supplementary materials


lh5396 scheme

Acta Cryst. (2012). E68, m82    [ doi:10.1107/S1600536811054262 ]

{4,4'-Dimethyl-2,2'-[(2,2-dimethylpropane-1,3-diyl)bis(nitrilomethanylylidene)]diphenolato}nickel(II) monohydrate

H. Kargar, R. Kia, Z. Sharafi and M. N. Tahir

Abstract top

In the title compound, [Ni(C21H24N2O2)]·H2O, both the complex molecule and the water molecule lie on a twofold rotation axis. The NiII ion is coordinated in a distorted square-planar geometry by the tetradentate ligand. The dihedral angle between the two symmetry-related benzene rings is 47.12 (8)°. In the crystal, pairs of symmetry-related O-H...O hydrogen bonds form R22(6) ring motifs. In addition, there are weak intermolecular C-H...O hydrogen bonds, and [pi]-[pi] stacking interactions with a centroid-centroid distance of 3.4760 (8) Å.

Comment top

In continuation of our work on the crystal structures of a Schiff base ligands and complexes (Fun et al., 2008; Kargar et al., 2008,2011; Rayati et al., 2011; Kia et al., 2010), we have determined the X-ray structure of the title compound.

The molecular structure of the title compound is ahown in Fig. 1. The asymmetric unit comprises half of Schiff base complex and half a water molecule. The NiII ion, the central carbon atom of the diamine segment (C10) and the O atom of water molecule lie on a two-fold rotation axis. The coordination geometry of Ni1 is distorted square-planar formed by the tetradentate ligand. The bond lengths (Allen et al., 1987) and angles are within the normal ranges and are comparable to related structures (Fun et al. 2008; Kargar et al. 2008; Rayati et al., 2011). The dihedral angle between the two symmetry related benzene rings is 47.12 (8)°. A pair of symmetry related intermolecular O—H···O hydrogen bonds form an R22(6) ring motif (Bernstein et al., 1995). In the crystal, molecules are linked through weak intermolecular C—H···O interactions. The crystal structure is further stabilized by intermolecular ππ interactions [Cg1···Cg1iii = 3.4760 (8)Å; (iii) -x, 1 - y, 1 - z; Cg1 is the centroid of the Ni1/O1/C1/C6/C8/N1 ring].

Related literature top

For related structures, see for example: Fun et al. (2008); Kargar et al. (2008, 2011); Rayati et al. (2011); Kia et al. (2010). For standard bond lengths, see: Allen et al. (1987). For hydrogen-bond motifs, see: Bernstein et al. (1995).

Experimental top

The title compound was synthesized by adding bis(5-methylsalicylaldehyde)-2,2-dimethyl-1,3-propanediimine (2 mmol) to a solution of nickel(II) chloride hexahydrate (2.1 mmol) in ethanol (30 ml). The mixture was refluxed with stirring for half an hour. The resultant solution was filtered. Yellow single crystals of the title compound suitable for X-ray structure determination were recrystallized from an ethanol solution of the title compound by slow evaporation of the solvent at room temperature over several days.

Refinement top

Hydrogen atoms bonded to C atoms were positioned geometrically with C—H = 0.93-0.97 Å and included in a riding model approximation with Uiso (H) = 1.2 or 1.5 Ueq (C) The unique water H atom was located in a difference Fourier map and then constrained to ride to the parent atom with Uiso (H) = 1.5 Ueq (O). A rotating group model was used only for the benzene- substituent methyl group.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, showing 40% probability displacement ellipsoids. The dashed lines show hydrogen bonds [symmetry code: (A) -x, y, -z+1/2].
[Figure 2] Fig. 2. A partial packing diagram of the title compound viewed approximately along the c-axis showing molecules linked through intermolecular hydrogen bonds (dashed lines). Only the H atoms involved in the interactions are shown.
{4,4'-Dimethyl-2,2'-[(2,2-dimethylpropane-1,3- diyl)bis(nitrilomethanylylidene)]diphenolato}nickel(II) monohydrate top
Crystal data top
[Ni(C21H24N2O2)]·H2OF(000) = 872
Mr = 413.15Dx = 1.335 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 3245 reflections
a = 13.3333 (4) Åθ = 2.8–27.8°
b = 15.9424 (5) ŵ = 0.97 mm1
c = 9.9965 (3) ÅT = 296 K
β = 104.736 (1)°Block, red
V = 2055.01 (11) Å30.25 × 0.12 × 0.08 mm
Z = 4
Data collection top
Bruker SMART APEXII CCD area-detector
diffractometer
2557 independent reflections
Radiation source: fine-focus sealed tube2131 reflections with I > 2σ(I)
graphiteRint = 0.040
φ and ω scansθmax = 28.3°, θmin = 2.6°
Absorption correction: multi-scan
(SADABS; Bruker, 2005)
h = 1716
Tmin = 0.794, Tmax = 0.927k = 2121
17468 measured reflectionsl = 1313
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)] = 0.031Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.083H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0485P)2]
where P = (Fo2 + 2Fc2)/3
2557 reflections(Δ/σ)max < 0.001
125 parametersΔρmax = 0.21 e Å3
0 restraintsΔρmin = 0.31 e Å3
Crystal data top
[Ni(C21H24N2O2)]·H2OV = 2055.01 (11) Å3
Mr = 413.15Z = 4
Monoclinic, C2/cMo Kα radiation
a = 13.3333 (4) ŵ = 0.97 mm1
b = 15.9424 (5) ÅT = 296 K
c = 9.9965 (3) Å0.25 × 0.12 × 0.08 mm
β = 104.736 (1)°
Data collection top
Bruker SMART APEXII CCD area-detector
diffractometer
2557 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2005)
2131 reflections with I > 2σ(I)
Tmin = 0.794, Tmax = 0.927Rint = 0.040
17468 measured reflectionsθmax = 28.3°
Refinement top
R[F2 > 2σ(F2)] = 0.031H-atom parameters constrained
wR(F2) = 0.083Δρmax = 0.21 e Å3
S = 1.06Δρmin = 0.31 e Å3
2557 reflectionsAbsolute structure: ?
125 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Ni10.00000.489837 (15)0.25000.03589 (11)
O10.09186 (9)0.57316 (6)0.34800 (11)0.0457 (3)
N10.04523 (10)0.40475 (8)0.39178 (12)0.0414 (3)
C10.16634 (12)0.56212 (9)0.46203 (15)0.0401 (3)
C20.23779 (14)0.62692 (10)0.50786 (17)0.0497 (4)
H2A0.23460.67470.45370.060*
C30.31279 (14)0.62162 (12)0.63132 (18)0.0567 (5)
H3A0.35890.66600.65810.068*
C40.32147 (14)0.55163 (13)0.71719 (17)0.0550 (4)
C50.25490 (14)0.48675 (11)0.67168 (18)0.0487 (4)
H5A0.26040.43900.72650.058*
C60.17758 (13)0.48878 (9)0.54427 (17)0.0410 (3)
C70.40114 (17)0.54821 (18)0.85526 (19)0.0817 (7)
H7A0.45560.51010.84940.123*
H7B0.36870.52920.92520.123*
H7C0.42970.60310.87880.123*
C80.11388 (13)0.41566 (10)0.50691 (15)0.0431 (4)
H8A0.12300.37250.57140.052*
C90.01669 (14)0.32780 (10)0.36982 (16)0.0488 (4)
H9A0.08950.34260.35120.059*
H9B0.00060.29490.45420.059*
C100.00000.27358 (15)0.25000.0564 (7)
C110.0973 (2)0.21930 (15)0.2981 (2)0.1038 (9)
H11A0.15690.25480.32870.156*
H11B0.10570.18510.22260.156*
H11C0.09030.18400.37290.156*
O1W0.00000.72531 (12)0.25000.0992 (8)
H10.05560.68780.20070.149*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.03715 (18)0.03024 (16)0.03666 (16)0.0000.00274 (11)0.000
O10.0462 (7)0.0353 (6)0.0472 (6)0.0002 (5)0.0032 (5)0.0020 (5)
N10.0448 (8)0.0367 (7)0.0424 (7)0.0023 (6)0.0110 (6)0.0012 (5)
C10.0364 (8)0.0408 (8)0.0418 (8)0.0035 (6)0.0075 (6)0.0040 (6)
C20.0470 (10)0.0449 (9)0.0540 (9)0.0035 (7)0.0069 (8)0.0022 (7)
C30.0434 (10)0.0635 (12)0.0586 (10)0.0101 (8)0.0047 (8)0.0118 (9)
C40.0391 (10)0.0794 (13)0.0432 (9)0.0003 (9)0.0042 (7)0.0047 (9)
C50.0428 (10)0.0604 (11)0.0413 (8)0.0055 (8)0.0076 (7)0.0051 (7)
C60.0373 (9)0.0449 (9)0.0390 (8)0.0040 (7)0.0065 (7)0.0010 (6)
C70.0590 (14)0.121 (2)0.0537 (11)0.0122 (13)0.0074 (10)0.0005 (12)
C80.0472 (10)0.0411 (8)0.0408 (8)0.0029 (7)0.0109 (7)0.0055 (6)
C90.0603 (11)0.0394 (9)0.0494 (9)0.0103 (8)0.0189 (8)0.0006 (7)
C100.0806 (19)0.0355 (12)0.0563 (14)0.0000.0236 (14)0.000
C110.159 (3)0.0726 (15)0.0929 (16)0.0629 (16)0.0553 (17)0.0332 (13)
O1W0.1069 (18)0.0426 (11)0.1201 (18)0.0000.0225 (15)0.000
Geometric parameters (Å, °) top
Ni1—O11.901 (1)C5—H5A0.9300
Ni1—O1i1.9010 (10)C6—C81.435 (2)
Ni1—N1i1.9436 (12)C7—H7A0.9600
Ni1—N11.9436 (12)C7—H7B0.9600
O1—C11.3194 (17)C7—H7C0.9600
N1—C81.2870 (19)C8—H8A0.9300
N1—C91.4638 (19)C9—C101.539 (2)
C1—C21.401 (2)C9—H9A0.9700
C1—C61.415 (2)C9—H9B0.9700
C2—C31.379 (2)C10—C111.532 (2)
C2—H2A0.9300C10—C11i1.532 (2)
C3—C41.394 (3)C10—C9i1.539 (2)
C3—H3A0.9300C11—H11A0.9600
C4—C51.364 (3)C11—H11B0.9600
C4—C71.513 (2)C11—H11C0.9600
C5—C61.421 (2)O1W—H10.9818
O1—Ni1—O1i91.34 (6)C4—C7—H7A109.5
O1—Ni1—N1i154.58 (6)C4—C7—H7B109.5
O1i—Ni1—N1i94.14 (5)H7A—C7—H7B109.5
O1—Ni1—N194.14 (5)C4—C7—H7C109.5
O1i—Ni1—N1154.58 (6)H7A—C7—H7C109.5
N1i—Ni1—N191.48 (7)H7B—C7—H7C109.5
C1—O1—Ni1126.63 (9)N1—C8—C6125.58 (15)
C8—N1—C9119.54 (13)N1—C8—H8A117.2
C8—N1—Ni1125.16 (11)C6—C8—H8A117.2
C9—N1—Ni1114.64 (10)N1—C9—C10113.57 (13)
O1—C1—C2118.94 (14)N1—C9—H9A108.9
O1—C1—C6123.87 (14)C10—C9—H9A108.9
C2—C1—C6117.16 (15)N1—C9—H9B108.9
C3—C2—C1121.69 (16)C10—C9—H9B108.9
C3—C2—H2A119.2H9A—C9—H9B107.7
C1—C2—H2A119.2C11—C10—C11i111.2 (3)
C2—C3—C4121.84 (17)C11—C10—C9i106.43 (11)
C2—C3—H3A119.1C11i—C10—C9i110.61 (11)
C4—C3—H3A119.1C11—C10—C9110.61 (11)
C5—C4—C3117.16 (16)C11i—C10—C9106.43 (11)
C5—C4—C7121.55 (19)C9i—C10—C9111.63 (18)
C3—C4—C7121.28 (19)C10—C11—H11A109.5
C4—C5—C6122.98 (17)C10—C11—H11B109.5
C4—C5—H5A118.5H11A—C11—H11B109.5
C6—C5—H5A118.5C10—C11—H11C109.5
C1—C6—C5119.02 (15)H11A—C11—H11C109.5
C1—C6—C8123.49 (15)H11B—C11—H11C109.5
C5—C6—C8117.48 (14)
O1i—Ni1—O1—C1163.48 (15)C7—C4—C5—C6178.41 (17)
N1i—Ni1—O1—C193.95 (16)O1—C1—C6—C5174.24 (15)
N1—Ni1—O1—C18.32 (13)C2—C1—C6—C54.2 (2)
O1—Ni1—N1—C81.34 (13)O1—C1—C6—C85.0 (2)
O1i—Ni1—N1—C8100.61 (16)C2—C1—C6—C8176.58 (15)
N1i—Ni1—N1—C8156.53 (16)C4—C5—C6—C12.0 (3)
O1—Ni1—N1—C9171.99 (11)C4—C5—C6—C8178.70 (16)
O1i—Ni1—N1—C970.04 (15)C9—N1—C8—C6177.90 (15)
N1i—Ni1—N1—C932.82 (8)Ni1—N1—C8—C67.7 (2)
Ni1—O1—C1—C2169.47 (11)C1—C6—C8—N15.6 (3)
Ni1—O1—C1—C612.1 (2)C5—C6—C8—N1175.14 (16)
O1—C1—C2—C3175.28 (15)C8—N1—C9—C10117.17 (16)
C6—C1—C2—C33.2 (2)Ni1—N1—C9—C1071.61 (15)
C1—C2—C3—C40.1 (3)N1—C9—C10—C1182.3 (2)
C2—C3—C4—C52.4 (3)N1—C9—C10—C11i156.78 (16)
C2—C3—C4—C7177.33 (18)N1—C9—C10—C9i36.00 (9)
C3—C4—C5—C61.3 (3)
Symmetry codes: (i) −x, y, −z+1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1···O1ii0.981.922.781 (2)145
C3—H3A···O1Wiii0.932.553.477 (2)173
Symmetry codes: (ii) −x, y, −z+1/2; (iii) −x+1/2, −y+3/2, −z+1.
Table 1
Hydrogen-bond geometry (Å, °)
top
D—H···AD—HH···AD···AD—H···A
O1W—H1···O1i0.981.922.781 (2)145
C3—H3A···O1Wii0.932.553.477 (2)173
Symmetry codes: (i) −x, y, −z+1/2; (ii) −x+1/2, −y+3/2, −z+1.
Acknowledgements top

HK thanks PNU for financial support. MNT thanks GC University of Sargodha, Pakistan, for research facilities.

references
References top

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Fun, H.-K., Kia, R. & Kargar, H. (2008). Acta Cryst. E64, o1895–o1896.

Kargar, H., Fun, H.-K. & Kia, R. (2008). Acta Cryst. E64, m1541–m1542.

Kargar, H., Kia, R., Pahlavani, E. & Tahir, M. N. (2011). Acta Cryst. E67, o614.

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