N1—C7—H7120 (2)C9—C22—H22C110 (2)
C6—C7—H7112 (2)H22A—C22—H22C102 (3)
N1—C8—C9114.7 (2)H22B—C22—H22C116 (3)
N1—C8—H8A110 (2)C7—N1—C8115.7 (2)
C9—C8—H8A110 (2)C7—N1—Ni123.39 (18)
N1—C8—H8B106.5 (18)C8—N1—Ni120.85 (18)
C9—C8—H8B106.9 (18)C11—N2—C10117.0 (2)
H8A—C8—H8B109 (3)C11—N2—Ni123.28 (18)
C21—C9—C8112.5 (3)C10—N2—Ni119.75 (18)
C21—C9—C10111.6 (3)O5—N3—O4116.7 (3)
C8—C9—C10111.3 (2)O5—N3—Ni125.9 (2)
C21—C9—C22108.2 (3)O4—N3—Ni117.27 (18)
C8—C9—C22105.8 (3)C18—N4—C19120.2 (3)
C10—C9—C22107.1 (3)C18—N4—C20121.7 (4)
N2—C10—C9114.3 (2)C19—N4—C20117.8 (4)
N2—C10—H10A105.6 (19)C18—O1—Ni118.33 (18)
C9—C10—H10A107 (2)C1—O2—Ni126.11 (15)
N2—C10—H10B107 (2)C1—O2—Mn138.63 (15)
C9—C10—H10B111 (2)Ni—O2—Mn95.25 (7)
H10A—C10—H10B112 (3)C17—O3—Ni124.94 (15)
N2—C11—C12127.5 (2)C17—O3—Mn139.50 (15)
N2—C11—H11121.2 (17)Ni—O3—Mn94.84 (7)
C12—C11—H11111.2 (17)O2—Ni—N190.91 (8)
C13—C12—C17118.8 (2)O2—Ni—N2171.73 (8)
C13—C12—C11116.7 (2)N1—Ni—N296.79 (8)
C17—C12—C11124.4 (2)O2—Ni—O382.00 (7)
C14—C13—C12122.3 (3)N1—Ni—O3172.91 (8)
C14—C13—H13119.5 (19)N2—Ni—O390.27 (8)
C12—C13—H13118.2 (19)O2—Ni—N387.79 (9)
C13—C14—C15118.5 (3)N1—Ni—N396.70 (9)
C13—C14—H14119 (2)N2—Ni—N394.26 (9)
C15—C14—H14122 (2)O3—Ni—N383.36 (8)
C16—C15—C14120.8 (3)O2—Ni—O188.18 (8)
C16—C15—H15121 (2)N1—Ni—O191.97 (8)
C14—C15—H15118 (2)N2—Ni—O188.56 (8)
C15—C16—C17121.5 (3)O3—Ni—O187.55 (7)
C15—C16—H16121.5 (18)N3—Ni—O1170.49 (8)
C17—C16—H16117.0 (18)O2—Mn—O2i180.0
O3—C17—C16120.1 (2)O2—Mn—O3i102.81 (7)
O3—C17—C12121.9 (2)O2i—Mn—O3i77.19 (7)
C16—C17—C12118.0 (2)O2—Mn—O377.19 (7)
O1—C18—N4125.1 (3)O2i—Mn—O3102.81 (7)
O1—C18—H18116 (2)O3i—Mn—O3180.0
N4—C18—H18119 (2)O3—Mn—O481.93 (7)
N4—C19—H19A109.5O2—Mn—O483.70 (8)
N4—C19—H19B109.5
O2—C1—C2—C3179.7 (3)C1—O2—Ni—O3154.1 (2)
C4—C5—C6—C7176.4 (4)Mn—O2—Ni—O324.99 (7)
O2—C1—C6—C5177.2 (3)C1—O2—Ni—N3122.3 (2)
C2—C1—C6—C7176.5 (3)Mn—O2—Ni—N358.61 (8)
C5—C6—C7—N1172.2 (3)C1—O2—Ni—O166.3 (2)
C1—C6—C7—N17.5 (5)Mn—O2—Ni—O1112.77 (8)
N1—C8—C9—C2156.6 (3)C7—N1—Ni—O215.3 (2)
N1—C8—C9—C1069.4 (3)C8—N1—Ni—O2166.5 (2)
N1—C8—C9—C22174.5 (3)C7—N1—Ni—N2161.7 (2)
C21—C9—C10—N255.2 (3)C8—N1—Ni—N216.5 (2)
C8—C9—C10—N271.4 (3)C7—N1—Ni—N3103.2 (2)
C22—C9—C10—N2173.4 (3)C8—N1—Ni—N378.6 (2)
N2—C11—C12—C13168.8 (3)C7—N1—Ni—O172.9 (2)
N2—C11—C12—C1714.0 (5)C8—N1—Ni—O1105.3 (2)
C17—C12—C13—C141.8 (5)C11—N2—Ni—N1160.4 (2)
C11—C12—C13—C14179.1 (3)C10—N2—Ni—N118.0 (2)
C12—C13—C14—C151.3 (5)C11—N2—Ni—O318.9 (2)
C13—C14—C15—C160.3 (5)C10—N2—Ni—O3162.6 (2)
C14—C15—C16—C171.4 (5)C11—N2—Ni—N3102.3 (2)
C15—C16—C17—O3179.3 (3)C10—N2—Ni—N379.3 (2)
C15—C16—C17—C120.8 (4)C11—N2—Ni—O168.6 (2)
C13—C12—C17—O3179.2 (3)C10—N2—Ni—O1109.8 (2)
C11—C12—C17—O32.1 (4)C17—O3—Ni—O2147.0 (2)
C13—C12—C17—C160.7 (4)Mn—O3—Ni—O224.96 (7)
C11—C12—C17—C16177.8 (3)C17—O3—Ni—N230.1 (2)
C6—C7—N1—C8178.3 (3)Mn—O3—Ni—N2157.99 (8)
C6—C7—N1—Ni3.4 (4)C17—O3—Ni—N3124.3 (2)
C9—C8—N1—C7135.7 (3)Mn—O3—Ni—N363.73 (9)
C9—C8—N1—Ni42.7 (3)C17—O3—Ni—O158.5 (2)
C12—C11—N2—C10179.0 (3)Mn—O3—Ni—O1113.47 (8)
C12—C11—N2—Ni2.6 (4)O5—N3—Ni—O2148.3 (2)
C9—C10—N2—C11132.8 (3)O4—N3—Ni—O236.30 (18)
C9—C10—N2—Ni45.7 (3)O5—N3—Ni—N157.6 (3)
O1—C18—N4—C193.6 (5)O4—N3—Ni—N1126.96 (18)
O1—C18—N4—C20177.5 (4)O5—N3—Ni—N239.7 (3)
N4—C18—O1—Ni139.9 (3)O4—N3—Ni—N2135.68 (19)
C2—C1—O2—Ni156.6 (2)O5—N3—Ni—O3129.5 (3)
C6—C1—O2—Ni23.0 (4)O4—N3—Ni—O345.90 (18)
C2—C1—O2—Mn22.0 (4)C18—O1—Ni—O256.2 (2)
C6—C1—O2—Mn158.4 (2)C18—O1—Ni—N1147.1 (2)
C16—C17—O3—Ni156.3 (2)C18—O1—Ni—N2116.2 (2)
C12—C17—O3—Ni23.8 (3)C18—O1—Ni—O325.8 (2)
C16—C17—O3—Mn11.3 (4)C1—O2—Mn—O3154.7 (3)
C12—C17—O3—Mn168.56 (19)Ni—O2—Mn—O324.15 (7)
C1—O2—Ni—N125.7 (2)C17—O3—Mn—O2145.9 (3)
Mn—O2—Ni—N1155.28 (8)Ni—O3—Mn—O223.97 (7)
Symmetry code: (i) x, y, z.

Experimental details

(I)(II)(III)
Crystal data
Chemical formula[CoNi2(NO2)2(C19H22N2O2)2(C3H7NO)2][CuNi2(NO2)2(C19H22N2O2)2(C3H7NO)2][MnNi2(NO2)2(C19H22N2O2)2(C3H7NO)2]
Mr1031.301035.911027.42
Crystal system, space groupMonoclinic, P21/nMonoclinic, P21/nMonoclinic, P21/n
Temperature (K)299293298
a, b, c (Å)10.942 (2), 10.223 (1), 21.092 (2)10.9520 (12), 10.2387 (13), 21.0884 (12)11.009 (2), 10.2060 (8), 21.216 (2)
β (°) 101.24 (1) 101.252 (3) 101.247 (7)
V3)2314.1 (5)2319.3 (4)2338.0 (5)
Z222
Radiation typeMo KαCu KαMo Kα
µ (mm1)1.232.021.13
Crystal size (mm)0.25 × 0.18 × 0.130.25 × 0.20 × 0.150.33 × 0.33 × 0.13
Data collection
DiffractometerEnraf-Nonius CAD-4
diffractometer
Enraf-Nonius CAD-4
diffractometer
Enraf-Nonius CAD-4
diffractometer
Absorption correctionψ-scan
empirical (using intensity measurements) (Fair, 1990)
ψ-scan
empirical (using intensity measurements) (Fair, 1990)
ψ-scan
empirical (using intensity measurements) (Fair, 1990)
Tmin, Tmax0.812, 0.8650.632, 0.7520.724, 0.879
No. of measured, independent and
observed [I > 2σ(I)] reflections
8277, 4548, 3019 4867, 4626, 3644 5026, 4589, 3436
Rint0.0300.0460.019
(sin θ/λ)max1)0.6170.6240.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.031, 0.085, 1.02 0.050, 0.159, 1.04 0.033, 0.099, 1.02
No. of reflections454846264589
No. of parameters346296359
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH-atom parameters constrainedH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.30, 0.270.44, 1.060.41, 0.54

Computer programs: CAD-4 EXPRESS (Enraf-Nonius, 1993), SHELXL97 (Sheldrick, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97, PLATON (Spek, 2000).

Selected geometric parameters (Å, º) for (I) top
N1—Ni2.006 (2)O2—Co2.0601 (18)
N2—Ni2.016 (2)O3—Ni2.0007 (18)
N3—Ni2.113 (3)O3—Co2.0542 (16)
O1—Ni2.169 (2)O4—Co2.161 (2)
O2—Ni2.0178 (16)Ni—Co2.9988 (5)
Ni—O2—Co94.67 (7)N2—Ni—N397.64 (9)
Ni—O3—Co95.38 (7)O2—Ni—N382.29 (8)
O3—Ni—O281.02 (7)O3—Co—O278.76 (7)
O3—Ni—N386.18 (9)O3—Co—O495.34 (7)
N1—Ni—N395.33 (10)O2—Co—O496.84 (7)
Selected geometric parameters (Å, º) for (II) top
Cu—O22.038 (2)N2—Ni2.010 (3)
Cu—O32.040 (2)N3—Ni2.127 (3)
Cu—O42.103 (2)Ni—O22.002 (2)
Cu—Ni2.9872 (5)Ni—O32.016 (2)
N1—Ni2.012 (3)Ni—O12.190 (3)
O2—Cu—O379.00 (9)N2—Ni—N395.79 (12)
O2—Cu—O485.98 (9)N1—Ni—N398.35 (11)
O3—Cu—O484.17 (9)O3—Ni—N381.38 (10)
O2—Ni—O380.43 (9)Ni—O2—Cu95.34 (9)
O2—Ni—N385.34 (11)Ni—O3—Cu94.86 (9)
Selected geometric parameters (Å, º) for (III) top
Ni—Mn3.0624 (8)O2—Ni2.0167 (18)
N1—Ni2.017 (2)O2—Mn2.1274 (16)
N2—Ni2.023 (2)O3—Ni2.0296 (16)
N3—Ni2.125 (3)O3—Mn2.1283 (17)
O1—Ni2.169 (2)Mn—O42.270 (3)
Ni—O2—Mn95.25 (7)N2—Ni—N394.26 (9)
Ni—O3—Mn94.84 (7)O3—Ni—N383.36 (8)
O2—Ni—O382.00 (7)O2—Mn—O377.19 (7)
O2—Ni—N387.79 (9)O3—Mn—O481.93 (7)
N1—Ni—N396.70 (9)O2—Mn—O483.70 (8)
Structural data, bridging angles and dihedral angles (ϕ and κ) for seven homo- or heterotrinuclear complexes (Å, °) top
ComplexM-ONi-MO-M-Oϕκ
(I)2.0542 (16)-2.161 (2)2.9988 (5)78.76 (7)-96.84 (7)30.88 (8)15.42 (11)-15.50 (10)
(II)2.038 (2)-2.103 (2)2.9872 (5)79.00 (9)-85.98 (9)31.40 (2)15.61 (2)-15.83 (2)
(III)2.1274 (16)-2.270 (3)3.0624 (8)77.19 (7)-83.70 (8)31.83 (2)15.15 (2)-16.72 (2)
(IV)2.024 (3)-2.098 (3)3.043 (2)79.4 (1)21.9 (1)33.1 (1)-35.06 (7)
(V)2.260 (1)-2.293 (2)3.227 (5)73.66 (5)23.10 (7)26.38 (6)-32.80 (7)
(VI)2.163 (1)-2.194 (2)3.133 (2)76.66 (6)23.68 (8)26.91 (7)-32.36 (9)
(VII)2.048 (2)-2.103 (2)2.9967 (4)78.70 (8)-85.86 (9)
(I) [CoNi2{(NO2)(dmSALPD)[(CH3)NCHO]}2], (II) [CuNi2{(NO2)(dmSALPD)[(CH3)NCHO]}2], (III) [MnNi2{(NO2)(dmSALPD)[(CH3)NCHO]}2], (IV) [Ni3{(CH3CO2)(SALPD)[(CH3)2SO]}2] (Ülkü, Ercan et al., 1997), (V) [CdNi2{(CH3CO2)(SALPD)[(CH3)2NCHO]}2] (Ülkü, Tahir et al., 1997), (VI) [MnNi2{(CH3CO2)(SALPD)[(CH3)NCHO]}2] (Ercan & Atakol, 1998), (VII) [CuNi2{(NO2)(SALPD)[(CH3)NCHO]2}2] (Tahir et al., 1998).
 

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