Azido­{2,4-dibromo-6-[(2-diethyl­amino­ethyl­imino)meth­yl]phenolato}nickel(II)

In the title mononuclear nickel(II) complex, [Ni(C₁₃H₁₇Br₂N₂O)(N₃)], the Ni^II atom is four-coordinated by the phenolate O, imine N and amine N atoms of one Schiff base ligand, and by the terminal N atom of an azide ligand, forming a square-planar geometry.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.036
• wR factor = 0.080
• Data-to-parameter ratio = 18.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.83
PLAT220_ALERT_2_C Large Non-Solvent    N     Ueq(max)/Ueq(min) ...       2.51 Ratio
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         N4
PLAT431_ALERT_2_C Short Inter HL..A Contact  Br2    ..  Br2     ..       3.50 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      0.829
            Tmax scaled      0.344 Tmin scaled      0.318
PLAT794_ALERT_5_G Check Predicted Bond Valency for Ni1         (3)       2.67

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 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

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S1. Comment

Nickel(II) complexes with Schiff base ligands have received much attention in recent years (Marganian et al., 1995). Some of the complexes have been found to have pharmacological and antitumor properties (Harrop et al., 2003; Brückner et al., 2000; Ren et al., 2002). Nickel is also present in the active sites of several important classes of metalloproteins, as either a homodinuclear or a heterodinuclear species. We have recently reported a few transition metal complexes (Diao, Huang et al., 2007; Diao, Shu et al., 2007; Diao, 2007a,b). In order to further develop the coordination chemistry of such nickel complexes, we report herein the title new nickel(II) compound.

The Ni^II atom in the mononuclear complex is four-coordinate in a square-planar geometry with one phenolate O, one imine N, and one amine N atoms of one Schiff base ligand and one terminal N atom of an azide ligand (Fig. 1). All the bond values (Table 1) subtended at the metal centres are comparable with the values observed in other Schiff base nickel(II) complexes (Arıcı et al., 2005; Usman et al., 2003; Van Hecke et al., 2007; Li et al., 2007).

Related literature

For related literature, see: Arıcı et al. (2005); Brückner et al. (2000); Diao (2007a); Diao (2007b); Diao, Huang et al. (2007); Diao, Shu et al. (2007); Harrop et al. (2003); Li et al. (2007); Marganian et al. (1995); Ren et al. (2002); Usman et al. (2003); Van Hecke et al. (2007).

S2. Experimental

3,5-Dibromosalicylaldehyde (0.1 mmol, 18.0 mg), N,N-diethylethane-1,2-diamine (0.1 mmol, 11.6 mg), sodium azide (0.1 mmol, 6.5 mg), and Ni(NO₃)₂·6H₂O (0.1 mmol, 29.0 mg) were dissolved in a methanol solution (10 ml). The mixture was stirred at room temperature for 30 min to give a red solution. After keeping the solution in air for a week, red block-like crystals were formed.

S3. Refinement

H atoms were placed in calculated positions and constrained to ride on their parent atoms, with C—H distances in the range 0.93–0.97 Å, and with U_iso(H) = 1.2U_eq(C) and 1.5U_eq(methyl C).

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. The structure of the complex with 30% probability level.

Azido{2,4-dibromo-6-[(2-diethylaminoethylimino)methyl]phenolato}nickel(II)

Crystal data

[Ni(C13H17Br2N2O)(N3)]	F(000) = 944
Mr = 477.85	Dx = 1.892 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2309 reflections
a = 16.565 (2) Å	θ = 2.3–25.0°
b = 9.9972 (14) Å	µ = 5.93 mm^−1
c = 10.1889 (15) Å	T = 298 K
β = 96.122 (2)°	Block, red
V = 1677.7 (4) Å^3	0.20 × 0.20 × 0.18 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	3640 independent reflections
Radiation source: fine-focus sealed tube	2428 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
ω scans	θmax = 27.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −21→18
Tmin = 0.384, Tmax = 0.415	k = −12→11
9529 measured reflections	l = −12→13

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.080	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0338P)^2 + 0.1742P] where P = (Fo^2 + 2Fc^2)/3
3640 reflections	(Δ/σ)max < 0.001
201 parameters	Δρmax = 0.42 e Å^−3
0 restraints	Δρmin = −0.58 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Ni1	0.28675 (2)	0.75958 (4)	0.36809 (4)	0.03799 (13)
Br1	0.16019 (3)	1.18409 (4)	0.39701 (5)	0.07939 (18)
Br2	0.00998 (3)	0.98626 (5)	0.83122 (5)	0.07886 (18)
O1	0.21837 (14)	0.9014 (2)	0.3894 (2)	0.0455 (6)
N1	0.23011 (15)	0.6439 (2)	0.4665 (3)	0.0381 (6)
N2	0.35931 (16)	0.6084 (3)	0.3421 (3)	0.0399 (7)
N3	0.34772 (18)	0.8696 (3)	0.2634 (3)	0.0557 (8)
N4	0.35300 (19)	0.9880 (4)	0.2758 (3)	0.0563 (8)
N5	0.3610 (3)	1.1018 (4)	0.2802 (4)	0.0957 (14)
C1	0.14857 (18)	0.8076 (3)	0.5639 (3)	0.0399 (8)
C2	0.16979 (19)	0.9133 (3)	0.4813 (4)	0.0405 (8)
C3	0.1356 (2)	1.0402 (3)	0.5052 (4)	0.0497 (9)
C4	0.0879 (2)	1.0608 (4)	0.6041 (4)	0.0579 (11)
H4	0.0666	1.1453	0.6168	0.069*
C5	0.0711 (2)	0.9553 (4)	0.6862 (4)	0.0523 (10)
C6	0.09968 (19)	0.8300 (4)	0.6656 (4)	0.0503 (9)
H6	0.0867	0.7595	0.7191	0.060*
C7	0.17848 (19)	0.6753 (3)	0.5458 (3)	0.0414 (8)
H7	0.1588	0.6070	0.5956	0.050*
C8	0.2532 (2)	0.5030 (3)	0.4539 (4)	0.0462 (9)
H8A	0.2226	0.4629	0.3774	0.055*
H8B	0.2424	0.4532	0.5318	0.055*
C9	0.3422 (2)	0.5013 (3)	0.4386 (3)	0.0451 (9)
H9A	0.3576	0.4146	0.4066	0.054*
H9B	0.3734	0.5176	0.5232	0.054*
C10	0.3358 (2)	0.5630 (4)	0.2019 (3)	0.0550 (10)
H10A	0.3403	0.6391	0.1440	0.066*
H10B	0.2791	0.5368	0.1938	0.066*
C11	0.3845 (3)	0.4478 (4)	0.1518 (4)	0.0873 (15)
H11A	0.4404	0.4738	0.1534	0.131*
H11B	0.3633	0.4258	0.0631	0.131*
H11C	0.3806	0.3711	0.2076	0.131*
C12	0.4480 (2)	0.6429 (4)	0.3606 (4)	0.0496 (9)
H12A	0.4613	0.6943	0.2851	0.060*
H12B	0.4794	0.5609	0.3634	0.060*
C13	0.4724 (2)	0.7220 (4)	0.4846 (4)	0.0592 (10)
H13A	0.4438	0.8056	0.4805	0.089*
H13B	0.5298	0.7386	0.4922	0.089*
H13C	0.4592	0.6720	0.5599	0.089*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0401 (2)	0.0350 (2)	0.0390 (3)	0.00371 (19)	0.00473 (18)	0.00248 (19)
Br1	0.0849 (3)	0.0361 (2)	0.1165 (4)	0.0036 (2)	0.0078 (3)	0.0110 (2)
Br2	0.0598 (3)	0.0985 (4)	0.0808 (4)	0.0171 (2)	0.0193 (2)	−0.0281 (3)
O1	0.0483 (14)	0.0345 (13)	0.0547 (16)	0.0054 (11)	0.0106 (12)	0.0059 (11)
N1	0.0334 (15)	0.0309 (14)	0.0496 (18)	0.0028 (12)	0.0029 (13)	−0.0026 (12)
N2	0.0448 (16)	0.0419 (16)	0.0328 (16)	0.0100 (13)	0.0034 (13)	0.0017 (12)
N3	0.067 (2)	0.0494 (19)	0.054 (2)	0.0063 (16)	0.0203 (16)	0.0124 (16)
N4	0.065 (2)	0.060 (2)	0.046 (2)	−0.0041 (18)	0.0141 (16)	0.0124 (17)
N5	0.139 (4)	0.061 (3)	0.094 (3)	−0.028 (3)	0.046 (3)	−0.002 (2)
C1	0.0310 (17)	0.0342 (18)	0.054 (2)	0.0009 (14)	0.0048 (16)	−0.0036 (16)
C2	0.0321 (18)	0.0346 (18)	0.053 (2)	−0.0019 (15)	−0.0038 (16)	−0.0042 (16)
C3	0.043 (2)	0.0356 (19)	0.069 (3)	0.0013 (16)	−0.0037 (19)	−0.0038 (17)
C4	0.041 (2)	0.048 (2)	0.082 (3)	0.0095 (18)	−0.006 (2)	−0.021 (2)
C5	0.037 (2)	0.062 (3)	0.058 (3)	0.0040 (18)	0.0061 (18)	−0.020 (2)
C6	0.0351 (19)	0.055 (2)	0.061 (3)	0.0003 (17)	0.0072 (18)	−0.0085 (19)
C7	0.0365 (19)	0.0366 (18)	0.051 (2)	−0.0031 (15)	0.0051 (16)	0.0022 (16)
C8	0.049 (2)	0.0317 (17)	0.059 (2)	0.0020 (15)	0.0076 (18)	−0.0005 (16)
C9	0.053 (2)	0.0368 (18)	0.045 (2)	0.0096 (16)	0.0068 (18)	0.0044 (16)
C10	0.070 (2)	0.057 (2)	0.038 (2)	0.016 (2)	0.0014 (19)	−0.0036 (18)
C11	0.131 (4)	0.074 (3)	0.056 (3)	0.043 (3)	0.006 (3)	−0.015 (2)
C12	0.043 (2)	0.055 (2)	0.053 (2)	0.0078 (17)	0.0120 (18)	0.0106 (19)
C13	0.048 (2)	0.064 (3)	0.064 (3)	−0.0058 (19)	0.0007 (19)	0.009 (2)

Geometric parameters (Å, º)

Ni1—O1	1.842 (2)	C5—C6	1.364 (5)
Ni1—N1	1.850 (3)	C6—H6	0.9300
Ni1—N3	1.897 (3)	C7—H7	0.9300
Ni1—N2	1.967 (3)	C8—C9	1.499 (5)
Br1—C3	1.883 (4)	C8—H8A	0.9700
Br2—C5	1.903 (4)	C8—H8B	0.9700
O1—C2	1.303 (4)	C9—H9A	0.9700
N1—C7	1.277 (4)	C9—H9B	0.9700
N1—C8	1.469 (4)	C10—C11	1.525 (5)
N2—C9	1.501 (4)	C10—H10A	0.9700
N2—C12	1.502 (4)	C10—H10B	0.9700
N2—C10	1.511 (4)	C11—H11A	0.9600
N3—N4	1.193 (4)	C11—H11B	0.9600
N4—N5	1.146 (4)	C11—H11C	0.9600
C1—C6	1.400 (5)	C12—C13	1.508 (5)
C1—C2	1.418 (5)	C12—H12A	0.9700
C1—C7	1.431 (4)	C12—H12B	0.9700
C2—C3	1.420 (4)	C13—H13A	0.9600
C3—C4	1.361 (5)	C13—H13B	0.9600
C4—C5	1.393 (5)	C13—H13C	0.9600
C4—H4	0.9300
O1—Ni1—N1	93.63 (11)	C1—C7—H7	117.5
O1—Ni1—N3	89.50 (12)	N1—C8—C9	106.8 (3)
N1—Ni1—N3	176.74 (13)	N1—C8—H8A	110.4
O1—Ni1—N2	179.04 (11)	C9—C8—H8A	110.4
N1—Ni1—N2	86.85 (11)	N1—C8—H8B	110.4
N3—Ni1—N2	90.00 (12)	C9—C8—H8B	110.4
C2—O1—Ni1	126.1 (2)	H8A—C8—H8B	108.6
C7—N1—C8	119.3 (3)	C8—C9—N2	108.4 (3)
C7—N1—Ni1	127.0 (2)	C8—C9—H9A	110.0
C8—N1—Ni1	113.6 (2)	N2—C9—H9A	110.0
C9—N2—C12	109.4 (2)	C8—C9—H9B	110.0
C9—N2—C10	111.0 (3)	N2—C9—H9B	110.0
C12—N2—C10	109.8 (3)	H9A—C9—H9B	108.4
C9—N2—Ni1	107.42 (19)	N2—C10—C11	116.8 (3)
C12—N2—Ni1	114.2 (2)	N2—C10—H10A	108.1
C10—N2—Ni1	104.97 (19)	C11—C10—H10A	108.1
N4—N3—Ni1	123.6 (3)	N2—C10—H10B	108.1
N5—N4—N3	175.2 (4)	C11—C10—H10B	108.1
C6—C1—C2	121.3 (3)	H10A—C10—H10B	107.3
C6—C1—C7	118.6 (3)	C10—C11—H11A	109.5
C2—C1—C7	120.1 (3)	C10—C11—H11B	109.5
O1—C2—C1	124.7 (3)	H11A—C11—H11B	109.5
O1—C2—C3	119.5 (3)	C10—C11—H11C	109.5
C1—C2—C3	115.8 (3)	H11A—C11—H11C	109.5
C4—C3—C2	122.4 (3)	H11B—C11—H11C	109.5
C4—C3—Br1	119.7 (3)	N2—C12—C13	113.4 (3)
C2—C3—Br1	117.8 (3)	N2—C12—H12A	108.9
C3—C4—C5	120.0 (3)	C13—C12—H12A	108.9
C3—C4—H4	120.0	N2—C12—H12B	108.9
C5—C4—H4	120.0	C13—C12—H12B	108.9
C6—C5—C4	120.5 (4)	H12A—C12—H12B	107.7
C6—C5—Br2	119.4 (3)	C12—C13—H13A	109.5
C4—C5—Br2	120.0 (3)	C12—C13—H13B	109.5
C5—C6—C1	119.9 (4)	H13A—C13—H13B	109.5
C5—C6—H6	120.0	C12—C13—H13C	109.5
C1—C6—H6	120.0	H13A—C13—H13C	109.5
N1—C7—C1	124.9 (3)	H13B—C13—H13C	109.5
N1—C7—H7	117.5