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In the title centrosymmetric complex, [Ni(C9H10Br2NO2)2], the NiII ion is chelated by two 2-[(3,5-dibromo-2-oxidophen­yl)methyl­amino]ethanol ligands in a slightly distorted octa­hedral geometry. In the crystal structure, inter­molecular O—H...O hydrogen bonds connect mol­ecules into one-dimensional chains, and there are short inter­molecular Br...Br contacts of 3.592 (1) Å.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807044996/lh2503sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807044996/lh2503Isup2.hkl
Contains datablock I

CCDC reference: 663619

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](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

Comment top

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).

Related literature top

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).

Experimental top

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.

Refinement top

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).

Structure description top

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).

Computing details top

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).

Figures top
[Figure 1] Fig. 1. The molecular structure showing 30% probability displacement ellipsoids for non-H atoms. hydrogen atoms have been omitted. symmetry codes: (i) 2 - x, 1 - y, -z.
[Figure 2] Fig. 2. Part of the crystal structure showing short Br···Br contacts as dashed lines.
Bis{2-[(3,5-Dibromo-2-oxidophenyl)methylamino]ethanol- κ3O,N,O'}nickel(II) top
Crystal data top
[Ni(C9H10Br2NO2)2]F(000) = 684
Mr = 706.71Dx = 2.292 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 4304 reflections
a = 4.865 (3) Åθ = 2.2–25.6°
b = 10.481 (6) ŵ = 8.78 mm1
c = 20.103 (11) ÅT = 293 K
β = 92.539 (10)°Block, green
V = 1024.0 (10) Å30.26 × 0.23 × 0.23 mm
Z = 2
Data collection top
Bruker SMART CCD area-detector
diffractometer
1880 independent reflections
Radiation source: fine-focus sealed tube1136 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.075
φ and ω scansθmax = 25.6°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 55
Tmin = 0.209, Tmax = 0.237k = 1212
4304 measured reflectionsl = 1124
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.065Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.187H-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 parametersΔρmax = 1.19 e Å3
24 restraintsΔρmin = 1.60 e Å3
Crystal data top
[Ni(C9H10Br2NO2)2]V = 1024.0 (10) Å3
Mr = 706.71Z = 2
Monoclinic, P21/nMo Kα radiation
a = 4.865 (3) ŵ = 8.78 mm1
b = 10.481 (6) ÅT = 293 K
c = 20.103 (11) Å0.26 × 0.23 × 0.23 mm
β = 92.539 (10)°
Data collection top
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 = 0.237Rint = 0.075
4304 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.06524 restraints
wR(F2) = 0.187H-atom parameters constrained
S = 1.09Δρmax = 1.19 e Å3
1880 reflectionsΔρmin = 1.60 e Å3
133 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
xyzUiso*/Ueq
Br11.4009 (3)0.32819 (14)0.20719 (6)0.0319 (4)
Br20.6079 (3)0.05668 (14)0.16826 (7)0.0377 (5)
C11.144 (2)0.2727 (11)0.0800 (6)0.019 (3)
C21.166 (2)0.2414 (11)0.1475 (6)0.019 (3)
C31.007 (3)0.1406 (11)0.1737 (6)0.026 (3)
H31.02720.11850.21850.031*
C40.817 (2)0.0745 (12)0.1308 (6)0.026 (3)
C50.804 (2)0.1025 (12)0.0650 (7)0.027 (3)
H50.68700.05550.03660.033*
C60.963 (3)0.2010 (13)0.0384 (6)0.027 (3)
C70.959 (3)0.2210 (12)0.0352 (5)0.024 (3)
H7A0.84970.15470.05720.029*
H7B1.14510.21490.05050.029*
C80.888 (2)0.3775 (14)0.1243 (6)0.030 (3)
H8A0.76560.44530.13990.036*
H8B0.84780.30220.15110.036*
C91.198 (2)0.4193 (14)0.1325 (7)0.033 (3)
H9A1.31760.34530.13150.040*
H9B1.21680.46370.17430.040*
N10.8410 (19)0.3495 (8)0.0538 (5)0.019 (2)
H10.66880.33770.03900.029*
Ni11.00000.50000.00000.0174 (5)
O11.2618 (14)0.3738 (8)0.0547 (4)0.0190 (18)
O21.2670 (15)0.5024 (9)0.0774 (4)0.0230 (19)
H21.27560.57940.08410.035*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0260 (7)0.0401 (9)0.0286 (7)0.0054 (6)0.0083 (5)0.0021 (6)
Br20.0267 (8)0.0384 (9)0.0481 (9)0.0097 (7)0.0023 (6)0.0112 (7)
C10.014 (6)0.016 (6)0.026 (7)0.002 (5)0.000 (5)0.006 (5)
C20.016 (6)0.015 (7)0.027 (7)0.004 (5)0.003 (5)0.004 (5)
C30.028 (7)0.023 (8)0.026 (7)0.001 (6)0.004 (5)0.002 (6)
C40.009 (5)0.033 (7)0.036 (6)0.001 (5)0.001 (5)0.000 (5)
C50.019 (7)0.018 (7)0.044 (8)0.002 (5)0.011 (6)0.001 (6)
C60.019 (7)0.041 (9)0.021 (6)0.009 (6)0.001 (5)0.003 (6)
C70.034 (8)0.022 (7)0.017 (6)0.009 (6)0.002 (5)0.002 (5)
C80.022 (7)0.046 (9)0.022 (7)0.002 (6)0.007 (5)0.001 (6)
C90.015 (6)0.044 (7)0.041 (6)0.007 (5)0.003 (5)0.009 (6)
N10.018 (5)0.015 (6)0.025 (5)0.003 (4)0.002 (4)0.007 (4)
Ni10.0071 (10)0.0236 (13)0.0214 (11)0.0016 (9)0.0012 (8)0.0003 (10)
O10.004 (4)0.016 (4)0.037 (4)0.003 (3)0.006 (3)0.003 (4)
O20.005 (4)0.031 (4)0.033 (4)0.005 (3)0.001 (3)0.009 (4)
Geometric parameters (Å, º) top
Br1—C21.859 (12)C8—N11.475 (15)
Br2—C41.888 (13)C8—C91.586 (17)
C1—O11.319 (13)C8—H8A0.9700
C1—C21.395 (16)C8—H8B0.9700
C1—C61.403 (16)C9—O21.436 (15)
C2—C31.425 (16)C9—H9A0.9700
C3—C41.415 (17)C9—H9B0.9700
C3—H30.9300N1—Ni12.045 (9)
C4—C51.354 (17)N1—H10.9099
C5—C61.409 (18)Ni1—N1i2.045 (9)
C5—H50.9300Ni1—O2i2.071 (8)
C6—C71.495 (15)Ni1—O22.071 (8)
C7—N11.505 (15)Ni1—O12.111 (7)
C7—H7A0.9700Ni1—O1i2.111 (7)
C7—H7B0.9700O2—H20.8200
O1—C1—C2123.2 (10)O2—C9—H9A110.5
O1—C1—C6118.2 (10)C8—C9—H9A110.5
C2—C1—C6118.2 (11)O2—C9—H9B110.5
C1—C2—C3121.0 (11)C8—C9—H9B110.5
C1—C2—Br1122.2 (9)H9A—C9—H9B108.7
C3—C2—Br1116.9 (8)C8—N1—C7110.0 (9)
C4—C3—C2119.1 (11)C8—N1—Ni1106.5 (7)
C4—C3—H3120.4C7—N1—Ni1115.3 (7)
C2—C3—H3120.4C8—N1—H1121.7
C5—C4—C3119.4 (11)C7—N1—H198.3
C5—C4—Br2123.0 (10)Ni1—N1—H1105.3
C3—C4—Br2117.5 (9)N1i—Ni1—N1180
C4—C5—C6121.8 (12)N1i—Ni1—O2i81.2 (3)
C4—C5—H5119.1N1—Ni1—O2i98.8 (3)
C6—C5—H5119.1N1i—Ni1—O298.8 (3)
C1—C6—C5120.4 (11)N1—Ni1—O281.2 (3)
C1—C6—C7119.6 (11)O2i—Ni1—O2180
C5—C6—C7119.7 (11)N1i—Ni1—O190.1 (3)
C6—C7—N1111.1 (10)N1—Ni1—O189.9 (3)
C6—C7—H7A109.4O2i—Ni1—O189.2 (3)
N1—C7—H7A109.4O2—Ni1—O190.8 (3)
C6—C7—H7B109.4N1i—Ni1—O1i89.9 (3)
N1—C7—H7B109.4N1—Ni1—O1i90.1 (3)
H7A—C7—H7B108.0O2i—Ni1—O1i90.8 (3)
N1—C8—C9110.0 (10)O2—Ni1—O1i89.2 (3)
N1—C8—H8A109.7O1—Ni1—O1i180
C9—C8—H8A109.7C1—O1—Ni1116.2 (6)
N1—C8—H8B109.7C9—O2—Ni1116.0 (7)
C9—C8—H8B109.7C9—O2—H2118.8
H8A—C8—H8B108.2Ni1—O2—H2100.0
O2—C9—C8106.2 (10)
Symmetry code: (i) x+2, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O1ii0.822.352.656 (10)103
Symmetry code: (ii) x+3, y+1, z.

Experimental details

Crystal data
Chemical formula[Ni(C9H10Br2NO2)2]
Mr706.71
Crystal system, space groupMonoclinic, P21/n
Temperature (K)293
a, b, c (Å)4.865 (3), 10.481 (6), 20.103 (11)
β (°) 92.539 (10)
V3)1024.0 (10)
Z2
Radiation typeMo Kα
µ (mm1)8.78
Crystal size (mm)0.26 × 0.23 × 0.23
Data collection
DiffractometerBruker SMART CCD area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.209, 0.237
No. of measured, independent and
observed [I > 2σ(I)] reflections
4304, 1880, 1136
Rint0.075
(sin θ/λ)max1)0.608
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.065, 0.187, 1.09
No. of reflections1880
No. of parameters133
No. of restraints24
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.19, 1.60

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2001).

Selected geometric parameters (Å, º) top
N1—Ni12.045 (9)Ni1—O12.111 (7)
Ni1—O22.071 (8)
N1i—Ni1—N1180O2—Ni1—O190.8 (3)
N1—Ni1—O2i98.8 (3)N1—Ni1—O1i90.1 (3)
N1—Ni1—O281.2 (3)O2—Ni1—O1i89.2 (3)
O2i—Ni1—O2180O1—Ni1—O1i180
N1—Ni1—O189.9 (3)
Symmetry code: (i) x+2, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O1ii0.822.352.656 (10)102.6
Symmetry code: (ii) x+3, y+1, z.
 

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