Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536809052349/nk2015sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536809052349/nk2015Isup2.hkl |
CCDC reference: 766663
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.004 Å
- Disorder in main residue
- R factor = 0.037
- wR factor = 0.094
- Data-to-parameter ratio = 12.3
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C11 PLAT366_ALERT_2_C Short? C(sp?)-C(sp?) Bond C10 - C11 ... 1.36 Ang. PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.595 35
Alert level G PLAT301_ALERT_3_G Note: Main Residue Disorder ................... 9.00 Perc. PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 3 N1 -CU1 -N1 -C1 14.00 0.00 2.666 1.555 1.555 1.555 PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 6 N1 -CU1 -N1 -C9 3.00 0.00 2.666 1.555 1.555 1.555 PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 39 O1 -CU1 -O1 -C3 1.00 0.00 2.666 1.555 1.555 1.555
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 4 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 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 3 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
The title compound was synthesized by Cu(NO3)2.3H2O and Schiff base ligand 2-methoxy-6-[(pyridin-3-ylmethylimino)-methyl]-phenol. All chemicals used (reagent grade) were commercially available. 2-Hydroxy-3-methoxy-benzaldehyde(0.108 g, 1 mmol) was dissolved in ethanol (5 mL) and ethanol solution (5 ml) containing 2-aminoethylpyri dine (0.152 g, 1 mmol) was added slowly with stirring. The resulting yellow solution was continuously stirred for about 30 min. at room temperature, and then Cu(NO3)2.3H2O (0.241 g, 1 mmol) in aqueous solution (5 ml) was added with stirring at room temperature. Brown crystals suitable for X-ray analysis were obtained by slow evaporation at room temperature over several days.
H atoms were placed in geometrical positions and refined using a riding model, with C—H distances in the range 0.93–0.97Å and Uiso(H) =1.5Ueq(C) for methyl groups and Uiso(H) =1.2Ueq(C) for all others. The N2 and C13 atoms in the pyridyl ring was refined using a disorder model with approximately 70% occupancy for the major component
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
[Cu(C14H13N2O2)2] | Z = 1 |
Mr = 546.07 | F(000) = 283 |
Triclinic, P1 | Dx = 1.491 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 5.175 (1) Å | Cell parameters from 13380 reflections |
b = 10.7291 (14) Å | θ = 3.0–25.0° |
c = 11.4369 (15) Å | µ = 0.94 mm−1 |
α = 99.689 (1)° | T = 298 K |
β = 91.361 (1)° | Prism, brown |
γ = 103.241 (2)° | 0.47 × 0.40 × 0.29 mm |
V = 608.03 (16) Å3 |
Siemens SMART CCD area-detector diffractometer | 2101 independent reflections |
Radiation source: sealed tube | 1908 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
Detector resolution: 8.192 pixels mm-1 | θmax = 25.0°, θmin = 1.8° |
Thin–slice ω scans | h = −5→6 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −11→12 |
Tmin = 0.666, Tmax = 0.772 | l = −13→13 |
3054 measured reflections |
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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.094 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0374P)2 + 0.3354P] where P = (Fo2 + 2Fc2)/3 |
2101 reflections | (Δ/σ)max < 0.001 |
171 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.40 e Å−3 |
[Cu(C14H13N2O2)2] | γ = 103.241 (2)° |
Mr = 546.07 | V = 608.03 (16) Å3 |
Triclinic, P1 | Z = 1 |
a = 5.175 (1) Å | Mo Kα radiation |
b = 10.7291 (14) Å | µ = 0.94 mm−1 |
c = 11.4369 (15) Å | T = 298 K |
α = 99.689 (1)° | 0.47 × 0.40 × 0.29 mm |
β = 91.361 (1)° |
Siemens SMART CCD area-detector diffractometer | 2101 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1908 reflections with I > 2σ(I) |
Tmin = 0.666, Tmax = 0.772 | Rint = 0.021 |
3054 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.094 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.23 e Å−3 |
2101 reflections | Δρmin = −0.40 e Å−3 |
171 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 | Occ. (<1) | |
Cu1 | 0.5000 | 0.5000 | 0.5000 | 0.03467 (17) | |
N1 | 0.5603 (4) | 0.3229 (2) | 0.44427 (19) | 0.0374 (5) | |
C1 | 0.4647 (5) | 0.2520 (3) | 0.3428 (2) | 0.0396 (6) | |
H1 | 0.5277 | 0.1775 | 0.3201 | 0.048* | |
C2 | 0.2735 (5) | 0.2746 (3) | 0.2613 (2) | 0.0386 (6) | |
C3 | 0.1569 (5) | 0.3815 (3) | 0.2862 (2) | 0.0352 (6) | |
C4 | −0.0381 (5) | 0.3930 (3) | 0.2004 (2) | 0.0405 (6) | |
C5 | −0.0989 (6) | 0.3047 (3) | 0.0952 (3) | 0.0501 (8) | |
H5 | −0.2233 | 0.3144 | 0.0395 | 0.060* | |
C6 | 0.0245 (6) | 0.2009 (3) | 0.0715 (3) | 0.0549 (8) | |
H6 | −0.0175 | 0.1423 | 0.0002 | 0.066* | |
C7 | 0.2054 (6) | 0.1856 (3) | 0.1523 (3) | 0.0503 (7) | |
H7 | 0.2857 | 0.1160 | 0.1362 | 0.060* | |
C8 | −0.3148 (6) | 0.5261 (4) | 0.1431 (3) | 0.0615 (9) | |
H8A | −0.2139 | 0.5422 | 0.0755 | 0.092* | |
H8B | −0.3757 | 0.6021 | 0.1751 | 0.092* | |
H8C | −0.4650 | 0.4540 | 0.1191 | 0.092* | |
C9 | 0.7366 (6) | 0.2684 (3) | 0.5141 (2) | 0.0413 (6) | |
H9A | 0.8854 | 0.3376 | 0.5512 | 0.050* | |
H9B | 0.8068 | 0.2052 | 0.4614 | 0.050* | |
C10 | 0.7083 (8) | 0.2181 (3) | 0.7196 (3) | 0.0675 (10) | |
H10 | 0.8760 | 0.2743 | 0.7354 | 0.081* | |
C11 | 0.5900 (5) | 0.2036 (2) | 0.6089 (2) | 0.0386 (6) | |
C12 | 0.3393 (7) | 0.1225 (4) | 0.5890 (3) | 0.0689 (10) | |
H12 | 0.2480 | 0.1087 | 0.5151 | 0.083* | |
N2 | 0.6057 (10) | 0.1590 (4) | 0.8074 (3) | 0.0946 (16) | 0.70 (4) |
C13 | 0.2220 (8) | 0.0611 (4) | 0.6786 (5) | 0.0910 (17) | 0.70 (4) |
H13A | 0.0530 | 0.0057 | 0.6658 | 0.109* | 0.70 (4) |
N2' | 0.2220 (8) | 0.0611 (4) | 0.6786 (5) | 0.0910 (17) | 0.30 (4) |
C13' | 0.6057 (10) | 0.1590 (4) | 0.8074 (3) | 0.0946 (16) | 0.30 (4) |
H13B | 0.6924 | 0.1680 | 0.8736 | 0.113* | 0.30 (4) |
C14 | 0.3650 (12) | 0.0834 (5) | 0.7849 (4) | 0.0863 (14) | |
H14 | 0.2856 | 0.0419 | 0.8446 | 0.104* | |
O1 | 0.2170 (4) | 0.47043 (18) | 0.38216 (16) | 0.0423 (5) | |
O2 | −0.1501 (4) | 0.4964 (2) | 0.23188 (18) | 0.0514 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0353 (3) | 0.0383 (3) | 0.0307 (3) | 0.00863 (19) | −0.00441 (18) | 0.00810 (19) |
N1 | 0.0374 (12) | 0.0430 (13) | 0.0360 (12) | 0.0136 (10) | 0.0011 (9) | 0.0134 (10) |
C1 | 0.0449 (16) | 0.0396 (15) | 0.0368 (15) | 0.0137 (12) | 0.0045 (12) | 0.0083 (12) |
C2 | 0.0395 (15) | 0.0416 (15) | 0.0320 (14) | 0.0029 (12) | 0.0028 (11) | 0.0080 (11) |
C3 | 0.0314 (14) | 0.0420 (15) | 0.0303 (14) | 0.0018 (11) | −0.0006 (10) | 0.0107 (11) |
C4 | 0.0332 (14) | 0.0480 (16) | 0.0386 (15) | 0.0008 (12) | −0.0024 (11) | 0.0152 (13) |
C5 | 0.0418 (17) | 0.068 (2) | 0.0350 (15) | −0.0004 (15) | −0.0078 (12) | 0.0134 (14) |
C6 | 0.057 (2) | 0.065 (2) | 0.0332 (16) | 0.0014 (16) | −0.0042 (14) | −0.0019 (14) |
C7 | 0.0575 (19) | 0.0477 (17) | 0.0406 (16) | 0.0074 (14) | 0.0005 (14) | 0.0011 (13) |
C8 | 0.0455 (18) | 0.080 (2) | 0.065 (2) | 0.0112 (16) | −0.0111 (15) | 0.0360 (18) |
C9 | 0.0396 (16) | 0.0445 (15) | 0.0444 (16) | 0.0183 (12) | −0.0024 (12) | 0.0100 (12) |
C10 | 0.081 (3) | 0.063 (2) | 0.048 (2) | −0.0061 (19) | −0.0108 (17) | 0.0142 (17) |
C11 | 0.0462 (16) | 0.0346 (14) | 0.0396 (15) | 0.0188 (12) | −0.0011 (12) | 0.0075 (11) |
C12 | 0.054 (2) | 0.087 (3) | 0.067 (2) | 0.0038 (19) | −0.0113 (17) | 0.036 (2) |
N2 | 0.138 (4) | 0.090 (3) | 0.049 (2) | 0.004 (3) | 0.003 (2) | 0.0261 (19) |
C13 | 0.063 (3) | 0.084 (3) | 0.140 (5) | 0.015 (2) | 0.026 (3) | 0.058 (3) |
N2' | 0.063 (3) | 0.084 (3) | 0.140 (5) | 0.015 (2) | 0.026 (3) | 0.058 (3) |
C13' | 0.138 (4) | 0.090 (3) | 0.049 (2) | 0.004 (3) | 0.003 (2) | 0.0261 (19) |
C14 | 0.125 (4) | 0.081 (3) | 0.080 (3) | 0.052 (3) | 0.049 (3) | 0.046 (3) |
O1 | 0.0422 (11) | 0.0475 (11) | 0.0375 (10) | 0.0166 (9) | −0.0117 (8) | 0.0017 (9) |
O2 | 0.0450 (12) | 0.0587 (13) | 0.0516 (12) | 0.0133 (10) | −0.0159 (9) | 0.0141 (10) |
Cu1—O1 | 1.9005 (18) | C8—O2 | 1.432 (3) |
Cu1—O1i | 1.9005 (18) | C8—H8A | 0.9600 |
Cu1—N1i | 1.997 (2) | C8—H8B | 0.9600 |
Cu1—N1 | 1.997 (2) | C8—H8C | 0.9600 |
N1—C1 | 1.294 (3) | C9—C11 | 1.512 (4) |
N1—C9 | 1.476 (3) | C9—H9A | 0.9700 |
C1—C2 | 1.432 (4) | C9—H9B | 0.9700 |
C1—H1 | 0.9300 | C10—N2 | 1.333 (5) |
C2—C3 | 1.406 (4) | C10—C11 | 1.362 (4) |
C2—C7 | 1.418 (4) | C10—H10 | 0.9300 |
C3—O1 | 1.306 (3) | C11—C12 | 1.377 (4) |
C3—C4 | 1.431 (4) | C12—C13 | 1.389 (5) |
C4—O2 | 1.366 (3) | C12—H12 | 0.9301 |
C4—C5 | 1.381 (4) | N2—C14 | 1.314 (7) |
C5—C6 | 1.397 (4) | N2—H13B | 0.8506 |
C5—H5 | 0.9300 | C13—C14 | 1.364 (7) |
C6—C7 | 1.356 (4) | C13—H13A | 0.9305 |
C6—H6 | 0.9300 | C14—H14 | 0.9300 |
C7—H7 | 0.9300 | ||
O1—Cu1—O1i | 180.000 (1) | O2—C8—H8B | 109.5 |
O1—Cu1—N1i | 88.69 (8) | H8A—C8—H8B | 109.5 |
O1i—Cu1—N1i | 91.31 (8) | O2—C8—H8C | 109.5 |
O1—Cu1—N1 | 91.31 (8) | H8A—C8—H8C | 109.5 |
O1i—Cu1—N1 | 88.69 (8) | H8B—C8—H8C | 109.5 |
N1i—Cu1—N1 | 180.000 (1) | N1—C9—C11 | 111.4 (2) |
C1—N1—C9 | 115.3 (2) | N1—C9—H9A | 109.3 |
C1—N1—Cu1 | 123.32 (19) | C11—C9—H9A | 109.3 |
C9—N1—Cu1 | 121.18 (18) | N1—C9—H9B | 109.3 |
N1—C1—C2 | 127.6 (3) | C11—C9—H9B | 109.3 |
N1—C1—H1 | 116.2 | H9A—C9—H9B | 108.0 |
C2—C1—H1 | 116.2 | N2—C10—C11 | 125.9 (4) |
C3—C2—C7 | 120.3 (3) | N2—C10—H10 | 117.1 |
C3—C2—C1 | 121.9 (2) | C11—C10—H10 | 117.0 |
C7—C2—C1 | 117.8 (3) | C10—C11—C12 | 115.8 (3) |
O1—C3—C2 | 124.0 (2) | C10—C11—C9 | 120.7 (3) |
O1—C3—C4 | 118.5 (2) | C12—C11—C9 | 123.4 (3) |
C2—C3—C4 | 117.5 (2) | C11—C12—C13 | 120.2 (4) |
O2—C4—C5 | 124.9 (3) | C11—C12—H12 | 119.9 |
O2—C4—C3 | 114.6 (2) | C13—C12—H12 | 119.8 |
C5—C4—C3 | 120.5 (3) | C14—N2—C10 | 116.2 (4) |
C4—C5—C6 | 120.7 (3) | C14—N2—H13B | 121.7 |
C4—C5—H5 | 119.6 | C10—N2—H13B | 122.0 |
C6—C5—H5 | 119.6 | C14—C13—C12 | 117.6 (4) |
C7—C6—C5 | 120.1 (3) | C14—C13—H13A | 121.5 |
C7—C6—H6 | 119.9 | C12—C13—H13A | 120.9 |
C5—C6—H6 | 119.9 | N2—C14—C13 | 124.1 (4) |
C6—C7—C2 | 120.8 (3) | N2—C14—H14 | 118.6 |
C6—C7—H7 | 119.6 | C13—C14—H14 | 117.3 |
C2—C7—H7 | 119.6 | C3—O1—Cu1 | 129.26 (17) |
O2—C8—H8A | 109.5 | C4—O2—C8 | 117.5 (2) |
O1—Cu1—N1—C1 | 15.6 (2) | C3—C2—C7—C6 | −1.0 (4) |
O1i—Cu1—N1—C1 | −164.4 (2) | C1—C2—C7—C6 | 179.6 (3) |
N1i—Cu1—N1—C1 | −141 (100) | C1—N1—C9—C11 | −99.3 (3) |
O1—Cu1—N1—C9 | −169.17 (19) | Cu1—N1—C9—C11 | 85.1 (2) |
O1i—Cu1—N1—C9 | 10.83 (19) | N2—C10—C11—C12 | 1.6 (6) |
N1i—Cu1—N1—C9 | 34 (100) | N2—C10—C11—C9 | −175.3 (4) |
C9—N1—C1—C2 | 174.5 (2) | N1—C9—C11—C10 | −139.2 (3) |
Cu1—N1—C1—C2 | −9.9 (4) | N1—C9—C11—C12 | 44.1 (4) |
N1—C1—C2—C3 | −1.8 (4) | C10—C11—C12—C13 | −0.1 (5) |
N1—C1—C2—C7 | 177.6 (3) | C9—C11—C12—C13 | 176.7 (3) |
C7—C2—C3—O1 | −177.1 (2) | C11—C10—N2—C14 | −2.3 (7) |
C1—C2—C3—O1 | 2.2 (4) | C11—C12—C13—C14 | −0.7 (6) |
C7—C2—C3—C4 | 2.5 (4) | C10—N2—C14—C13 | 1.4 (7) |
C1—C2—C3—C4 | −178.1 (2) | C12—C13—C14—N2 | 0.0 (7) |
O1—C3—C4—O2 | −2.5 (3) | C2—C3—O1—Cu1 | 10.5 (4) |
C2—C3—C4—O2 | 177.9 (2) | C4—C3—O1—Cu1 | −169.14 (17) |
O1—C3—C4—C5 | 177.0 (2) | O1i—Cu1—O1—C3 | −12 (100) |
C2—C3—C4—C5 | −2.7 (4) | N1i—Cu1—O1—C3 | 163.5 (2) |
O2—C4—C5—C6 | −179.3 (3) | N1—Cu1—O1—C3 | −16.5 (2) |
C3—C4—C5—C6 | 1.3 (4) | C5—C4—O2—C8 | −9.1 (4) |
C4—C5—C6—C7 | 0.3 (4) | C3—C4—O2—C8 | 170.4 (2) |
C5—C6—C7—C2 | −0.5 (5) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C14H13N2O2)2] |
Mr | 546.07 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 5.175 (1), 10.7291 (14), 11.4369 (15) |
α, β, γ (°) | 99.689 (1), 91.361 (1), 103.241 (2) |
V (Å3) | 608.03 (16) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.94 |
Crystal size (mm) | 0.47 × 0.40 × 0.29 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.666, 0.772 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3054, 2101, 1908 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.094, 1.09 |
No. of reflections | 2101 |
No. of parameters | 171 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.23, −0.40 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXTL (Sheldrick, 2008).
Cu1—O1 | 1.9005 (18) | Cu1—N1i | 1.997 (2) |
Cu1—O1i | 1.9005 (18) | Cu1—N1 | 1.997 (2) |
O1—Cu1—N1i | 88.69 (8) | O1—Cu1—N1 | 91.31 (8) |
O1i—Cu1—N1i | 91.31 (8) | O1i—Cu1—N1 | 88.69 (8) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Recent developments in functional switching materials (Sato et al., 2003) have shown that a good way to discover candidate metal complexes is to examine compounds that show any changes between two or more states, such as structural phase transitions, isomerism, mixed valences and spin-crossover. In this respect, bis-(N-alkysalicylideneimine)copper(II) complexes have potential for induced structural phase transitions (Yamada, 1999) and the structural isomers can be isolated (Chia et al., 1997).
Herein, we reported a new crystal strucure of the title compound (I). The stucture of (I) is shown in Fig.1. It can be clearly seen that this compound possesses a slightly distorted square-planar trans-[CuN2O2] coordination geomentry with the CuII ion located on a crystallographic inversion center. In addition, the phenyl ring is almost on the same plane with the [CuN2O2] square plane with a dihedral angle of approximately 6.293° between the two planes, while the pyridyl ring is nearly vertical with the [CuN2O2] square plane with a dihedral angle of approximately 83.12°. The pyridyl ring was refined using a two-part disorder model, interchanging the positions of N2 and C13 with approximately 70% occupancy for the major component; this conformation is the most likely according to the ring geometry and the surrounding environment.