Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807037920/hb2463sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807037920/hb2463Isup2.hkl |
CCDC reference: 660073
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.004 Å
- R factor = 0.027
- wR factor = 0.075
- Data-to-parameter ratio = 14.1
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT601_ALERT_2_B Structure Contains Solvent Accessible VOIDS of . 151.00 A 3
Alert level C CELLV02_ALERT_1_C The supplied cell volume s.u. differs from that calculated from the cell parameter s.u.'s by > 2 Calculated cell volume su = 15.17 Cell volume su given = 13.00 PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.88 PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ..... ? PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 1 C44 H52 Cu4 N4 O16
Alert level G ABSTM02_ALERT_3_G When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.885 Tmax scaled 0.431 Tmin scaled 0.405 PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1 (2) 2.23
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 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 2 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
Trihydroxymethylaminomethane (1 mmol, 121.14 mg) was dissolved in hot methanol (10 ml) and added in portions to a methanol solution (3 ml) of salicylaldehyde (1 mmol, 0.11 ml). The mixture was then stirred at 323 K for 2 h. Subsequently, an aqueous solution (2 ml) of cupric acetate hydrate (1 mmol, 199.7 mg) was added dropwise and stirred for another 5 h. The solution was held at room temperature for ten days, whereupon blue blocks of (I) were obtained.
All the H atoms were placed in calculated positions (C—H = 0.93–0.97 Å, O—H = 0.82 Å) and refined as riding with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(Cmethyl, O).
Considerable efforts have been devoted to the study of polynuclear CuII complexes due to their importance as models for enzymatic systems (Beinert, 1980) and in studying metal-metal interactions. The chemistry of transition metal complexes of hydroxy(aryl-OH and alkyl-OH) rich molecules containing imine/amine group is important in the biomimetic studies of metalloproteins (Mishtu et al., 2002).
A few structurally characterized multinuclear complexes containing Schiff base ligands has been reported (Mishtu et al., 2002). As part of our ongoing studies (Dong et al., 2007) in this area, we report here the synthesis and crystal structure of the title compound, (I), a tetracopper(II) complex with a tridentate Schiff base ligand derived from the condensation of salicylaldehyde and trihydroxymethylaminomethane. Mishtu et al. (2002) reported the same cluster as a hydrate in a different space group.
Compound (I) contains a teranuclear cubane core based on an approximately cubic array of alternating copper and oxygen atoms (Fig. 1). Each CuII atom resides in a distorted square-pyramid coordination environment with one nitrogen and two oxygen atoms from one Schiff base ligand and two oxygen atoms from the neighboring units of the cubane. The Cu atom deviates from the basal plane formed by O1, N1, O2 and O2i (i = y - 1/4, -x + 5/4, -z + 9/4) by 0.0672 (12) Å, with a significantly longer Cu—Oapical bond distance (Table 1).
Within the cluster, the Cu···Cu distances [3.591 (4) Å, 3.154 (3) Å] are similar to the reported values for related structures (Si et al., 2002; Mishtu et al., 2002), indicating no significant bonding interactions between the CuII ions in (I).
In the crystal structure, the intermolecular O—H···O hydrogen bonds help to form a three-dimensional network (Fig. 2, Table 2).
For related literature, see: Beinert (1980); Dong et al. (2007); Mishtu et al. (2002); Si et al. (2002).
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.
[Cu4(C11H13NO4)4] | Dx = 1.528 Mg m−3 |
Mr = 1147.06 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, I41/a | Cell parameters from 5431 reflections |
Hall symbol: -I 4ad | θ = 2.4–28.1° |
a = 17.209 (3) Å | µ = 1.75 mm−1 |
c = 16.836 (3) Å | T = 298 K |
V = 4986.0 (13) Å3 | Block, blue |
Z = 4 | 0.53 × 0.49 × 0.48 mm |
F(000) = 2352 |
Siemens SMART CCD area-detector diffractometer | 2203 independent reflections |
Radiation source: fine-focus sealed tube | 1821 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.050 |
ω scans | θmax = 25.0°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −20→18 |
Tmin = 0.457, Tmax = 0.487 | k = −20→16 |
12748 measured reflections | l = −18→20 |
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)] = 0.028 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.075 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0407P)2 + 3.0697P] where P = (Fo2 + 2Fc2)/3 |
2203 reflections | (Δ/σ)max = 0.002 |
156 parameters | Δρmax = 0.32 e Å−3 |
0 restraints | Δρmin = −0.19 e Å−3 |
[Cu4(C11H13NO4)4] | Z = 4 |
Mr = 1147.06 | Mo Kα radiation |
Tetragonal, I41/a | µ = 1.75 mm−1 |
a = 17.209 (3) Å | T = 298 K |
c = 16.836 (3) Å | 0.53 × 0.49 × 0.48 mm |
V = 4986.0 (13) Å3 |
Siemens SMART CCD area-detector diffractometer | 2203 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1821 reflections with I > 2σ(I) |
Tmin = 0.457, Tmax = 0.487 | Rint = 0.050 |
12748 measured reflections |
R[F2 > 2σ(F2)] = 0.028 | 0 restraints |
wR(F2) = 0.075 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.32 e Å−3 |
2203 reflections | Δρmin = −0.19 e Å−3 |
156 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 | ||
Cu1 | 0.396178 (15) | 0.739558 (15) | 1.069439 (16) | 0.02320 (12) | |
N1 | 0.37415 (11) | 0.69497 (11) | 0.96723 (11) | 0.0261 (4) | |
O1 | 0.31430 (10) | 0.81400 (10) | 1.06436 (10) | 0.0347 (4) | |
O2 | 0.48427 (9) | 0.66875 (9) | 1.07064 (8) | 0.0235 (4) | |
O3 | 0.36321 (12) | 0.57702 (11) | 0.82462 (11) | 0.0452 (5) | |
H3 | 0.3518 | 0.5309 | 0.8286 | 0.068* | |
O4 | 0.32782 (10) | 0.58053 (12) | 1.07332 (10) | 0.0393 (5) | |
H4 | 0.3644 | 0.5761 | 1.1042 | 0.059* | |
C1 | 0.32492 (15) | 0.72192 (14) | 0.91698 (15) | 0.0341 (6) | |
H1 | 0.3192 | 0.6951 | 0.8694 | 0.041* | |
C2 | 0.27757 (15) | 0.79070 (15) | 0.92818 (15) | 0.0343 (6) | |
C3 | 0.27275 (14) | 0.83153 (14) | 1.00084 (15) | 0.0293 (5) | |
C4 | 0.22008 (15) | 0.89372 (15) | 1.00520 (17) | 0.0400 (7) | |
H4A | 0.2151 | 0.9208 | 1.0527 | 0.048* | |
C5 | 0.17574 (18) | 0.91569 (17) | 0.94118 (18) | 0.0492 (8) | |
H5A | 0.1420 | 0.9577 | 0.9459 | 0.059* | |
C6 | 0.18063 (19) | 0.87623 (18) | 0.87002 (19) | 0.0543 (9) | |
H6 | 0.1508 | 0.8914 | 0.8267 | 0.065* | |
C7 | 0.23011 (18) | 0.81440 (18) | 0.86439 (17) | 0.0497 (8) | |
H7 | 0.2326 | 0.7870 | 0.8168 | 0.060* | |
C8 | 0.40970 (14) | 0.61676 (13) | 0.95857 (14) | 0.0262 (5) | |
C9 | 0.48709 (13) | 0.61901 (14) | 1.00416 (14) | 0.0285 (5) | |
H9A | 0.5000 | 0.5669 | 1.0217 | 0.034* | |
H9B | 0.5279 | 0.6364 | 0.9686 | 0.034* | |
C10 | 0.42851 (15) | 0.59321 (15) | 0.87300 (15) | 0.0355 (6) | |
H10A | 0.4581 | 0.6347 | 0.8484 | 0.043* | |
H10B | 0.4614 | 0.5475 | 0.8743 | 0.043* | |
C11 | 0.35195 (14) | 0.55883 (15) | 0.99569 (15) | 0.0328 (6) | |
H11A | 0.3066 | 0.5549 | 0.9617 | 0.039* | |
H11B | 0.3761 | 0.5079 | 0.9980 | 0.039* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.02486 (18) | 0.02156 (18) | 0.02318 (18) | 0.00370 (11) | −0.00404 (12) | −0.00364 (11) |
N1 | 0.0298 (11) | 0.0224 (10) | 0.0260 (10) | 0.0035 (8) | −0.0045 (9) | −0.0034 (8) |
O1 | 0.0382 (10) | 0.0368 (10) | 0.0291 (9) | 0.0146 (8) | −0.0113 (8) | −0.0098 (8) |
O2 | 0.0288 (9) | 0.0195 (8) | 0.0222 (9) | 0.0043 (6) | −0.0045 (7) | −0.0024 (6) |
O3 | 0.0653 (14) | 0.0341 (11) | 0.0362 (10) | 0.0008 (9) | −0.0197 (10) | −0.0073 (9) |
O4 | 0.0288 (10) | 0.0581 (12) | 0.0310 (10) | 0.0011 (9) | 0.0001 (8) | 0.0036 (9) |
C1 | 0.0433 (16) | 0.0315 (14) | 0.0273 (13) | 0.0041 (12) | −0.0095 (12) | −0.0054 (11) |
C2 | 0.0384 (15) | 0.0309 (14) | 0.0336 (14) | 0.0049 (11) | −0.0102 (12) | 0.0015 (11) |
C3 | 0.0303 (14) | 0.0229 (12) | 0.0346 (14) | 0.0016 (10) | −0.0066 (11) | 0.0009 (11) |
C4 | 0.0381 (16) | 0.0364 (15) | 0.0456 (16) | 0.0106 (12) | −0.0080 (13) | −0.0057 (13) |
C5 | 0.0496 (18) | 0.0366 (16) | 0.061 (2) | 0.0180 (13) | −0.0146 (15) | 0.0033 (14) |
C6 | 0.061 (2) | 0.0534 (19) | 0.0489 (19) | 0.0191 (16) | −0.0243 (15) | 0.0073 (15) |
C7 | 0.064 (2) | 0.0486 (18) | 0.0360 (16) | 0.0164 (15) | −0.0187 (14) | −0.0041 (14) |
C8 | 0.0288 (13) | 0.0239 (12) | 0.0258 (12) | 0.0027 (10) | −0.0032 (10) | −0.0069 (10) |
C9 | 0.0254 (13) | 0.0289 (13) | 0.0312 (14) | 0.0042 (10) | −0.0018 (11) | −0.0075 (11) |
C10 | 0.0441 (16) | 0.0339 (15) | 0.0287 (14) | 0.0027 (12) | −0.0008 (12) | −0.0082 (11) |
C11 | 0.0323 (14) | 0.0298 (14) | 0.0364 (15) | 0.0016 (10) | −0.0008 (11) | −0.0002 (11) |
Cu1—O1 | 1.9063 (16) | C3—C4 | 1.404 (3) |
Cu1—N1 | 1.9218 (19) | C4—C5 | 1.374 (4) |
Cu1—O2i | 1.9438 (15) | C4—H4A | 0.9300 |
Cu1—O2 | 1.9451 (16) | C5—C6 | 1.380 (4) |
Cu1—O2ii | 2.5930 (16) | C5—H5A | 0.9300 |
N1—C1 | 1.284 (3) | C6—C7 | 1.366 (4) |
N1—C8 | 1.486 (3) | C6—H6 | 0.9300 |
O1—C3 | 1.321 (3) | C7—H7 | 0.9300 |
O2—C9 | 1.410 (3) | C8—C10 | 1.531 (3) |
O2—Cu1iii | 1.9438 (15) | C8—C9 | 1.538 (3) |
O3—C10 | 1.416 (3) | C8—C11 | 1.540 (3) |
O3—H3 | 0.8200 | C9—H9A | 0.9700 |
O4—C11 | 1.421 (3) | C9—H9B | 0.9700 |
O4—H4 | 0.8200 | C10—H10A | 0.9700 |
C1—C2 | 1.449 (3) | C10—H10B | 0.9700 |
C1—H1 | 0.9300 | C11—H11A | 0.9700 |
C2—C7 | 1.410 (4) | C11—H11B | 0.9700 |
C2—C3 | 1.413 (3) | ||
O1—Cu1—N1 | 94.72 (7) | C6—C5—H5A | 119.6 |
O1—Cu1—O2i | 91.99 (7) | C7—C6—C5 | 118.8 (3) |
N1—Cu1—O2i | 169.85 (7) | C7—C6—H6 | 120.6 |
O1—Cu1—O2 | 176.00 (7) | C5—C6—H6 | 120.6 |
N1—Cu1—O2 | 85.00 (7) | C6—C7—C2 | 122.3 (3) |
O2i—Cu1—O2 | 88.83 (7) | C6—C7—H7 | 118.9 |
N1—Cu1—O2ii | 113.99 (7) | C2—C7—H7 | 118.9 |
O2i—Cu1—O2ii | 72.12 (6) | N1—C8—C10 | 114.8 (2) |
O2—Cu1—O2ii | 76.28 (6) | N1—C8—C9 | 106.55 (18) |
C1—N1—C8 | 122.3 (2) | C10—C8—C9 | 107.05 (19) |
C1—N1—Cu1 | 125.16 (17) | N1—C8—C11 | 106.31 (19) |
C8—N1—Cu1 | 111.62 (14) | C10—C8—C11 | 110.29 (19) |
C3—O1—Cu1 | 126.14 (15) | C9—C8—C11 | 111.9 (2) |
C9—O2—Cu1iii | 128.79 (14) | O2—C9—C8 | 112.44 (18) |
C9—O2—Cu1 | 113.51 (13) | O2—C9—H9A | 109.1 |
Cu1iii—O2—Cu1 | 108.40 (7) | C8—C9—H9A | 109.1 |
C10—O3—H3 | 109.5 | O2—C9—H9B | 109.1 |
C11—O4—H4 | 109.5 | C8—C9—H9B | 109.1 |
N1—C1—C2 | 125.5 (2) | H9A—C9—H9B | 107.8 |
N1—C1—H1 | 117.3 | O3—C10—C8 | 115.2 (2) |
C2—C1—H1 | 117.3 | O3—C10—H10A | 108.5 |
C7—C2—C3 | 118.8 (2) | C8—C10—H10A | 108.5 |
C7—C2—C1 | 117.6 (2) | O3—C10—H10B | 108.5 |
C3—C2—C1 | 123.5 (2) | C8—C10—H10B | 108.5 |
O1—C3—C4 | 118.7 (2) | H10A—C10—H10B | 107.5 |
O1—C3—C2 | 123.7 (2) | O4—C11—C8 | 113.1 (2) |
C4—C3—C2 | 117.5 (2) | O4—C11—H11A | 109.0 |
C5—C4—C3 | 121.8 (3) | C8—C11—H11A | 109.0 |
C5—C4—H4A | 119.1 | O4—C11—H11B | 109.0 |
C3—C4—H4A | 119.1 | C8—C11—H11B | 109.0 |
C4—C5—C6 | 120.8 (3) | H11A—C11—H11B | 107.8 |
C4—C5—H5A | 119.6 | ||
N1—Cu1—O2—O1 | 86.3 (9) |
Symmetry codes: (i) y−1/4, −x+5/4, −z+9/4; (ii) −x+1, −y+3/2, z; (iii) −y+5/4, x+1/4, −z+9/4. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O4iv | 0.82 | 1.91 | 2.723 (3) | 172 |
O4—H4···O1iii | 0.82 | 1.85 | 2.668 (2) | 171 |
Symmetry codes: (iii) −y+5/4, x+1/4, −z+9/4; (iv) y−1/4, −x+3/4, z−1/4. |
Experimental details
Crystal data | |
Chemical formula | [Cu4(C11H13NO4)4] |
Mr | 1147.06 |
Crystal system, space group | Tetragonal, I41/a |
Temperature (K) | 298 |
a, c (Å) | 17.209 (3), 16.836 (3) |
V (Å3) | 4986.0 (13) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.75 |
Crystal size (mm) | 0.53 × 0.49 × 0.48 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.457, 0.487 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12748, 2203, 1821 |
Rint | 0.050 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.028, 0.075, 1.06 |
No. of reflections | 2203 |
No. of parameters | 156 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.32, −0.19 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXTL.
Cu1—O1 | 1.9063 (16) | Cu1—O2 | 1.9451 (16) |
Cu1—N1 | 1.9218 (19) | Cu1—O2ii | 2.5930 (16) |
Cu1—O2i | 1.9438 (15) |
Symmetry codes: (i) y−1/4, −x+5/4, −z+9/4; (ii) −x+1, −y+3/2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O4iii | 0.82 | 1.91 | 2.723 (3) | 172 |
O4—H4···O1iv | 0.82 | 1.85 | 2.668 (2) | 171 |
Symmetry codes: (iii) y−1/4, −x+3/4, z−1/4; (iv) −y+5/4, x+1/4, −z+9/4. |
Considerable efforts have been devoted to the study of polynuclear CuII complexes due to their importance as models for enzymatic systems (Beinert, 1980) and in studying metal-metal interactions. The chemistry of transition metal complexes of hydroxy(aryl-OH and alkyl-OH) rich molecules containing imine/amine group is important in the biomimetic studies of metalloproteins (Mishtu et al., 2002).
A few structurally characterized multinuclear complexes containing Schiff base ligands has been reported (Mishtu et al., 2002). As part of our ongoing studies (Dong et al., 2007) in this area, we report here the synthesis and crystal structure of the title compound, (I), a tetracopper(II) complex with a tridentate Schiff base ligand derived from the condensation of salicylaldehyde and trihydroxymethylaminomethane. Mishtu et al. (2002) reported the same cluster as a hydrate in a different space group.
Compound (I) contains a teranuclear cubane core based on an approximately cubic array of alternating copper and oxygen atoms (Fig. 1). Each CuII atom resides in a distorted square-pyramid coordination environment with one nitrogen and two oxygen atoms from one Schiff base ligand and two oxygen atoms from the neighboring units of the cubane. The Cu atom deviates from the basal plane formed by O1, N1, O2 and O2i (i = y - 1/4, -x + 5/4, -z + 9/4) by 0.0672 (12) Å, with a significantly longer Cu—Oapical bond distance (Table 1).
Within the cluster, the Cu···Cu distances [3.591 (4) Å, 3.154 (3) Å] are similar to the reported values for related structures (Si et al., 2002; Mishtu et al., 2002), indicating no significant bonding interactions between the CuII ions in (I).
In the crystal structure, the intermolecular O—H···O hydrogen bonds help to form a three-dimensional network (Fig. 2, Table 2).