Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807044893/dn2227sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807044893/dn2227Isup2.hkl |
CCDC reference: 663629
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.003 Å
- R factor = 0.024
- wR factor = 0.060
- Data-to-parameter ratio = 12.8
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Ni1 - O1 .. 6.23 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Ni1 - O6 .. 7.24 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Ni1 - N1 .. 5.09 su PLAT417_ALERT_2_C Short Inter D-H..H-D H1W .. H4W .. 2.12 Ang.
Alert level G PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 6
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 4 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
The title complex was prepared by the addition of a stoichiometric amount of nickel chloride (1 mmol) to a hot methanol solution (10 ml) of egtaH4 (1 mmol). The resulting solution was filtered, and pale green blocky crystals were obtained on slow evaporation of the solvent over several days at room temperature.
Carbon-bound H atoms were placed at calculated positions and were treated as riding on the parent C atoms with C—H= 97Å and with Uiso(H) = 1.2Ueq(C). H atoms attached to water molecules were found in a difference map and their positions were refined using restraints (O—H= 0.84 (2)Å and H···H= 1.38 Å) with Uiso(H) = 1.5Ueq(O).
The coordination of multipyridine and multi-carboxylate ligands to metal centers has proved to be an excellent tool in the assembly process and has been highly influenced by the structural characterizations of tectonic spacers. Polydentate amino-polycarboxylate acid [H4egta=3,12-bis (carboxymethyl)-6, 9-dioxa-3, 12-diazatetradecanedioic acid], being extensively used as a calcium buffer in biological research, possesses symmetrical four potential coordinating sites and renders it an appropriate candidate to improve the extension of the ferrimagnetic lattice from one dimensional (one-dimensional) systems to two-dimensional and three-dimensional networks (Bomas-Almenar et al., 1993). In this paper, we report the synthesis and crystal structure of the title complex,(I).
As illustrated in Fig. 1, the neutral dinuclear molecule, lies on a centre of symmetry. Both nickel(II) centers are pentacoordinated to one N atom and three O atoms of egta, forming the basal plane, and one O donors of water molecule being in axial position, then leading to a distorted square-pyramid environment. The structural components are connected through O—H···O hydrogen bonding involving the lattice water molecules as donors and the uncoordinated O atoms as acceptors thus forming a three dimensionnal supramolecular network structure (Table 1).
For related literature, see: Bomas-Almenar et al. (1993).
Data collection: APEX2 (Bruker, 1998); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Ref??).
[Ni2(C14H20N2O10)(H2O)2]·2H2O | F(000) = 1176 |
Mr = 565.80 | Dx = 1.748 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 2007 reflections |
a = 21.031 (2) Å | θ = 2.9–25.5° |
b = 7.5299 (9) Å | µ = 1.83 mm−1 |
c = 13.5789 (16) Å | T = 298 K |
β = 90.464 (1)° | Block, green |
V = 2150.3 (4) Å3 | 0.34 × 0.12 × 0.04 mm |
Z = 4 |
Bruker APEXII area-detector diffractometer | 2007 independent reflections |
Radiation source: fine-focus sealed tube | 1756 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.027 |
φ and ω scans | θmax = 25.5°, θmin = 2.9° |
Absorption correction: multi-scan SADABS (Sheldrick, 1996) | h = −25→25 |
Tmin = 0.580, Tmax = 0.931 | k = −9→9 |
7928 measured reflections | l = −16→15 |
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)] = 0.024 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.060 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0294P)2 + 0.9421P] where P = (Fo2 + 2Fc2)/3 |
2007 reflections | (Δ/σ)max = 0.002 |
157 parameters | Δρmax = 0.34 e Å−3 |
6 restraints | Δρmin = −0.19 e Å−3 |
[Ni2(C14H20N2O10)(H2O)2]·2H2O | V = 2150.3 (4) Å3 |
Mr = 565.80 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 21.031 (2) Å | µ = 1.83 mm−1 |
b = 7.5299 (9) Å | T = 298 K |
c = 13.5789 (16) Å | 0.34 × 0.12 × 0.04 mm |
β = 90.464 (1)° |
Bruker APEXII area-detector diffractometer | 2007 independent reflections |
Absorption correction: multi-scan SADABS (Sheldrick, 1996) | 1756 reflections with I > 2σ(I) |
Tmin = 0.580, Tmax = 0.931 | Rint = 0.027 |
7928 measured reflections |
R[F2 > 2σ(F2)] = 0.024 | 6 restraints |
wR(F2) = 0.060 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | Δρmax = 0.34 e Å−3 |
2007 reflections | Δρmin = −0.19 e Å−3 |
157 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 | ||
Ni1 | 0.628725 (12) | 0.21993 (3) | 0.564464 (18) | 0.02584 (10) | |
O1 | 0.67589 (7) | 0.37797 (18) | 0.47843 (11) | 0.0328 (3) | |
O2 | 0.74168 (7) | 0.3724 (2) | 0.35187 (12) | 0.0412 (4) | |
O3 | 0.60468 (7) | 0.02307 (18) | 0.64666 (10) | 0.0352 (4) | |
O4 | 0.62324 (9) | −0.2649 (2) | 0.66266 (12) | 0.0497 (5) | |
O5 | 0.53305 (7) | 0.28393 (19) | 0.47083 (11) | 0.0336 (4) | |
O6 | 0.61807 (8) | 0.3871 (2) | 0.67071 (12) | 0.0383 (4) | |
H1W | 0.6396 (12) | 0.354 (3) | 0.7181 (16) | 0.057* | |
H2W | 0.6247 (12) | 0.492 (2) | 0.6580 (18) | 0.057* | |
O7 | 0.70120 (9) | 0.2874 (2) | 0.80982 (13) | 0.0453 (4) | |
H3W | 0.7178 (12) | 0.385 (3) | 0.828 (2) | 0.068* | |
H4W | 0.7255 (12) | 0.239 (3) | 0.7706 (19) | 0.068* | |
N1 | 0.63903 (8) | 0.0375 (2) | 0.45889 (11) | 0.0250 (4) | |
C1 | 0.70315 (10) | 0.2990 (3) | 0.40776 (16) | 0.0290 (5) | |
C2 | 0.68935 (9) | 0.1023 (3) | 0.39122 (15) | 0.0282 (5) | |
H2A | 0.6757 | 0.0840 | 0.3236 | 0.034* | |
H2B | 0.7280 | 0.0344 | 0.4020 | 0.034* | |
C3 | 0.65593 (10) | −0.1272 (3) | 0.51335 (15) | 0.0306 (5) | |
H3A | 0.7018 | −0.1353 | 0.5206 | 0.037* | |
H3B | 0.6414 | −0.2300 | 0.4765 | 0.037* | |
C4 | 0.62514 (10) | −0.1259 (3) | 0.61503 (15) | 0.0318 (5) | |
C5 | 0.57655 (10) | 0.0158 (3) | 0.40651 (15) | 0.0315 (5) | |
H5A | 0.5477 | −0.0502 | 0.4482 | 0.038* | |
H5B | 0.5829 | −0.0522 | 0.3467 | 0.038* | |
C6 | 0.54713 (10) | 0.1921 (3) | 0.38073 (16) | 0.0346 (5) | |
H6A | 0.5764 | 0.2617 | 0.3416 | 0.042* | |
H6B | 0.5084 | 0.1742 | 0.3426 | 0.042* | |
C7 | 0.51520 (11) | 0.4654 (3) | 0.45390 (16) | 0.0399 (6) | |
H7A | 0.4855 | 0.4729 | 0.3991 | 0.048* | |
H7B | 0.5524 | 0.5357 | 0.4382 | 0.048* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.03413 (17) | 0.01904 (16) | 0.02442 (16) | −0.00075 (11) | 0.00398 (11) | −0.00223 (11) |
O1 | 0.0396 (8) | 0.0230 (8) | 0.0360 (8) | −0.0019 (6) | 0.0064 (7) | −0.0023 (6) |
O2 | 0.0463 (10) | 0.0303 (9) | 0.0472 (10) | −0.0061 (7) | 0.0184 (8) | 0.0033 (7) |
O3 | 0.0509 (9) | 0.0244 (8) | 0.0305 (8) | −0.0004 (7) | 0.0112 (7) | −0.0017 (6) |
O4 | 0.0880 (14) | 0.0262 (9) | 0.0349 (9) | 0.0034 (9) | 0.0107 (9) | 0.0057 (7) |
O5 | 0.0361 (9) | 0.0321 (8) | 0.0326 (8) | 0.0080 (7) | 0.0034 (7) | 0.0013 (6) |
O6 | 0.0560 (11) | 0.0231 (8) | 0.0358 (9) | 0.0043 (8) | 0.0001 (8) | −0.0041 (7) |
O7 | 0.0633 (12) | 0.0324 (9) | 0.0404 (10) | −0.0015 (8) | 0.0109 (9) | −0.0031 (8) |
N1 | 0.0269 (9) | 0.0236 (9) | 0.0247 (9) | −0.0006 (7) | 0.0034 (7) | 0.0001 (7) |
C1 | 0.0274 (11) | 0.0259 (11) | 0.0336 (12) | 0.0016 (9) | −0.0005 (9) | 0.0032 (9) |
C2 | 0.0288 (11) | 0.0267 (11) | 0.0293 (11) | −0.0013 (9) | 0.0066 (9) | −0.0014 (9) |
C3 | 0.0390 (12) | 0.0225 (11) | 0.0306 (11) | 0.0030 (9) | 0.0043 (9) | −0.0015 (9) |
C4 | 0.0390 (13) | 0.0285 (12) | 0.0279 (11) | −0.0033 (9) | 0.0005 (9) | 0.0008 (10) |
C5 | 0.0318 (12) | 0.0320 (12) | 0.0308 (11) | −0.0044 (9) | 0.0027 (9) | −0.0060 (9) |
C6 | 0.0325 (12) | 0.0442 (14) | 0.0273 (12) | 0.0036 (10) | 0.0003 (9) | −0.0013 (10) |
C7 | 0.0415 (13) | 0.0351 (13) | 0.0433 (14) | 0.0119 (10) | 0.0036 (10) | 0.0064 (11) |
Ni1—O3 | 1.9255 (14) | N1—C5 | 1.498 (3) |
Ni1—O6 | 1.9293 (15) | C1—C2 | 1.525 (3) |
Ni1—O1 | 1.9451 (14) | C2—H2A | 0.9700 |
Ni1—N1 | 1.9986 (16) | C2—H2B | 0.9700 |
O1—C1 | 1.270 (2) | C3—C4 | 1.530 (3) |
O2—C1 | 1.244 (2) | C3—H3A | 0.9700 |
O3—C4 | 1.277 (2) | C3—H3B | 0.9700 |
O4—C4 | 1.231 (3) | C5—C6 | 1.505 (3) |
O5—C7 | 1.436 (3) | C5—H5A | 0.9700 |
O5—C6 | 1.438 (2) | C5—H5B | 0.9700 |
O6—H1W | 0.823 (16) | C6—H6A | 0.9700 |
O6—H2W | 0.821 (16) | C6—H6B | 0.9700 |
O7—H3W | 0.847 (16) | C7—C7i | 1.503 (4) |
O7—H4W | 0.826 (16) | C7—H7A | 0.9700 |
N1—C3 | 1.486 (2) | C7—H7B | 0.9700 |
N1—C2 | 1.489 (2) | ||
O3—Ni1—O6 | 92.08 (7) | N1—C3—C4 | 110.04 (16) |
O3—Ni1—O1 | 163.08 (6) | N1—C3—H3A | 109.7 |
O6—Ni1—O1 | 96.47 (7) | C4—C3—H3A | 109.7 |
O3—Ni1—N1 | 85.25 (6) | N1—C3—H3B | 109.7 |
O6—Ni1—N1 | 177.32 (7) | C4—C3—H3B | 109.7 |
O1—Ni1—N1 | 86.04 (6) | H3A—C3—H3B | 108.2 |
C1—O1—Ni1 | 113.76 (13) | O4—C4—O3 | 123.9 (2) |
C4—O3—Ni1 | 112.98 (13) | O4—C4—C3 | 118.98 (19) |
C7—O5—C6 | 112.13 (16) | O3—C4—C3 | 117.09 (18) |
Ni1—O6—H1W | 108.7 (19) | N1—C5—C6 | 111.81 (17) |
Ni1—O6—H2W | 116.7 (19) | N1—C5—H5A | 109.3 |
H1W—O6—H2W | 111 (2) | C6—C5—H5A | 109.3 |
H3W—O7—H4W | 108 (2) | N1—C5—H5B | 109.3 |
C3—N1—C2 | 114.36 (16) | C6—C5—H5B | 109.3 |
C3—N1—C5 | 110.52 (16) | H5A—C5—H5B | 107.9 |
C2—N1—C5 | 111.58 (15) | O5—C6—C5 | 108.25 (17) |
C3—N1—Ni1 | 104.10 (11) | O5—C6—H6A | 110.0 |
C2—N1—Ni1 | 107.40 (12) | C5—C6—H6A | 110.0 |
C5—N1—Ni1 | 108.41 (12) | O5—C6—H6B | 110.0 |
O2—C1—O1 | 123.58 (19) | C5—C6—H6B | 110.0 |
O2—C1—C2 | 117.76 (18) | H6A—C6—H6B | 108.4 |
O1—C1—C2 | 118.65 (18) | O5—C7—C7i | 108.0 (2) |
N1—C2—C1 | 111.27 (16) | O5—C7—H7A | 110.1 |
N1—C2—H2A | 109.4 | C7i—C7—H7A | 110.1 |
C1—C2—H2A | 109.4 | O5—C7—H7B | 110.1 |
N1—C2—H2B | 109.4 | C7i—C7—H7B | 110.1 |
C1—C2—H2B | 109.4 | H7A—C7—H7B | 108.4 |
H2A—C2—H2B | 108.0 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O6—H1W···O7 | 0.82 (2) | 1.86 (2) | 2.671 (3) | 169 (3) |
O6—H2W···O4ii | 0.82 (2) | 1.83 (2) | 2.625 (2) | 162 (3) |
O7—H3W···O2iii | 0.85 (2) | 1.92 (2) | 2.758 (2) | 168 (3) |
O7—H4W···O2iv | 0.83 (2) | 1.99 (2) | 2.785 (2) | 161 (3) |
Symmetry codes: (ii) x, y+1, z; (iii) x, −y+1, z+1/2; (iv) −x+3/2, −y+1/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Ni2(C14H20N2O10)(H2O)2]·2H2O |
Mr | 565.80 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 298 |
a, b, c (Å) | 21.031 (2), 7.5299 (9), 13.5789 (16) |
β (°) | 90.464 (1) |
V (Å3) | 2150.3 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.83 |
Crystal size (mm) | 0.34 × 0.12 × 0.04 |
Data collection | |
Diffractometer | Bruker APEXII area-detector diffractometer |
Absorption correction | Multi-scan SADABS (Sheldrick, 1996) |
Tmin, Tmax | 0.580, 0.931 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7928, 2007, 1756 |
Rint | 0.027 |
(sin θ/λ)max (Å−1) | 0.606 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.024, 0.060, 1.08 |
No. of reflections | 2007 |
No. of parameters | 157 |
No. of restraints | 6 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.34, −0.19 |
Computer programs: APEX2 (Bruker, 1998), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996); ORTEP-3 for Windows (Farrugia, 1997), SHELXTL (Ref??).
D—H···A | D—H | H···A | D···A | D—H···A |
O6—H1W···O7 | 0.823 (16) | 1.859 (17) | 2.671 (3) | 169 (3) |
O6—H2W···O4i | 0.821 (16) | 1.832 (18) | 2.625 (2) | 162 (3) |
O7—H3W···O2ii | 0.847 (16) | 1.924 (17) | 2.758 (2) | 168 (3) |
O7—H4W···O2iii | 0.826 (16) | 1.991 (17) | 2.785 (2) | 161 (3) |
Symmetry codes: (i) x, y+1, z; (ii) x, −y+1, z+1/2; (iii) −x+3/2, −y+1/2, −z+1. |
The coordination of multipyridine and multi-carboxylate ligands to metal centers has proved to be an excellent tool in the assembly process and has been highly influenced by the structural characterizations of tectonic spacers. Polydentate amino-polycarboxylate acid [H4egta=3,12-bis (carboxymethyl)-6, 9-dioxa-3, 12-diazatetradecanedioic acid], being extensively used as a calcium buffer in biological research, possesses symmetrical four potential coordinating sites and renders it an appropriate candidate to improve the extension of the ferrimagnetic lattice from one dimensional (one-dimensional) systems to two-dimensional and three-dimensional networks (Bomas-Almenar et al., 1993). In this paper, we report the synthesis and crystal structure of the title complex,(I).
As illustrated in Fig. 1, the neutral dinuclear molecule, lies on a centre of symmetry. Both nickel(II) centers are pentacoordinated to one N atom and three O atoms of egta, forming the basal plane, and one O donors of water molecule being in axial position, then leading to a distorted square-pyramid environment. The structural components are connected through O—H···O hydrogen bonding involving the lattice water molecules as donors and the uncoordinated O atoms as acceptors thus forming a three dimensionnal supramolecular network structure (Table 1).