Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807049124/dn2240sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807049124/dn2240Isup2.hkl |
CCDC reference: 627044
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.006 Å
- R factor = 0.040
- wR factor = 0.118
- Data-to-parameter ratio = 11.9
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 100 Deg. PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 = 4 PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Co1 - O4 .. 5.50 su PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.13
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Co1 (2) 2.56 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 3
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 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 0 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
citric acid(0.032 g, 0.062 mmol), CoCl2 (0.18 g, 0.21 mmol) and bpa (0.026 g, 0.019 mmol) and NaOH(0.048 mmol,0.12 mmol), were added in a mixed solvent of ethanol and acetonitrile, the mixture was heated for five hours under reflux. during the process stirring and influx were required. The resultant was then filtered to give a pure solution which was infiltrated by diethyl ether freely in a closed vessel, a weeks later some single crystals of the size suitable for X-Ray diffraction analysis.
All H atoms attached to C atoms and N atom were fixed geometrically and treated as riding with C—H = 0.93 Å (aromatic) or 0.97 Å (methylene) and N—H = 0.86 Å with Uiso(H) = 1.2Ueq(C or N). H atoms of water molecule were located in difference Fourier maps and included in the subsequent refinement using restraints (O—H= 0.85 (1)Å and H···H= 1.39 (2) Å) with Uiso(H) = 1.5Ueq(O).
The prevalent citric acid has been widely known for its abundance in physiological fluids(Srere, 1972). Binuclear iron complexes were studied long ago by the pioneer Marray (Marray, 1974). The structures and properties of such systems depend on the coordination and geometric preferences of both the central metals ions and bridging building blocks as well as the influence of weaker non-covalent interactions, such as hydrogen bonds and π-π stacking interactions. In this paper, we report the synthesis and crystal structure of the title complex,(I).
The anionic complex I is an edge-shared bi-octahedral dimer with centro-symmetric structure, in which the two iron atoms are bridged by two alkoxide oxygen atoms of the fully deprotonated citrate ligands. All of the carboxylate groups coordinate in a mono-dentate fashion to terminal positions, and two water molecules complete the slightly distorted octahedral coordination spheres. This structure is very similar to those reported by Shweky and coworkers (Shweky et al., 1994). The chelating of the deprotonated hydroxyl and carboxylic groups of the citrate ion leads to two six-membered rings and one five-membered ring, perhaps stabilizing the overall dimeric moiety. Fe—O bond lengths range from 1.9682 (2) -2.0294 (19) Å. Supramolecular interactions (O—H···O and N—H···O) stabilize the architecture(Table 1).
For related literature, see: Shweky et al. (1994); Srere (1972); Marray (1974).
Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Bruker, 2004).
(C12H14N2)[Co2(C6H4O7)2(H2O)2] | Z = 1 |
Mr = 716.33 | F(000) = 366 |
Triclinic, P1 | Dx = 1.798 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.2975 (6) Å | Cell parameters from 2437 reflections |
b = 9.2340 (6) Å | θ = 2.4–25.5° |
c = 9.9647 (7) Å | µ = 1.34 mm−1 |
α = 65.242 (1)° | T = 298 K |
β = 72.803 (1)° | Block, purple |
γ = 85.004 (1)° | 0.25 × 0.20 × 0.18 mm |
V = 661.72 (8) Å3 |
Bruker APEXII area-detector diffractometer | 2437 independent reflections |
Radiation source: fine-focus sealed tube | 1949 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
φ and ω scans | θmax = 25.5°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | h = −10→10 |
Tmin = 0.730, Tmax = 0.794 | k = −11→11 |
5003 measured reflections | l = −11→12 |
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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.118 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.15 | w = 1/[σ2(Fo2) + (0.0605P)2 + 0.3131P] where P = (Fo2 + 2Fc2)/3 |
2437 reflections | (Δ/σ)max = 0.001 |
205 parameters | Δρmax = 0.41 e Å−3 |
3 restraints | Δρmin = −0.42 e Å−3 |
(C12H14N2)[Co2(C6H4O7)2(H2O)2] | γ = 85.004 (1)° |
Mr = 716.33 | V = 661.72 (8) Å3 |
Triclinic, P1 | Z = 1 |
a = 8.2975 (6) Å | Mo Kα radiation |
b = 9.2340 (6) Å | µ = 1.34 mm−1 |
c = 9.9647 (7) Å | T = 298 K |
α = 65.242 (1)° | 0.25 × 0.20 × 0.18 mm |
β = 72.803 (1)° |
Bruker APEXII area-detector diffractometer | 2437 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | 1949 reflections with I > 2σ(I) |
Tmin = 0.730, Tmax = 0.794 | Rint = 0.024 |
5003 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 3 restraints |
wR(F2) = 0.118 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.15 | Δρmax = 0.41 e Å−3 |
2437 reflections | Δρmin = −0.42 e Å−3 |
205 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 | ||
C1 | 0.1731 (5) | 0.4450 (5) | −0.1202 (5) | 0.0362 (9) | |
H1 | 0.1984 | 0.5364 | −0.2121 | 0.043* | |
C2 | 0.0838 (5) | 0.3211 (5) | −0.1064 (5) | 0.0362 (9) | |
H2 | 0.0476 | 0.3280 | −0.1887 | 0.043* | |
C3 | 0.0457 (5) | 0.1833 (4) | 0.0304 (5) | 0.0301 (9) | |
C4 | 0.1005 (5) | 0.1797 (5) | 0.1488 (5) | 0.0387 (10) | |
H4 | 0.0756 | 0.0902 | 0.2423 | 0.046* | |
C5 | 0.1921 (6) | 0.3075 (5) | 0.1301 (5) | 0.0424 (10) | |
H5 | 0.2307 | 0.3037 | 0.2101 | 0.051* | |
C6 | −0.0508 (5) | 0.0426 (5) | 0.0481 (5) | 0.0408 (10) | |
H6A | −0.1532 | 0.0790 | 0.0181 | 0.049* | |
H6B | −0.0834 | −0.0321 | 0.1558 | 0.049* | |
C7 | 0.3768 (4) | 0.8568 (4) | 0.5276 (4) | 0.0250 (8) | |
C8 | 0.4315 (5) | 0.8961 (4) | 0.3551 (4) | 0.0249 (8) | |
H8A | 0.5501 | 0.9299 | 0.3119 | 0.030* | |
H8B | 0.3672 | 0.9835 | 0.3034 | 0.030* | |
C9 | 0.4036 (4) | 0.7508 (4) | 0.3268 (4) | 0.0223 (7) | |
C10 | 0.4320 (5) | 0.7938 (4) | 0.1559 (4) | 0.0266 (8) | |
H10A | 0.3629 | 0.8829 | 0.1161 | 0.032* | |
H10B | 0.5492 | 0.8290 | 0.1014 | 0.032* | |
C11 | 0.3911 (4) | 0.6584 (4) | 0.1209 (4) | 0.0270 (8) | |
C12 | 0.2187 (4) | 0.6843 (4) | 0.4158 (4) | 0.0263 (8) | |
Co1 | 0.59943 (6) | 0.58334 (5) | 0.56194 (6) | 0.02524 (19) | |
N1 | 0.2251 (4) | 0.4365 (4) | −0.0025 (4) | 0.0354 (8) | |
H1A | 0.2812 | 0.5164 | −0.0128 | 0.043* | |
O2 | 0.4294 (3) | 0.7270 (3) | 0.6167 (3) | 0.0266 (6) | |
O3 | 0.2835 (3) | 0.9445 (3) | 0.5786 (3) | 0.0369 (7) | |
O4 | 0.5154 (3) | 0.6288 (2) | 0.3798 (3) | 0.0197 (5) | |
O5 | 0.1040 (3) | 0.7783 (3) | 0.3903 (4) | 0.0434 (8) | |
O6 | 0.1985 (3) | 0.5377 (3) | 0.5056 (3) | 0.0258 (6) | |
O7 | 0.3682 (4) | 0.6921 (3) | −0.0064 (3) | 0.0396 (7) | |
O8 | 0.3806 (3) | 0.5148 (3) | 0.2227 (3) | 0.0310 (6) | |
O1W | 0.7770 (3) | 0.7550 (3) | 0.4890 (4) | 0.0345 (7) | |
H1W | 0.8825 (16) | 0.746 (5) | 0.474 (5) | 0.052* | |
H2W | 0.751 (5) | 0.842 (3) | 0.497 (5) | 0.052* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.036 (2) | 0.029 (2) | 0.036 (2) | 0.0009 (17) | −0.0031 (18) | −0.0102 (18) |
C2 | 0.035 (2) | 0.041 (2) | 0.039 (2) | −0.0038 (18) | −0.0100 (19) | −0.021 (2) |
C3 | 0.0242 (19) | 0.026 (2) | 0.040 (2) | −0.0006 (15) | −0.0032 (17) | −0.0178 (18) |
C4 | 0.044 (2) | 0.028 (2) | 0.040 (2) | −0.0026 (18) | −0.013 (2) | −0.0076 (19) |
C5 | 0.048 (3) | 0.038 (2) | 0.049 (3) | −0.001 (2) | −0.019 (2) | −0.023 (2) |
C6 | 0.032 (2) | 0.037 (2) | 0.055 (3) | −0.0074 (18) | −0.005 (2) | −0.023 (2) |
C7 | 0.0204 (18) | 0.0183 (18) | 0.039 (2) | −0.0032 (14) | −0.0100 (16) | −0.0130 (16) |
C8 | 0.0284 (19) | 0.0135 (17) | 0.036 (2) | 0.0015 (14) | −0.0163 (16) | −0.0085 (16) |
C9 | 0.0240 (18) | 0.0166 (17) | 0.0276 (19) | 0.0044 (14) | −0.0131 (15) | −0.0073 (15) |
C10 | 0.0290 (19) | 0.0185 (18) | 0.031 (2) | 0.0011 (15) | −0.0143 (16) | −0.0046 (16) |
C11 | 0.0259 (19) | 0.024 (2) | 0.033 (2) | 0.0018 (15) | −0.0118 (16) | −0.0113 (17) |
C12 | 0.0257 (19) | 0.025 (2) | 0.032 (2) | −0.0001 (15) | −0.0097 (16) | −0.0141 (17) |
Co1 | 0.0252 (3) | 0.0191 (3) | 0.0329 (3) | 0.00227 (19) | −0.0123 (2) | −0.0098 (2) |
N1 | 0.0302 (18) | 0.0284 (18) | 0.052 (2) | −0.0042 (14) | −0.0089 (16) | −0.0214 (17) |
O2 | 0.0298 (14) | 0.0190 (13) | 0.0310 (14) | 0.0063 (10) | −0.0096 (11) | −0.0109 (11) |
O3 | 0.0383 (16) | 0.0238 (14) | 0.0491 (18) | 0.0085 (12) | −0.0081 (13) | −0.0199 (13) |
O4 | 0.0202 (12) | 0.0143 (11) | 0.0268 (13) | 0.0037 (9) | −0.0114 (10) | −0.0080 (10) |
O5 | 0.0209 (14) | 0.0209 (14) | 0.075 (2) | 0.0064 (11) | −0.0141 (14) | −0.0082 (14) |
O6 | 0.0220 (13) | 0.0151 (12) | 0.0352 (15) | −0.0006 (10) | −0.0063 (11) | −0.0067 (11) |
O7 | 0.063 (2) | 0.0270 (15) | 0.0338 (16) | −0.0007 (13) | −0.0263 (15) | −0.0089 (13) |
O8 | 0.0460 (16) | 0.0192 (13) | 0.0326 (15) | 0.0016 (11) | −0.0199 (13) | −0.0094 (12) |
O1W | 0.0210 (13) | 0.0172 (13) | 0.0636 (19) | 0.0006 (10) | −0.0119 (14) | −0.0152 (13) |
C1—N1 | 1.336 (5) | C9—O4 | 1.421 (4) |
C1—C2 | 1.354 (5) | C9—C10 | 1.525 (5) |
C1—H1 | 0.9300 | C9—C12 | 1.556 (5) |
C2—C3 | 1.392 (5) | C10—C11 | 1.519 (5) |
C2—H2 | 0.9300 | C10—H10A | 0.9700 |
C3—C4 | 1.372 (6) | C10—H10B | 0.9700 |
C3—C6 | 1.505 (5) | C11—O7 | 1.243 (4) |
C4—C5 | 1.376 (5) | C11—O8 | 1.279 (4) |
C4—H4 | 0.9300 | C12—O5 | 1.240 (4) |
C5—N1 | 1.328 (5) | C12—O6 | 1.264 (4) |
C5—H5 | 0.9300 | Co1—O2 | 1.968 (2) |
C6—C6i | 1.512 (8) | Co1—O8ii | 2.002 (2) |
C6—H6A | 0.9700 | Co1—O4 | 2.004 (2) |
C6—H6B | 0.9700 | Co1—O1W | 2.005 (2) |
C7—O3 | 1.231 (4) | Co1—O4ii | 2.031 (2) |
C7—O2 | 1.289 (4) | Co1—O6ii | 2.037 (2) |
C7—C8 | 1.529 (5) | N1—H1A | 0.8600 |
C8—C9 | 1.530 (4) | O1W—H1W | 0.84 (3) |
C8—H8A | 0.9700 | O1W—H2W | 0.84 (3) |
C8—H8B | 0.9700 | ||
N1—C1—C2 | 120.3 (4) | C9—C10—H10A | 108.6 |
N1—C1—H1 | 119.9 | C11—C10—H10B | 108.6 |
C2—C1—H1 | 119.9 | C9—C10—H10B | 108.6 |
C1—C2—C3 | 120.4 (4) | H10A—C10—H10B | 107.6 |
C1—C2—H2 | 119.8 | O7—C11—O8 | 122.4 (3) |
C3—C2—H2 | 119.8 | O7—C11—C10 | 118.3 (3) |
C4—C3—C2 | 117.5 (3) | O8—C11—C10 | 119.4 (3) |
C4—C3—C6 | 120.9 (4) | O5—C12—O6 | 125.6 (3) |
C2—C3—C6 | 121.5 (4) | O5—C12—C9 | 117.5 (3) |
C3—C4—C5 | 120.4 (4) | O6—C12—C9 | 116.9 (3) |
C3—C4—H4 | 119.8 | O2—Co1—O8ii | 90.26 (10) |
C5—C4—H4 | 119.8 | O2—Co1—O4 | 87.83 (9) |
N1—C5—C4 | 119.8 (4) | O8ii—Co1—O4 | 161.06 (10) |
N1—C5—H5 | 120.1 | O2—Co1—O1W | 88.52 (10) |
C4—C5—H5 | 120.1 | O8ii—Co1—O1W | 93.52 (11) |
C3—C6—C6i | 112.5 (4) | O4—Co1—O1W | 105.27 (11) |
C3—C6—H6A | 109.1 | O2—Co1—O4ii | 109.39 (10) |
C6i—C6—H6A | 109.1 | O8ii—Co1—O4ii | 85.02 (9) |
C3—C6—H6B | 109.1 | O4—Co1—O4ii | 77.87 (10) |
C6i—C6—H6B | 109.1 | O1W—Co1—O4ii | 162.01 (10) |
H6A—C6—H6B | 107.8 | O2—Co1—O6ii | 171.24 (9) |
O3—C7—O2 | 121.8 (3) | O8ii—Co1—O6ii | 90.27 (10) |
O3—C7—C8 | 120.9 (3) | O4—Co1—O6ii | 94.46 (9) |
O2—C7—C8 | 117.2 (3) | O1W—Co1—O6ii | 82.72 (10) |
C7—C8—C9 | 110.9 (3) | O4ii—Co1—O6ii | 79.36 (9) |
C7—C8—H8A | 109.5 | C5—N1—C1 | 121.5 (3) |
C9—C8—H8A | 109.5 | C5—N1—H1A | 119.2 |
C7—C8—H8B | 109.5 | C1—N1—H1A | 119.2 |
C9—C8—H8B | 109.5 | C7—O2—Co1 | 129.2 (2) |
H8A—C8—H8B | 108.0 | C9—O4—Co1 | 125.0 (2) |
O4—C9—C10 | 107.7 (3) | C9—O4—Co1ii | 107.50 (18) |
O4—C9—C8 | 111.2 (3) | Co1—O4—Co1ii | 102.13 (10) |
C10—C9—C8 | 111.7 (3) | C12—O6—Co1ii | 110.2 (2) |
O4—C9—C12 | 108.8 (3) | C11—O8—Co1ii | 133.7 (2) |
C10—C9—C12 | 108.7 (3) | Co1—O1W—H1W | 128 (3) |
C8—C9—C12 | 108.7 (3) | Co1—O1W—H2W | 121 (3) |
C11—C10—C9 | 114.5 (3) | H1W—O1W—H2W | 109 (5) |
C11—C10—H10A | 108.6 |
Symmetry codes: (i) −x, −y, −z; (ii) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O7 | 0.86 | 1.86 | 2.714 (4) | 169 |
O1W—H1W···O5iii | 0.84 (3) | 1.77 (2) | 2.593 (3) | 163 (4) |
O1W—H2W···O3iv | 0.84 (3) | 1.82 (2) | 2.608 (3) | 154 (4) |
Symmetry codes: (iii) x+1, y, z; (iv) −x+1, −y+2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | (C12H14N2)[Co2(C6H4O7)2(H2O)2] |
Mr | 716.33 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 8.2975 (6), 9.2340 (6), 9.9647 (7) |
α, β, γ (°) | 65.242 (1), 72.803 (1), 85.004 (1) |
V (Å3) | 661.72 (8) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.34 |
Crystal size (mm) | 0.25 × 0.20 × 0.18 |
Data collection | |
Diffractometer | Bruker APEXII area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2004) |
Tmin, Tmax | 0.730, 0.794 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5003, 2437, 1949 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.606 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.118, 1.15 |
No. of reflections | 2437 |
No. of parameters | 205 |
No. of restraints | 3 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.41, −0.42 |
Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997), SHELXTL (Bruker, 2004).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O7 | 0.86 | 1.86 | 2.714 (4) | 169.3 |
O1W—H1W···O5i | 0.84 (3) | 1.773 (17) | 2.593 (3) | 163 (4) |
O1W—H2W···O3ii | 0.84 (3) | 1.82 (2) | 2.608 (3) | 154 (4) |
Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y+2, −z+1. |
The prevalent citric acid has been widely known for its abundance in physiological fluids(Srere, 1972). Binuclear iron complexes were studied long ago by the pioneer Marray (Marray, 1974). The structures and properties of such systems depend on the coordination and geometric preferences of both the central metals ions and bridging building blocks as well as the influence of weaker non-covalent interactions, such as hydrogen bonds and π-π stacking interactions. In this paper, we report the synthesis and crystal structure of the title complex,(I).
The anionic complex I is an edge-shared bi-octahedral dimer with centro-symmetric structure, in which the two iron atoms are bridged by two alkoxide oxygen atoms of the fully deprotonated citrate ligands. All of the carboxylate groups coordinate in a mono-dentate fashion to terminal positions, and two water molecules complete the slightly distorted octahedral coordination spheres. This structure is very similar to those reported by Shweky and coworkers (Shweky et al., 1994). The chelating of the deprotonated hydroxyl and carboxylic groups of the citrate ion leads to two six-membered rings and one five-membered ring, perhaps stabilizing the overall dimeric moiety. Fe—O bond lengths range from 1.9682 (2) -2.0294 (19) Å. Supramolecular interactions (O—H···O and N—H···O) stabilize the architecture(Table 1).