metal-organic compounds
Triaqua[2,2′-(propane-1,3-diyl)bis(5-carboxy-1H-imidazole-4-carboxylato-κ2N3,O4)]calcium(II) tetrahydrate
aDepartment of Chemistry and Chemical Engineering, Henan University of Urban Construction, Pingdingshan, Henan, 467044, People's Republic of China
*Correspondence e-mail: dlz701106@126.com
In the title compound, [Ca(C13H10N4O8)(H2O)3]·4H2O, the CaII ion is hepta-coordinated by two N atoms and two O atoms from a tetradentate 1,3-bis-(1H-imidazole-4,5-dicarboxylate) propane dianion and three water O atoms, giving a distorted pentagonal–bipyramidal coordination environment. The Ca—O bond lengths are in the range 2.354 (3)–2.453 (2) Å, while the Ca—N bond lengths are in the range 2.523 (2)–2.548 (2) Å. An intramolecular O—H⋯O hydrogen bond between the carboxy and carboxylate groups stabilizes the molecular configuration. A three-dimensional network of N—H⋯O and O—H⋯O hydrogen bonds help to stabilize the crystal packing.
Related literature
For complexes based on 4,5-imidazoledicarboxylic acid, see: Zhu et al. (2010); Lu et al. (2010). For complexes based on 2-methyl-1H-imidazole-4,5-dicarboxylic acid, see: Song et al. (2010). For complexes based on 2-ethyl-1H-imidazole-4,5-dicarboxylic acid, see: Zhang et al. (2010); Wang et al. (2008). For complexes based on 2-propyl-1H-imidazole-4,5-dicarboxylic acid, see: Feng et al. (2010); Liu et al. (2010). For complexes based on 2-(hydroxymethyl)-1H-imidazole-4,5-dicarboxylic acid, see: Zheng et al. (2011). For complexes based on 2-phenyl-1H-imidazole-4,5-dicarboxylic acid, see: Zhu et al. (2011). For complexes based on 2-pyridyl-1H-imidazole-4,5-dicarboxylic acid, see: Li et al. (2009, 2010).
Experimental
Crystal data
|
Refinement
|
Data collection: SMART (Bruker, 2001); cell SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.
Supporting information
10.1107/S1600536812035544/ff2078sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812035544/ff2078Isup2.hkl
A mixture of calcium chloride dihydrate (0.0146 g, 0.1 mmol), 1,3-Bis-(1H-imidazole-4,5-dicarboxylate acid) propane (0.0352 g, 0.1 mmol), pyridine (0.8 ml) and H2O (10 ml) was sealed into a Teflon-lined stainless autoclave and heated at 413 K for 3 days. The bomb was allowed to cool to room temperature gradually and colorless block crystals of (I) were obtained.
H atoms attached to N and O atoms were located in a difference Fourier maps and refined as riding in their as-found relative positions, with Uiso(H) = 1.5Ueq(O,N). Other H atoms were positioned geometrically with C—H = 0.93 and 0.97 Å for aromatic and methyl H, and constrained to ride on their parent atoms with Uiso(H) = 1.2Ueq(C).
Data collection: SMART (Bruker, 2001); cell
SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).Fig. 1. The molecular structure of the title compound, showing the atomic numbering and 30% probability displacement ellipsoids. |
[Ca(C13H10N4O8)(H2O3)3]·4H2O | Z = 2 |
Mr = 516.44 | F(000) = 540 |
Triclinic, P1 | Dx = 1.571 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.7794 (12) Å | Cell parameters from 1354 reflections |
b = 12.172 (2) Å | θ = 2.5–23.1° |
c = 13.718 (2) Å | µ = 0.37 mm−1 |
α = 98.776 (2)° | T = 296 K |
β = 102.420 (2)° | Block, colourless |
γ = 90.444 (2)° | 0.16 × 0.16 × 0.14 mm |
V = 1091.6 (3) Å3 |
Bruker SMART CCD diffractometer | 4031 independent reflections |
Radiation source: X-ray tube | 2595 reflections with I > 2σ(I) |
Phi and omega scans monochromator | Rint = 0.040 |
ϕ and ω scans | θmax = 25.5°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | h = −8→8 |
Tmin = 0.943, Tmax = 0.950 | k = −14→14 |
8318 measured reflections | l = −16→16 |
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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.098 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0327P)2 + 0.2508P] where P = (Fo2 + 2Fc2)/3 |
4031 reflections | (Δ/σ)max < 0.001 |
344 parameters | Δρmax = 0.24 e Å−3 |
14 restraints | Δρmin = −0.32 e Å−3 |
[Ca(C13H10N4O8)(H2O3)3]·4H2O | γ = 90.444 (2)° |
Mr = 516.44 | V = 1091.6 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.7794 (12) Å | Mo Kα radiation |
b = 12.172 (2) Å | µ = 0.37 mm−1 |
c = 13.718 (2) Å | T = 296 K |
α = 98.776 (2)° | 0.16 × 0.16 × 0.14 mm |
β = 102.420 (2)° |
Bruker SMART CCD diffractometer | 4031 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | 2595 reflections with I > 2σ(I) |
Tmin = 0.943, Tmax = 0.950 | Rint = 0.040 |
8318 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 14 restraints |
wR(F2) = 0.098 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 0.24 e Å−3 |
4031 reflections | Δρmin = −0.32 e Å−3 |
344 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 | ||
Ca1 | 0.34365 (10) | 0.10418 (5) | 0.30772 (5) | 0.02902 (18) | |
O1 | 0.4347 (3) | 0.17772 (16) | 0.48632 (15) | 0.0339 (5) | |
O2 | 0.4429 (3) | 0.31736 (17) | 0.61241 (15) | 0.0404 (6) | |
O3 | 0.3556 (3) | 0.51623 (17) | 0.63708 (15) | 0.0381 (6) | |
H3 | 0.3814 | 0.4502 | 0.6309 | 0.046* | |
O4 | 0.2140 (3) | 0.63567 (16) | 0.53912 (16) | 0.0375 (6) | |
O5 | 0.2380 (4) | 0.07270 (19) | −0.21218 (17) | 0.0498 (7) | |
O6 | 0.1955 (4) | −0.08158 (19) | −0.14977 (16) | 0.0489 (7) | |
H6 | 0.1955 | −0.0984 | −0.0941 | 0.059* | |
O7 | 0.2100 (3) | −0.14045 (16) | 0.01549 (16) | 0.0406 (6) | |
O8 | 0.2447 (3) | −0.05781 (16) | 0.17484 (16) | 0.0379 (6) | |
O9 | 0.0695 (4) | 0.03304 (19) | 0.36754 (17) | 0.0414 (6) | |
O10 | 0.5458 (4) | −0.0399 (2) | 0.36928 (19) | 0.0464 (6) | |
O11 | 0.6575 (4) | 0.1900 (2) | 0.31047 (19) | 0.0432 (6) | |
O12 | 0.9370 (5) | 0.1553 (2) | 0.5324 (2) | 0.0604 (8) | |
O13 | 0.3808 (5) | 0.3595 (3) | 0.8695 (2) | 0.0670 (8) | |
O14 | −0.0383 (4) | 0.6606 (2) | 0.2953 (2) | 0.0514 (7) | |
O15 | 0.2804 (4) | 0.7234 (2) | 0.21968 (19) | 0.0511 (7) | |
N1 | 0.2148 (4) | 0.29607 (19) | 0.34785 (17) | 0.0282 (6) | |
N2 | 0.1366 (4) | 0.47230 (19) | 0.36829 (18) | 0.0278 (6) | |
H2 | 0.0902 | 0.5349 | 0.3542 | 0.033* | |
N3 | 0.2951 (4) | 0.14885 (19) | 0.12881 (17) | 0.0296 (6) | |
N4 | 0.2984 (4) | 0.1999 (2) | −0.01827 (18) | 0.0322 (6) | |
H4 | 0.3066 | 0.2417 | −0.0626 | 0.039* | |
C1 | 0.2844 (4) | 0.3426 (2) | 0.4475 (2) | 0.0246 (7) | |
C2 | 0.2362 (4) | 0.4526 (2) | 0.4611 (2) | 0.0248 (7) | |
C3 | 0.1233 (5) | 0.3772 (2) | 0.3025 (2) | 0.0281 (7) | |
C4 | 0.3947 (5) | 0.2746 (2) | 0.5201 (2) | 0.0288 (7) | |
C5 | 0.2698 (4) | 0.5412 (2) | 0.5491 (2) | 0.0282 (7) | |
C6 | 0.0236 (5) | 0.3679 (3) | 0.1933 (2) | 0.0382 (9) | |
H6A | −0.1009 | 0.4076 | 0.1872 | 0.046* | |
H6B | −0.0116 | 0.2902 | 0.1661 | 0.046* | |
C7 | 0.1548 (6) | 0.4140 (3) | 0.1298 (2) | 0.0471 (10) | |
H7A | 0.1873 | 0.4922 | 0.1560 | 0.056* | |
H7B | 0.0775 | 0.4087 | 0.0609 | 0.056* | |
C8 | 0.3519 (5) | 0.3533 (2) | 0.1291 (2) | 0.0421 (9) | |
H8A | 0.4324 | 0.3909 | 0.0926 | 0.050* | |
H8B | 0.4284 | 0.3574 | 0.1981 | 0.050* | |
C9 | 0.3172 (5) | 0.2347 (2) | 0.0816 (2) | 0.0311 (8) | |
C10 | 0.2618 (4) | 0.0566 (2) | 0.0547 (2) | 0.0271 (7) | |
C11 | 0.2642 (4) | 0.0872 (2) | −0.0371 (2) | 0.0300 (7) | |
C12 | 0.2371 (4) | −0.0524 (2) | 0.0845 (2) | 0.0305 (7) | |
C13 | 0.2322 (5) | 0.0231 (3) | −0.1405 (3) | 0.0376 (8) | |
H5W | 0.720 (5) | 0.247 (2) | 0.350 (2) | 0.083 (15)* | |
H6W | 0.726 (5) | 0.167 (3) | 0.266 (2) | 0.080 (15)* | |
H4W | 0.542 (5) | −0.083 (2) | 0.4128 (19) | 0.054 (12)* | |
H3W | 0.612 (5) | −0.067 (3) | 0.325 (2) | 0.070 (14)* | |
H13W | 0.370 (5) | 0.728 (4) | 0.276 (2) | 0.106* | |
H12W | 0.062 (5) | 0.683 (4) | 0.273 (3) | 0.106* | |
H2W | −0.032 (4) | 0.000 (3) | 0.324 (3) | 0.106* | |
H14W | 0.269 (7) | 0.7895 (16) | 0.205 (3) | 0.106* | |
H11W | −0.052 (7) | 0.709 (3) | 0.346 (2) | 0.106* | |
H9W | 0.498 (3) | 0.345 (4) | 0.858 (4) | 0.106* | |
H7W | 0.904 (7) | 0.102 (3) | 0.560 (3) | 0.106* | |
H10W | 0.280 (5) | 0.360 (4) | 0.820 (2) | 0.106* | |
H1W | 0.026 (6) | 0.074 (3) | 0.415 (2) | 0.106* | |
H8W | 0.844 (5) | 0.197 (3) | 0.509 (3) | 0.106* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ca1 | 0.0426 (4) | 0.0223 (3) | 0.0218 (4) | 0.0014 (3) | 0.0072 (3) | 0.0021 (3) |
O1 | 0.0529 (15) | 0.0228 (11) | 0.0259 (13) | 0.0087 (10) | 0.0080 (11) | 0.0040 (9) |
O2 | 0.0593 (16) | 0.0390 (13) | 0.0192 (12) | 0.0103 (11) | 0.0017 (11) | 0.0028 (10) |
O3 | 0.0533 (15) | 0.0305 (12) | 0.0266 (13) | 0.0024 (11) | 0.0052 (11) | −0.0029 (10) |
O4 | 0.0464 (14) | 0.0253 (12) | 0.0377 (14) | 0.0017 (11) | 0.0076 (11) | −0.0020 (10) |
O5 | 0.0657 (18) | 0.0576 (16) | 0.0262 (14) | −0.0151 (13) | 0.0167 (12) | −0.0011 (12) |
O6 | 0.0706 (18) | 0.0461 (15) | 0.0284 (14) | −0.0049 (13) | 0.0158 (12) | −0.0062 (11) |
O7 | 0.0509 (15) | 0.0258 (12) | 0.0396 (14) | 0.0010 (11) | 0.0072 (12) | −0.0082 (10) |
O8 | 0.0527 (15) | 0.0292 (12) | 0.0305 (14) | 0.0000 (11) | 0.0054 (11) | 0.0054 (10) |
O9 | 0.0456 (16) | 0.0444 (15) | 0.0321 (15) | −0.0064 (12) | 0.0074 (12) | 0.0017 (11) |
O10 | 0.0652 (18) | 0.0437 (15) | 0.0390 (16) | 0.0190 (13) | 0.0217 (14) | 0.0182 (13) |
O11 | 0.0504 (17) | 0.0382 (14) | 0.0371 (16) | −0.0096 (12) | 0.0149 (13) | −0.0127 (12) |
O12 | 0.087 (2) | 0.0513 (18) | 0.0465 (17) | 0.0267 (15) | 0.0146 (15) | 0.0186 (13) |
O13 | 0.075 (2) | 0.075 (2) | 0.058 (2) | −0.0009 (19) | 0.0211 (17) | 0.0238 (16) |
O14 | 0.0622 (18) | 0.0382 (15) | 0.0601 (19) | 0.0109 (14) | 0.0211 (15) | 0.0165 (12) |
O15 | 0.0573 (18) | 0.0431 (15) | 0.0495 (17) | −0.0013 (14) | −0.0018 (13) | 0.0165 (13) |
N1 | 0.0368 (16) | 0.0250 (13) | 0.0210 (14) | 0.0012 (12) | 0.0037 (12) | 0.0015 (11) |
N2 | 0.0352 (16) | 0.0204 (13) | 0.0263 (15) | 0.0020 (11) | 0.0053 (12) | 0.0015 (11) |
N3 | 0.0404 (17) | 0.0260 (14) | 0.0195 (14) | −0.0014 (12) | 0.0030 (12) | −0.0004 (11) |
N4 | 0.0396 (17) | 0.0356 (15) | 0.0225 (15) | −0.0009 (13) | 0.0082 (12) | 0.0063 (12) |
C1 | 0.0309 (18) | 0.0224 (16) | 0.0207 (17) | 0.0006 (13) | 0.0073 (14) | 0.0015 (13) |
C2 | 0.0263 (17) | 0.0258 (16) | 0.0215 (16) | 0.0012 (13) | 0.0061 (14) | 0.0004 (13) |
C3 | 0.0319 (19) | 0.0247 (16) | 0.0279 (18) | 0.0013 (14) | 0.0057 (15) | 0.0057 (14) |
C4 | 0.0320 (19) | 0.0275 (17) | 0.0275 (19) | −0.0011 (14) | 0.0081 (15) | 0.0045 (14) |
C5 | 0.0250 (18) | 0.0281 (18) | 0.0306 (19) | −0.0040 (14) | 0.0071 (15) | 0.0005 (14) |
C6 | 0.050 (2) | 0.0294 (18) | 0.0276 (19) | 0.0061 (16) | −0.0030 (16) | −0.0017 (15) |
C7 | 0.086 (3) | 0.0274 (18) | 0.0260 (19) | 0.0087 (19) | 0.0066 (19) | 0.0060 (15) |
C8 | 0.066 (3) | 0.0328 (19) | 0.0253 (19) | −0.0139 (18) | 0.0116 (18) | −0.0024 (15) |
C9 | 0.042 (2) | 0.0301 (17) | 0.0214 (18) | −0.0005 (15) | 0.0074 (15) | 0.0034 (14) |
C10 | 0.0255 (17) | 0.0289 (16) | 0.0253 (18) | 0.0015 (14) | 0.0050 (14) | 0.0001 (14) |
C11 | 0.0282 (18) | 0.0314 (18) | 0.0276 (19) | −0.0001 (14) | 0.0074 (15) | −0.0058 (14) |
C12 | 0.0256 (18) | 0.0288 (17) | 0.034 (2) | 0.0036 (14) | 0.0026 (15) | 0.0004 (15) |
C13 | 0.035 (2) | 0.046 (2) | 0.030 (2) | −0.0069 (17) | 0.0116 (16) | −0.0051 (17) |
Ca1—O11 | 2.354 (3) | O14—H11W | 0.860 (10) |
Ca1—O10 | 2.379 (3) | O15—H13W | 0.864 (10) |
Ca1—O9 | 2.393 (3) | O15—H14W | 0.859 (10) |
Ca1—O1 | 2.420 (2) | N1—C3 | 1.333 (3) |
Ca1—O8 | 2.453 (2) | N1—C1 | 1.377 (3) |
Ca1—N1 | 2.523 (2) | N2—C3 | 1.345 (3) |
Ca1—N3 | 2.548 (2) | N2—C2 | 1.364 (3) |
Ca1—H3W | 2.78 (3) | N2—H2 | 0.8600 |
O1—C4 | 1.253 (3) | N3—C9 | 1.333 (4) |
O2—C4 | 1.265 (3) | N3—C10 | 1.376 (3) |
O3—C5 | 1.304 (3) | N4—C9 | 1.349 (3) |
O3—H3 | 0.8200 | N4—C11 | 1.366 (4) |
O4—C5 | 1.232 (3) | N4—H4 | 0.8600 |
O5—C13 | 1.237 (4) | C1—C2 | 1.375 (4) |
O6—C13 | 1.279 (4) | C1—C4 | 1.475 (4) |
O6—H6 | 0.8200 | C2—C5 | 1.467 (4) |
O7—C12 | 1.301 (3) | C3—C6 | 1.492 (4) |
O8—C12 | 1.242 (3) | C6—C7 | 1.529 (5) |
O9—H2W | 0.861 (10) | C6—H6A | 0.9700 |
O9—H1W | 0.859 (10) | C6—H6B | 0.9700 |
O10—H4W | 0.859 (10) | C7—C8 | 1.533 (5) |
O10—H3W | 0.855 (10) | C7—H7A | 0.9700 |
O11—H5W | 0.855 (10) | C7—H7B | 0.9700 |
O11—H6W | 0.858 (10) | C8—C9 | 1.486 (4) |
O12—H7W | 0.858 (10) | C8—H8A | 0.9700 |
O12—H8W | 0.852 (10) | C8—H8B | 0.9700 |
O13—H9W | 0.856 (10) | C10—C11 | 1.370 (4) |
O13—H10W | 0.856 (10) | C10—C12 | 1.465 (4) |
O14—H12W | 0.862 (10) | C11—C13 | 1.482 (4) |
O11—Ca1—O10 | 83.73 (10) | C10—N3—Ca1 | 114.06 (19) |
O11—Ca1—O9 | 159.80 (9) | C9—N4—C11 | 108.4 (2) |
O10—Ca1—O9 | 89.24 (9) | C9—N4—H4 | 125.8 |
O11—Ca1—O1 | 81.93 (8) | C11—N4—H4 | 125.8 |
O10—Ca1—O1 | 79.49 (8) | C2—C1—N1 | 109.7 (3) |
O9—Ca1—O1 | 78.17 (8) | C2—C1—C4 | 130.5 (3) |
O11—Ca1—O8 | 114.31 (8) | N1—C1—C4 | 119.9 (2) |
O10—Ca1—O8 | 75.75 (8) | N2—C2—C1 | 105.6 (2) |
O9—Ca1—O8 | 81.96 (8) | N2—C2—C5 | 120.8 (3) |
O1—Ca1—O8 | 148.28 (7) | C1—C2—C5 | 133.6 (3) |
O11—Ca1—N1 | 87.84 (8) | N1—C3—N2 | 110.8 (3) |
O10—Ca1—N1 | 146.79 (9) | N1—C3—C6 | 126.0 (3) |
O9—Ca1—N1 | 87.76 (8) | N2—C3—C6 | 123.1 (3) |
O1—Ca1—N1 | 67.53 (7) | O1—C4—O2 | 124.0 (3) |
O8—Ca1—N1 | 136.25 (8) | O1—C4—C1 | 117.8 (3) |
O11—Ca1—N3 | 77.65 (9) | O2—C4—C1 | 118.2 (3) |
O10—Ca1—N3 | 124.49 (9) | O4—C5—O3 | 121.7 (3) |
O9—Ca1—N3 | 121.47 (8) | O4—C5—C2 | 120.1 (3) |
O1—Ca1—N3 | 145.79 (7) | O3—C5—C2 | 118.3 (3) |
O8—Ca1—N3 | 65.91 (7) | C3—C6—C7 | 113.7 (3) |
N1—Ca1—N3 | 84.44 (8) | C3—C6—H6A | 108.8 |
O11—Ca1—H3W | 76.2 (7) | C7—C6—H6A | 108.8 |
O10—Ca1—H3W | 16.9 (5) | C3—C6—H6B | 108.8 |
O9—Ca1—H3W | 101.5 (6) | C7—C6—H6B | 108.8 |
O1—Ca1—H3W | 93.4 (6) | H6A—C6—H6B | 107.7 |
O8—Ca1—H3W | 66.6 (7) | C6—C7—C8 | 113.6 (3) |
N1—Ca1—H3W | 156.9 (8) | C6—C7—H7A | 108.9 |
N3—Ca1—H3W | 107.8 (5) | C8—C7—H7A | 108.9 |
C4—O1—Ca1 | 121.77 (19) | C6—C7—H7B | 108.9 |
C5—O3—H3 | 109.5 | C8—C7—H7B | 108.9 |
C13—O6—H6 | 109.5 | H7A—C7—H7B | 107.7 |
C12—O8—Ca1 | 121.90 (19) | C9—C8—C7 | 112.8 (3) |
Ca1—O9—H2W | 118 (3) | C9—C8—H8A | 109.0 |
Ca1—O9—H1W | 119 (3) | C7—C8—H8A | 109.0 |
H2W—O9—H1W | 109 (4) | C9—C8—H8B | 109.0 |
Ca1—O10—H4W | 136 (2) | C7—C8—H8B | 109.0 |
Ca1—O10—H3W | 109 (3) | H8A—C8—H8B | 107.8 |
H4W—O10—H3W | 112 (4) | N3—C9—N4 | 110.5 (2) |
Ca1—O11—H5W | 130 (3) | N3—C9—C8 | 126.2 (3) |
Ca1—O11—H6W | 121 (3) | N4—C9—C8 | 123.3 (3) |
H5W—O11—H6W | 109 (4) | C11—C10—N3 | 110.0 (3) |
H7W—O12—H8W | 118 (5) | C11—C10—C12 | 131.7 (3) |
H9W—O13—H10W | 120 (5) | N3—C10—C12 | 118.3 (3) |
H12W—O14—H11W | 108 (4) | N4—C11—C10 | 105.5 (3) |
H13W—O15—H14W | 106 (4) | N4—C11—C13 | 122.0 (3) |
C3—N1—C1 | 105.5 (2) | C10—C11—C13 | 132.5 (3) |
C3—N1—Ca1 | 141.1 (2) | O8—C12—O7 | 122.1 (3) |
C1—N1—Ca1 | 112.41 (17) | O8—C12—C10 | 119.0 (3) |
C3—N2—C2 | 108.4 (2) | O7—C12—C10 | 118.9 (3) |
C3—N2—H2 | 125.8 | O5—C13—O6 | 124.0 (3) |
C2—N2—H2 | 125.8 | O5—C13—C11 | 119.3 (3) |
C9—N3—C10 | 105.6 (2) | O6—C13—C11 | 116.7 (3) |
C9—N3—Ca1 | 139.60 (19) | ||
O11—Ca1—O1—C4 | 86.6 (2) | Ca1—N1—C3—N2 | −165.8 (2) |
O10—Ca1—O1—C4 | 171.7 (2) | C1—N1—C3—C6 | 179.7 (3) |
O9—Ca1—O1—C4 | −96.9 (2) | Ca1—N1—C3—C6 | 12.4 (5) |
O8—Ca1—O1—C4 | −149.2 (2) | C2—N2—C3—N1 | −1.6 (3) |
N1—Ca1—O1—C4 | −4.4 (2) | C2—N2—C3—C6 | −179.9 (3) |
N3—Ca1—O1—C4 | 33.0 (3) | Ca1—O1—C4—O2 | −178.5 (2) |
O11—Ca1—O8—C12 | −54.5 (2) | Ca1—O1—C4—C1 | 1.6 (4) |
O10—Ca1—O8—C12 | −130.7 (2) | C2—C1—C4—O1 | −173.7 (3) |
O9—Ca1—O8—C12 | 138.0 (2) | N1—C1—C4—O1 | 5.3 (4) |
O1—Ca1—O8—C12 | −170.5 (2) | C2—C1—C4—O2 | 6.3 (5) |
N1—Ca1—O8—C12 | 59.8 (3) | N1—C1—C4—O2 | −174.7 (3) |
N3—Ca1—O8—C12 | 8.2 (2) | N2—C2—C5—O4 | −2.5 (4) |
O11—Ca1—N1—C3 | 90.9 (3) | C1—C2—C5—O4 | 177.9 (3) |
O10—Ca1—N1—C3 | 166.0 (3) | N2—C2—C5—O3 | 176.2 (3) |
O9—Ca1—N1—C3 | −108.8 (3) | C1—C2—C5—O3 | −3.4 (5) |
O1—Ca1—N1—C3 | 173.1 (3) | N1—C3—C6—C7 | −99.3 (4) |
O8—Ca1—N1—C3 | −32.8 (4) | N2—C3—C6—C7 | 78.7 (4) |
N3—Ca1—N1—C3 | 13.2 (3) | C3—C6—C7—C8 | 61.5 (3) |
O11—Ca1—N1—C1 | −75.75 (19) | C6—C7—C8—C9 | 63.7 (4) |
O10—Ca1—N1—C1 | −0.7 (3) | C10—N3—C9—N4 | 0.2 (3) |
O9—Ca1—N1—C1 | 84.53 (19) | Ca1—N3—C9—N4 | 169.1 (2) |
O1—Ca1—N1—C1 | 6.41 (18) | C10—N3—C9—C8 | 178.6 (3) |
O8—Ca1—N1—C1 | 160.45 (17) | Ca1—N3—C9—C8 | −12.6 (5) |
N3—Ca1—N1—C1 | −153.55 (19) | C11—N4—C9—N3 | −0.4 (4) |
O11—Ca1—N3—C9 | −51.1 (3) | C11—N4—C9—C8 | −178.8 (3) |
O10—Ca1—N3—C9 | −124.4 (3) | C7—C8—C9—N3 | −89.7 (4) |
O9—Ca1—N3—C9 | 121.9 (3) | C7—C8—C9—N4 | 88.5 (4) |
O1—Ca1—N3—C9 | 3.7 (4) | C9—N3—C10—C11 | 0.0 (3) |
O8—Ca1—N3—C9 | −175.1 (3) | Ca1—N3—C10—C11 | −172.1 (2) |
N1—Ca1—N3—C9 | 37.9 (3) | C9—N3—C10—C12 | 178.3 (3) |
O11—Ca1—N3—C10 | 117.1 (2) | Ca1—N3—C10—C12 | 6.3 (3) |
O10—Ca1—N3—C10 | 43.8 (2) | C9—N4—C11—C10 | 0.4 (3) |
O9—Ca1—N3—C10 | −69.9 (2) | C9—N4—C11—C13 | 178.7 (3) |
O1—Ca1—N3—C10 | 171.85 (18) | N3—C10—C11—N4 | −0.3 (3) |
O8—Ca1—N3—C10 | −6.88 (19) | C12—C10—C11—N4 | −178.3 (3) |
N1—Ca1—N3—C10 | −153.9 (2) | N3—C10—C11—C13 | −178.3 (3) |
C3—N1—C1—C2 | −0.8 (3) | C12—C10—C11—C13 | 3.7 (6) |
Ca1—N1—C1—C2 | 170.56 (19) | Ca1—O8—C12—O7 | 171.1 (2) |
C3—N1—C1—C4 | 180.0 (3) | Ca1—O8—C12—C10 | −8.2 (4) |
Ca1—N1—C1—C4 | −8.6 (3) | C11—C10—C12—O8 | 178.6 (3) |
C3—N2—C2—C1 | 1.0 (3) | N3—C10—C12—O8 | 0.8 (4) |
C3—N2—C2—C5 | −178.7 (3) | C11—C10—C12—O7 | −0.6 (5) |
N1—C1—C2—N2 | −0.1 (3) | N3—C10—C12—O7 | −178.5 (3) |
C4—C1—C2—N2 | 179.0 (3) | N4—C11—C13—O5 | 0.5 (5) |
N1—C1—C2—C5 | 179.5 (3) | C10—C11—C13—O5 | 178.2 (3) |
C4—C1—C2—C5 | −1.4 (6) | N4—C11—C13—O6 | −178.0 (3) |
C1—N1—C3—N2 | 1.5 (3) | C10—C11—C13—O6 | −0.3 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4···O13i | 0.86 | 1.94 | 2.778 (4) | 164 |
O10—H3W···O5ii | 0.86 (1) | 2.03 (2) | 2.839 (3) | 159 (4) |
O10—H4W···O1iii | 0.86 (1) | 1.91 (1) | 2.768 (3) | 174 (3) |
O9—H2W···O5iv | 0.86 (1) | 1.93 (1) | 2.784 (3) | 172 (4) |
O9—H1W···O12v | 0.86 (1) | 1.97 (1) | 2.829 (4) | 174 (5) |
O14—H11W···O12vi | 0.86 (1) | 2.17 (2) | 2.957 (4) | 152 (4) |
O15—H13W···O2vi | 0.86 (1) | 1.93 (2) | 2.752 (3) | 159 (4) |
O15—H14W···O8vii | 0.86 (1) | 1.97 (1) | 2.824 (3) | 179 (4) |
O13—H9W···O15vi | 0.86 (1) | 2.13 (2) | 2.943 (4) | 158 (4) |
O13—H10W···O14viii | 0.86 (1) | 2.00 (1) | 2.851 (4) | 173 (5) |
O11—H6W···O6ii | 0.86 (1) | 1.94 (2) | 2.770 (3) | 161 (4) |
O11—H5W···O4vi | 0.86 (1) | 1.90 (2) | 2.717 (3) | 160 (4) |
O12—H7W···O9iii | 0.86 (1) | 2.03 (2) | 2.851 (3) | 160 (5) |
N2—H2···O14 | 0.86 | 1.96 | 2.809 (3) | 169 |
O14—H12W···O15 | 0.86 (1) | 1.88 (1) | 2.740 (4) | 177 (5) |
O6—H6···O7 | 0.82 | 1.64 | 2.462 (3) | 175 |
O3—H3···O2 | 0.82 | 1.67 | 2.487 (3) | 176 |
Symmetry codes: (i) x, y, z−1; (ii) −x+1, −y, −z; (iii) −x+1, −y, −z+1; (iv) −x, −y, −z; (v) x−1, y, z; (vi) −x+1, −y+1, −z+1; (vii) x, y+1, z; (viii) −x, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Ca(C13H10N4O8)(H2O3)3]·4H2O |
Mr | 516.44 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 296 |
a, b, c (Å) | 6.7794 (12), 12.172 (2), 13.718 (2) |
α, β, γ (°) | 98.776 (2), 102.420 (2), 90.444 (2) |
V (Å3) | 1091.6 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.37 |
Crystal size (mm) | 0.16 × 0.16 × 0.14 |
Data collection | |
Diffractometer | Bruker SMART CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2001) |
Tmin, Tmax | 0.943, 0.950 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8318, 4031, 2595 |
Rint | 0.040 |
(sin θ/λ)max (Å−1) | 0.606 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.098, 1.01 |
No. of reflections | 4031 |
No. of parameters | 344 |
No. of restraints | 14 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.24, −0.32 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4···O13i | 0.86 | 1.94 | 2.778 (4) | 163.6 |
O10—H3W···O5ii | 0.855 (10) | 2.025 (17) | 2.839 (3) | 159 (4) |
O10—H4W···O1iii | 0.859 (10) | 1.912 (11) | 2.768 (3) | 174 (3) |
O9—H2W···O5iv | 0.861 (10) | 1.929 (12) | 2.784 (3) | 172 (4) |
O9—H1W···O12v | 0.859 (10) | 1.973 (12) | 2.829 (4) | 174 (5) |
O14—H11W···O12vi | 0.860 (10) | 2.17 (2) | 2.957 (4) | 152 (4) |
O15—H13W···O2vi | 0.864 (10) | 1.927 (19) | 2.752 (3) | 159 (4) |
O15—H14W···O8vii | 0.859 (10) | 1.965 (11) | 2.824 (3) | 179 (4) |
O13—H9W···O15vi | 0.856 (10) | 2.13 (2) | 2.943 (4) | 158 (4) |
O13—H10W···O14viii | 0.856 (10) | 1.999 (12) | 2.851 (4) | 173 (5) |
O11—H6W···O6ii | 0.858 (10) | 1.944 (16) | 2.770 (3) | 161 (4) |
O11—H5W···O4vi | 0.855 (10) | 1.897 (17) | 2.717 (3) | 160 (4) |
O12—H7W···O9iii | 0.858 (10) | 2.03 (2) | 2.851 (3) | 160 (5) |
N2—H2···O14 | 0.86 | 1.96 | 2.809 (3) | 168.5 |
O14—H12W···O15 | 0.862 (10) | 1.879 (11) | 2.740 (4) | 177 (5) |
O6—H6···O7 | 0.82 | 1.64 | 2.462 (3) | 175.0 |
O3—H3···O2 | 0.82 | 1.67 | 2.487 (3) | 176.1 |
Symmetry codes: (i) x, y, z−1; (ii) −x+1, −y, −z; (iii) −x+1, −y, −z+1; (iv) −x, −y, −z; (v) x−1, y, z; (vi) −x+1, −y+1, −z+1; (vii) x, y+1, z; (viii) −x, −y+1, −z+1. |
Acknowledgements
We gratefully acknowledge financial support by the Foundation of Henan Key Science and Technology Research (Nos. 122102210414 and 122102210415), the Foundation of Henan Education Committee (No. 2010 A150003 and 2011B150001) and the Foundation of Henan University of Urban Construction (Nos. 2010JYB007 and 2010JYB008).
References
Bruker (2001). SMART and SAINT. Bruker AXS GmbH, Karlsruhe, Germany. Google Scholar
Feng, X., Zhao, J. S., Liu, B., Wang, L. Y., Ng, S., Zhang, G., Wang, J. G., Shi, X. G. & Liu, Y. Y. (2010). Cryst. Growth Des. 10, 1399–1408. Web of Science CSD CrossRef CAS Google Scholar
Li, X., Wu, B. L., Niu, C. Y., Niu, Y. Y. & Zhang, H. Y. (2009). Cryst. Growth Des. 9, 3423–3431. Web of Science CSD CrossRef CAS Google Scholar
Li, X., Wu, B. L., Wang, R. Y., Zhang, H. Y., Niu, C. Y., Niu, Y. Y. & Hou, H. W. (2010). Inorg. Chem. 49, 2600–2613. Web of Science CSD CrossRef CAS PubMed Google Scholar
Liu, X. F., Wang, L. Y., Ma, L. F. & Li, R. F. (2010). Chin. J. Struct. Chem. 29, 280–284. Google Scholar
Lu, W. G., Jiang, L. & Lu, T. B. (2010). Cryst. Growth Des. 10, 4310–4318. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2001). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Song, J. F., Zhou, R. S., Hu, T. P., Zhuo, C. & Wang, B. B. (2010). J. Coord. Chem. 63, 4201–4214. Web of Science CSD CrossRef CAS Google Scholar
Wang, S., Zhang, L. R., Li, G. H., Huo, Q. S. & Liu, Y. L. (2008). CrystEngComm, 10, 1662–1666. Web of Science CSD CrossRef CAS Google Scholar
Zhang, F. W., Li, Z. F., Ge, T. Z., Yao, H. C., Li, G., Lu, H. J. & Zhu, Y. Y. (2010). Inorg. Chem. 49, 3776–3788. Web of Science CSD CrossRef CAS PubMed Google Scholar
Zheng, S. R., Cai, S. L., Pan, M., Fan, J., Xiao, T. T. & Zhang, W. G. (2011). CrystEngComm, 13, 883–888. Web of Science CSD CrossRef CAS Google Scholar
Zhu, Y., Wang, W. Y., Guo, M. W., Li, G. & Lu, H. J. (2011). Inorg. Chem. Commun. 14, 1432–1435. Web of Science CSD CrossRef CAS Google Scholar
Zhu, L. C., Zhao, Y., Yu, S. J. & Zhao, M. M. (2010). Inorg. Chem. Commun. 13, 1299–1303. Web of Science CSD CrossRef CAS Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Aromatic polycarboxylates, especially the N-heterocyclic carboxylates, are excellent candidates for preparing novel metal-organic frameworks, because of their versatile coordination modes and their ability to act as hydrogen-bonding donors and acceptors. For example, 4,5-imidazoledicarboxylate acid (Zhu et al., 2010; Lu et al., 2010), a planar rigid N-heterocyclic dicarboxylate acid, has been widely used to synthesize various coordination polymers because it has very flexible coordination modes, which derives from both imidazole and carboxylate functionality. Recently, in order to inherit the outstanding coordination properties of 4,5-imidazoledicarboxylic group, many 2-position substituent derivatives, such as 2-methyl-1H-imidazole-4,5-dicarboxylic acid (Song et al., 2010), 2-ethyl-1H-imidazole-4,5-dicarboxylic acid (Zhang et al., 2010; Wang et al., 2008), 2-propyl-1H-imidazole-4,5-dicarboxylic acid (Feng et al., 2010; Liu et al., 2010), 2-(hydroxymethyl)-1H-imidazole-4,5-dicarboxylic acid (Zheng et al., 20111), 2-phenyl-1H-imidazole-4,5-dicarboxylic acid (Zhu et al., 2011) and 2-pyridyl-1H-imidazole-4,5-dicarboxylic acid (Li et al., 2009; Li et al., 2010) have been designed and used construct various metal complexes. Here, we want to report a calcium(II) complex, Ca(C13H10O4)(H2O)3].4H2O, based on a new imidazole dicarboxylate ligand, 1,3-Bis-(1H-imidazole-4,5-dicarboxylate acid).
As shown in Fig. 1, the molecule of (I) is a discrete neutral monomer, in which the asymmetric unit comprises a CaII ion, one 1,3-Bis-(1H-imidazole-4,5-dicarboxylate) propane dianion, three coordinated water molecules and four free water molecules. The CaII ion is hepta-coordinated, showing a distorted pentagonal-bipyramidal coordination environment. The equatorial plane is defined by two nitrogen atoms (N1, N3) and two oxygen atoms (O1, O8) from a 1,3-Bis-(1H-imidazole-4,5-dicarboxylate) propane dianion and one water molecule (O10). The axial positions are occupied by two coordinated water molecules with the bond angle of O9—Ca1—O11 being 159.80 (9) °. The Ca—O bond distances are in the range of 2.354 (3) - 2.453 (2) Å, while the Ca—N bond distances are in the range of 2.523 (2) - 2.548 (2) Å. An intramolecular O—H···O hydrogen bond between the carboxy and carboxylate groups stabilizes the molecular configuration. A three-dimensional network of N—H···O and O—H···O hydrogen bonds help to stabilize the crystal packing.