The synthesis and characterization of a copper(II) complex of salicylaldimine, [Cu2(C2O4)2(C13H20N2O2)2]·2H2O, is described. The reaction of 2,4-dihydroxybenzaldehyde and N,N-diethylethylenediamine with K2[Cu(C2O4)2] produces a centrosymmetric binuclear CuII complex. Its structure reveals that the copper(II) ion is five-coordinate and situated in a distorted square-pyramidal environment.
Supporting information
CCDC reference: 241541
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.003 Å
- R factor = 0.031
- wR factor = 0.081
- Data-to-parameter ratio = 15.2
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ?
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature 293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature . 293 K
PLAT369_ALERT_2_C Long C(sp2)-C(sp2) Bond C14 - C15 ... 1.55 Ang.
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
5 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
4 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
0 ALERT type 3 Indicator that the structure quality may be low
0 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.
Bis{[
N-(4-hydroxysalicylidene)-
N',
N'-diethylethyldiamine-
κ2N,
O] copper(II)oxalate} dihydrate
top
Crystal data top
[Cu(C13H20N2O2)2(C2O4)2]·2H2O | Z = 1 |
Mr = 811.79 | F(000) = 422 |
Triclinic, P1 | Dx = 1.573 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.372 (3) Å | Cell parameters from 843 reflections |
b = 10.449 (3) Å | θ = 3.0–26.3° |
c = 10.781 (3) Å | µ = 1.32 mm−1 |
α = 96.099 (5)° | T = 293 K |
β = 110.379 (5)° | Block, green |
γ = 99.826 (5)° | 0.24 × 0.20 × 0.16 mm |
V = 857.0 (5) Å3 | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 3482 independent reflections |
Radiation source: fine-focus sealed tube | 2871 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.017 |
φ and ω scans | θmax = 26.4°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −10→10 |
Tmin = 0.737, Tmax = 0.810 | k = −9→13 |
4966 measured reflections | l = −13→13 |
Refinement top
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)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.081 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0427P)2 + 0.0467P] where P = (Fo2 + 2Fc2)/3 |
3482 reflections | (Δ/σ)max = 0.001 |
229 parameters | Δρmax = 0.33 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cu1 | 0.68053 (4) | 0.59968 (3) | 0.58104 (3) | 0.02960 (10) | |
N1 | 0.7357 (2) | 0.66085 (17) | 0.43212 (18) | 0.0284 (4) | |
N2 | 0.4213 (2) | 0.72709 (18) | 0.24261 (17) | 0.0304 (4) | |
H2A | 0.4182 | 0.6442 | 0.2618 | 0.037* | |
O1 | 0.6615 (2) | 0.41781 (14) | 0.51685 (15) | 0.0331 (4) | |
O2 | 0.8314 (3) | 0.06267 (15) | 0.33285 (18) | 0.0448 (4) | |
H2 | 0.8675 | 0.0402 | 0.2742 | 0.067* | |
O3 | 0.7123 (2) | 0.77806 (15) | 0.67491 (16) | 0.0360 (4) | |
O4 | 0.7647 (3) | 0.88293 (18) | 0.87933 (19) | 0.0528 (5) | |
O5 | 0.6519 (2) | 0.54687 (15) | 0.74117 (15) | 0.0356 (4) | |
O6 | 0.6665 (3) | 0.6356 (2) | 0.94337 (18) | 0.0546 (5) | |
C1 | 0.7984 (3) | 0.4543 (2) | 0.3566 (2) | 0.0295 (5) | |
C2 | 0.7328 (3) | 0.3732 (2) | 0.4341 (2) | 0.0269 (5) | |
C3 | 0.7456 (3) | 0.2413 (2) | 0.4202 (2) | 0.0331 (5) | |
H3 | 0.7024 | 0.1863 | 0.4691 | 0.040* | |
C4 | 0.8205 (3) | 0.1897 (2) | 0.3361 (2) | 0.0291 (5) | |
C5 | 0.8841 (3) | 0.2687 (2) | 0.2598 (2) | 0.0343 (5) | |
H5 | 0.9338 | 0.2343 | 0.2027 | 0.041* | |
C6 | 0.8718 (3) | 0.3973 (2) | 0.2707 (2) | 0.0349 (5) | |
H6 | 0.9137 | 0.4500 | 0.2194 | 0.042* | |
C7 | 0.7910 (3) | 0.5894 (2) | 0.3581 (2) | 0.0316 (5) | |
H7 | 0.8306 | 0.6309 | 0.2987 | 0.038* | |
C8 | 0.7347 (3) | 0.7971 (2) | 0.4093 (2) | 0.0321 (5) | |
H8A | 0.7812 | 0.8135 | 0.3403 | 0.039* | |
H8B | 0.8091 | 0.8584 | 0.4915 | 0.039* | |
C9 | 0.5518 (3) | 0.8200 (2) | 0.3664 (2) | 0.0312 (5) | |
H9A | 0.5115 | 0.8121 | 0.4399 | 0.037* | |
H9B | 0.5553 | 0.9097 | 0.3499 | 0.037* | |
C10 | 0.2433 (3) | 0.7532 (3) | 0.2194 (2) | 0.0412 (6) | |
H10A | 0.2167 | 0.7430 | 0.2990 | 0.049* | |
H10B | 0.2452 | 0.8439 | 0.2069 | 0.049* | |
C11 | 0.1009 (4) | 0.6636 (3) | 0.1001 (3) | 0.0535 (7) | |
H11A | 0.1138 | 0.6847 | 0.0191 | 0.080* | |
H11B | −0.0107 | 0.6753 | 0.0994 | 0.080* | |
H11C | 0.1083 | 0.5736 | 0.1053 | 0.080* | |
C12 | 0.4698 (3) | 0.7281 (2) | 0.1202 (2) | 0.0386 (6) | |
H12A | 0.5856 | 0.7103 | 0.1424 | 0.046* | |
H12B | 0.3886 | 0.6573 | 0.0492 | 0.046* | |
C13 | 0.4685 (4) | 0.8564 (3) | 0.0681 (3) | 0.0488 (7) | |
H13A | 0.3540 | 0.8743 | 0.0446 | 0.073* | |
H13B | 0.4989 | 0.8498 | −0.0100 | 0.073* | |
H13C | 0.5518 | 0.9266 | 0.1365 | 0.073* | |
C14 | 0.7195 (3) | 0.7812 (2) | 0.7952 (2) | 0.0352 (5) | |
C15 | 0.6737 (3) | 0.6446 (2) | 0.8342 (2) | 0.0342 (5) | |
O7 | 0.0501 (2) | 0.04607 (19) | 0.84101 (18) | 0.0514 (5) | |
H7A | 0.1242 | 0.0736 | 0.9208 | 0.077* | |
H7B | −0.0454 | 0.0039 | 0.8422 | 0.077* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.03940 (17) | 0.02189 (15) | 0.02811 (16) | 0.00457 (11) | 0.01505 (12) | 0.00230 (10) |
N1 | 0.0308 (10) | 0.0213 (9) | 0.0331 (10) | 0.0043 (8) | 0.0122 (8) | 0.0062 (8) |
N2 | 0.0382 (10) | 0.0259 (10) | 0.0302 (10) | 0.0089 (8) | 0.0149 (8) | 0.0073 (8) |
O1 | 0.0476 (9) | 0.0223 (8) | 0.0365 (9) | 0.0041 (7) | 0.0269 (8) | 0.0022 (7) |
O2 | 0.0682 (12) | 0.0252 (9) | 0.0558 (11) | 0.0130 (9) | 0.0402 (10) | 0.0061 (8) |
O3 | 0.0464 (10) | 0.0264 (8) | 0.0353 (9) | 0.0061 (7) | 0.0173 (8) | 0.0020 (7) |
O4 | 0.0699 (13) | 0.0360 (10) | 0.0478 (10) | −0.0002 (9) | 0.0276 (9) | −0.0129 (8) |
O5 | 0.0505 (10) | 0.0277 (8) | 0.0329 (8) | 0.0074 (7) | 0.0219 (8) | 0.0044 (7) |
O6 | 0.0769 (13) | 0.0571 (12) | 0.0409 (10) | 0.0147 (11) | 0.0360 (10) | 0.0070 (9) |
C1 | 0.0317 (11) | 0.0295 (11) | 0.0313 (11) | 0.0087 (10) | 0.0150 (10) | 0.0085 (9) |
C2 | 0.0280 (11) | 0.0260 (11) | 0.0245 (10) | 0.0022 (9) | 0.0094 (9) | 0.0019 (9) |
C3 | 0.0439 (13) | 0.0243 (11) | 0.0357 (12) | 0.0026 (10) | 0.0227 (11) | 0.0052 (10) |
C4 | 0.0308 (11) | 0.0247 (11) | 0.0302 (11) | 0.0044 (9) | 0.0114 (9) | 0.0004 (9) |
C5 | 0.0373 (12) | 0.0366 (13) | 0.0379 (12) | 0.0135 (11) | 0.0225 (11) | 0.0064 (10) |
C6 | 0.0413 (13) | 0.0350 (13) | 0.0389 (13) | 0.0111 (11) | 0.0245 (11) | 0.0136 (10) |
C7 | 0.0340 (12) | 0.0314 (12) | 0.0346 (12) | 0.0048 (10) | 0.0181 (10) | 0.0129 (10) |
C8 | 0.0390 (12) | 0.0232 (11) | 0.0359 (12) | 0.0032 (10) | 0.0173 (10) | 0.0075 (9) |
C9 | 0.0411 (13) | 0.0249 (11) | 0.0305 (11) | 0.0094 (10) | 0.0165 (10) | 0.0037 (9) |
C10 | 0.0376 (13) | 0.0495 (15) | 0.0412 (14) | 0.0149 (12) | 0.0176 (11) | 0.0098 (12) |
C11 | 0.0444 (15) | 0.0598 (18) | 0.0513 (16) | 0.0070 (14) | 0.0129 (13) | 0.0136 (14) |
C12 | 0.0481 (14) | 0.0410 (14) | 0.0315 (12) | 0.0120 (12) | 0.0201 (11) | 0.0058 (11) |
C13 | 0.0571 (17) | 0.0525 (16) | 0.0396 (14) | 0.0053 (14) | 0.0225 (13) | 0.0165 (13) |
C14 | 0.0300 (12) | 0.0352 (13) | 0.0387 (13) | 0.0055 (10) | 0.0144 (10) | −0.0032 (11) |
C15 | 0.0341 (12) | 0.0371 (13) | 0.0332 (12) | 0.0100 (10) | 0.0148 (10) | 0.0021 (10) |
O7 | 0.0570 (11) | 0.0509 (11) | 0.0475 (11) | 0.0087 (9) | 0.0265 (9) | −0.0047 (9) |
Geometric parameters (Å, º) top
Cu1—O1 | 1.9121 (16) | C5—C6 | 1.361 (3) |
Cu1—O5 | 1.9462 (16) | C5—H5 | 0.93 |
Cu1—O3 | 1.9523 (16) | C6—H6 | 0.93 |
Cu1—N1 | 1.9579 (19) | C7—H7 | 0.93 |
N1—C7 | 1.287 (3) | C8—C9 | 1.507 (3) |
N1—C8 | 1.472 (3) | C8—H8A | 0.97 |
N2—C10 | 1.500 (3) | C8—H8B | 0.97 |
N2—C9 | 1.505 (3) | C9—H9A | 0.97 |
N2—C12 | 1.511 (3) | C9—H9B | 0.97 |
N2—H2A | 0.91 | C10—C11 | 1.499 (4) |
O1—C2 | 1.321 (2) | C10—H10A | 0.97 |
O2—C4 | 1.344 (3) | C10—H10B | 0.97 |
O2—H2 | 0.82 | C11—H11A | 0.96 |
O3—C14 | 1.274 (3) | C11—H11B | 0.96 |
O4—C14 | 1.230 (3) | C11—H11C | 0.96 |
O5—C15 | 1.293 (3) | C12—C13 | 1.507 (4) |
O6—C15 | 1.212 (3) | C12—H12A | 0.97 |
C1—C6 | 1.412 (3) | C12—H12B | 0.97 |
C1—C7 | 1.422 (3) | C13—H13A | 0.96 |
C1—C2 | 1.424 (3) | C13—H13B | 0.96 |
C2—C3 | 1.397 (3) | C13—H13C | 0.96 |
C3—C4 | 1.383 (3) | C14—C15 | 1.554 (3) |
C3—H3 | 0.93 | O7—H7A | 0.85 |
C4—C5 | 1.393 (3) | O7—H7B | 0.85 |
| | | |
O1—Cu1—O5 | 87.76 (6) | C9—C8—H8A | 109.5 |
O1—Cu1—O3 | 170.92 (7) | N1—C8—H8B | 109.5 |
O5—Cu1—O3 | 83.98 (7) | C9—C8—H8B | 109.5 |
O1—Cu1—N1 | 94.05 (7) | H8A—C8—H8B | 108.1 |
O5—Cu1—N1 | 173.84 (7) | N2—C9—C8 | 114.74 (18) |
O3—Cu1—N1 | 93.78 (7) | N2—C9—H9A | 108.6 |
C7—N1—C8 | 116.54 (19) | C8—C9—H9A | 108.6 |
C7—N1—Cu1 | 122.13 (16) | N2—C9—H9B | 108.6 |
C8—N1—Cu1 | 120.98 (14) | C8—C9—H9B | 108.6 |
C10—N2—C9 | 108.79 (17) | H9A—C9—H9B | 107.6 |
C10—N2—C12 | 113.39 (18) | C11—C10—N2 | 113.7 (2) |
C9—N2—C12 | 114.09 (17) | C11—C10—H10A | 108.8 |
C10—N2—H2A | 106.7 | N2—C10—H10A | 108.8 |
C9—N2—H2A | 106.7 | C11—C10—H10B | 108.8 |
C12—N2—H2A | 106.7 | N2—C10—H10B | 108.8 |
C2—O1—Cu1 | 125.53 (13) | H10A—C10—H10B | 107.7 |
C4—O2—H2 | 109.5 | C10—C11—H11A | 109.5 |
C14—O3—Cu1 | 112.91 (15) | C10—C11—H11B | 109.5 |
C15—O5—Cu1 | 114.13 (15) | H11A—C11—H11B | 109.5 |
C6—C1—C7 | 117.6 (2) | C10—C11—H11C | 109.5 |
C6—C1—C2 | 118.5 (2) | H11A—C11—H11C | 109.5 |
C7—C1—C2 | 123.8 (2) | H11B—C11—H11C | 109.5 |
O1—C2—C3 | 119.72 (19) | C13—C12—N2 | 113.9 (2) |
O1—C2—C1 | 122.8 (2) | C13—C12—H12A | 108.8 |
C3—C2—C1 | 117.47 (19) | N2—C12—H12A | 108.8 |
C4—C3—C2 | 122.2 (2) | C13—C12—H12B | 108.8 |
C4—C3—H3 | 118.9 | N2—C12—H12B | 108.8 |
C2—C3—H3 | 118.9 | H12A—C12—H12B | 107.7 |
O2—C4—C3 | 117.6 (2) | C12—C13—H13A | 109.5 |
O2—C4—C5 | 121.9 (2) | C12—C13—H13B | 109.5 |
C3—C4—C5 | 120.4 (2) | H13A—C13—H13B | 109.5 |
C6—C5—C4 | 118.5 (2) | C12—C13—H13C | 109.5 |
C6—C5—H5 | 120.7 | H13A—C13—H13C | 109.5 |
C4—C5—H5 | 120.7 | H13B—C13—H13C | 109.5 |
C5—C6—C1 | 122.8 (2) | O4—C14—O3 | 124.2 (2) |
C5—C6—H6 | 118.6 | O4—C14—C15 | 120.3 (2) |
C1—C6—H6 | 118.6 | O3—C14—C15 | 115.47 (19) |
N1—C7—C1 | 127.5 (2) | O6—C15—O5 | 125.8 (2) |
N1—C7—H7 | 116.3 | O6—C15—C14 | 121.3 (2) |
C1—C7—H7 | 116.3 | O5—C15—C14 | 112.9 (2) |
N1—C8—C9 | 110.70 (18) | H7A—O7—H7B | 110.1 |
N1—C8—H8A | 109.5 | | |
| | | |
O1—Cu1—N1—C7 | −18.56 (18) | C7—C1—C6—C5 | −179.3 (2) |
O3—Cu1—N1—C7 | 156.84 (18) | C2—C1—C6—C5 | −0.6 (4) |
O1—Cu1—N1—C8 | 168.43 (16) | C8—N1—C7—C1 | −177.3 (2) |
O3—Cu1—N1—C8 | −16.18 (16) | Cu1—N1—C7—C1 | 9.4 (3) |
O5—Cu1—O1—C2 | −152.05 (18) | C6—C1—C7—N1 | −177.2 (2) |
N1—Cu1—O1—C2 | 22.05 (18) | C2—C1—C7—N1 | 4.3 (4) |
O5—Cu1—O3—C14 | 6.99 (15) | C7—N1—C8—C9 | 119.2 (2) |
N1—Cu1—O3—C14 | −167.25 (15) | Cu1—N1—C8—C9 | −67.4 (2) |
O1—Cu1—O5—C15 | 173.03 (16) | C10—N2—C9—C8 | 174.83 (19) |
O3—Cu1—O5—C15 | −3.19 (16) | C12—N2—C9—C8 | −57.5 (3) |
Cu1—O1—C2—C3 | 164.55 (16) | N1—C8—C9—N2 | −56.8 (3) |
Cu1—O1—C2—C1 | −15.5 (3) | C9—N2—C10—C11 | −178.5 (2) |
C6—C1—C2—O1 | −179.9 (2) | C12—N2—C10—C11 | 53.4 (3) |
C7—C1—C2—O1 | −1.3 (3) | C10—N2—C12—C13 | 58.7 (3) |
C6—C1—C2—C3 | 0.1 (3) | C9—N2—C12—C13 | −66.6 (3) |
C7—C1—C2—C3 | 178.6 (2) | Cu1—O3—C14—O4 | 168.6 (2) |
O1—C2—C3—C4 | −179.3 (2) | Cu1—O3—C14—C15 | −9.0 (2) |
C1—C2—C3—C4 | 0.7 (3) | Cu1—O5—C15—O6 | −178.1 (2) |
C2—C3—C4—O2 | 178.0 (2) | Cu1—O5—C15—C14 | −0.6 (2) |
C2—C3—C4—C5 | −1.0 (4) | O4—C14—C15—O6 | 6.5 (4) |
O2—C4—C5—C6 | −178.5 (2) | O3—C14—C15—O6 | −175.8 (2) |
C3—C4—C5—C6 | 0.4 (4) | O4—C14—C15—O5 | −171.2 (2) |
C4—C5—C6—C1 | 0.4 (4) | O3—C14—C15—O5 | 6.6 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O5i | 0.91 | 1.98 | 2.861 (3) | 164 |
O2—H2···O7ii | 0.82 | 1.84 | 2.648 (2) | 166 |
O7—H7A···O4iii | 0.85 | 1.99 | 2.815 (3) | 163 |
O7—H7B···O4iv | 0.85 | 2.04 | 2.869 (3) | 166 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y, −z+1; (iii) −x+1, −y+1, −z+2; (iv) x−1, y−1, z. |