Bis{2-[imino­(phen­yl)meth­yl]-5-meth­oxy­phenolato-κ²N,O¹}nickel(II)

The title complex, [Ni(C₁₄H₁₂NO₂)₂], lies about an inversion center. The Ni^II atom is coordinated in a slightly distorted square-planar geometry by two O atoms and two N atoms from two 2-[imino­(phen­yl)meth­yl]-5-meth­oxy­phenolate ligands. The dihedral angle between the symmetry-unique phenyl and benzene rings is 73.2 (1)°.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.025
• wR factor = 0.064
• Data-to-parameter ratio = 12.5

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Ni1    --  O1      ..        5.3 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Ni1    --  N1      ..        5.7 su
PLAT420_ALERT_2_C D-H Without Acceptor       N1     -   H1A    ...          ?
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.595         12

Alert level G
PLAT003_ALERT_2_G Number of Uiso or Uij Restrained Atom Sites ....          3
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?
PLAT007_ALERT_5_G Note: Number of Unrefined D-H Atoms ............          1
PLAT128_ALERT_4_G Alternate Setting of Space-group P21/c   .......      P21/n
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          2
PLAT909_ALERT_3_G Percentage of Observed Data at Theta(Max) still          67 Perc.

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   4 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   6 ALERT level G = General information/check it is not something unexpected

   0 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
   2 ALERT type 5 Informative message, check

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S1. Comment

2-Imino(methyl)phenol compounds have been studied for many years (Jiang et al., 2003; Zhang et al., 2008, 2009; Bernés 2010; Liu et al., 2009) and have attracted interest because of their magnetic properties. The crystal structure of the title compound (I) is presented herein.

The molecular structure of (I) is shown in Fig .1. The Ni^II ion lies on a centre of inversion and is coordinated by two O atoms and two N atoms from two bidentate ligands, forming a slightly distorted square-planar geometry. The dihedral angle between the symmetry unique phenyl and benzene rings is 73.2 (1) °.

Related literature

For background to 2-imino(methyl)phenol compounds, see: Zhang et al. (2008, 2009); Jiang et al. (2003); Liu et al. (2009). For a related structure, see: Bernès (2010).

S2. Experimental

Complex (I) was prepared from a mixture of 2-hydroxy-4-methoxy benzophenone (1 mmol, 0.228 g), ammonia (25%, 0.5 ml), triethylamine (0.5 ml), nickel(II) acetate tetrahydrate (0.5 mmol, 0.127 g) and methanol(8 mL) sealed in a 15 mL teflon-lined stainless steel bomb, and kept at 393 K for 120 h under autogenous pressure. After the reaction was slowly cooled to room temperature, green rectangular plates were produced (yield: 63%, based on Nickel). Anal. Calcd for C₂₈H₂₄N₂NiO₄(%): C, 65.78; H, 4.73; N, 5.48. Found(%): C, 65.72; H, 4.76; N, 5.53.

S3. Refinement

H atoms were positioned geometrically and refined with a riding model, with distances 0.86(N—H), 0.96(CH₃) or 0.93 Å (aromatic ring), and with U_iso(H) = 1.2 U_eq(aromatic ring, N—H) or U_iso(H) = 1.5 U_eq(CH₃).

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

Fig. 1. The molecular structure of (I), showing 30 % probability displacement ellipsoids. H atoms bonded to atoms are not shown. Symmetry code (a); 1-x, -y, 2-z.

Bis{2-[imino(phenyl)methyl]-5-methoxyphenolato- κ²N,O¹}nickel(II)

Crystal data

[Ni(C14H12NO2)2]	F(000) = 532
Mr = 511.20	Dx = 1.486 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2010 reflections
a = 11.882 (2) Å	θ = 2.0–25.0°
b = 5.4983 (10) Å	µ = 0.89 mm^−1
c = 17.494 (3) Å	T = 296 K
β = 91.913 (2)°	Plate, green
V = 1142.3 (4) Å^3	0.24 × 0.15 × 0.10 mm
Z = 2

Data collection

Bruker SMART CCD diffractometer	2010 independent reflections
Radiation source: fine-focus sealed tube	1680 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
ϕ and ω scans	θmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −14→11
Tmin = 0.244, Tmax = 0.453	k = −6→6
5526 measured reflections	l = −20→20

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.064	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0308P)^2 + 0.224P] where P = (Fo^2 + 2Fc^2)/3
2010 reflections	(Δ/σ)max < 0.001
161 parameters	Δρmax = 0.19 e Å^−3
2 restraints	Δρmin = −0.15 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.47072 (17)	0.1107 (4)	0.71936 (11)	0.0451 (5)
H1	0.5182	−0.0211	0.7290	0.054*
C2	0.41390 (18)	0.1315 (4)	0.64899 (11)	0.0538 (5)
H2	0.4237	0.0140	0.6116	0.065*
C3	0.34319 (17)	0.3250 (4)	0.63443 (11)	0.0514 (5)
H3	0.3044	0.3374	0.5875	0.062*
C4	0.33005 (16)	0.4994 (4)	0.68923 (12)	0.0495 (5)
H4	0.2828	0.6311	0.6792	0.059*
C5	0.38659 (15)	0.4814 (3)	0.75956 (11)	0.0428 (5)
H5	0.3773	0.6012	0.7963	0.051*
C6	0.45685 (14)	0.2859 (3)	0.77523 (9)	0.0338 (4)
C7	0.50867 (14)	0.2546 (3)	0.85404 (9)	0.0346 (4)
C8	0.59499 (14)	0.4187 (3)	0.88197 (9)	0.0336 (4)
C9	0.63412 (15)	0.4204 (3)	0.96059 (10)	0.0359 (4)
C10	0.71438 (15)	0.5983 (4)	0.98239 (10)	0.0410 (4)
H10	0.7376	0.6093	1.0336	0.049*
C11	0.75958 (15)	0.7561 (4)	0.93082 (11)	0.0411 (4)
C12	0.72465 (16)	0.7507 (4)	0.85333 (10)	0.0428 (5)
H12	0.7555	0.8556	0.8180	0.051*
C13	0.64357 (15)	0.5853 (4)	0.83168 (10)	0.0389 (4)
H13	0.6191	0.5830	0.7806	0.047*
C14	0.88453 (18)	1.0924 (4)	0.91151 (13)	0.0564 (6)
H14A	0.9237	1.0160	0.8708	0.085*
H14B	0.9358	1.1940	0.9406	0.085*
H14C	0.8241	1.1898	0.8904	0.085*
Ni1	0.5000	0.0000	1.0000	0.03463 (12)
N1	0.47005 (13)	0.0801 (3)	0.89494 (8)	0.0404 (4)
H1A	0.4234	−0.0153	0.8712	0.048*
O2	0.84011 (12)	0.9107 (3)	0.96004 (8)	0.0573 (4)
O1	0.60041 (10)	0.2698 (2)	1.01257 (7)	0.0437 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0554 (12)	0.0395 (11)	0.0399 (10)	0.0065 (10)	−0.0067 (9)	0.0015 (9)
C2	0.0702 (14)	0.0538 (14)	0.0369 (11)	−0.0003 (12)	−0.0086 (10)	−0.0047 (10)
C3	0.0531 (12)	0.0599 (14)	0.0401 (11)	−0.0120 (11)	−0.0150 (9)	0.0128 (10)
C4	0.0407 (11)	0.0483 (12)	0.0587 (13)	0.0024 (10)	−0.0116 (9)	0.0105 (11)
C5	0.0416 (10)	0.0390 (11)	0.0475 (11)	0.0029 (9)	−0.0031 (8)	−0.0009 (9)
C6	0.0330 (9)	0.0353 (10)	0.0329 (9)	−0.0041 (8)	−0.0017 (7)	0.0061 (8)
C7	0.0343 (9)	0.0371 (10)	0.0322 (9)	0.0030 (8)	0.0011 (7)	−0.0004 (8)
C8	0.0350 (10)	0.0356 (9)	0.0301 (9)	0.0030 (8)	−0.0002 (7)	0.0006 (7)
C9	0.0369 (10)	0.0369 (10)	0.0339 (9)	0.0031 (8)	0.0009 (8)	0.0010 (8)
C10	0.0449 (11)	0.0458 (11)	0.0320 (9)	−0.0028 (9)	−0.0037 (8)	−0.0015 (9)
C11	0.0365 (10)	0.0430 (11)	0.0439 (10)	−0.0048 (9)	0.0016 (8)	−0.0052 (9)
C12	0.0426 (10)	0.0463 (12)	0.0397 (10)	−0.0081 (9)	0.0045 (8)	0.0035 (9)
C13	0.0400 (10)	0.0433 (11)	0.0334 (10)	0.0005 (9)	0.0001 (8)	0.0030 (8)
C14	0.0523 (13)	0.0493 (12)	0.0680 (14)	−0.0138 (11)	0.0090 (11)	−0.0067 (11)
Ni1	0.0386 (2)	0.0381 (2)	0.02698 (17)	−0.00429 (15)	−0.00215 (12)	0.00705 (14)
N1	0.0476 (9)	0.0416 (9)	0.0316 (7)	−0.0113 (7)	−0.0048 (7)	0.0054 (7)
O2	0.0616 (9)	0.0619 (9)	0.0483 (8)	−0.0262 (8)	−0.0007 (7)	−0.0050 (7)
O1	0.0501 (8)	0.0482 (8)	0.0323 (6)	−0.0107 (6)	−0.0051 (5)	0.0080 (6)

Geometric parameters (Å, º)

C1—C6	1.387 (3)	C9—C10	1.410 (3)
C1—C2	1.389 (3)	C10—C11	1.374 (3)
C1—H1	0.9300	C10—H10	0.9300
C2—C3	1.374 (3)	C11—O2	1.366 (2)
C2—H2	0.9300	C11—C12	1.405 (3)
C3—C4	1.369 (3)	C12—C13	1.369 (3)
C3—H3	0.9300	C12—H12	0.9300
C4—C5	1.385 (3)	C13—H13	0.9300
C4—H4	0.9300	C14—O2	1.424 (3)
C5—C6	1.383 (2)	C14—H14A	0.9600
C5—H5	0.9300	C14—H14B	0.9600
C6—C7	1.501 (2)	C14—H14C	0.9600
C7—N1	1.290 (2)	Ni1—N1	1.9118 (14)
C7—C8	1.439 (2)	Ni1—N1^i	1.9118 (14)
C8—C13	1.407 (3)	Ni1—O1	1.9120 (13)
C8—C9	1.437 (2)	Ni1—O1^i	1.9120 (13)
C9—O1	1.303 (2)	N1—H1A	0.8600
C6—C1—C2	120.12 (19)	C11—C10—H10	118.8
C6—C1—H1	119.9	C9—C10—H10	118.8
C2—C1—H1	119.9	O2—C11—C10	115.56 (16)
C3—C2—C1	120.3 (2)	O2—C11—C12	123.72 (17)
C3—C2—H2	119.9	C10—C11—C12	120.71 (17)
C1—C2—H2	119.9	C13—C12—C11	117.63 (17)
C4—C3—C2	119.73 (18)	C13—C12—H12	121.2
C4—C3—H3	120.1	C11—C12—H12	121.2
C2—C3—H3	120.1	C12—C13—C8	123.98 (16)
C3—C4—C5	120.59 (19)	C12—C13—H13	118.0
C3—C4—H4	119.7	C8—C13—H13	118.0
C5—C4—H4	119.7	O2—C14—H14A	109.5
C6—C5—C4	120.21 (18)	O2—C14—H14B	109.5
C6—C5—H5	119.9	H14A—C14—H14B	109.5
C4—C5—H5	119.9	O2—C14—H14C	109.5
C5—C6—C1	119.06 (16)	H14A—C14—H14C	109.5
C5—C6—C7	119.85 (16)	H14B—C14—H14C	109.5
C1—C6—C7	120.87 (16)	N1—Ni1—N1^i	180.00 (2)
N1—C7—C8	122.72 (15)	N1—Ni1—O1	91.56 (6)
N1—C7—C6	116.88 (15)	N1^i—Ni1—O1	88.44 (6)
C8—C7—C6	120.39 (15)	N1—Ni1—O1^i	88.44 (6)
C13—C8—C9	117.89 (16)	N1^i—Ni1—O1^i	91.56 (6)
C13—C8—C7	119.90 (15)	O1—Ni1—O1^i	180.0
C9—C8—C7	122.21 (16)	C7—N1—Ni1	130.26 (13)
O1—C9—C10	118.23 (15)	C7—N1—H1A	114.9
O1—C9—C8	124.53 (16)	Ni1—N1—H1A	114.9
C10—C9—C8	117.24 (16)	C11—O2—C14	118.83 (16)
C11—C10—C9	122.44 (17)	C9—O1—Ni1	128.17 (11)

Symmetry code: (i) −x+1, −y, −z+2.