Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101006692/fr1331sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101006692/fr1331Isup2.hkl |
CCDC reference: 169927
The compound was synthesized using literature methods (Kitamura & Shibata, 1993). Suitable crystals were obtained by evaporation of an aqueous solution of (I) containing excess KHCO3.
H atoms were refined isotropically in observed positions. Final N—H distances were 0.80 (2) and 0.87 (2) Å; C—H distances were 0.95 (2) and 0.924 (18) Å; the O—H distance was 0.72 (2) Å.
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SHELXTL (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
K[Co(CO3)2(C2H8N2)]·H2O | F(000) = 300 |
Mr = 296.17 | Dx = 2.005 Mg m−3 |
Monoclinic, P2/n | Mo Kα radiation, λ = 0.71073 Å |
a = 8.2527 (13) Å | Cell parameters from 4154 reflections |
b = 7.3864 (12) Å | θ = 2.5–28.3° |
c = 8.5085 (14) Å | µ = 2.19 mm−1 |
β = 108.947 (2)° | T = 173 K |
V = 490.56 (14) Å3 | Block, purple |
Z = 2 | 0.24 × 0.20 × 0.20 mm |
Bruker SMART CCD area detector diffractometer | 1193 independent reflections |
Radiation source: normal-focus sealed tube | 1139 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
ω scans | θmax = 28.3°, θmin = 2.8° |
Absorption correction: multi-scan (SADABS; Blessing, 1995) | h = −10→10 |
Tmin = 0.538, Tmax = 0.645 | k = −9→9 |
5227 measured reflections | l = −11→11 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.021 | All H-atom parameters refined |
wR(F2) = 0.057 | w = 1/[σ2(Fo2) + (0.04P)2 + 0.12P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max < 0.001 |
1193 reflections | Δρmax = 0.44 e Å−3 |
91 parameters | Δρmin = −0.52 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=3DkFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.030 (3) |
K[Co(CO3)2(C2H8N2)]·H2O | V = 490.56 (14) Å3 |
Mr = 296.17 | Z = 2 |
Monoclinic, P2/n | Mo Kα radiation |
a = 8.2527 (13) Å | µ = 2.19 mm−1 |
b = 7.3864 (12) Å | T = 173 K |
c = 8.5085 (14) Å | 0.24 × 0.20 × 0.20 mm |
β = 108.947 (2)° |
Bruker SMART CCD area detector diffractometer | 1193 independent reflections |
Absorption correction: multi-scan (SADABS; Blessing, 1995) | 1139 reflections with I > 2σ(I) |
Tmin = 0.538, Tmax = 0.645 | Rint = 0.022 |
5227 measured reflections |
R[F2 > 2σ(F2)] = 0.021 | 0 restraints |
wR(F2) = 0.057 | All H-atom parameters refined |
S = 1.07 | Δρmax = 0.44 e Å−3 |
1193 reflections | Δρmin = −0.52 e Å−3 |
91 parameters |
Experimental. An approximate sphere of data was collected to 0.75 Å resolution with 98% coverage and 4.3 average redundancy. Crystal stability was monitored by recollection of the first fifty frames after data collection was complete. No significant change was observed in the 87 reflections measured. |
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. |
x | y | z | Uiso*/Ueq | ||
Co | 0.2500 | 0.49378 (3) | 0.2500 | 0.01380 (11) | |
N | 0.20522 (17) | 0.30274 (17) | 0.08522 (15) | 0.0183 (2) | |
O1 | 0.02113 (13) | 0.53391 (14) | 0.24827 (13) | 0.0189 (2) | |
O2 | 0.24457 (12) | 0.67035 (13) | 0.41367 (12) | 0.0178 (2) | |
O3 | −0.01352 (14) | 0.72829 (16) | 0.44064 (13) | 0.0254 (2) | |
O4 | 0.2500 | 1.0228 (3) | 0.7500 | 0.0466 (6) | |
C1 | 0.07802 (18) | 0.65065 (18) | 0.37111 (17) | 0.0181 (3) | |
C2 | 0.1848 (2) | 0.1283 (2) | 0.16346 (19) | 0.0230 (3) | |
K | 0.2500 | 0.67304 (6) | 0.7500 | 0.01818 (13) | |
H0A | 0.113 (3) | 0.331 (3) | 0.005 (3) | 0.026 (5)* | |
H0B | 0.280 (3) | 0.303 (3) | 0.044 (3) | 0.025 (5)* | |
H2A | 0.205 (3) | 0.029 (3) | 0.102 (3) | 0.034 (6)* | |
H2B | 0.075 (2) | 0.123 (2) | 0.168 (2) | 0.018 (4)* | |
H4A | 0.181 (3) | 1.080 (3) | 0.702 (3) | 0.041 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co | 0.01435 (16) | 0.01518 (16) | 0.01043 (16) | 0.000 | 0.00203 (10) | 0.000 |
N | 0.0191 (6) | 0.0200 (6) | 0.0141 (5) | 0.0001 (5) | 0.0030 (5) | −0.0017 (4) |
O1 | 0.0157 (5) | 0.0221 (5) | 0.0175 (5) | −0.0011 (4) | 0.0035 (4) | 0.0005 (4) |
O2 | 0.0187 (5) | 0.0194 (5) | 0.0145 (4) | −0.0011 (4) | 0.0042 (4) | −0.0023 (4) |
O3 | 0.0253 (5) | 0.0315 (6) | 0.0214 (5) | 0.0094 (4) | 0.0104 (4) | 0.0034 (4) |
O4 | 0.0483 (13) | 0.0203 (9) | 0.0467 (13) | 0.000 | −0.0185 (11) | 0.000 |
C1 | 0.0197 (6) | 0.0197 (6) | 0.0141 (6) | 0.0022 (5) | 0.0046 (5) | 0.0041 (5) |
C2 | 0.0266 (7) | 0.0177 (7) | 0.0230 (7) | −0.0033 (5) | 0.0060 (6) | −0.0025 (5) |
K | 0.0173 (2) | 0.0207 (2) | 0.0155 (2) | 0.000 | 0.00406 (15) | 0.000 |
Co—O1i | 1.9073 (11) | O2—K | 2.8475 (10) |
Co—O1 | 1.9073 (11) | O3—C1 | 1.2409 (17) |
Co—O2 | 1.9190 (10) | O3—K | 2.8473 (11) |
Co—O2i | 1.9190 (10) | O4—K | 2.583 (2) |
Co—N | 1.9383 (12) | O4—H4A | 0.72 (2) |
Co—Ni | 1.9383 (12) | C2—C2i | 1.516 (3) |
N—C2 | 1.4846 (19) | C2—H2A | 0.95 (2) |
N—H0A | 0.87 (2) | C2—H2B | 0.924 (18) |
N—H0B | 0.80 (2) | K—O1ii | 2.7138 (11) |
O1—C1 | 1.3182 (18) | K—O1iii | 2.7138 (11) |
O1—Kii | 2.7138 (11) | K—O3iv | 2.8473 (11) |
O2—C1 | 1.3109 (17) | K—O2iv | 2.8475 (11) |
O1i—Co—O1 | 162.12 (7) | O3—C1—O1 | 124.41 (13) |
O1i—Co—O2 | 98.35 (4) | O2—C1—O1 | 111.30 (12) |
O1—Co—O2 | 69.12 (4) | N—C2—C2i | 106.70 (9) |
O1i—Co—O2i | 69.12 (4) | N—C2—H2A | 111.2 (14) |
O1—Co—O2i | 98.35 (4) | C2i—C2—H2A | 109.8 (15) |
O2—Co—O2i | 94.37 (6) | N—C2—H2B | 108.2 (11) |
O1i—Co—N | 94.27 (5) | C2i—C2—H2B | 110.8 (11) |
O1—Co—N | 98.73 (5) | H2A—C2—H2B | 110.1 (18) |
O2—Co—N | 167.36 (5) | O4—K—O1ii | 124.28 (2) |
O2i—Co—N | 90.79 (5) | O4—K—O1iii | 124.28 (2) |
O1i—Co—Ni | 98.73 (5) | O1ii—K—O1iii | 111.43 (5) |
O1—Co—Ni | 94.27 (5) | O4—K—O3iv | 81.76 (3) |
O2—Co—Ni | 90.79 (5) | O1ii—K—O3iv | 117.34 (3) |
O2i—Co—Ni | 167.36 (5) | O1iii—K—O3iv | 72.67 (3) |
N—Co—Ni | 86.56 (8) | O4—K—O3 | 81.76 (3) |
C2—N—Co | 109.27 (9) | O1ii—K—O3 | 72.67 (3) |
C2—N—H0A | 111.4 (13) | O1iii—K—O3 | 117.34 (3) |
Co—N—H0A | 107.8 (13) | O3iv—K—O3 | 163.52 (5) |
C2—N—H0B | 114.6 (14) | O4—K—O2iv | 90.40 (2) |
Co—N—H0B | 108.4 (14) | O1ii—K—O2iv | 74.61 (3) |
H0A—N—H0B | 105.1 (19) | O1iii—K—O2iv | 104.93 (3) |
C1—O1—Co | 89.92 (8) | O3iv—K—O2iv | 46.68 (3) |
C1—O1—Kii | 116.50 (8) | O3—K—O2iv | 133.48 (3) |
Co—O1—Kii | 136.77 (5) | O4—K—O2 | 90.40 (2) |
C1—O2—Co | 89.63 (8) | O1ii—K—O2 | 104.93 (3) |
C1—O2—K | 87.21 (7) | O1iii—K—O2 | 74.61 (3) |
Co—O2—K | 137.52 (5) | O3iv—K—O2 | 133.48 (3) |
C1—O3—K | 88.51 (8) | O3—K—O2 | 46.68 (3) |
K—O4—H4A | 126 (2) | O2iv—K—O2 | 179.20 (4) |
O3—C1—O2 | 124.27 (13) | ||
O1i—Co—N—C2 | 112.70 (10) | K—O3—C1—O2 | −38.95 (13) |
O1—Co—N—C2 | −79.61 (10) | K—O3—C1—O1 | 139.00 (13) |
O2—Co—N—C2 | −64.0 (2) | K—O2—C1—O3 | 38.99 (13) |
O2i—Co—N—C2 | −178.18 (10) | K—O2—C1—O1 | −139.19 (10) |
Ni—Co—N—C2 | 14.19 (7) | Kii—O1—C1—O3 | −32.16 (17) |
O1i—Co—O1—C1 | −48.52 (18) | Kii—O1—C1—O2 | 146.01 (8) |
O2—Co—O1—C1 | −1.07 (7) | Co—N—C2—C2i | −38.67 (17) |
O2i—Co—O1—C1 | −92.59 (8) | N—C2—C2i—Ni | 50.1 (2) |
N—Co—O1—C1 | 175.31 (8) | C1—O3—K—O4 | 117.60 (9) |
Ni—Co—O1—C1 | 88.14 (8) | C1—O3—K—O1ii | −112.50 (9) |
O1i—Co—O1—Kii | −179.06 (7) | C1—O3—K—O1iii | −6.86 (10) |
O2—Co—O1—Kii | −131.62 (8) | C1—O3—K—O3iv | 117.60 (9) |
O2i—Co—O1—Kii | 136.86 (7) | C1—O3—K—O2iv | −159.73 (8) |
N—Co—O1—Kii | 44.77 (8) | C1—O3—K—O2 | 19.19 (8) |
Ni—Co—O1—Kii | −42.40 (8) | C1—O2—K—O4 | −96.40 (7) |
O1i—Co—O2—C1 | 167.86 (7) | Co—O2—K—O4 | 177.20 (6) |
O1—Co—O2—C1 | 1.08 (7) | C1—O2—K—O1ii | 29.39 (8) |
O2i—Co—O2—C1 | 98.36 (8) | Co—O2—K—O1ii | −57.01 (7) |
N—Co—O2—C1 | −15.5 (2) | C1—O2—K—O1iii | 137.98 (8) |
Ni—Co—O2—C1 | −93.19 (8) | Co—O2—K—O1iii | 51.59 (6) |
O1i—Co—O2—K | −106.67 (7) | C1—O2—K—O3iv | −175.40 (7) |
O1—Co—O2—K | 86.54 (7) | Co—O2—K—O3iv | 98.21 (7) |
O2i—Co—O2—K | −176.18 (9) | C1—O2—K—O3 | −18.15 (7) |
N—Co—O2—K | 70.0 (2) | Co—O2—K—O3 | −104.55 (8) |
Ni—Co—O2—K | −7.73 (7) |
Symmetry codes: (i) −x+1/2, y, −z+1/2; (ii) −x, −y+1, −z+1; (iii) x+1/2, −y+1, z+1/2; (iv) −x+1/2, y, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N—H0A···O1v | 0.87 (2) | 2.30 (2) | 3.0910 (17) | 150.8 (17) |
N—H0B···O3vi | 0.80 (2) | 2.17 (2) | 2.9678 (17) | 173.3 (19) |
O4—H4A···O3vii | 0.72 (2) | 2.07 (2) | 2.7866 (17) | 171 (3) |
Symmetry codes: (v) −x, −y+1, −z; (vi) x+1/2, −y+1, z−1/2; (vii) −x, −y+2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | K[Co(CO3)2(C2H8N2)]·H2O |
Mr | 296.17 |
Crystal system, space group | Monoclinic, P2/n |
Temperature (K) | 173 |
a, b, c (Å) | 8.2527 (13), 7.3864 (12), 8.5085 (14) |
β (°) | 108.947 (2) |
V (Å3) | 490.56 (14) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.19 |
Crystal size (mm) | 0.24 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART CCD area detector diffractometer |
Absorption correction | Multi-scan (SADABS; Blessing, 1995) |
Tmin, Tmax | 0.538, 0.645 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5227, 1193, 1139 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.021, 0.057, 1.07 |
No. of reflections | 1193 |
No. of parameters | 91 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.44, −0.52 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXTL (Bruker, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL.
Co—O1 | 1.9073 (11) | O2—C1 | 1.3109 (17) |
Co—O2 | 1.9190 (10) | O2—K | 2.8475 (10) |
Co—N | 1.9383 (12) | O3—C1 | 1.2409 (17) |
N—C2 | 1.4846 (19) | O3—K | 2.8473 (11) |
O1—C1 | 1.3182 (18) | O4—K | 2.583 (2) |
O1—Ki | 2.7138 (11) | C2—C2ii | 1.516 (3) |
O1ii—Co—O1 | 162.12 (7) | O4—K—O3 | 81.76 (3) |
O1—Co—O2 | 69.12 (4) | O1i—K—O3 | 72.67 (3) |
O1—Co—O2ii | 98.35 (4) | O1iii—K—O3 | 117.34 (3) |
O2—Co—O2ii | 94.37 (6) | O3iv—K—O3 | 163.52 (5) |
O1ii—Co—N | 94.27 (5) | O4—K—O2 | 90.40 (2) |
O1—Co—N | 98.73 (5) | O1i—K—O2 | 104.93 (3) |
O2—Co—N | 167.36 (5) | O1iii—K—O2 | 74.61 (3) |
O2ii—Co—N | 90.79 (5) | O3iv—K—O2 | 133.48 (3) |
N—Co—Nii | 86.56 (8) | O3—K—O2 | 46.68 (3) |
O4—K—O1i | 124.28 (2) | O2iv—K—O2 | 179.20 (4) |
O1i—K—O1iii | 111.43 (5) | ||
Co—N—C2—C2ii | −38.67 (17) | N—C2—C2ii—Nii | 50.1 (2) |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1/2, y, −z+1/2; (iii) x+1/2, −y+1, z+1/2; (iv) −x+1/2, y, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N—H0A···O1v | 0.87 (2) | 2.30 (2) | 3.0910 (17) | 150.8 (17) |
N—H0B···O3vi | 0.80 (2) | 2.17 (2) | 2.9678 (17) | 173.3 (19) |
O4—H4A···O3vii | 0.72 (2) | 2.07 (2) | 2.7866 (17) | 171 (3) |
Symmetry codes: (v) −x, −y+1, −z; (vi) x+1/2, −y+1, z−1/2; (vii) −x, −y+2, −z+1. |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- Purchase subscription
- Reduced-price subscriptions
- If you have already subscribed, you may need to register
Carbonato complexes of cobalt(III) are important intermediates, allowing access to a wide range of cobalt complexes (Kitamura & Shibata, 1993; Shibata, 1983). There have been several reports of the structure of [CoCO3(en)2]+ with various anions (Bigoli et al., 1980; Healy et al., 1981; Bernal et al., 1993; Garcia-Granda et al., 1993; Hu et al., 1997) (en is ethylenediamine). Structures of other monocarbonato cobalt(III) complexes have also been reported. To our knowledge the only previous structure report of a cobalt(III) complex containing two coordinated carbonates on a single Co atom is the binuclear complex (NH3)4Co(µ –NH2)(µ –OH)Co(CO3)2 (Churchill et al., 1979). \sch
The title salt, K[Co(CO3)2(NH2CH2CH2NH2)]·H2O, (I), contains a distorted octahedral cobalt(III) anion (Fig. 1) with a crystallographic twofold axis passing through the Co and the C–C bond of the en ligand. The main distortions from octahedral geometry arise from the narrow 'bite' of the carbonato ligand, with a O1—Co—O2 angle of 69.12 (4)°. The C1≐O3 bond is slightly shorter (by about 0.07 Å) than C1≐O1 and C1≐O2, suggesting partial localization of the charge on the coordinated carbonate. Other distances and angles of the anion are as expected.
The potassium cation is seven-coordinate (Fig. 2). The carbonate is bidentate to Co through O1 and O2, and also bidentate to K through O2 and O3. The water oxygen O4 is bound to K along a crystallographic twofold axis, and carbonates from two neighboring anions bind in a monodentate fashion through O1. The two O1 carbonate O atoms and the O4 water oxygen form a trigonal plane with the K atom, having O—K—O angles of 124.28 (2), 124.28 (2) and 111.43 (5)°. The remaining O atoms from the bidentate carbonates form another approximate plane nearly perpendicular to the trigonal plane. Thus the K coordination might be described as a type of trigonal bipyramidal geometry where each axial ligand is split in two. This arrangement, which is facilitated by the small bite angle of carbonate [the O2—K—O3 angle is 46.68 (3)°], allows the O4 water oxygen to have less steric interaction with the other O atoms around the K atom. This partially accounts for the short O4—K distance of 2.583 (2) Å.
In addition the displacement ellipsoid of O4 is elongated along an axis perpendicular to the K—O bond indicating a librational shortening of the bond length. A libration calculation using the full Schomaker-Trueblood tensor analysis (Schomaker & Trueblood, 1968) yielded a corrected K—O4 bond length of 2.598 Å, while the `riding model' correction (Johnson, 1970) was similar, giving a corrected length of 2.600 Å with an upper limit of 2.638 Å. Use of the riding model was justified based on parallel and perpendicular RMS amplitudes of K and O4.