Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101008150/br1331sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101008150/br1331Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101008150/br1331IIsup3.hkl |
CCDC references: 169931; 169932
N,N'-Bis(salicylidene)-2,2-dimethyl-1,3-propanediamine (0.620 g, 0.002 mol) was dissolved in a hot dioxane–MeOH mixture (1:1, 50 ml). To this solution were added triethylamine (1 ml) and a solution of NiCl2·6H2O (0.476 g, 0.002 mol) in hot MeOH (30 ml) for the Ni complex and a solution of CuCl2·2H2O (0.340 g, 0.002 mol) in hot MeOH (30 ml) for the Cu complex. The mixture was set aside for 2 d and the dark-brown crystals of the nickel(II) complex and dark-green crystals of the copper(II) complex which formed were filtered off and dried in an oven at 373 K.
H atoms bonded to C atoms were placed geometrically. All H atoms were refined as riding with Ueq(H) = 1.2Uiso(C).
For both 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.
[Ni(C19H20N2O2)] | Z = 4 |
Mr = 367.08 | Dx = 1.406 Mg m−3 |
Monoclinic, P21/n | Cu Kα radiation, λ = 1.54180 Å |
Hall symbol: -P 2yn | Cell parameters from 25 reflections |
a = 9.9329 (12) Å | θ = 4.9–74.2° |
b = 15.8778 (11) Å | µ = 1.72 mm−1 |
c = 11.8793 (10) Å | T = 301 K |
β = 112.200 (3)° | Prism, dark brown |
V = 1734.6 (3) Å3 | 0.35 × 0.30 × 0.25 mm |
CAD-4 EXPRESS diffractometer | Rint = 0.036 |
ω/2θ scans | θmax = 74.2° |
Absorption correction: ψ scan empirical (using intensity measurements) via ψ scans (Fair, 1990) | h = −12→0 |
Tmin = 0.585, Tmax = 0.673 | k = −19→0 |
3704 measured reflections | l = −13→14 |
3503 independent reflections | 3 standard reflections every 120 min |
3058 reflections with I > 2σ(I) | intensity decay: 2.2% |
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)] = 0.036 | H-atom parameters constrained |
wR(F2) = 0.106 | w = 1/[σ2(Fo2) + (0.0548P)2 + 0.6415P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max = 0.001 |
3503 reflections | Δρmax = 0.29 e Å−3 |
218 parameters | Δρmin = −0.28 e Å−3 |
0 restraints | Extinction correction: Larson (1970), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0072 (4) |
[Ni(C19H20N2O2)] | V = 1734.6 (3) Å3 |
Mr = 367.08 | Z = 4 |
Monoclinic, P21/n | Cu Kα radiation |
a = 9.9329 (12) Å | µ = 1.72 mm−1 |
b = 15.8778 (11) Å | T = 301 K |
c = 11.8793 (10) Å | 0.35 × 0.30 × 0.25 mm |
β = 112.200 (3)° |
CAD-4 EXPRESS diffractometer | 3058 reflections with I > 2σ(I) |
Absorption correction: ψ scan empirical (using intensity measurements) via ψ scans (Fair, 1990) | Rint = 0.036 |
Tmin = 0.585, Tmax = 0.673 | 3 standard reflections every 120 min |
3704 measured reflections | intensity decay: 2.2% |
3503 independent reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.106 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.29 e Å−3 |
3503 reflections | Δρmin = −0.28 e Å−3 |
218 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Ni | 0.08080 (3) | 0.84458 (2) | 0.03050 (3) | 0.04271 (14) | |
O1 | −0.03878 (16) | 0.86878 (10) | −0.12785 (13) | 0.0533 (4) | |
O2 | −0.06158 (18) | 0.76706 (12) | 0.02109 (14) | 0.0661 (5) | |
N1 | 0.19661 (16) | 0.94094 (11) | 0.04913 (15) | 0.0435 (4) | |
N2 | 0.21126 (16) | 0.79860 (11) | 0.17515 (15) | 0.0457 (4) | |
C1 | −0.0227 (2) | 0.92728 (13) | −0.19938 (17) | 0.0449 (4) | |
C2 | −0.1143 (2) | 0.92654 (16) | −0.32386 (19) | 0.0541 (5) | |
C3 | −0.1071 (3) | 0.98985 (17) | −0.4003 (2) | 0.0613 (6) | |
C4 | −0.0095 (3) | 1.05648 (17) | −0.3573 (2) | 0.0634 (6) | |
C5 | 0.0805 (2) | 1.05831 (15) | −0.2384 (2) | 0.0564 (5) | |
C6 | 0.0791 (2) | 0.99361 (13) | −0.15711 (19) | 0.0456 (4) | |
C7 | 0.1773 (2) | 0.99832 (13) | −0.0332 (2) | 0.0468 (4) | |
C8 | 0.2948 (2) | 0.96133 (14) | 0.17390 (19) | 0.0510 (5) | |
C9 | 0.4209 (2) | 0.89987 (16) | 0.2274 (2) | 0.0557 (5) | |
C10 | 0.3666 (2) | 0.80918 (16) | 0.1963 (2) | 0.0563 (5) | |
C11 | 0.5389 (3) | 0.9152 (2) | 0.1765 (3) | 0.0858 (9) | |
C12 | 0.4821 (3) | 0.9131 (2) | 0.3656 (3) | 0.0906 (10) | |
C13 | 0.1777 (2) | 0.75188 (13) | 0.24973 (19) | 0.0492 (5) | |
C14 | 0.0331 (2) | 0.72554 (13) | 0.23033 (18) | 0.0459 (4) | |
C15 | 0.0031 (3) | 0.68684 (17) | 0.3251 (2) | 0.0630 (6) | |
C16 | −0.1313 (3) | 0.65550 (19) | 0.3073 (3) | 0.0761 (8) | |
C17 | −0.2391 (3) | 0.6585 (2) | 0.1920 (3) | 0.0792 (8) | |
C18 | −0.2124 (3) | 0.69404 (19) | 0.0979 (2) | 0.0724 (8) | |
C19 | −0.0785 (2) | 0.73099 (14) | 0.11370 (19) | 0.0515 (5) | |
H2 | −0.1817 | 0.8818 | −0.3550 | 0.065* | |
H3 | −0.1694 | 0.9882 | −0.4837 | 0.074* | |
H4 | −0.0062 | 1.1002 | −0.4107 | 0.076* | |
H5 | 0.1460 | 1.1041 | −0.2091 | 0.068* | |
H7 | 0.2338 | 1.0482 | −0.0088 | 0.056* | |
H8A | 0.2379 | 0.9623 | 0.2266 | 0.061* | |
H8B | 0.3346 | 1.0186 | 0.1746 | 0.061* | |
H10A | 0.3826 | 0.7913 | 0.1224 | 0.068* | |
H10B | 0.4250 | 0.7717 | 0.2637 | 0.068* | |
H11A | 0.6181 | 0.8746 | 0.2123 | 0.129* | |
H11B | 0.5768 | 0.9725 | 0.1965 | 0.129* | |
H11C | 0.4975 | 0.9081 | 0.0880 | 0.129* | |
H12A | 0.5639 | 0.8745 | 0.4037 | 0.136* | |
H12B | 0.4059 | 0.9017 | 0.3972 | 0.136* | |
H12C | 0.5157 | 0.9713 | 0.3842 | 0.136* | |
H13 | 0.2541 | 0.7339 | 0.3221 | 0.059* | |
H15 | 0.0784 | 0.6825 | 0.4033 | 0.076* | |
H16 | −0.1507 | 0.6319 | 0.3732 | 0.091* | |
H17 | −0.3324 | 0.6356 | 0.1782 | 0.095* | |
H18 | −0.2871 | 0.6937 | 0.0190 | 0.087* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni | 0.03443 (19) | 0.0535 (2) | 0.0356 (2) | −0.00042 (14) | 0.00791 (14) | −0.00660 (13) |
O1 | 0.0494 (8) | 0.0631 (9) | 0.0385 (7) | 0.0025 (6) | 0.0065 (6) | −0.0155 (7) |
O2 | 0.0581 (9) | 0.0876 (12) | 0.0383 (7) | 0.0096 (7) | 0.0020 (7) | −0.0319 (8) |
N1 | 0.0335 (7) | 0.0513 (9) | 0.0435 (8) | −0.0049 (7) | 0.0119 (6) | −0.0008 (6) |
N2 | 0.0324 (8) | 0.0538 (10) | 0.0461 (9) | −0.0013 (7) | 0.0094 (7) | −0.0013 (7) |
C1 | 0.0406 (9) | 0.0555 (11) | 0.0405 (9) | 0.0023 (8) | 0.0174 (8) | 0.0023 (8) |
C2 | 0.0516 (11) | 0.0660 (14) | 0.0425 (10) | 0.0013 (9) | 0.0155 (9) | 0.0033 (10) |
C3 | 0.0597 (13) | 0.0827 (17) | 0.0440 (11) | 0.0118 (11) | 0.0224 (10) | 0.0156 (12) |
C4 | 0.0630 (14) | 0.0734 (16) | 0.0621 (14) | 0.0225 (12) | 0.0332 (12) | 0.0150 (12) |
C5 | 0.0482 (11) | 0.0602 (13) | 0.0668 (14) | 0.0102 (11) | 0.0287 (10) | 0.0045 (10) |
C6 | 0.0377 (9) | 0.0527 (11) | 0.0501 (11) | 0.0040 (9) | 0.0210 (8) | 0.0047 (8) |
C7 | 0.0362 (9) | 0.0496 (11) | 0.0569 (12) | −0.0034 (9) | 0.0203 (8) | −0.0030 (8) |
C8 | 0.0412 (10) | 0.0586 (12) | 0.0469 (11) | −0.0103 (9) | 0.0096 (8) | −0.0053 (9) |
C9 | 0.0327 (9) | 0.0677 (14) | 0.0578 (12) | −0.0058 (10) | 0.0071 (9) | −0.0046 (9) |
C10 | 0.0326 (9) | 0.0648 (14) | 0.0666 (14) | 0.0008 (11) | 0.0134 (9) | 0.0042 (9) |
C11 | 0.0465 (13) | 0.091 (2) | 0.124 (3) | −0.0004 (19) | 0.0368 (16) | −0.0065 (13) |
C12 | 0.0733 (18) | 0.106 (2) | 0.0601 (16) | −0.0091 (16) | −0.0117 (14) | −0.0009 (17) |
C13 | 0.0415 (10) | 0.0542 (12) | 0.0431 (10) | 0.0028 (9) | 0.0061 (8) | 0.0041 (9) |
C14 | 0.0460 (10) | 0.0477 (11) | 0.0401 (10) | 0.0036 (8) | 0.0117 (8) | −0.0002 (8) |
C15 | 0.0685 (15) | 0.0708 (15) | 0.0446 (11) | 0.0097 (11) | 0.0155 (11) | −0.0054 (12) |
C16 | 0.0839 (19) | 0.087 (2) | 0.0640 (16) | 0.0126 (14) | 0.0355 (15) | −0.0196 (15) |
C17 | 0.0615 (15) | 0.094 (2) | 0.0799 (18) | 0.0191 (15) | 0.0246 (14) | −0.0229 (14) |
C18 | 0.0537 (13) | 0.0895 (19) | 0.0603 (14) | 0.0183 (13) | 0.0060 (11) | −0.0246 (13) |
C19 | 0.0466 (11) | 0.0586 (12) | 0.0427 (10) | 0.0052 (9) | 0.0094 (8) | −0.0117 (9) |
C1—O1 | 1.309 (2) | C11—H11A | 0.98 |
C1—C2 | 1.414 (3) | C11—H11B | 0.98 |
C1—C6 | 1.414 (3) | C11—H11C | 0.98 |
C2—C3 | 1.375 (3) | C12—H12A | 0.98 |
C2—H2 | 0.95 | C12—H12B | 0.98 |
C3—C4 | 1.394 (4) | C12—H12C | 0.98 |
C3—H3 | 0.95 | C13—N2 | 1.292 (3) |
C4—C5 | 1.357 (3) | C13—C14 | 1.429 (3) |
C4—H4 | 0.95 | C13—H13 | 0.95 |
C5—C6 | 1.414 (3) | C14—C15 | 1.410 (3) |
C5—H5 | 0.95 | C14—C19 | 1.413 (3) |
C6—C7 | 1.428 (3) | C15—C16 | 1.364 (4) |
C7—N1 | 1.297 (3) | C15—H15 | 0.95 |
C7—H7 | 0.95 | C16—C17 | 1.385 (4) |
C8—N1 | 1.470 (2) | C16—H16 | 0.95 |
C8—C9 | 1.524 (3) | C17—C18 | 1.365 (4) |
C8—H8A | 0.99 | C17—H17 | 0.95 |
C8—H8B | 0.99 | C18—C19 | 1.399 (3) |
C9—C11 | 1.528 (3) | C18—H18 | 0.95 |
C9—C12 | 1.534 (4) | C19—O2 | 1.306 (3) |
C9—C10 | 1.533 (3) | Ni—N1 | 1.8764 (17) |
C10—N2 | 1.477 (2) | Ni—N2 | 1.8660 (17) |
C10—H10A | 0.99 | Ni—O2 | 1.8461 (15) |
C10—H10B | 0.99 | Ni—O1 | 1.8463 (14) |
O1—C1—C2 | 119.00 (19) | H11A—C11—H11C | 109.5 |
O1—C1—C6 | 122.98 (18) | H11B—C11—H11C | 109.5 |
C2—C1—C6 | 117.98 (19) | C9—C12—H12A | 109.5 |
C3—C2—C1 | 120.7 (2) | C9—C12—H12B | 109.5 |
C3—C2—H2 | 119.6 | H12A—C12—H12B | 109.5 |
C1—C2—H2 | 119.6 | C9—C12—H12C | 109.5 |
C2—C3—C4 | 121.0 (2) | H12A—C12—H12C | 109.5 |
C2—C3—H3 | 119.5 | H12B—C12—H12C | 109.5 |
C4—C3—H3 | 119.5 | N2—C13—C14 | 124.16 (18) |
C5—C4—C3 | 119.4 (2) | N2—C13—H13 | 117.9 |
C5—C4—H4 | 120.3 | C14—C13—H13 | 117.9 |
C3—C4—H4 | 120.3 | C15—C14—C19 | 119.1 (2) |
C4—C5—C6 | 121.5 (2) | C15—C14—C13 | 120.12 (19) |
C4—C5—H5 | 119.2 | C19—C14—C13 | 120.58 (18) |
C6—C5—H5 | 119.2 | C16—C15—C14 | 121.7 (2) |
C5—C6—C1 | 119.27 (19) | C16—C15—H15 | 119.2 |
C5—C6—C7 | 119.1 (2) | C14—C15—H15 | 119.2 |
C1—C6—C7 | 121.57 (18) | C15—C16—C17 | 119.1 (2) |
N1—C7—C6 | 126.12 (19) | C15—C16—H16 | 120.5 |
N1—C7—H7 | 116.9 | C17—C16—H16 | 120.5 |
C6—C7—H7 | 116.9 | C18—C17—C16 | 120.5 (2) |
N1—C8—C9 | 114.02 (18) | C18—C17—H17 | 119.7 |
N1—C8—H8A | 108.7 | C16—C17—H17 | 119.7 |
C9—C8—H8A | 108.7 | C17—C18—C19 | 122.2 (2) |
N1—C8—H8B | 108.7 | C17—C18—H18 | 118.9 |
C9—C8—H8B | 108.7 | C19—C18—H18 | 118.9 |
H8A—C8—H8B | 107.6 | O2—C19—C18 | 119.3 (2) |
C8—C9—C11 | 111.4 (2) | O2—C19—C14 | 123.36 (19) |
C8—C9—C12 | 106.8 (2) | C18—C19—C14 | 117.4 (2) |
C11—C9—C12 | 110.4 (2) | C7—N1—C8 | 117.30 (18) |
C8—C9—C10 | 110.00 (16) | C7—N1—Ni | 125.06 (14) |
C11—C9—C10 | 107.8 (2) | C8—N1—Ni | 116.24 (14) |
C12—C9—C10 | 110.3 (2) | C13—N2—C10 | 118.20 (18) |
N2—C10—C9 | 113.42 (18) | C13—N2—Ni | 125.93 (13) |
N2—C10—H10A | 108.9 | C10—N2—Ni | 115.43 (14) |
C9—C10—H10A | 108.9 | O2—Ni—O1 | 83.91 (7) |
N2—C10—H10B | 108.9 | O2—Ni—N2 | 92.55 (7) |
C9—C10—H10B | 108.9 | O1—Ni—N2 | 167.22 (8) |
H10A—C10—H10B | 107.7 | O2—Ni—N1 | 166.48 (8) |
C9—C11—H11A | 109.5 | O1—Ni—N1 | 94.60 (7) |
C9—C11—H11B | 109.5 | N2—Ni—N1 | 91.66 (7) |
H11A—C11—H11B | 109.5 | C1—O1—Ni | 128.30 (13) |
C9—C11—H11C | 109.5 | C19—O2—Ni | 125.50 (14) |
O1—C1—C2—C3 | 175.9 (2) | C9—C10—N2—C13 | −115.2 (2) |
C4—C5—C6—C7 | 179.3 (2) | C9—C10—N2—Ni | 71.9 (2) |
O1—C1—C6—C5 | −174.39 (19) | C13—N2—Ni—O2 | −20.54 (19) |
C2—C1—C6—C7 | −178.95 (18) | C10—N2—Ni—O2 | 151.73 (16) |
C5—C6—C7—N1 | −174.19 (19) | C13—N2—Ni—O1 | −94.0 (3) |
C1—C6—C7—N1 | 7.9 (3) | C10—N2—Ni—O1 | 78.2 (4) |
N1—C8—C9—C11 | 76.6 (3) | C13—N2—Ni—N1 | 146.61 (19) |
N1—C8—C9—C12 | −162.7 (2) | C10—N2—Ni—N1 | −41.12 (16) |
N1—C8—C9—C10 | −42.9 (3) | C7—N1—Ni—O2 | −81.7 (3) |
C8—C9—C10—N2 | −25.9 (3) | C8—N1—Ni—O2 | 84.3 (3) |
C11—C9—C10—N2 | −147.7 (2) | C8—N1—Ni—O1 | 167.38 (14) |
C12—C9—C10—N2 | 91.7 (2) | C7—N1—Ni—N2 | 170.17 (17) |
N2—C13—C14—C15 | −169.3 (2) | C8—N1—Ni—N2 | −23.77 (14) |
N2—C13—C14—C19 | 16.4 (3) | C2—C1—O1—Ni | 169.90 (15) |
C13—C14—C15—C16 | −175.2 (3) | C6—C1—O1—Ni | −12.6 (3) |
C17—C18—C19—O2 | −177.2 (3) | O2—Ni—O1—C1 | 175.94 (19) |
C15—C14—C19—O2 | 178.7 (2) | N2—Ni—O1—C1 | −109.6 (3) |
C13—C14—C19—O2 | −6.9 (4) | N1—Ni—O1—C1 | 9.43 (19) |
C13—C14—C19—C18 | 171.8 (2) | C18—C19—O2—Ni | 160.9 (2) |
C6—C7—N1—C8 | −175.18 (18) | C14—C19—O2—Ni | −20.4 (4) |
C6—C7—N1—Ni | −9.3 (3) | O1—Ni—O2—C19 | −162.7 (2) |
C9—C8—N1—C7 | −123.0 (2) | N2—Ni—O2—C19 | 29.6 (2) |
C9—C8—N1—Ni | 69.8 (2) | N1—Ni—O2—C19 | −78.4 (4) |
C14—C13—N2—C10 | −169.9 (2) |
[Cu(C19H20N2O2)] | Z = 4 |
Mr = 371.91 | Dx = 1.407 Mg m−3 |
Monoclinic, P21/n | Cu Kα radiation, λ = 1.54180 Å |
Hall symbol: -P 2yn | Cell parameters from 15 reflections |
a = 9.7452 (12) Å | θ = 5.0–74.2° |
b = 17.2276 (14) Å | µ = 1.86 mm−1 |
c = 11.3606 (10) Å | T = 301 K |
β = 112.981 (3)° | Prism, dark green |
V = 1755.9 (3) Å3 | 0.30 × 0.20 × 0.20 mm |
CAD-4 EXPRESS diffractometer | Rint = 0.036 |
ω/2θ scans | θmax = 74.2° |
Absorption correction: ψ scan empirical (using intensity measurements) via ψ scans (Fair, 1990) | h = −11→12 |
Tmin = 0.606, Tmax = 0.707 | k = 0→21 |
3591 measured reflections | l = −14→0 |
3419 independent reflections | 3 standard reflections every 120 min |
2982 reflections with I > 2σ(I) | intensity decay: 1.3% |
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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.106 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0581P)2 + 0.8826P] where P = (Fo2 + 2Fc2)/3 |
3419 reflections | (Δ/σ)max = 0.001 |
218 parameters | Δρmax = 0.47 e Å−3 |
0 restraints | Δρmin = −0.28 e Å−3 |
[Cu(C19H20N2O2)] | V = 1755.9 (3) Å3 |
Mr = 371.91 | Z = 4 |
Monoclinic, P21/n | Cu Kα radiation |
a = 9.7452 (12) Å | µ = 1.86 mm−1 |
b = 17.2276 (14) Å | T = 301 K |
c = 11.3606 (10) Å | 0.30 × 0.20 × 0.20 mm |
β = 112.981 (3)° |
CAD-4 EXPRESS diffractometer | 2982 reflections with I > 2σ(I) |
Absorption correction: ψ scan empirical (using intensity measurements) via ψ scans (Fair, 1990) | Rint = 0.036 |
Tmin = 0.606, Tmax = 0.707 | 3 standard reflections every 120 min |
3591 measured reflections | intensity decay: 1.3% |
3419 independent reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.106 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.47 e Å−3 |
3419 reflections | Δρmin = −0.28 e Å−3 |
218 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Cu | 0.54580 (3) | 0.85029 (2) | 0.50685 (3) | 0.04307 (14) | |
O1 | 0.37681 (18) | 0.79780 (10) | 0.51132 (17) | 0.0512 (4) | |
O2 | 0.4367 (2) | 0.87954 (11) | 0.33448 (17) | 0.0554 (5) | |
N1 | 0.6881 (2) | 0.78903 (12) | 0.6416 (2) | 0.0484 (5) | |
N2 | 0.6845 (2) | 0.93727 (11) | 0.54226 (19) | 0.0424 (4) | |
C1 | 0.3761 (3) | 0.74868 (14) | 0.5991 (2) | 0.0451 (5) | |
C2 | 0.2376 (3) | 0.72296 (17) | 0.5969 (3) | 0.0591 (7) | |
C3 | 0.2291 (4) | 0.6712 (2) | 0.6858 (3) | 0.0718 (8) | |
C4 | 0.3569 (4) | 0.6419 (2) | 0.7811 (3) | 0.0761 (9) | |
C5 | 0.4924 (4) | 0.66565 (18) | 0.7862 (3) | 0.0654 (8) | |
C6 | 0.5069 (3) | 0.71909 (14) | 0.6973 (2) | 0.0481 (6) | |
C7 | 0.6554 (3) | 0.73841 (15) | 0.7104 (2) | 0.0517 (6) | |
C8 | 0.8451 (3) | 0.80062 (16) | 0.6600 (3) | 0.0558 (7) | |
C9 | 0.9083 (3) | 0.87958 (17) | 0.7201 (3) | 0.0533 (6) | |
C10 | 0.7883 (3) | 0.94358 (15) | 0.6758 (2) | 0.0484 (6) | |
C11 | 0.9638 (4) | 0.8752 (2) | 0.8661 (3) | 0.0808 (10) | |
C12 | 1.0369 (3) | 0.8997 (2) | 0.6805 (4) | 0.0786 (10) | |
C13 | 0.6724 (2) | 0.99340 (14) | 0.4645 (2) | 0.0436 (5) | |
C14 | 0.5688 (2) | 0.99732 (14) | 0.3333 (2) | 0.0435 (5) | |
C15 | 0.5763 (3) | 1.06304 (16) | 0.2616 (3) | 0.0546 (6) | |
C16 | 0.4832 (4) | 1.07150 (19) | 0.1362 (3) | 0.0670 (8) | |
C17 | 0.3784 (3) | 1.01392 (19) | 0.0769 (3) | 0.0641 (7) | |
C18 | 0.3667 (3) | 0.94992 (18) | 0.1440 (2) | 0.0556 (6) | |
C19 | 0.4589 (3) | 0.93972 (14) | 0.2746 (2) | 0.0442 (5) | |
H2 | 0.1482 | 0.7419 | 0.5326 | 0.071* | |
H3 | 0.1341 | 0.6551 | 0.6819 | 0.086* | |
H4 | 0.3500 | 0.6058 | 0.8419 | 0.091* | |
H5 | 0.5799 | 0.6457 | 0.8515 | 0.078* | |
H7 | 0.7356 | 0.7120 | 0.7743 | 0.062* | |
H8A | 0.8535 | 0.7963 | 0.5762 | 0.067* | |
H8B | 0.9062 | 0.7588 | 0.7157 | 0.067* | |
H10A | 0.7307 | 0.9420 | 0.7308 | 0.058* | |
H10B | 0.8385 | 0.9947 | 0.6885 | 0.058* | |
H11A | 0.8804 | 0.8623 | 0.8903 | 0.121* | |
H11B | 1.0058 | 0.9255 | 0.9031 | 0.121* | |
H11C | 1.0408 | 0.8351 | 0.8982 | 0.121* | |
H12A | 1.0797 | 0.9498 | 0.7176 | 0.118* | |
H12B | 0.9999 | 0.9027 | 0.5871 | 0.118* | |
H12C | 1.1137 | 0.8594 | 0.7115 | 0.118* | |
H13 | 0.7378 | 1.0363 | 0.4965 | 0.052* | |
H15 | 0.6479 | 1.1023 | 0.3016 | 0.065* | |
H16 | 0.4898 | 1.1162 | 0.0898 | 0.080* | |
H17 | 0.3146 | 1.0191 | −0.0107 | 0.077* | |
H18 | 0.2946 | 0.9114 | 0.1016 | 0.067* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu | 0.03387 (19) | 0.0422 (2) | 0.0458 (2) | 0.00270 (14) | 0.00764 (14) | −0.00282 (13) |
O1 | 0.0374 (8) | 0.0556 (10) | 0.0509 (9) | 0.0077 (8) | 0.0068 (7) | −0.0054 (7) |
O2 | 0.0524 (10) | 0.0524 (10) | 0.0472 (9) | 0.0043 (8) | 0.0040 (8) | −0.0125 (8) |
N1 | 0.0345 (9) | 0.0455 (11) | 0.0563 (12) | 0.0013 (9) | 0.0081 (9) | 0.0017 (8) |
N2 | 0.0323 (9) | 0.0431 (10) | 0.0473 (10) | −0.0035 (8) | 0.0106 (8) | 0.0000 (8) |
C1 | 0.0427 (12) | 0.0428 (12) | 0.0455 (12) | −0.0026 (10) | 0.0125 (10) | −0.0049 (10) |
C2 | 0.0477 (14) | 0.0601 (16) | 0.0650 (17) | 0.0014 (13) | 0.0172 (12) | −0.0118 (12) |
C3 | 0.0666 (19) | 0.077 (2) | 0.075 (2) | 0.0009 (17) | 0.0310 (16) | −0.0243 (16) |
C4 | 0.090 (2) | 0.072 (2) | 0.0672 (19) | 0.0125 (16) | 0.0315 (18) | −0.0235 (18) |
C5 | 0.0700 (18) | 0.0584 (17) | 0.0580 (16) | 0.0125 (13) | 0.0143 (14) | −0.0063 (14) |
C6 | 0.0489 (13) | 0.0415 (12) | 0.0478 (13) | 0.0023 (10) | 0.0123 (11) | −0.0039 (10) |
C7 | 0.0441 (12) | 0.0442 (13) | 0.0531 (14) | 0.0069 (11) | 0.0043 (11) | 0.0048 (10) |
C8 | 0.0339 (12) | 0.0548 (15) | 0.0726 (17) | 0.0042 (13) | 0.0143 (11) | 0.0069 (10) |
C9 | 0.0313 (11) | 0.0603 (15) | 0.0604 (15) | 0.0011 (13) | 0.0094 (10) | 0.0010 (10) |
C10 | 0.0388 (12) | 0.0517 (14) | 0.0473 (13) | −0.0065 (11) | 0.0088 (10) | −0.0030 (10) |
C11 | 0.0649 (19) | 0.089 (2) | 0.0622 (19) | 0.0051 (17) | −0.0038 (15) | 0.0028 (17) |
C12 | 0.0436 (15) | 0.078 (2) | 0.115 (3) | −0.006 (2) | 0.0312 (17) | −0.0061 (14) |
C13 | 0.0351 (10) | 0.0421 (12) | 0.0549 (14) | −0.0045 (10) | 0.0190 (10) | −0.0028 (9) |
C14 | 0.0394 (11) | 0.0444 (12) | 0.0506 (13) | 0.0007 (10) | 0.0219 (10) | 0.0030 (9) |
C15 | 0.0514 (14) | 0.0532 (15) | 0.0659 (16) | 0.0079 (13) | 0.0303 (13) | 0.0007 (11) |
C16 | 0.0744 (19) | 0.0695 (19) | 0.0664 (18) | 0.0230 (15) | 0.0378 (16) | 0.0100 (16) |
C17 | 0.0702 (18) | 0.075 (2) | 0.0474 (14) | 0.0093 (14) | 0.0230 (13) | 0.0129 (16) |
C18 | 0.0540 (14) | 0.0623 (16) | 0.0466 (13) | −0.0011 (12) | 0.0153 (11) | 0.0030 (12) |
C19 | 0.0413 (12) | 0.0449 (12) | 0.0453 (12) | 0.0001 (10) | 0.0158 (10) | 0.0036 (9) |
C1—O1 | 1.310 (3) | C11—H11A | 0.98 |
C1—C2 | 1.412 (3) | C11—H11B | 0.98 |
C1—C6 | 1.421 (3) | C11—H11C | 0.98 |
C2—C3 | 1.374 (4) | C12—H12A | 0.98 |
C2—H2 | 0.95 | C12—H12B | 0.98 |
C3—C4 | 1.388 (5) | C12—H12C | 0.98 |
C3—H3 | 0.95 | C13—N2 | 1.284 (3) |
C4—C5 | 1.362 (5) | C13—C14 | 1.439 (3) |
C4—H4 | 0.95 | C13—H13 | 0.95 |
C5—C6 | 1.414 (4) | C14—C15 | 1.413 (3) |
C5—H5 | 0.95 | C14—C19 | 1.421 (3) |
C6—C7 | 1.435 (4) | C15—C16 | 1.365 (4) |
C7—N1 | 1.291 (3) | C15—H15 | 0.95 |
C7—H7 | 0.95 | C16—C17 | 1.394 (4) |
C8—N1 | 1.475 (3) | C16—H16 | 0.95 |
C8—C9 | 1.538 (4) | C17—C18 | 1.370 (4) |
C8—H8A | 0.99 | C17—H17 | 0.95 |
C8—H8B | 0.99 | C18—C19 | 1.414 (3) |
C9—C12 | 1.528 (4) | C18—H18 | 0.95 |
C9—C11 | 1.532 (4) | C19—O2 | 1.304 (3) |
C9—C10 | 1.542 (3) | Cu—O2 | 1.8956 (17) |
C10—N2 | 1.463 (3) | Cu—O1 | 1.8967 (17) |
C10—H10A | 0.99 | Cu—N1 | 1.929 (2) |
C10—H10B | 0.99 | Cu—N2 | 1.9518 (19) |
O1—C1—C2 | 118.6 (2) | H11A—C11—H11C | 109.5 |
O1—C1—C6 | 124.0 (2) | H11B—C11—H11C | 109.5 |
C2—C1—C6 | 117.4 (2) | C9—C12—H12A | 109.5 |
C3—C2—C1 | 121.5 (3) | C9—C12—H12B | 109.5 |
C3—C2—H2 | 119.3 | H12A—C12—H12B | 109.5 |
C1—C2—H2 | 119.3 | C9—C12—H12C | 109.5 |
C2—C3—C4 | 121.1 (3) | H12A—C12—H12C | 109.5 |
C2—C3—H3 | 119.5 | H12B—C12—H12C | 109.5 |
C4—C3—H3 | 119.5 | N2—C13—C14 | 125.9 (2) |
C5—C4—C3 | 118.9 (3) | N2—C13—H13 | 117.0 |
C5—C4—H4 | 120.5 | C14—C13—H13 | 117.0 |
C3—C4—H4 | 120.5 | C15—C14—C19 | 119.3 (2) |
C4—C5—C6 | 122.1 (3) | C15—C14—C13 | 117.5 (2) |
C4—C5—H5 | 119.0 | C19—C14—C13 | 123.3 (2) |
C6—C5—H5 | 119.0 | C16—C15—C14 | 121.6 (3) |
C5—C6—C1 | 119.0 (2) | C16—C15—H15 | 119.2 |
C5—C6—C7 | 117.1 (2) | C14—C15—H15 | 119.2 |
C1—C6—C7 | 123.9 (2) | C15—C16—C17 | 119.4 (3) |
N1—C7—C6 | 124.8 (2) | C15—C16—H16 | 120.3 |
N1—C7—H7 | 117.6 | C17—C16—H16 | 120.3 |
C6—C7—H7 | 117.6 | C18—C17—C16 | 120.6 (3) |
N1—C8—C9 | 113.3 (2) | C18—C17—H17 | 119.7 |
N1—C8—H8A | 108.9 | C16—C17—H17 | 119.7 |
C9—C8—H8A | 108.9 | C17—C18—C19 | 121.8 (3) |
N1—C8—H8B | 108.9 | C17—C18—H18 | 119.1 |
C9—C8—H8B | 108.9 | C19—C18—H18 | 119.1 |
H8A—C8—H8B | 107.7 | O2—C19—C18 | 118.6 (2) |
C12—C9—C11 | 110.2 (2) | O2—C19—C14 | 124.0 (2) |
C12—C9—C8 | 107.6 (2) | C18—C19—C14 | 117.3 (2) |
C11—C9—C8 | 110.4 (3) | O2—Cu—O1 | 90.67 (8) |
C12—C9—C10 | 110.3 (2) | O2—Cu—N1 | 154.76 (9) |
C11—C9—C10 | 106.9 (2) | O1—Cu—N1 | 94.61 (8) |
C8—C9—C10 | 111.51 (19) | O2—Cu—N2 | 94.18 (8) |
N2—C10—C9 | 114.5 (2) | O1—Cu—N2 | 154.05 (9) |
N2—C10—H10A | 108.6 | N1—Cu—N2 | 91.78 (8) |
C9—C10—H10A | 108.6 | C7—N1—C8 | 119.5 (2) |
N2—C10—H10B | 108.6 | C7—N1—Cu | 125.40 (17) |
C9—C10—H10B | 108.6 | C8—N1—Cu | 115.03 (17) |
H10A—C10—H10B | 107.6 | C13—N2—C10 | 119.9 (2) |
C9—C11—H11A | 109.5 | C13—N2—Cu | 124.49 (16) |
C9—C11—H11B | 109.5 | C10—N2—Cu | 114.44 (16) |
H11A—C11—H11B | 109.5 | C1—O1—Cu | 126.24 (15) |
C9—C11—H11C | 109.5 | C19—O2—Cu | 127.58 (16) |
O1—C1—C2—C3 | 179.6 (3) | N2—Cu—N1—C7 | 147.9 (2) |
C4—C5—C6—C7 | −178.6 (3) | O2—Cu—N1—C8 | 68.8 (3) |
O1—C1—C6—C5 | −179.4 (3) | O1—Cu—N1—C8 | 170.30 (18) |
C2—C1—C6—C7 | 178.6 (3) | N2—Cu—N1—C8 | −34.88 (19) |
C5—C6—C7—N1 | −176.2 (3) | C14—C13—N2—C10 | −175.8 (2) |
C1—C6—C7—N1 | 5.7 (4) | C14—C13—N2—Cu | −8.9 (3) |
N1—C8—C9—C12 | −155.2 (2) | C9—C10—N2—C13 | −121.4 (2) |
N1—C8—C9—C11 | 84.5 (3) | C9—C10—N2—Cu | 70.4 (2) |
N1—C8—C9—C10 | −34.1 (3) | O2—Cu—N2—C13 | 6.9 (2) |
C12—C9—C10—N2 | 82.1 (3) | O1—Cu—N2—C13 | −93.3 (3) |
C11—C9—C10—N2 | −158.1 (2) | N1—Cu—N2—C13 | 162.3 (2) |
C8—C9—C10—N2 | −37.4 (3) | O2—Cu—N2—C10 | 174.41 (16) |
N2—C13—C14—C15 | −177.8 (2) | O1—Cu—N2—C10 | 74.2 (2) |
N2—C13—C14—C19 | 3.7 (4) | N1—Cu—N2—C10 | −30.13 (17) |
C13—C14—C15—C16 | 179.5 (2) | C2—C1—O1—Cu | 171.53 (19) |
C17—C18—C19—O2 | 176.4 (3) | C6—C1—O1—Cu | −8.6 (4) |
C15—C14—C19—O2 | −175.6 (2) | O2—Cu—O1—C1 | 166.3 (2) |
C13—C14—C19—C18 | −178.5 (2) | N1—Cu—O1—C1 | 11.0 (2) |
C6—C7—N1—C8 | −176.8 (3) | N2—Cu—O1—C1 | −92.7 (3) |
C9—C8—N1—C7 | −110.8 (3) | C18—C19—O2—Cu | 178.28 (18) |
C9—C8—N1—Cu | 71.8 (3) | C14—C19—O2—Cu | −3.2 (4) |
O2—Cu—N1—C7 | −108.4 (3) | O1—Cu—O2—C19 | 153.4 (2) |
O1—Cu—N1—C7 | −6.9 (2) | N1—Cu—O2—C19 | −104.2 (3) |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [Ni(C19H20N2O2)] | [Cu(C19H20N2O2)] |
Mr | 367.08 | 371.91 |
Crystal system, space group | Monoclinic, P21/n | Monoclinic, P21/n |
Temperature (K) | 301 | 301 |
a, b, c (Å) | 9.9329 (12), 15.8778 (11), 11.8793 (10) | 9.7452 (12), 17.2276 (14), 11.3606 (10) |
β (°) | 112.200 (3) | 112.981 (3) |
V (Å3) | 1734.6 (3) | 1755.9 (3) |
Z | 4 | 4 |
Radiation type | Cu Kα | Cu Kα |
µ (mm−1) | 1.72 | 1.86 |
Crystal size (mm) | 0.35 × 0.30 × 0.25 | 0.30 × 0.20 × 0.20 |
Data collection | ||
Diffractometer | CAD-4 EXPRESS diffractometer | CAD-4 EXPRESS diffractometer |
Absorption correction | ψ scan empirical (using intensity measurements) via ψ scans (Fair, 1990) | ψ scan empirical (using intensity measurements) via ψ scans (Fair, 1990) |
Tmin, Tmax | 0.585, 0.673 | 0.606, 0.707 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3704, 3503, 3058 | 3591, 3419, 2982 |
Rint | 0.036 | 0.036 |
(sin θ/λ)max (Å−1) | 0.624 | 0.624 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.106, 1.01 | 0.038, 0.106, 1.04 |
No. of reflections | 3503 | 3419 |
No. of parameters | 218 | 218 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.29, −0.28 | 0.47, −0.28 |
Computer programs: CAD-4 EXPRESS (Enraf-Nonius, 1993), SHELXL97 (Sheldrick, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97, PLATON (Spek, 2000).
Ni—N1 | 1.8764 (17) | Ni—O2 | 1.8461 (15) |
Ni—N2 | 1.8660 (17) | Ni—O1 | 1.8463 (14) |
O2—Ni—O1—C1 | 175.94 (19) | O1—Ni—O2—C19 | −162.7 (2) |
N2—Ni—O1—C1 | −109.6 (3) | N2—Ni—O2—C19 | 29.6 (2) |
N1—Ni—O1—C1 | 9.43 (19) | N1—Ni—O2—C19 | −78.4 (4) |
Cu—O2 | 1.8956 (17) | Cu—N1 | 1.929 (2) |
Cu—O1 | 1.8967 (17) | Cu—N2 | 1.9518 (19) |
N2—Cu—N1—C7 | 147.9 (2) | O2—Cu—N2—C10 | 174.41 (16) |
O2—Cu—N1—C8 | 68.8 (3) | O1—Cu—N2—C10 | 74.2 (2) |
O1—Cu—N1—C8 | 170.30 (18) | N1—Cu—N2—C10 | −30.13 (17) |
N2—Cu—N1—C8 | −34.88 (19) | O1—Cu—O2—C19 | 153.4 (2) |
N1—Cu—N2—C13 | 162.3 (2) | N1—Cu—O2—C19 | −104.2 (3) |
The chemistry of metal complexes with Schiff base ligands and their application has aroused considerable attention mainly because of their preparative accessibility, diversity and structural variability. For example, there has been interest in CuII–imine–phenols because of their color isomerism (Yao et al., 1997) and the NiII complexes have been used to probe the structural and electronic consequences of small modifications of the ligand skeleton (Gomes et al., 1999). Nickel(II) and copper(II) complexes of diamine Schiff bases generally display square-planar coordination (Akhtar et al., 1981; Radha et al., 1985; Drew et al., 1985). We have synthesized NiII[(SALPD)(CH3)2], (I), and CuII[(SALPD)(CH3)2], (II), and report their structures here.
In both compounds, the structure consists of asymmetric monomers (Figs. 1 and 2) which have a monoclinic unit cell containing four molecules. In the structure of (I), the Ni atom has a square-planar coordination involving two O and two N atoms of the tetradentate SALPD2- ligand. The Ni atom is located 0.013 (3) Å from the best coordination plane consisting of atoms N1, N2, O1 and O2; the dihedral angle between the two Ni/N/O planes is 17.20 (6)°.
Complexes of (N,N'-trimethylenedisalicylideneaminato)nickel(II), [Ni(salpd)], and (N,N'-trimethylenedisalicylideneaminato)copper(II), [Cu(salpd)] (Drew et al., 1985), show a similar structure apart from the methyl groups. Comparison of the Ni—N and Ni—O bond distances, and the O—Ni—O angles of the present work and [Ni(salpd)] show then to be very similar. In the present work, The Ni—N1, Ni—N2, Ni—O1 and Ni—O2 bond distances are 1.8764 (17), 1.8660 (17), 1.8463 (14) and 1.8461 (15) Å, respectively. In [Ni(salpd)], the Ni—N and Ni—O distances are 1.901 (4) and 1.845 (3) Å, respectively. The O1—Ni—O2 angle of 83.91° in (I) is is greater than the value of 78.31 (13)° in [Ni(salpd)].
In the structure of (II), the Cu atom is coordinated in a distorted planar coordination geometry by two N [Cu—N1 1.929 (2) Å and Cu—N2 1.9518 (19) Å] and two O [Cu—O1 1.8967 (17) Å and Cu—O2 1.8956 (17) Å] of the imine–phenol ligand. The tetrahedral distortion between the Cu/N/O planes is 35.13 (7)°. Similar distortions are found in the literature for CuII structures. This angle between planes can be compared to the value of 21.0 (1)° for [Cu(salpd)] and 42.7 (1)° for [N,N'-bis(salicylidene)-1,4-diiminobutane]copper(II) (Yao et al., 1997).
The SALPD2- ligand is not planar. The chelate ring composed of atoms M (Ni or Cu), N1, C8, C9, C10 and N2 has a distorted boat conformation. The distances of the two para-positioned boat atoms, M and C9, from the best plane of the six atoms are 0.0001 (3) and 0.06 (2) Å for Cu, and 0.0036 (3) and 0.155 (2) Å for Ni, respectively.