The title compound, [Co(C
14H
18N
2O
6)], is the first structurally characterized example of a β-ketoiminato Co
II complex without axial ligands. It adopts a square-planar
cis-[CoN
2O
2] coordination geometry, and lies on a mirror plane. The planar complexes are stacked along 2
1 screw axes parallel to
b to form columns, the Co
Co distance in the column being 3.5213 (2) Å.
Supporting information
CCDC reference: 234789
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.004 Å
- R factor = 0.041
- wR factor = 0.135
- Data-to-parameter ratio = 11.1
checkCIF/PLATON results
No syntax errors found
Alert level B
PLAT222_ALERT_3_B Large Non-Solvent H Ueq(max)/Ueq(min) ... 4.14 Ratio
PLAT241_ALERT_2_B Check High U(eq) as Compared to Neighbors .... C5
Alert level C
PLAT242_ALERT_2_C Check Low U(eq) as Compared to Neighbors .... C13
PLAT250_ALERT_2_C Large U3/U1 ratio for average U(i,j) tensor .... 2.75
PLAT301_ALERT_3_C Main Residue Disorder ......................... 4.00 Perc.
PLAT380_ALERT_4_C Incorrectly Oriented X(sp2)-Methyl Moiety ...... C1
PLAT380_ALERT_4_C Incorrectly Oriented X(sp2)-Methyl Moiety ...... C8
0 ALERT level A = In general: serious problem
2 ALERT level B = Potentially serious problem
5 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
3 ALERT type 2 Indicator that the structure model may be wrong or deficient
2 ALERT type 3 Indicator that the structure quality may be low
2 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: WinAFC Diffractometer Control Software (Rigaku, 1999); cell refinement: WinAFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 2001); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: TEXSAN.
Crystal data top
C14H18CoN2O6 | F(000) = 764.0 |
Mr = 369.23 | Dx = 1.549 Mg m−3 |
Orthorhombic, Pnma | Mo Kα radiation, λ = 0.7107 Å |
Hall symbol: -P 2ac 2n | Cell parameters from 25 reflections |
a = 14.791 (2) Å | θ = 10.0–12.1° |
b = 6.939 (1) Å | µ = 1.12 mm−1 |
c = 15.424 (3) Å | T = 298 K |
V = 1583.0 (4) Å3 | Needle, red |
Z = 4 | 0.50 × 0.23 × 0.20 mm |
Data collection top
Rigaku AFC-7R diffractometer | Rint = 0.050 |
ω–2θ scans | θmax = 27.5° |
Absorption correction: ψ scan (North et al., 1968) | h = −7→19 |
Tmin = 0.742, Tmax = 0.800 | k = −9→3 |
2447 measured reflections | l = −20→0 |
1963 independent reflections | 3 standard reflections every 150 reflections |
1581 reflections with I > 2σ(I) | intensity decay: 0.6% |
Refinement top
Refinement on F2 | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.041 | w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.135 | (Δ/σ)max < 0.001 |
S = 1.05 | Δρmax = 0.44 e Å−3 |
1581 reflections | Δρmin = −0.78 e Å−3 |
142 parameters | |
Special details top
Refinement. Refinement using reflections with F2 > 0.0 σ(F2). The
weighted R-factor (wR), goodness of fit (S) and
R-factor (gt) are based on F, with F set to zero for
negative F. The threshold expression of F2 > 2.0
σ(F2) is used only for calculating R-factor (gt). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Co1 | 0.50923 (3) | 0.2500 | 0.98257 (3) | 0.0360 (2) | |
O1 | 0.5773 (2) | 0.2500 | 0.8809 (2) | 0.0449 (6) | |
O2 | 0.4834 (2) | 0.2500 | 0.6226 (2) | 0.070 (1) | |
O3 | 0.3441 (2) | 0.2500 | 0.6744 (2) | 0.0690 (9) | |
O4 | 0.6176 (2) | 0.2500 | 1.0443 (1) | 0.0443 (5) | |
O5 | 0.6521 (3) | 0.2500 | 1.3160 (2) | 0.106 (2) | |
O6 | 0.5053 (2) | 0.2500 | 1.3285 (2) | 0.078 (1) | |
N1 | 0.4016 (2) | 0.2500 | 0.9228 (2) | 0.0415 (6) | |
N2 | 0.4412 (2) | 0.2500 | 1.0821 (2) | 0.0467 (7) | |
C1 | 0.6280 (3) | 0.2500 | 0.7369 (3) | 0.082 (2) | |
C2 | 0.5518 (2) | 0.2500 | 0.8010 (2) | 0.0435 (7) | |
C3 | 0.4606 (2) | 0.2500 | 0.7764 (2) | 0.0385 (7) | |
C4 | 0.3906 (2) | 0.2500 | 0.8393 (2) | 0.0433 (7) | |
C5 | 0.3214 (3) | 0.2500 | 0.9798 (3) | 0.078 (2) | |
C6 | 0.4351 (2) | 0.2500 | 0.6841 (2) | 0.0446 (8) | |
C7 | 0.3115 (3) | 0.2500 | 0.5870 (3) | 0.082 (2) | |
C8 | 0.7296 (3) | 0.2500 | 1.1516 (3) | 0.076 (2) | |
C9 | 0.6317 (2) | 0.2500 | 1.1266 (2) | 0.0445 (7) | |
C10 | 0.5621 (2) | 0.2500 | 1.1877 (2) | 0.0425 (7) | |
C11 | 0.4700 (3) | 0.2500 | 1.1614 (2) | 0.0496 (8) | |
C12 | 0.3443 (3) | 0.1965 (7) | 1.0658 (3) | 0.048 (2) | 0.50 |
C13 | 0.5810 (3) | 0.2500 | 1.2824 (2) | 0.0551 (9) | |
C14 | 0.5142 (4) | 0.2500 | 1.4220 (3) | 0.084 (2) | |
H1 | 0.6650 | 0.1382 | 0.7449 | 0.1042* | |
H2 | 0.6056 | 0.2500 | 0.6791 | 0.1042* | |
H3 | 0.3292 | 0.2500 | 0.8184 | 0.0508* | |
H4A | 0.2951 | 0.3755 | 0.9805 | 0.0929* | 0.50 |
H4B | 0.2777 | 0.1609 | 0.9578 | 0.0929* | 0.50 |
H5 | 0.2468 | 0.2500 | 0.5860 | 0.0967* | |
H6 | 0.3316 | 0.1371 | 0.5573 | 0.0967* | |
H7 | 0.7353 | 0.2500 | 1.2140 | 0.0926* | |
H8 | 0.7595 | 0.1393 | 1.1292 | 0.0926* | |
H9 | 0.4246 | 0.2500 | 1.2060 | 0.0580* | |
H10 | 0.4573 | 0.2500 | 1.4495 | 0.1023* | |
H11 | 0.5485 | 0.1393 | 1.4401 | 0.1023* | |
H12 | 0.3357 | 0.0617 | 1.0738 | 0.0252* | 0.50 |
H13 | 0.3057 | 0.2635 | 1.1061 | 0.0252* | 0.50 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Co1 | 0.0277 (3) | 0.0518 (3) | 0.0285 (3) | 0.0000 | 0.0039 (2) | 0.0000 |
O1 | 0.029 (1) | 0.074 (2) | 0.032 (1) | 0.0000 | 0.0019 (8) | 0.0000 |
O2 | 0.046 (2) | 0.132 (3) | 0.032 (1) | 0.0000 | 0.002 (1) | 0.0000 |
O3 | 0.037 (1) | 0.130 (3) | 0.040 (1) | 0.0000 | −0.006 (1) | 0.0000 |
O4 | 0.035 (1) | 0.067 (1) | 0.031 (1) | 0.0000 | 0.0019 (9) | 0.0000 |
O5 | 0.072 (2) | 0.207 (5) | 0.040 (2) | 0.0000 | −0.011 (2) | 0.0000 |
O6 | 0.084 (3) | 0.125 (3) | 0.027 (1) | 0.0000 | 0.007 (1) | 0.0000 |
N1 | 0.027 (1) | 0.062 (2) | 0.035 (1) | 0.0000 | 0.008 (1) | 0.0000 |
N2 | 0.034 (1) | 0.072 (2) | 0.035 (1) | 0.0000 | 0.007 (1) | 0.0000 |
C1 | 0.035 (2) | 0.170 (5) | 0.040 (2) | 0.0000 | 0.009 (2) | 0.0000 |
C2 | 0.034 (2) | 0.064 (2) | 0.032 (2) | 0.0000 | 0.006 (1) | 0.0000 |
C3 | 0.033 (1) | 0.051 (2) | 0.032 (2) | 0.0000 | 0.002 (1) | 0.0000 |
C4 | 0.032 (2) | 0.060 (2) | 0.037 (2) | 0.0000 | 0.001 (1) | 0.0000 |
C5 | 0.030 (2) | 0.162 (5) | 0.043 (2) | 0.0000 | 0.011 (1) | 0.0000 |
C6 | 0.038 (2) | 0.061 (2) | 0.035 (2) | 0.0000 | 0.001 (1) | 0.0000 |
C7 | 0.049 (2) | 0.158 (5) | 0.038 (2) | 0.0000 | −0.016 (2) | 0.0000 |
C8 | 0.045 (2) | 0.137 (5) | 0.046 (2) | 0.0000 | −0.008 (2) | 0.0000 |
C9 | 0.042 (2) | 0.052 (2) | 0.040 (2) | 0.0000 | −0.006 (1) | 0.0000 |
C10 | 0.047 (2) | 0.050 (2) | 0.030 (2) | 0.0000 | 0.001 (1) | 0.0000 |
C11 | 0.047 (2) | 0.068 (2) | 0.034 (2) | 0.0000 | 0.011 (1) | 0.0000 |
C12 | 0.033 (2) | 0.068 (4) | 0.042 (2) | −0.002 (2) | 0.013 (2) | 0.002 (2) |
C13 | 0.066 (2) | 0.065 (2) | 0.034 (2) | 0.0000 | −0.001 (2) | 0.0000 |
C14 | 0.113 (4) | 0.115 (5) | 0.025 (2) | 0.0000 | 0.003 (2) | 0.0000 |
Geometric parameters (Å, º) top
Co1—O1 | 1.864 (2) | C4—H3 | 0.965 |
Co1—O4 | 1.865 (2) | C5—C12 | 1.418 (6) |
Co1—N1 | 1.840 (3) | C5—H4A | 0.954 |
Co1—N2 | 1.836 (3) | C5—H4Ai | 0.954 |
O1—C2 | 1.288 (4) | C5—H4B | 0.957 |
O2—C6 | 1.187 (4) | C5—H4Bi | 0.957 |
O3—C6 | 1.354 (4) | C7—H5 | 0.956 |
O3—C7 | 1.431 (5) | C7—H6 | 0.955 |
O4—C9 | 1.286 (4) | C7—H6i | 0.955 |
O5—C13 | 1.172 (6) | C8—C9 | 1.499 (6) |
O6—C13 | 1.326 (5) | C8—H7 | 0.966 |
O6—C14 | 1.448 (5) | C8—H8 | 0.951 |
N1—C4 | 1.299 (4) | C8—H8i | 0.951 |
N1—C5 | 1.477 (5) | C9—C10 | 1.395 (5) |
N2—C11 | 1.295 (4) | C10—C11 | 1.421 (5) |
N2—C12 | 1.502 (5) | C10—C13 | 1.486 (5) |
C1—C2 | 1.500 (5) | C11—H9 | 0.961 |
C1—H1 | 0.957 | C12—H12 | 0.952 |
C1—H1i | 0.957 | C12—H13 | 0.964 |
C1—H2 | 0.951 | C14—H10 | 0.943 |
C2—C3 | 1.401 (5) | C14—H11 | 0.962 |
C3—C4 | 1.418 (4) | C14—H11i | 0.962 |
C3—C6 | 1.472 (4) | | |
| | | |
O1—Co1—O4 | 88.04 (10) | O2—C6—C3 | 128.2 (3) |
O1—Co1—N1 | 92.6 (1) | O3—C6—C3 | 111.2 (3) |
O1—Co1—N2 | 179.5 (1) | O3—C7—H5 | 110.6 |
O4—Co1—N1 | 179.4 (1) | O3—C7—H6 | 110.3 |
O4—Co1—N2 | 92.5 (1) | O3—C7—H6i | 110.3 |
N1—Co1—N2 | 86.8 (1) | H5—C7—H6 | 107.7 |
Co1—O1—C2 | 130.3 (2) | H5—C7—H6i | 107.7 |
C6—O3—C7 | 116.0 (3) | H6—C7—H6i | 110.2 |
Co1—O4—C9 | 130.0 (2) | C9—C8—H7 | 109.8 |
C13—O6—C14 | 117.2 (4) | C9—C8—H8 | 110.9 |
Co1—N1—C4 | 127.2 (2) | C9—C8—H8i | 110.9 |
Co1—N1—C5 | 113.4 (2) | H7—C8—H8 | 108.8 |
C4—N1—C5 | 119.4 (3) | H7—C8—H8i | 108.8 |
Co1—N2—C11 | 127.6 (3) | H8—C8—H8i | 107.7 |
Co1—N2—C12 | 112.5 (2) | O4—C9—C8 | 114.1 (3) |
C11—N2—C12 | 118.2 (3) | O4—C9—C10 | 123.2 (3) |
C2—C1—H1 | 110.1 | C8—C9—C10 | 122.7 (3) |
C2—C1—H1i | 110.1 | C9—C10—C11 | 120.9 (3) |
C2—C1—H2 | 110.8 | C9—C10—C13 | 121.6 (3) |
H1—C1—H1i | 108.2 | C11—C10—C13 | 117.4 (3) |
H1—C1—H2 | 108.8 | N2—C11—C10 | 125.8 (3) |
H1i—C1—H2 | 108.8 | N2—C11—H9 | 116.4 |
O1—C2—C1 | 114.3 (3) | C10—C11—H9 | 117.8 |
O1—C2—C3 | 122.7 (3) | N2—C12—C5 | 108.7 (3) |
C1—C2—C3 | 123.0 (3) | N2—C12—H12 | 110.4 |
C2—C3—C4 | 121.1 (3) | N2—C12—H13 | 109.7 |
C2—C3—C6 | 120.6 (3) | C5—C12—H12 | 110.3 |
C4—C3—C6 | 118.3 (3) | C5—C12—H13 | 109.6 |
N1—C4—C3 | 126.0 (3) | H12—C12—H13 | 108.1 |
N1—C4—H3 | 116.7 | O5—C13—O6 | 121.3 (4) |
C3—C4—H3 | 117.4 | O5—C13—C10 | 127.1 (4) |
N1—C5—C12 | 111.4 (3) | O6—C13—C10 | 111.6 (3) |
N1—C5—H4A | 109.5 | O6—C14—H10 | 111.6 |
N1—C5—H4B | 109.3 | O6—C14—H11 | 109.7 |
C12—C5—H4A | 109.1 | O6—C14—H11i | 109.7 |
C12—C5—H4B | 108.9 | H10—C14—H11 | 109.9 |
H4A—C5—H4B | 108.5 | H10—C14—H11i | 109.9 |
O2—C6—O3 | 120.6 (3) | H11—C14—H11i | 105.9 |
| | | |
Co1—O1—C2—C1 | 180.0 | O5—C13—C10—C11 | −180.0 |
Co1—O1—C2—C3 | 0.0000 (1) | O6—C13—C10—C9 | 180.0000 (1) |
Co1—O4—C9—C8 | −180.0 | O6—C13—C10—C11 | 0.0000 (1) |
Co1—O4—C9—C10 | 0.0000 (2) | N1—Co1—O1—C2 | 0.0000 (4) |
Co1—N1—C4—C3 | 0.0000 (1) | N1—Co1—N2—C11 | 180.0 |
Co1—N1—C5—C12 | −16.3 (2) | N1—Co1—N2—C12 | 15.5 (2) |
Co1—N2—C11—C10 | 0.0000 (1) | N1—C4—C3—C2 | 0.0000 (1) |
Co1—N2—C12—C5 | −27.9 (3) | N1—C4—C3—C6 | 180.0 |
O1—Co1—O4—C9 | −180.0 | N1—C5—C12—N2 | 27.3 (3) |
O1—Co1—N1—C4 | 0.0000 (1) | N2—Co1—O4—C9 | 0.0 |
O1—Co1—N1—C5 | 180.0000 (1) | N2—Co1—N1—C4 | 180.0 |
O1—C2—C3—C4 | 0.0 | N2—Co1—N1—C5 | 0.0000 (1) |
O1—C2—C3—C6 | 180.0 | N2—C11—C10—C9 | 0.0000 (1) |
O2—C6—O3—C7 | 0.0000 (2) | N2—C11—C10—C13 | −180.0 |
O2—C6—C3—C2 | 0.0000 (2) | C1—C2—C3—C4 | −180.0 |
O2—C6—C3—C4 | −180.0 | C1—C2—C3—C6 | 0.0 |
O3—C6—C3—C2 | 180.0 | C3—C4—N1—C5 | 180.0 |
O3—C6—C3—C4 | 0.0000 (2) | C3—C6—O3—C7 | 180.0 |
O4—Co1—O1—C2 | −180.0 | C4—N1—C5—C12 | 163.7 (2) |
O4—Co1—N2—C11 | 0.0000 (1) | C5—C12—N2—C11 | 166.1 (2) |
O4—Co1—N2—C12 | −164.5 (2) | C8—C9—C10—C11 | 180.0 |
O4—C9—C10—C11 | 0.0000 (2) | C8—C9—C10—C13 | 0.0000 (3) |
O4—C9—C10—C13 | 180.0 | C10—C11—N2—C12 | 163.7 (2) |
O5—C13—O6—C14 | 0.0000 (1) | C10—C13—O6—C14 | −180.0 |
O5—C13—C10—C9 | 0.0 | | |
Symmetry code: (i) x, −y+1/2, z. |