The reaction of Co(acac)3 with N-(2-aminoethyl)-1,3-propanediamine in the presence of NaNO2 results in the preparation of an unexpected dinitrocobalt(III) compound, (11-amino-4-methyl-5,8-diazaundeca-2,4-dien-2-olato-κ4N5,8,11,O)-dinitrocobalt(III), [Co(C10H20N3O)(NO2)2], containing the tetradentate anion of 11-amino-4-methyl-5,8-diazaundeca-2,4-dien-2-ol. Two isomers of the compound were obtained by recrystallization of the crude product. In one isomer, the two trans nitro groups are staggered, and in the other they are eclipsed.
Supporting information
CCDC references: 158234; 158235
A aqueous solution (5 ml) containing NaNO2 (15 mmol) was added to an
acetonitrile solution (25 ml) of Co(acac)3 (Bryan & Fernelius, 1957) (5 mmol). The solution was mildly heated, and
N-(2-aminoethyl)-1,3-propanediamine (10 mmol) was added. After further
heating for 30 minutes, the solution was cooled to room temperature. A dark
brown residue obtained after the solution dried out (3 weeks) was washed with
water (20 ml) (yield 45%). The crude product was dissolved in hot water,
filtered through charcoal and recrystallized to give rod-shaped crystals of
deep red color (I). The crystals were collected by filtration. Upon further
standing, the filtrate gave dark red, brick-shaped crystals of larger size
(II). Analysis found (calc) for the mixture: C 34.37 (34.39), H 5.77 (5.78), N
19.88 (20.06)%. 13C NMR (CDCl3, 300 MHz, TMS): δ (p.p.m.) = 176.97 (C═
N), 166.24 (C–O), 96.11 (CH), 52.23, 51.00, 49.83, 39.60, 27.46 (5 CH2),
25.14, 22.44 (2 CH3).
For both compounds, data collection: CAD-4-PC (Enraf-Nonius, 1989); cell refinement: CAD-4-PC; data reduction: NRCVAX DATRD2 (Le Page & Gabe, 1979); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL93 (Sheldrick, 1993); molecular graphics: ORTEPIII (Burnett & Johnson, 1996).
(I)
trans-dinitro[2-hydroxo-4-methyl-5,8,12-triazadodec-2-ene-4-imine]
cobalt(III)
top
Crystal data top
[Co(C10H20N3O)(NO2)2] | F(000) = 728 |
Mr = 349.24 | Dx = 1.599 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 7.375 (2) Å | Cell parameters from 25 reflections |
b = 20.065 (3) Å | θ = 8.7–13.5° |
c = 9.8088 (9) Å | µ = 1.21 mm−1 |
β = 91.717 (7)° | T = 293 K |
V = 1450.8 (4) Å3 | Rod, dark red |
Z = 4 | 0.60 × 0.17 × 0.14 mm |
Data collection top
Enraf-Nonius CAD-4 diffractometer | 1855 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.015 |
Graphite monochromator | θmax = 25.0°, θmin = 2.0° |
ω–2θ scans | h = −8→8 |
Absorption correction: ψ scan (NRCVAX ABSORP; Gabe et al., 1989) | k = 0→23 |
Tmin = 0.776, Tmax = 0.844 | l = 0→11 |
2702 measured reflections | 3 standard reflections every 240 min |
2554 independent reflections | intensity decay: none |
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)] = 0.026 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.064 | All H-atom parameters refined |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0428P)2] where P = (Fo2 + 2Fc2)/3 |
2554 reflections | (Δ/σ)max = −0.004 |
270 parameters | Δρmax = 0.25 e Å−3 |
0 restraints | Δρmin = −0.36 e Å−3 |
Crystal data top
[Co(C10H20N3O)(NO2)2] | V = 1450.8 (4) Å3 |
Mr = 349.24 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.375 (2) Å | µ = 1.21 mm−1 |
b = 20.065 (3) Å | T = 293 K |
c = 9.8088 (9) Å | 0.60 × 0.17 × 0.14 mm |
β = 91.717 (7)° | |
Data collection top
Enraf-Nonius CAD-4 diffractometer | 1855 reflections with I > 2σ(I) |
Absorption correction: ψ scan (NRCVAX ABSORP; Gabe et al., 1989) | Rint = 0.015 |
Tmin = 0.776, Tmax = 0.844 | 3 standard reflections every 240 min |
2702 measured reflections | intensity decay: none |
2554 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.026 | 0 restraints |
wR(F2) = 0.064 | All H-atom parameters refined |
S = 1.01 | Δρmax = 0.25 e Å−3 |
2554 reflections | Δρmin = −0.36 e Å−3 |
270 parameters | |
Special details top
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 0 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Co | 0.19333 (4) | 0.084501 (14) | 0.25009 (3) | 0.02674 (11) | |
N1 | 0.3185 (3) | 0.16449 (10) | 0.2080 (2) | 0.0395 (5) | |
N2 | 0.4010 (2) | 0.03760 (10) | 0.1744 (2) | 0.0353 (5) | |
H1N | 0.357 (3) | 0.0277 (12) | 0.088 (3) | 0.044 (7)* | |
N3 | 0.0611 (3) | 0.00080 (9) | 0.2815 (2) | 0.0287 (4) | |
H2N | −0.009 (3) | 0.0116 (12) | 0.343 (3) | 0.039 (7)* | |
H3N | −0.004 (3) | −0.0096 (11) | 0.209 (2) | 0.034 (7)* | |
N4 | 0.0831 (3) | 0.08965 (10) | 0.0641 (2) | 0.0360 (4) | |
N5 | 0.2978 (2) | 0.08213 (9) | 0.4336 (2) | 0.0323 (4) | |
O1 | −0.0113 (2) | 0.12628 (7) | 0.32371 (15) | 0.0341 (4) | |
O2 | 0.1471 (2) | 0.05617 (11) | −0.0308 (2) | 0.0573 (5) | |
O3 | −0.0459 (3) | 0.12607 (10) | 0.0387 (2) | 0.0603 (5) | |
O4 | 0.4535 (2) | 0.10143 (9) | 0.4583 (2) | 0.0482 (5) | |
O5 | 0.2061 (2) | 0.06127 (9) | 0.5272 (2) | 0.0474 (4) | |
C1 | −0.1819 (4) | 0.2097 (2) | 0.4291 (4) | 0.0573 (8) | |
H1C | −0.281 (5) | 0.196 (2) | 0.390 (4) | 0.111 (16)* | |
H2C | −0.206 (5) | 0.2558 (19) | 0.430 (4) | 0.097 (12)* | |
H3C | −0.156 (5) | 0.200 (2) | 0.521 (4) | 0.121 (16)* | |
C2 | −0.0198 (3) | 0.18921 (11) | 0.3490 (2) | 0.0387 (5) | |
C3 | 0.1033 (4) | 0.23601 (12) | 0.3106 (3) | 0.0518 (7) | |
H4C | 0.080 (4) | 0.2809 (16) | 0.328 (3) | 0.082 (10)* | |
C4 | 0.2607 (4) | 0.22401 (13) | 0.2352 (3) | 0.0483 (7) | |
C5 | 0.3635 (7) | 0.2840 (2) | 0.1864 (6) | 0.0861 (13) | |
H5C | 0.480 (7) | 0.286 (3) | 0.226 (5) | 0.17 (2)* | |
H6C | 0.304 (5) | 0.3206 (19) | 0.214 (3) | 0.078 (12)* | |
H7C | 0.367 (7) | 0.284 (3) | 0.094 (5) | 0.16 (3)* | |
C6 | 0.4764 (4) | 0.1518 (2) | 0.1238 (3) | 0.0551 (8) | |
H8C | 0.445 (4) | 0.1547 (13) | 0.024 (3) | 0.059 (8)* | |
H9C | 0.562 (4) | 0.1830 (13) | 0.136 (3) | 0.049 (7)* | |
C7 | 0.5535 (3) | 0.0853 (2) | 0.1627 (3) | 0.0483 (7) | |
H10C | 0.615 (3) | 0.0858 (11) | 0.251 (3) | 0.036 (6)* | |
H11C | 0.635 (3) | 0.0667 (12) | 0.099 (3) | 0.045 (7)* | |
C8 | 0.4606 (3) | −0.02644 (14) | 0.2362 (3) | 0.0437 (6) | |
H12C | 0.561 (3) | −0.0429 (11) | 0.183 (2) | 0.036 (6)* | |
H13C | 0.504 (3) | −0.0184 (12) | 0.331 (2) | 0.042 (7)* | |
C9 | 0.3109 (3) | −0.07728 (13) | 0.2352 (3) | 0.0447 (6) | |
H14C | 0.267 (3) | −0.0846 (11) | 0.141 (2) | 0.035 (6)* | |
H15C | 0.360 (3) | −0.1202 (14) | 0.267 (2) | 0.049 (7)* | |
C10 | 0.1575 (4) | −0.06063 (12) | 0.3272 (3) | 0.0391 (6) | |
H16C | 0.200 (3) | −0.0543 (12) | 0.421 (3) | 0.042 (7)* | |
H17C | 0.070 (4) | −0.0954 (12) | 0.330 (2) | 0.043 (7)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Co | 0.0228 (2) | 0.0321 (2) | 0.0254 (2) | −0.00557 (12) | 0.00108 (10) | 0.00118 (13) |
N1 | 0.0369 (11) | 0.0452 (12) | 0.0363 (11) | −0.0184 (9) | −0.0002 (9) | 0.0056 (9) |
N2 | 0.0255 (10) | 0.0548 (13) | 0.0256 (9) | −0.0051 (9) | 0.0011 (8) | −0.0028 (9) |
N3 | 0.0254 (9) | 0.0309 (10) | 0.0298 (10) | −0.0011 (8) | 0.0019 (9) | 0.0006 (8) |
N4 | 0.0319 (10) | 0.0418 (11) | 0.0340 (10) | −0.0124 (9) | −0.0050 (8) | 0.0069 (9) |
N5 | 0.0300 (10) | 0.0390 (10) | 0.0281 (9) | −0.0049 (8) | 0.0016 (8) | −0.0029 (9) |
O1 | 0.0300 (8) | 0.0292 (8) | 0.0432 (9) | 0.0000 (6) | 0.0038 (7) | −0.0008 (7) |
O2 | 0.0527 (11) | 0.0884 (15) | 0.0305 (9) | 0.0024 (10) | −0.0054 (8) | −0.0106 (10) |
O3 | 0.0528 (12) | 0.0686 (13) | 0.0580 (12) | 0.0118 (10) | −0.0202 (9) | 0.0068 (10) |
O4 | 0.0343 (9) | 0.0734 (13) | 0.0364 (9) | −0.0158 (9) | −0.0049 (7) | −0.0040 (8) |
O5 | 0.0414 (9) | 0.0729 (12) | 0.0283 (8) | −0.0129 (9) | 0.0072 (7) | 0.0037 (8) |
C1 | 0.049 (2) | 0.047 (2) | 0.076 (2) | 0.0141 (14) | 0.001 (2) | −0.016 (2) |
C2 | 0.0398 (13) | 0.0320 (13) | 0.0436 (13) | 0.0030 (10) | −0.0093 (11) | −0.0011 (10) |
C3 | 0.058 (2) | 0.0281 (14) | 0.068 (2) | −0.0045 (12) | −0.0094 (14) | −0.0001 (13) |
C4 | 0.051 (2) | 0.0421 (15) | 0.051 (2) | −0.0210 (12) | −0.0115 (13) | 0.0127 (12) |
C5 | 0.084 (3) | 0.051 (2) | 0.123 (4) | −0.031 (2) | 0.002 (3) | 0.023 (2) |
C6 | 0.050 (2) | 0.072 (2) | 0.044 (2) | −0.034 (2) | 0.0115 (13) | 0.0024 (14) |
C7 | 0.0283 (13) | 0.078 (2) | 0.0392 (14) | −0.0129 (13) | 0.0108 (11) | −0.0075 (14) |
C8 | 0.0311 (13) | 0.061 (2) | 0.0390 (14) | 0.0141 (12) | 0.0022 (11) | −0.0023 (12) |
C9 | 0.0438 (14) | 0.0425 (15) | 0.0479 (15) | 0.0142 (13) | 0.0019 (12) | −0.0022 (13) |
C10 | 0.0417 (14) | 0.0326 (12) | 0.0434 (15) | 0.0073 (11) | 0.0052 (11) | 0.0058 (11) |
Geometric parameters (Å, º) top
Co—O1 | 1.8886 (15) | C1—H3C | 0.94 (4) |
Co—N1 | 1.903 (2) | C2—C3 | 1.367 (4) |
Co—N5 | 1.937 (2) | C3—C4 | 1.416 (4) |
Co—N2 | 1.962 (2) | C3—H4C | 0.93 (3) |
Co—N3 | 1.971 (2) | C4—C5 | 1.508 (4) |
Co—N4 | 1.977 (2) | C5—H5C | 0.93 (5) |
N1—C4 | 1.298 (3) | C5—H6C | 0.90 (4) |
N1—C6 | 1.471 (3) | C5—H7C | 0.91 (5) |
N2—C8 | 1.482 (3) | C6—C7 | 1.495 (4) |
N2—C7 | 1.484 (3) | C6—H8C | 1.00 (3) |
N2—H1N | 0.92 (2) | C6—H9C | 0.89 (3) |
N3—C10 | 1.485 (3) | C7—H10C | 0.96 (2) |
N3—H2N | 0.83 (2) | C7—H11C | 0.96 (2) |
N3—H3N | 0.87 (2) | C8—C9 | 1.503 (4) |
N4—O3 | 1.219 (3) | C8—H12C | 0.97 (2) |
N4—O2 | 1.252 (3) | C8—H13C | 0.99 (2) |
N5—O4 | 1.229 (2) | C9—C10 | 1.506 (3) |
N5—O5 | 1.230 (2) | C9—H14C | 0.98 (2) |
O1—C2 | 1.289 (3) | C9—H15C | 0.98 (3) |
C1—C2 | 1.506 (4) | C10—H16C | 0.97 (2) |
C1—H1C | 0.86 (4) | C10—H17C | 0.95 (3) |
C1—H2C | 0.94 (4) | | |
| | | |
O1—Co—N1 | 96.13 (8) | O1—C2—C1 | 114.3 (2) |
O1—Co—N5 | 87.46 (7) | C3—C2—C1 | 120.0 (2) |
N1—Co—N5 | 92.31 (8) | C2—C3—C4 | 126.1 (2) |
O1—Co—N2 | 177.67 (7) | C2—C3—H4C | 119 (2) |
N1—Co—N2 | 86.19 (9) | C4—C3—H4C | 115 (2) |
N5—Co—N2 | 92.68 (8) | N1—C4—C3 | 122.9 (2) |
O1—Co—N3 | 85.05 (7) | N1—C4—C5 | 119.9 (3) |
N1—Co—N3 | 176.48 (8) | C3—C4—C5 | 117.2 (3) |
N5—Co—N3 | 91.05 (8) | C4—C5—H5C | 111 (3) |
N2—Co—N3 | 92.62 (8) | C4—C5—H6C | 108 (2) |
O1—Co—N4 | 91.05 (8) | H5C—C5—H6C | 107 (4) |
N1—Co—N4 | 86.83 (8) | C4—C5—H7C | 110 (3) |
N5—Co—N4 | 178.19 (8) | H5C—C5—H7C | 111 (4) |
N2—Co—N4 | 88.85 (8) | H6C—C5—H7C | 110 (4) |
N3—Co—N4 | 89.84 (8) | N1—C6—C7 | 108.2 (2) |
C4—N1—C6 | 123.0 (2) | N1—C6—H8C | 112.2 (15) |
C4—N1—Co | 124.6 (2) | C7—C6—H8C | 112.1 (16) |
C6—N1—Co | 111.9 (2) | N1—C6—H9C | 112.0 (17) |
C8—N2—C7 | 112.0 (2) | C7—C6—H9C | 109.3 (17) |
C8—N2—Co | 119.11 (15) | H8C—C6—H9C | 103 (2) |
C7—N2—Co | 108.8 (2) | N2—C7—C6 | 108.2 (2) |
C8—N2—H1N | 106.4 (15) | N2—C7—H10C | 105.9 (14) |
C7—N2—H1N | 108.3 (15) | C6—C7—H10C | 112.6 (14) |
Co—N2—H1N | 101.2 (15) | N2—C7—H11C | 106.9 (15) |
C10—N3—Co | 121.3 (2) | C6—C7—H11C | 114.9 (15) |
C10—N3—H2N | 107.5 (16) | H10C—C7—H11C | 108 (2) |
Co—N3—H2N | 102.3 (17) | N2—C8—C9 | 112.1 (2) |
C10—N3—H3N | 107.2 (15) | N2—C8—H12C | 107.2 (13) |
Co—N3—H3N | 109.9 (15) | C9—C8—H12C | 109.6 (13) |
H2N—N3—H3N | 108 (2) | N2—C8—H13C | 109.1 (14) |
O3—N4—O2 | 118.6 (2) | C9—C8—H13C | 109.4 (14) |
O3—N4—Co | 121.1 (2) | H12C—C8—H13C | 109.4 (18) |
O2—N4—Co | 120.3 (2) | C8—C9—C10 | 114.2 (2) |
O4—N5—O5 | 119.4 (2) | C8—C9—H14C | 109.3 (13) |
O4—N5—Co | 121.25 (14) | C10—C9—H14C | 111.4 (14) |
O5—N5—Co | 119.34 (14) | C8—C9—H15C | 109.2 (15) |
C2—O1—Co | 123.55 (15) | C10—C9—H15C | 106.5 (14) |
C2—C1—H1C | 111 (3) | H14C—C9—H15C | 105.9 (19) |
C2—C1—H2C | 115 (2) | N3—C10—C9 | 111.4 (2) |
H1C—C1—H2C | 99 (3) | N3—C10—H16C | 108.4 (14) |
C2—C1—H3C | 108 (2) | C9—C10—H16C | 111.6 (14) |
H1C—C1—H3C | 121 (4) | N3—C10—H17C | 107.4 (15) |
H2C—C1—H3C | 103 (3) | C9—C10—H17C | 112.3 (15) |
O1—C2—C3 | 125.7 (2) | H16C—C10—H17C | 105 (2) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H2N···O5i | 0.83 (2) | 2.45 (2) | 3.029 (3) | 127.8 (2.1) |
N3—H3N···O2ii | 0.87 (2) | 2.22 (2) | 3.080 (3) | 168.5 (2.1) |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x, −y, −z. |
(II)
trans-dinitro[2-hydroxo-4-methyl-5,8,12-triazadodec-2-ene-4-imine]
cobalt(III)
top
Crystal data top
[Co(C10H20N3O)(NO2)2] | F(000) = 728 |
Mr = 349.24 | Dx = 1.594 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 7.923 (3) Å | Cell parameters from 25 reflections |
b = 13.105 (1) Å | θ = 8.2–13.1° |
c = 14.0273 (13) Å | µ = 1.21 mm−1 |
β = 91.908 (10)° | T = 293 K |
V = 1455.7 (5) Å3 | Brick, dark red |
Z = 4 | 0.52 × 0.40 × 0.30 mm |
Data collection top
Enraf-Nonius CAD-4 diffractometer | 1985 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.039 |
Graphite monochromator | θmax = 25.0°, θmin = 2.1° |
ω–2θ scans | h = −9→9 |
Absorption correction: ψ scan (NRCVAX ABSORP; Gabe et al., 1989) | k = 0→15 |
Tmin = 0.648, Tmax = 0.696 | l = 0→16 |
2672 measured reflections | 3 standard reflections every 240 min |
2568 independent reflections | intensity decay: none |
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)] = 0.032 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.105 | All H-atom parameters refined |
S = 1.14 | w = 1/[σ2(Fo2) + (0.0464P)2 + 2.1606P] where P = (Fo2 + 2Fc2)/3 |
2568 reflections | (Δ/σ)max = −0.002 |
270 parameters | Δρmax = 0.37 e Å−3 |
0 restraints | Δρmin = −0.48 e Å−3 |
Crystal data top
[Co(C10H20N3O)(NO2)2] | V = 1455.7 (5) Å3 |
Mr = 349.24 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.923 (3) Å | µ = 1.21 mm−1 |
b = 13.105 (1) Å | T = 293 K |
c = 14.0273 (13) Å | 0.52 × 0.40 × 0.30 mm |
β = 91.908 (10)° | |
Data collection top
Enraf-Nonius CAD-4 diffractometer | 1985 reflections with I > 2σ(I) |
Absorption correction: ψ scan (NRCVAX ABSORP; Gabe et al., 1989) | Rint = 0.039 |
Tmin = 0.648, Tmax = 0.696 | 3 standard reflections every 240 min |
2672 measured reflections | intensity decay: none |
2568 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.105 | All H-atom parameters refined |
S = 1.14 | Δρmax = 0.37 e Å−3 |
2568 reflections | Δρmin = −0.48 e Å−3 |
270 parameters | |
Special details top
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 0 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Co | 0.05180 (6) | 0.22034 (3) | 0.08760 (3) | 0.0255 (2) | |
N1 | −0.0635 (4) | 0.1707 (2) | 0.1949 (2) | 0.0310 (7) | |
N2 | 0.2067 (4) | 0.1057 (2) | 0.1088 (2) | 0.0319 (7) | |
H1N | 0.174 (5) | 0.060 (3) | 0.071 (3) | 0.028 (10)* | |
N3 | 0.1679 (4) | 0.2711 (3) | −0.0248 (3) | 0.0363 (7) | |
H2N | 0.117 (6) | 0.242 (4) | −0.075 (4) | 0.053 (14)* | |
H3N | 0.144 (6) | 0.332 (4) | −0.024 (3) | 0.052 (15)* | |
N4 | 0.1841 (4) | 0.3144 (2) | 0.1681 (2) | 0.0386 (8) | |
N5 | −0.0885 (4) | 0.1326 (2) | 0.0035 (2) | 0.0345 (7) | |
O1 | −0.0980 (3) | 0.3281 (2) | 0.0588 (2) | 0.0389 (6) | |
O2 | 0.2272 (5) | 0.2945 (3) | 0.2509 (2) | 0.0641 (10) | |
O3 | 0.2236 (5) | 0.3977 (2) | 0.1346 (2) | 0.0611 (9) | |
O4 | −0.1636 (4) | 0.0589 (2) | 0.0350 (2) | 0.0562 (8) | |
O5 | −0.1049 (5) | 0.1494 (3) | −0.0817 (2) | 0.0726 (11) | |
C1 | −0.3194 (6) | 0.4441 (4) | 0.0750 (4) | 0.0463 (11) | |
H1C | −0.349 (7) | 0.443 (4) | 0.010 (4) | 0.079 (18)* | |
H2C | −0.248 (7) | 0.499 (4) | 0.083 (4) | 0.076 (17)* | |
H3C | −0.419 (8) | 0.460 (5) | 0.105 (4) | 0.09 (2)* | |
C2 | −0.2264 (4) | 0.3504 (3) | 0.1094 (3) | 0.0315 (8) | |
C3 | −0.2795 (5) | 0.2974 (3) | 0.1863 (3) | 0.0367 (9) | |
H4C | −0.377 (6) | 0.319 (3) | 0.218 (3) | 0.045 (12)* | |
C4 | −0.2026 (5) | 0.2080 (3) | 0.2258 (3) | 0.0339 (8) | |
C5 | −0.2909 (7) | 0.1557 (5) | 0.3057 (4) | 0.0531 (12) | |
H5C | −0.235 (7) | 0.159 (4) | 0.363 (4) | 0.070 (17)* | |
H6C | −0.399 (8) | 0.184 (4) | 0.312 (4) | 0.080 (18)* | |
H7C | −0.315 (7) | 0.089 (5) | 0.294 (4) | 0.074 (18)* | |
C6 | 0.0069 (6) | 0.0738 (3) | 0.2329 (3) | 0.0428 (10) | |
H8C | −0.056 (5) | 0.018 (3) | 0.202 (3) | 0.046 (12)* | |
H9C | −0.002 (6) | 0.070 (4) | 0.300 (3) | 0.052 (13)* | |
C7 | 0.1906 (6) | 0.0683 (3) | 0.2078 (3) | 0.0417 (10) | |
H10C | 0.229 (5) | 0.001 (4) | 0.214 (3) | 0.046 (12)* | |
H11C | 0.260 (5) | 0.112 (3) | 0.249 (3) | 0.034 (10)* | |
C8 | 0.3892 (5) | 0.1186 (4) | 0.0849 (3) | 0.0437 (10) | |
H12C | 0.442 (6) | 0.054 (4) | 0.095 (3) | 0.049 (13)* | |
H13C | 0.427 (5) | 0.167 (3) | 0.127 (3) | 0.039 (11)* | |
C9 | 0.4079 (6) | 0.1530 (4) | −0.0164 (4) | 0.0492 (11) | |
H14C | 0.348 (6) | 0.110 (3) | −0.062 (3) | 0.048 (12)* | |
H15C | 0.514 (7) | 0.149 (4) | −0.029 (3) | 0.056 (14)* | |
C10 | 0.3502 (6) | 0.2612 (4) | −0.0341 (4) | 0.0464 (11) | |
H16C | 0.377 (6) | 0.282 (3) | −0.099 (3) | 0.051 (13)* | |
H17C | 0.411 (5) | 0.305 (3) | 0.012 (3) | 0.040 (11)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Co | 0.0241 (3) | 0.0240 (3) | 0.0284 (3) | 0.0005 (2) | 0.0022 (2) | 0.0023 (2) |
N1 | 0.032 (2) | 0.030 (2) | 0.031 (2) | −0.0013 (13) | 0.0024 (12) | 0.0053 (13) |
N2 | 0.034 (2) | 0.027 (2) | 0.035 (2) | −0.0010 (13) | −0.0015 (13) | −0.0046 (14) |
N3 | 0.035 (2) | 0.039 (2) | 0.036 (2) | −0.003 (2) | 0.0087 (14) | 0.003 (2) |
N4 | 0.043 (2) | 0.031 (2) | 0.042 (2) | 0.0001 (14) | 0.008 (2) | −0.0060 (15) |
N5 | 0.033 (2) | 0.033 (2) | 0.038 (2) | 0.0045 (14) | −0.0002 (14) | −0.0001 (14) |
O1 | 0.041 (2) | 0.0329 (14) | 0.044 (2) | 0.0086 (12) | 0.0080 (12) | 0.0089 (12) |
O2 | 0.088 (3) | 0.057 (2) | 0.046 (2) | −0.015 (2) | −0.022 (2) | −0.002 (2) |
O3 | 0.090 (3) | 0.034 (2) | 0.060 (2) | −0.022 (2) | 0.010 (2) | −0.006 (2) |
O4 | 0.067 (2) | 0.048 (2) | 0.053 (2) | −0.027 (2) | 0.001 (2) | −0.004 (2) |
O5 | 0.090 (3) | 0.082 (3) | 0.044 (2) | −0.034 (2) | −0.023 (2) | 0.011 (2) |
C1 | 0.039 (3) | 0.038 (2) | 0.061 (3) | 0.011 (2) | −0.012 (2) | −0.006 (2) |
C2 | 0.020 (2) | 0.032 (2) | 0.041 (2) | 0.0010 (14) | −0.0088 (15) | −0.010 (2) |
C3 | 0.029 (2) | 0.038 (2) | 0.042 (2) | 0.004 (2) | 0.004 (2) | −0.009 (2) |
C4 | 0.032 (2) | 0.040 (2) | 0.030 (2) | −0.008 (2) | 0.003 (2) | −0.005 (2) |
C5 | 0.051 (3) | 0.065 (3) | 0.044 (3) | −0.010 (3) | 0.020 (2) | 0.003 (2) |
C6 | 0.052 (3) | 0.037 (2) | 0.039 (2) | 0.001 (2) | 0.002 (2) | 0.013 (2) |
C7 | 0.046 (2) | 0.035 (2) | 0.044 (2) | 0.006 (2) | −0.007 (2) | 0.007 (2) |
C8 | 0.026 (2) | 0.045 (3) | 0.059 (3) | 0.007 (2) | −0.004 (2) | −0.007 (2) |
C9 | 0.025 (2) | 0.063 (3) | 0.060 (3) | 0.000 (2) | 0.011 (2) | −0.014 (2) |
C10 | 0.041 (2) | 0.052 (3) | 0.048 (3) | −0.013 (2) | 0.014 (2) | −0.002 (2) |
Geometric parameters (Å, º) top
Co—O1 | 1.880 (3) | C1—H3C | 0.93 (6) |
Co—N1 | 1.901 (3) | C2—C3 | 1.362 (6) |
Co—N4 | 1.953 (3) | C3—C4 | 1.423 (6) |
Co—N2 | 1.956 (3) | C3—H4C | 0.94 (4) |
Co—N5 | 1.965 (3) | C4—C5 | 1.506 (6) |
Co—N3 | 1.968 (3) | C5—H5C | 0.90 (6) |
N1—C4 | 1.294 (5) | C5—H6C | 0.94 (6) |
N1—C6 | 1.480 (5) | C5—H7C | 0.91 (6) |
N2—C7 | 1.482 (5) | C6—C7 | 1.511 (6) |
N2—C8 | 1.505 (5) | C6—H8C | 0.98 (4) |
N2—H1N | 0.84 (4) | C6—H9C | 0.95 (5) |
N3—C10 | 1.460 (6) | C7—H10C | 0.94 (5) |
N3—H2N | 0.88 (5) | C7—H11C | 0.97 (4) |
N3—H3N | 0.82 (5) | C8—C9 | 1.503 (7) |
N4—O2 | 1.227 (4) | C8—H12C | 0.95 (5) |
N4—O3 | 1.233 (4) | C8—H13C | 0.90 (4) |
N5—O5 | 1.219 (4) | C9—C10 | 1.508 (7) |
N5—O4 | 1.225 (4) | C9—H14C | 0.97 (5) |
O1—C2 | 1.293 (4) | C9—H15C | 0.87 (5) |
C1—C2 | 1.503 (6) | C10—H16C | 0.97 (5) |
C1—H1C | 0.93 (6) | C10—H17C | 0.98 (4) |
C1—H2C | 0.92 (6) | | |
| | | |
O1—Co—N1 | 96.35 (12) | O1—C2—C1 | 113.3 (4) |
O1—Co—N4 | 88.44 (13) | C3—C2—C1 | 120.7 (4) |
N1—Co—N4 | 91.19 (13) | C2—C3—C4 | 126.1 (4) |
O1—Co—N2 | 176.28 (13) | C2—C3—H4C | 120 (3) |
N1—Co—N2 | 86.13 (13) | C4—C3—H4C | 114 (3) |
N4—Co—N2 | 94.29 (14) | N1—C4—C3 | 122.6 (3) |
O1—Co—N5 | 88.30 (13) | N1—C4—C5 | 119.9 (4) |
N1—Co—N5 | 89.90 (13) | C3—C4—C5 | 117.4 (4) |
N4—Co—N5 | 176.66 (13) | C4—C5—H5C | 114 (4) |
N2—Co—N5 | 88.94 (13) | C4—C5—H6C | 110 (4) |
O1—Co—N3 | 83.25 (13) | H5C—C5—H6C | 109 (5) |
N1—Co—N3 | 179.06 (14) | C4—C5—H7C | 114 (3) |
N4—Co—N3 | 89.7 (2) | H5C—C5—H7C | 108 (5) |
N2—Co—N3 | 94.23 (14) | H6C—C5—H7C | 102 (5) |
N5—Co—N3 | 89.24 (15) | N1—C6—C7 | 108.1 (3) |
C4—N1—C6 | 121.2 (3) | N1—C6—H8C | 107 (2) |
C4—N1—Co | 125.0 (3) | C7—C6—H8C | 110 (3) |
C6—N1—Co | 113.2 (2) | N1—C6—H9C | 111 (3) |
C7—N2—C8 | 111.0 (3) | C7—C6—H9C | 109 (3) |
C7—N2—Co | 108.9 (2) | H8C—C6—H9C | 111 (4) |
C8—N2—Co | 118.9 (3) | N2—C7—C6 | 108.4 (3) |
C7—N2—H1N | 109 (3) | N2—C7—H10C | 111 (3) |
C8—N2—H1N | 103 (3) | C6—C7—H10C | 109 (3) |
Co—N2—H1N | 106 (3) | N2—C7—H11C | 108 (2) |
C10—N3—Co | 122.1 (3) | C6—C7—H11C | 111 (2) |
C10—N3—H2N | 109 (3) | H10C—C7—H11C | 109 (3) |
Co—N3—H2N | 106 (3) | C9—C8—N2 | 111.7 (3) |
C10—N3—H3N | 109 (3) | C9—C8—H12C | 111 (3) |
Co—N3—H3N | 101 (3) | N2—C8—H12C | 107 (3) |
H2N—N3—H3N | 110 (5) | C9—C8—H13C | 111 (3) |
O2—N4—O3 | 118.9 (4) | N2—C8—H13C | 104 (3) |
O2—N4—Co | 122.7 (3) | H12C—C8—H13C | 113 (4) |
O3—N4—Co | 118.4 (3) | C8—C9—C10 | 113.5 (4) |
O5—N5—O4 | 117.3 (3) | C8—C9—H14C | 113 (3) |
O5—N5—Co | 121.6 (3) | C10—C9—H14C | 108 (3) |
O4—N5—Co | 121.1 (3) | C8—C9—H15C | 107 (3) |
C2—O1—Co | 123.7 (2) | C10—C9—H15C | 109 (3) |
C2—C1—H1C | 114 (3) | H14C—C9—H15C | 106 (4) |
C2—C1—H2C | 108 (3) | N3—C10—C9 | 111.3 (4) |
H1C—C1—H2C | 105 (5) | N3—C10—H16C | 108 (3) |
C2—C1—H3C | 117 (4) | C9—C10—H16C | 110 (3) |
H1C—C1—H3C | 105 (5) | N3—C10—H17C | 111 (2) |
H2C—C1—H3C | 108 (5) | C9—C10—H17C | 108 (2) |
O1—C2—C3 | 126.1 (3) | H16C—C10—H17C | 109 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H1N···O4i | 0.84 (4) | 2.15 (4) | 2.966 (4) | 164.13 (3.59) |
Symmetry code: (i) −x, −y, −z. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | [Co(C10H20N3O)(NO2)2] | [Co(C10H20N3O)(NO2)2] |
Mr | 349.24 | 349.24 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/c |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 7.375 (2), 20.065 (3), 9.8088 (9) | 7.923 (3), 13.105 (1), 14.0273 (13) |
β (°) | 91.717 (7) | 91.908 (10) |
V (Å3) | 1450.8 (4) | 1455.7 (5) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 1.21 | 1.21 |
Crystal size (mm) | 0.60 × 0.17 × 0.14 | 0.52 × 0.40 × 0.30 |
|
Data collection |
Diffractometer | Enraf-Nonius CAD-4 diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (NRCVAX ABSORP; Gabe et al., 1989) | ψ scan (NRCVAX ABSORP; Gabe et al., 1989) |
Tmin, Tmax | 0.776, 0.844 | 0.648, 0.696 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2702, 2554, 1855 | 2672, 2568, 1985 |
Rint | 0.015 | 0.039 |
(sin θ/λ)max (Å−1) | 0.594 | 0.594 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.064, 1.01 | 0.032, 0.105, 1.14 |
No. of reflections | 2554 | 2568 |
No. of parameters | 270 | 270 |
H-atom treatment | All H-atom parameters refined | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.25, −0.36 | 0.37, −0.48 |
Selected geometric parameters (Å, º) for (I) topCo—O1 | 1.8886 (15) | Co—N4 | 1.977 (2) |
Co—N1 | 1.903 (2) | N1—C4 | 1.298 (3) |
Co—N5 | 1.937 (2) | O1—C2 | 1.289 (3) |
Co—N2 | 1.962 (2) | C2—C3 | 1.367 (4) |
Co—N3 | 1.971 (2) | C3—C4 | 1.416 (4) |
| | | |
O1—Co—N1 | 96.13 (8) | N5—Co—N4 | 178.19 (8) |
O1—Co—N5 | 87.46 (7) | O1—C2—C3 | 125.7 (2) |
O1—Co—N2 | 177.67 (7) | C2—C3—C4 | 126.1 (2) |
N1—Co—N3 | 176.48 (8) | N1—C4—C3 | 122.9 (2) |
N1—Co—N4 | 86.83 (8) | | |
Selected geometric parameters (Å, º) for (II) topCo—O1 | 1.880 (3) | Co—N3 | 1.968 (3) |
Co—N1 | 1.901 (3) | N1—C4 | 1.294 (5) |
Co—N4 | 1.953 (3) | O1—C2 | 1.293 (4) |
Co—N2 | 1.956 (3) | C2—C3 | 1.362 (6) |
Co—N5 | 1.965 (3) | C3—C4 | 1.423 (6) |
| | | |
O1—Co—N1 | 96.35 (12) | N1—Co—N3 | 179.06 (14) |
N1—Co—N4 | 91.19 (13) | O1—C2—C3 | 126.1 (3) |
O1—Co—N2 | 176.28 (13) | C2—C3—C4 | 126.1 (4) |
O1—Co—N5 | 88.30 (13) | N1—C4—C3 | 122.6 (3) |
N4—Co—N5 | 176.66 (13) | | |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H1N···O4i | 0.84 (4) | 2.15 (4) | 2.966 (4) | 164.13(3.59) |
Symmetry code: (i) −x, −y, −z. |
Tris(acetylacetonato)cobalt(III), Co(acac)3, is a useful starting material for the preparation of various CoIII complexes. Although the same is true for the anionic complex, [Co(CO3)3]3-, Co(acac)3 has an advantage when there is a need for using organic solvents for the reaction. Also, a coordinated acac ligand can undergo an organic reaction with nucleophilic reagents to generate a new chelating ligand.
The title compounds, (I) amd (II), were obtained while trying to prepare trinitrocobalt(III) complexes with facial configurations by replacing the acac ligands of Co(acac)3 with a tridentate amine ligand and nitro groups. Instead, a condensation reaction occurred between an –NH2 group of the amine ligand and a carbonyl group of a coordinated acac ligand to give the monoanionic tetradentate ligand. Compound (I) has two nitro groups in a staggered conformation [O2—N4···N5—O5 = 63.7 (2)°] and appears to be less soluble than compound (II) in which the two nitro groups are almost eclipsed [O2—N4···N5—O5 = 13.3 (5)°]. A similar case is known in which two conformational isomers of mer-Co(en)(NH3)(NO2)3 crystallize with different crystal habits and color (brown and yellow), but in the same space group (P21/c) (Jensen et al., 1970) \sch
The geometry of the tetradentate ligand around the cobalt atom is quite similar in both structures. For example, N1—C4 [1.298 (3) for (I); 1.294 (5) Å for (II)] and C2—C3 [1.367 (4) for (I); 1.362 Å for (II)] are considered as double bonds and the single negative charge is mostly assigned to O1 since the O1—C2 bond [1.289 (3) for (I); 1.293 (4) Å for (II)] is rather long for a carbonyl group. Also, the relatively short distance of Co—O1 [1.889 (2) for (I); 1.880 (3) Å for (II)] reflects an anionic character of the ligand atom. The distances between cobalt and NO2 nitrogen atoms of (I) are uneven with the difference being 20σ; in (II), the difference is only 4σ. No severe distortion is observed in the angular geometry of the octahedral cobalt atom. The four N—O bond distances in the two nitro groups of (II) fall within the 3 σ range with an average of 1.226 (4) Å. In (I), N4—O2 [1.252 (3) Å] is significantly longer than the other three N—O bonds whose average is 1.226 (2) Å, probably because of the short intramolecular contact between O2 and the hydrogen atom of N2 [1.993 (24) Å].
In the packing structure of (I) (Fig. 3), the two nitro groups, staggered to each other, form hydrogen bonds with –NH2 hydrogen atoms of neighboring molecules, related by inversion symmetry. This one-dimensional interaction extends along the c direction of the unit cell, and no other hydrogen bonding is found in other directions. The structure can therefore be described as a stack of one-dimensional strings along which the chirality of the molecules alternates. Also, the molecules of (I) are arranged such that the approximate planes of the tetradentate ligand are parallel to one another over the whole structure.
The packing diagram of (II) shows that there is only one intermolecular hydrogen bond, involving O4 and the hydrogen atom of N2 [d(O···H) = 2.151 (40) Å]. The oxygen atoms of the other nitro group have only very weak interactions with amine hydrogen atoms [d(O···H) > 2.6 Å]. As Fig. 4 clearly shows, the hydrogen bond is always formed by a pair of molecules around crystallographic inversion centers; and, unlike the other isomer, the planes of the tetradentate ligands are not parallel but alternate along the c direction.