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The title compounds, bis(dimethylformamide)-1κ
O,3κ
O-bis{μ-2,2′-[2,2′-dimethylpropane-1,3-diylbis(nitrilomethylidyne)]diphenolato}-1κ
4N,
N′,
O,
O′:2κ
2O,
O′;2κ
2O,
O′:3κ
4N,
N′,
O,
O′-di-μ-nitrito-1:2κ
2N:
O;2:3κ
2O:
N-dinickel(II)cobalt(II), [CoNi
2(NO
2)
2(C
19H
22N
2O
2)
2(C
3H
7NO)
2], (I), -copper(II), [CuNi
2(NO
2)
2(C
19H
22N
2O
2)
2(C
3H
7NO)
2], (II), and -manganese(II), [MnNi
2(NO
2)
2(C
19H
22N
2O
2)
2(C
3H
7NO)
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 Co
2+, Cu
2+ or Mn
2+) 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 Co
2+, Cu
2+, Mn
2+ or Ni
2+, 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
CCDC references: 182987; 182988; 182989
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.
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).
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.
(I) [bis(dimethylformamide)-1
κO,3
κO-bis{µ-2,2'-[2,2'-dimethylpropane- 1,3-diylbis(nitrilomethylidyne)]diphenolato-
1
κ4N,
N',
O,
O':2
κ2O,
O';2
κ2O,
O':3
κ4N,
N',
O,
O'-di-µ-nitrito-
1:2
κ2N:
O;2:3
κ2O:
N-dinickel(II)]cobalt(II)
top
Crystal data top
[CoNi2(NO2)2(C19H22N2O2)2(C3H7NO)2] | F(000) = 1074 |
Mr = 1031.30 | Dx = 1.480 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 25 reflections |
a = 10.942 (2) Å | θ = 2.3–26.0° |
b = 10.223 (1) Å | µ = 1.23 mm−1 |
c = 21.092 (2) Å | T = 299 K |
β = 101.24 (1)° | Prism, dark brown |
V = 2314.1 (5) Å3 | 0.25 × 0.18 × 0.13 mm |
Z = 2 | |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.030 |
ω/2θ scans | θmax = 26.0° |
Absorption correction: ψ-scan empirical (using intensity measurements) (Fair, 1990) | h = −13→9 |
Tmin = 0.812, Tmax = 0.865 | k = −12→0 |
8277 measured reflections | l = −25→25 |
4548 independent reflections | 3 standard reflections every 120 min |
3019 reflections with I > 2σ(I) | intensity decay: 0.9% |
Refinement top
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)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.085 | H 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 parameters | Δρmax = 0.30 e Å−3 |
0 restraints | Δρmin = −0.27 e Å−3 |
Crystal data top
[CoNi2(NO2)2(C19H22N2O2)2(C3H7NO)2] | V = 2314.1 (5) Å3 |
Mr = 1031.30 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 10.942 (2) Å | µ = 1.23 mm−1 |
b = 10.223 (1) Å | T = 299 K |
c = 21.092 (2) Å | 0.25 × 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 = 0.865 | 3 standard reflections every 120 min |
8277 measured reflections | intensity decay: 0.9% |
4548 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.031 | 0 restraints |
wR(F2) = 0.085 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.30 e Å−3 |
4548 reflections | Δρmin = −0.27 e Å−3 |
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 | x | y | z | Uiso*/Ueq | |
C1 | 0.7374 (2) | 0.1165 (3) | 0.01305 (11) | 0.0343 (6) | |
C2 | 0.7751 (3) | 0.1600 (3) | 0.07677 (13) | 0.0443 (7) | |
C3 | 0.6927 (3) | 0.2168 (4) | 0.10956 (14) | 0.0554 (8) | |
C4 | 0.5679 (3) | 0.2306 (4) | 0.08127 (15) | 0.0572 (9) | |
C5 | 0.5292 (3) | 0.1865 (3) | 0.01973 (15) | 0.0497 (8) | |
C6 | 0.6103 (2) | 0.1310 (3) | −0.01640 (12) | 0.0380 (6) | |
C7 | 0.5561 (3) | 0.0868 (3) | −0.08138 (12) | 0.0393 (6) | |
C8 | 0.5366 (3) | 0.0090 (3) | −0.18772 (12) | 0.0470 (7) | |
H8A | 0.4502 | 0.0294 | −0.1875 | 0.056* | |
H8B | 0.5436 | −0.0852 | −0.1910 | 0.056* | |
C9 | 0.5729 (3) | 0.0722 (3) | −0.24754 (12) | 0.0448 (7) | |
C10 | 0.6976 (3) | 0.0194 (3) | −0.25826 (13) | 0.0509 (8) | |
H10A | 0.6941 | −0.0754 | −0.2584 | 0.061* | |
H10B | 0.7095 | 0.0472 | −0.3006 | 0.061* | |
C11 | 0.9018 (3) | 0.0987 (3) | −0.23105 (13) | 0.0457 (8) | |
C12 | 1.0210 (3) | 0.1407 (3) | −0.19433 (12) | 0.0431 (7) | |
C13 | 1.1045 (3) | 0.1944 (4) | −0.22998 (15) | 0.0621 (10) | |
C14 | 1.2170 (3) | 0.2442 (4) | −0.20059 (17) | 0.0698 (11) | |
C15 | 1.2502 (3) | 0.2411 (4) | −0.13426 (17) | 0.0578 (9) | |
C16 | 1.1732 (3) | 0.1851 (3) | −0.09762 (14) | 0.0465 (7) | |
C17 | 1.0578 (2) | 0.1329 (3) | −0.12626 (12) | 0.0376 (6) | |
C18 | 0.8330 (3) | 0.3322 (3) | −0.06480 (15) | 0.0522 (8) | |
C19 | 0.6636 (4) | 0.4792 (4) | −0.0707 (2) | 0.0912 (14) | |
H19A | 0.6420 | 0.5533 | −0.0472 | 0.109* | |
H19B | 0.6035 | 0.4109 | −0.0705 | 0.109* | |
H19C | 0.6641 | 0.5046 | −0.1145 | 0.109* | |
C20 | 0.8439 (6) | 0.4947 (5) | 0.0188 (2) | 0.117 (2) | |
H20A | 0.7937 | 0.5664 | 0.0283 | 0.140* | |
H20B | 0.9245 | 0.5265 | 0.0146 | 0.140* | |
H20C | 0.8532 | 0.4319 | 0.0533 | 0.140* | |
C21 | 0.5712 (3) | 0.2185 (4) | −0.24332 (17) | 0.0535 (9) | |
C22 | 0.4770 (4) | 0.0283 (5) | −0.30661 (17) | 0.0656 (11) | |
N1 | 0.6139 (2) | 0.0524 (2) | −0.12601 (10) | 0.0382 (5) | |
N2 | 0.8068 (2) | 0.0611 (2) | −0.20985 (10) | 0.0392 (5) | |
N3 | 0.8293 (2) | −0.1412 (3) | −0.09816 (11) | 0.0447 (6) | |
N4 | 0.7841 (3) | 0.4331 (3) | −0.04106 (12) | 0.0630 (8) | |
O1 | 0.78600 (19) | 0.2727 (2) | −0.11392 (9) | 0.0476 (5) | |
O2 | 0.81824 (16) | 0.06480 (19) | −0.01796 (8) | 0.0392 (4) | |
O3 | 0.98536 (16) | 0.07896 (19) | −0.09073 (8) | 0.0395 (4) | |
O4 | 1.08137 (19) | 0.17210 (19) | 0.05094 (8) | 0.0467 (5) | |
O5 | 0.7680 (2) | −0.2304 (3) | −0.12502 (11) | 0.0718 (7) | |
Ni | 0.80003 (3) | 0.06113 (4) | −0.115005 (14) | 0.03394 (11) | |
Co | 1.0000 | 0.0000 | 0.0000 | 0.03373 (14) | |
H2 | 0.858 (3) | 0.148 (3) | 0.0946 (12) | 0.040* | |
H3 | 0.719 (3) | 0.245 (3) | 0.1482 (14) | 0.040* | |
H4 | 0.510 (3) | 0.263 (3) | 0.1017 (13) | 0.040* | |
H5 | 0.456 (3) | 0.193 (3) | 0.0048 (13) | 0.040* | |
H7 | 0.465 (3) | 0.082 (3) | −0.0890 (12) | 0.040* | |
H11 | 0.903 (2) | 0.103 (3) | −0.2747 (13) | 0.040* | |
H13 | 1.081 (2) | 0.197 (3) | −0.2742 (13) | 0.040* | |
H14 | 1.271 (3) | 0.291 (3) | −0.2226 (13) | 0.040* | |
H15 | 1.318 (3) | 0.285 (3) | −0.1157 (12) | 0.040* | |
H16 | 1.196 (2) | 0.183 (3) | −0.0544 (13) | 0.040* | |
H18 | 0.908 (3) | 0.302 (3) | −0.0419 (13) | 0.040* | |
H21A | 0.624 (3) | 0.254 (3) | −0.2095 (14) | 0.040* | |
H21B | 0.501 (3) | 0.251 (3) | −0.2394 (13) | 0.040* | |
H21C | 0.592 (3) | 0.258 (3) | −0.2784 (14) | 0.040* | |
H22A | 0.495 (3) | 0.074 (3) | −0.3413 (14) | 0.040* | |
H22B | 0.479 (3) | −0.066 (3) | −0.3126 (13) | 0.040* | |
H22C | 0.409 (3) | 0.051 (3) | −0.3012 (14) | 0.040* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0386 (15) | 0.0370 (15) | 0.0289 (12) | 0.0009 (11) | 0.0102 (11) | 0.0030 (12) |
C2 | 0.0400 (17) | 0.060 (2) | 0.0334 (14) | −0.0014 (13) | 0.0078 (12) | 0.0095 (15) |
C3 | 0.058 (2) | 0.075 (2) | 0.0347 (15) | −0.0117 (16) | 0.0134 (14) | 0.0074 (18) |
C4 | 0.056 (2) | 0.072 (2) | 0.0496 (18) | −0.0017 (16) | 0.0268 (16) | 0.0199 (18) |
C5 | 0.0371 (17) | 0.069 (2) | 0.0448 (16) | 0.0061 (15) | 0.0114 (13) | 0.0128 (16) |
C6 | 0.0354 (15) | 0.0433 (16) | 0.0368 (13) | 0.0048 (12) | 0.0106 (11) | 0.0045 (13) |
C7 | 0.0298 (14) | 0.0478 (18) | 0.0397 (14) | 0.0039 (12) | 0.0052 (12) | 0.0027 (13) |
C8 | 0.0412 (17) | 0.0590 (19) | 0.0372 (14) | −0.0014 (14) | −0.0013 (12) | −0.0091 (15) |
C9 | 0.0398 (16) | 0.061 (2) | 0.0299 (13) | −0.0013 (13) | −0.0029 (11) | −0.0033 (14) |
C10 | 0.0551 (19) | 0.065 (2) | 0.0289 (13) | −0.0075 (13) | 0.0003 (13) | −0.0024 (16) |
C11 | 0.0490 (18) | 0.063 (2) | 0.0257 (13) | 0.0039 (13) | 0.0099 (12) | 0.0086 (15) |
C12 | 0.0393 (16) | 0.0584 (19) | 0.0334 (13) | 0.0073 (13) | 0.0111 (12) | 0.0084 (14) |
C13 | 0.047 (2) | 0.103 (3) | 0.0381 (15) | 0.0144 (18) | 0.0145 (14) | 0.0034 (19) |
C14 | 0.045 (2) | 0.109 (3) | 0.061 (2) | 0.032 (2) | 0.0217 (16) | 0.001 (2) |
C15 | 0.0370 (18) | 0.071 (2) | 0.065 (2) | 0.0129 (18) | 0.0084 (16) | −0.0014 (17) |
C16 | 0.0393 (17) | 0.059 (2) | 0.0397 (15) | 0.0082 (14) | 0.0050 (13) | 0.0033 (14) |
C17 | 0.0336 (15) | 0.0444 (16) | 0.0359 (13) | 0.0065 (12) | 0.0100 (11) | 0.0099 (13) |
C18 | 0.059 (2) | 0.0450 (19) | 0.0472 (17) | 0.0041 (15) | −0.0015 (15) | −0.0006 (16) |
C19 | 0.107 (4) | 0.067 (3) | 0.112 (4) | 0.010 (2) | 0.051 (3) | 0.023 (3) |
C20 | 0.196 (6) | 0.074 (3) | 0.075 (3) | −0.032 (3) | 0.016 (3) | −0.026 (3) |
C21 | 0.045 (2) | 0.068 (2) | 0.0433 (17) | 0.0102 (17) | −0.0005 (15) | 0.0032 (17) |
C22 | 0.061 (2) | 0.085 (3) | 0.0427 (18) | 0.0005 (18) | −0.0102 (17) | −0.008 (2) |
N1 | 0.0358 (12) | 0.0467 (14) | 0.0302 (11) | 0.0019 (10) | 0.0016 (9) | −0.0021 (11) |
N2 | 0.0418 (13) | 0.0479 (14) | 0.0266 (10) | −0.0015 (10) | 0.0036 (9) | 0.0049 (12) |
N3 | 0.0508 (15) | 0.0462 (15) | 0.0390 (12) | −0.0043 (11) | 0.0137 (11) | 0.0005 (13) |
N4 | 0.096 (2) | 0.0452 (16) | 0.0489 (15) | −0.0044 (13) | 0.0162 (15) | 0.0021 (16) |
O1 | 0.0540 (13) | 0.0444 (12) | 0.0402 (10) | −0.0011 (9) | −0.0009 (9) | 0.0023 (10) |
O2 | 0.0348 (10) | 0.0573 (12) | 0.0258 (8) | −0.0003 (8) | 0.0068 (7) | 0.0118 (9) |
O3 | 0.0337 (10) | 0.0568 (12) | 0.0284 (8) | 0.0075 (8) | 0.0068 (7) | 0.0010 (9) |
O4 | 0.0531 (13) | 0.0476 (12) | 0.0381 (10) | 0.0034 (9) | 0.0056 (9) | 0.0095 (10) |
O5 | 0.0822 (19) | 0.0621 (16) | 0.0659 (15) | −0.0120 (13) | 0.0012 (13) | −0.0080 (14) |
Ni | 0.03378 (19) | 0.0428 (2) | 0.02447 (16) | 0.00079 (15) | 0.00383 (12) | 0.00312 (16) |
Co | 0.0333 (3) | 0.0436 (3) | 0.0240 (2) | 0.0037 (2) | 0.00486 (19) | 0.0083 (2) |
Geometric parameters (Å, º) top
C1—O2 | 1.310 (3) | C15—H15 | 0.89 (3) |
C1—C2 | 1.399 (4) | C16—C17 | 1.395 (4) |
C1—C6 | 1.416 (4) | C16—H16 | 0.90 (3) |
C2—C3 | 1.368 (4) | C17—O3 | 1.314 (3) |
C2—H2 | 0.92 (3) | C18—O1 | 1.225 (3) |
C3—C4 | 1.387 (5) | C18—N4 | 1.306 (4) |
C3—H3 | 0.86 (3) | C18—H18 | 0.92 (3) |
C4—C5 | 1.361 (4) | C19—N4 | 1.425 (5) |
C4—H4 | 0.89 (3) | C19—H19A | 0.9600 |
C5—C6 | 1.398 (4) | C19—H19B | 0.9600 |
C5—H5 | 0.81 (3) | C19—H19C | 0.9600 |
C6—C7 | 1.455 (4) | C20—N4 | 1.449 (5) |
C7—N1 | 1.282 (3) | C20—H20A | 0.9600 |
C7—H7 | 0.98 (3) | C20—H20B | 0.9600 |
C8—N1 | 1.475 (3) | C20—H20C | 0.9600 |
C8—C9 | 1.537 (4) | C21—H21A | 0.90 (3) |
C8—H8A | 0.9700 | C21—H21B | 0.86 (3) |
C8—H8B | 0.9700 | C21—H21C | 0.91 (3) |
C9—C21 | 1.499 (5) | C22—H22A | 0.92 (3) |
C9—C10 | 1.525 (4) | C22—H22B | 0.98 (3) |
C9—C22 | 1.532 (4) | C22—H22C | 0.81 (3) |
C10—N2 | 1.475 (3) | N1—Ni | 2.006 (2) |
C10—H10A | 0.9700 | N2—Ni | 2.016 (2) |
C10—H10B | 0.9700 | N3—O5 | 1.206 (3) |
C11—N2 | 1.269 (4) | N3—O4i | 1.292 (3) |
C11—C12 | 1.446 (4) | N3—Ni | 2.113 (3) |
C11—H11 | 0.92 (3) | O1—Ni | 2.169 (2) |
C12—C13 | 1.404 (4) | O2—Ni | 2.0178 (16) |
C12—C17 | 1.416 (3) | O2—Co | 2.0601 (18) |
C13—C14 | 1.364 (5) | O3—Ni | 2.0007 (18) |
C13—H13 | 0.92 (3) | O3—Co | 2.0542 (16) |
C14—C15 | 1.376 (5) | O4—Co | 2.161 (2) |
C14—H14 | 0.95 (3) | Ni—Co | 2.9988 (5) |
C15—C16 | 1.375 (4) | | |
| | | |
O2—C1—C2 | 120.4 (2) | N4—C19—H19C | 109.5 |
O2—C1—C6 | 121.6 (2) | H19A—C19—H19C | 109.5 |
C2—C1—C6 | 118.0 (2) | H19B—C19—H19C | 109.5 |
C3—C2—C1 | 121.4 (3) | N4—C20—H20A | 109.5 |
C3—C2—H2 | 122.8 (17) | N4—C20—H20B | 109.5 |
C1—C2—H2 | 115.8 (17) | H20A—C20—H20B | 109.5 |
C2—C3—C4 | 121.1 (3) | N4—C20—H20C | 109.5 |
C2—C3—H3 | 119.7 (19) | H20A—C20—H20C | 109.5 |
C4—C3—H3 | 119.2 (19) | H20B—C20—H20C | 109.5 |
C5—C4—C3 | 118.3 (3) | C9—C21—H21A | 115.8 (18) |
C5—C4—H4 | 117.7 (18) | C9—C21—H21B | 115 (2) |
C3—C4—H4 | 123.9 (18) | H21A—C21—H21B | 102 (3) |
C4—C5—C6 | 122.8 (3) | C9—C21—H21C | 112.8 (18) |
C4—C5—H5 | 117 (2) | H21A—C21—H21C | 104 (3) |
C6—C5—H5 | 120 (2) | H21B—C21—H21C | 106 (3) |
C5—C6—C1 | 118.5 (2) | C9—C22—H22A | 106.3 (18) |
C5—C6—C7 | 117.0 (3) | C9—C22—H22B | 111.6 (17) |
C1—C6—C7 | 124.5 (2) | H22A—C22—H22B | 113 (2) |
N1—C7—C6 | 127.4 (3) | C9—C22—H22C | 108 (2) |
N1—C7—H7 | 120.0 (15) | H22A—C22—H22C | 108 (3) |
C6—C7—H7 | 112.6 (15) | H22B—C22—H22C | 110 (3) |
N1—C8—C9 | 113.7 (2) | C7—N1—C8 | 116.8 (2) |
N1—C8—H8A | 108.8 | C7—N1—Ni | 122.56 (18) |
C9—C8—H8A | 108.8 | C8—N1—Ni | 120.64 (18) |
N1—C8—H8B | 108.8 | C11—N2—C10 | 116.9 (2) |
C9—C8—H8B | 108.8 | C11—N2—Ni | 122.73 (19) |
H8A—C8—H8B | 107.7 | C10—N2—Ni | 120.36 (19) |
C21—C9—C10 | 112.6 (3) | O5—N3—Ni | 127.5 (2) |
C21—C9—C22 | 109.1 (3) | C18—N4—C19 | 120.4 (3) |
C10—C9—C22 | 105.5 (3) | C18—N4—C20 | 121.9 (4) |
C21—C9—C8 | 111.3 (3) | C19—N4—C20 | 117.5 (4) |
C10—C9—C8 | 110.8 (2) | C18—O1—Ni | 119.04 (19) |
C22—C9—C8 | 107.4 (3) | C1—O2—Ni | 124.84 (15) |
N2—C10—C9 | 115.0 (2) | C1—O2—Co | 139.44 (15) |
N2—C10—H10A | 108.5 | Ni—O2—Co | 94.67 (7) |
C9—C10—H10A | 108.5 | C17—O3—Ni | 125.90 (15) |
N2—C10—H10B | 108.5 | C17—O3—Co | 138.62 (16) |
C9—C10—H10B | 108.5 | Ni—O3—Co | 95.38 (7) |
H10A—C10—H10B | 107.5 | O3—Ni—N1 | 171.51 (8) |
N2—C11—C12 | 128.1 (2) | O3—Ni—N2 | 91.28 (8) |
N2—C11—H11 | 122.6 (17) | N1—Ni—N2 | 96.78 (9) |
C12—C11—H11 | 109.4 (17) | O3—Ni—O2 | 81.02 (7) |
C13—C12—C17 | 118.6 (3) | N1—Ni—O2 | 90.89 (8) |
C13—C12—C11 | 116.3 (3) | N2—Ni—O2 | 172.30 (8) |
C17—C12—C11 | 125.1 (3) | O3—Ni—N3 | 86.18 (9) |
C14—C13—C12 | 121.8 (3) | N1—Ni—N3 | 95.33 (10) |
C14—C13—H13 | 119.8 (17) | N2—Ni—N3 | 97.64 (9) |
C12—C13—H13 | 118.4 (17) | O2—Ni—N3 | 82.29 (8) |
C13—C14—C15 | 119.3 (3) | O3—Ni—O1 | 88.67 (8) |
C13—C14—H14 | 124.1 (16) | N1—Ni—O1 | 88.46 (9) |
C15—C14—H14 | 116.2 (17) | N2—Ni—O1 | 91.56 (8) |
C16—C15—C14 | 120.8 (3) | O2—Ni—O1 | 87.93 (8) |
C16—C15—H15 | 120.8 (18) | N3—Ni—O1 | 169.55 (8) |
C14—C15—H15 | 117.9 (18) | O3—Ni—Co | 43.00 (5) |
C15—C16—C17 | 121.2 (3) | N1—Ni—Co | 130.43 (6) |
C15—C16—H16 | 120.4 (18) | N2—Ni—Co | 129.81 (7) |
C17—C16—H16 | 118.4 (18) | O2—Ni—Co | 43.21 (5) |
O3—C17—C16 | 120.6 (2) | N3—Ni—Co | 66.25 (7) |
O3—C17—C12 | 121.2 (2) | O1—Ni—Co | 103.96 (5) |
C16—C17—C12 | 118.2 (3) | O3i—Co—O2 | 101.24 (7) |
O1—C18—N4 | 125.5 (3) | O3—Co—O2 | 78.76 (7) |
O1—C18—H18 | 117.7 (17) | O3—Co—O4 | 95.34 (7) |
N4—C18—H18 | 116.8 (17) | O2—Co—O4 | 96.84 (7) |
N4—C19—H19A | 109.5 | O3—Co—Ni | 41.62 (5) |
N4—C19—H19B | 109.5 | O2—Co—Ni | 42.12 (4) |
H19A—C19—H19B | 109.5 | O4—Co—Ni | 113.42 (5) |
| | | |
O2—C1—C2—C3 | 178.6 (3) | C7—N1—Ni—N3 | 102.1 (2) |
C6—C1—C2—C3 | −1.0 (4) | C8—N1—Ni—N3 | −79.8 (2) |
C1—C2—C3—C4 | 1.5 (5) | C7—N1—Ni—O1 | −68.2 (2) |
C2—C3—C4—C5 | −0.2 (5) | C8—N1—Ni—O1 | 109.9 (2) |
C3—C4—C5—C6 | −1.5 (5) | C7—N1—Ni—Co | 38.9 (3) |
C4—C5—C6—C1 | 2.0 (5) | C8—N1—Ni—Co | −142.95 (18) |
C4—C5—C6—C7 | 179.4 (3) | C11—N2—Ni—O3 | −15.9 (3) |
O2—C1—C6—C5 | 179.7 (3) | C10—N2—Ni—O3 | 165.7 (2) |
C2—C1—C6—C5 | −0.7 (4) | C11—N2—Ni—N1 | 161.4 (2) |
O2—C1—C6—C7 | 2.5 (4) | C10—N2—Ni—N1 | −17.0 (2) |
C2—C1—C6—C7 | −177.9 (3) | C11—N2—Ni—N3 | −102.2 (3) |
C5—C6—C7—N1 | 168.3 (3) | C10—N2—Ni—N3 | 79.4 (2) |
C1—C6—C7—N1 | −14.4 (5) | C11—N2—Ni—O1 | 72.8 (2) |
N1—C8—C9—C21 | −55.2 (3) | C10—N2—Ni—O1 | −105.6 (2) |
N1—C8—C9—C10 | 70.8 (3) | C11—N2—Ni—Co | −36.9 (3) |
N1—C8—C9—C22 | −174.5 (3) | C10—N2—Ni—Co | 144.72 (19) |
C21—C9—C10—N2 | 55.5 (3) | C1—O2—Ni—O3 | 146.3 (2) |
C22—C9—C10—N2 | 174.4 (3) | Co—O2—Ni—O3 | −24.04 (8) |
C8—C9—C10—N2 | −69.8 (3) | C1—O2—Ni—N1 | −31.1 (2) |
N2—C11—C12—C13 | −171.5 (3) | Co—O2—Ni—N1 | 158.55 (9) |
N2—C11—C12—C17 | 7.7 (5) | C1—O2—Ni—N3 | −126.4 (2) |
C17—C12—C13—C14 | −3.0 (6) | Co—O2—Ni—N3 | 63.29 (9) |
C11—C12—C13—C14 | 176.3 (4) | C1—O2—Ni—O1 | 57.3 (2) |
C12—C13—C14—C15 | 0.5 (6) | Co—O2—Ni—O1 | −113.02 (8) |
C13—C14—C15—C16 | 1.9 (6) | C1—O2—Ni—Co | 170.3 (3) |
C14—C15—C16—C17 | −1.7 (5) | O5—N3—Ni—O3 | −148.2 (3) |
C15—C16—C17—O3 | 179.6 (3) | O5—N3—Ni—N1 | 40.1 (3) |
C15—C16—C17—C12 | −0.9 (5) | O5—N3—Ni—N2 | −57.4 (3) |
C13—C12—C17—O3 | −177.3 (3) | O5—N3—Ni—O2 | 130.3 (3) |
C11—C12—C17—O3 | 3.4 (5) | O5—N3—Ni—O1 | 151.1 (4) |
C13—C12—C17—C16 | 3.1 (5) | O5—N3—Ni—Co | 172.3 (3) |
C11—C12—C17—C16 | −176.1 (3) | C18—O1—Ni—O3 | −56.1 (2) |
C6—C7—N1—C8 | 178.9 (3) | C18—O1—Ni—N1 | 115.9 (3) |
C6—C7—N1—Ni | −2.9 (4) | C18—O1—Ni—N2 | −147.3 (3) |
C9—C8—N1—C7 | 132.3 (3) | C18—O1—Ni—O2 | 25.0 (2) |
C9—C8—N1—Ni | −46.0 (3) | C18—O1—Ni—N3 | 4.4 (6) |
C12—C11—N2—C10 | −178.2 (3) | C18—O1—Ni—Co | −15.5 (3) |
C12—C11—N2—Ni | 3.4 (5) | C17—O3—Co—O2 | 152.4 (3) |
C9—C10—N2—C11 | −135.1 (3) | Ni—O3—Co—O2 | −23.79 (8) |
C9—C10—N2—Ni | 43.4 (3) | C17—O3—Co—O4 | 56.4 (3) |
O1—C18—N4—C19 | 3.1 (5) | Ni—O3—Co—O4 | −119.73 (8) |
O1—C18—N4—C20 | 177.5 (4) | C17—O3—Co—Ni | 176.2 (3) |
N4—C18—O1—Ni | −140.0 (3) | C1—O2—Co—O3 | −144.2 (3) |
C2—C1—O2—Ni | −155.3 (2) | Ni—O2—Co—O3 | 23.55 (8) |
C6—C1—O2—Ni | 24.3 (4) | C1—O2—Co—O4 | −50.1 (3) |
C2—C1—O2—Co | 9.7 (4) | Ni—O2—Co—O4 | 117.66 (8) |
C6—C1—O2—Co | −170.67 (19) | C1—O2—Co—Ni | −167.7 (3) |
C16—C17—O3—Ni | 155.4 (2) | N1—Ni—Co—O3 | −172.55 (12) |
C12—C17—O3—Ni | −24.2 (4) | N2—Ni—Co—O3 | 31.67 (12) |
C16—C17—O3—Co | −19.9 (4) | O2—Ni—Co—O3 | −143.84 (12) |
C12—C17—O3—Co | 160.6 (2) | N3—Ni—Co—O3 | 111.43 (11) |
C17—O3—Ni—N2 | 26.9 (2) | O1—Ni—Co—O3 | −72.44 (10) |
Co—O3—Ni—N2 | −156.21 (9) | O3—Ni—Co—O2 | 143.84 (12) |
C17—O3—Ni—O2 | −152.7 (2) | N1—Ni—Co—O2 | −28.71 (12) |
Co—O3—Ni—O2 | 24.14 (8) | N2—Ni—Co—O2 | 175.51 (12) |
C17—O3—Ni—N3 | 124.5 (2) | N3—Ni—Co—O2 | −104.73 (11) |
Co—O3—Ni—N3 | −58.64 (8) | O1—Ni—Co—O2 | 71.40 (10) |
C17—O3—Ni—O1 | −64.6 (2) | O3—Ni—Co—O4 | 70.44 (10) |
Co—O3—Ni—O1 | 112.26 (8) | N1—Ni—Co—O4 | −102.11 (11) |
C17—O3—Ni—Co | −176.9 (3) | N2—Ni—Co—O4 | 102.10 (11) |
C7—N1—Ni—N2 | −159.6 (2) | O2—Ni—Co—O4 | −73.40 (10) |
C8—N1—Ni—N2 | 18.6 (2) | N3—Ni—Co—O4 | −178.14 (9) |
C7—N1—Ni—O2 | 19.7 (2) | O1—Ni—Co—O4 | −2.01 (8) |
C8—N1—Ni—O2 | −162.2 (2) | | |
Symmetry code: (i) −x+2, −y, −z. |
(II) [bis(dimethylformamide)-1
κO,3
κO-bis{µ-2,2'-[2,2'-dimethylpropane- 1,3-diylbis(nitrilomethylidyne)]diphenolato-
1
κ4N,
N',
O,
O':2
κ2O,
O';2
κ2O,
O':3
κ4N,
N',
O,
O'-di-µ-nitrito-
1:2
κ2N:
O;2:3
κ2O:
N-dinickel(II)]copper(II)
top
Crystal data top
[CuNi2(NO2)2(C19H22N2O2)2(C3H7NO)2] | F(000) = 1078 |
Mr = 1035.91 | Dx = 1.483 Mg m−3 |
Monoclinic, P21/n | Cu Kα radiation, λ = 1.54180 Å |
Hall symbol: -P 2yn | Cell parameters from 25 reflections |
a = 10.9520 (12) Å | θ = 4.3–74.2° |
b = 10.2387 (13) Å | µ = 2.02 mm−1 |
c = 21.0884 (12) Å | T = 293 K |
β = 101.252 (3)° | Prism, blue green |
V = 2319.3 (4) Å3 | 0.25 × 0.20 × 0.15 mm |
Z = 2 | |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.046 |
ω/2θ scans | θmax = 74.2° |
Absorption correction: ψ-scan empirical (using intensity measurements) (Fair, 1990) | h = −13→0 |
Tmin = 0.632, Tmax = 0.752 | k = −12→0 |
4867 measured reflections | l = −25→26 |
4626 independent reflections | 3 standard reflections every 120 min |
3644 reflections with I > 2σ(I) | intensity decay: 1.1% |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.050 | H-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 reflections | Δρmax = 0.44 e Å−3 |
296 parameters | Δρmin = −1.06 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997) |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: none |
Crystal data top
[CuNi2(NO2)2(C19H22N2O2)2(C3H7NO)2] | V = 2319.3 (4) Å3 |
Mr = 1035.91 | Z = 2 |
Monoclinic, P21/n | Cu Kα radiation |
a = 10.9520 (12) Å | µ = 2.02 mm−1 |
b = 10.2387 (13) Å | T = 293 K |
c = 21.0884 (12) Å | 0.25 × 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 = 0.752 | 3 standard reflections every 120 min |
4867 measured reflections | intensity decay: 1.1% |
4626 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.159 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.44 e Å−3 |
4626 reflections | Δρmin = −1.06 e Å−3 |
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 | x | y | z | Uiso*/Ueq | |
C1 | −0.0592 (3) | 0.1320 (3) | 0.12558 (15) | 0.0380 (7) | |
C2 | −0.1750 (3) | 0.1842 (4) | 0.09629 (17) | 0.0471 (8) | |
H2 | −0.1996 | 0.1810 | 0.0515 | 0.057* | |
C3 | −0.2529 (3) | 0.2402 (4) | 0.1327 (2) | 0.0571 (10) | |
H3 | −0.3283 | 0.2761 | 0.1122 | 0.069* | |
C4 | −0.2199 (4) | 0.2434 (5) | 0.1996 (2) | 0.0667 (12) | |
H4 | −0.2735 | 0.2793 | 0.2241 | 0.080* | |
C5 | −0.1064 (4) | 0.1927 (5) | 0.22928 (19) | 0.0637 (11) | |
H5 | −0.0844 | 0.1943 | 0.2742 | 0.076* | |
C6 | −0.0229 (3) | 0.1385 (4) | 0.19334 (15) | 0.0451 (8) | |
C7 | 0.0960 (3) | 0.0965 (4) | 0.23058 (15) | 0.0477 (8) | |
H7 | 0.1033 | 0.0966 | 0.2753 | 0.057* | |
C8 | 0.3012 (3) | 0.0181 (4) | 0.25837 (16) | 0.0514 (9) | |
H8A | 0.3045 | −0.0766 | 0.2591 | 0.062* | |
H8B | 0.2897 | 0.0469 | 0.3006 | 0.062* | |
C9 | 0.4259 (3) | 0.0699 (4) | 0.24708 (16) | 0.0460 (8) | |
C10 | 0.4619 (3) | 0.0067 (4) | 0.18770 (16) | 0.0476 (8) | |
H10A | 0.5485 | 0.0266 | 0.1875 | 0.057* | |
H10B | 0.4546 | −0.0874 | 0.1911 | 0.057* | |
C11 | 0.4422 (3) | 0.0854 (3) | 0.08119 (16) | 0.0427 (7) | |
H11 | 0.5287 | 0.0826 | 0.0916 | 0.051* | |
C12 | 0.3875 (3) | 0.1297 (3) | 0.01584 (15) | 0.0384 (7) | |
C13 | 0.4696 (3) | 0.1855 (4) | −0.01981 (17) | 0.0499 (8) | |
H13 | 0.5536 | 0.1920 | −0.0009 | 0.060* | |
C14 | 0.4301 (4) | 0.2310 (4) | −0.08171 (18) | 0.0573 (10) | |
H14 | 0.4857 | 0.2702 | −0.1040 | 0.069* | |
C15 | 0.3050 (4) | 0.2172 (4) | −0.11039 (17) | 0.0553 (10) | |
H15 | 0.2773 | 0.2466 | −0.1525 | 0.066* | |
C16 | 0.2213 (3) | 0.1603 (4) | −0.07730 (15) | 0.0466 (8) | |
H16 | 0.1384 | 0.1511 | −0.0975 | 0.056* | |
C17 | 0.2606 (3) | 0.1164 (3) | −0.01341 (14) | 0.0357 (6) | |
C18 | 0.1666 (4) | 0.3322 (4) | 0.06460 (17) | 0.0517 (9) | |
H18 | 0.0898 | 0.3029 | 0.0423 | 0.062* | |
C19 | 0.1536 (7) | 0.4940 (6) | −0.0197 (3) | 0.108 (2) | |
H19A | 0.2028 | 0.5659 | −0.0298 | 0.162* | |
H19B | 0.0732 | 0.5252 | −0.0150 | 0.162* | |
H19C | 0.1439 | 0.4310 | −0.0541 | 0.162* | |
C20 | 0.3380 (5) | 0.4782 (5) | 0.0709 (3) | 0.0862 (16) | |
H20A | 0.3596 | 0.5525 | 0.0476 | 0.129* | |
H20B | 0.3977 | 0.4099 | 0.0702 | 0.129* | |
H20C | 0.3380 | 0.5028 | 0.1148 | 0.129* | |
C21 | 0.4273 (4) | 0.2176 (4) | 0.24303 (18) | 0.0526 (9) | |
H21A | 0.5069 | 0.2463 | 0.2358 | 0.079* | |
H21B | 0.4125 | 0.2541 | 0.2828 | 0.079* | |
H21C | 0.3633 | 0.2462 | 0.2079 | 0.079* | |
C22 | 0.5226 (4) | 0.0256 (5) | 0.30663 (18) | 0.0639 (11) | |
H22A | 0.5222 | −0.0680 | 0.3095 | 0.096* | |
H22B | 0.5020 | 0.0624 | 0.3451 | 0.096* | |
H22C | 0.6039 | 0.0548 | 0.3023 | 0.096* | |
Cu | 0.0000 | 0.0000 | 0.0000 | 0.0454 (2) | |
N1 | 0.1917 (3) | 0.0595 (3) | 0.20952 (12) | 0.0406 (6) | |
N2 | 0.3849 (3) | 0.0502 (3) | 0.12563 (13) | 0.0403 (6) | |
N3 | 0.1662 (3) | −0.1423 (3) | 0.09601 (14) | 0.0472 (7) | |
N4 | 0.2161 (4) | 0.4326 (3) | 0.04097 (16) | 0.0631 (9) | |
Ni | 0.19866 (5) | 0.06010 (5) | 0.11486 (2) | 0.03483 (18) | |
O1 | 0.2139 (2) | 0.2733 (3) | 0.11420 (11) | 0.0509 (6) | |
O2 | 0.0135 (2) | 0.0785 (2) | 0.08992 (10) | 0.0410 (5) | |
O3 | 0.1798 (2) | 0.0642 (2) | 0.01788 (10) | 0.0397 (5) | |
O4 | 0.0764 (2) | −0.1700 (2) | 0.04788 (11) | 0.0467 (6) | |
O5 | 0.2252 (3) | −0.2355 (3) | 0.12251 (15) | 0.0725 (9) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0344 (14) | 0.0459 (17) | 0.0346 (15) | −0.0076 (13) | 0.0091 (12) | −0.0098 (13) |
C2 | 0.0413 (17) | 0.059 (2) | 0.0402 (17) | −0.0046 (15) | 0.0057 (14) | −0.0047 (15) |
C3 | 0.0365 (17) | 0.074 (3) | 0.061 (2) | −0.018 (2) | 0.0095 (16) | −0.0040 (18) |
C4 | 0.046 (2) | 0.100 (4) | 0.058 (2) | −0.026 (2) | 0.0205 (17) | −0.002 (2) |
C5 | 0.049 (2) | 0.102 (3) | 0.0427 (19) | −0.019 (2) | 0.0154 (16) | −0.007 (2) |
C6 | 0.0429 (17) | 0.061 (2) | 0.0330 (15) | −0.0054 (14) | 0.0103 (13) | −0.0071 (15) |
C7 | 0.0497 (19) | 0.069 (2) | 0.0243 (14) | −0.0028 (14) | 0.0070 (13) | −0.0092 (17) |
C8 | 0.052 (2) | 0.070 (2) | 0.0281 (15) | 0.0084 (15) | −0.0024 (14) | 0.0005 (18) |
C9 | 0.0450 (17) | 0.059 (2) | 0.0294 (15) | −0.0011 (14) | −0.0053 (13) | 0.0016 (16) |
C10 | 0.0450 (18) | 0.058 (2) | 0.0353 (17) | 0.0034 (15) | −0.0028 (14) | 0.0107 (16) |
C11 | 0.0346 (15) | 0.053 (2) | 0.0382 (16) | −0.0026 (14) | 0.0026 (12) | −0.0021 (14) |
C12 | 0.0361 (15) | 0.0468 (18) | 0.0325 (14) | −0.0040 (13) | 0.0072 (12) | −0.0051 (13) |
C13 | 0.0414 (17) | 0.067 (2) | 0.0424 (17) | −0.0046 (16) | 0.0100 (14) | −0.0111 (16) |
C14 | 0.056 (2) | 0.072 (3) | 0.048 (2) | 0.0030 (18) | 0.0216 (17) | −0.0175 (19) |
C15 | 0.059 (2) | 0.074 (3) | 0.0334 (17) | 0.0063 (16) | 0.0099 (15) | −0.0080 (19) |
C16 | 0.0444 (17) | 0.063 (2) | 0.0313 (15) | 0.0035 (15) | 0.0052 (13) | −0.0069 (16) |
C17 | 0.0362 (15) | 0.0423 (16) | 0.0294 (14) | −0.0024 (12) | 0.0083 (11) | −0.0045 (13) |
C18 | 0.060 (2) | 0.046 (2) | 0.0438 (19) | −0.0058 (15) | −0.0013 (16) | 0.0008 (17) |
C19 | 0.169 (7) | 0.081 (4) | 0.068 (3) | 0.032 (3) | 0.007 (4) | 0.018 (4) |
C20 | 0.096 (4) | 0.065 (3) | 0.105 (4) | −0.010 (3) | 0.039 (3) | −0.020 (3) |
C21 | 0.0483 (19) | 0.060 (2) | 0.0444 (19) | −0.0058 (17) | −0.0028 (15) | −0.0021 (17) |
C22 | 0.059 (2) | 0.084 (3) | 0.0380 (19) | 0.0033 (19) | −0.0161 (17) | 0.008 (2) |
Cu | 0.0453 (4) | 0.0565 (5) | 0.0332 (4) | −0.0036 (3) | 0.0049 (3) | −0.0079 (3) |
N1 | 0.0425 (14) | 0.0495 (16) | 0.0275 (12) | 0.0019 (11) | 0.0009 (10) | −0.0056 (12) |
N2 | 0.0392 (13) | 0.0474 (16) | 0.0321 (13) | −0.0020 (11) | 0.0013 (10) | 0.0025 (12) |
N3 | 0.0505 (16) | 0.0555 (18) | 0.0359 (14) | 0.0066 (13) | 0.0094 (12) | 0.0012 (14) |
N4 | 0.095 (3) | 0.0467 (18) | 0.0472 (18) | 0.0022 (14) | 0.0115 (18) | −0.0017 (18) |
Ni | 0.0350 (3) | 0.0447 (3) | 0.0236 (3) | −0.0007 (2) | 0.00273 (19) | −0.0031 (2) |
O1 | 0.0596 (15) | 0.0497 (14) | 0.0376 (12) | 0.0020 (10) | −0.0047 (11) | −0.0041 (12) |
O2 | 0.0374 (11) | 0.0581 (14) | 0.0269 (10) | −0.0083 (9) | 0.0052 (8) | −0.0029 (10) |
O3 | 0.0350 (11) | 0.0566 (14) | 0.0270 (10) | −0.0001 (9) | 0.0048 (8) | −0.0117 (10) |
O4 | 0.0506 (13) | 0.0489 (13) | 0.0389 (12) | −0.0014 (10) | 0.0047 (10) | −0.0066 (11) |
O5 | 0.083 (2) | 0.0641 (19) | 0.0651 (18) | 0.0155 (15) | 0.0006 (16) | 0.0129 (16) |
Geometric parameters (Å, º) top
C1—O2 | 1.316 (4) | C15—H15 | 0.9300 |
C1—C2 | 1.404 (5) | C16—C17 | 1.406 (4) |
C1—C6 | 1.408 (4) | C16—H16 | 0.9300 |
C2—C3 | 1.379 (5) | C17—O3 | 1.316 (4) |
C2—H2 | 0.9300 | C18—O1 | 1.230 (4) |
C3—C4 | 1.386 (6) | C18—N4 | 1.305 (5) |
C3—H3 | 0.9300 | C18—H18 | 0.9300 |
C4—C5 | 1.379 (6) | C19—N4 | 1.470 (6) |
C4—H4 | 0.9300 | C19—H19A | 0.9600 |
C5—C6 | 1.410 (5) | C19—H19B | 0.9600 |
C5—H5 | 0.9300 | C19—H19C | 0.9600 |
C6—C7 | 1.449 (5) | C20—N4 | 1.439 (7) |
C7—N1 | 1.273 (5) | C20—H20A | 0.9600 |
C7—H7 | 0.9300 | C20—H20B | 0.9600 |
C8—N1 | 1.482 (4) | C20—H20C | 0.9600 |
C8—C9 | 1.526 (5) | C21—H21A | 0.9600 |
C8—H8A | 0.9700 | C21—H21B | 0.9600 |
C8—H8B | 0.9700 | C21—H21C | 0.9600 |
C9—C21 | 1.515 (6) | C22—H22A | 0.9600 |
C9—C10 | 1.528 (5) | C22—H22B | 0.9600 |
C9—C22 | 1.545 (4) | C22—H22C | 0.9600 |
C10—N2 | 1.481 (4) | Cu—O2 | 2.038 (2) |
C10—H10A | 0.9700 | Cu—O3 | 2.040 (2) |
C10—H10B | 0.9700 | Cu—O4 | 2.103 (2) |
C11—N2 | 1.277 (4) | Cu—Ni | 2.9872 (5) |
C11—C12 | 1.463 (4) | N1—Ni | 2.012 (3) |
C11—H11 | 0.9300 | N2—Ni | 2.010 (3) |
C12—C13 | 1.402 (5) | N3—O5 | 1.224 (4) |
C12—C17 | 1.413 (4) | N3—O4 | 1.299 (4) |
C13—C14 | 1.374 (5) | N3—Ni | 2.127 (3) |
C13—H13 | 0.9300 | Ni—O2 | 2.002 (2) |
C14—C15 | 1.392 (5) | Ni—O3 | 2.016 (2) |
C14—H14 | 0.9300 | Ni—O1 | 2.190 (3) |
C15—C16 | 1.384 (5) | | |
| | | |
O2—C1—C2 | 120.2 (3) | H19A—C19—H19C | 109.5 |
O2—C1—C6 | 121.2 (3) | H19B—C19—H19C | 109.5 |
C2—C1—C6 | 118.7 (3) | N4—C20—H20A | 109.5 |
C3—C2—C1 | 121.1 (3) | N4—C20—H20B | 109.5 |
C3—C2—H2 | 119.4 | H20A—C20—H20B | 109.5 |
C1—C2—H2 | 119.4 | N4—C20—H20C | 109.5 |
C2—C3—C4 | 120.7 (4) | H20A—C20—H20C | 109.5 |
C2—C3—H3 | 119.7 | H20B—C20—H20C | 109.5 |
C4—C3—H3 | 119.7 | C9—C21—H21A | 109.5 |
C5—C4—C3 | 119.1 (4) | C9—C21—H21B | 109.5 |
C5—C4—H4 | 120.5 | H21A—C21—H21B | 109.5 |
C3—C4—H4 | 120.5 | C9—C21—H21C | 109.5 |
C4—C5—C6 | 121.7 (4) | H21A—C21—H21C | 109.5 |
C4—C5—H5 | 119.2 | H21B—C21—H21C | 109.5 |
C6—C5—H5 | 119.2 | C9—C22—H22A | 109.5 |
C1—C6—C5 | 118.7 (3) | C9—C22—H22B | 109.5 |
C1—C6—C7 | 125.6 (3) | H22A—C22—H22B | 109.5 |
C5—C6—C7 | 115.7 (3) | C9—C22—H22C | 109.5 |
N1—C7—C6 | 127.8 (3) | H22A—C22—H22C | 109.5 |
N1—C7—H7 | 116.1 | H22B—C22—H22C | 109.5 |
C6—C7—H7 | 116.1 | O2—Cu—O3 | 79.00 (9) |
N1—C8—C9 | 114.8 (3) | O2—Cu—O4 | 85.98 (9) |
N1—C8—H8A | 108.6 | O3—Cu—O4 | 84.17 (9) |
C9—C8—H8A | 108.6 | O2—Cu—Ni | 41.87 (6) |
N1—C8—H8B | 108.6 | O3—Cu—Ni | 42.25 (6) |
C9—C8—H8B | 108.6 | O4—Cu—Ni | 67.82 (6) |
H8A—C8—H8B | 107.5 | C7—N1—C8 | 116.9 (3) |
C21—C9—C8 | 112.0 (3) | C7—N1—Ni | 122.6 (2) |
C21—C9—C10 | 111.7 (3) | C8—N1—Ni | 120.5 (2) |
C8—C9—C10 | 111.3 (3) | C11—N2—C10 | 117.2 (3) |
C21—C9—C22 | 109.0 (3) | C11—N2—Ni | 122.4 (2) |
C8—C9—C22 | 105.3 (3) | C10—N2—Ni | 120.4 (2) |
C10—C9—C22 | 107.2 (3) | O5—N3—O4 | 116.0 (3) |
N2—C10—C9 | 113.8 (3) | O5—N3—Ni | 128.3 (3) |
N2—C10—H10A | 108.8 | O4—N3—Ni | 115.6 (2) |
C9—C10—H10A | 108.8 | C18—N4—C20 | 120.5 (4) |
N2—C10—H10B | 108.8 | C18—N4—C19 | 120.8 (4) |
C9—C10—H10B | 108.8 | C20—N4—C19 | 118.5 (5) |
H10A—C10—H10B | 107.7 | O2—Ni—N2 | 171.03 (10) |
N2—C11—C12 | 127.5 (3) | O2—Ni—N1 | 91.63 (10) |
N2—C11—H11 | 116.2 | N2—Ni—N1 | 96.99 (11) |
C12—C11—H11 | 116.2 | O2—Ni—O3 | 80.43 (9) |
C13—C12—C17 | 119.0 (3) | N2—Ni—O3 | 90.93 (10) |
C13—C12—C11 | 116.3 (3) | N1—Ni—O3 | 172.06 (10) |
C17—C12—C11 | 124.7 (3) | O2—Ni—N3 | 85.34 (11) |
C14—C13—C12 | 122.1 (3) | N2—Ni—N3 | 95.79 (12) |
C14—C13—H13 | 118.9 | N1—Ni—N3 | 98.35 (11) |
C12—C13—H13 | 118.9 | O3—Ni—N3 | 81.38 (10) |
C13—C14—C15 | 118.6 (3) | O2—Ni—O1 | 88.81 (10) |
C13—C14—H14 | 120.7 | N2—Ni—O1 | 88.51 (11) |
C15—C14—H14 | 120.7 | N1—Ni—O1 | 91.55 (11) |
C16—C15—C14 | 121.1 (3) | O3—Ni—O1 | 88.04 (9) |
C16—C15—H15 | 119.5 | N3—Ni—O1 | 168.62 (10) |
C14—C15—H15 | 119.5 | O2—Ni—Cu | 42.79 (6) |
C15—C16—C17 | 120.6 (3) | N2—Ni—Cu | 130.06 (8) |
C15—C16—H16 | 119.7 | N1—Ni—Cu | 129.88 (8) |
C17—C16—H16 | 119.7 | O3—Ni—Cu | 42.89 (6) |
O3—C17—C16 | 120.0 (3) | N3—Ni—Cu | 65.11 (8) |
O3—C17—C12 | 121.3 (3) | O1—Ni—Cu | 104.15 (6) |
C16—C17—C12 | 118.6 (3) | C18—O1—Ni | 118.3 (2) |
O1—C18—N4 | 124.9 (4) | C1—O2—Ni | 125.67 (19) |
O1—C18—H18 | 117.5 | C1—O2—Cu | 138.92 (19) |
N4—C18—H18 | 117.5 | Ni—O2—Cu | 95.34 (9) |
N4—C19—H19A | 109.5 | C17—O3—Ni | 124.86 (18) |
N4—C19—H19B | 109.5 | C17—O3—Cu | 139.22 (19) |
H19A—C19—H19B | 109.5 | Ni—O3—Cu | 94.86 (9) |
N4—C19—H19C | 109.5 | N3—O4—Cu | 111.3 (2) |
| | | |
O2—C1—C2—C3 | 179.6 (3) | O2i—Cu—Ni—O2 | 180.0 |
C6—C1—C2—C3 | −0.4 (5) | O3—Cu—Ni—O2 | 143.44 (15) |
C1—C2—C3—C4 | −1.6 (6) | O4—Cu—Ni—O2 | −109.97 (13) |
C2—C3—C4—C5 | 1.6 (7) | O2—Cu—Ni—N2 | −172.49 (15) |
C3—C4—C5—C6 | 0.4 (7) | O3—Cu—Ni—N2 | −29.06 (15) |
O2—C1—C6—C5 | −177.7 (3) | O4—Cu—Ni—N2 | 77.54 (13) |
C2—C1—C6—C5 | 2.4 (5) | O2—Cu—Ni—N1 | 32.01 (15) |
O2—C1—C6—C7 | 3.8 (6) | O3—Cu—Ni—N1 | 175.45 (16) |
C2—C1—C6—C7 | −176.1 (4) | O4—Cu—Ni—N1 | −77.96 (13) |
C4—C5—C6—C1 | −2.4 (7) | O2—Cu—Ni—O3 | −143.44 (15) |
C4—C5—C6—C7 | 176.2 (4) | O4—Cu—Ni—O3 | 106.60 (13) |
C1—C6—C7—N1 | 7.7 (7) | O2—Cu—Ni—N3 | 111.69 (14) |
C5—C6—C7—N1 | −170.9 (4) | O3—Cu—Ni—N3 | −104.88 (13) |
N1—C8—C9—C21 | 56.4 (4) | O4—Cu—Ni—N3 | 1.72 (11) |
N1—C8—C9—C10 | −69.5 (4) | O2—Cu—Ni—O1 | −72.30 (13) |
N1—C8—C9—C22 | 174.8 (3) | O3—Cu—Ni—O1 | 71.14 (13) |
C21—C9—C10—N2 | −54.9 (4) | O4—Cu—Ni—O1 | 177.73 (10) |
C8—C9—C10—N2 | 71.1 (4) | N4—C18—O1—Ni | −140.1 (3) |
C22—C9—C10—N2 | −174.3 (3) | O2—Ni—O1—C18 | −55.7 (3) |
N2—C11—C12—C13 | 168.6 (4) | N2—Ni—O1—C18 | 115.7 (3) |
N2—C11—C12—C17 | −13.2 (6) | N1—Ni—O1—C18 | −147.3 (3) |
C11—C12—C13—C14 | −180.0 (4) | O3—Ni—O1—C18 | 24.8 (3) |
C15—C16—C17—O3 | 179.1 (3) | N3—Ni—O1—C18 | 3.3 (7) |
C13—C12—C17—O3 | 179.7 (3) | Cu—Ni—O1—C18 | −15.4 (3) |
C11—C12—C17—C16 | −178.3 (3) | C2—C1—O2—Ni | 155.8 (3) |
C6—C7—N1—C8 | −178.5 (4) | C6—C1—O2—Ni | −24.1 (4) |
C6—C7—N1—Ni | 3.0 (6) | C2—C1—O2—Cu | −20.3 (5) |
C9—C8—N1—C7 | −136.1 (4) | C6—C1—O2—Cu | 159.8 (3) |
C9—C8—N1—Ni | 42.4 (4) | N1—Ni—O2—C1 | 26.6 (3) |
C12—C11—N2—C10 | 178.8 (3) | O3—Ni—O2—C1 | −153.1 (3) |
C12—C11—N2—Ni | −4.0 (5) | N3—Ni—O2—C1 | 124.9 (3) |
C9—C10—N2—C11 | 131.5 (4) | O1—Ni—O2—C1 | −64.9 (3) |
C9—C10—N2—Ni | −45.7 (4) | Cu—Ni—O2—C1 | −177.4 (3) |
O1—C18—N4—C20 | 3.7 (7) | N1—Ni—O2—Cu | −155.99 (11) |
O1—C18—N4—C19 | 178.3 (5) | O3—Ni—O2—Cu | 24.28 (10) |
C11—N2—Ni—N1 | −159.0 (3) | N3—Ni—O2—Cu | −57.74 (11) |
C10—N2—Ni—N1 | 18.1 (3) | O1—Ni—O2—Cu | 112.49 (10) |
C11—N2—Ni—O3 | 20.4 (3) | O3—Cu—O2—C1 | 152.7 (3) |
C10—N2—Ni—O3 | −162.5 (3) | O4—Cu—O2—C1 | −122.5 (3) |
C11—N2—Ni—N3 | 101.8 (3) | O4i—Cu—O2—C1 | 57.5 (3) |
C10—N2—Ni—N3 | −81.1 (3) | Ni—Cu—O2—C1 | 176.8 (4) |
C11—N2—Ni—O1 | −67.6 (3) | O3—Cu—O2—Ni | −24.08 (10) |
C10—N2—Ni—O1 | 109.5 (3) | O4—Cu—O2—Ni | 60.75 (10) |
C11—N2—Ni—Cu | 39.7 (3) | C16—C17—O3—Ni | −155.2 (3) |
C10—N2—Ni—Cu | −143.2 (2) | C12—C17—O3—Ni | 24.9 (4) |
C7—N1—Ni—O2 | −15.4 (3) | C16—C17—O3—Cu | 9.8 (5) |
C8—N1—Ni—O2 | 166.1 (3) | C12—C17—O3—Cu | −170.1 (2) |
C7—N1—Ni—N2 | 162.1 (3) | O2—Ni—O3—C17 | 146.0 (3) |
C8—N1—Ni—N2 | −16.4 (3) | N2—Ni—O3—C17 | −31.6 (3) |
C7—N1—Ni—N3 | −100.9 (3) | N3—Ni—O3—C17 | −127.4 (3) |
C8—N1—Ni—N3 | 80.6 (3) | O1—Ni—O3—C17 | 56.8 (3) |
C7—N1—Ni—O1 | 73.4 (3) | Cu—Ni—O3—C17 | 170.2 (3) |
C8—N1—Ni—O1 | −105.0 (3) | O2—Ni—O3—Cu | −24.23 (10) |
C7—N1—Ni—Cu | −36.5 (3) | N2—Ni—O3—Cu | 158.18 (11) |
C8—N1—Ni—Cu | 145.0 (2) | N3—Ni—O3—Cu | 62.46 (11) |
O5—N3—Ni—O2 | −147.6 (3) | O1—Ni—O3—Cu | −113.35 (10) |
O4—N3—Ni—O2 | 36.4 (2) | O2i—Cu—O3—C17 | 36.3 (3) |
O5—N3—Ni—N2 | 41.3 (3) | O2—Cu—O3—C17 | −143.7 (3) |
O4—N3—Ni—N2 | −134.6 (2) | O4—Cu—O3—C17 | 129.2 (3) |
O5—N3—Ni—N1 | −56.7 (3) | Ni—Cu—O3—C17 | −167.6 (4) |
O4—N3—Ni—N1 | 127.4 (2) | O2—Cu—O3—Ni | 23.89 (10) |
O5—N3—Ni—O3 | 131.4 (3) | O4—Cu—O3—Ni | −63.13 (10) |
O4—N3—Ni—O3 | −44.6 (2) | O5—N3—O4—Cu | −172.5 (2) |
O5—N3—Ni—O1 | 153.1 (5) | Ni—N3—O4—Cu | 4.0 (3) |
O4—N3—Ni—O1 | −22.8 (7) | O2—Cu—O4—N3 | −41.7 (2) |
O5—N3—Ni—Cu | 173.1 (3) | O3—Cu—O4—N3 | 37.6 (2) |
O4—N3—Ni—Cu | −2.86 (19) | Ni—Cu—O4—N3 | −2.74 (18) |
Symmetry code: (i) −x, −y, −z. |
(III) [bis(dimethylformamide)-1
κO,3
κO-bis{µ-2,2'-[2,2'-dimethylpropane- 1,3-diylbis(nitrilomethylidyne)]diphenolato-
1
κ4N,
N',
O,
O':2
κ2O,
O';2
κ2O,
O':3
κ4N,
N',
O,
O'-di-µ-nitrito-
1:2
κ2N:
O;2:3
κ2O:
N-dinickel(II)]manganese(II)
top
Crystal data top
[MnNi2(NO2)2(C19H22N2O2)2(C3H7NO)2] | F(000) = 1070 |
Mr = 1027.42 | Dx = 1.459 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 25 reflections |
a = 11.009 (2) Å | θ = 2.3–26.0° |
b = 10.2060 (8) Å | µ = 1.13 mm−1 |
c = 21.216 (2) Å | T = 298 K |
β = 101.247 (7)° | Prism, light brown |
V = 2338.0 (5) Å3 | 0.33 × 0.33 × 0.13 mm |
Z = 2 | |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.019 |
ω/2θ scans | θmax = 26.0° |
Absorption correction: ψ-scan empirical (using intensity measurements) (Fair, 1990) | h = −13→1 |
Tmin = 0.724, Tmax = 0.879 | k = −12→0 |
5026 measured reflections | l = −25→26 |
4589 independent reflections | 3 standard reflections every 120 min |
3436 reflections with I > 2σ(I) | intensity decay: 1.3% |
Refinement top
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)] = 0.033 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.099 | H 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 parameters | Δρmax = 0.41 e Å−3 |
0 restraints | Δρmin = −0.54 e Å−3 |
Crystal data top
[MnNi2(NO2)2(C19H22N2O2)2(C3H7NO)2] | V = 2338.0 (5) Å3 |
Mr = 1027.42 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.009 (2) Å | µ = 1.13 mm−1 |
b = 10.2060 (8) Å | T = 298 K |
c = 21.216 (2) Å | 0.33 × 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 = 0.879 | 3 standard reflections every 120 min |
5026 measured reflections | intensity decay: 1.3% |
4589 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.099 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.41 e Å−3 |
4589 reflections | Δρmin = −0.54 e Å−3 |
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 | x | y | z | Uiso*/Ueq | |
C1 | −0.0537 (2) | 0.1361 (3) | 0.12894 (12) | 0.0377 (5) | |
C2 | −0.1696 (3) | 0.1873 (3) | 0.10123 (14) | 0.0477 (7) | |
H2 | −0.189 (3) | 0.189 (3) | 0.0571 (15) | 0.057* | |
C3 | −0.2468 (3) | 0.2419 (4) | 0.13784 (16) | 0.0577 (8) | |
H3 | −0.323 (3) | 0.288 (3) | 0.1146 (13) | 0.049 (8)* | |
C4 | −0.2129 (3) | 0.2445 (4) | 0.20438 (17) | 0.0700 (10) | |
H4 | −0.271 (4) | 0.282 (4) | 0.2283 (18) | 0.084* | |
C5 | −0.1000 (3) | 0.1952 (4) | 0.23257 (15) | 0.0645 (9) | |
H5 | −0.077 (3) | 0.202 (4) | 0.2790 (17) | 0.077* | |
C6 | −0.0167 (2) | 0.1435 (3) | 0.19667 (12) | 0.0431 (6) | |
C7 | 0.1031 (3) | 0.1016 (3) | 0.23273 (12) | 0.0458 (7) | |
H7 | 0.106 (3) | 0.105 (3) | 0.2740 (15) | 0.055* | |
C8 | 0.3056 (3) | 0.0240 (4) | 0.25926 (13) | 0.0487 (7) | |
H8A | 0.294 (3) | 0.048 (3) | 0.3002 (17) | 0.058* | |
H8B | 0.310 (3) | −0.075 (3) | 0.2566 (15) | 0.058* | |
C9 | 0.4289 (3) | 0.0767 (3) | 0.24806 (12) | 0.0450 (6) | |
C10 | 0.4652 (3) | 0.0136 (3) | 0.18901 (13) | 0.0479 (7) | |
H10A | 0.451 (3) | −0.078 (3) | 0.1915 (15) | 0.057* | |
H10B | 0.549 (3) | 0.032 (3) | 0.1876 (15) | 0.057* | |
C11 | 0.4470 (2) | 0.0891 (3) | 0.08319 (13) | 0.0415 (6) | |
H11 | 0.538 (3) | 0.083 (3) | 0.0898 (14) | 0.050* | |
C12 | 0.3942 (2) | 0.1324 (3) | 0.01821 (12) | 0.0388 (5) | |
C13 | 0.4766 (3) | 0.1853 (3) | −0.01760 (14) | 0.0495 (7) | |
H13 | 0.560 (3) | 0.192 (3) | 0.0018 (14) | 0.059* | |
C14 | 0.4388 (3) | 0.2277 (3) | −0.07933 (15) | 0.0572 (8) | |
H14 | 0.500 (3) | 0.256 (3) | −0.1034 (16) | 0.069* | |
C15 | 0.3145 (3) | 0.2153 (4) | −0.10770 (14) | 0.0577 (8) | |
H15 | 0.288 (3) | 0.248 (3) | −0.1510 (17) | 0.069* | |
C16 | 0.2315 (3) | 0.1611 (3) | −0.07459 (13) | 0.0472 (7) | |
H16 | 0.146 (3) | 0.152 (3) | −0.0935 (14) | 0.057* | |
C17 | 0.2678 (2) | 0.1192 (3) | −0.01126 (11) | 0.0354 (5) | |
C18 | 0.1683 (3) | 0.3350 (3) | 0.06544 (15) | 0.0529 (7) | |
H18 | 0.092 (3) | 0.305 (3) | 0.0453 (16) | 0.063* | |
C19 | 0.3363 (5) | 0.4816 (4) | 0.0698 (2) | 0.0976 (15) | |
H19A | 0.3573 | 0.5555 | 0.0461 | 0.117* | |
H19B | 0.3958 | 0.4130 | 0.0694 | 0.117* | |
H19C | 0.3367 | 0.5073 | 0.1134 | 0.117* | |
C20 | 0.1559 (6) | 0.4952 (5) | −0.0187 (2) | 0.127 (2) | |
H20A | 0.2051 | 0.5671 | −0.0287 | 0.153* | |
H20B | 0.0757 | 0.5267 | −0.0144 | 0.153* | |
H20C | 0.1468 | 0.4314 | −0.0525 | 0.153* | |
C21 | 0.4306 (3) | 0.2252 (4) | 0.24425 (16) | 0.0551 (8) | |
H21A | 0.378 (3) | 0.253 (3) | 0.2115 (17) | 0.066* | |
H21B | 0.414 (3) | 0.265 (3) | 0.2812 (17) | 0.066* | |
H21C | 0.512 (3) | 0.261 (3) | 0.2405 (16) | 0.066* | |
C22 | 0.5263 (4) | 0.0339 (5) | 0.30714 (17) | 0.0660 (9) | |
H22A | 0.508 (4) | 0.087 (4) | 0.3416 (19) | 0.079* | |
H22B | 0.519 (4) | −0.053 (4) | 0.3123 (19) | 0.079* | |
H22C | 0.607 (4) | 0.064 (4) | 0.3034 (19) | 0.079* | |
N1 | 0.1969 (2) | 0.0648 (2) | 0.21077 (9) | 0.0385 (5) | |
N2 | 0.38940 (19) | 0.0566 (2) | 0.12700 (10) | 0.0372 (5) | |
N3 | 0.1776 (2) | −0.1397 (2) | 0.10145 (11) | 0.0478 (6) | |
N4 | 0.2163 (3) | 0.4355 (3) | 0.04107 (14) | 0.0658 (8) | |
O1 | 0.21634 (18) | 0.27722 (19) | 0.11464 (9) | 0.0493 (5) | |
O2 | 0.01728 (16) | 0.08439 (19) | 0.09301 (8) | 0.0420 (4) | |
O3 | 0.18599 (16) | 0.06902 (18) | 0.01938 (8) | 0.0404 (4) | |
O4 | 0.08938 (19) | −0.17680 (19) | 0.05540 (9) | 0.0530 (5) | |
O5 | 0.2423 (3) | −0.2243 (2) | 0.12945 (12) | 0.0741 (7) | |
Ni | 0.20295 (3) | 0.06525 (3) | 0.116356 (14) | 0.03349 (11) | |
Mn | 0.0000 | 0.0000 | 0.0000 | 0.03603 (15) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0315 (12) | 0.0452 (14) | 0.0379 (13) | −0.0053 (11) | 0.0107 (10) | −0.0108 (11) |
C2 | 0.0379 (14) | 0.0614 (18) | 0.0438 (15) | −0.0059 (14) | 0.0078 (12) | −0.0078 (13) |
C3 | 0.0355 (15) | 0.074 (2) | 0.0638 (19) | −0.0156 (17) | 0.0108 (14) | −0.0033 (15) |
C4 | 0.0432 (17) | 0.109 (3) | 0.062 (2) | −0.027 (2) | 0.0214 (15) | 0.0004 (18) |
C5 | 0.0479 (17) | 0.106 (3) | 0.0431 (16) | −0.0173 (18) | 0.0176 (13) | −0.0084 (18) |
C6 | 0.0384 (13) | 0.0585 (17) | 0.0342 (13) | −0.0073 (12) | 0.0116 (11) | −0.0078 (13) |
C7 | 0.0489 (16) | 0.0640 (19) | 0.0259 (12) | −0.0041 (12) | 0.0103 (11) | −0.0083 (14) |
C8 | 0.0489 (16) | 0.0641 (19) | 0.0301 (13) | 0.0068 (13) | 0.0004 (12) | 0.0009 (14) |
C9 | 0.0406 (14) | 0.0596 (17) | 0.0304 (13) | −0.0004 (12) | −0.0039 (11) | 0.0020 (13) |
C10 | 0.0414 (15) | 0.0590 (18) | 0.0396 (14) | 0.0049 (14) | −0.0013 (12) | 0.0078 (14) |
C11 | 0.0312 (13) | 0.0494 (16) | 0.0428 (14) | −0.0054 (12) | 0.0048 (11) | −0.0030 (11) |
C12 | 0.0361 (13) | 0.0440 (14) | 0.0373 (13) | −0.0045 (12) | 0.0095 (10) | −0.0043 (11) |
C13 | 0.0389 (15) | 0.0637 (19) | 0.0478 (16) | −0.0062 (14) | 0.0134 (12) | −0.0121 (13) |
C14 | 0.0556 (18) | 0.072 (2) | 0.0504 (17) | −0.0008 (16) | 0.0262 (14) | −0.0195 (16) |
C15 | 0.0561 (18) | 0.080 (2) | 0.0396 (15) | 0.0091 (15) | 0.0151 (13) | −0.0077 (16) |
C16 | 0.0420 (15) | 0.0646 (19) | 0.0350 (13) | 0.0028 (13) | 0.0077 (11) | −0.0081 (14) |
C17 | 0.0357 (13) | 0.0404 (13) | 0.0313 (12) | −0.0046 (11) | 0.0100 (10) | −0.0064 (11) |
C18 | 0.0606 (19) | 0.0424 (16) | 0.0508 (17) | −0.0031 (13) | −0.0009 (14) | 0.0029 (14) |
C19 | 0.117 (4) | 0.067 (3) | 0.121 (4) | −0.012 (3) | 0.053 (3) | −0.025 (3) |
C20 | 0.210 (7) | 0.085 (3) | 0.080 (3) | 0.038 (3) | 0.012 (4) | 0.027 (4) |
C21 | 0.0477 (18) | 0.064 (2) | 0.0483 (17) | −0.0057 (15) | −0.0030 (14) | −0.0061 (15) |
C22 | 0.058 (2) | 0.090 (3) | 0.0418 (17) | 0.0014 (18) | −0.0110 (15) | 0.009 (2) |
N1 | 0.0405 (12) | 0.0476 (13) | 0.0265 (10) | 0.0019 (9) | 0.0041 (9) | −0.0060 (10) |
N2 | 0.0345 (11) | 0.0444 (12) | 0.0308 (10) | −0.0037 (9) | 0.0022 (8) | 0.0004 (9) |
N3 | 0.0568 (14) | 0.0453 (14) | 0.0449 (13) | 0.0039 (11) | 0.0187 (11) | −0.0006 (12) |
N4 | 0.098 (2) | 0.0442 (15) | 0.0553 (16) | 0.0053 (12) | 0.0159 (15) | −0.0022 (15) |
O1 | 0.0561 (12) | 0.0447 (11) | 0.0426 (10) | 0.0006 (9) | −0.0017 (9) | −0.0024 (9) |
O2 | 0.0337 (9) | 0.0605 (12) | 0.0317 (9) | −0.0097 (8) | 0.0064 (7) | −0.0019 (8) |
O3 | 0.0350 (9) | 0.0585 (12) | 0.0277 (8) | 0.0014 (8) | 0.0059 (7) | −0.0133 (8) |
O4 | 0.0602 (13) | 0.0479 (11) | 0.0495 (11) | −0.0040 (9) | 0.0072 (10) | −0.0116 (10) |
O5 | 0.0841 (17) | 0.0610 (15) | 0.0716 (15) | 0.0091 (13) | 0.0013 (13) | 0.0055 (13) |
Ni | 0.03218 (17) | 0.04194 (19) | 0.02571 (16) | −0.00051 (13) | 0.00412 (12) | −0.00366 (14) |
Mn | 0.0326 (3) | 0.0489 (3) | 0.0261 (3) | −0.0056 (2) | 0.0046 (2) | −0.0109 (2) |
Geometric parameters (Å, º) top
Ni—Mn | 3.0624 (8) | C15—H15 | 0.97 (3) |
C1—O2 | 1.304 (3) | C16—C17 | 1.392 (3) |
C1—C2 | 1.398 (4) | C16—H16 | 0.95 (3) |
C1—C6 | 1.417 (3) | C17—O3 | 1.313 (3) |
C2—C3 | 1.376 (4) | C18—O1 | 1.225 (3) |
C2—H2 | 0.92 (3) | C18—N4 | 1.306 (4) |
C3—C4 | 1.388 (5) | C18—H18 | 0.91 (3) |
C3—H3 | 1.00 (3) | C19—N4 | 1.422 (5) |
C4—C5 | 1.366 (5) | C19—H19A | 0.9600 |
C4—H4 | 0.97 (4) | C19—H19B | 0.9600 |
C5—C6 | 1.404 (4) | C19—H19C | 0.9600 |
C5—H5 | 0.97 (4) | C20—N4 | 1.446 (5) |
C6—C7 | 1.453 (4) | C20—H20A | 0.9600 |
C7—N1 | 1.270 (4) | C20—H20B | 0.9600 |
C7—H7 | 0.87 (3) | C20—H20C | 0.9600 |
C8—N1 | 1.478 (3) | C21—H21A | 0.86 (4) |
C8—C9 | 1.521 (4) | C21—H21B | 0.93 (4) |
C8—H8A | 0.93 (3) | C21—H21C | 0.99 (4) |
C8—H8B | 1.02 (3) | C22—H22A | 0.96 (4) |
C9—C21 | 1.518 (5) | C22—H22B | 0.90 (4) |
C9—C10 | 1.529 (4) | C22—H22C | 0.95 (4) |
C9—C22 | 1.545 (4) | N1—Ni | 2.017 (2) |
C10—N2 | 1.480 (3) | N2—Ni | 2.023 (2) |
C10—H10A | 0.95 (3) | N3—O5 | 1.200 (3) |
C10—H10B | 0.95 (3) | N3—O4 | 1.293 (3) |
C11—N2 | 1.267 (3) | N3—Ni | 2.125 (3) |
C11—C12 | 1.457 (4) | O1—Ni | 2.169 (2) |
C11—H11 | 0.99 (3) | O2—Ni | 2.0167 (18) |
C12—C13 | 1.400 (4) | O2—Mn | 2.1274 (16) |
C12—C17 | 1.416 (3) | O3—Ni | 2.0296 (16) |
C13—C14 | 1.365 (4) | O3—Mn | 2.1283 (17) |
C13—H13 | 0.93 (3) | Mn—O2i | 2.1274 (16) |
C14—C15 | 1.389 (4) | Mn—O3i | 2.1283 (17) |
C14—H14 | 0.97 (3) | Mn—O4 | 2.270 (3) |
C15—C16 | 1.373 (4) | | |
| | | |
O2—C1—C2 | 120.5 (2) | H19A—C19—H19B | 109.5 |
O2—C1—C6 | 121.8 (2) | N4—C19—H19C | 109.5 |
C2—C1—C6 | 117.7 (2) | H19A—C19—H19C | 109.5 |
C3—C2—C1 | 121.8 (3) | H19B—C19—H19C | 109.5 |
C3—C2—H2 | 121 (2) | N4—C20—H20A | 109.5 |
C1—C2—H2 | 117 (2) | N4—C20—H20B | 109.5 |
C2—C3—C4 | 120.6 (3) | H20A—C20—H20B | 109.5 |
C2—C3—H3 | 117.5 (16) | N4—C20—H20C | 109.5 |
C4—C3—H3 | 121.6 (16) | H20A—C20—H20C | 109.5 |
C5—C4—C3 | 118.6 (3) | H20B—C20—H20C | 109.5 |
C5—C4—H4 | 123 (2) | C9—C21—H21A | 111 (2) |
C3—C4—H4 | 118 (2) | C9—C21—H21B | 112 (2) |
C4—C5—C6 | 122.4 (3) | H21A—C21—H21B | 109 (3) |
C4—C5—H5 | 117 (2) | C9—C21—H21C | 113 (2) |
C6—C5—H5 | 120 (2) | H21A—C21—H21C | 107 (3) |
C5—C6—C1 | 118.7 (3) | H21B—C21—H21C | 104 (3) |
C5—C6—C7 | 116.5 (2) | C9—C22—H22A | 104 (2) |
C1—C6—C7 | 124.8 (2) | C9—C22—H22B | 108 (3) |
N1—C7—C6 | 127.8 (2) | H22A—C22—H22B | 115 (4) |
N1—C7—H7 | 120 (2) | C9—C22—H22C | 110 (2) |
C6—C7—H7 | 112 (2) | H22A—C22—H22C | 102 (3) |
N1—C8—C9 | 114.7 (2) | H22B—C22—H22C | 116 (3) |
N1—C8—H8A | 110 (2) | C7—N1—C8 | 115.7 (2) |
C9—C8—H8A | 110 (2) | C7—N1—Ni | 123.39 (18) |
N1—C8—H8B | 106.5 (18) | C8—N1—Ni | 120.85 (18) |
C9—C8—H8B | 106.9 (18) | C11—N2—C10 | 117.0 (2) |
H8A—C8—H8B | 109 (3) | C11—N2—Ni | 123.28 (18) |
C21—C9—C8 | 112.5 (3) | C10—N2—Ni | 119.75 (18) |
C21—C9—C10 | 111.6 (3) | O5—N3—O4 | 116.7 (3) |
C8—C9—C10 | 111.3 (2) | O5—N3—Ni | 125.9 (2) |
C21—C9—C22 | 108.2 (3) | O4—N3—Ni | 117.27 (18) |
C8—C9—C22 | 105.8 (3) | C18—N4—C19 | 120.2 (3) |
C10—C9—C22 | 107.1 (3) | C18—N4—C20 | 121.7 (4) |
N2—C10—C9 | 114.3 (2) | C19—N4—C20 | 117.8 (4) |
N2—C10—H10A | 105.6 (19) | C18—O1—Ni | 118.33 (18) |
C9—C10—H10A | 107 (2) | C1—O2—Ni | 126.11 (15) |
N2—C10—H10B | 107 (2) | C1—O2—Mn | 138.63 (15) |
C9—C10—H10B | 111 (2) | Ni—O2—Mn | 95.25 (7) |
H10A—C10—H10B | 112 (3) | C17—O3—Ni | 124.94 (15) |
N2—C11—C12 | 127.5 (2) | C17—O3—Mn | 139.50 (15) |
N2—C11—H11 | 121.2 (17) | Ni—O3—Mn | 94.84 (7) |
C12—C11—H11 | 111.2 (17) | O2—Ni—N1 | 90.91 (8) |
C13—C12—C17 | 118.8 (2) | O2—Ni—N2 | 171.73 (8) |
C13—C12—C11 | 116.7 (2) | N1—Ni—N2 | 96.79 (8) |
C17—C12—C11 | 124.4 (2) | O2—Ni—O3 | 82.00 (7) |
C14—C13—C12 | 122.3 (3) | N1—Ni—O3 | 172.91 (8) |
C14—C13—H13 | 119.5 (19) | N2—Ni—O3 | 90.27 (8) |
C12—C13—H13 | 118.2 (19) | O2—Ni—N3 | 87.79 (9) |
C13—C14—C15 | 118.5 (3) | N1—Ni—N3 | 96.70 (9) |
C13—C14—H14 | 119 (2) | N2—Ni—N3 | 94.26 (9) |
C15—C14—H14 | 122 (2) | O3—Ni—N3 | 83.36 (8) |
C16—C15—C14 | 120.8 (3) | O2—Ni—O1 | 88.18 (8) |
C16—C15—H15 | 121 (2) | N1—Ni—O1 | 91.97 (8) |
C14—C15—H15 | 118 (2) | N2—Ni—O1 | 88.56 (8) |
C15—C16—C17 | 121.5 (3) | O3—Ni—O1 | 87.55 (7) |
C15—C16—H16 | 121.5 (18) | N3—Ni—O1 | 170.49 (8) |
C17—C16—H16 | 117.0 (18) | O2—Mn—O2i | 180.0 |
O3—C17—C16 | 120.1 (2) | O2—Mn—O3i | 102.81 (7) |
O3—C17—C12 | 121.9 (2) | O2i—Mn—O3i | 77.19 (7) |
C16—C17—C12 | 118.0 (2) | O2—Mn—O3 | 77.19 (7) |
O1—C18—N4 | 125.1 (3) | O2i—Mn—O3 | 102.81 (7) |
O1—C18—H18 | 116 (2) | O3i—Mn—O3 | 180.0 |
N4—C18—H18 | 119 (2) | O3—Mn—O4 | 81.93 (7) |
N4—C19—H19A | 109.5 | O2—Mn—O4 | 83.70 (8) |
N4—C19—H19B | 109.5 | | |
| | | |
O2—C1—C2—C3 | 179.7 (3) | C1—O2—Ni—O3 | −154.1 (2) |
C4—C5—C6—C7 | 176.4 (4) | Mn—O2—Ni—O3 | 24.99 (7) |
O2—C1—C6—C5 | −177.2 (3) | C1—O2—Ni—N3 | 122.3 (2) |
C2—C1—C6—C7 | −176.5 (3) | Mn—O2—Ni—N3 | −58.61 (8) |
C5—C6—C7—N1 | −172.2 (3) | C1—O2—Ni—O1 | −66.3 (2) |
C1—C6—C7—N1 | 7.5 (5) | Mn—O2—Ni—O1 | 112.77 (8) |
N1—C8—C9—C21 | 56.6 (3) | C7—N1—Ni—O2 | −15.3 (2) |
N1—C8—C9—C10 | −69.4 (3) | C8—N1—Ni—O2 | 166.5 (2) |
N1—C8—C9—C22 | 174.5 (3) | C7—N1—Ni—N2 | 161.7 (2) |
C21—C9—C10—N2 | −55.2 (3) | C8—N1—Ni—N2 | −16.5 (2) |
C8—C9—C10—N2 | 71.4 (3) | C7—N1—Ni—N3 | −103.2 (2) |
C22—C9—C10—N2 | −173.4 (3) | C8—N1—Ni—N3 | 78.6 (2) |
N2—C11—C12—C13 | 168.8 (3) | C7—N1—Ni—O1 | 72.9 (2) |
N2—C11—C12—C17 | −14.0 (5) | C8—N1—Ni—O1 | −105.3 (2) |
C17—C12—C13—C14 | 1.8 (5) | C11—N2—Ni—N1 | −160.4 (2) |
C11—C12—C13—C14 | 179.1 (3) | C10—N2—Ni—N1 | 18.0 (2) |
C12—C13—C14—C15 | −1.3 (5) | C11—N2—Ni—O3 | 18.9 (2) |
C13—C14—C15—C16 | −0.3 (5) | C10—N2—Ni—O3 | −162.6 (2) |
C14—C15—C16—C17 | 1.4 (5) | C11—N2—Ni—N3 | 102.3 (2) |
C15—C16—C17—O3 | 179.3 (3) | C10—N2—Ni—N3 | −79.3 (2) |
C15—C16—C17—C12 | −0.8 (4) | C11—N2—Ni—O1 | −68.6 (2) |
C13—C12—C17—O3 | 179.2 (3) | C10—N2—Ni—O1 | 109.8 (2) |
C11—C12—C17—O3 | 2.1 (4) | C17—O3—Ni—O2 | 147.0 (2) |
C13—C12—C17—C16 | −0.7 (4) | Mn—O3—Ni—O2 | −24.96 (7) |
C11—C12—C17—C16 | −177.8 (3) | C17—O3—Ni—N2 | −30.1 (2) |
C6—C7—N1—C8 | −178.3 (3) | Mn—O3—Ni—N2 | 157.99 (8) |
C6—C7—N1—Ni | 3.4 (4) | C17—O3—Ni—N3 | −124.3 (2) |
C9—C8—N1—C7 | −135.7 (3) | Mn—O3—Ni—N3 | 63.73 (9) |
C9—C8—N1—Ni | 42.7 (3) | C17—O3—Ni—O1 | 58.5 (2) |
C12—C11—N2—C10 | 179.0 (3) | Mn—O3—Ni—O1 | −113.47 (8) |
C12—C11—N2—Ni | −2.6 (4) | O5—N3—Ni—O2 | −148.3 (2) |
C9—C10—N2—C11 | 132.8 (3) | O4—N3—Ni—O2 | 36.30 (18) |
C9—C10—N2—Ni | −45.7 (3) | O5—N3—Ni—N1 | −57.6 (3) |
O1—C18—N4—C19 | 3.6 (5) | O4—N3—Ni—N1 | 126.96 (18) |
O1—C18—N4—C20 | 177.5 (4) | O5—N3—Ni—N2 | 39.7 (3) |
N4—C18—O1—Ni | −139.9 (3) | O4—N3—Ni—N2 | −135.68 (19) |
C2—C1—O2—Ni | 156.6 (2) | O5—N3—Ni—O3 | 129.5 (3) |
C6—C1—O2—Ni | −23.0 (4) | O4—N3—Ni—O3 | −45.90 (18) |
C2—C1—O2—Mn | −22.0 (4) | C18—O1—Ni—O2 | −56.2 (2) |
C6—C1—O2—Mn | 158.4 (2) | C18—O1—Ni—N1 | −147.1 (2) |
C16—C17—O3—Ni | −156.3 (2) | C18—O1—Ni—N2 | 116.2 (2) |
C12—C17—O3—Ni | 23.8 (3) | C18—O1—Ni—O3 | 25.8 (2) |
C16—C17—O3—Mn | 11.3 (4) | C1—O2—Mn—O3 | 154.7 (3) |
C12—C17—O3—Mn | −168.56 (19) | Ni—O2—Mn—O3 | −24.15 (7) |
C1—O2—Ni—N1 | 25.7 (2) | C17—O3—Mn—O2 | −145.9 (3) |
Mn—O2—Ni—N1 | −155.28 (8) | Ni—O3—Mn—O2 | 23.97 (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] |
Mr | 1031.30 | 1035.91 | 1027.42 |
Crystal system, space group | Monoclinic, P21/n | Monoclinic, P21/n | Monoclinic, P21/n |
Temperature (K) | 299 | 293 | 298 |
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) |
V (Å3) | 2314.1 (5) | 2319.3 (4) | 2338.0 (5) |
Z | 2 | 2 | 2 |
Radiation type | Mo Kα | Cu Kα | Mo Kα |
µ (mm−1) | 1.23 | 2.02 | 1.13 |
Crystal size (mm) | 0.25 × 0.18 × 0.13 | 0.25 × 0.20 × 0.15 | 0.33 × 0.33 × 0.13 |
|
Data collection |
Diffractometer | Enraf-Nonius CAD-4 diffractometer | Enraf-Nonius CAD-4 diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | ψ-scan empirical (using intensity measurements) (Fair, 1990) | ψ-scan empirical (using intensity measurements) (Fair, 1990) | ψ-scan empirical (using intensity measurements) (Fair, 1990) |
Tmin, Tmax | 0.812, 0.865 | 0.632, 0.752 | 0.724, 0.879 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8277, 4548, 3019 | 4867, 4626, 3644 | 5026, 4589, 3436 |
Rint | 0.030 | 0.046 | 0.019 |
(sin θ/λ)max (Å−1) | 0.617 | 0.624 | 0.617 |
|
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 reflections | 4548 | 4626 | 4589 |
No. of parameters | 346 | 296 | 359 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H-atom parameters constrained | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.30, −0.27 | 0.44, −1.06 | 0.41, −0.54 |
Selected geometric parameters (Å, º) for (I) topN1—Ni | 2.006 (2) | O2—Co | 2.0601 (18) |
N2—Ni | 2.016 (2) | O3—Ni | 2.0007 (18) |
N3—Ni | 2.113 (3) | O3—Co | 2.0542 (16) |
O1—Ni | 2.169 (2) | O4—Co | 2.161 (2) |
O2—Ni | 2.0178 (16) | Ni—Co | 2.9988 (5) |
| | | |
Ni—O2—Co | 94.67 (7) | N2—Ni—N3 | 97.64 (9) |
Ni—O3—Co | 95.38 (7) | O2—Ni—N3 | 82.29 (8) |
O3—Ni—O2 | 81.02 (7) | O3—Co—O2 | 78.76 (7) |
O3—Ni—N3 | 86.18 (9) | O3—Co—O4 | 95.34 (7) |
N1—Ni—N3 | 95.33 (10) | O2—Co—O4 | 96.84 (7) |
Selected geometric parameters (Å, º) for (II) topCu—O2 | 2.038 (2) | N2—Ni | 2.010 (3) |
Cu—O3 | 2.040 (2) | N3—Ni | 2.127 (3) |
Cu—O4 | 2.103 (2) | Ni—O2 | 2.002 (2) |
Cu—Ni | 2.9872 (5) | Ni—O3 | 2.016 (2) |
N1—Ni | 2.012 (3) | Ni—O1 | 2.190 (3) |
| | | |
O2—Cu—O3 | 79.00 (9) | N2—Ni—N3 | 95.79 (12) |
O2—Cu—O4 | 85.98 (9) | N1—Ni—N3 | 98.35 (11) |
O3—Cu—O4 | 84.17 (9) | O3—Ni—N3 | 81.38 (10) |
O2—Ni—O3 | 80.43 (9) | Ni—O2—Cu | 95.34 (9) |
O2—Ni—N3 | 85.34 (11) | Ni—O3—Cu | 94.86 (9) |
Selected geometric parameters (Å, º) for (III) topNi—Mn | 3.0624 (8) | O2—Ni | 2.0167 (18) |
N1—Ni | 2.017 (2) | O2—Mn | 2.1274 (16) |
N2—Ni | 2.023 (2) | O3—Ni | 2.0296 (16) |
N3—Ni | 2.125 (3) | O3—Mn | 2.1283 (17) |
O1—Ni | 2.169 (2) | Mn—O4 | 2.270 (3) |
| | | |
Ni—O2—Mn | 95.25 (7) | N2—Ni—N3 | 94.26 (9) |
Ni—O3—Mn | 94.84 (7) | O3—Ni—N3 | 83.36 (8) |
O2—Ni—O3 | 82.00 (7) | O2—Mn—O3 | 77.19 (7) |
O2—Ni—N3 | 87.79 (9) | O3—Mn—O4 | 81.93 (7) |
N1—Ni—N3 | 96.70 (9) | O2—Mn—O4 | 83.70 (8) |
Structural data, bridging angles and dihedral angles (ϕ and κ) for
seven homo- or heterotrinuclear complexes (Å, °) topComplex | M-O | Ni-M | O-M-O | ϕ | κ |
(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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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.