metal-organic compounds
Bis(2-{[2-(2-hydroxybenzylamino)ethyl]aminomethyl}phenolato-κ3N,N′,O1)cobalt(III) nitrate monohydrate
aDépartement de Chimie, Faculté des Sciences et Techniques, Université Cheikh Anta Diop, Dakar, Senegal, and bICSN-CNRS, Laboratoire de Cristallochimie, 1 Avenue la Terasse, 91198 Gif-sur-Yvette, France
*Correspondence e-mail: mlgayeastou@yahoo.fr
In the title compound, [Co(C16H19N2O2)2]NO3·H2O, the CoIII ion is located on an inversion center and is six-coordinated by two phenolate O atoms and four amino N atoms from two diamine ligands, forming an octahedral geometry. The water molecule and the nitrate anion are located close to an inversion center, and are thus equally disordered by symmetry. The crystal packing is stabilized by intermolecular O—H⋯O hydrogen bonds involving the uncoordinated water molecule and the free phenol hydroxyl group with the nitrate anion. N—H⋯O hydrogen bonds involving the amino groups and the nitrate anions connect the complex molecules along the c axis.
Experimental
Crystal data
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Refinement
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Data collection: COLLECT (Nonius, 1998) and DENZO (Otwinowski & Minor, 1997); cell COLLECT and DENZO; data reduction: SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) and CRYSTALBUILDER (Welter, 2006); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97.
Supporting information
10.1107/S1600536811055851/bh2406sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536811055851/bh2406Isup2.hkl
Diethylenetriamine (1.0311 g, 10 mmol) and salicylaldehyde (2.4408 g, 20 mmol) were dissolved in 20 ml of ethanol with few drops of glacial acetic acid. The mixture was refluxed for 3 h. On cooling, a yellow oil was isolated. To 20 ml of anhydrous methanol was added the yellow oil (1.5 g, 5.59 mmol). The mixture was cooled to 273 K before NaBH4 (0.63 g, 16.7 mmol) was added in small portions. A white precipitate was isolated after 30 mn of stirring by filtration. In a round-bottom flask, 15 ml of methanol and the prepared ligand (0.2 g, 0.735 mmol) were mixed. Cobalt nitrate hexahydrate (0.21, 0.735 mmol) dissolved in 5 ml of methanol was introduced. Immediate color change was observed, indicating instant occurrence of the formation of the complex. The mixture was stirred at room temperature for 2 h. The brown solution was filtered off and the filtrate was left at room temperature. After two weeks, brown crystals suitable for X-ray analyses were obtained. Yield: 75%. Anal. Calc. for [C32H40N5O8Co]: C 56.39, H 5.91, N 10.27%. Found: C 56.38, H 5.93, N 10.28%. Selected IR data (cm-1, KBr pellet): 400, 3216, 1600, 1582, 1458, 764.
Five low-resolution reflections affected by the backstop were omitted from the
The indicated that a water molecule and a nitrate ion reside alternatively on the same inversion site with half-occupancy. These form with the hydroxyl group a molecular H-bonded chain running in the [221] direction. Similarity restraints on 1–2 and 1–3 distances (s.u. = 0.01 and 0.04 Å, respectively) were applied to keep the nitrate ion geometry reasonable. In addition, similarity restraints on displacement parameters for the nitrate ion and water molecule (s.u. = 0.05 Å2), and rigid-bond restraints for anisotropic displacement parameters (s.u. = 0.01 Å2) in the nitrate ion were applied. Except for the water molecule, all H atoms were initially located in difference maps, then their positions were geometrically optimized and refined as riding on their parent atoms with C—H = 0.93 or 0.97 Å (aromatic CH and methylene CH2), N—H = 0.847–0.860 Å, and with Uiso(H) = 1.2Ueq(C or N), while the hydroxyl H atom was allowed to rotate about the parent C—O bond [AFIX 147 instruction in SHELXL97 (Sheldrick, 2008)], with O2—H2O = 0.807 Å and Uiso(H2O) = 1.5Ueq(O2). H atoms of the water molecule were placed in calculated idealized positions using DFIX and DANG instructions, until being constrained with AFIX 3 instructions for the last run of in order to optimize H-bond interactions with oxygen atoms of the nitrate ion.Data collection: COLLECT (Nonius, 1998) and DENZO (Otwinowski & Minor, 1997); cell
COLLECT (Nonius, 1998) and DENZO (Otwinowski & Minor, 1997); data reduction: SCALEPACK (Otwinowski & Minor 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) and CRYSTALBUILDER (Welter, 2006); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).Fig. 1. An ORTEP view of the title compound, showing displacement ellipsoids at the 50% probability level. [Symmetry operator a: -x + 1, -y, -z + 1]. A single position for nitrate and water groups has been retained. | |
Fig. 2. Molecular representation of the compound showing hydrogen bonds. Broken lines stand for hydrogen bonds. |
[Co(C16H19N2O2)2]NO3·H2O | Z = 1 |
Mr = 681.62 | F(000) = 358 |
Triclinic, P1 | Dx = 1.525 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71070 Å |
a = 8.989 (3) Å | Cell parameters from 2525 reflections |
b = 9.032 (3) Å | θ = 0.4–25.4° |
c = 10.621 (4) Å | µ = 0.64 mm−1 |
α = 106.680 (2)° | T = 293 K |
β = 99.950 (3)° | Parallelepipedic stick, brown |
γ = 109.720 (2)° | 0.42 × 0.14 × 0.12 mm |
V = 742.0 (4) Å3 |
Nonius KappaCCD diffractometer | 2694 independent reflections |
Radiation source: fine-focus sealed tube | 2303 reflections with I > 2σigma(I) |
Horizontally mounted graphite crystal monochromator | Rint = 0.019 |
Detector resolution: 9 pixels mm-1 | θmax = 25.7°, θmin = 2.8° |
ϕ and ω scans | h = −10→10 |
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997) | k = −10→10 |
Tmin = 0.640, Tmax = 0.930 | l = −12→12 |
16124 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.047 | H-atom parameters constrained |
wR(F2) = 0.126 | w = 1/[σ2(Fo2) + (0.0583P)2 + 0.3846P] where P = (Fo2 + 2Fc2)/3 |
S = 1.10 | (Δ/σ)max < 0.001 |
2689 reflections | Δρmax = 0.25 e Å−3 |
234 parameters | Δρmin = −0.48 e Å−3 |
29 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 constraints | Extinction coefficient: 0.058 (9) |
Primary atom site location: structure-invariant direct methods |
[Co(C16H19N2O2)2]NO3·H2O | γ = 109.720 (2)° |
Mr = 681.62 | V = 742.0 (4) Å3 |
Triclinic, P1 | Z = 1 |
a = 8.989 (3) Å | Mo Kα radiation |
b = 9.032 (3) Å | µ = 0.64 mm−1 |
c = 10.621 (4) Å | T = 293 K |
α = 106.680 (2)° | 0.42 × 0.14 × 0.12 mm |
β = 99.950 (3)° |
Nonius KappaCCD diffractometer | 2694 independent reflections |
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997) | 2303 reflections with I > 2σigma(I) |
Tmin = 0.640, Tmax = 0.930 | Rint = 0.019 |
16124 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | 29 restraints |
wR(F2) = 0.126 | H-atom parameters constrained |
S = 1.10 | Δρmax = 0.25 e Å−3 |
2689 reflections | Δρmin = −0.48 e Å−3 |
234 parameters |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Co1 | 0.5000 | 0.0000 | 0.5000 | 0.0525 (2) | |
O1 | 0.5163 (2) | 0.1737 (3) | 0.4297 (2) | 0.0576 (5) | |
O2 | −0.0155 (3) | −0.4955 (3) | 0.1901 (3) | 0.0811 (7) | |
H2O | −0.0938 | −0.5812 | 0.1814 | 0.122* | |
N1 | 0.4113 (3) | 0.0896 (3) | 0.6449 (2) | 0.0568 (6) | |
H1N | 0.4568 | 0.0862 | 0.7215 | 0.068* | |
N2 | 0.2647 (3) | −0.1449 (3) | 0.3863 (2) | 0.0568 (6) | |
H2N | 0.2543 | −0.2386 | 0.3935 | 0.068* | |
C1 | 0.4130 (3) | 0.2510 (4) | 0.4369 (3) | 0.0572 (7) | |
C2 | 0.3471 (4) | 0.2816 (4) | 0.3232 (3) | 0.0631 (7) | |
H2 | 0.3774 | 0.2503 | 0.2435 | 0.076* | |
C3 | 0.2380 (4) | 0.3575 (4) | 0.3273 (4) | 0.0705 (8) | |
H3 | 0.1945 | 0.3762 | 0.2502 | 0.085* | |
C4 | 0.1928 (4) | 0.4059 (4) | 0.4441 (4) | 0.0735 (9) | |
H4 | 0.1179 | 0.4561 | 0.4461 | 0.088* | |
C5 | 0.2590 (4) | 0.3796 (4) | 0.5582 (4) | 0.0700 (8) | |
H5 | 0.2302 | 0.4149 | 0.6381 | 0.084* | |
C6 | 0.3679 (4) | 0.3016 (4) | 0.5563 (3) | 0.0602 (7) | |
C7 | 0.4394 (4) | 0.2700 (4) | 0.6785 (3) | 0.0649 (8) | |
H7A | 0.5575 | 0.3400 | 0.7142 | 0.078* | |
H7B | 0.3898 | 0.3029 | 0.7501 | 0.078* | |
C8 | 0.2337 (3) | −0.0254 (4) | 0.6089 (3) | 0.0646 (8) | |
H8A | 0.1770 | 0.0346 | 0.6580 | 0.077* | |
H8B | 0.2245 | −0.1213 | 0.6358 | 0.077* | |
C9 | 0.1554 (3) | −0.0863 (4) | 0.4564 (3) | 0.0632 (8) | |
H9A | 0.0471 | −0.1785 | 0.4286 | 0.076* | |
H9B | 0.1419 | 0.0050 | 0.4320 | 0.076* | |
C10 | 0.2197 (3) | −0.1723 (4) | 0.2372 (3) | 0.0650 (8) | |
H10A | 0.2601 | −0.2527 | 0.1904 | 0.078* | |
H10B | 0.2779 | −0.0659 | 0.2277 | 0.078* | |
C11 | 0.0387 (3) | −0.2355 (4) | 0.1642 (3) | 0.0593 (7) | |
C12 | −0.0188 (4) | −0.1310 (4) | 0.1179 (3) | 0.0673 (8) | |
H12 | 0.0539 | −0.0202 | 0.1376 | 0.081* | |
C13 | −0.1816 (4) | −0.1876 (5) | 0.0434 (3) | 0.0698 (8) | |
H13 | −0.2187 | −0.1153 | 0.0138 | 0.084* | |
C14 | −0.2878 (4) | −0.3500 (4) | 0.0135 (3) | 0.0670 (8) | |
H14 | −0.3973 | −0.3893 | −0.0388 | 0.080* | |
C15 | −0.2359 (4) | −0.4569 (4) | 0.0591 (3) | 0.0644 (8) | |
H15 | −0.3095 | −0.5679 | 0.0380 | 0.077* | |
C16 | −0.0727 (4) | −0.3981 (4) | 0.1370 (3) | 0.0602 (7) | |
O11 | 0.7320 (11) | 0.1846 (10) | 0.1338 (9) | 0.123 (3) | 0.50 |
N11 | 0.5877 (7) | 0.0882 (8) | 0.0550 (6) | 0.0742 (14) | 0.50 |
O12 | 0.5389 (14) | 0.1116 (12) | −0.0485 (10) | 0.104 (3) | 0.50 |
O13 | 0.5023 (13) | −0.0330 (11) | 0.0776 (11) | 0.097 (3) | 0.50 |
O21 | 0.7119 (11) | 0.2509 (10) | 0.2025 (9) | 0.111 (3) | 0.50 |
H21O | 0.6490 | 0.1443 | 0.2054 | 0.167* | 0.50 |
H22O | 0.6628 | 0.2429 | 0.1127 | 0.167* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.0430 (3) | 0.0580 (4) | 0.0498 (3) | 0.0179 (2) | 0.0079 (2) | 0.0177 (2) |
O1 | 0.0520 (11) | 0.0630 (12) | 0.0589 (11) | 0.0241 (9) | 0.0139 (8) | 0.0252 (9) |
O2 | 0.0661 (14) | 0.0758 (16) | 0.0986 (18) | 0.0311 (12) | 0.0078 (13) | 0.0361 (14) |
N1 | 0.0479 (12) | 0.0637 (15) | 0.0515 (13) | 0.0188 (11) | 0.0079 (10) | 0.0201 (11) |
N2 | 0.0479 (12) | 0.0655 (15) | 0.0518 (13) | 0.0213 (11) | 0.0100 (10) | 0.0201 (11) |
C1 | 0.0450 (14) | 0.0562 (16) | 0.0628 (17) | 0.0167 (12) | 0.0093 (12) | 0.0204 (13) |
C2 | 0.0539 (16) | 0.0654 (19) | 0.0664 (18) | 0.0210 (14) | 0.0105 (13) | 0.0281 (15) |
C3 | 0.0584 (18) | 0.073 (2) | 0.080 (2) | 0.0257 (16) | 0.0103 (15) | 0.0351 (17) |
C4 | 0.0567 (18) | 0.072 (2) | 0.095 (3) | 0.0299 (16) | 0.0163 (17) | 0.0352 (18) |
C5 | 0.0600 (18) | 0.0657 (19) | 0.078 (2) | 0.0246 (15) | 0.0203 (15) | 0.0201 (16) |
C6 | 0.0527 (15) | 0.0572 (17) | 0.0623 (17) | 0.0197 (13) | 0.0107 (13) | 0.0179 (13) |
C7 | 0.0602 (17) | 0.069 (2) | 0.0585 (17) | 0.0270 (15) | 0.0133 (13) | 0.0152 (14) |
C8 | 0.0470 (15) | 0.081 (2) | 0.0590 (17) | 0.0194 (14) | 0.0154 (12) | 0.0248 (15) |
C9 | 0.0418 (14) | 0.076 (2) | 0.0610 (17) | 0.0170 (13) | 0.0119 (12) | 0.0208 (15) |
C10 | 0.0478 (15) | 0.080 (2) | 0.0512 (16) | 0.0180 (14) | 0.0062 (12) | 0.0179 (14) |
C11 | 0.0480 (15) | 0.0691 (19) | 0.0486 (15) | 0.0186 (14) | 0.0071 (11) | 0.0158 (13) |
C12 | 0.0589 (17) | 0.070 (2) | 0.0611 (18) | 0.0168 (15) | 0.0104 (14) | 0.0232 (15) |
C13 | 0.0622 (18) | 0.080 (2) | 0.0670 (19) | 0.0297 (17) | 0.0109 (15) | 0.0320 (17) |
C14 | 0.0483 (15) | 0.087 (2) | 0.0565 (17) | 0.0240 (16) | 0.0074 (13) | 0.0230 (16) |
C15 | 0.0514 (16) | 0.0666 (19) | 0.0599 (17) | 0.0169 (14) | 0.0086 (13) | 0.0155 (14) |
C16 | 0.0531 (16) | 0.0650 (18) | 0.0565 (16) | 0.0243 (14) | 0.0101 (12) | 0.0178 (14) |
O11 | 0.129 (6) | 0.083 (5) | 0.122 (7) | 0.026 (4) | −0.011 (5) | 0.041 (5) |
N11 | 0.070 (3) | 0.073 (4) | 0.079 (4) | 0.027 (3) | 0.021 (3) | 0.032 (3) |
O12 | 0.113 (7) | 0.107 (7) | 0.078 (5) | 0.028 (6) | 0.011 (4) | 0.044 (5) |
O13 | 0.094 (5) | 0.089 (6) | 0.090 (5) | 0.012 (4) | 0.018 (4) | 0.042 (5) |
O21 | 0.100 (5) | 0.081 (5) | 0.134 (7) | 0.017 (4) | 0.016 (5) | 0.050 (5) |
Co1—O1i | 1.896 (2) | N11—O13 | 1.222 (9) |
Co1—O1 | 1.896 (2) | N11—O13ii | 1.348 (12) |
Co1—N1i | 1.950 (2) | N11—N11ii | 1.728 (12) |
Co1—N1 | 1.950 (2) | N11—O12ii | 1.753 (10) |
Co1—N2i | 1.997 (2) | O12—O13ii | 0.627 (11) |
Co1—N2 | 1.997 (2) | O12—N11ii | 1.753 (10) |
O1—C1 | 1.337 (3) | O13—O12ii | 0.627 (11) |
O2—C16 | 1.358 (4) | O13—N11ii | 1.348 (12) |
N1—C7 | 1.484 (4) | O2—H2O | 0.8200 |
N1—C8 | 1.488 (4) | N1—H1N | 0.8595 |
N2—C9 | 1.475 (4) | N2—H2N | 0.8468 |
N2—C10 | 1.490 (4) | C2—H2 | 0.9300 |
C1—C2 | 1.393 (4) | C3—H3 | 0.9300 |
C1—C6 | 1.397 (4) | C4—H4 | 0.9300 |
C2—C3 | 1.373 (4) | C5—H5 | 0.9300 |
C3—C4 | 1.370 (5) | C7—H7A | 0.9700 |
C4—C5 | 1.375 (5) | C7—H7B | 0.9700 |
C5—C6 | 1.385 (4) | C8—H8A | 0.9700 |
C6—C7 | 1.493 (4) | C8—H8B | 0.9700 |
C8—C9 | 1.502 (4) | C9—H9A | 0.9700 |
C10—C11 | 1.502 (4) | C9—H9B | 0.9700 |
C11—C12 | 1.381 (4) | C10—H10A | 0.9700 |
C11—C16 | 1.381 (4) | C10—H10B | 0.9700 |
C12—C13 | 1.375 (4) | C12—H12 | 0.9300 |
C13—C14 | 1.359 (5) | C13—H13 | 0.9300 |
C14—C15 | 1.371 (5) | C14—H14 | 0.9300 |
C15—C16 | 1.386 (4) | C15—H15 | 0.9300 |
O11—N11 | 1.259 (9) | O21—H21O | 0.9503 |
N11—O12 | 1.214 (11) | O21—H22O | 0.9504 |
O1i—Co1—O1 | 180 | O12—N11—O11 | 118.7 (8) |
O1i—Co1—N1i | 94.28 (10) | O13—N11—O11 | 120.6 (8) |
O1—Co1—N1i | 85.72 (10) | C16—O2—H2O | 109.5 |
O1i—Co1—N1 | 85.72 (9) | C7—N1—H1N | 104.3 |
O1—Co1—N1 | 94.28 (10) | C8—N1—H1N | 104.2 |
N1i—Co1—N1 | 180 | Co1—N1—H1N | 111.3 |
O1i—Co1—N2i | 93.87 (9) | C9—N2—H2N | 107.1 |
O1—Co1—N2i | 86.13 (9) | C10—N2—H2N | 108.3 |
N1i—Co1—N2i | 86.32 (10) | Co1—N2—H2N | 100.6 |
N1—Co1—N2i | 93.68 (9) | C3—C2—H2 | 119.6 |
O1i—Co1—N2 | 86.13 (9) | C1—C2—H2 | 119.6 |
O1—Co1—N2 | 93.87 (9) | C4—C3—H3 | 119.8 |
N1i—Co1—N2 | 93.68 (9) | C2—C3—H3 | 119.8 |
N1—Co1—N2 | 86.32 (10) | C3—C4—H4 | 120.3 |
N2i—Co1—N2 | 180 | C5—C4—H4 | 120.3 |
C1—O1—Co1 | 122.22 (18) | C4—C5—H5 | 119.4 |
C7—N1—C8 | 113.1 (2) | C6—C5—H5 | 119.4 |
C7—N1—Co1 | 114.85 (19) | N1—C7—H7A | 109.1 |
C8—N1—Co1 | 108.49 (18) | C6—C7—H7A | 109.1 |
C9—N2—C10 | 112.6 (2) | N1—C7—H7B | 109.1 |
C9—N2—Co1 | 109.04 (17) | C6—C7—H7B | 109.1 |
C10—N2—Co1 | 117.92 (18) | H7A—C7—H7B | 107.9 |
O1—C1—C2 | 119.8 (3) | N1—C8—H8A | 109.8 |
O1—C1—C6 | 121.5 (3) | C9—C8—H8A | 109.8 |
C2—C1—C6 | 118.6 (3) | N1—C8—H8B | 109.8 |
C3—C2—C1 | 120.8 (3) | C9—C8—H8B | 109.8 |
C4—C3—C2 | 120.5 (3) | H8A—C8—H8B | 108.3 |
C3—C4—C5 | 119.5 (3) | N2—C9—H9A | 110.1 |
C4—C5—C6 | 121.2 (3) | C8—C9—H9A | 110.1 |
C5—C6—C1 | 119.4 (3) | N2—C9—H9B | 110.1 |
C5—C6—C7 | 122.0 (3) | C8—C9—H9B | 110.1 |
C1—C6—C7 | 118.7 (3) | H9A—C9—H9B | 108.4 |
N1—C7—C6 | 112.3 (2) | N2—C10—H10A | 108.2 |
N1—C8—C9 | 109.2 (2) | C11—C10—H10A | 108.2 |
N2—C9—C8 | 108.0 (2) | N2—C10—H10B | 108.2 |
N2—C10—C11 | 116.5 (2) | C11—C10—H10B | 108.2 |
C12—C11—C16 | 118.2 (3) | H10A—C10—H10B | 107.3 |
C12—C11—C10 | 119.6 (3) | C13—C12—H12 | 119.3 |
C16—C11—C10 | 122.1 (3) | C11—C12—H12 | 119.3 |
C13—C12—C11 | 121.3 (3) | C14—C13—H13 | 120.3 |
C14—C13—C12 | 119.4 (3) | C12—C13—H13 | 120.3 |
C13—C14—C15 | 121.0 (3) | C13—C14—H14 | 119.5 |
C14—C15—C16 | 119.4 (3) | C15—C14—H14 | 119.5 |
O2—C16—C11 | 117.3 (3) | C14—C15—H15 | 120.3 |
O2—C16—C15 | 122.2 (3) | C16—C15—H15 | 120.3 |
C11—C16—C15 | 120.6 (3) | H21O—O21—H22O | 104.1 |
O12—N11—O13 | 120.6 (8) | ||
N1i—Co1—O1—C1 | 149.8 (2) | C7—N1—C8—C9 | 90.2 (3) |
N1—Co1—O1—C1 | −30.2 (2) | Co1—N1—C8—C9 | −38.5 (3) |
N2i—Co1—O1—C1 | −123.6 (2) | C10—N2—C9—C8 | −167.3 (3) |
N2—Co1—O1—C1 | 56.4 (2) | Co1—N2—C9—C8 | −34.4 (3) |
O1i—Co1—N1—C7 | 161.25 (19) | N1—C8—C9—N2 | 48.1 (3) |
O1—Co1—N1—C7 | −18.75 (19) | C9—N2—C10—C11 | −33.9 (4) |
N2i—Co1—N1—C7 | 67.64 (19) | Co1—N2—C10—C11 | −162.3 (2) |
N2—Co1—N1—C7 | −112.36 (19) | N2—C10—C11—C12 | 112.2 (3) |
O1i—Co1—N1—C8 | −71.16 (19) | N2—C10—C11—C16 | −70.1 (4) |
O1—Co1—N1—C8 | 108.84 (19) | C16—C11—C12—C13 | −1.8 (5) |
N2i—Co1—N1—C8 | −164.77 (19) | C10—C11—C12—C13 | 176.0 (3) |
N2—Co1—N1—C8 | 15.23 (19) | C11—C12—C13—C14 | −0.7 (5) |
O1i—Co1—N2—C9 | 96.9 (2) | C12—C13—C14—C15 | 1.5 (5) |
O1—Co1—N2—C9 | −83.1 (2) | C13—C14—C15—C16 | 0.0 (5) |
N1i—Co1—N2—C9 | −169.1 (2) | C12—C11—C16—O2 | −176.4 (3) |
N1—Co1—N2—C9 | 10.9 (2) | C10—C11—C16—O2 | 5.8 (4) |
O1i—Co1—N2—C10 | −133.0 (2) | C12—C11—C16—C15 | 3.4 (4) |
O1—Co1—N2—C10 | 47.0 (2) | C10—C11—C16—C15 | −174.4 (3) |
N1i—Co1—N2—C10 | −39.0 (2) | C14—C15—C16—O2 | 177.2 (3) |
N1—Co1—N2—C10 | 141.0 (2) | C14—C15—C16—C11 | −2.5 (5) |
Co1—O1—C1—C2 | −136.5 (2) | O13—N11—O12—O13ii | −29 (3) |
Co1—O1—C1—C6 | 43.1 (3) | O11—N11—O12—O13ii | 147 (2) |
O1—C1—C2—C3 | 178.6 (3) | N11ii—N11—O12—O13ii | −18 (2) |
C6—C1—C2—C3 | −1.0 (5) | O12ii—N11—O12—O13ii | −18 (2) |
C1—C2—C3—C4 | 0.5 (5) | O13—N11—O12—N11ii | −10.6 (13) |
C2—C3—C4—C5 | 0.7 (5) | O11—N11—O12—N11ii | 164.8 (9) |
C3—C4—C5—C6 | −1.5 (5) | O13ii—N11—O12—N11ii | 18 (2) |
C4—C5—C6—C1 | 0.9 (5) | O12ii—N11—O12—N11ii | 0.0 |
C4—C5—C6—C7 | −179.2 (3) | O12—N11—O13—O12ii | 49 (5) |
O1—C1—C6—C5 | −179.3 (3) | O11—N11—O13—O12ii | −127 (4) |
C2—C1—C6—C5 | 0.3 (4) | O13ii—N11—O13—O12ii | 36 (4) |
O1—C1—C6—C7 | 0.8 (4) | N11ii—N11—O13—O12ii | 36 (4) |
C2—C1—C6—C7 | −179.6 (3) | O12—N11—O13—N11ii | 12.9 (16) |
C8—N1—C7—C6 | −67.3 (3) | O11—N11—O13—N11ii | −162.4 (9) |
Co1—N1—C7—C6 | 57.9 (3) | O13ii—N11—O13—N11ii | 0.0 |
C5—C6—C7—N1 | 126.1 (3) | O12ii—N11—O13—N11ii | −36 (4) |
C1—C6—C7—N1 | −54.0 (4) |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O21—H21O···O12ii | 0.95 | 2.27 | 3.025 (12) | 136 |
O21—H22O···O13ii | 0.95 | 2.18 | 2.922 (13) | 134 |
O2—H2O···O21iii | 0.82 | 1.99 | 2.787 (9) | 165 |
O2—H2O···O11iii | 0.82 | 2.01 | 2.823 (9) | 169 |
N1—H1N···O12iv | 0.86 | 2.35 | 3.185 (10) | 165 |
N1—H1N···O13i | 0.86 | 2.31 | 3.145 (11) | 163 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, −y, −z; (iii) x−1, y−1, z; (iv) x, y, z+1. |
Experimental details
Crystal data | |
Chemical formula | [Co(C16H19N2O2)2]NO3·H2O |
Mr | 681.62 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 8.989 (3), 9.032 (3), 10.621 (4) |
α, β, γ (°) | 106.680 (2), 99.950 (3), 109.720 (2) |
V (Å3) | 742.0 (4) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.64 |
Crystal size (mm) | 0.42 × 0.14 × 0.12 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SCALEPACK; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.640, 0.930 |
No. of measured, independent and observed [I > 2σigma(I)] reflections | 16124, 2694, 2303 |
Rint | 0.019 |
(sin θ/λ)max (Å−1) | 0.610 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.126, 1.10 |
No. of reflections | 2689 |
No. of parameters | 234 |
No. of restraints | 29 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.25, −0.48 |
Computer programs: COLLECT (Nonius, 1998) and DENZO (Otwinowski & Minor, 1997), SCALEPACK (Otwinowski & Minor 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and CRYSTALBUILDER (Welter, 2006), PLATON (Spek, 2009) and Mercury (Macrae et al., 2006), SHELXL97 (Sheldrick, 2008).
Co1—O1 | 1.896 (2) | Co1—N2 | 1.997 (2) |
Co1—N1 | 1.950 (2) | ||
O1i—Co1—O1 | 180 | O1—Co1—N2 | 93.87 (9) |
O1—Co1—N1i | 85.72 (10) | N1i—Co1—N2 | 93.68 (9) |
O1—Co1—N1 | 94.28 (10) | N1—Co1—N2 | 86.32 (10) |
N1i—Co1—N1 | 180 | N2i—Co1—N2 | 180 |
O1i—Co1—N2 | 86.13 (9) |
Symmetry code: (i) −x+1, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O21—H21O···O12ii | 0.95 | 2.27 | 3.025 (12) | 135.8 |
O21—H22O···O13ii | 0.95 | 2.18 | 2.922 (13) | 134.2 |
O2—H2O···O21iii | 0.82 | 1.99 | 2.787 (9) | 165.4 |
O2—H2O···O11iii | 0.82 | 2.01 | 2.823 (9) | 168.7 |
N1—H1N···O12iv | 0.86 | 2.35 | 3.185 (10) | 165.3 |
N1—H1N···O13i | 0.86 | 2.31 | 3.145 (11) | 162.9 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, −y, −z; (iii) x−1, y−1, z; (iv) x, y, z+1. |
Acknowledgements
The authors thank Professor Amadou Tidiane, BA Minister of Higher Education of Senegal, for his financial support.
References
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Schiff bases with N2O2 inners have been used to synthesize complexes, due to their chelating ability for metal atoms. In this paper, the title new cobalt(III) complex with the diamine ligand [2-((2-hydroxybenzylamino)ethylamino)methyl]phenol, is reported. The CoIII ion is six-coordinated by four amino N atoms and two phenolate O atoms from two ligands, forming an octahedral geometry (Fig. 1). The ligands present one of the hydroxyl groups protonated while the coordinated one is deprotonated. The equatorial sites are occupied by two amino N atoms and two phenolate O atoms from the same arm of the ligand and the two axial sites are occupied by the amino N atoms owned by the arm bearing the non deprotonated phenol group. The Co—O and Co—N equatorial bond lengths are 1.896 (2) and 1.950 (2) Å, while Co—N axial bond lengths is 1.997 (2) Å (Table 1). They are comparable to the bond lengths in similar octahedral cobalt complexes (Zhou, 2009; Zhang, 2010; Khalaji et al., 2010). The NO3- ion and the lattice water molecule are disordered over two sets of sites, with relative occupancies of 0.5 for each group. In the crystal structure, the molecules of the compound are linked into a three-dimensional framework by a combination of O—H···O, N—H···O, and C—H···π(arene) hydrogen bonds and also π–π stacking interactions. The first hydrogen bond type utilizes hydroxyl atoms O2 as donors to link the Co complexes through either a water molecule or a nitrate ion (the water molecule being H-bonded to the nitrate ion over a crystallographic inversion center) into an infinite chain along the [221] direction. Benzyl ring at general position form π–π interactions with its neighbor at (1 - x, 1 - y, 1 - z), with distance between ring centroids of 3.534 (3) Å. This pair is further sandwiched by C—H···π(arene) hydrogen bond developed by atom C9 with H9B···Cg distance of 2.76 Å, and X—H ··· Cg angle of 145°, and even more weakly by the edge of the phenolic group. These aromatic interactions interspersed by the solvent molecules but propagating along the [231] direction combine with the previous linear H-bond chain to form a molecular sheet lying parallel to (-102) (Fig. 2). Orthogonally to the sheet, the third dimensionality is developed by an hydrogen bond between the amine atom N1 and the nitrate ion, along the c axis.