Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100000329/de1121sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100000329/de1121Isup2.hkl |
CCDC reference: 144617
Compound (I) was synthesized by the reaction of a 1:1 mole ratio of diacetyl monoxime salicyloyl hydrazone and nickel(II) acetate tetrahydrate in ethanol at room temperature. Green single crystals of (I) suitable for X-ray diffraction were obtained by evaporating the solution in air for several weeks.
Data collection: CAD-4 Software (Enraf-Nonius, 1989)?; program(s) used to solve structure: SHELXS86 (Sheldrick, 1990a); program(s) used to refine structure: SHELXL93 (Sheldrick, 1993); molecular graphics: SHELXTL-Plus (Sheldrick, 1990b); software used to prepare material for publication: SHELXL93.
Fig. 1. The structure of (I) showing 50% probability displacement ellipsoids and the atom-numbering scheme. H atoms are shown as spheres of arbitrary radii. | |
Fig. 2. Packing diagram for (I). |
[Ni(C11H12N3O3)(C2H3O2)(H2O)2]·C2H5OH | Z = 2 |
Mr = 434.09 | F(000) = 456 |
Triclinic, P1 | Dx = 1.449 Mg m−3 |
a = 7.4120 (15) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.505 (2) Å | Cell parameters from 25 reflections |
c = 13.255 (3) Å | θ = 1.6–6.7° |
α = 103.13 (3)° | µ = 1.02 mm−1 |
β = 103.97 (3)° | T = 293 K |
γ = 106.80 (3)° | Prism, green |
V = 995.0 (3) Å3 | 0.40 × 0.20 × 0.05 mm |
FR590 CAD-4 diffractometer | 2472 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.022 |
Graphite monochromator | θmax = 25.0°, θmin = 1.7° |
2θ/ω scans | h = 0→8 |
Absorption correction: empirical (using intensity measurements) via ψ scan (North et al., 1968) | k = −13→13 |
Tmin = 0.654, Tmax = 0.947 | l = −15→15 |
3784 measured reflections | 3 standard reflections every 97 reflections |
3486 independent reflections | intensity decay: none |
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)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.134 | H-atom parameters constrained |
S = 1.00 | Calculated w = 1/[σ2(Fo2) + (0.0842P)2] where P = (Fo2 + 2Fc2)/3 |
3484 reflections | (Δ/σ)max < 0.001 |
244 parameters | Δρmax = 0.63 e Å−3 |
12 restraints | Δρmin = −0.59 e Å−3 |
[Ni(C11H12N3O3)(C2H3O2)(H2O)2]·C2H5OH | γ = 106.80 (3)° |
Mr = 434.09 | V = 995.0 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.4120 (15) Å | Mo Kα radiation |
b = 11.505 (2) Å | µ = 1.02 mm−1 |
c = 13.255 (3) Å | T = 293 K |
α = 103.13 (3)° | 0.40 × 0.20 × 0.05 mm |
β = 103.97 (3)° |
FR590 CAD-4 diffractometer | 2472 reflections with I > 2σ(I) |
Absorption correction: empirical (using intensity measurements) via ψ scan (North et al., 1968) | Rint = 0.022 |
Tmin = 0.654, Tmax = 0.947 | 3 standard reflections every 97 reflections |
3784 measured reflections | intensity decay: none |
3486 independent reflections |
R[F2 > 2σ(F2)] = 0.047 | 12 restraints |
wR(F2) = 0.134 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.63 e Å−3 |
3484 reflections | Δρmin = −0.59 e Å−3 |
244 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement on F2 for ALL reflections except for 2 with very negative F2 or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating R-factor obs 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 | ||
Ni1 | −0.95134 (8) | 0.25295 (4) | 0.23640 (4) | 0.0304 (2) | |
N1 | −1.0929 (5) | 0.0716 (3) | 0.1346 (2) | 0.0305 (7) | |
N2 | −0.9171 (5) | 0.1378 (3) | 0.3365 (3) | 0.0363 (8) | |
N3 | −1.1903 (5) | 0.0604 (3) | 0.0295 (2) | 0.0335 (8) | |
H3A | −1.2606 | −0.0127 | −0.0200 | 0.040* | |
O1W | −0.6908 (4) | 0.2616 (3) | 0.2069 (3) | 0.0505 (8) | |
H1W | −0.5784 | 0.3375 | 0.2423 | 0.061* | |
H2W | −0.6541 | 0.1965 | 0.2028 | 0.061* | |
O2W | −1.2076 (4) | 0.2539 (2) | 0.2669 (2) | 0.0411 (7) | |
H3W | −1.3167 | 0.2030 | 0.2380 | 0.049* | |
H4W | −1.2134 | 0.3320 | 0.2782 | 0.049* | |
O1 | −0.8240 (4) | 0.4371 (2) | 0.3269 (2) | 0.0420 (7) | |
O2 | −0.7556 (5) | 0.4196 (3) | 0.4951 (2) | 0.0538 (9) | |
O3 | −0.3284 (5) | 0.4624 (3) | 0.2937 (2) | 0.0451 (7) | |
H6A | −0.2927 | 0.4998 | 0.3597 | 0.068* | |
O4 | −0.8149 (5) | 0.1788 (3) | 0.4474 (2) | 0.0517 (8) | |
H4A | −0.7736 | 0.2573 | 0.4710 | 0.078* | |
O5 | −1.0607 (4) | 0.2772 (2) | 0.0800 (2) | 0.0412 (7) | |
O6 | −1.4390 (4) | −0.0671 (3) | −0.1595 (2) | 0.0403 (7) | |
C1 | −1.1683 (6) | 0.1727 (4) | 0.0086 (3) | 0.0328 (9) | |
C2 | −1.2767 (6) | 0.1614 (4) | −0.1042 (3) | 0.0330 (9) | |
C3 | −1.2509 (7) | 0.2738 (4) | −0.1314 (3) | 0.0424 (10) | |
H3 | −1.1455 | 0.3536 | −0.0820 | 0.051* | |
C4 | −1.3482 (7) | 0.2730 (5) | −0.2330 (4) | 0.0511 (12) | |
H4 | −1.3202 | 0.3498 | −0.2626 | 0.061* | |
C5 | −1.4760 (7) | 0.1554 (5) | −0.3110 (4) | 0.0532 (12) | |
H5A | −1.5428 | 0.1530 | −0.3810 | 0.064* | |
C6 | −1.5048 (7) | 0.0441 (5) | −0.2865 (3) | 0.0472 (11) | |
H6 | −1.6127 | −0.0459 | −0.3363 | 0.057* | |
C7 | −1.4064 (6) | 0.0417 (4) | −0.1821 (3) | 0.0352 (9) | |
C8 | −1.1026 (6) | −0.0237 (4) | 0.1700 (3) | 0.0319 (9) | |
C9 | −0.9899 (6) | 0.0160 (4) | 0.2894 (3) | 0.0346 (9) | |
C10 | −1.2192 (7) | −0.1608 (4) | 0.1040 (4) | 0.0445 (11) | |
H10A | −1.2809 | −0.1671 | 0.0294 | 0.067* | |
H10B | −1.3203 | −0.1955 | 0.1339 | 0.067* | |
H10C | −1.1314 | −0.2080 | 0.1061 | 0.067* | |
C11 | −0.9705 (7) | −0.0796 (4) | 0.3464 (4) | 0.0497 (12) | |
H11A | −0.8931 | −0.0358 | 0.4224 | 0.075* | |
H11B | −0.9051 | −0.1305 | 0.3131 | 0.075* | |
H11C | −1.1007 | −0.1342 | 0.3404 | 0.075* | |
C12 | −0.3206 (14) | 0.4900 (7) | 0.1225 (6) | 0.113 (3) | |
H12A | −0.2727 | 0.5529 | 0.0889 | 0.169* | |
H12B | −0.4635 | 0.4520 | 0.0925 | 0.169* | |
H12C | −0.2648 | 0.4248 | 0.1085 | 0.169* | |
C13 | −0.2613 (10) | 0.5510 (5) | 0.2398 (5) | 0.071 (2) | |
H13A | −0.1170 | 0.5907 | 0.2696 | 0.085* | |
H13B | −0.3158 | 0.6180 | 0.2536 | 0.085* | |
C14 | −0.7693 (6) | 0.4834 (4) | 0.4296 (3) | 0.0394 (10) | |
C15 | −0.7206 (8) | 0.6247 (4) | 0.4781 (4) | 0.0568 (13) | |
H15A | −0.6810 | 0.6478 | 0.5566 | 0.085* | |
H15B | −0.8362 | 0.6450 | 0.4512 | 0.085* | |
H15C | −0.6135 | 0.6716 | 0.4574 | 0.085* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0328 (3) | 0.0234 (3) | 0.0277 (3) | 0.0071 (2) | 0.0055 (2) | 0.0037 (2) |
N1 | 0.031 (2) | 0.029 (2) | 0.027 (2) | 0.0103 (14) | 0.0053 (14) | 0.0065 (14) |
N2 | 0.041 (2) | 0.032 (2) | 0.027 (2) | 0.011 (2) | 0.0029 (15) | 0.0067 (14) |
N3 | 0.042 (2) | 0.022 (2) | 0.027 (2) | 0.0082 (14) | 0.0047 (15) | 0.0012 (13) |
O1W | 0.037 (2) | 0.028 (2) | 0.077 (2) | 0.0066 (13) | 0.019 (2) | 0.0067 (15) |
O2W | 0.032 (2) | 0.0253 (14) | 0.057 (2) | 0.0068 (12) | 0.0133 (14) | 0.0037 (13) |
O1 | 0.051 (2) | 0.0277 (15) | 0.032 (2) | 0.0025 (13) | 0.0098 (14) | 0.0004 (12) |
O2 | 0.079 (2) | 0.033 (2) | 0.035 (2) | 0.014 (2) | 0.011 (2) | 0.0032 (14) |
O3 | 0.056 (2) | 0.030 (2) | 0.042 (2) | 0.0098 (14) | 0.0151 (15) | 0.0047 (13) |
O4 | 0.065 (2) | 0.040 (2) | 0.031 (2) | 0.012 (2) | −0.0056 (14) | 0.0074 (13) |
O5 | 0.049 (2) | 0.0258 (15) | 0.034 (2) | 0.0062 (13) | 0.0041 (13) | 0.0035 (12) |
O6 | 0.040 (2) | 0.0306 (15) | 0.036 (2) | 0.0066 (13) | 0.0036 (13) | 0.0031 (12) |
C1 | 0.034 (2) | 0.031 (2) | 0.031 (2) | 0.009 (2) | 0.011 (2) | 0.008 (2) |
C2 | 0.037 (2) | 0.033 (2) | 0.029 (2) | 0.013 (2) | 0.011 (2) | 0.008 (2) |
C3 | 0.048 (3) | 0.039 (2) | 0.036 (2) | 0.013 (2) | 0.012 (2) | 0.010 (2) |
C4 | 0.058 (3) | 0.054 (3) | 0.045 (3) | 0.020 (2) | 0.016 (2) | 0.025 (2) |
C5 | 0.047 (3) | 0.072 (3) | 0.036 (2) | 0.018 (3) | 0.006 (2) | 0.022 (2) |
C6 | 0.043 (3) | 0.056 (3) | 0.033 (2) | 0.012 (2) | 0.005 (2) | 0.012 (2) |
C7 | 0.033 (2) | 0.037 (2) | 0.030 (2) | 0.013 (2) | 0.008 (2) | 0.004 (2) |
C8 | 0.033 (2) | 0.025 (2) | 0.035 (2) | 0.010 (2) | 0.013 (2) | 0.006 (2) |
C9 | 0.035 (2) | 0.037 (2) | 0.033 (2) | 0.013 (2) | 0.011 (2) | 0.012 (2) |
C10 | 0.051 (3) | 0.028 (2) | 0.044 (2) | 0.006 (2) | 0.012 (2) | 0.006 (2) |
C11 | 0.061 (3) | 0.039 (2) | 0.050 (3) | 0.017 (2) | 0.014 (2) | 0.021 (2) |
C12 | 0.182 (7) | 0.086 (5) | 0.078 (4) | 0.044 (4) | 0.043 (4) | 0.044 (4) |
C13 | 0.096 (4) | 0.045 (3) | 0.068 (4) | 0.016 (3) | 0.024 (3) | 0.025 (3) |
C14 | 0.037 (2) | 0.028 (2) | 0.040 (2) | 0.002 (2) | 0.010 (2) | 0.001 (2) |
C15 | 0.082 (4) | 0.032 (2) | 0.043 (3) | 0.012 (2) | 0.019 (3) | 0.001 (2) |
Ni1—O1 | 1.990 (3) | O5—C1 | 1.241 (5) |
Ni1—N1 | 2.012 (3) | O6—C7 | 1.321 (5) |
Ni1—O2W | 2.037 (3) | C1—C2 | 1.473 (5) |
Ni1—O1W | 2.040 (3) | C2—C3 | 1.393 (6) |
Ni1—N2 | 2.100 (3) | C2—C7 | 1.413 (5) |
Ni1—O5 | 2.148 (3) | C3—C4 | 1.363 (6) |
N1—C8 | 1.278 (5) | C4—C5 | 1.396 (7) |
N1—N3 | 1.363 (4) | C5—C6 | 1.363 (7) |
N2—C9 | 1.283 (5) | C6—C7 | 1.410 (6) |
N2—O4 | 1.378 (4) | C8—C10 | 1.489 (5) |
N3—C1 | 1.355 (5) | C8—C9 | 1.491 (5) |
O1—C14 | 1.258 (5) | C9—C11 | 1.490 (6) |
O2—C14 | 1.261 (5) | C12—C13 | 1.448 (8) |
O3—C13 | 1.417 (6) | C14—C15 | 1.504 (6) |
O1—Ni1—N1 | 174.98 (12) | O5—C1—N3 | 121.6 (4) |
O1—Ni1—O2W | 88.09 (12) | O5—C1—C2 | 123.0 (4) |
N1—Ni1—O2W | 90.55 (12) | N3—C1—C2 | 115.4 (3) |
O1—Ni1—O1W | 89.34 (12) | C3—C2—C7 | 120.6 (4) |
N1—Ni1—O1W | 91.90 (13) | C3—C2—C1 | 117.6 (3) |
O2W—Ni1—O1W | 177.10 (11) | C7—C2—C1 | 121.7 (4) |
O1—Ni1—N2 | 109.91 (12) | C4—C3—C2 | 121.8 (4) |
N1—Ni1—N2 | 74.92 (13) | C3—C4—C5 | 118.2 (4) |
O2W—Ni1—N2 | 89.82 (13) | C6—C5—C4 | 121.2 (4) |
O1W—Ni1—N2 | 92.31 (14) | C5—C6—C7 | 122.0 (4) |
O1—Ni1—O5 | 98.23 (11) | O6—C7—C6 | 121.0 (4) |
N1—Ni1—O5 | 76.94 (12) | O6—C7—C2 | 122.8 (4) |
O2W—Ni1—O5 | 90.42 (12) | C6—C7—C2 | 116.2 (4) |
O1W—Ni1—O5 | 88.64 (13) | N1—C8—C10 | 125.6 (4) |
N2—Ni1—O5 | 151.86 (12) | N1—C8—C9 | 112.6 (3) |
C8—N1—N3 | 123.8 (3) | C10—C8—C9 | 121.7 (4) |
C8—N1—Ni1 | 121.3 (3) | N2—C9—C11 | 124.5 (4) |
N3—N1—Ni1 | 114.7 (2) | N2—C9—C8 | 113.7 (3) |
C9—N2—O4 | 115.7 (3) | C11—C9—C8 | 121.7 (4) |
C9—N2—Ni1 | 117.2 (3) | O3—C13—C12 | 111.9 (5) |
O4—N2—Ni1 | 127.0 (2) | O1—C14—O2 | 124.8 (4) |
C1—N3—N1 | 115.1 (3) | O1—C14—C15 | 117.7 (4) |
C14—O1—Ni1 | 127.4 (3) | O2—C14—C15 | 117.5 (4) |
C1—O5—Ni1 | 111.2 (2) |
D—H···A | D···A | D—H···A |
O4—H4A···O2 | 2.576 (5) | 163 |
O1Wi—H2i···O6 | 2.688 (5) | 164 |
O2Wii—H3ii···O6 | 2.658 (5) | 172 |
O1W—H1···O3 | 2.754 (4) | 166 |
O2Wiii—H4iii···O3 | 2.773 (5) | 158 |
O3—H6A···O2iv | 2.648 (4) | 173 |
N3—H3A···O6 | ? | ? |
Symmetry codes: (i) −x−2, −y, −z; (ii) −x−3, −y, −z; (iii) x+1, y, z; (iv) −x−1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Ni(C11H12N3O3)(C2H3O2)(H2O)2]·C2H5OH |
Mr | 434.09 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 7.4120 (15), 11.505 (2), 13.255 (3) |
α, β, γ (°) | 103.13 (3), 103.97 (3), 106.80 (3) |
V (Å3) | 995.0 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.02 |
Crystal size (mm) | 0.40 × 0.20 × 0.05 |
Data collection | |
Diffractometer | FR590 CAD-4 diffractometer |
Absorption correction | Empirical (using intensity measurements) via ψ scan (North et al., 1968) |
Tmin, Tmax | 0.654, 0.947 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3784, 3486, 2472 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.134, 1.00 |
No. of reflections | 3484 |
No. of parameters | 244 |
No. of restraints | 12 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.63, −0.59 |
Computer programs: CAD-4 Software (Enraf-Nonius, 1989)?, SHELXS86 (Sheldrick, 1990a), SHELXL93 (Sheldrick, 1993), SHELXTL-Plus (Sheldrick, 1990b), SHELXL93.
Ni1—O1 | 1.990 (3) | Ni1—O1W | 2.040 (3) |
Ni1—N1 | 2.012 (3) | Ni1—N2 | 2.100 (3) |
Ni1—O2W | 2.037 (3) | Ni1—O5 | 2.148 (3) |
O2W—Ni1—O1W | 177.10 (11) | O1—Ni1—O5 | 98.23 (11) |
O1—Ni1—N2 | 109.91 (12) | N1—Ni1—O5 | 76.94 (12) |
N1—Ni1—N2 | 74.92 (13) |
D—H···A | D···A | D—H···A |
O4—H4A···O2 | 2.576 (5) | 163 |
O1Wi—H2i···O6 | 2.688 (5) | 164 |
O2Wii—H3ii···O6 | 2.658 (5) | 172 |
O1W—H1···O3 | 2.754 (4) | 166 |
O2Wiii—H4iii···O3 | 2.773 (5) | 158 |
O3—H6A···O2iv | 2.648 (4) | 173 |
N3—H3A···O6 | ? | ? |
Symmetry codes: (i) −x−2, −y, −z; (ii) −x−3, −y, −z; (iii) x+1, y, z; (iv) −x−1, −y+1, −z+1. |
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Salicylhydroxamic acid and analogous derivatives, because of the nature of these polydentate ligands, may function as cation recognition agents to form metallacrown ether compounds (Gibney et al., 1994; Psomas et al., 1998), but salicylic hydrazide, with a similar structure, does not have this function. Compared with salicylic hydrazide, salicyloyl hydrazone Schiff bases have additional donor atoms, whose presence introduces a wider range of properties (Kwak et al., 1998) as new types of the inorganic host molecules. We report here the crystal structure of a new nickel(II) salicyloyl hydrazone complex, (I), derived from salicylic hydrazide.
The coordination geometry of NiII in (I) is a distorted octahedron. The two water molecules occupy the axial positions, while atom O5 of the carbonyl and the two atoms N1 and N2 of the imino in the hydrazone, together with atom O1 of the acetate, comprise the basal plane (mean deviation from the plane 0.0084 Å). The basal plane is stabilized by intramolecular O4—H4A···O2 hydrogen bonds, in which O4 is from the oxime and O2 from the acetate. Atom O6 of the hydrazone ligand and atom O3 of the ethanol molecule do not form coordination bonds but can both link two water molecules from two neighbouring molecules of the complex by strong intermolecular hydrogen bonds of the form O1Wi—H2i···O6, O2Wii—H3ii···O6, O1W—H1···O3 and O2Wiii—H4iii···O3; atom O6 has additional intramolecular hydrogen bonding with N3 (N3—H3A···O6) [symmetry codes: (i) -x - 2, -y, -z; (ii) -x - 3, -y, -z; (iii) x + 1, y, z]. Thus, two rows of complex molecules are connected by these hydrogen bonds to form polymeric chains, which are then connected by O3—H6A···O2iv hydrogen bonds to yield a two-dimensional layer structure (see Fig. 2) [symmetry code: (iv) -x - 1, 1 - y, 1 - z].