Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807052592/rz2168sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807052592/rz2168Isup2.hkl |
CCDC reference: 667253
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.004 Å
- R factor = 0.029
- wR factor = 0.070
- Data-to-parameter ratio = 18.9
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT415_ALERT_2_B Short Inter D-H..H-X H3A .. H6A .. 1.97 Ang.
Alert level C GOODF01_ALERT_2_C The least squares goodness of fit parameter lies outside the range 0.80 <> 2.00 Goodness of fit given = 0.781 PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Co1 - O4 .. 7.99 su
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT793_ALERT_1_G Check the Absolute Configuration of P1 = ... R PLAT794_ALERT_5_G Check Predicted Bond Valency for Co1 (9) 1.74
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 4 ALERT level G = General alerts; check 3 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 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
For related literature, see: Clearfield (1998); Cheetham et al. (1999); Stock et al. (2000); Serpaggi & Férey (1999); Ying & Mao (2004); Ying et al. (2006, 2007).
A mixture of cobalt(II) acetate (0.5 mmol, 0.123 g), 2-carboxyethylphosphonic acid (0.5 mmol, 0.078 g), and 2,2'-bipyridine (0.5 mmol, 0.078 g) in 10 ml of distilled water was sealed in an autoclave equipped with a Teflon liner (20 ml) and then heated at 160°C for 4 days. Crystals of the title compound were obtained.
All hydrogen atoms were positioned geometrically and with C—H = 0.93–0.98 Å, O—H = 0.82 Å, and refined in the riding-model approximation, with Uiso(H) = 1.2 Ueq(C) or 1.5 Ueq(O).
Recently, the chemistry of metal phosphonates has been a research field of rapid expansion, mainly due to their potential application in the area of catalysis, ion exchange, proton conductivity, intercalation chemistry, photochemistry and material chemistry (Clearfield 1998). Many metal phosphonates have been reported (Cheetham et al., 1999; Stock et al., 2000; Serpaggi & Férey, 1999; Ying & Mao, 2004; Ying et al., 2006). The metal phosphonates can exhibit various kinds of structure. We report here the crystal structure of a new cobalt(II) carboxyalkylphosphonate complex synthesized by the hydrothermal method.
The asymmetric unit of the title compound contains one cobalt(II) ion, one doubly deprotonated 2-carboxyethylphosphonic acid ligand, one 2,2'-bipyridine and one coordinated water molecule. The cobalt(II) ion is six-coordinated by one phosphonate oxygen atom, one water molecule, two carboxylate oxygen atoms and two N atoms of a 2,2'-bipyridine molecule. The Co—O distances range from 2.0076 (13) to 2.2112 (15) Å and the Co—N distances are 2.1038 (16) and 2.1471 (17) Å. Two cobalt(II) ions are linked by two 2-carboxyethylphosphonic acid ligands forming a dimer (Fig. 1). The dimers are further interlinked by O—H···O hydrogen bonds (Table 1) and π-π stacking interactions to form a three-dimensional supermolecular structure (Fig. 2). The compound is isostructural with the analogous zinc(II) complex reported recently (Ying et al., 2007).
For related literature, see: Clearfield (1998); Cheetham et al. (1999); Stock et al. (2000); Serpaggi & Férey (1999); Ying & Mao (2004); Ying et al. (2006, 2007).
Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).
[Co2(C3H5O5P)2(C10H8N2)2(H2O)2] | F(000) = 1576 |
Mr = 770.34 | Dx = 1.623 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 7543 reflections |
a = 8.6384 (18) Å | θ = 2.3–28.2° |
b = 17.701 (4) Å | µ = 1.22 mm−1 |
c = 20.619 (4) Å | T = 293 K |
V = 3152.8 (11) Å3 | Plate, pink |
Z = 4 | 0.34 × 0.33 × 0.06 mm |
Bruker APEX area-detector diffractometer | 3924 independent reflections |
Radiation source: fine-focus sealed tube | 2241 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.044 |
φ and ω scans | θmax = 28.4°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | h = −11→10 |
Tmin = 0.682, Tmax = 0.930 | k = −23→23 |
22346 measured reflections | l = −26→27 |
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)] = 0.029 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.070 | H-atom parameters constrained |
S = 0.78 | w = 1/[σ2(Fo2) + (0.0378P)2] where P = (Fo2 + 2Fc2)/3 |
3924 reflections | (Δ/σ)max = 0.025 |
208 parameters | Δρmax = 0.49 e Å−3 |
0 restraints | Δρmin = −0.53 e Å−3 |
[Co2(C3H5O5P)2(C10H8N2)2(H2O)2] | V = 3152.8 (11) Å3 |
Mr = 770.34 | Z = 4 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 8.6384 (18) Å | µ = 1.22 mm−1 |
b = 17.701 (4) Å | T = 293 K |
c = 20.619 (4) Å | 0.34 × 0.33 × 0.06 mm |
Bruker APEX area-detector diffractometer | 3924 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | 2241 reflections with I > 2σ(I) |
Tmin = 0.682, Tmax = 0.930 | Rint = 0.044 |
22346 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | 0 restraints |
wR(F2) = 0.070 | H-atom parameters constrained |
S = 0.78 | Δρmax = 0.49 e Å−3 |
3924 reflections | Δρmin = −0.53 e Å−3 |
208 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 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. |
x | y | z | Uiso*/Ueq | ||
Co1 | 0.67017 (3) | 0.427251 (15) | 0.405818 (12) | 0.02945 (9) | |
P1 | 1.15669 (6) | 0.69676 (3) | 0.49404 (3) | 0.03041 (14) | |
N1 | 0.7003 (2) | 0.38302 (10) | 0.31196 (8) | 0.0380 (5) | |
N2 | 0.5524 (2) | 0.50685 (9) | 0.34466 (8) | 0.0379 (4) | |
O5 | 0.87439 (17) | 0.50256 (8) | 0.40645 (6) | 0.0410 (4) | |
O4 | 0.69834 (16) | 0.51179 (8) | 0.48183 (7) | 0.0383 (4) | |
O3 | 1.05769 (16) | 0.76527 (7) | 0.50687 (7) | 0.0429 (4) | |
O2 | 1.21917 (16) | 0.66098 (7) | 0.55427 (6) | 0.0360 (4) | |
O1 | 1.28912 (17) | 0.71919 (8) | 0.44566 (7) | 0.0428 (4) | |
H1B | 1.3711 | 0.7228 | 0.4654 | 0.064* | |
O6 | 0.45576 (15) | 0.39234 (7) | 0.43781 (6) | 0.0386 (4) | |
H6B | 0.4259 | 0.4205 | 0.4668 | 0.046* | |
H6A | 0.4103 | 0.3516 | 0.4199 | 0.046* | |
C13 | 0.8227 (2) | 0.53500 (11) | 0.45580 (10) | 0.0308 (5) | |
C12 | 0.9046 (2) | 0.60169 (12) | 0.48543 (10) | 0.0382 (5) | |
H12A | 0.9347 | 0.5885 | 0.5293 | 0.046* | |
H12B | 0.8321 | 0.6434 | 0.4882 | 0.046* | |
C11 | 1.0474 (2) | 0.62845 (11) | 0.44921 (10) | 0.0390 (5) | |
H11A | 1.0159 | 0.6505 | 0.4082 | 0.047* | |
H11B | 1.1129 | 0.5853 | 0.4398 | 0.047* | |
C5 | 0.6405 (3) | 0.42324 (12) | 0.26241 (9) | 0.0389 (5) | |
C6 | 0.5562 (3) | 0.49213 (12) | 0.28068 (10) | 0.0380 (5) | |
C4 | 0.6598 (3) | 0.39995 (15) | 0.19871 (11) | 0.0565 (7) | |
H4A | 0.6182 | 0.4282 | 0.1649 | 0.068* | |
C10 | 0.4766 (3) | 0.56851 (13) | 0.36431 (11) | 0.0539 (7) | |
H10A | 0.4737 | 0.5787 | 0.4085 | 0.065* | |
C7 | 0.4842 (3) | 0.53934 (15) | 0.23605 (11) | 0.0552 (7) | |
H7A | 0.4881 | 0.5285 | 0.1919 | 0.066* | |
C1 | 0.7808 (3) | 0.31957 (13) | 0.29949 (11) | 0.0504 (7) | |
H1A | 0.8227 | 0.2921 | 0.3337 | 0.060* | |
C3 | 0.7403 (4) | 0.33528 (16) | 0.18596 (13) | 0.0680 (9) | |
H3A | 0.7531 | 0.3190 | 0.1434 | 0.082* | |
C9 | 0.4028 (3) | 0.61769 (14) | 0.32318 (12) | 0.0667 (8) | |
H9A | 0.3516 | 0.6601 | 0.3390 | 0.080* | |
C8 | 0.4071 (3) | 0.60219 (16) | 0.25800 (12) | 0.0672 (8) | |
H8A | 0.3579 | 0.6342 | 0.2287 | 0.081* | |
C2 | 0.8023 (3) | 0.29448 (15) | 0.23620 (14) | 0.0652 (8) | |
H2A | 0.8580 | 0.2506 | 0.2280 | 0.078* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.03229 (17) | 0.02827 (15) | 0.02781 (14) | −0.00034 (13) | 0.00030 (13) | −0.00079 (12) |
P1 | 0.0257 (3) | 0.0270 (3) | 0.0385 (3) | −0.0013 (2) | −0.0008 (3) | 0.0023 (2) |
N1 | 0.0425 (13) | 0.0365 (11) | 0.0351 (10) | −0.0059 (9) | 0.0035 (9) | −0.0090 (9) |
N2 | 0.0425 (12) | 0.0410 (11) | 0.0302 (10) | 0.0029 (9) | −0.0015 (8) | 0.0016 (8) |
O5 | 0.0475 (11) | 0.0392 (9) | 0.0362 (8) | −0.0118 (7) | 0.0076 (7) | −0.0070 (7) |
O4 | 0.0339 (10) | 0.0326 (8) | 0.0485 (9) | −0.0061 (7) | 0.0075 (7) | −0.0067 (7) |
O3 | 0.0304 (9) | 0.0276 (8) | 0.0708 (10) | 0.0049 (6) | 0.0001 (8) | 0.0038 (7) |
O2 | 0.0374 (9) | 0.0327 (8) | 0.0379 (8) | 0.0052 (7) | −0.0020 (7) | 0.0039 (7) |
O1 | 0.0335 (10) | 0.0529 (10) | 0.0420 (9) | −0.0100 (7) | 0.0022 (7) | 0.0050 (8) |
O6 | 0.0352 (9) | 0.0345 (8) | 0.0461 (9) | −0.0045 (7) | 0.0035 (7) | −0.0085 (7) |
C13 | 0.0313 (13) | 0.0255 (11) | 0.0355 (12) | 0.0000 (10) | −0.0047 (10) | 0.0036 (9) |
C12 | 0.0304 (13) | 0.0368 (12) | 0.0476 (13) | −0.0056 (10) | 0.0026 (11) | −0.0064 (10) |
C11 | 0.0398 (15) | 0.0394 (13) | 0.0380 (12) | −0.0098 (10) | −0.0028 (10) | 0.0009 (10) |
C5 | 0.0422 (15) | 0.0463 (13) | 0.0281 (11) | −0.0168 (11) | −0.0001 (9) | −0.0049 (11) |
C6 | 0.0378 (14) | 0.0436 (13) | 0.0326 (12) | −0.0115 (11) | −0.0038 (10) | 0.0028 (10) |
C4 | 0.081 (2) | 0.0582 (16) | 0.0306 (13) | −0.0185 (15) | 0.0051 (13) | −0.0086 (12) |
C10 | 0.0689 (19) | 0.0539 (15) | 0.0389 (13) | 0.0184 (14) | −0.0041 (12) | 0.0003 (12) |
C7 | 0.0644 (19) | 0.0675 (17) | 0.0336 (13) | −0.0051 (15) | −0.0102 (12) | 0.0079 (13) |
C1 | 0.0569 (18) | 0.0458 (15) | 0.0485 (15) | −0.0023 (13) | 0.0051 (12) | −0.0138 (12) |
C3 | 0.094 (2) | 0.070 (2) | 0.0392 (15) | −0.0225 (18) | 0.0194 (16) | −0.0194 (15) |
C9 | 0.081 (2) | 0.0611 (18) | 0.0577 (18) | 0.0288 (16) | −0.0069 (16) | 0.0063 (14) |
C8 | 0.078 (2) | 0.0700 (19) | 0.0533 (17) | 0.0161 (17) | −0.0152 (16) | 0.0185 (15) |
C2 | 0.072 (2) | 0.0529 (17) | 0.071 (2) | −0.0049 (14) | 0.0217 (16) | −0.0284 (15) |
Co1—O2i | 2.0076 (13) | C12—H12A | 0.9700 |
Co1—O6 | 2.0610 (14) | C12—H12B | 0.9700 |
Co1—N1 | 2.1038 (16) | C11—H11A | 0.9700 |
Co1—N2 | 2.1471 (17) | C11—H11B | 0.9700 |
Co1—O4 | 2.1806 (14) | C5—C4 | 1.387 (3) |
Co1—O5 | 2.2112 (15) | C5—C6 | 1.469 (3) |
P1—O2 | 1.4948 (14) | C6—C7 | 1.390 (3) |
P1—O3 | 1.5074 (14) | C4—C3 | 1.365 (3) |
P1—O1 | 1.5690 (15) | C4—H4A | 0.9300 |
P1—C11 | 1.791 (2) | C10—C9 | 1.373 (3) |
N1—C5 | 1.348 (3) | C10—H10A | 0.9300 |
N1—C1 | 1.346 (3) | C7—C8 | 1.373 (3) |
N2—C10 | 1.336 (3) | C7—H7A | 0.9300 |
N2—C6 | 1.345 (3) | C1—C2 | 1.391 (3) |
O5—C13 | 1.251 (2) | C1—H1A | 0.9300 |
O4—C13 | 1.269 (2) | C3—C2 | 1.372 (4) |
O2—Co1i | 2.0076 (13) | C3—H3A | 0.9300 |
O1—H1B | 0.8200 | C9—C8 | 1.372 (3) |
O6—H6B | 0.8200 | C9—H9A | 0.9300 |
O6—H6A | 0.9000 | C8—H8A | 0.9300 |
C13—C12 | 1.506 (3) | C2—H2A | 0.9300 |
C12—C11 | 1.517 (3) | ||
O2i—Co1—O6 | 93.64 (6) | C13—C12—H12B | 108.5 |
O2i—Co1—N1 | 91.64 (6) | C11—C12—H12B | 108.5 |
O6—Co1—N1 | 107.10 (6) | H12A—C12—H12B | 107.5 |
O2i—Co1—N2 | 167.65 (6) | C12—C11—P1 | 112.65 (14) |
O6—Co1—N2 | 87.65 (6) | C12—C11—H11A | 109.1 |
N1—Co1—N2 | 76.26 (7) | P1—C11—H11A | 109.1 |
O2i—Co1—O4 | 100.73 (6) | C12—C11—H11B | 109.1 |
O6—Co1—O4 | 94.36 (5) | P1—C11—H11B | 109.1 |
N1—Co1—O4 | 154.52 (6) | H11A—C11—H11B | 107.8 |
N2—Co1—O4 | 91.42 (6) | N1—C5—C4 | 121.0 (2) |
O2i—Co1—O5 | 94.97 (6) | N1—C5—C6 | 115.71 (17) |
O6—Co1—O5 | 153.62 (5) | C4—C5—C6 | 123.3 (2) |
N1—Co1—O5 | 97.53 (6) | N2—C6—C7 | 121.5 (2) |
N2—Co1—O5 | 89.19 (6) | N2—C6—C5 | 115.10 (19) |
O4—Co1—O5 | 59.54 (5) | C7—C6—C5 | 123.4 (2) |
O2—P1—O3 | 113.57 (8) | C3—C4—C5 | 119.5 (2) |
O2—P1—O1 | 111.85 (8) | C3—C4—H4A | 120.2 |
O3—P1—O1 | 108.76 (8) | C5—C4—H4A | 120.2 |
O2—P1—C11 | 109.46 (9) | N2—C10—C9 | 124.0 (2) |
O3—P1—C11 | 109.55 (10) | N2—C10—H10A | 118.0 |
O1—P1—C11 | 103.13 (9) | C9—C10—H10A | 118.0 |
C5—N1—C1 | 119.60 (19) | C8—C7—C6 | 119.1 (2) |
C5—N1—Co1 | 116.95 (14) | C8—C7—H7A | 120.5 |
C1—N1—Co1 | 123.39 (16) | C6—C7—H7A | 120.5 |
C10—N2—C6 | 117.89 (19) | N1—C1—C2 | 121.0 (2) |
C10—N2—Co1 | 126.17 (14) | N1—C1—H1A | 119.5 |
C6—N2—Co1 | 115.94 (14) | C2—C1—H1A | 119.5 |
C13—O5—Co1 | 89.81 (12) | C4—C3—C2 | 119.7 (2) |
C13—O4—Co1 | 90.73 (12) | C4—C3—H3A | 120.2 |
P1—O2—Co1i | 147.36 (9) | C2—C3—H3A | 120.2 |
P1—O1—H1B | 109.5 | C8—C9—C10 | 117.8 (2) |
Co1—O6—H6B | 109.5 | C8—C9—H9A | 121.1 |
Co1—O6—H6A | 120.0 | C10—C9—H9A | 121.1 |
H6B—O6—H6A | 130.5 | C7—C8—C9 | 119.9 (2) |
O5—C13—O4 | 119.84 (19) | C7—C8—H8A | 120.1 |
O5—C13—C12 | 121.47 (19) | C9—C8—H8A | 120.1 |
O4—C13—C12 | 118.69 (18) | C3—C2—C1 | 119.2 (3) |
C13—C12—C11 | 115.28 (18) | C3—C2—H2A | 120.4 |
C13—C12—H12A | 108.5 | C1—C2—H2A | 120.4 |
C11—C12—H12A | 108.5 |
Symmetry code: (i) −x+2, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O6—H6B···O4ii | 0.82 | 1.93 | 2.7198 (19) | 163 |
O1—H1B···O3iii | 0.82 | 1.72 | 2.533 (2) | 169 |
Symmetry codes: (ii) −x+1, −y+1, −z+1; (iii) x+1/2, −y+3/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Co2(C3H5O5P)2(C10H8N2)2(H2O)2] |
Mr | 770.34 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 293 |
a, b, c (Å) | 8.6384 (18), 17.701 (4), 20.619 (4) |
V (Å3) | 3152.8 (11) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.22 |
Crystal size (mm) | 0.34 × 0.33 × 0.06 |
Data collection | |
Diffractometer | Bruker APEX area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2002) |
Tmin, Tmax | 0.682, 0.930 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 22346, 3924, 2241 |
Rint | 0.044 |
(sin θ/λ)max (Å−1) | 0.670 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.070, 0.78 |
No. of reflections | 3924 |
No. of parameters | 208 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.49, −0.53 |
Computer programs: SMART (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b).
D—H···A | D—H | H···A | D···A | D—H···A |
O6—H6B···O4i | 0.82 | 1.93 | 2.7198 (19) | 162.6 |
O1—H1B···O3ii | 0.82 | 1.72 | 2.533 (2) | 169.3 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1/2, −y+3/2, −z+1. |
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Recently, the chemistry of metal phosphonates has been a research field of rapid expansion, mainly due to their potential application in the area of catalysis, ion exchange, proton conductivity, intercalation chemistry, photochemistry and material chemistry (Clearfield 1998). Many metal phosphonates have been reported (Cheetham et al., 1999; Stock et al., 2000; Serpaggi & Férey, 1999; Ying & Mao, 2004; Ying et al., 2006). The metal phosphonates can exhibit various kinds of structure. We report here the crystal structure of a new cobalt(II) carboxyalkylphosphonate complex synthesized by the hydrothermal method.
The asymmetric unit of the title compound contains one cobalt(II) ion, one doubly deprotonated 2-carboxyethylphosphonic acid ligand, one 2,2'-bipyridine and one coordinated water molecule. The cobalt(II) ion is six-coordinated by one phosphonate oxygen atom, one water molecule, two carboxylate oxygen atoms and two N atoms of a 2,2'-bipyridine molecule. The Co—O distances range from 2.0076 (13) to 2.2112 (15) Å and the Co—N distances are 2.1038 (16) and 2.1471 (17) Å. Two cobalt(II) ions are linked by two 2-carboxyethylphosphonic acid ligands forming a dimer (Fig. 1). The dimers are further interlinked by O—H···O hydrogen bonds (Table 1) and π-π stacking interactions to form a three-dimensional supermolecular structure (Fig. 2). The compound is isostructural with the analogous zinc(II) complex reported recently (Ying et al., 2007).