Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536811009056/hy2415sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536811009056/hy2415Isup2.hkl |
CCDC reference: 820055
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.009 Å
- R factor = 0.073
- wR factor = 0.211
- Data-to-parameter ratio = 21.6
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT934_ALERT_3_B Number of (Iobs-Icalc)/SigmaW .gt. 10 Outliers . 2
Alert level C RINTA01_ALERT_3_C The value of Rint is greater than 0.12 Rint given 0.142 PLAT020_ALERT_3_C The value of Rint is greater than 0.12 ......... 0.14 PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang .. 9 PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) ..... 2 PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.600 7 PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L= 0.600 15 PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF .... 1 PLAT918_ALERT_3_C Reflection(s) # with I(obs) much smaller I(calc) 1
Alert level G PLAT794_ALERT_5_G Note: Tentative Bond Valency for Ni1 (III) 2.86
0 ALERT level A = Most likely a serious problem - resolve or explain 1 ALERT level B = A potentially serious problem, consider carefully 8 ALERT level C = Check. Ensure it is not caused by an omission or oversight 1 ALERT level G = General information/check it is not something unexpected 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 8 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
N,N'-Bis(5-bromo-2-hydroxybenzylidene)- 2,2-dimethylpropane-1,3-diamine was prepared according to the described procedure (Fairhurst et al., 1995). To a stirred ethanolic solution (30 ml) of 2,2-dimethylpropylenediamine (0.102 g, 1 mmol), 5-bromo-2-hydroxybenzaldehyde (0.402 g, 2 mmol) was added. The bright yellow solution was stirred and heated to reflux for 1 h. A yellow precipitate was obtained that was filtered off, washed with diethyl ether (yield: 70%; m.p.: 140 °C).
The title complex was prepared by the following procedure. The Schiff base ligand (0.467 g, 1 mmol) was dissolved in 20 ml ethanol. A solution of nickel(II) acetate (0.248 g, 1 mmol) in ethanol was added to the solution of ligand and the reaction mixture was refluxed for 1 h. The colored solution was concentrated to yield brown powders. The product washed with ethanol and air dried (yield: 95%; decomposition temperature: 242°C).
H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93 (aromatic), 0.97 (CH2) and 0.96 (CH3) Å and with Uiso(H) = 1.2 or 1.5Ueq(C).
Data collection: X-AREA (Stoe & Cie, 2005); cell refinement: X-AREA (Stoe & Cie, 2005); data reduction: X-AREA (Stoe & Cie, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
[Ni(C19H18Br2N2O2)] | F(000) = 1040.0 |
Mr = 524.84 | Dx = 1.820 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 2575 reflections |
a = 24.227 (6) Å | θ = 3.2–29.2° |
b = 11.030 (3) Å | µ = 5.20 mm−1 |
c = 7.535 (2) Å | T = 298 K |
β = 107.939 (19)° | Plate, brown |
V = 1915.6 (9) Å3 | 0.30 × 0.20 × 0.15 mm |
Z = 4 |
Stoe IPDS-2 diffractometer | 2575 independent reflections |
Radiation source: fine-focus sealed tube | 1892 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.142 |
ω scans | θmax = 29.2°, θmin = 3.2° |
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2005) | h = −33→24 |
Tmin = 0.289, Tmax = 0.449 | k = −15→13 |
7514 measured reflections | l = −10→10 |
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)] = 0.073 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.211 | H-atom parameters constrained |
S = 1.16 | w = 1/[σ2(Fo2) + (0.0955P)2 + 1.9321P] where P = (Fo2 + 2Fc2)/3 |
2575 reflections | (Δ/σ)max < 0.001 |
119 parameters | Δρmax = 0.74 e Å−3 |
0 restraints | Δρmin = −0.99 e Å−3 |
[Ni(C19H18Br2N2O2)] | V = 1915.6 (9) Å3 |
Mr = 524.84 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 24.227 (6) Å | µ = 5.20 mm−1 |
b = 11.030 (3) Å | T = 298 K |
c = 7.535 (2) Å | 0.30 × 0.20 × 0.15 mm |
β = 107.939 (19)° |
Stoe IPDS-2 diffractometer | 2575 independent reflections |
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2005) | 1892 reflections with I > 2σ(I) |
Tmin = 0.289, Tmax = 0.449 | Rint = 0.142 |
7514 measured reflections |
R[F2 > 2σ(F2)] = 0.073 | 0 restraints |
wR(F2) = 0.211 | H-atom parameters constrained |
S = 1.16 | Δρmax = 0.74 e Å−3 |
2575 reflections | Δρmin = −0.99 e Å−3 |
119 parameters |
x | y | z | Uiso*/Ueq | ||
C1 | 0.0516 (4) | 0.4164 (6) | 0.2433 (9) | 0.0606 (17) | |
H1A | 0.0407 | 0.4647 | 0.1319 | 0.073* | |
H1B | 0.0836 | 0.3650 | 0.2432 | 0.073* | |
H1C | 0.0629 | 0.4685 | 0.3505 | 0.073* | |
C2 | 0.0000 | 0.3381 (7) | 0.2500 | 0.0386 (14) | |
C3 | −0.0173 (2) | 0.2567 (5) | 0.0764 (6) | 0.0376 (10) | |
H3A | −0.0428 | 0.3023 | −0.0268 | 0.045* | |
H3B | 0.0173 | 0.2364 | 0.0438 | 0.045* | |
C4 | −0.0989 (2) | 0.1277 (5) | −0.0094 (7) | 0.0411 (11) | |
H4 | −0.1172 | 0.1946 | −0.0780 | 0.049* | |
C5 | −0.1317 (2) | 0.0172 (5) | −0.0337 (7) | 0.0425 (11) | |
C6 | −0.1902 (3) | 0.0171 (7) | −0.1506 (8) | 0.0546 (14) | |
H6 | −0.2078 | 0.0894 | −0.2018 | 0.065* | |
C7 | −0.2206 (3) | −0.0880 (7) | −0.1878 (9) | 0.0591 (17) | |
C8 | −0.1955 (3) | −0.1976 (7) | −0.1126 (9) | 0.0587 (16) | |
H8 | −0.2172 | −0.2687 | −0.1381 | 0.070* | |
C9 | −0.1388 (3) | −0.2006 (6) | −0.0009 (8) | 0.0518 (14) | |
H9 | −0.1223 | −0.2746 | 0.0462 | 0.062* | |
C10 | −0.1048 (2) | −0.0934 (5) | 0.0447 (7) | 0.0404 (11) | |
N1 | −0.04685 (19) | 0.1431 (4) | 0.0982 (5) | 0.0357 (9) | |
O1 | −0.05103 (17) | −0.1011 (3) | 0.1491 (5) | 0.0427 (8) | |
Ni1 | 0.0000 | 0.02440 (9) | 0.2500 | 0.0336 (3) | |
Br1 | −0.29838 (4) | −0.08575 (11) | −0.35030 (14) | 0.0979 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.074 (5) | 0.048 (4) | 0.053 (3) | −0.013 (3) | 0.010 (3) | 0.002 (3) |
C2 | 0.037 (3) | 0.038 (4) | 0.036 (3) | 0.000 | 0.004 (3) | 0.000 |
C3 | 0.041 (3) | 0.035 (3) | 0.036 (2) | 0.000 (2) | 0.0104 (19) | 0.0032 (18) |
C4 | 0.046 (3) | 0.040 (3) | 0.036 (2) | 0.004 (2) | 0.0100 (19) | 0.0043 (19) |
C5 | 0.038 (2) | 0.046 (3) | 0.039 (2) | −0.005 (2) | 0.0036 (19) | −0.001 (2) |
C6 | 0.040 (3) | 0.058 (4) | 0.054 (3) | 0.000 (3) | −0.003 (2) | 0.008 (3) |
C7 | 0.031 (3) | 0.073 (5) | 0.060 (3) | −0.014 (3) | −0.007 (2) | −0.003 (3) |
C8 | 0.045 (3) | 0.060 (4) | 0.064 (3) | −0.018 (3) | 0.007 (3) | −0.005 (3) |
C9 | 0.057 (4) | 0.039 (3) | 0.055 (3) | −0.007 (3) | 0.011 (3) | −0.003 (2) |
C10 | 0.040 (3) | 0.044 (3) | 0.036 (2) | −0.005 (2) | 0.0105 (19) | −0.0033 (19) |
N1 | 0.040 (2) | 0.036 (2) | 0.0277 (15) | −0.0035 (18) | 0.0057 (14) | −0.0005 (14) |
O1 | 0.0371 (19) | 0.0349 (19) | 0.0495 (19) | 0.0004 (15) | 0.0035 (15) | −0.0030 (14) |
Ni1 | 0.0339 (5) | 0.0315 (5) | 0.0325 (4) | 0.000 | 0.0060 (3) | 0.000 |
Br1 | 0.0519 (5) | 0.1002 (8) | 0.1070 (7) | −0.0251 (5) | −0.0265 (4) | 0.0188 (5) |
C1—C2 | 1.533 (8) | C5—C6 | 1.421 (8) |
C1—H1A | 0.9600 | C5—C10 | 1.423 (8) |
C1—H1B | 0.9600 | C6—C7 | 1.354 (10) |
C1—H1C | 0.9600 | C6—H6 | 0.9300 |
C2—C1i | 1.533 (8) | C7—C8 | 1.393 (11) |
C2—C3 | 1.535 (7) | C7—Br1 | 1.906 (6) |
C2—C3i | 1.535 (7) | C8—C9 | 1.372 (9) |
C3—N1 | 1.476 (7) | C8—H8 | 0.9300 |
C3—H3A | 0.9700 | C9—C10 | 1.423 (8) |
C3—H3B | 0.9700 | C9—H9 | 0.9300 |
C4—N1 | 1.284 (7) | C10—O1 | 1.300 (7) |
C4—C5 | 1.435 (8) | Ni1—N1 | 1.874 (4) |
C4—H4 | 0.9300 | Ni1—O1 | 1.856 (4) |
C2—C1—H1A | 109.5 | C7—C6—H6 | 119.9 |
C2—C1—H1B | 109.5 | C5—C6—H6 | 119.9 |
H1A—C1—H1B | 109.5 | C6—C7—C8 | 121.2 (6) |
C2—C1—H1C | 109.5 | C6—C7—Br1 | 119.2 (5) |
H1A—C1—H1C | 109.5 | C8—C7—Br1 | 119.5 (5) |
H1B—C1—H1C | 109.5 | C9—C8—C7 | 119.9 (6) |
C1—C2—C1i | 111.4 (8) | C9—C8—H8 | 120.0 |
C1—C2—C3 | 108.3 (3) | C7—C8—H8 | 120.0 |
C1i—C2—C3 | 110.2 (3) | C8—C9—C10 | 121.7 (6) |
C1—C2—C3i | 110.2 (3) | C8—C9—H9 | 119.2 |
C1i—C2—C3i | 108.3 (3) | C10—C9—H9 | 119.2 |
C3—C2—C3i | 108.4 (6) | O1—C10—C5 | 123.6 (5) |
N1—C3—C2 | 114.6 (4) | O1—C10—C9 | 119.4 (5) |
N1—C3—H3A | 108.6 | C5—C10—C9 | 117.0 (5) |
C2—C3—H3A | 108.6 | C4—N1—C3 | 117.2 (4) |
N1—C3—H3B | 108.6 | C4—N1—Ni1 | 125.9 (4) |
C2—C3—H3B | 108.6 | C3—N1—Ni1 | 116.0 (3) |
H3A—C3—H3B | 107.6 | C10—O1—Ni1 | 128.0 (4) |
N1—C4—C5 | 126.2 (5) | O1—Ni1—O1i | 83.5 (2) |
N1—C4—H4 | 116.9 | O1—Ni1—N1i | 166.70 (17) |
C5—C4—H4 | 116.9 | O1i—Ni1—N1i | 93.97 (18) |
C6—C5—C10 | 119.9 (6) | O1—Ni1—N1 | 93.97 (18) |
C6—C5—C4 | 119.1 (6) | O1i—Ni1—N1 | 166.70 (17) |
C10—C5—C4 | 120.7 (5) | N1i—Ni1—N1 | 91.3 (3) |
C7—C6—C5 | 120.2 (6) | ||
C1—C2—C3—N1 | 154.4 (5) | C8—C9—C10—C5 | −1.2 (9) |
C1i—C2—C3—N1 | −83.4 (6) | C5—C4—N1—C3 | 168.8 (5) |
C3i—C2—C3—N1 | 34.9 (3) | C5—C4—N1—Ni1 | 0.5 (7) |
N1—C4—C5—C6 | 176.4 (5) | C2—C3—N1—C4 | 118.2 (5) |
N1—C4—C5—C10 | −8.9 (8) | C2—C3—N1—Ni1 | −72.3 (5) |
C10—C5—C6—C7 | 0.0 (9) | C5—C10—O1—Ni1 | 9.6 (7) |
C4—C5—C6—C7 | 174.6 (6) | C9—C10—O1—Ni1 | −172.6 (4) |
C5—C6—C7—C8 | 0.3 (11) | C10—O1—Ni1—O1i | 179.3 (5) |
C5—C6—C7—Br1 | −178.4 (5) | C10—O1—Ni1—N1i | 99.5 (8) |
C6—C7—C8—C9 | −1.0 (11) | C10—O1—Ni1—N1 | −13.9 (4) |
Br1—C7—C8—C9 | 177.7 (5) | C4—N1—Ni1—O1 | 8.7 (4) |
C7—C8—C9—C10 | 1.5 (10) | C3—N1—Ni1—O1 | −159.7 (3) |
C6—C5—C10—O1 | 178.3 (5) | C4—N1—Ni1—O1i | 87.3 (9) |
C4—C5—C10—O1 | 3.7 (8) | C3—N1—Ni1—O1i | −81.1 (9) |
C6—C5—C10—C9 | 0.4 (8) | C4—N1—Ni1—N1i | −159.1 (5) |
C4—C5—C10—C9 | −174.1 (5) | C3—N1—Ni1—N1i | 32.5 (3) |
C8—C9—C10—O1 | −179.1 (6) |
Symmetry code: (i) −x, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3B···O1ii | 0.97 | 2.40 | 3.210 (6) | 141 |
Symmetry code: (ii) −x, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | [Ni(C19H18Br2N2O2)] |
Mr | 524.84 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 298 |
a, b, c (Å) | 24.227 (6), 11.030 (3), 7.535 (2) |
β (°) | 107.939 (19) |
V (Å3) | 1915.6 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 5.20 |
Crystal size (mm) | 0.30 × 0.20 × 0.15 |
Data collection | |
Diffractometer | Stoe IPDS2 diffractometer |
Absorption correction | Numerical (X-SHAPE and X-RED32; Stoe & Cie, 2005) |
Tmin, Tmax | 0.289, 0.449 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7514, 2575, 1892 |
Rint | 0.142 |
(sin θ/λ)max (Å−1) | 0.686 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.073, 0.211, 1.16 |
No. of reflections | 2575 |
No. of parameters | 119 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.74, −0.99 |
Computer programs: X-AREA (Stoe & Cie, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3B···O1i | 0.97 | 2.40 | 3.210 (6) | 141 |
Symmetry code: (i) −x, −y, −z. |
Schiff base complexes are found to exhibit large applications such as catalytic properties (Cozzi, 2004). N,N'-Bis(5-bromo-2-hydroxybenzylidene)- 2,2-dimethylpropane-1,3-diamine ligand has been previously synthesized and structurally characterized by X-ray diffraction (Fun et al., 2008). The structure of a copper(II) complex of this Schiff base ligand has been also reported by Fun's group (Kargar et al., 2008).
Herein, we report the synthesis and crystal structure of an Ni(II) complex with this Schiff base ligand. The molecular structure of the title compound is shown in Fig. 1. The asymmetric unit of the title compound contains half of the molecule. The NiII ion, lying on a twofold rotation axis, is coordinated by two N atoms and two O atoms from a Schiff base ligand (Table 1). The coordination environment around the NiII ion can be described as distorted squar-planar. In the crystal, weak intermolecular C—H···O hydrogen bonds stabilize the structure (Table 2, Fig. 2).