Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807057376/at2461sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807057376/at2461Isup2.hkl |
CCDC reference: 672637
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.009 Å
- R factor = 0.079
- wR factor = 0.184
- Data-to-parameter ratio = 16.7
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.97 PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.99 PLAT220_ALERT_2_C Large Non-Solvent O Ueq(max)/Ueq(min) ... 2.86 Ratio PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 9
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1 (2) 2.07
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 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
5-Nitro-2-hydroxybenzaldehyde (0.1 mmol, 16.7 mg), N,N-dimethylpropane-1,3-diamine (0.1 mmol, 10.2 mg), and copper(II) acetate monohydrate (0.1 mmol, 19.9 mg) were mixed in methanol (20 ml) and the mixture was stirred for 30 min at room temperature. The reaction mixture was fitered. Blue block-shaped single crystals suitable for X-ray diffraction were formed from the filtrate after a week.
All H atom positions were positioned geometrically (C—H = 0.93–0.97 Å) and refined as riding, with Uiso(H) values set at 1.2Ueq(C) and 1.5Ueq(methyl C).
Data collection: SMART (Bruker, 1998); cell refinement: SMART (Bruker, 1998); data reduction: SAINT (Bruker, 1998); 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 (Sheldrick, 1997b).
Fig. 1. The molecular structure of (I), shown with 30% probability displacement ellipsoids. | |
Fig. 2. Molecular packing of (I). |
[Cu(C12H16N3O3)(C2H3O2)] | F(000) = 772 |
Mr = 372.86 | Dx = 1.560 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 1027 reflections |
a = 13.834 (3) Å | θ = 2.3–24.5° |
b = 11.661 (2) Å | µ = 1.41 mm−1 |
c = 9.988 (2) Å | T = 298 K |
β = 99.86 (3)° | Block, blue |
V = 1587.5 (6) Å3 | 0.27 × 0.23 × 0.20 mm |
Z = 4 |
Bruker SMART APEX CCD area-detector diffractometer | 3522 independent reflections |
Radiation source: fine-focus sealed tube | 2037 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.087 |
ω scans | θmax = 27.5°, θmin = 1.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −17→17 |
Tmin = 0.703, Tmax = 0.767 | k = −15→12 |
9081 measured reflections | l = −12→12 |
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)] = 0.079 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.184 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0706P)2] where P = (Fo2 + 2Fc2)/3 |
3522 reflections | (Δ/σ)max < 0.001 |
211 parameters | Δρmax = 0.85 e Å−3 |
0 restraints | Δρmin = −0.61 e Å−3 |
[Cu(C12H16N3O3)(C2H3O2)] | V = 1587.5 (6) Å3 |
Mr = 372.86 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.834 (3) Å | µ = 1.41 mm−1 |
b = 11.661 (2) Å | T = 298 K |
c = 9.988 (2) Å | 0.27 × 0.23 × 0.20 mm |
β = 99.86 (3)° |
Bruker SMART APEX CCD area-detector diffractometer | 3522 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2037 reflections with I > 2σ(I) |
Tmin = 0.703, Tmax = 0.767 | Rint = 0.087 |
9081 measured reflections |
R[F2 > 2σ(F2)] = 0.079 | 0 restraints |
wR(F2) = 0.184 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.85 e Å−3 |
3522 reflections | Δρmin = −0.61 e Å−3 |
211 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 | 0.82621 (5) | 0.77042 (6) | 0.15549 (7) | 0.0297 (3) | |
O1 | 0.4913 (4) | 0.3131 (5) | 0.2555 (6) | 0.0722 (16) | |
O2 | 0.6056 (5) | 0.1905 (6) | 0.3039 (8) | 0.105 (3) | |
O3 | 0.8450 (3) | 0.6052 (4) | 0.1489 (4) | 0.0371 (11) | |
O4 | 0.9473 (3) | 0.7753 (4) | 0.2908 (4) | 0.0368 (10) | |
O5 | 0.8694 (3) | 0.7033 (4) | 0.4489 (4) | 0.0398 (11) | |
N1 | 0.6858 (4) | 0.7516 (4) | 0.0710 (5) | 0.0359 (13) | |
N2 | 0.8117 (4) | 0.9467 (4) | 0.1846 (5) | 0.0375 (13) | |
N3 | 0.5767 (5) | 0.2850 (6) | 0.2657 (7) | 0.0584 (17) | |
C1 | 0.6773 (4) | 0.5540 (5) | 0.1479 (6) | 0.0331 (14) | |
C2 | 0.7805 (4) | 0.5326 (5) | 0.1707 (5) | 0.0301 (14) | |
C3 | 0.8105 (5) | 0.4200 (6) | 0.2173 (6) | 0.0438 (17) | |
H3 | 0.8766 | 0.4006 | 0.2282 | 0.053* | |
C4 | 0.7456 (5) | 0.3407 (6) | 0.2461 (7) | 0.0453 (17) | |
H4 | 0.7677 | 0.2688 | 0.2781 | 0.054* | |
C5 | 0.6451 (5) | 0.3667 (6) | 0.2278 (6) | 0.0401 (16) | |
C6 | 0.6122 (5) | 0.4719 (5) | 0.1788 (6) | 0.0384 (15) | |
H6 | 0.5455 | 0.4884 | 0.1661 | 0.046* | |
C7 | 0.6381 (4) | 0.6600 (6) | 0.0865 (6) | 0.0363 (15) | |
H7 | 0.5708 | 0.6619 | 0.0547 | 0.044* | |
C8 | 0.6331 (5) | 0.8417 (6) | −0.0144 (7) | 0.0504 (19) | |
H8A | 0.5644 | 0.8207 | −0.0362 | 0.061* | |
H8B | 0.6585 | 0.8453 | −0.0991 | 0.061* | |
C9 | 0.6408 (5) | 0.9577 (6) | 0.0489 (7) | 0.055 (2) | |
H9A | 0.6170 | 0.9539 | 0.1347 | 0.065* | |
H9B | 0.5986 | 1.0102 | −0.0099 | 0.065* | |
C10 | 0.7438 (5) | 1.0050 (6) | 0.0742 (7) | 0.0496 (18) | |
H10A | 0.7706 | 0.9991 | −0.0092 | 0.060* | |
H10B | 0.7410 | 1.0858 | 0.0964 | 0.060* | |
C11 | 0.7785 (6) | 0.9636 (6) | 0.3160 (6) | 0.057 (2) | |
H11A | 0.7702 | 1.0440 | 0.3311 | 0.085* | |
H11B | 0.8266 | 0.9329 | 0.3878 | 0.085* | |
H11C | 0.7172 | 0.9248 | 0.3147 | 0.085* | |
C12 | 0.9085 (5) | 1.0048 (6) | 0.1915 (8) | 0.056 (2) | |
H12A | 0.9020 | 1.0846 | 0.2119 | 0.084* | |
H12B | 0.9303 | 0.9972 | 0.1057 | 0.084* | |
H12C | 0.9556 | 0.9700 | 0.2615 | 0.084* | |
C13 | 1.0367 (5) | 0.7595 (6) | 0.5095 (7) | 0.054 (2) | |
H13A | 1.0349 | 0.8321 | 0.5545 | 0.081* | |
H13B | 1.0914 | 0.7581 | 0.4619 | 0.081* | |
H13C | 1.0437 | 0.6990 | 0.5757 | 0.081* | |
C14 | 0.9432 (5) | 0.7429 (5) | 0.4103 (6) | 0.0332 (15) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0299 (4) | 0.0322 (5) | 0.0270 (4) | −0.0009 (3) | 0.0052 (3) | 0.0021 (3) |
O1 | 0.057 (4) | 0.059 (4) | 0.109 (5) | −0.012 (3) | 0.038 (3) | 0.006 (3) |
O2 | 0.086 (5) | 0.052 (4) | 0.183 (7) | −0.002 (4) | 0.043 (5) | 0.040 (5) |
O3 | 0.032 (2) | 0.032 (3) | 0.048 (3) | −0.0026 (19) | 0.0119 (19) | −0.008 (2) |
O4 | 0.044 (2) | 0.041 (3) | 0.025 (2) | −0.003 (2) | 0.0045 (17) | 0.004 (2) |
O5 | 0.038 (2) | 0.054 (3) | 0.029 (2) | −0.006 (2) | 0.0133 (18) | 0.001 (2) |
N1 | 0.034 (3) | 0.040 (4) | 0.033 (3) | −0.001 (2) | 0.006 (2) | 0.006 (2) |
N2 | 0.050 (3) | 0.032 (3) | 0.033 (3) | 0.002 (2) | 0.013 (2) | 0.002 (2) |
N3 | 0.059 (4) | 0.040 (4) | 0.081 (5) | −0.002 (3) | 0.024 (4) | 0.000 (4) |
C1 | 0.047 (4) | 0.028 (4) | 0.026 (3) | −0.005 (3) | 0.009 (3) | −0.007 (3) |
C2 | 0.033 (3) | 0.030 (4) | 0.028 (3) | −0.001 (3) | 0.006 (2) | −0.010 (3) |
C3 | 0.049 (4) | 0.036 (4) | 0.046 (4) | 0.005 (3) | 0.004 (3) | 0.001 (3) |
C4 | 0.054 (4) | 0.029 (4) | 0.052 (4) | 0.000 (3) | 0.007 (3) | 0.001 (3) |
C5 | 0.049 (4) | 0.031 (4) | 0.043 (4) | −0.006 (3) | 0.015 (3) | −0.005 (3) |
C6 | 0.038 (3) | 0.036 (4) | 0.043 (4) | −0.007 (3) | 0.012 (3) | −0.010 (3) |
C7 | 0.030 (3) | 0.046 (4) | 0.032 (3) | −0.007 (3) | 0.001 (3) | −0.003 (3) |
C8 | 0.052 (4) | 0.051 (5) | 0.044 (4) | 0.003 (3) | −0.004 (3) | 0.008 (4) |
C9 | 0.052 (4) | 0.044 (5) | 0.061 (5) | 0.003 (4) | −0.009 (4) | 0.022 (4) |
C10 | 0.063 (5) | 0.035 (4) | 0.052 (4) | 0.007 (3) | 0.012 (4) | 0.011 (3) |
C11 | 0.082 (6) | 0.055 (5) | 0.033 (4) | 0.021 (4) | 0.009 (4) | 0.006 (4) |
C12 | 0.054 (4) | 0.035 (4) | 0.074 (5) | −0.007 (3) | 0.000 (4) | 0.003 (4) |
C13 | 0.051 (4) | 0.081 (6) | 0.031 (3) | −0.003 (4) | 0.007 (3) | −0.001 (4) |
C14 | 0.036 (3) | 0.032 (4) | 0.031 (3) | 0.008 (3) | 0.005 (3) | −0.001 (3) |
Cu1—O3 | 1.946 (4) | C4—C5 | 1.404 (9) |
Cu1—O4 | 1.965 (4) | C4—H4 | 0.9300 |
Cu1—N1 | 1.992 (5) | C5—C6 | 1.370 (9) |
Cu1—N2 | 2.091 (5) | C6—H6 | 0.9300 |
Cu1—O5i | 2.265 (4) | C7—H7 | 0.9300 |
O1—N3 | 1.215 (8) | C8—C9 | 1.490 (10) |
O2—N3 | 1.211 (8) | C8—H8A | 0.9700 |
O3—C2 | 1.276 (7) | C8—H8B | 0.9700 |
O4—C14 | 1.262 (7) | C9—C10 | 1.509 (9) |
O5—C14 | 1.241 (7) | C9—H9A | 0.9700 |
O5—Cu1ii | 2.265 (4) | C9—H9B | 0.9700 |
N1—C7 | 1.280 (7) | C10—H10A | 0.9700 |
N1—C8 | 1.467 (8) | C10—H10B | 0.9700 |
N2—C11 | 1.476 (8) | C11—H11A | 0.9600 |
N2—C10 | 1.485 (8) | C11—H11B | 0.9600 |
N2—C12 | 1.492 (8) | C11—H11C | 0.9600 |
N3—C5 | 1.438 (9) | C12—H12A | 0.9600 |
C1—C6 | 1.385 (8) | C12—H12B | 0.9600 |
C1—C2 | 1.429 (8) | C12—H12C | 0.9600 |
C1—C7 | 1.444 (9) | C13—C14 | 1.502 (9) |
C2—C3 | 1.431 (9) | C13—H13A | 0.9600 |
C3—C4 | 1.353 (9) | C13—H13B | 0.9600 |
C3—H3 | 0.9300 | C13—H13C | 0.9600 |
O3—Cu1—O4 | 87.07 (17) | N1—C7—C1 | 127.0 (6) |
O3—Cu1—N1 | 90.17 (18) | N1—C7—H7 | 116.5 |
O4—Cu1—N1 | 161.58 (19) | C1—C7—H7 | 116.5 |
O3—Cu1—N2 | 173.93 (19) | N1—C8—C9 | 114.3 (5) |
O4—Cu1—N2 | 88.09 (19) | N1—C8—H8A | 108.7 |
N1—Cu1—N2 | 93.3 (2) | C9—C8—H8A | 108.7 |
O3—Cu1—O5i | 92.62 (16) | N1—C8—H8B | 108.7 |
O4—Cu1—O5i | 107.21 (17) | C9—C8—H8B | 108.7 |
N1—Cu1—O5i | 91.10 (18) | H8A—C8—H8B | 107.6 |
N2—Cu1—O5i | 92.32 (18) | C8—C9—C10 | 113.5 (6) |
C2—O3—Cu1 | 123.4 (4) | C8—C9—H9A | 108.9 |
C14—O4—Cu1 | 118.0 (4) | C10—C9—H9A | 108.9 |
C14—O5—Cu1ii | 126.3 (4) | C8—C9—H9B | 108.9 |
C7—N1—C8 | 116.9 (5) | C10—C9—H9B | 108.9 |
C7—N1—Cu1 | 121.8 (4) | H9A—C9—H9B | 107.7 |
C8—N1—Cu1 | 121.3 (4) | N2—C10—C9 | 114.6 (5) |
C11—N2—C10 | 110.3 (5) | N2—C10—H10A | 108.6 |
C11—N2—C12 | 108.2 (5) | C9—C10—H10A | 108.6 |
C10—N2—C12 | 105.9 (5) | N2—C10—H10B | 108.6 |
C11—N2—Cu1 | 107.9 (4) | C9—C10—H10B | 108.6 |
C10—N2—Cu1 | 114.2 (4) | H10A—C10—H10B | 107.6 |
C12—N2—Cu1 | 110.2 (4) | N2—C11—H11A | 109.5 |
O2—N3—O1 | 122.4 (7) | N2—C11—H11B | 109.5 |
O2—N3—C5 | 119.3 (7) | H11A—C11—H11B | 109.5 |
O1—N3—C5 | 118.3 (6) | N2—C11—H11C | 109.5 |
C6—C1—C2 | 120.9 (6) | H11A—C11—H11C | 109.5 |
C6—C1—C7 | 118.3 (6) | H11B—C11—H11C | 109.5 |
C2—C1—C7 | 120.7 (6) | N2—C12—H12A | 109.5 |
O3—C2—C1 | 124.4 (6) | N2—C12—H12B | 109.5 |
O3—C2—C3 | 119.5 (6) | H12A—C12—H12B | 109.5 |
C1—C2—C3 | 116.0 (6) | N2—C12—H12C | 109.5 |
C4—C3—C2 | 122.0 (6) | H12A—C12—H12C | 109.5 |
C4—C3—H3 | 119.0 | H12B—C12—H12C | 109.5 |
C2—C3—H3 | 119.0 | C14—C13—H13A | 109.5 |
C3—C4—C5 | 120.2 (6) | C14—C13—H13B | 109.5 |
C3—C4—H4 | 119.9 | H13A—C13—H13B | 109.5 |
C5—C4—H4 | 119.9 | C14—C13—H13C | 109.5 |
C6—C5—C4 | 120.1 (6) | H13A—C13—H13C | 109.5 |
C6—C5—N3 | 119.6 (6) | H13B—C13—H13C | 109.5 |
C4—C5—N3 | 120.3 (6) | O5—C14—O4 | 125.4 (6) |
C5—C6—C1 | 120.7 (6) | O5—C14—C13 | 120.3 (5) |
C5—C6—H6 | 119.7 | O4—C14—C13 | 114.3 (6) |
C1—C6—H6 | 119.7 |
Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) x, −y+3/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C12H16N3O3)(C2H3O2)] |
Mr | 372.86 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 13.834 (3), 11.661 (2), 9.988 (2) |
β (°) | 99.86 (3) |
V (Å3) | 1587.5 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.41 |
Crystal size (mm) | 0.27 × 0.23 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.703, 0.767 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9081, 3522, 2037 |
Rint | 0.087 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.079, 0.184, 1.00 |
No. of reflections | 3522 |
No. of parameters | 211 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.85, −0.61 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b).
Cu1—O3 | 1.946 (4) | Cu1—N2 | 2.091 (5) |
Cu1—O4 | 1.965 (4) | Cu1—O5i | 2.265 (4) |
Cu1—N1 | 1.992 (5) | ||
O3—Cu1—O4 | 87.07 (17) | N1—Cu1—N2 | 93.3 (2) |
O3—Cu1—N1 | 90.17 (18) | O3—Cu1—O5i | 92.62 (16) |
O4—Cu1—N1 | 161.58 (19) | O4—Cu1—O5i | 107.21 (17) |
O3—Cu1—N2 | 173.93 (19) | N1—Cu1—O5i | 91.10 (18) |
O4—Cu1—N2 | 88.09 (19) | N2—Cu1—O5i | 92.32 (18) |
Symmetry code: (i) x, −y+3/2, z−1/2. |
Polynuclear complexes are very interesting in both structures and properties in coordination chemistry. The azide, thiocyanate, and cyanide anions are often used to construct versatile polynuclear complexes (Escuer & Aromí, 2006; Massoud et al., 2007; Zhang et al., 2001; Dey et al., 2004; Liu et al., 2006; Mondal et al., 2001). In comparison, the acetato-bridged polynuclear complexes are rarely seen. Recently, we have reported the crystal structures of some Schiff base complexes (Li, 2007a,b). In order to investigate the coordination modes of the acetate anions, the author reports herein the crystal structure of an acetato-bridged polynuclear copper(II) complex with Schiff base ligand 4-chloro-2-[(3-dimethylaminopropylimino)methyl]phenol (CMP).
The Cu atom in the acetato-bridged polynuclear complex is square-pyramidal coordinated by one Schiff base ligand CMP and two acetate anions (Fig. 1). The Schiff base molecule acts as a tridentate ligand coordinating the copper ion through the phenolic O atom, imine N atom and amine N atom. The acetate anion acts as a bridging group coordinating adjacent two copper ions through the two O atoms, one at the basal plane and the other one at the apical position. All the coordinated bond lengths and angles (Table 1) are comparable to the values in other similar Schiff base copper(II) complexes (Hebbachi & Benali-Cherif, 2005; Wang & You, 2007; Diao et al., 2007; Usman et al., 2003).
In the crystal structure, the [Cu(CMP)] units are linked through the bridging acetate groups, forming chains running along the c axis (Fig. 2).