The structure of the title complex, [Cu
4(C
4H
10NO
2)
4(H
2O)
4](NO
3)
4·14/3 H
2O, consists of tetranuclear [Cu
4(Hdea)
4(H
2O)
4]
4+ cations (H
2dea is diethanolamine), uncoordinated nitrate anions and water molecules. Each copper centre in the two independent cations (one on a twofold rotation axis and the other with
crystallographic symmetry) is similarly coordinated by two alkoxo O atoms, one amine N atom of the monodeprotonated Hdea ligands and one O atom from a water molecule in a square-planar geometry [Cu-O/N bond lengths are in the range 1.939 (6)-2.045 (8) Å]. The two axial positions of the Cu atoms are occupied by a weakly bound ethanol group of the chelating Hdea ligand and an alkoxo O atom from a neighbouring Hdea ligand [average Cu-O = 2.532 (7) Å]. The coordination geometry of the Cu atoms can, therefore, be best described as distorted elongated octahedral. The intermolecular hydrogen bonds that involve OH and NH groups of the ligands, uncoordinated NO
3- anions and water molecules reinforce the crystal structure by forming an extended three-dimensional network.
Supporting information
CCDC reference: 209882
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (C-C) = 0.014 Å
- H-atom completeness 84%
- Disorder in solvent or counterion
- R factor = 0.064
- wR factor = 0.087
- Data-to-parameter ratio = 9.6
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level C:
REFNR_01 Alert C Ratio of reflections to parameters is < 10 for a
centrosymmetric structure
sine(theta)/lambda 0.6249
Proportion of unique data used 0.5698
Ratio reflections to parameters 9.5793
PLAT_302 Alert C Anion/Solvent Disorder ....................... 26.00 Perc.
General Notes
FORMU_01 There is a discrepancy between the atom counts in the
_chemical_formula_sum and the formula from the _atom_site* data.
Atom count from _chemical_formula_sum:C16 H57.33329 Cu4 N8 O28.66669
Atom count from the _atom_site data: C16 H48 Cu4 N8 O28.66666
CELLZ_01
From the CIF: _cell_formula_units_Z 6
From the CIF: _chemical_formula_sum C16 H57.3333 Cu4 N8 O28.6667
TEST: Compare cell contents of formula and atom_site data
atom Z*formula cif sites diff
C 96.00 96.00 0.00
H 344.00 288.00 56.00
Cu 24.00 24.00 0.00
N 48.00 48.00 0.00
O 172.00 172.00 0.00
Difference between formula and atom_site contents detected.
WARNING: H atoms missing from atom site list. Is this intentional?
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
2 Alert Level C = Please check
To synthesize (I), copper powder (0.32 g, 5 mmol), Ni(NO3)2·4H2O
(2.90 g, 10 mmol), NH4NO3 (0.8 g, 10 mmol), CH3OH (20 ml) and H2dea (2 ml) were heated to 333 K and magnetically stirred until total dissolution of
Cu was observed (20 min). Dark-blue crystals of (I) adequate for an X-ray
crystallographic study were isolated next day as a first crop (0.49 g).
All non-H atoms were assigned anisotropic displacement parameters, except for
the O atoms of half-weighted solvent water molecules, viz. O6aq, O7aq
and O8aq. H atoms on O and N atoms were found in difference maps, while those
of the remainder of the cation were placed in calculated positions and fixed
in the refinement. For water molecules O1aq–O3aq, H atoms were refined with
their geometry restrained to ideal values but those for the solvent water
molecules O4aq–O8aq were not located. Nitrates N6 and N7 are half-weighted,
with water molecules O8aq and O7aq occupying the other half of the sites. The
N7/O16/O17/O18 nitrate anion and the O7aq solvent water were modelled to be
disordered about a crystallographic inversion centre. All nitrate ions were
refined as rigid bodies. Several other peaks in difference map such as that on
(1/4, 1/4, 1/4), which was modelled as an Aq(8) in the original structure
determination, refined with oxygen population less than 1/4 with an
insignificant decrease in the R factor, and hence these sites as
possible solvent water molecules were ignored.
Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: Xtal3.5 (Hall et al., 1995); program(s) used to solve structure: Xtal3.5; program(s) used to refine structure: Xtal3.5 CRYLSQ; molecular graphics: Xtal3.5; software used to prepare material for publication: Xtal3.5 BONDLA CIFIO.
Tetraaquatetrakis[2-(2-hydroxyethylamino)ethanolato]tetracopper(II) tetranitrate
14/3-hydrate
top
Crystal data top
[Cu4(C4H10NO2)4(H2O)4](NO3)4·14/3H2O | Dx = 1.641 Mg m−3 |
Mr = 1074.85 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, P42/n | Cell parameters from 8192 reflections |
Hall symbol: -p 4bc | θ = 2.4–23.6° |
a = 17.797 (2) Å | µ = 2.03 mm−1 |
c = 20.600 (2) Å | T = 150 K |
V = 6524.7 (12) Å3 | Tetragonal prism, dark blue |
Z = 6 | 0.35 × 0.14 × 0.11 mm |
F(000) = 3328 | |
Data collection top
Bruker SMART CCD diffractometer | 6674 independent reflections |
Radiation source: sealed tube | 3803 reflections with F > 4σ(F) |
Graphite monochromator | Rint = 0.077 |
ω scans | θmax = 26.4°, θmin = 1.5° |
Absorption correction: multi-scan SADABS; Sheldrick, 1996 | h = 0→22 |
Tmin = 0.67, Tmax = 0.84 | k = 0→22 |
63965 measured reflections | l = −25→0 |
Refinement top
Refinement on F | 9 restraints |
Least-squares matrix: full | 0 constraints |
R[F2 > 2σ(F2)] = 0.064 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.087 | w = 1/[σ2(F) + 0.003F2] |
S = 1.02 | (Δ/σ)max = 0.011 |
3803 reflections | Δρmax = 1.46 e Å−3 |
397 parameters | Δρmin = −0.86 e Å−3 |
Crystal data top
[Cu4(C4H10NO2)4(H2O)4](NO3)4·14/3H2O | Z = 6 |
Mr = 1074.85 | Mo Kα radiation |
Tetragonal, P42/n | µ = 2.03 mm−1 |
a = 17.797 (2) Å | T = 150 K |
c = 20.600 (2) Å | 0.35 × 0.14 × 0.11 mm |
V = 6524.7 (12) Å3 | |
Data collection top
Bruker SMART CCD diffractometer | 6674 independent reflections |
Absorption correction: multi-scan SADABS; Sheldrick, 1996 | 3803 reflections with F > 4σ(F) |
Tmin = 0.67, Tmax = 0.84 | Rint = 0.077 |
63965 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.064 | 9 restraints |
wR(F2) = 0.087 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 1.46 e Å−3 |
3803 reflections | Δρmin = −0.86 e Å−3 |
397 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Cu1 | 0.33549 (6) | 0.70430 (6) | 0.48988 (4) | 0.0305 (5) | |
Cu2 | 0.20561 (6) | 0.66346 (6) | 0.39050 (4) | 0.0325 (5) | |
Cu3 | 0.65627 (6) | 0.74570 (6) | 0.19713 (5) | 0.0384 (6) | |
O1 | 0.2295 (4) | 0.5247 (4) | 0.4157 (3) | 0.053 (4) | |
O2 | 0.3102 (3) | 0.6937 (3) | 0.3976 (2) | 0.032 (3) | |
O3 | 0.4730 (3) | 0.7311 (4) | 0.4653 (3) | 0.045 (4) | |
O4 | 0.3052 (3) | 0.8091 (3) | 0.4829 (2) | 0.031 (3) | |
O5 | 0.7315 (3) | 0.6682 (3) | 0.2095 (3) | 0.039 (3) | |
O6 | 0.5474 (4) | 0.6628 (4) | 0.2184 (4) | 0.061 (4) | |
N1 | 0.2364 (4) | 0.6190 (4) | 0.3036 (3) | 0.039 (4) | |
N2 | 0.3768 (4) | 0.7345 (4) | 0.5775 (3) | 0.036 (4) | |
N3 | 0.6398 (5) | 0.6953 (5) | 0.1090 (4) | 0.057 (5) | |
N4 | 0.7103 (2) | 0.40073 (18) | 0.30881 (14) | 0.042 (4) | |
O7 | 0.7260 (4) | 0.4350 (3) | 0.25878 (17) | 0.053 (4) | |
O8 | 0.6900 (4) | 0.3345 (2) | 0.3057 (2) | 0.043 (3) | |
O9 | 0.7148 (4) | 0.4327 (3) | 0.36188 (16) | 0.064 (4) | |
N5 | 0.4695 (4) | −0.0198 (5) | 0.1967 (5) | 0.122 (12) | |
O10 | 0.4650 (8) | −0.0514 (7) | 0.1438 (5) | 0.182 (15) | |
O11 | 0.4615 (8) | −0.0564 (7) | 0.2472 (5) | 0.143 (11) | |
O12 | 0.4822 (9) | 0.0483 (5) | 0.1992 (7) | 0.201 (7)* | |
N6 | 0.3191 (8) | 0.3768 (7) | 0.4799 (6) | 0.10 (2) | .50000 |
O13 | 0.3305 (13) | 0.4112 (11) | 0.5307 (7) | 0.121 (18) | .50000 |
O14 | 0.3653 (10) | 0.3805 (14) | 0.4353 (8) | 0.109 (7)* | .50000 |
O15 | 0.2616 (11) | 0.3387 (13) | 0.4736 (9) | 0.17 (3) | .50000 |
N7 | 0.0320 (9) | 0.4898 (7) | 0.4551 (7) | 0.088 (17) | .50000 |
O16 | −0.0042 (18) | 0.5458 (14) | 0.4708 (11) | 0.094 (14) | .50000 |
O17 | 0.0773 (13) | 0.494 (2) | 0.4098 (10) | 0.075 (12) | .50000 |
O18 | 0.023 (2) | 0.4301 (10) | 0.4845 (11) | 0.25 (2)* | .50000 |
C1 | 0.2545 (7) | 0.4955 (6) | 0.3550 (5) | 0.060 (6) | |
C2 | 0.2220 (6) | 0.5379 (5) | 0.2992 (4) | 0.051 (6) | |
C3 | 0.3140 (5) | 0.6424 (5) | 0.2907 (4) | 0.041 (5) | |
C4 | 0.3567 (5) | 0.6514 (5) | 0.3541 (4) | 0.035 (4) | |
C5 | 0.5016 (5) | 0.7523 (5) | 0.5274 (4) | 0.044 (5) | |
C6 | 0.4587 (5) | 0.7193 (5) | 0.5827 (4) | 0.043 (5) | |
C7 | 0.3550 (5) | 0.8133 (5) | 0.5892 (4) | 0.041 (5) | |
C8 | 0.3463 (5) | 0.8549 (4) | 0.5267 (4) | 0.035 (4) | |
C9 | 0.7181 (5) | 0.6051 (5) | 0.1682 (4) | 0.048 (5) | |
C10 | 0.6965 (6) | 0.6336 (6) | 0.1028 (5) | 0.060 (7) | |
C11 | 0.5624 (7) | 0.6711 (9) | 0.0998 (6) | 0.079 (9) | |
C12 | 0.5345 (7) | 0.6235 (8) | 0.1577 (8) | 0.097 (10) | |
O1aq | 0.3489 (4) | 0.5935 (4) | 0.5046 (3) | 0.057 (4) | |
O2aq | 0.0958 (4) | 0.6526 (4) | 0.3744 (4) | 0.061 (5) | |
O3aq | 0.5960 (5) | 0.8374 (5) | 0.1788 (4) | 0.069 (5) | |
O4aq | 0.1134 (10) | 0.0341 (10) | 0.1819 (8) | 0.194 (16) | |
O5aq | 0.0211 (8) | 0.0884 (7) | 0.5537 (5) | 0.158 (11) | |
O6aq | 0.6433 (18) | 0.784 (2) | 0.7069 (16) | 0.176 (12)* | .50000 |
O7aq | 0.083 (2) | 0.4648 (19) | 0.4225 (17) | 0.136 (14)* | .50000 |
O8aq | 0.4014 (12) | 0.4315 (12) | 0.4407 (10) | 0.102 (6)* | .50000 |
H3 | 0.64704 | 0.73053 | 0.07541 | 0.07300* | |
H1a | 0.24091 | 0.44214 | 0.35128 | 0.07500* | |
H1b | 0.30831 | 0.49741 | 0.35200 | 0.07500* | |
H2a | 0.24165 | 0.51812 | 0.25857 | 0.06400* | |
H2b | 0.16803 | 0.52824 | 0.29794 | 0.06400* | |
H3a | 0.31508 | 0.68946 | 0.26748 | 0.05300* | |
H3b | 0.33918 | 0.60574 | 0.26478 | 0.05300* | |
H4a | 0.36807 | 0.60458 | 0.37251 | 0.04800* | |
H4b | 0.40277 | 0.67902 | 0.34729 | 0.04800* | |
H5a | 0.50170 | 0.80599 | 0.53095 | 0.05400* | |
H5b | 0.55412 | 0.73636 | 0.53073 | 0.05400* | |
H6a | 0.46702 | 0.66633 | 0.58437 | 0.05500* | |
H6b | 0.47664 | 0.74032 | 0.62329 | 0.05500* | |
H7a | 0.39163 | 0.83774 | 0.61681 | 0.05000* | |
H7b | 0.30752 | 0.81518 | 0.61326 | 0.05000* | |
H8a | 0.39524 | 0.86508 | 0.50906 | 0.04800* | |
H8b | 0.32115 | 0.90170 | 0.53304 | 0.04800* | |
H9a | 0.67743 | 0.57631 | 0.18606 | 0.06100* | |
H9b | 0.76189 | 0.57433 | 0.16746 | 0.06100* | |
H10a | 0.67923 | 0.59523 | 0.07522 | 0.07300* | |
H10b | 0.74266 | 0.65464 | 0.08120 | 0.07300* | |
H11a | 0.52945 | 0.71243 | 0.09675 | 0.09900* | |
H11b | 0.55703 | 0.63962 | 0.06287 | 0.09900* | |
H12a | 0.48095 | 0.61433 | 0.15362 | 0.10400* | |
H12b | 0.55936 | 0.57682 | 0.15918 | 0.10400* | |
H1 | 0.20476 | 0.63805 | 0.27081 | 0.05200* | |
H2 | 0.35655 | 0.70297 | 0.60981 | 0.04400* | |
H1O | 0.19401 | 0.48582 | 0.42444 | 0.06900* | |
H3O | 0.48769 | 0.67957 | 0.46273 | 0.05600* | |
H6O | 0.51583 | 0.70593 | 0.22963 | 0.07700* | |
H1aqA | 0.314 | 0.560 | 0.491 | 0.08600* | |
H1aqB | 0.396 | 0.571 | 0.500 | 0.08600* | |
H2aqA | 0.077 | 0.607 | 0.382 | 0.09400* | |
H2aqB | 0.071 | 0.688 | 0.401 | 0.09400* | |
H3aqA | 0.548 | 0.827 | 0.186 | 0.10300* | |
H3aqB | 0.605 | 0.884 | 0.189 | 0.10300* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.0362 (6) | 0.0334 (6) | 0.0220 (4) | 0.0083 (4) | 0.0014 (4) | 0.0020 (4) |
Cu2 | 0.0371 (6) | 0.0368 (6) | 0.0235 (4) | 0.0078 (5) | −0.0004 (4) | −0.0015 (4) |
Cu3 | 0.0366 (6) | 0.0446 (6) | 0.0341 (5) | 0.0090 (4) | −0.0038 (5) | −0.0049 (5) |
O1 | 0.069 (5) | 0.052 (4) | 0.039 (3) | −0.005 (3) | 0.003 (3) | −0.001 (3) |
O2 | 0.033 (3) | 0.038 (3) | 0.026 (3) | 0.009 (2) | 0.002 (2) | 0.003 (2) |
O3 | 0.042 (3) | 0.058 (4) | 0.036 (3) | 0.009 (3) | 0.004 (3) | 0.008 (3) |
O4 | 0.039 (3) | 0.032 (3) | 0.023 (2) | 0.005 (2) | −0.002 (2) | −0.001 (2) |
O5 | 0.041 (3) | 0.040 (3) | 0.036 (3) | 0.005 (2) | −0.007 (3) | −0.003 (3) |
O6 | 0.047 (4) | 0.058 (4) | 0.079 (5) | 0.004 (3) | −0.016 (4) | −0.013 (4) |
N1 | 0.045 (4) | 0.045 (4) | 0.028 (3) | 0.009 (3) | −0.001 (3) | −0.003 (3) |
N2 | 0.043 (4) | 0.043 (4) | 0.023 (3) | 0.002 (3) | 0.004 (3) | 0.008 (3) |
N3 | 0.059 (5) | 0.069 (6) | 0.045 (4) | 0.026 (4) | −0.016 (4) | −0.013 (4) |
N4 | 0.064 (5) | 0.039 (4) | 0.023 (3) | 0.001 (3) | −0.000 (3) | 0.007 (3) |
O7 | 0.091 (5) | 0.044 (4) | 0.024 (3) | −0.010 (3) | −0.000 (3) | 0.005 (3) |
O8 | 0.060 (4) | 0.038 (3) | 0.031 (3) | −0.015 (3) | 0.002 (3) | 0.003 (3) |
O9 | 0.123 (7) | 0.048 (4) | 0.021 (3) | −0.005 (4) | 0.003 (3) | −0.004 (3) |
N5 | 0.123 (12) | 0.067 (8) | 0.175 (16) | −0.017 (8) | −0.011 (12) | 0.000 (10) |
O10 | 0.136 (12) | 0.198 (16) | 0.212 (16) | 0.034 (11) | −0.065 (12) | −0.083 (14) |
O11 | 0.129 (10) | 0.156 (12) | 0.144 (10) | 0.002 (9) | 0.050 (9) | 0.070 (10) |
N6 | 0.12 (2) | 0.084 (18) | 0.093 (18) | 0.055 (16) | 0.040 (17) | 0.047 (15) |
O13 | 0.121 (17) | 0.16 (2) | 0.080 (13) | 0.079 (16) | 0.041 (13) | 0.049 (14) |
O15 | 0.23 (3) | 0.19 (3) | 0.102 (18) | 0.05 (2) | 0.11 (2) | 0.053 (18) |
N7 | 0.067 (15) | 0.067 (15) | 0.13 (2) | −0.030 (13) | −0.002 (14) | 0.006 (15) |
O16 | 0.141 (19) | 0.049 (10) | 0.094 (14) | −0.037 (11) | −0.036 (13) | 0.040 (10) |
O17 | 0.082 (13) | 0.043 (10) | 0.101 (14) | −0.021 (9) | −0.000 (11) | 0.016 (10) |
C1 | 0.084 (8) | 0.044 (6) | 0.051 (6) | 0.008 (5) | −0.000 (5) | −0.008 (5) |
C2 | 0.069 (7) | 0.051 (6) | 0.033 (4) | 0.003 (5) | 0.002 (4) | −0.015 (4) |
C3 | 0.049 (5) | 0.052 (5) | 0.023 (4) | 0.012 (4) | 0.009 (3) | −0.004 (4) |
C4 | 0.037 (5) | 0.039 (5) | 0.029 (4) | 0.006 (4) | 0.003 (3) | −0.005 (3) |
C5 | 0.034 (5) | 0.049 (5) | 0.048 (5) | 0.006 (4) | 0.000 (4) | 0.006 (4) |
C6 | 0.034 (5) | 0.056 (6) | 0.038 (4) | 0.011 (4) | −0.004 (4) | 0.001 (4) |
C7 | 0.040 (5) | 0.051 (5) | 0.032 (4) | 0.004 (4) | −0.000 (4) | −0.003 (4) |
C8 | 0.045 (5) | 0.033 (4) | 0.025 (4) | 0.003 (4) | −0.001 (3) | −0.004 (3) |
C9 | 0.049 (6) | 0.053 (6) | 0.041 (5) | 0.013 (5) | −0.008 (4) | −0.011 (4) |
C10 | 0.062 (7) | 0.070 (7) | 0.048 (6) | 0.026 (6) | −0.018 (5) | −0.026 (5) |
C11 | 0.065 (8) | 0.115 (11) | 0.056 (7) | 0.022 (7) | −0.024 (6) | −0.026 (7) |
C12 | 0.065 (8) | 0.099 (10) | 0.126 (12) | 0.021 (7) | −0.041 (8) | −0.074 (10) |
O1aq | 0.064 (5) | 0.052 (4) | 0.054 (4) | 0.016 (4) | 0.002 (4) | 0.008 (3) |
O2aq | 0.061 (5) | 0.064 (5) | 0.058 (4) | 0.006 (4) | −0.004 (4) | −0.005 (4) |
O3aq | 0.058 (5) | 0.066 (5) | 0.083 (6) | 0.008 (4) | −0.005 (4) | −0.001 (4) |
O4aq | 0.206 (17) | 0.209 (16) | 0.167 (14) | 0.127 (14) | 0.001 (11) | −0.003 (11) |
O5aq | 0.260 (15) | 0.141 (10) | 0.073 (6) | 0.142 (10) | 0.027 (8) | 0.025 (6) |
Geometric parameters (Å, º) top
Cu1—O2 | 1.964 (5) | N6—O13 | 1.23 |
Cu1—O3 | 2.544 (6) | N6—O14 | 1.23 |
Cu1—O4 | 1.946 (5) | N6—O15 | 1.23 |
Cu1—N2 | 2.022 (6) | N7—O16 | 1.23 |
Cu1—O1aq | 2.010 (7) | N7—O17 | 1.23 |
Cu1—O4 | 2.520 (5) | N7—O18 | 1.23 |
Cu2—O1 | 2.558 (7) | C1—C2 | 1.491 (14) |
Cu2—O2 | 1.942 (5) | C1—H1a | 0.983 |
Cu2—N1 | 2.032 (7) | C1—H1b | 0.960 |
Cu2—O2aq | 1.992 (8) | C2—H2a | 0.974 |
Cu2—O2 | 2.562 (5) | C2—H2b | 0.976 |
Cu2—O4 | 1.974 (5) | C3—C4 | 1.518 (11) |
Cu3—O5 | 1.939 (6) | C3—H3a | 0.965 |
Cu3—O6 | 2.475 (7) | C3—H3b | 0.955 |
Cu3—N3 | 2.045 (8) | C4—H4a | 0.939 |
Cu3—O3aq | 1.989 (8) | C4—H4b | 0.966 |
Cu3—O5 | 2.531 (6) | C5—C6 | 1.492 (12) |
Cu3—O5 | 1.977 (6) | C5—H5a | 0.958 |
O1—C1 | 1.425 (12) | C5—H5b | 0.979 |
O1—H1O | 0.955 | C6—H6a | 0.954 |
O2—C4 | 1.432 (9) | C6—H6b | 0.970 |
O3—C5 | 1.429 (11) | C7—C8 | 1.495 (11) |
O3—H3O | 0.955 | C7—H7a | 0.968 |
O4—C8 | 1.419 (9) | C7—H7b | 0.980 |
O5—C9 | 1.430 (11) | C8—H8a | 0.961 |
O6—C12 | 1.452 (18) | C8—H8b | 0.954 |
O6—H6O | 0.979 | C9—C10 | 1.490 (14) |
N1—C2 | 1.469 (12) | C9—H9a | 0.959 |
N1—C3 | 1.466 (12) | C9—H9b | 0.953 |
N1—H1 | 0.943 | C10—H10a | 0.941 |
N2—C6 | 1.487 (11) | C10—H10b | 1.006 |
N2—C7 | 1.475 (12) | C11—C12 | 1.54 (2) |
N2—H2 | 0.941 | C11—H11a | 0.943 |
N3—C10 | 1.496 (14) | C11—H11b | 0.950 |
N3—C11 | 1.456 (16) | C12—H12a | 0.970 |
N3—H3 | 0.944 | C12—H12b | 0.941 |
N4—O7 | 1.230 | O1aq—H1aqA | 0.90 |
N4—O8 | 1.234 | O1aq—H1aqB | 0.93 |
N4—O9 | 1.235 | O2aq—H2aqA | 0.89 |
N5—O10 | 1.230 | O2aq—H2aqB | 0.94 |
N5—O11 | 1.235 | O3aq—H3aqA | 0.89 |
N5—O12 | 1.234 | O3aq—H3aqB | 0.87 |
| | | |
O2—Cu1—O3 | 92.6 (2) | O8—N4—O9 | 120.3 |
O2—Cu1—O4 | 87.5 (2) | O10—N5—O11 | 119.9 |
O2—Cu1—N2 | 166.9 (3) | O10—N5—O12 | 119.8 |
O2—Cu1—O1aq | 94.5 (3) | O11—N5—O12 | 120.3 |
O2—Cu1—O4 | 73.0 (2) | O13—N6—O14 | 119.9 |
O3—Cu1—O4 | 94.1 (2) | O13—N6—O15 | 119.9 |
O3—Cu1—N2 | 77.2 (2) | O14—N6—O15 | 120.3 |
O3—Cu1—O1aq | 95.7 (3) | O16—N7—O17 | 120 |
O3—Cu1—O4 | 164.23 (17) | O16—N7—O18 | 120 |
O4—Cu1—N2 | 85.0 (2) | O17—N7—O18 | 120 |
O4—Cu1—O1aq | 169.8 (3) | O1—C1—C2 | 111.7 (8) |
O4—Cu1—O4 | 79.1 (2) | O1—C1—H1a | 110.1 |
N2—Cu1—O1aq | 94.7 (3) | O1—C1—H1b | 110.8 |
N2—Cu1—O4 | 115.9 (2) | C2—C1—H1a | 109.5 |
O1aq—Cu1—O4 | 92.0 (3) | C2—C1—H1b | 108.6 |
O1—Cu2—O2 | 95.3 (2) | H1a—C1—H1b | 106.0 |
O1—Cu2—N1 | 76.0 (2) | N1—C2—C1 | 112.5 (8) |
O1—Cu2—O2aq | 95.9 (3) | N1—C2—H2a | 110.2 |
O1—Cu2—O2 | 164.66 (18) | N1—C2—H2b | 110.3 |
O1—Cu2—O4 | 93.4 (2) | C1—C2—H2a | 109.9 |
O2—Cu2—N1 | 85.1 (2) | C1—C2—H2b | 108.3 |
O2—Cu2—O2aq | 168.3 (3) | H2a—C2—H2b | 105.4 |
O2—Cu2—O2 | 80.0 (2) | N1—C3—C4 | 110.2 (6) |
O2—Cu2—O4 | 87.3 (2) | N1—C3—H3a | 110.8 |
N1—Cu2—O2aq | 94.6 (3) | N1—C3—H3b | 110.4 |
N1—Cu2—O2 | 117.8 (2) | C4—C3—H3a | 109.0 |
N1—Cu2—O4 | 166.3 (3) | C4—C3—H3b | 108.6 |
O2aq—Cu2—O2 | 89.9 (3) | H3a—C3—H3b | 107.8 |
O2aq—Cu2—O4 | 95.1 (3) | O2—C4—C3 | 107.7 (6) |
O2—Cu2—O4 | 71.86 (19) | O2—C4—H4a | 109.8 |
O5—Cu3—O6 | 95.3 (2) | O2—C4—H4b | 108.3 |
O5—Cu3—N3 | 84.5 (3) | C3—C4—H4a | 111.2 |
O5—Cu3—O3aq | 168.8 (3) | C3—C4—H4b | 110.7 |
O5—Cu3—O5 | 82.7 (2) | H4a—C4—H4b | 109.0 |
O5—Cu3—O5 | 86.8 (2) | O3—C5—C6 | 113.4 (7) |
O6—Cu3—N3 | 77.5 (3) | O3—C5—H5a | 109.4 |
O6—Cu3—O3aq | 95.8 (3) | O3—C5—H5b | 109.0 |
O6—Cu3—O5 | 164.0 (2) | C6—C5—H5a | 109.6 |
O6—Cu3—O5 | 92.0 (2) | C6—C5—H5b | 108.7 |
N3—Cu3—O3aq | 96.6 (4) | H5a—C5—H5b | 106.5 |
N3—Cu3—O5 | 117.9 (3) | N2—C6—C5 | 112.1 (7) |
N3—Cu3—O5 | 165.6 (3) | N2—C6—H6a | 109.5 |
O3aq—Cu3—O5 | 87.0 (3) | N2—C6—H6b | 108.3 |
O3aq—Cu3—O5 | 94.2 (3) | C5—C6—H6a | 109.8 |
O5—Cu3—O5 | 72.1 (2) | C5—C6—H6b | 109.7 |
Cu2—O1—C1 | 103.1 (5) | H6a—C6—H6b | 107.4 |
Cu2—O1—H1O | 128.9 | N2—C7—C8 | 111.0 (7) |
C1—O1—H1O | 96.2 | N2—C7—H7a | 110.3 |
Cu1—O2—Cu2 | 108.6 (2) | N2—C7—H7b | 110.0 |
Cu1—O2—C4 | 121.6 (4) | C8—C7—H7a | 110.6 |
Cu1—O2—Cu2 | 89.1 (2) | C8—C7—H7b | 109.2 |
Cu2—O2—C4 | 111.2 (4) | H7a—C7—H7b | 105.6 |
Cu2—O2—Cu2 | 99.5 (2) | O4—C8—C7 | 108.4 (6) |
C4—O2—Cu2 | 123.3 (4) | O4—C8—H8a | 109.6 |
Cu1—O3—C5 | 102.4 (5) | O4—C8—H8b | 110.3 |
Cu1—O3—H3O | 95.5 | C7—C8—H8a | 109.0 |
C5—O3—H3O | 101.9 | C7—C8—H8b | 111.3 |
Cu1—O4—C8 | 111.2 (4) | H8a—C8—H8b | 108.2 |
Cu1—O4—Cu1 | 100.4 (2) | O5—C9—C10 | 108.2 (8) |
Cu1—O4—Cu2 | 109.6 (2) | O5—C9—H9a | 108.5 |
C8—O4—Cu1 | 122.0 (4) | O5—C9—H9b | 108.9 |
C8—O4—Cu2 | 121.4 (4) | C10—C9—H9a | 109.6 |
Cu1—O4—Cu2 | 88.9 (2) | C10—C9—H9b | 113.1 |
Cu3—O5—C9 | 111.4 (5) | H9a—C9—H9b | 108.5 |
Cu3—O5—Cu3 | 95.8 (2) | N3—C10—C9 | 110.3 (8) |
Cu3—O5—Cu3 | 110.3 (3) | N3—C10—H10a | 111.3 |
C9—O5—Cu3 | 123.2 (5) | N3—C10—H10b | 108.4 |
C9—O5—Cu3 | 122.0 (5) | C9—C10—H10a | 112.5 |
Cu3—O5—Cu3 | 90.0 (2) | C9—C10—H10b | 108.5 |
Cu3—O6—C12 | 105.0 (7) | H10a—C10—H10b | 105.6 |
Cu3—O6—H6O | 91.3 | N3—C11—C12 | 111.5 (10) |
C12—O6—H6O | 119.4 | N3—C11—H11a | 111.5 |
Cu2—N1—C2 | 112.9 (5) | N3—C11—H11b | 112.0 |
Cu2—N1—C3 | 107.7 (5) | C12—C11—H11a | 106.3 |
Cu2—N1—H1 | 109.3 | C12—C11—H11b | 105.3 |
C2—N1—C3 | 115.6 (7) | H11a—C11—H11b | 110.1 |
C2—N1—H1 | 101.8 | O6—C12—C11 | 110.5 (11) |
C3—N1—H1 | 109.4 | O6—C12—H12a | 108.1 |
Cu1—N2—C6 | 111.8 (5) | O6—C12—H12b | 108.8 |
Cu1—N2—C7 | 107.6 (5) | C11—C12—H12a | 110.0 |
Cu1—N2—H2 | 109.5 | C11—C12—H12b | 111.0 |
C6—N2—C7 | 114.8 (7) | H12a—C12—H12b | 108.5 |
C6—N2—H2 | 102.5 | Cu1—O1aq—H1aqA | 121 |
C7—N2—H2 | 110.5 | Cu1—O1aq—H1aqB | 121 |
Cu3—N3—C10 | 107.5 (6) | H1aqA—O1aq—H1aqB | 108 |
Cu3—N3—C11 | 112.4 (7) | Cu2—O2aq—H2aqA | 116 |
Cu3—N3—H3 | 109.9 | Cu2—O2aq—H2aqB | 107 |
C10—N3—C11 | 114.2 (9) | H2aqA—O2aq—H2aqB | 109 |
C10—N3—H3 | 109.4 | Cu3—O3aq—H3aqA | 109 |
C11—N3—H3 | 103.3 | Cu3—O3aq—H3aqB | 129 |
O7—N4—O8 | 119.8 | H3aqA—O3aq—H3aqB | 109 |
O7—N4—O9 | 119.9 | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1O···O17 | 0.96 | 2.10 | 2.77 (2) | 125 |
O1—H1O···O7aq | 0.96 | 2.02 | 2.83 (4) | 141 |
O3—H3O···O5aqi | 0.96 | 1.76 | 2.71 (1) | 171 |
O6—H6O···O7ii | 0.98 | 1.89 | 2.852 (9) | 165 |
N1—H1···O8iii | 0.94 | 1.96 | 2.875 (8) | 164 |
N2—H2···O8iv | 0.94 | 2.04 | 2.950 (8) | 162 |
O1aq—H1aqA···O1 | 0.90 | 2.25 | 3.06 (1) | 149 |
O2aq—H2aqB···O3v | 0.94 | 2.10 | 3.05 (1) | 174 |
O2aq—H2aqA···O17 | 0.89 | 2.10 | 2.94 (3) | 157 |
O5aq—-···O10vi | - | - | 2.92 (2) | - |
O17—-···O4aqvii | - | - | 2.79 (4) | - |
O4aq—-···O12vii | - | - | 2.72 (2) | - |
O4aq—-···O6aqviii | - | - | 2.71 (4) | - |
O4aq—-···O7aqiii | - | - | 2.70 (4) | - |
O5aq—-···O13ix | - | - | 2.68 (3) | - |
O5aq—-···O8aqix | - | - | 2.73 (2) | - |
Symmetry codes: (i) x+1/2, y+1/2, −z+1; (ii) y, −x+3/2, −z+1/2; (iii) −y+1/2, x, −z+1/2; (iv) −x+1, −y+1, −z+1; (v) −x+1/2, −y+3/2, z; (vi) −y, x−1/2, z+1/2; (vii) y, −x+1/2, −z+1/2; (viii) −y+1, x−1/2, z−1/2; (ix) −x+1/2, −y+1/2, z. |
Experimental details
Crystal data |
Chemical formula | [Cu4(C4H10NO2)4(H2O)4](NO3)4·14/3H2O |
Mr | 1074.85 |
Crystal system, space group | Tetragonal, P42/n |
Temperature (K) | 150 |
a, c (Å) | 17.797 (2), 20.600 (2) |
V (Å3) | 6524.7 (12) |
Z | 6 |
Radiation type | Mo Kα |
µ (mm−1) | 2.03 |
Crystal size (mm) | 0.35 × 0.14 × 0.11 |
|
Data collection |
Diffractometer | Bruker SMART CCD diffractometer |
Absorption correction | Multi-scan SADABS; Sheldrick, 1996 |
Tmin, Tmax | 0.67, 0.84 |
No. of measured, independent and observed [F > 4σ(F)] reflections | 63965, 6674, 3803 |
Rint | 0.077 |
(sin θ/λ)max (Å−1) | 0.625 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.064, 0.087, 1.02 |
No. of reflections | 3803 |
No. of parameters | 397 |
No. of restraints | 9 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.46, −0.86 |
Selected geometric parameters (Å, º) topCu1—O2 | 1.964 (5) | Cu2—O2aq | 1.992 (8) |
Cu1—O3 | 2.544 (6) | Cu2—O2 | 2.562 (5) |
Cu1—O4 | 1.946 (5) | Cu2—O4 | 1.974 (5) |
Cu1—N2 | 2.022 (6) | Cu3—O5 | 1.939 (6) |
Cu1—O1aq | 2.010 (7) | Cu3—O6 | 2.475 (7) |
Cu1—O4 | 2.520 (5) | Cu3—N3 | 2.045 (8) |
Cu2—O1 | 2.558 (7) | Cu3—O3aq | 1.989 (8) |
Cu2—O2 | 1.942 (5) | Cu3—O5 | 2.531 (6) |
Cu2—N1 | 2.032 (7) | Cu3—O5 | 1.977 (6) |
| | | |
O2—Cu1—O3 | 92.6 (2) | O2—Cu2—O4 | 87.3 (2) |
O2—Cu1—O4 | 87.5 (2) | N1—Cu2—O2aq | 94.6 (3) |
O2—Cu1—N2 | 166.9 (3) | N1—Cu2—O2 | 117.8 (2) |
O2—Cu1—O1aq | 94.5 (3) | N1—Cu2—O4 | 166.3 (3) |
O2—Cu1—O4 | 73.0 (2) | O2aq—Cu2—O2 | 89.9 (3) |
O3—Cu1—O4 | 94.1 (2) | O2aq—Cu2—O4 | 95.1 (3) |
O3—Cu1—N2 | 77.2 (2) | O2—Cu2—O4 | 71.86 (19) |
O3—Cu1—O1aq | 95.7 (3) | O5—Cu3—O6 | 95.3 (2) |
O3—Cu1—O4 | 164.23 (17) | O5—Cu3—N3 | 84.5 (3) |
O4—Cu1—N2 | 85.0 (2) | O5—Cu3—O3aq | 168.8 (3) |
O4—Cu1—O1aq | 169.8 (3) | O5—Cu3—O5 | 82.7 (2) |
O4—Cu1—O4 | 79.1 (2) | O5—Cu3—O5 | 86.8 (2) |
N2—Cu1—O1aq | 94.7 (3) | O6—Cu3—N3 | 77.5 (3) |
N2—Cu1—O4 | 115.9 (2) | O6—Cu3—O3aq | 95.8 (3) |
O1aq—Cu1—O4 | 92.0 (3) | O6—Cu3—O5 | 164.0 (2) |
O1—Cu2—O2 | 95.3 (2) | O6—Cu3—O5 | 92.0 (2) |
O1—Cu2—N1 | 76.0 (2) | N3—Cu3—O3aq | 96.6 (4) |
O1—Cu2—O2aq | 95.9 (3) | N3—Cu3—O5 | 117.9 (3) |
O1—Cu2—O2 | 164.66 (18) | N3—Cu3—O5 | 165.6 (3) |
O1—Cu2—O4 | 93.4 (2) | O3aq—Cu3—O5 | 87.0 (3) |
O2—Cu2—N1 | 85.1 (2) | O3aq—Cu3—O5 | 94.2 (3) |
O2—Cu2—O2aq | 168.3 (3) | O5—Cu3—O5 | 72.1 (2) |
O2—Cu2—O2 | 80.0 (2) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1O···O17 | 0.96 | 2.10 | 2.77 (2) | 125 |
O1—H1O···O7aq | 0.96 | 2.02 | 2.83 (4) | 141 |
O3—H3O···O5aqi | 0.96 | 1.76 | 2.71 (1) | 171 |
O6—H6O···O7ii | 0.98 | 1.89 | 2.852 (9) | 165 |
N1—H1···O8iii | 0.94 | 1.96 | 2.875 (8) | 164 |
N2—H2···O8iv | 0.94 | 2.04 | 2.950 (8) | 162 |
O1aq—H1aqA···O1 | 0.90 | 2.25 | 3.06 (1) | 149 |
O2aq—H2aqB···O3v | 0.94 | 2.10 | 3.05 (1) | 174 |
O2aq—H2aqA···O17 | 0.89 | 2.10 | 2.94 (3) | 157 |
O5aq—-···O10vi | - | - | 2.92 (2) | - |
O17—-···O4aqvii | - | - | 2.79 (4) | - |
O4aq—-···O12vii | - | - | 2.72 (2) | - |
O4aq—-···O6aqviii | - | - | 2.71 (4) | - |
O4aq—-···O7aqiii | - | - | 2.70 (4) | - |
O5aq—-···O13ix | - | - | 2.68 (3) | - |
O5aq—-···O8aqix | - | - | 2.73 (2) | - |
Symmetry codes: (i) x+1/2, y+1/2, −z+1; (ii) y, −x+3/2, −z+1/2; (iii) −y+1/2, x, −z+1/2; (iv) −x+1, −y+1, −z+1; (v) −x+1/2, −y+3/2, z; (vi) −y, x−1/2, z+1/2; (vii) y, −x+1/2, −z+1/2; (viii) −y+1, x−1/2, z−1/2; (ix) −x+1/2, −y+1/2, z. |
We have recently succeeded in the preparation of a number of new Cu/M (M = Pb, Co, Zn, Ni) mixed-metal complexes by reacting copper powder with a salt of another metal (or metal oxide and ammonium salt) in a non-aqueous solution of an amino alcohol (Kovbasyuk et al., 1998; Vinogradova et al., 2001; Makhankova et al., 2002, 2003; Vinogradova et al., 2002). However, the direct interaction of metallic copper and nickel nitrate in the presence of diethanolamine (H2dea) in CH3OH, in air, did not result in the desired Cu/Ni mixed-metal compound, but afforded the tetranuclear copper complex [Cu4(Hdea)4(H2O)4](NO3)4.14/3H2O, (I).
The structure of (I) has been crystallographically investigated previously (Ivanova et al., 1994). However the insufficient amount of data afforded a structure of low precision, with H atoms on the ligand O and N atoms not being located, and there was also some difficulty in determining the number and location of the nitrate ions. With the availability of a diffractometer with a CCD detector and low-temperature device, a better and significantly different model has been obtained in the present determination with the location of the nitrate ions and ligand H atoms, allowing the number of charges on the cation to be assigned.
In the structure of (I), the three independent sets of metal atoms, Cu1, Cu2 and Cu3, form two crystallographically inequivalent tetranuclear [Cu4(Hdea)4(H2O)4]4+ cations, with largely similar structural data (Fig. 1 and Table 1). The cation containing Cu1 and Cu2 lies on a twofold axis and that formed from Cu3 has 4 symmetry. Each copper centre is similarly coordinated by two alkoxo O atoms, one amine N atom of the monodeprotonated Hdea ligands and one O atom from a water molecule in a square-planar geometry [Cu—O/N bond lengths are in the range 1.939 (6)–2.045 (8) Å]. As shown in the diagram, the two axial positions of the Cu atoms are occupied by a weakly bound ethanol group of the chelating Hdea ligand and an alkoxo O atom from a neighbouring Hdea ligand [average Cu—O = 2.532 (7) Å]. The geometry of the Cu atoms can therefore be best described as distorted elongated octahedra. Each Hdea ligand adopts a chelating-bridging mode forming five-membered rings with the ethanol group weakly coordinated, a coordination mode that is common for dinuclear copper complexes of this ligand (Karadag et al., 2001; Madarasz et al., 2000; Yilmaz et al., 2001). However, in (I), the triply bridging function of the alkoxo O atoms is realised and results in the formation of a Cu4O4 cluster made up of a copper tetrahedron interlocked with an oxygen tetrahedron that is closely related to the cubane-type structure (see the diagram). The bridged Cu···Cu distances lie in the range 3.172 (1)–3.213 (1) Å. All faces of the heterocubane core are remarkably non-planar, their edges are of different length and the least-squares rhombohedral planes of the faces are mutually non-orthogonal. In the structure of another copper tetramer [Cu4(Hdea)4(OAc)4] published recently (Saalfrank et al., 2001) four copper centres are linked in an alternating way by bridging O atoms in an anti-tricyclo[4.2.0.02,5]octane-like fashion.
The X-ray investigation shows possible intra- and intermolecular hydrogen bonds involving the OH and NH groups of the ligands, coordinated and uncoordinated water molecules and uncoordinated NO3- anions, as indicated by the O···O and O···N distances (Table 2). The hydrogen bonding maintains the crystal structure by forming an extended three-dimensional network (Fig. 2).
All bond distances and angles within the monodeprotonated diethanolamine are as expected.