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Pyrazole (pz)-derived ligands can, besides exhibiting a strong coordination ability toward different metal ions, exhibit a great diversity in their coordination geometry and nuclearity, which can be achieved by varying the type and position of the pz substituents. The present study reports the synthesis and crystal structure of two binuclear complexes, namely bis(μ-4-nitro-1H-imidazol-1-ide-5-carboxylato)-κ3N1,O:N2;κ3N2:N1,O-bis[aqua(dimethylformamide-κO)copper(II)], [Cu2(C4HN3O4)2(C3H7NO)2(H2O)2], (II), and bis(μ-4-nitro-1H-imidazol-1-ide-5-carboxylato)-κ2N1,O:N2;κ2N2:N1,O-bis[triaquacobalt(II)] dihydrate, [Co2(C4HN3O4)2(H2O)6]·2H2O, (III). These compounds represent rare examples of metal complexes comprising 3,4-substituted pz derivatives as a bridging ligand and also the first crystal structures of transition-metal complexes with ligands derived from 4-nitropyrazole-3-carboxylic acid. Recently, the crystal structures of the same ligand in the neutral and mixed neutral/anionic forms have been reported. We present here the third form of this ligand, where it is present in a fully deprotonated anionic form within a salt, i.e. ammonium 4-nitropyrazole-3-carboxylate, NH4+·C4H2N3O4−, (I). Single-crystal X-ray diffraction revealed that in the present complexes, the CuII and CoII centres adopt distorted square-pyramidal and octahedral geometries, respectively. In both cases, the N,N′,O-coordinated pz ligand shows simultaneously chelating and bridging coordination modes, leading to the formation of a nearly planar six-membered M2N4 metallocycle. In all three crystal structures, the supramolecular arrangement is controlled by strong hydrogen bonds which primarily engage the carboxylate O atoms as acceptors, while the nitro group adopts the role of an acceptor only in structures with an increased number of donors, as is the case with CoII complex (III). The electrostatic potential, as a descriptor of reactivity, was also calculated in order to examine the changes in ligand electrostatic preferences upon coordination to metal ions.
Supporting information
CCDC references: 1892801; 1892800; 1892799
For all structures, data collection: SAINT (Bruker, 2008); cell refinement: APEX2 (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: ORTEP-3 (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: PLATON (Spek, 2009).
Ammonium 4-nitro-1
H-imidazole-3-carboxylate (I)
top
Crystal data top
NH4+·C4H2N3O4− | Dx = 1.652 Mg m−3 |
Mr = 174.13 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 9913 reflections |
a = 6.6562 (3) Å | θ = 5.9–66.2° |
b = 8.3692 (4) Å | µ = 0.15 mm−1 |
c = 12.5687 (7) Å | T = 200 K |
V = 700.17 (6) Å3 | Prism, colorless |
Z = 4 | 0.3 × 0.18 × 0.15 mm |
F(000) = 360 | |
Data collection top
Bruker ApexII CCD diffractometer | 2534 reflections with I > 2σ(I) |
Radiation source: Incoatec ImS | Rint = 0.028 |
phi and ω scans | θmax = 33.2°, θmin = 2.9° |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −10→10 |
| k = −12→12 |
24957 measured reflections | l = −19→19 |
2667 independent reflections | |
Refinement top
Refinement on F2 | Hydrogen site location: difference Fourier map |
Least-squares matrix: full | All H-atom parameters refined |
R[F2 > 2σ(F2)] = 0.033 | w = 1/[σ2(Fo2) + (0.0476P)2 + 0.0759P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.085 | (Δ/σ)max < 0.001 |
S = 1.11 | Δρmax = 0.36 e Å−3 |
2667 reflections | Δρmin = −0.24 e Å−3 |
133 parameters | Absolute structure: Flack x determined using 1031 quotients [(I+)-(I-)]/[(I+)+(I-)]
(Parsons et al., 2013) |
0 restraints | Absolute structure parameter: −0.1 (2) |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.21035 (16) | 0.42064 (13) | 0.56805 (9) | 0.0275 (2) | |
O2 | 0.10726 (14) | 0.56168 (12) | 0.70720 (7) | 0.02180 (19) | |
O3 | 0.13435 (19) | 0.87520 (15) | 0.60192 (10) | 0.0354 (3) | |
O4 | 0.3726 (2) | 1.05110 (13) | 0.60574 (11) | 0.0417 (3) | |
N1 | 0.73828 (18) | 0.66614 (15) | 0.64740 (10) | 0.0238 (2) | |
N2 | 0.59780 (16) | 0.54844 (13) | 0.64592 (9) | 0.0206 (2) | |
N3 | 0.3119 (2) | 0.91298 (14) | 0.61119 (9) | 0.0255 (2) | |
C1 | 0.42304 (17) | 0.62251 (14) | 0.63434 (9) | 0.0166 (2) | |
C2 | 0.45564 (19) | 0.78917 (14) | 0.62828 (10) | 0.0196 (2) | |
C3 | 0.6606 (2) | 0.81120 (16) | 0.63634 (11) | 0.0243 (2) | |
C4 | 0.23150 (17) | 0.52781 (13) | 0.63563 (9) | 0.0165 (2) | |
N4 | 0.34946 (19) | 0.24629 (13) | 0.39153 (9) | 0.0218 (2) | |
H41 | 0.255 (3) | 0.171 (3) | 0.3816 (17) | 0.034 (5)* | |
H42 | 0.473 (4) | 0.200 (3) | 0.405 (2) | 0.040 (6)* | |
H43 | 0.369 (3) | 0.308 (3) | 0.3307 (17) | 0.030 (5)* | |
H44 | 0.317 (4) | 0.305 (3) | 0.4446 (18) | 0.039 (6)* | |
H1 | 0.858 (4) | 0.640 (3) | 0.662 (2) | 0.048 (7)* | |
H3 | 0.731 (3) | 0.903 (3) | 0.6350 (18) | 0.033 (5)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0263 (5) | 0.0275 (5) | 0.0287 (5) | −0.0087 (4) | 0.0062 (4) | −0.0119 (4) |
O2 | 0.0168 (4) | 0.0285 (4) | 0.0201 (4) | 0.0015 (4) | 0.0022 (3) | −0.0037 (3) |
O3 | 0.0298 (6) | 0.0369 (6) | 0.0395 (6) | 0.0120 (5) | −0.0020 (5) | 0.0040 (5) |
O4 | 0.0628 (9) | 0.0184 (4) | 0.0440 (7) | 0.0031 (5) | 0.0073 (6) | 0.0059 (4) |
N1 | 0.0156 (5) | 0.0278 (5) | 0.0280 (5) | −0.0032 (4) | −0.0017 (4) | −0.0024 (4) |
N2 | 0.0155 (4) | 0.0210 (4) | 0.0253 (5) | 0.0004 (4) | −0.0007 (4) | −0.0016 (4) |
N3 | 0.0366 (6) | 0.0200 (5) | 0.0198 (5) | 0.0068 (4) | 0.0034 (4) | 0.0016 (4) |
C1 | 0.0155 (5) | 0.0168 (4) | 0.0175 (4) | 0.0003 (4) | 0.0006 (4) | −0.0020 (4) |
C2 | 0.0220 (5) | 0.0169 (5) | 0.0200 (5) | 0.0001 (4) | 0.0002 (4) | −0.0004 (4) |
C3 | 0.0242 (6) | 0.0232 (5) | 0.0256 (6) | −0.0070 (5) | 0.0000 (5) | −0.0023 (5) |
C4 | 0.0150 (5) | 0.0176 (5) | 0.0170 (4) | 0.0000 (4) | −0.0006 (4) | 0.0005 (4) |
N4 | 0.0257 (5) | 0.0191 (4) | 0.0206 (5) | 0.0037 (4) | 0.0020 (4) | −0.0001 (4) |
Geometric parameters (Å, º) top
O1—C4 | 1.2432 (15) | C1—C2 | 1.4137 (17) |
O2—C4 | 1.2544 (15) | C1—C4 | 1.5013 (16) |
O3—N3 | 1.2287 (19) | C2—C3 | 1.3802 (19) |
O4—N3 | 1.2264 (16) | C3—H3 | 0.90 (2) |
N1—C3 | 1.3269 (19) | N4—H41 | 0.90 (2) |
N1—N2 | 1.3583 (16) | N4—H42 | 0.92 (3) |
N1—H1 | 0.85 (3) | N4—H43 | 0.93 (2) |
N2—C1 | 1.3261 (16) | N4—H44 | 0.86 (2) |
N3—C2 | 1.4267 (17) | | |
| | | |
C3—N1—N2 | 113.19 (11) | N1—C3—C2 | 105.71 (11) |
C3—N1—H1 | 128.8 (19) | N1—C3—H3 | 125.6 (14) |
N2—N1—H1 | 117.5 (19) | C2—C3—H3 | 128.7 (14) |
C1—N2—N1 | 105.45 (11) | O1—C4—O2 | 125.33 (11) |
O4—N3—O3 | 123.64 (14) | O1—C4—C1 | 118.01 (11) |
O4—N3—C2 | 118.17 (14) | O2—C4—C1 | 116.64 (10) |
O3—N3—C2 | 118.19 (12) | H41—N4—H42 | 110 (2) |
N2—C1—C2 | 109.42 (10) | H41—N4—H43 | 112.1 (18) |
N2—C1—C4 | 119.80 (10) | H42—N4—H43 | 105 (2) |
C2—C1—C4 | 130.68 (10) | H41—N4—H44 | 110 (2) |
C3—C2—C1 | 106.23 (11) | H42—N4—H44 | 109 (2) |
C3—C2—N3 | 125.24 (12) | H43—N4—H44 | 111 (2) |
C1—C2—N3 | 128.44 (12) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H41···N2i | 0.90 (2) | 2.14 (2) | 3.0186 (16) | 165 (2) |
N4—H42···O1ii | 0.92 (3) | 1.91 (3) | 2.8249 (16) | 173 (2) |
N4—H43···O2iii | 0.93 (2) | 1.90 (2) | 2.8343 (14) | 176 (2) |
N4—H44···O1 | 0.86 (2) | 1.96 (2) | 2.8123 (15) | 172 (2) |
N1—H1···O2iv | 0.85 (3) | 1.87 (3) | 2.7132 (16) | 172 (3) |
Symmetry codes: (i) x−1/2, −y+1/2, −z+1; (ii) x+1/2, −y+1/2, −z+1; (iii) −x+1/2, −y+1, z−1/2; (iv) x+1, y, z. |
Bis(µ-4-nitro-1
H-imidazol-1-ide-5-carboxylato)-
κ3N1,
O:
N2;
κ3N2:
N1,
O-bis[aqua(dimethylformamide-
κO)copper(II)] (II)
top
Crystal data top
[Cu2(C4HN3O4)2(C3H7NO)2(H2O)2] | Z = 1 |
Mr = 619.46 | F(000) = 314 |
Triclinic, P1 | Dx = 1.830 Mg m−3 |
a = 5.0863 (6) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.8110 (9) Å | Cell parameters from 7645 reflections |
c = 12.7192 (14) Å | θ = 4.7–66.3° |
α = 83.977 (4)° | µ = 1.97 mm−1 |
β = 88.281 (3)° | T = 200 K |
γ = 82.743 (3)° | Prism, blue |
V = 562.25 (11) Å3 | 0.3 × 0.2 × 0.15 mm |
Data collection top
Bruker ApexII CCD diffractometer | 3680 reflections with I > 2σ(I) |
Radiation source: Incoatec ImS | Rint = 0.033 |
phi and ω scans | θmax = 33.3°, θmin = 3.8° |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −7→7 |
| k = −13→13 |
22093 measured reflections | l = −19→19 |
4331 independent reflections | |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.031 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.072 | w = 1/[σ2(Fo2) + (0.0288P)2 + 0.3153P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max < 0.001 |
4331 reflections | Δρmax = 0.70 e Å−3 |
175 parameters | Δρmin = −0.48 e Å−3 |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cu1 | 0.78303 (3) | 0.36979 (2) | 0.43045 (2) | 0.01790 (6) | |
N1 | 0.4804 (2) | 0.46722 (15) | 0.63364 (10) | 0.0198 (2) | |
N2 | 0.6832 (2) | 0.39226 (14) | 0.58022 (10) | 0.0184 (2) | |
N3 | 0.8354 (3) | 0.25064 (17) | 0.85095 (11) | 0.0281 (3) | |
N4 | 1.2141 (3) | 0.22711 (16) | 0.17290 (11) | 0.0242 (3) | |
O1 | 1.0837 (2) | 0.23625 (14) | 0.49816 (9) | 0.0251 (2) | |
O2 | 1.1996 (3) | 0.09823 (15) | 0.65048 (10) | 0.0357 (3) | |
O3 | 1.0610 (3) | 0.1849 (2) | 0.85699 (12) | 0.0528 (5) | |
O4 | 0.6884 (3) | 0.26862 (17) | 0.92809 (10) | 0.0370 (3) | |
O5 | 0.9580 (2) | 0.35710 (14) | 0.28987 (9) | 0.0263 (2) | |
O6 | 0.5724 (3) | 0.17305 (15) | 0.41168 (13) | 0.0407 (4) | |
H62 | 0.6456 | 0.0850 | 0.4069 | 0.025 (5)* | |
H61 | 0.4499 | 0.1673 | 0.4553 | 0.046 (7)* | |
C1 | 0.8404 (3) | 0.29964 (17) | 0.64834 (11) | 0.0189 (3) | |
C2 | 0.7358 (3) | 0.31558 (18) | 0.74997 (12) | 0.0209 (3) | |
C3 | 0.5105 (3) | 0.42085 (18) | 0.73665 (12) | 0.0220 (3) | |
C4 | 1.0618 (3) | 0.20185 (17) | 0.59886 (12) | 0.0215 (3) | |
C5 | 1.0935 (3) | 0.23715 (19) | 0.26521 (12) | 0.0225 (3) | |
C6 | 1.3893 (5) | 0.0897 (2) | 0.15032 (17) | 0.0440 (5) | |
H6A | 1.3908 | 0.0120 | 0.2115 | 0.066* | |
H6B | 1.5693 | 0.1161 | 0.1359 | 0.066* | |
H6C | 1.3255 | 0.0486 | 0.0884 | 0.066* | |
C7 | 1.1880 (4) | 0.3550 (2) | 0.09044 (14) | 0.0363 (4) | |
H7A | 1.0516 | 0.4355 | 0.1115 | 0.054* | |
H7B | 1.1371 | 0.3191 | 0.0245 | 0.054* | |
H7C | 1.3577 | 0.3966 | 0.0798 | 0.054* | |
H3 | 0.392 (4) | 0.453 (2) | 0.7866 (16) | 0.023 (5)* | |
H5 | 1.107 (4) | 0.144 (2) | 0.3100 (17) | 0.026 (5)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.01620 (9) | 0.01963 (9) | 0.01646 (9) | 0.00359 (6) | 0.00468 (6) | −0.00367 (6) |
N1 | 0.0194 (6) | 0.0212 (6) | 0.0175 (5) | 0.0035 (4) | 0.0045 (4) | −0.0046 (4) |
N2 | 0.0175 (5) | 0.0181 (5) | 0.0182 (5) | 0.0032 (4) | 0.0045 (4) | −0.0033 (4) |
N3 | 0.0314 (7) | 0.0310 (7) | 0.0191 (6) | 0.0053 (6) | 0.0015 (5) | −0.0013 (5) |
N4 | 0.0286 (7) | 0.0234 (6) | 0.0193 (6) | 0.0028 (5) | 0.0063 (5) | −0.0053 (5) |
O1 | 0.0200 (5) | 0.0312 (6) | 0.0213 (5) | 0.0079 (4) | 0.0040 (4) | −0.0036 (4) |
O2 | 0.0436 (8) | 0.0312 (6) | 0.0261 (6) | 0.0197 (6) | 0.0004 (5) | −0.0040 (5) |
O3 | 0.0398 (8) | 0.0818 (12) | 0.0272 (7) | 0.0284 (8) | −0.0054 (6) | −0.0035 (7) |
O4 | 0.0415 (8) | 0.0467 (8) | 0.0187 (6) | 0.0063 (6) | 0.0076 (5) | −0.0004 (5) |
O5 | 0.0257 (6) | 0.0288 (6) | 0.0214 (5) | 0.0066 (4) | 0.0079 (4) | −0.0029 (4) |
O6 | 0.0236 (6) | 0.0277 (6) | 0.0739 (11) | −0.0046 (5) | 0.0202 (6) | −0.0233 (7) |
C1 | 0.0183 (6) | 0.0184 (6) | 0.0191 (6) | 0.0017 (5) | 0.0025 (5) | −0.0030 (5) |
C2 | 0.0230 (7) | 0.0214 (7) | 0.0170 (6) | 0.0016 (5) | 0.0020 (5) | −0.0018 (5) |
C3 | 0.0217 (7) | 0.0247 (7) | 0.0181 (6) | 0.0023 (5) | 0.0042 (5) | −0.0029 (5) |
C4 | 0.0204 (7) | 0.0201 (6) | 0.0230 (7) | 0.0037 (5) | 0.0024 (5) | −0.0051 (5) |
C5 | 0.0228 (7) | 0.0244 (7) | 0.0194 (7) | −0.0001 (5) | 0.0044 (5) | −0.0028 (5) |
C6 | 0.0584 (13) | 0.0314 (9) | 0.0370 (10) | 0.0141 (9) | 0.0160 (9) | −0.0080 (8) |
C7 | 0.0520 (12) | 0.0328 (9) | 0.0208 (8) | 0.0032 (8) | 0.0099 (7) | −0.0003 (7) |
Geometric parameters (Å, º) top
Cu1—N1i | 1.9637 (13) | O2—C4 | 1.2231 (19) |
Cu1—N2 | 1.9803 (12) | O5—C5 | 1.2502 (19) |
Cu1—O1 | 1.9688 (11) | O6—H62 | 0.8242 |
Cu1—O5 | 1.9807 (11) | O6—H61 | 0.8246 |
Cu1—O6 | 2.1868 (13) | C1—C2 | 1.397 (2) |
N1—C3 | 1.338 (2) | C1—C4 | 1.4941 (19) |
N1—N2 | 1.3571 (16) | C2—C3 | 1.383 (2) |
N1—Cu1i | 1.9637 (13) | C3—H3 | 0.91 (2) |
N2—C1 | 1.3357 (19) | C5—H5 | 0.94 (2) |
N3—O3 | 1.219 (2) | C6—H6A | 0.9800 |
N3—O4 | 1.2270 (18) | C6—H6B | 0.9800 |
N3—C2 | 1.430 (2) | C6—H6C | 0.9800 |
N4—C5 | 1.3144 (19) | C7—H7A | 0.9800 |
N4—C7 | 1.452 (2) | C7—H7B | 0.9800 |
N4—C6 | 1.459 (2) | C7—H7C | 0.9800 |
O1—C4 | 1.2898 (19) | | |
| | | |
N1i—Cu1—N2 | 97.51 (5) | N2—C1—C2 | 107.73 (12) |
O1—Cu1—N2 | 81.12 (5) | N2—C1—C4 | 115.04 (13) |
N1i—Cu1—O5 | 88.89 (5) | C2—C1—C4 | 137.06 (14) |
O1—Cu1—O5 | 90.73 (5) | C3—C2—C1 | 105.61 (13) |
N1i—Cu1—O1 | 169.87 (5) | C3—C2—N3 | 123.74 (13) |
N2—Cu1—O5 | 167.70 (5) | C1—C2—N3 | 130.52 (14) |
N1i—Cu1—O6 | 98.19 (6) | N1—C3—C2 | 109.24 (13) |
O1—Cu1—O6 | 91.94 (6) | N1—C3—H3 | 122.5 (13) |
N2—Cu1—O6 | 97.68 (6) | C2—C3—H3 | 128.2 (13) |
O5—Cu1—O6 | 91.76 (6) | O2—C4—O1 | 125.08 (14) |
C3—N1—N2 | 107.73 (12) | O2—C4—C1 | 121.93 (14) |
C3—N1—Cu1i | 127.14 (10) | O1—C4—C1 | 112.96 (13) |
N2—N1—Cu1i | 124.82 (10) | O5—C5—N4 | 123.13 (15) |
C1—N2—N1 | 109.69 (12) | O5—C5—H5 | 122.2 (13) |
C1—N2—Cu1 | 113.22 (9) | N4—C5—H5 | 114.5 (13) |
N1—N2—Cu1 | 136.75 (10) | N4—C6—H6A | 109.5 |
O3—N3—O4 | 123.38 (15) | N4—C6—H6B | 109.5 |
O3—N3—C2 | 119.34 (14) | H6A—C6—H6B | 109.5 |
O4—N3—C2 | 117.25 (14) | N4—C6—H6C | 109.5 |
C5—N4—C7 | 121.43 (14) | H6A—C6—H6C | 109.5 |
C5—N4—C6 | 121.52 (15) | H6B—C6—H6C | 109.5 |
C7—N4—C6 | 117.00 (14) | N4—C7—H7A | 109.5 |
C4—O1—Cu1 | 116.11 (9) | N4—C7—H7B | 109.5 |
C5—O5—Cu1 | 122.22 (11) | H7A—C7—H7B | 109.5 |
Cu1—O6—H62 | 124.2 | N4—C7—H7C | 109.5 |
Cu1—O6—H61 | 111.2 | H7A—C7—H7C | 109.5 |
H62—O6—H61 | 107.6 | H7B—C7—H7C | 109.5 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O6—H62···O2ii | 0.82 | 1.91 | 2.7064 (17) | 162 |
O6—H61···O1iii | 0.82 | 1.96 | 2.7043 (16) | 149 |
C7—H7B···O3iv | 0.98 | 2.60 | 3.574 (3) | 171 |
C3—H3···O5i | 0.91 (2) | 2.43 (2) | 2.8897 (19) | 111.5 (15) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y, −z+1; (iii) x−1, y, z; (iv) x, y, z−1. |
Bis(µ-4-nitro-1
H-imidazol-1-ide-5-carboxylato)-
κ2N1,
O:
N2;
κ2N2:
N1,
O-bis[triaquacobalt(II)] dihydrate (III)
top
Crystal data top
[Co2(C4HN3O4)2(H2O)6]·2H2O | F(000) = 580 |
Mr = 572.14 | Dx = 2.063 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 8.9689 (11) Å | Cell parameters from 9652 reflections |
b = 6.4035 (8) Å | θ = 4.8–66.5° |
c = 16.4509 (19) Å | µ = 1.90 mm−1 |
β = 102.930 (2)° | T = 200 K |
V = 920.86 (19) Å3 | Prism, pink |
Z = 2 | 0.25 × 0.2 × 0.2 mm |
Data collection top
Bruker ApexII CCD diffractometer | 3366 reflections with I > 2σ(I) |
Radiation source: Incoatec ImS | Rint = 0.020 |
phi and ωs scans | θmax = 33.3°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −13→13 |
| k = −9→9 |
32322 measured reflections | l = −25→25 |
3531 independent reflections | |
Refinement top
Refinement on F2 | Hydrogen site location: difference Fourier map |
Least-squares matrix: full | Only H-atom displacement parameters refined |
R[F2 > 2σ(F2)] = 0.018 | w = 1/[σ2(Fo2) + (0.0219P)2 + 0.4119P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.049 | (Δ/σ)max = 0.003 |
S = 1.07 | Δρmax = 0.55 e Å−3 |
3531 reflections | Δρmin = −0.23 e Å−3 |
158 parameters | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0055 (6) |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Co1 | 0.54038 (2) | 0.42345 (2) | 0.61617 (2) | 0.01153 (4) | |
N1 | 0.30153 (8) | 0.44370 (11) | 0.44295 (4) | 0.01216 (12) | |
N2 | 0.33878 (8) | 0.40488 (11) | 0.52622 (4) | 0.01154 (12) | |
N3 | −0.05351 (8) | 0.22978 (11) | 0.46872 (5) | 0.01379 (12) | |
O1 | 0.38462 (8) | 0.30168 (14) | 0.68119 (4) | 0.02258 (15) | |
O2 | 0.14273 (8) | 0.22062 (12) | 0.67655 (4) | 0.01982 (13) | |
O3 | −0.09788 (8) | 0.16438 (12) | 0.52924 (5) | 0.02031 (13) | |
O4 | −0.13543 (8) | 0.23438 (13) | 0.39720 (5) | 0.02273 (14) | |
O5 | 0.70987 (8) | 0.39060 (11) | 0.72657 (4) | 0.01854 (13) | |
H51 | 0.7700 | 0.2920 | 0.7305 | 0.031 (4)* | |
H52 | 0.7536 | 0.4842 | 0.7545 | 0.041 (5)* | |
O6 | 0.59608 (9) | 0.11727 (12) | 0.58071 (6) | 0.02531 (15) | |
H61 | 0.5528 | 0.0063 | 0.5917 | 0.083 (8)* | |
H62 | 0.6779 | 0.0778 | 0.5982 | 0.076 (8)* | |
O7 | 0.48522 (8) | 0.73298 (12) | 0.65320 (4) | 0.02057 (13) | |
H71 | 0.5204 | 0.7528 | 0.7034 | 0.044 (5)* | |
H72 | 0.3970 | 0.7507 | 0.6470 | 0.047 (5)* | |
O8 | 0.87397 (9) | 0.04984 (13) | 0.70392 (6) | 0.02685 (16) | |
H81 | 0.8873 | −0.0546 | 0.7344 | 0.038 (5)* | |
H82 | 0.9590 | 0.0711 | 0.6876 | 0.044 (5)* | |
C1 | 0.21906 (9) | 0.32173 (12) | 0.55080 (5) | 0.01140 (13) | |
C2 | 0.09860 (9) | 0.30611 (13) | 0.47940 (5) | 0.01174 (13) | |
C3 | 0.15660 (9) | 0.38416 (13) | 0.41377 (5) | 0.01329 (13) | |
C4 | 0.24662 (10) | 0.27626 (14) | 0.64224 (5) | 0.01460 (14) | |
H3 | 0.1067 (18) | 0.396 (2) | 0.3569 (10) | 0.026 (4)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Co1 | 0.00962 (5) | 0.01590 (6) | 0.00893 (5) | −0.00178 (3) | 0.00177 (4) | 0.00088 (4) |
N1 | 0.0109 (3) | 0.0159 (3) | 0.0095 (3) | −0.0013 (2) | 0.0020 (2) | 0.0001 (2) |
N2 | 0.0102 (3) | 0.0151 (3) | 0.0094 (3) | −0.0011 (2) | 0.0025 (2) | 0.0006 (2) |
N3 | 0.0104 (3) | 0.0117 (3) | 0.0192 (3) | −0.0010 (2) | 0.0033 (2) | −0.0027 (2) |
O1 | 0.0138 (3) | 0.0402 (4) | 0.0127 (3) | −0.0068 (3) | 0.0009 (2) | 0.0077 (3) |
O2 | 0.0161 (3) | 0.0283 (3) | 0.0166 (3) | −0.0047 (2) | 0.0070 (2) | 0.0034 (2) |
O3 | 0.0159 (3) | 0.0224 (3) | 0.0251 (3) | −0.0037 (2) | 0.0099 (2) | 0.0008 (3) |
O4 | 0.0139 (3) | 0.0297 (4) | 0.0213 (3) | −0.0042 (3) | −0.0028 (2) | −0.0036 (3) |
O5 | 0.0167 (3) | 0.0218 (3) | 0.0147 (3) | 0.0012 (2) | −0.0018 (2) | −0.0004 (2) |
O6 | 0.0172 (3) | 0.0192 (3) | 0.0387 (4) | −0.0003 (3) | 0.0045 (3) | 0.0003 (3) |
O7 | 0.0186 (3) | 0.0268 (3) | 0.0172 (3) | 0.0016 (3) | 0.0059 (2) | −0.0049 (2) |
O8 | 0.0222 (3) | 0.0268 (4) | 0.0352 (4) | 0.0031 (3) | 0.0140 (3) | 0.0053 (3) |
C1 | 0.0098 (3) | 0.0130 (3) | 0.0117 (3) | −0.0009 (2) | 0.0030 (2) | 0.0004 (2) |
C2 | 0.0090 (3) | 0.0127 (3) | 0.0134 (3) | −0.0016 (2) | 0.0024 (2) | −0.0008 (2) |
C3 | 0.0113 (3) | 0.0163 (3) | 0.0118 (3) | −0.0016 (3) | 0.0015 (2) | −0.0003 (3) |
C4 | 0.0139 (3) | 0.0176 (4) | 0.0126 (3) | −0.0016 (3) | 0.0037 (3) | 0.0020 (3) |
Geometric parameters (Å, º) top
Co1—N1i | 2.0729 (7) | O2—C4 | 1.2446 (10) |
Co1—N2 | 2.0679 (7) | O5—H51 | 0.8232 |
Co1—O1 | 2.0911 (7) | O5—H52 | 0.8023 |
Co1—O5 | 2.1018 (7) | O6—H61 | 0.8481 |
Co1—O6 | 2.1365 (8) | O6—H62 | 0.7683 |
Co1—O7 | 2.1632 (8) | O7—H71 | 0.8251 |
N1—C3 | 1.3364 (10) | O7—H72 | 0.7830 |
N1—N2 | 1.3583 (10) | O8—H81 | 0.8286 |
N1—Co1i | 2.0730 (7) | O8—H82 | 0.8736 |
N2—C1 | 1.3395 (10) | C1—C2 | 1.4103 (11) |
N3—O3 | 1.2257 (10) | C1—C4 | 1.4975 (11) |
N3—O4 | 1.2402 (10) | C2—C3 | 1.3919 (11) |
N3—C2 | 1.4226 (10) | C3—H3 | 0.945 (16) |
O1—C4 | 1.2705 (10) | | |
| | | |
N2—Co1—N1i | 105.56 (3) | C4—O1—Co1 | 118.47 (6) |
N2—Co1—O1 | 76.55 (3) | Co1—O5—H51 | 118.6 |
N1i—Co1—O5 | 90.47 (3) | Co1—O5—H52 | 125.9 |
O1—Co1—O5 | 87.56 (3) | H51—O5—H52 | 107.5 |
N2—Co1—O5 | 163.76 (3) | Co1—O6—H61 | 124.4 |
N1i—Co1—O1 | 176.78 (3) | Co1—O6—H62 | 117.5 |
O6—Co1—O7 | 179.48 (3) | H61—O6—H62 | 95.1 |
N2—Co1—O6 | 88.41 (3) | Co1—O7—H71 | 111.3 |
N1i—Co1—O6 | 91.27 (3) | Co1—O7—H72 | 112.6 |
O1—Co1—O6 | 91.22 (3) | H71—O7—H72 | 104.9 |
O5—Co1—O6 | 88.63 (3) | H81—O8—H82 | 107.1 |
N2—Co1—O7 | 92.05 (3) | N2—C1—C2 | 107.05 (7) |
N1i—Co1—O7 | 88.83 (3) | N2—C1—C4 | 114.66 (7) |
O1—Co1—O7 | 88.66 (3) | C2—C1—C4 | 138.27 (7) |
O5—Co1—O7 | 90.87 (3) | C3—C2—C1 | 105.71 (7) |
C3—N1—N2 | 108.05 (7) | C3—C2—N3 | 122.83 (7) |
C3—N1—Co1i | 131.37 (6) | C1—C2—N3 | 131.45 (7) |
N2—N1—Co1i | 120.57 (5) | N1—C3—C2 | 109.04 (7) |
C1—N2—N1 | 110.14 (7) | N1—C3—H3 | 122.6 (9) |
C1—N2—Co1 | 116.01 (5) | C2—C3—H3 | 128.3 (9) |
N1—N2—Co1 | 133.59 (5) | O2—C4—O1 | 123.48 (8) |
O3—N3—O4 | 123.21 (8) | O2—C4—C1 | 122.62 (8) |
O3—N3—C2 | 119.59 (7) | O1—C4—C1 | 113.89 (7) |
O4—N3—C2 | 117.20 (7) | | |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H51···O8 | 0.82 | 1.91 | 2.7041 (11) | 162 |
O5—H52···O2ii | 0.80 | 1.99 | 2.7949 (10) | 179 |
O6—H61···O7iii | 0.85 | 2.17 | 2.9995 (12) | 164 |
O6—H62···O3iv | 0.77 | 2.58 | 3.0629 (11) | 123 |
O6—H62···O8 | 0.77 | 2.19 | 2.8716 (12) | 149 |
O7—H71···O1ii | 0.83 | 1.92 | 2.7488 (10) | 176 |
O7—H72···O4v | 0.78 | 2.30 | 3.0675 (11) | 168 |
O7—H72···O5ii | 0.78 | 2.63 | 3.0889 (10) | 119 |
O8—H81···O2vi | 0.83 | 2.11 | 2.9096 (12) | 161 |
O8—H82···O2iv | 0.87 | 1.95 | 2.7739 (11) | 157 |
O8—H82···O3iv | 0.87 | 2.61 | 3.0304 (12) | 111 |
Symmetry codes: (ii) −x+1, y+1/2, −z+3/2; (iii) x, y−1, z; (iv) x+1, y, z; (v) −x, −y+1, −z+1; (vi) −x+1, y−1/2, −z+3/2. |
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