In the title compound, [Co(C5H7O2)2(C13H14N2)]n or [Co(acac)2(dadpm)]n, where acac is acetylacetonate and dadpm is 4,4′-methylenedianiline, the Co atom is on a centre of symmetry and is octahedrally coordinated by four O atoms from two acac anions and by two N atoms from two dadpm ligands. Each dadpm ligand, which has a twofold axis passing through its methylene C atom, bridges two Co atoms to form a spiral polymeric chain. Neighbouring chains connect via hydrogen bonds to form a two-dimensional network.
Supporting information
CCDC reference: 256986
An ethanol solution (3.5 ml) of 4,4'-diaminodiphenylmethane (0.103 g, 0.1 mmol) was added to [Co(acac)2(CH3CO2)2]·6H20 (0.035 g, 0.1 mmol) in N,N-dimethylformamide (1.5 ml) at room temperature and stirred for 1 h. The mixture was layered with propan-2-ol and pink plates of (I) were formed (yield 0.023 g, 51% based on Co). The crystal used for the present crystal structure determination was obtained directly from the above preparation. Analysis, found: C 60.85, H 6.18, N 6.22%; calculated for C23H28CoN2O4: C 60.66, H 6.20, N 6.15%. Spectroscopic analysis: IR (KBr, ν, cm−1): 3368 (w), 3271 (w), 1589 (s), 1512 (s), 1458 (s), 1408 (s), 1358 (w), 1253 (m), 972 (m), 760 (w), 555 (w).
All H atoms were placed in geometrically idealized positions and refined with isotropic displacement parameters.
Data collection: CrystalClear (Rigaku, 2001); cell refinement: CrystalClear; data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.
catena-Poly[(µ-4,4'-diaminodiphenylmethane-
κ2N:
N')bis(2,4-pentanedionato-
κ2O,
O')cobalt(II)]
top
Crystal data top
[Co(C5H10O2)2(C13H14N2)] | F(000) = 478 |
Mr = 455.40 | Dx = 1.380 Mg m−3 |
Monoclinic, P2/c | Mo Kα radiation, λ = 0.71070 Å |
Hall symbol: -p 2yc | Cell parameters from 3781 reflections |
a = 5.5805 (5) Å | θ = 3.6–25.3° |
b = 8.9808 (9) Å | µ = 0.81 mm−1 |
c = 21.955 (2) Å | T = 193 K |
β = 94.976 (3)° | Plate, pink |
V = 1096.20 (19) Å3 | 0.36 × 0.35 × 0.07 mm |
Z = 2 | |
Data collection top
Rigaku Mercury CCD area-detector diffractometer | 2005 independent reflections |
Radiation source: fine-focus sealed tube | 1887 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
Detector resolution: 7.31 pixels mm-1 | θmax = 25.4°, θmin = 3.6° |
ω scans | h = −6→6 |
Absorption correction: multi-scan (Jacobson, 1998) | k = −10→10 |
Tmin = 0.758, Tmax = 0.945 | l = −23→26 |
10160 measured reflections | |
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) = 0.074 | All H-atom parameters refined |
S = 1.11 | w = 1/[σ2(Fo2) + (0.0316P)2 + 0.6071P] where P = (Fo2 + 2Fc2)/3 |
2005 reflections | (Δ/σ)max < 0.001 |
195 parameters | Δρmax = 0.20 e Å−3 |
0 restraints | Δρmin = −0.29 e Å−3 |
Crystal data top
[Co(C5H10O2)2(C13H14N2)] | V = 1096.20 (19) Å3 |
Mr = 455.40 | Z = 2 |
Monoclinic, P2/c | Mo Kα radiation |
a = 5.5805 (5) Å | µ = 0.81 mm−1 |
b = 8.9808 (9) Å | T = 193 K |
c = 21.955 (2) Å | 0.36 × 0.35 × 0.07 mm |
β = 94.976 (3)° | |
Data collection top
Rigaku Mercury CCD area-detector diffractometer | 2005 independent reflections |
Absorption correction: multi-scan (Jacobson, 1998) | 1887 reflections with I > 2σ(I) |
Tmin = 0.758, Tmax = 0.945 | Rint = 0.023 |
10160 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.031 | 0 restraints |
wR(F2) = 0.074 | All H-atom parameters refined |
S = 1.11 | Δρmax = 0.20 e Å−3 |
2005 reflections | Δρmin = −0.29 e Å−3 |
195 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 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 | |
Co1 | 0.0000 | 0.5000 | 0.5000 | 0.02176 (13) | |
O1 | 0.2376 (2) | 0.34789 (14) | 0.46817 (6) | 0.0286 (3) | |
O2 | −0.1826 (2) | 0.50661 (13) | 0.41586 (6) | 0.0246 (3) | |
N1 | 0.2241 (3) | 0.6936 (2) | 0.47784 (8) | 0.0294 (4) | |
C1 | 0.4097 (4) | 0.1786 (3) | 0.40172 (12) | 0.0377 (5) | |
C2 | 0.2272 (3) | 0.2965 (2) | 0.41414 (9) | 0.0262 (4) | |
C3 | 0.0631 (3) | 0.3401 (2) | 0.36595 (9) | 0.0332 (5) | |
C4 | −0.1228 (3) | 0.4435 (2) | 0.36828 (8) | 0.0270 (4) | |
C5 | −0.2690 (5) | 0.4847 (3) | 0.30967 (10) | 0.0455 (6) | |
C6 | 0.1677 (3) | 0.7684 (2) | 0.42117 (8) | 0.0250 (4) | |
C7 | 0.3085 (3) | 0.7474 (2) | 0.37302 (9) | 0.0302 (4) | |
C8 | 0.2490 (4) | 0.8169 (2) | 0.31764 (9) | 0.0328 (4) | |
C9 | 0.0500 (3) | 0.9100 (2) | 0.30851 (8) | 0.0275 (4) | |
C10 | −0.0914 (3) | 0.9275 (2) | 0.35693 (9) | 0.0303 (4) | |
C11 | −0.0359 (3) | 0.8577 (2) | 0.41257 (9) | 0.0308 (4) | |
C12 | 0.0000 | 0.9980 (3) | 0.2500 | 0.0356 (7) | |
H10 | −0.228 (4) | 0.987 (2) | 0.3519 (10) | 0.036 (6)* | |
H7 | 0.446 (4) | 0.687 (2) | 0.3799 (10) | 0.039 (6)* | |
H1A | 0.368 (4) | 0.669 (2) | 0.4835 (10) | 0.034 (6)* | |
H11 | −0.142 (4) | 0.867 (2) | 0.4456 (10) | 0.035 (5)* | |
H1E | 0.566 (5) | 0.221 (3) | 0.3996 (11) | 0.051 (7)* | |
H8 | 0.349 (4) | 0.803 (2) | 0.2844 (10) | 0.042 (6)* | |
H1B | 0.191 (5) | 0.748 (3) | 0.5073 (12) | 0.053 (8)* | |
H3 | 0.080 (4) | 0.294 (3) | 0.3269 (11) | 0.044 (6)* | |
H5A | −0.235 (5) | 0.424 (3) | 0.2771 (13) | 0.064 (8)* | |
H12 | 0.139 (4) | 1.064 (3) | 0.2445 (10) | 0.049 (7)* | |
H5B | −0.431 (5) | 0.477 (3) | 0.3153 (12) | 0.054 (8)* | |
H1C | 0.429 (5) | 0.108 (3) | 0.4376 (13) | 0.069 (8)* | |
H1D | 0.366 (5) | 0.126 (3) | 0.3645 (14) | 0.081 (9)* | |
H5C | −0.242 (6) | 0.588 (4) | 0.3000 (14) | 0.088 (11)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Co1 | 0.0212 (2) | 0.0269 (2) | 0.01690 (19) | 0.00470 (13) | 0.00046 (13) | 0.00037 (13) |
O1 | 0.0255 (6) | 0.0347 (7) | 0.0252 (7) | 0.0080 (5) | 0.0009 (5) | −0.0029 (6) |
O2 | 0.0251 (6) | 0.0299 (7) | 0.0183 (6) | 0.0043 (5) | −0.0003 (5) | −0.0007 (5) |
N1 | 0.0241 (9) | 0.0343 (9) | 0.0288 (9) | 0.0017 (7) | −0.0038 (7) | 0.0061 (7) |
C1 | 0.0278 (11) | 0.0359 (12) | 0.0488 (14) | 0.0044 (9) | −0.0002 (9) | −0.0183 (10) |
C2 | 0.0218 (9) | 0.0245 (9) | 0.0325 (10) | −0.0024 (7) | 0.0038 (7) | −0.0065 (8) |
C3 | 0.0321 (10) | 0.0393 (11) | 0.0279 (11) | 0.0041 (9) | 0.0002 (8) | −0.0131 (9) |
C4 | 0.0269 (9) | 0.0304 (10) | 0.0233 (9) | −0.0038 (8) | −0.0009 (7) | −0.0017 (8) |
C5 | 0.0458 (15) | 0.0671 (18) | 0.0218 (11) | 0.0157 (12) | −0.0077 (10) | −0.0081 (11) |
C6 | 0.0225 (9) | 0.0234 (9) | 0.0283 (10) | −0.0034 (7) | −0.0020 (7) | 0.0021 (7) |
C7 | 0.0269 (10) | 0.0292 (10) | 0.0347 (11) | 0.0065 (8) | 0.0038 (8) | −0.0003 (8) |
C8 | 0.0369 (11) | 0.0332 (11) | 0.0297 (11) | 0.0036 (9) | 0.0109 (9) | −0.0015 (8) |
C9 | 0.0359 (10) | 0.0212 (9) | 0.0247 (9) | −0.0025 (8) | −0.0017 (8) | −0.0024 (7) |
C10 | 0.0276 (10) | 0.0290 (10) | 0.0338 (11) | 0.0067 (8) | 0.0003 (8) | 0.0029 (8) |
C11 | 0.0256 (9) | 0.0354 (11) | 0.0325 (10) | 0.0048 (8) | 0.0082 (8) | 0.0030 (8) |
C12 | 0.057 (2) | 0.0240 (14) | 0.0247 (15) | 0.000 | −0.0009 (13) | 0.000 |
Geometric parameters (Å, º) top
Co1—O2i | 2.0319 (12) | C2—C3 | 1.394 (3) |
Co1—O2 | 2.0319 (12) | C3—C4 | 1.396 (3) |
Co1—O1 | 2.0672 (12) | C3—H3 | 0.96 (2) |
Co1—O1i | 2.0672 (12) | C4—C5 | 1.509 (3) |
Co1—N1 | 2.2201 (17) | C5—H5A | 0.93 (3) |
Co1—N1i | 2.2201 (17) | C5—H5B | 0.92 (3) |
O1—C2 | 1.269 (2) | C5—H5C | 0.96 (3) |
O2—C4 | 1.259 (2) | C6—C7 | 1.384 (3) |
N1—C6 | 1.425 (2) | C6—C11 | 1.390 (3) |
N1—H1A | 0.83 (2) | C7—C8 | 1.381 (3) |
N1—H1B | 0.84 (3) | C7—H7 | 0.94 (2) |
C1—C2 | 1.511 (3) | C8—C9 | 1.390 (3) |
C1—H1E | 0.96 (3) | C8—H8 | 0.97 (2) |
C1—H1C | 1.01 (3) | C9—C10 | 1.387 (3) |
C1—H1D | 0.96 (3) | C9—C12 | 1.514 (2) |
| | | |
O2i—Co1—O2 | 180.0 | O2—C4—C5 | 115.77 (17) |
O1i—Co1—O1 | 180.00 (6) | C3—C4—C5 | 118.71 (18) |
N1i—Co1—N1 | 180.0 | C4—C5—H5A | 112.3 (17) |
O2i—Co1—O1 | 90.13 (5) | C4—C5—H5B | 109.3 (17) |
O2—Co1—O1 | 89.87 (5) | H5A—C5—H5B | 109 (2) |
O2i—Co1—N1 | 88.54 (6) | C4—C5—H5C | 110 (2) |
O2—Co1—N1 | 91.46 (6) | H5A—C5—H5C | 110 (3) |
O1—Co1—N1 | 93.07 (6) | H5B—C5—H5C | 106 (2) |
O1i—Co1—N1 | 86.93 (6) | C7—C6—C11 | 119.12 (17) |
C2—O1—Co1 | 125.27 (11) | C7—C6—N1 | 120.37 (17) |
C4—O2—Co1 | 126.39 (12) | C11—C6—N1 | 120.43 (17) |
C6—N1—Co1 | 118.35 (12) | C8—C7—C6 | 120.10 (17) |
C6—N1—H1A | 113.1 (15) | C8—C7—H7 | 122.2 (13) |
Co1—N1—H1A | 108.2 (15) | C6—C7—H7 | 117.7 (13) |
C6—N1—H1B | 110.4 (18) | C7—C8—C9 | 121.77 (18) |
Co1—N1—H1B | 97.0 (18) | C7—C8—H8 | 119.8 (13) |
H1A—N1—H1B | 108 (2) | C9—C8—H8 | 118.5 (13) |
C2—C1—H1E | 111.3 (15) | C10—C9—C8 | 117.28 (17) |
C2—C1—H1C | 109.1 (15) | C10—C9—C12 | 121.06 (16) |
H1E—C1—H1C | 104 (2) | C8—C9—C12 | 121.49 (16) |
C2—C1—H1D | 112.1 (18) | C11—C10—C9 | 121.75 (18) |
H1E—C1—H1D | 109 (2) | C11—C10—H10 | 119.0 (14) |
H1C—C1—H1D | 111 (2) | C9—C10—H10 | 119.2 (14) |
O1—C2—C3 | 125.51 (16) | C10—C11—C6 | 119.94 (18) |
O1—C2—C1 | 116.53 (17) | C10—C11—H11 | 120.6 (12) |
C3—C2—C1 | 117.96 (17) | C6—C11—H11 | 119.4 (12) |
C2—C3—C4 | 126.89 (17) | C9ii—C12—C9 | 117.0 (2) |
C2—C3—H3 | 116.5 (13) | C9ii—C12—H12 | 107.2 (13) |
C4—C3—H3 | 116.6 (13) | C9—C12—H12 | 109.0 (14) |
O2—C4—C3 | 125.52 (17) | | |
| | | |
O2i—Co1—O1—C2 | 179.37 (14) | Co1—O1—C2—C3 | 4.1 (3) |
O2—Co1—O1—C2 | −0.63 (14) | Co1—O1—C2—C1 | −176.07 (13) |
N1—Co1—O1—C2 | −92.08 (15) | O1—C2—C3—C4 | −2.1 (3) |
N1i—Co1—O1—C2 | 87.92 (15) | C1—C2—C3—C4 | 178.1 (2) |
O1—Co1—O2—C4 | −5.88 (15) | Co1—O2—C4—C3 | 9.4 (3) |
O1i—Co1—O2—C4 | 174.12 (15) | Co1—O2—C4—C5 | −171.09 (16) |
N1—Co1—O2—C4 | 87.19 (15) | C2—C3—C4—O2 | −5.4 (3) |
N1i—Co1—O2—C4 | −92.81 (15) | C2—C3—C4—C5 | 175.1 (2) |
O2i—Co1—N1—C6 | −174.04 (15) | Co1—N1—C6—C7 | −104.33 (18) |
O2—Co1—N1—C6 | 5.96 (15) | Co1—N1—C6—C11 | 72.5 (2) |
O1—Co1—N1—C6 | 95.91 (15) | C11—C6—C7—C8 | 1.3 (3) |
O1i—Co1—N1—C6 | −84.09 (15) | | |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1iii | 0.83 (2) | 2.36 (2) | 3.155 (2) | 159 (2) |
Symmetry code: (iii) −x+1, −y+1, −z+1. |
Experimental details
Crystal data |
Chemical formula | [Co(C5H10O2)2(C13H14N2)] |
Mr | 455.40 |
Crystal system, space group | Monoclinic, P2/c |
Temperature (K) | 193 |
a, b, c (Å) | 5.5805 (5), 8.9808 (9), 21.955 (2) |
β (°) | 94.976 (3) |
V (Å3) | 1096.20 (19) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.81 |
Crystal size (mm) | 0.36 × 0.35 × 0.07 |
|
Data collection |
Diffractometer | Rigaku Mercury CCD area-detector diffractometer |
Absorption correction | Multi-scan (Jacobson, 1998) |
Tmin, Tmax | 0.758, 0.945 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10160, 2005, 1887 |
Rint | 0.023 |
(sin θ/λ)max (Å−1) | 0.602 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.074, 1.11 |
No. of reflections | 2005 |
No. of parameters | 195 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.20, −0.29 |
Selected geometric parameters (Å, º) topCo1—O2 | 2.0319 (12) | O1—C2 | 1.269 (2) |
Co1—O1 | 2.0672 (12) | O2—C4 | 1.259 (2) |
Co1—N1 | 2.2201 (17) | N1—C6 | 1.425 (2) |
| | | |
O2—Co1—O1 | 89.87 (5) | C6—N1—Co1 | 118.35 (12) |
O2—Co1—N1 | 91.46 (6) | C9i—C12—C9 | 117.0 (2) |
O1—Co1—N1 | 93.07 (6) | | |
Symmetry code: (i) −x, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1ii | 0.83 (2) | 2.36 (2) | 3.155 (2) | 159 (2) |
Symmetry code: (ii) −x+1, −y+1, −z+1. |
`Spirality' is an important structural feature of great interest in inorganic and coordination chemistry (Constable, 1992; Carina et al., 1993; Lehn, 1995). Much effort has been devoted in recent decades to the design of metal complexes exhibiting spiral, particularly helical, architectures (Constable, 1992; Carina et al., 1993; Lehn, 1995; Zaworotko, 1998). Suitably tailored polydentate ligands, particularly oligopyridines, have been widely used to coordinate with metals to creat spirality of the resulting oligonuclear complexes and polymers (Hasenknopf et al., 1996; Jung et al., 1998; Abrahams et al., 1999).
On the other hand, ligands containing amino groups are well known to coordinate with various metals to give coordination polymers (Dickman, 2000; Alcock et al., 1997; Lu et al., 1994). Among these ligands, 4,4'-diaminodiphenylmethane (dadpm) has frequently been employed for the construction of coordination polymers, e.g. the one-dimensional polymer [Cu2(dadpm)2(trans-oxpy)]·2NO3·6H2O (trans-oxpy is ?; Zhang Kang et al., 2001), the one-dimensional polymer {[Cu(dadpm)(C3H4O4)Cl]Cl}2 (C3H4O4 is malonic acid; Zhang et al., 1999), the three-dimensional polymer [Ni(dadpm)4(H2O)2](NO3)2·2H2O (Zhang Lei et al., 2001) and the three-dimensional polymer [Cd(dadpm)2Cl](dca) (dca is dicyanamide; Luo et al., 2003). Here, we report the crystal structure of the title cobalt(II) acac-dadpm complex, (I) (acac is acetylacetonate). \sch
The polymer backbone of (I) is made up of [Co(acac)2] fragments and bridging dadpm ligands. Each dadpm ligand links two fragments through two Co—N bonds, forming an interesting one-dimensional spiral array of repeating [Co(acac)2(dadpm)] units, which is stacked along the crystallographic c axis (Fig. 1). The Co atom in (I) lies on a centre of symmetry, and is coordinated by four O atoms from two chelated acac anions and two N atoms from two different dadpm ligands, forming a distorted octahedral coordination geometry. Four O atoms (O1, O2, O1A and O2A) occupy the equatorial positions, with bond lengths of 2.0672 (12) and 2.0319 (12) Å (Table 1), and two N atoms (N1 and N1A) are located in the axial positions, with Co1—N1 2.2201 (17) Å.
The Co1—O bond lengths in (I) are similar to those found in related CoII-acac complexes, such as [Co(acac)2(pz)] (2.0382 Å; pz is pyrazine; Ma et al., 2001), [Co(acac)2(4,4'-bipy)] (2.032 Å; 4,4'-bipy is 4,4'-bipyridine; Ma et al., 2001) and [Co2(acac)4(H2O)2][Co(acac)(H2O)4](ClO4)·EtOH (2.051 Å; McCann et al., 2001). The Co—N bond length of 2.2201 (17) Å in (I) is comparable with that in compounds with similar motifs, such as [Co(hfac)2(opda)2] (2.2243 Å; hfac is ? and opda is ?; Dickman, 2000), but longer than those observed in [Co(azpy)(pht)(H2O)3] (2.188 Å; azpy is ? and pht is ?; Zhu et al., 2003) and [Co(3,3'-azpy)(H2O)4][ClO4]2.3(3,3'-azpy) (2.176 Å; 3,3'-azpy is ?; Li et al., 2001). Please define all lignads in cited compounds.
There is a twofold axis passing through the methylene atom C12 of the dadpm ligand in (I). The dadpm ligand adopts a trans-gauche confirmation. The dihedral angle between the two phenyl rings in the dadpm ligand in (I) [75.78 (7)°] is smaller than that in [Cd(dadpm)2Br](dca) [98.7 (5)°; dca is ?; Luo et al., 2003], but larger than that in [Cd(dadpm)(dca)2] [55.3 (2)°; Luo & Hong et al., 2003]. The C(Ph)—C—C(Ph) bond angle between the two phenyl groups of dadpm in (I) is 117.0 (2)°, which is slightly larger than the values reported for [Cd(dadpm)2Cl](dca) [115.8 (4)°; Luo et al., 2003], [Cd(dadpm)2Br](dca) [115.9 (1)°; Luo et al., 2003] and {[Cu(dadpm)(C3H4O4)Cl]Cl}2 [114.7 (7)°; Zhang et al., 1999].
The NH2 groups of the dadpm ligand of (I) interact with the O atoms of acac anions from the adjacent chain to afford intermolecular hydrogen bonds via atom H1A (Table 2), thereby forming a two-dimensional network (Fig. 2). The second atom, H1B, is located 2.51 (3) Å above the Co(acac) group and in contact with an adjacent atom, H1E(1 − x,1 − y,1 − z), at 2.37 (4) Å.