In the title centrosymmetric mononuclear nickel(II) complex, [Ni(C
13H
20N
2O
2)
2](ClO
4)
2, the Ni
II atom is four-coordinated by the imine N and phenolate O atoms of the zwitterionic forms of two Schiff base ligands in a square-planar coordination geometry. In the crystal structure, molecules are linked through intermolecular N—H

O hydrogen bonds, forming chains running along the
a axis.
Supporting information
CCDC reference: 700405
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean
(C-C) = 0.004 Å
- R factor = 0.040
- wR factor = 0.103
- Data-to-parameter ratio = 16.2
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.82 Ratio
PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.22 Ratio
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C12
PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for Cl1
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
4 ALERT level C = Check and explain
0 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
1 ALERT type 3 Indicator that the structure quality may be low
1 ALERT type 4 Improvement, methodology, query or suggestion
0 ALERT type 5 Informative message, check
The Schiff base compound was prepared by the condensation of equimolar amounts
of 3-ethoxysalicylaldehyde with N-ethylethane-1,2-diamine in a methanol
solution. The complex was prepared by the following method. To a methanol
solution (5 ml) of Ni(ClO4)2.6H2O (36.6 mg, 0.1 mmol) was added a
methanol solution (10 ml) of the Schiff base compound (23.6 mg, 0.1 mmol) with
stirring. The mixture was stirred for 30 min at room temperature and filtered.
Upon keeping the filtrate in air for a few days, red block-shaped crystals
formed at the bottom of the vessel on slow evaporation of the solvent.
All H atoms were placed in geometrically idealized positions and constrained to
ride on their parent atoms, with C–H distances in the range 0.93–0.97 Å,
N–H distances of 0.90 Å, and with Uiso(H) =
1.2Ueq(C,N) and 1.5Ueq(methyl C).
Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
Bis{(
E)-2-Ethoxy-6-[2-(ethylammonio)ethyliminomethyl]phenolato}nickel(II)
bis(perchlorate)
top
Crystal data top
[Ni(C13H20N2O2)2](ClO4)2 | F(000) = 764 |
Mr = 730.23 | Dx = 1.564 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 3252 reflections |
a = 8.386 (3) Å | θ = 2.5–25.4° |
b = 8.566 (3) Å | µ = 0.87 mm−1 |
c = 21.862 (6) Å | T = 298 K |
β = 99.068 (4)° | Block, red |
V = 1550.8 (9) Å3 | 0.23 × 0.20 × 0.20 mm |
Z = 2 | |
Data collection top
Bruker APEXII CCD area-detector diffractometer | 3363 independent reflections |
Radiation source: fine-focus sealed tube | 2770 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.041 |
ω scans | θmax = 27.0°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | h = −10→10 |
Tmin = 0.826, Tmax = 0.846 | k = −10→10 |
12509 measured reflections | l = −27→27 |
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)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.102 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0512P)2 + 0.4599P] where P = (Fo2 + 2Fc2)/3 |
3363 reflections | (Δ/σ)max = 0.001 |
207 parameters | Δρmax = 0.28 e Å−3 |
0 restraints | Δρmin = −0.34 e Å−3 |
Crystal data top
[Ni(C13H20N2O2)2](ClO4)2 | V = 1550.8 (9) Å3 |
Mr = 730.23 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.386 (3) Å | µ = 0.87 mm−1 |
b = 8.566 (3) Å | T = 298 K |
c = 21.862 (6) Å | 0.23 × 0.20 × 0.20 mm |
β = 99.068 (4)° | |
Data collection top
Bruker APEXII CCD area-detector diffractometer | 3363 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | 2770 reflections with I > 2σ(I) |
Tmin = 0.826, Tmax = 0.846 | Rint = 0.041 |
12509 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.102 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.28 e Å−3 |
3363 reflections | Δρmin = −0.34 e Å−3 |
207 parameters | |
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. |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Ni1 | 1.0000 | 0.5000 | 0.0000 | 0.02592 (13) | |
Cl1 | 0.39043 (7) | 0.71469 (7) | 0.09059 (3) | 0.03882 (17) | |
O1 | 1.06353 (18) | 0.41002 (18) | 0.07614 (7) | 0.0333 (4) | |
O2 | 1.1550 (2) | 0.2125 (2) | 0.16406 (8) | 0.0451 (4) | |
O3 | 0.4539 (3) | 0.6169 (2) | 0.04665 (9) | 0.0624 (6) | |
O4 | 0.5075 (2) | 0.8315 (2) | 0.11174 (9) | 0.0547 (5) | |
O5 | 0.3594 (3) | 0.6194 (2) | 0.14062 (9) | 0.0652 (6) | |
O6 | 0.2480 (3) | 0.7874 (3) | 0.06108 (13) | 0.0790 (7) | |
N1 | 0.8973 (2) | 0.6697 (2) | 0.03503 (8) | 0.0272 (4) | |
N2 | 0.6314 (2) | 0.7051 (2) | −0.07021 (9) | 0.0342 (4) | |
H2A | 0.6031 | 0.6259 | −0.0471 | 0.041* | |
H2B | 0.7139 | 0.6718 | −0.0886 | 0.041* | |
C1 | 0.8960 (3) | 0.5512 (3) | 0.13583 (10) | 0.0307 (5) | |
C2 | 1.0022 (3) | 0.4303 (3) | 0.12705 (9) | 0.0281 (5) | |
C3 | 1.0473 (3) | 0.3232 (3) | 0.17637 (10) | 0.0322 (5) | |
C4 | 0.9828 (3) | 0.3361 (3) | 0.22998 (10) | 0.0385 (6) | |
H4 | 1.0109 | 0.2640 | 0.2616 | 0.046* | |
C5 | 0.8759 (3) | 0.4560 (3) | 0.23756 (11) | 0.0436 (6) | |
H5 | 0.8327 | 0.4634 | 0.2741 | 0.052* | |
C6 | 0.8344 (3) | 0.5623 (3) | 0.19183 (11) | 0.0399 (6) | |
H6 | 0.7644 | 0.6433 | 0.1976 | 0.048* | |
C7 | 0.8602 (3) | 0.6692 (3) | 0.09004 (10) | 0.0308 (5) | |
H7 | 0.8036 | 0.7555 | 0.1010 | 0.037* | |
C8 | 0.8632 (3) | 0.8182 (2) | 0.00079 (11) | 0.0317 (5) | |
H8A | 0.9308 | 0.8242 | −0.0313 | 0.038* | |
H8B | 0.8923 | 0.9044 | 0.0291 | 0.038* | |
C9 | 0.6887 (3) | 0.8363 (3) | −0.02871 (11) | 0.0333 (5) | |
H9A | 0.6219 | 0.8436 | 0.0036 | 0.040* | |
H9B | 0.6765 | 0.9328 | −0.0522 | 0.040* | |
C10 | 0.4917 (3) | 0.7422 (3) | −0.11922 (13) | 0.0487 (7) | |
H10A | 0.5245 | 0.8215 | −0.1464 | 0.058* | |
H10B | 0.4629 | 0.6493 | −0.1439 | 0.058* | |
C11 | 0.3475 (3) | 0.7982 (4) | −0.09446 (14) | 0.0568 (8) | |
H11A | 0.3152 | 0.7211 | −0.0670 | 0.085* | |
H11B | 0.2610 | 0.8158 | −0.1281 | 0.085* | |
H11C | 0.3728 | 0.8940 | −0.0723 | 0.085* | |
C12 | 1.1937 (3) | 0.0850 (3) | 0.20663 (12) | 0.0465 (6) | |
H12A | 1.2110 | 0.1255 | 0.2486 | 0.056* | |
H12B | 1.2937 | 0.0372 | 0.1992 | 0.056* | |
C13 | 1.0661 (5) | −0.0355 (4) | 0.2011 (2) | 0.0790 (11) | |
H13A | 0.9690 | 0.0091 | 0.2116 | 0.119* | |
H13B | 1.1007 | −0.1201 | 0.2288 | 0.119* | |
H13C | 1.0458 | −0.0737 | 0.1593 | 0.119* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ni1 | 0.0286 (2) | 0.0257 (2) | 0.0236 (2) | 0.00323 (15) | 0.00463 (15) | 0.00429 (15) |
Cl1 | 0.0470 (4) | 0.0310 (3) | 0.0392 (3) | −0.0058 (2) | 0.0091 (3) | −0.0041 (2) |
O1 | 0.0407 (9) | 0.0352 (9) | 0.0255 (7) | 0.0112 (7) | 0.0096 (7) | 0.0078 (6) |
O2 | 0.0555 (11) | 0.0445 (10) | 0.0376 (9) | 0.0190 (8) | 0.0145 (8) | 0.0175 (8) |
O3 | 0.1038 (17) | 0.0375 (10) | 0.0533 (12) | −0.0086 (11) | 0.0357 (11) | −0.0095 (9) |
O4 | 0.0541 (12) | 0.0456 (11) | 0.0639 (13) | −0.0157 (9) | 0.0075 (9) | −0.0132 (9) |
O5 | 0.1053 (17) | 0.0525 (12) | 0.0438 (11) | −0.0208 (12) | 0.0300 (11) | −0.0021 (9) |
O6 | 0.0493 (13) | 0.0656 (14) | 0.116 (2) | −0.0016 (11) | −0.0058 (12) | 0.0108 (14) |
N1 | 0.0264 (9) | 0.0250 (9) | 0.0292 (9) | −0.0002 (7) | 0.0015 (7) | 0.0020 (7) |
N2 | 0.0319 (10) | 0.0294 (10) | 0.0408 (11) | 0.0026 (8) | 0.0038 (8) | −0.0007 (8) |
C1 | 0.0301 (11) | 0.0345 (12) | 0.0277 (11) | −0.0006 (9) | 0.0048 (9) | −0.0003 (9) |
C2 | 0.0290 (11) | 0.0310 (11) | 0.0244 (10) | −0.0028 (9) | 0.0043 (9) | 0.0013 (9) |
C3 | 0.0323 (12) | 0.0354 (12) | 0.0284 (11) | −0.0017 (10) | 0.0030 (9) | 0.0047 (9) |
C4 | 0.0413 (14) | 0.0464 (14) | 0.0271 (11) | −0.0036 (11) | 0.0034 (10) | 0.0079 (10) |
C5 | 0.0465 (15) | 0.0580 (16) | 0.0288 (12) | 0.0011 (13) | 0.0132 (11) | 0.0006 (11) |
C6 | 0.0391 (13) | 0.0466 (14) | 0.0356 (13) | 0.0061 (11) | 0.0107 (10) | −0.0031 (11) |
C7 | 0.0292 (11) | 0.0299 (12) | 0.0333 (12) | 0.0024 (9) | 0.0048 (9) | −0.0033 (9) |
C8 | 0.0359 (12) | 0.0224 (11) | 0.0362 (12) | −0.0029 (9) | 0.0033 (10) | 0.0010 (9) |
C9 | 0.0374 (13) | 0.0232 (11) | 0.0387 (12) | 0.0043 (9) | 0.0042 (10) | 0.0019 (9) |
C10 | 0.0474 (15) | 0.0519 (16) | 0.0429 (14) | −0.0002 (13) | −0.0052 (12) | 0.0011 (12) |
C11 | 0.0354 (14) | 0.0620 (19) | 0.068 (2) | −0.0005 (13) | −0.0059 (13) | 0.0023 (15) |
C12 | 0.0508 (16) | 0.0441 (15) | 0.0445 (14) | 0.0123 (12) | 0.0072 (12) | 0.0191 (12) |
C13 | 0.078 (2) | 0.0510 (19) | 0.107 (3) | −0.0058 (18) | 0.011 (2) | 0.010 (2) |
Geometric parameters (Å, º) top
Ni1—O1i | 1.836 (2) | C4—H4 | 0.9300 |
Ni1—O1 | 1.836 (2) | C5—C6 | 1.357 (4) |
Ni1—N1i | 1.910 (2) | C5—H5 | 0.9300 |
Ni1—N1 | 1.910 (2) | C6—H6 | 0.9300 |
Cl1—O6 | 1.410 (2) | C7—H7 | 0.9300 |
Cl1—O5 | 1.421 (2) | C8—C9 | 1.512 (3) |
Cl1—O4 | 1.4268 (18) | C8—H8A | 0.9700 |
Cl1—O3 | 1.4384 (19) | C8—H8B | 0.9700 |
O1—C2 | 1.309 (2) | C9—H9A | 0.9700 |
O2—C3 | 1.365 (3) | C9—H9B | 0.9700 |
O2—C12 | 1.439 (3) | C10—C11 | 1.481 (4) |
N1—C7 | 1.289 (3) | C10—H10A | 0.9700 |
N1—C8 | 1.481 (3) | C10—H10B | 0.9700 |
N2—C9 | 1.476 (3) | C11—H11A | 0.9600 |
N2—C10 | 1.492 (3) | C11—H11B | 0.9600 |
N2—H2A | 0.9000 | C11—H11C | 0.9600 |
N2—H2B | 0.9000 | C12—C13 | 1.478 (4) |
C1—C2 | 1.399 (3) | C12—H12A | 0.9700 |
C1—C6 | 1.405 (3) | C12—H12B | 0.9700 |
C1—C7 | 1.421 (3) | C13—H13A | 0.9600 |
C2—C3 | 1.421 (3) | C13—H13B | 0.9600 |
C3—C4 | 1.370 (3) | C13—H13C | 0.9600 |
C4—C5 | 1.390 (4) | | |
| | | |
O1i—Ni1—O1 | 180.0 | C1—C6—H6 | 119.7 |
O1i—Ni1—N1i | 92.33 (7) | N1—C7—C1 | 127.2 (2) |
O1—Ni1—N1i | 87.67 (7) | N1—C7—H7 | 116.4 |
O1i—Ni1—N1 | 87.67 (7) | C1—C7—H7 | 116.4 |
O1—Ni1—N1 | 92.33 (7) | N1—C8—C9 | 113.63 (18) |
N1i—Ni1—N1 | 180.0 | N1—C8—H8A | 108.8 |
O6—Cl1—O5 | 111.19 (15) | C9—C8—H8A | 108.8 |
O6—Cl1—O4 | 109.16 (13) | N1—C8—H8B | 108.8 |
O5—Cl1—O4 | 110.69 (13) | C9—C8—H8B | 108.8 |
O6—Cl1—O3 | 109.13 (15) | H8A—C8—H8B | 107.7 |
O5—Cl1—O3 | 108.15 (12) | N2—C9—C8 | 112.54 (18) |
O4—Cl1—O3 | 108.46 (13) | N2—C9—H9A | 109.1 |
C2—O1—Ni1 | 128.20 (14) | C8—C9—H9A | 109.1 |
C3—O2—C12 | 119.27 (19) | N2—C9—H9B | 109.1 |
C7—N1—C8 | 114.76 (18) | C8—C9—H9B | 109.1 |
C7—N1—Ni1 | 124.19 (15) | H9A—C9—H9B | 107.8 |
C8—N1—Ni1 | 120.95 (14) | C11—C10—N2 | 113.6 (2) |
C9—N2—C10 | 114.96 (19) | C11—C10—H10A | 108.8 |
C9—N2—H2A | 108.5 | N2—C10—H10A | 108.8 |
C10—N2—H2A | 108.5 | C11—C10—H10B | 108.8 |
C9—N2—H2B | 108.5 | N2—C10—H10B | 108.8 |
C10—N2—H2B | 108.5 | H10A—C10—H10B | 107.7 |
H2A—N2—H2B | 107.5 | C10—C11—H11A | 109.5 |
C2—C1—C6 | 119.9 (2) | C10—C11—H11B | 109.5 |
C2—C1—C7 | 119.90 (19) | H11A—C11—H11B | 109.5 |
C6—C1—C7 | 120.0 (2) | C10—C11—H11C | 109.5 |
O1—C2—C1 | 123.96 (19) | H11A—C11—H11C | 109.5 |
O1—C2—C3 | 117.8 (2) | H11B—C11—H11C | 109.5 |
C1—C2—C3 | 118.25 (19) | O2—C12—C13 | 113.0 (2) |
O2—C3—C4 | 126.0 (2) | O2—C12—H12A | 109.0 |
O2—C3—C2 | 113.84 (19) | C13—C12—H12A | 109.0 |
C4—C3—C2 | 120.2 (2) | O2—C12—H12B | 109.0 |
C3—C4—C5 | 120.7 (2) | C13—C12—H12B | 109.0 |
C3—C4—H4 | 119.7 | H12A—C12—H12B | 107.8 |
C5—C4—H4 | 119.7 | C12—C13—H13A | 109.5 |
C6—C5—C4 | 120.2 (2) | C12—C13—H13B | 109.5 |
C6—C5—H5 | 119.9 | H13A—C13—H13B | 109.5 |
C4—C5—H5 | 119.9 | C12—C13—H13C | 109.5 |
C5—C6—C1 | 120.7 (2) | H13A—C13—H13C | 109.5 |
C5—C6—H6 | 119.7 | H13B—C13—H13C | 109.5 |
Symmetry code: (i) −x+2, −y+1, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2B···O2i | 0.90 | 2.34 | 3.013 (3) | 131 |
N2—H2B···O1i | 0.90 | 1.97 | 2.764 (2) | 146 |
N2—H2A···O3 | 0.90 | 2.56 | 3.242 (3) | 132 |
N2—H2A···O3ii | 0.90 | 2.13 | 2.916 (3) | 145 |
Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x+1, −y+1, −z. |
Experimental details
Crystal data |
Chemical formula | [Ni(C13H20N2O2)2](ClO4)2 |
Mr | 730.23 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 298 |
a, b, c (Å) | 8.386 (3), 8.566 (3), 21.862 (6) |
β (°) | 99.068 (4) |
V (Å3) | 1550.8 (9) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.87 |
Crystal size (mm) | 0.23 × 0.20 × 0.20 |
|
Data collection |
Diffractometer | Bruker APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2004) |
Tmin, Tmax | 0.826, 0.846 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12509, 3363, 2770 |
Rint | 0.041 |
(sin θ/λ)max (Å−1) | 0.639 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.102, 1.04 |
No. of reflections | 3363 |
No. of parameters | 207 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.28, −0.34 |
Selected geometric parameters (Å, º) topNi1—O1 | 1.836 (2) | Ni1—N1 | 1.910 (2) |
| | | |
O1i—Ni1—O1 | 180.0 | O1—Ni1—N1 | 92.33 (7) |
O1i—Ni1—N1 | 87.67 (7) | N1i—Ni1—N1 | 180.0 |
Symmetry code: (i) −x+2, −y+1, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2B···O2i | 0.90 | 2.34 | 3.013 (3) | 131 |
N2—H2B···O1i | 0.90 | 1.97 | 2.764 (2) | 146 |
N2—H2A···O3 | 0.90 | 2.56 | 3.242 (3) | 132 |
N2—H2A···O3ii | 0.90 | 2.13 | 2.916 (3) | 145 |
Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x+1, −y+1, −z. |
Schiff bases have widely been used as versatile ligands in coordination chemistry (Biswas et al., 2008; Wu et al., 2008; Kawamoto et al., 2008; Ali et al., 2008; Habibi et al., 2007), and their metal complexes are of great interest in many fields (Chen et al., 2008; Yuan et al., 2007; Tomat et al., 2007; Darensbourg & Frantz, 2007). Nickel(II) is present in the active sites of urease (Carlsson et al., 2002, 2004). In this paper, a new nickel(II) complex, (I), Fig. 1, with the Schiff base ligand (E)-2-ethoxy-6-((3-(methylamino)propylimino)methyl)phenol has been synthesized and structurally characterized.
Complex (I) consists of a centrosymmetric mononuclear nickel(II) complex cation and two perchlorate anions. The NiII atom in the cation, lies on an inversion centre, with the asymmetric unit made up from one half of the Ni(II) complex and one perchlorate anion. The Ni(II) atom is four-coordinated by two imine N and two phenolate O atoms from two zwitterionic Schiff base ligands in a square-planar coordination geometry. The coordinate bond lengths (Table 1) are typical and comparable to the corresponding values observed in similar nickel(II) Schiff base complexes (Zhao, 2007; Skovsgaard et al., 2005; Ma et al., 2008).
In the crystal structure, molecules are linked through intermolecular N–H···O hydrogen bonds (Table 2), forming chains running along the a axis (Fig. 2).