Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807044996/lh2503sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807044996/lh2503Isup2.hkl |
CCDC reference: 663619
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.017 Å
- R factor = 0.064
- wR factor = 0.187
- Data-to-parameter ratio = 14.1
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT341_ALERT_3_B Low Bond Precision on C-C Bonds (x 1000) Ang ... 17
Alert level C PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.56 PLAT213_ALERT_2_C Atom O1 has ADP max/min Ratio ............. 4.00 prola PLAT213_ALERT_2_C Atom O2 has ADP max/min Ratio ............. 3.20 oblat PLAT420_ALERT_2_C D-H Without Acceptor N1 - H1 ... ? PLAT431_ALERT_2_C Short Inter HL..A Contact Br1 .. Br2 .. 3.59 Ang.
Alert level G ABSTM02_ALERT_3_G When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.559 Tmax scaled 0.133 Tmin scaled 0.117 PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT793_ALERT_1_G Check the Absolute Configuration of N1 = ... R PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 24
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 5 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 4 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 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
A solution of (2 mmol, 0.120 g) 2-Amino-ethanol and (2 mmol, 0.112 g) caustic potash in distilled water was added slowly to a solution of (2 mmol, 0.562 g) 3,5-Dibromo-2-hydroxy-benzaldehyde in methanol. The mixture was stirred for 30 min at room temperature, then added to solid (2 mmol, 0.076 g) sodium borohydride and stirred 2 h; the yellow solution become colourless. Then this mixture was slowly added to a solution of (1 mmol, 0.291 g) nickel nitrate in distilled water. The mixture was stirred for 4 h at room temperature and filtration and the filtrate was left to stand at room temperature. The green block single crystals suitable for X-ray diffration were obtained in a yield of 66%(base on nickel nitrate). analysis found(%):C, 30.52; H, 2.96; N, 3.93; C18H20Br4N2NiO4 requires (%):C, 30.59; H, 2.85; N, 3.96.
All hydrogen atoms were positioned geometrically and refined with a riding model, with C—H = 0.97 (CH2) or 0.93 Å(aromatic ring); Uiso(H) = 1.2 Ueq(C) and O—H = 0.82 Å; N—H =0.91Å with Uiso(H) = 1.5 Ueq(O,N).
Halogens have a ubiquitous presence in both inorganic and organic chemisry, serving as mondentate or bridging ligands for a wide variety of d-block, f-block, and main group metals as well as being common substituents in a large number of organic compounds. Most frequently they lie at the periphery of molecules. The resultant steric accessibility has the potential to make halogenated compounds an attractive target for use in supramolecular chemistry and crystal engineering wherein the halogen atoms are directly involved in forming intermolecular interactions. Indeed interest in packing arrangements of halogenated compounds goes back many years to what was called the "chloro effect", wherein the presence of chloro substituents on aromatic compounds frequently resulted in stacking arrangements with a resultant short(ca 4 Å) crystallographic axis (Cohen, et al., 1964, Desiraju, 1989). Herein, we chose LH, to construct a new mononuclear nickel coordination complex Ni(L)2 {LH = [(3,5-dibromo-2-oxidophenyl)methyleneamino]ethanol}.
The molecular structure of the tile complex is shown in Fig. 1. The NiII atom, which lies on a crystallographic inversion center, is coordinated by four O atoms and two N atoms from two difference tridentate L- ligands, to furnish a slightly distorted octahedral geometry as defined by the bond lengths and angles in Table 1.
All other bond distances and angles are within the normal ranges (Allen et al., 1987). In the crystal structure close Br···Br contacts of 3.592 (1)Å are observed (Fiorenzo, et al., 2005, Zaman, et al., 2004, Jagarlapudi & Gautam, 1986) (Fig.2).
For a related structure, see: Zhang et al. (2007). For related literature, see: Allen et al. (1987); Cohen et al. (1964); Desiraju (1989); Fiorenzo et al. (2005); Jagarlapudi & Gautam (1986); Zaman et al. (2004); Zhang et al. (2007).
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL (Bruker, 2001).
[Ni(C9H10Br2NO2)2] | F(000) = 684 |
Mr = 706.71 | Dx = 2.292 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 4304 reflections |
a = 4.865 (3) Å | θ = 2.2–25.6° |
b = 10.481 (6) Å | µ = 8.78 mm−1 |
c = 20.103 (11) Å | T = 293 K |
β = 92.539 (10)° | Block, green |
V = 1024.0 (10) Å3 | 0.26 × 0.23 × 0.23 mm |
Z = 2 |
Bruker SMART CCD area-detector diffractometer | 1880 independent reflections |
Radiation source: fine-focus sealed tube | 1136 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.075 |
φ and ω scans | θmax = 25.6°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −5→5 |
Tmin = 0.209, Tmax = 0.237 | k = −12→12 |
4304 measured reflections | l = −11→24 |
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)] = 0.065 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.187 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0856P)2 + 3.284P] where P = (Fo2 + 2Fc2)/3 |
1880 reflections | (Δ/σ)max < 0.001 |
133 parameters | Δρmax = 1.19 e Å−3 |
24 restraints | Δρmin = −1.60 e Å−3 |
[Ni(C9H10Br2NO2)2] | V = 1024.0 (10) Å3 |
Mr = 706.71 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 4.865 (3) Å | µ = 8.78 mm−1 |
b = 10.481 (6) Å | T = 293 K |
c = 20.103 (11) Å | 0.26 × 0.23 × 0.23 mm |
β = 92.539 (10)° |
Bruker SMART CCD area-detector diffractometer | 1880 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1136 reflections with I > 2σ(I) |
Tmin = 0.209, Tmax = 0.237 | Rint = 0.075 |
4304 measured reflections |
R[F2 > 2σ(F2)] = 0.065 | 24 restraints |
wR(F2) = 0.187 | H-atom parameters constrained |
S = 1.09 | Δρmax = 1.19 e Å−3 |
1880 reflections | Δρmin = −1.60 e Å−3 |
133 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 | ||
Br1 | 1.4009 (3) | 0.32819 (14) | 0.20719 (6) | 0.0319 (4) | |
Br2 | 0.6079 (3) | −0.05668 (14) | 0.16826 (7) | 0.0377 (5) | |
C1 | 1.144 (2) | 0.2727 (11) | 0.0800 (6) | 0.019 (3) | |
C2 | 1.166 (2) | 0.2414 (11) | 0.1475 (6) | 0.019 (3) | |
C3 | 1.007 (3) | 0.1406 (11) | 0.1737 (6) | 0.026 (3) | |
H3 | 1.0272 | 0.1185 | 0.2185 | 0.031* | |
C4 | 0.817 (2) | 0.0745 (12) | 0.1308 (6) | 0.026 (3) | |
C5 | 0.804 (2) | 0.1025 (12) | 0.0650 (7) | 0.027 (3) | |
H5 | 0.6870 | 0.0555 | 0.0366 | 0.033* | |
C6 | 0.963 (3) | 0.2010 (13) | 0.0384 (6) | 0.027 (3) | |
C7 | 0.959 (3) | 0.2210 (12) | −0.0352 (5) | 0.024 (3) | |
H7A | 0.8497 | 0.1547 | −0.0572 | 0.029* | |
H7B | 1.1451 | 0.2149 | −0.0505 | 0.029* | |
C8 | 0.888 (2) | 0.3775 (14) | −0.1243 (6) | 0.030 (3) | |
H8A | 0.7656 | 0.4453 | −0.1399 | 0.036* | |
H8B | 0.8478 | 0.3022 | −0.1511 | 0.036* | |
C9 | 1.198 (2) | 0.4193 (14) | −0.1325 (7) | 0.033 (3) | |
H9A | 1.3176 | 0.3453 | −0.1315 | 0.040* | |
H9B | 1.2168 | 0.4637 | −0.1743 | 0.040* | |
N1 | 0.8410 (19) | 0.3495 (8) | −0.0538 (5) | 0.019 (2) | |
H1 | 0.6688 | 0.3377 | −0.0390 | 0.029* | |
Ni1 | 1.0000 | 0.5000 | 0.0000 | 0.0174 (5) | |
O1 | 1.2618 (14) | 0.3738 (8) | 0.0547 (4) | 0.0190 (18) | |
O2 | 1.2670 (15) | 0.5024 (9) | −0.0774 (4) | 0.0230 (19) | |
H2 | 1.2756 | 0.5794 | −0.0841 | 0.035* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0260 (7) | 0.0401 (9) | 0.0286 (7) | −0.0054 (6) | −0.0083 (5) | 0.0021 (6) |
Br2 | 0.0267 (8) | 0.0384 (9) | 0.0481 (9) | −0.0097 (7) | 0.0023 (6) | 0.0112 (7) |
C1 | 0.014 (6) | 0.016 (6) | 0.026 (7) | −0.002 (5) | 0.000 (5) | −0.006 (5) |
C2 | 0.016 (6) | 0.015 (7) | 0.027 (7) | 0.004 (5) | −0.003 (5) | 0.004 (5) |
C3 | 0.028 (7) | 0.023 (8) | 0.026 (7) | −0.001 (6) | −0.004 (5) | 0.002 (6) |
C4 | 0.009 (5) | 0.033 (7) | 0.036 (6) | −0.001 (5) | 0.001 (5) | 0.000 (5) |
C5 | 0.019 (7) | 0.018 (7) | 0.044 (8) | −0.002 (5) | −0.011 (6) | −0.001 (6) |
C6 | 0.019 (7) | 0.041 (9) | 0.021 (6) | −0.009 (6) | 0.001 (5) | −0.003 (6) |
C7 | 0.034 (8) | 0.022 (7) | 0.017 (6) | −0.009 (6) | −0.002 (5) | 0.002 (5) |
C8 | 0.022 (7) | 0.046 (9) | 0.022 (7) | −0.002 (6) | −0.007 (5) | 0.001 (6) |
C9 | 0.015 (6) | 0.044 (7) | 0.041 (6) | −0.007 (5) | 0.003 (5) | −0.009 (6) |
N1 | 0.018 (5) | 0.015 (6) | 0.025 (5) | 0.003 (4) | 0.002 (4) | 0.007 (4) |
Ni1 | 0.0071 (10) | 0.0236 (13) | 0.0214 (11) | −0.0016 (9) | −0.0012 (8) | −0.0003 (10) |
O1 | 0.004 (4) | 0.016 (4) | 0.037 (4) | −0.003 (3) | −0.006 (3) | 0.003 (4) |
O2 | 0.005 (4) | 0.031 (4) | 0.033 (4) | −0.005 (3) | 0.001 (3) | −0.009 (4) |
Br1—C2 | 1.859 (12) | C8—N1 | 1.475 (15) |
Br2—C4 | 1.888 (13) | C8—C9 | 1.586 (17) |
C1—O1 | 1.319 (13) | C8—H8A | 0.9700 |
C1—C2 | 1.395 (16) | C8—H8B | 0.9700 |
C1—C6 | 1.403 (16) | C9—O2 | 1.436 (15) |
C2—C3 | 1.425 (16) | C9—H9A | 0.9700 |
C3—C4 | 1.415 (17) | C9—H9B | 0.9700 |
C3—H3 | 0.9300 | N1—Ni1 | 2.045 (9) |
C4—C5 | 1.354 (17) | N1—H1 | 0.9099 |
C5—C6 | 1.409 (18) | Ni1—N1i | 2.045 (9) |
C5—H5 | 0.9300 | Ni1—O2i | 2.071 (8) |
C6—C7 | 1.495 (15) | Ni1—O2 | 2.071 (8) |
C7—N1 | 1.505 (15) | Ni1—O1 | 2.111 (7) |
C7—H7A | 0.9700 | Ni1—O1i | 2.111 (7) |
C7—H7B | 0.9700 | O2—H2 | 0.8200 |
O1—C1—C2 | 123.2 (10) | O2—C9—H9A | 110.5 |
O1—C1—C6 | 118.2 (10) | C8—C9—H9A | 110.5 |
C2—C1—C6 | 118.2 (11) | O2—C9—H9B | 110.5 |
C1—C2—C3 | 121.0 (11) | C8—C9—H9B | 110.5 |
C1—C2—Br1 | 122.2 (9) | H9A—C9—H9B | 108.7 |
C3—C2—Br1 | 116.9 (8) | C8—N1—C7 | 110.0 (9) |
C4—C3—C2 | 119.1 (11) | C8—N1—Ni1 | 106.5 (7) |
C4—C3—H3 | 120.4 | C7—N1—Ni1 | 115.3 (7) |
C2—C3—H3 | 120.4 | C8—N1—H1 | 121.7 |
C5—C4—C3 | 119.4 (11) | C7—N1—H1 | 98.3 |
C5—C4—Br2 | 123.0 (10) | Ni1—N1—H1 | 105.3 |
C3—C4—Br2 | 117.5 (9) | N1i—Ni1—N1 | 180 |
C4—C5—C6 | 121.8 (12) | N1i—Ni1—O2i | 81.2 (3) |
C4—C5—H5 | 119.1 | N1—Ni1—O2i | 98.8 (3) |
C6—C5—H5 | 119.1 | N1i—Ni1—O2 | 98.8 (3) |
C1—C6—C5 | 120.4 (11) | N1—Ni1—O2 | 81.2 (3) |
C1—C6—C7 | 119.6 (11) | O2i—Ni1—O2 | 180 |
C5—C6—C7 | 119.7 (11) | N1i—Ni1—O1 | 90.1 (3) |
C6—C7—N1 | 111.1 (10) | N1—Ni1—O1 | 89.9 (3) |
C6—C7—H7A | 109.4 | O2i—Ni1—O1 | 89.2 (3) |
N1—C7—H7A | 109.4 | O2—Ni1—O1 | 90.8 (3) |
C6—C7—H7B | 109.4 | N1i—Ni1—O1i | 89.9 (3) |
N1—C7—H7B | 109.4 | N1—Ni1—O1i | 90.1 (3) |
H7A—C7—H7B | 108.0 | O2i—Ni1—O1i | 90.8 (3) |
N1—C8—C9 | 110.0 (10) | O2—Ni1—O1i | 89.2 (3) |
N1—C8—H8A | 109.7 | O1—Ni1—O1i | 180 |
C9—C8—H8A | 109.7 | C1—O1—Ni1 | 116.2 (6) |
N1—C8—H8B | 109.7 | C9—O2—Ni1 | 116.0 (7) |
C9—C8—H8B | 109.7 | C9—O2—H2 | 118.8 |
H8A—C8—H8B | 108.2 | Ni1—O2—H2 | 100.0 |
O2—C9—C8 | 106.2 (10) |
Symmetry code: (i) −x+2, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1ii | 0.82 | 2.35 | 2.656 (10) | 103 |
Symmetry code: (ii) −x+3, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | [Ni(C9H10Br2NO2)2] |
Mr | 706.71 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 4.865 (3), 10.481 (6), 20.103 (11) |
β (°) | 92.539 (10) |
V (Å3) | 1024.0 (10) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 8.78 |
Crystal size (mm) | 0.26 × 0.23 × 0.23 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.209, 0.237 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4304, 1880, 1136 |
Rint | 0.075 |
(sin θ/λ)max (Å−1) | 0.608 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.065, 0.187, 1.09 |
No. of reflections | 1880 |
No. of parameters | 133 |
No. of restraints | 24 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.19, −1.60 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2001).
N1—Ni1 | 2.045 (9) | Ni1—O1 | 2.111 (7) |
Ni1—O2 | 2.071 (8) | ||
N1i—Ni1—N1 | 180 | O2—Ni1—O1 | 90.8 (3) |
N1—Ni1—O2i | 98.8 (3) | N1—Ni1—O1i | 90.1 (3) |
N1—Ni1—O2 | 81.2 (3) | O2—Ni1—O1i | 89.2 (3) |
O2i—Ni1—O2 | 180 | O1—Ni1—O1i | 180 |
N1—Ni1—O1 | 89.9 (3) |
Symmetry code: (i) −x+2, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1ii | 0.82 | 2.35 | 2.656 (10) | 102.6 |
Symmetry code: (ii) −x+3, −y+1, −z. |
Halogens have a ubiquitous presence in both inorganic and organic chemisry, serving as mondentate or bridging ligands for a wide variety of d-block, f-block, and main group metals as well as being common substituents in a large number of organic compounds. Most frequently they lie at the periphery of molecules. The resultant steric accessibility has the potential to make halogenated compounds an attractive target for use in supramolecular chemistry and crystal engineering wherein the halogen atoms are directly involved in forming intermolecular interactions. Indeed interest in packing arrangements of halogenated compounds goes back many years to what was called the "chloro effect", wherein the presence of chloro substituents on aromatic compounds frequently resulted in stacking arrangements with a resultant short(ca 4 Å) crystallographic axis (Cohen, et al., 1964, Desiraju, 1989). Herein, we chose LH, to construct a new mononuclear nickel coordination complex Ni(L)2 {LH = [(3,5-dibromo-2-oxidophenyl)methyleneamino]ethanol}.
The molecular structure of the tile complex is shown in Fig. 1. The NiII atom, which lies on a crystallographic inversion center, is coordinated by four O atoms and two N atoms from two difference tridentate L- ligands, to furnish a slightly distorted octahedral geometry as defined by the bond lengths and angles in Table 1.
All other bond distances and angles are within the normal ranges (Allen et al., 1987). In the crystal structure close Br···Br contacts of 3.592 (1)Å are observed (Fiorenzo, et al., 2005, Zaman, et al., 2004, Jagarlapudi & Gautam, 1986) (Fig.2).