Diaqua­bis{2,4-dibromo-6-[2-(isopropyl­ammonio)ethyl­imino­methyl]­phenol­ato}­nickel(II) dichloride hemihydrate

The title complex, [Ni(C₁₂H₁₆Br₂N₂O₂)₂(H₂O)₂]Cl₂·0.5H₂O, consists of a centrosymmetric mononuclear nickel(II) complex cation, two symmetry-related chloride anions and a half-occupancy water mol­ecule. The Ni atom, lying on an inversion centre, is six-coordinated by two phenol O atoms, two imine N atoms from two Schiff base ligands, and the O atoms from two water mol­ecules, forming an octa­hedral geometry. Adjacent mol­ecules are linked through inter­molecular hydrogen bonds, forming chains running along the b axis.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.009 Å
• Disorder in solvent or counterion
• R factor = 0.050
• wR factor = 0.126
• Data-to-parameter ratio = 15.7

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT432_ALERT_2_B Short Inter X...Y Contact  Br2    ..  C4      ..       3.24 Ang.

Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       0.50 Ratio
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.78
PLAT164_ALERT_4_C Nr. of Refined C-H H-Atoms in Heavy-At Struct...          1
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.80 Ratio
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C10
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................      13.00 Perc.
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          9
PLAT360_ALERT_2_C Short  C(sp3)-C(sp3) Bond  C8     -   C9     ...       1.43 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      0.782
            Tmax scaled      0.290 Tmin scaled      0.258
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          6

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

   5 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
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Nickel(II) complexes play an important role in both bioinorganic chemistry and coordination chemistry (Suh et al., 1996; Angulo et al., 2001; Dey et al., 2004; Edison et al., 2004; Ramadevi et al., 2005). Recently, the author has reported a mononuclear nickel(II) complex derived from the Schiff base ligand 2-bromo-4-chloro-6-[2-(diethylamino)ethyliminomethyl]phenol (Tang, 2006). As a further study of the structures of such complexes, the title mononuclear nickel(II) complex, derived from the Schiff base ligand 2,4-dibromo-6-[(2-isopropylaminoethylimino)methyl]phenol, is reported in this paper.

The title complex consists of a centrosymmetric mononuclear nickel(II) complex cation, two symmetry-related chloride anions, and half water molecule (Fig. 1). The Ni atom, lying on the inversion centre, is six-coordinated by two phenolic oxygen atoms, two imine N atoms from two Schiff base ligands, and by two oxygen atoms from two water molecules, forming an octahedral geometry. The coordinative bond lengths and angles are within normal ranges and comparable with the corresponding values observed in other similar nickel(II) complexes (Zhu et al., 2004; Liu et al., 2006; Zhang, 2006; Diao, 2007; Diao et al., 2007).

In the crystal structure, ajacent molecules are linked through intermolecular N—H···O, N–H···Cl, N—H···Br and O–H···Cl hydrogen bonds, forming chains running along the b axis, as shown in Fig. 2.

Related literature

For related literature, see: Angulo et al. (2001); Dey et al. (2004); Diao (2007); Diao et al. (2007); Edison et al. (2004); Liu et al. (2006); Ramadevi et al. (2005); Suh et al. (1996); Tang (2006); Zhang (2006); Zhu et al. (2004).

S2. Experimental

3,5-Dibromo-2-hydroxybenzaldehyde (0.2 mmol, 56.0 mg) and N-isopropyl-1,2-diaminoethane (0.2 mmol, 20.4 mg) were dissolved in methanol (10 ml). To the mixture was added an aqueous solution (1 ml) of nickel(II) chloride hexahydrate (0.1 mmol, 23.8 mg). The final mixture was stirred at room temperature for 30 min, resulting in a green solution. The solution was allowed to stand still in air for a week, yielding green block-shaped crystals of the complex.

S3. Refinement

H3A, H3B, H2C and H2D were located from a difference Fourier map and refined isotropically, with O—H distances restrained to 0.85 (1) Å, and H···H distance restrained to 1.37 (2) Å. Other H atoms were constrained to ideal geometries, with C—H = 0.93–0.98 Å, N—H = 0.90 Å, and with U_iso(H) set to 1.2U_eq(C,N) and 1.5U_eq(methyl C). The lattice water molecule is disordered, with occupancy of 0.25.

Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997b).

Figures

	Fig. 1. The structure of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Unlabelled atoms are at the symmetry position 1 - x, 2 - y, 1 - z.
	Fig. 2. Packing diagram of the title compound viewed along the b axis. Hydrogen atoms not involved in hydrogen bonding interactions (dashed lines) are omitted for clarity.

Diaquabis{2,4-dibromo-6-[2- (isopropylammonio)ethyliminomethyl]phenolato}nickel(II) dichloride hemihydrate

Crystal data

[Ni(C12H16Br2N2O2)2(H2O)2]Cl2·0.5H2O	F(000) = 894
Mr = 902.83	Dx = 2.000 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1836 reflections
a = 12.685 (3) Å	θ = 2.4–24.9°
b = 7.0450 (14) Å	µ = 6.20 mm^−1
c = 17.501 (4) Å	T = 293 K
β = 106.57 (3)°	Block, green
V = 1499.0 (6) Å^3	0.23 × 0.22 × 0.20 mm
Z = 2

Data collection

Bruker SMART CCD area-detector diffractometer	3094 independent reflections
Radiation source: fine-focus sealed tube	1968 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.073
ω scans	θmax = 26.5°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −15→15
Tmin = 0.330, Tmax = 0.370	k = −8→8
11682 measured reflections	l = −21→21

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.126	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0625P)^2] where P = (Fo^2 + 2Fc^2)/3
3094 reflections	(Δ/σ)max < 0.001
197 parameters	Δρmax = 0.70 e Å^−3
6 restraints	Δρmin = −0.76 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	Occ. (<1)
Ni1	0.5000	1.0000	0.5000	0.0260 (3)
Br1	0.12695 (6)	0.84155 (9)	0.49949 (4)	0.0434 (2)
Br2	0.05294 (7)	0.59011 (13)	0.18878 (5)	0.0616 (3)
Cl1	0.48050 (17)	0.4909 (2)	0.63566 (10)	0.0487 (5)
O1	0.3353 (3)	0.9775 (5)	0.4683 (2)	0.0301 (10)
O2	0.4839 (4)	1.2618 (5)	0.4926 (3)	0.0423 (12)
N1	0.4928 (4)	0.9890 (6)	0.3815 (3)	0.0273 (11)
N2	0.6982 (4)	0.8048 (6)	0.4195 (3)	0.0345 (13)
H2A	0.6499	0.7117	0.4200	0.041*
H2B	0.6982	0.8856	0.4593	0.041*
C1	0.3097 (5)	0.8639 (7)	0.3374 (3)	0.0269 (14)
C2	0.2780 (5)	0.8899 (8)	0.4081 (4)	0.0286 (14)
C3	0.1762 (5)	0.8157 (8)	0.4078 (4)	0.0320 (15)
C4	0.1117 (5)	0.7276 (8)	0.3449 (4)	0.0345 (15)
H4	0.0440	0.6804	0.3467	0.041*
C5	0.1440 (5)	0.7056 (8)	0.2772 (4)	0.0356 (15)
C6	0.2421 (5)	0.7774 (9)	0.2732 (4)	0.0322 (15)
H6	0.264 (5)	0.741 (9)	0.232 (4)	0.040 (19)*
C7	0.4103 (5)	0.9311 (8)	0.3266 (4)	0.0317 (15)
H7	0.4162	0.9326	0.2748	0.038*
C8	0.5861 (5)	1.0499 (8)	0.3532 (4)	0.0313 (15)
H8A	0.5569	1.1118	0.3020	0.038*
H8B	0.6274	1.1444	0.3901	0.038*
C9	0.6611 (5)	0.9057 (9)	0.3444 (4)	0.0361 (16)
H9A	0.7232	0.9623	0.3310	0.043*
H9B	0.6247	0.8189	0.3021	0.043*
C10	0.8093 (6)	0.7205 (9)	0.4351 (4)	0.0416 (17)
H10	0.8615	0.8233	0.4353	0.050*
C11	0.8067 (7)	0.5971 (10)	0.3689 (5)	0.066 (2)
H11A	0.7412	0.5212	0.3568	0.099*
H11B	0.8701	0.5159	0.3826	0.099*
H11C	0.8071	0.6722	0.3232	0.099*
C12	0.8337 (7)	0.6441 (11)	0.5172 (5)	0.076 (3)
H12A	0.7781	0.5540	0.5198	0.114*
H12B	0.8346	0.7462	0.5537	0.114*
H12C	0.9042	0.5828	0.5313	0.114*
H2C	0.496 (8)	1.325 (10)	0.455 (3)	0.114*
H2D	0.503 (8)	1.327 (10)	0.535 (3)	0.114*
O3	0.728 (2)	0.810 (3)	0.1714 (8)	0.146 (14)	0.25
H3A	0.7048	0.7449	0.1289	0.219*	0.25
H3B	0.7013	0.7704	0.2079	0.219*	0.25

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0331 (7)	0.0166 (5)	0.0314 (6)	−0.0026 (5)	0.0141 (5)	−0.0012 (4)
Br1	0.0462 (5)	0.0374 (4)	0.0562 (5)	−0.0086 (3)	0.0300 (4)	−0.0085 (3)
Br2	0.0564 (6)	0.0652 (6)	0.0616 (5)	−0.0223 (4)	0.0140 (4)	−0.0286 (4)
Cl1	0.0817 (14)	0.0268 (8)	0.0444 (10)	−0.0077 (9)	0.0289 (10)	−0.0023 (7)
O1	0.033 (3)	0.025 (2)	0.035 (2)	−0.0034 (18)	0.014 (2)	−0.0050 (19)
O2	0.073 (3)	0.015 (2)	0.047 (3)	−0.004 (2)	0.028 (3)	0.003 (2)
N1	0.034 (3)	0.014 (2)	0.038 (3)	0.001 (2)	0.016 (3)	−0.001 (2)
N2	0.041 (3)	0.020 (3)	0.047 (3)	−0.001 (2)	0.019 (3)	−0.008 (2)
C1	0.035 (4)	0.015 (3)	0.030 (3)	−0.002 (2)	0.007 (3)	0.000 (2)
C2	0.032 (4)	0.018 (3)	0.039 (4)	0.001 (3)	0.015 (3)	0.003 (3)
C3	0.035 (4)	0.021 (3)	0.043 (4)	0.002 (3)	0.017 (3)	0.000 (3)
C4	0.031 (4)	0.025 (3)	0.049 (4)	−0.004 (3)	0.014 (3)	0.000 (3)
C5	0.035 (4)	0.024 (3)	0.048 (4)	−0.004 (3)	0.012 (3)	−0.008 (3)
C6	0.040 (4)	0.026 (3)	0.033 (4)	0.001 (3)	0.014 (3)	0.001 (3)
C7	0.043 (4)	0.021 (3)	0.033 (4)	−0.001 (3)	0.014 (3)	0.001 (3)
C8	0.041 (4)	0.018 (3)	0.041 (4)	−0.001 (3)	0.022 (3)	0.002 (3)
C9	0.048 (4)	0.031 (3)	0.036 (4)	−0.004 (3)	0.022 (3)	−0.001 (3)
C10	0.037 (4)	0.025 (3)	0.062 (5)	0.000 (3)	0.013 (4)	−0.003 (3)
C11	0.068 (6)	0.037 (4)	0.099 (7)	0.005 (4)	0.034 (5)	−0.022 (4)
C12	0.080 (7)	0.042 (5)	0.098 (7)	0.028 (4)	0.012 (6)	0.014 (5)
O3	0.19 (4)	0.15 (3)	0.07 (2)	0.00 (3)	−0.02 (2)	0.00 (2)

Geometric parameters (Å, º)

Ni1—O2^i	1.856 (4)	C4—C5	1.368 (8)
Ni1—O2	1.856 (4)	C4—H4	0.9300
Ni1—O1^i	2.009 (4)	C5—C6	1.363 (8)
Ni1—O1	2.009 (4)	C6—H6	0.88 (6)
Ni1—N1^i	2.052 (5)	C7—H7	0.9300
Ni1—N1	2.052 (5)	C8—C9	1.430 (8)
Br1—C3	1.890 (6)	C8—H8A	0.9700
Br2—C5	1.836 (6)	C8—H8B	0.9700
O1—C2	1.258 (7)	C9—H9A	0.9700
O2—H2C	0.84 (7)	C9—H9B	0.9700
O2—H2D	0.85 (6)	C10—C11	1.442 (9)
N1—C7	1.269 (7)	C10—C12	1.482 (10)
N1—C8	1.471 (7)	C10—H10	0.9800
N2—C9	1.449 (8)	C11—H11A	0.9600
N2—C10	1.481 (8)	C11—H11B	0.9600
N2—H2A	0.9000	C11—H11C	0.9600
N2—H2B	0.9000	C12—H12A	0.9600
C1—C6	1.348 (8)	C12—H12B	0.9600
C1—C2	1.419 (8)	C12—H12C	0.9600
C1—C7	1.423 (8)	O3—H3A	0.8524
C2—C3	1.392 (8)	O3—H3B	0.8518
C3—C4	1.323 (8)
O2^i—Ni1—O2	180.000 (1)	C6—C5—C4	120.3 (6)
O2^i—Ni1—O1^i	88.52 (19)	C6—C5—Br2	119.1 (5)
O2—Ni1—O1^i	91.48 (19)	C4—C5—Br2	120.5 (5)
O2^i—Ni1—O1	91.48 (19)	C1—C6—C5	119.9 (6)
O2—Ni1—O1	88.52 (19)	C1—C6—H6	123 (4)
O1^i—Ni1—O1	180.00 (7)	C5—C6—H6	116 (4)
O2^i—Ni1—N1^i	89.71 (18)	N1—C7—C1	125.7 (6)
O2—Ni1—N1^i	90.29 (18)	N1—C7—H7	117.1
O1^i—Ni1—N1^i	88.57 (18)	C1—C7—H7	117.1
O1—Ni1—N1^i	91.43 (18)	C9—C8—N1	116.9 (5)
O2^i—Ni1—N1	90.29 (18)	C9—C8—H8A	108.1
O2—Ni1—N1	89.71 (18)	N1—C8—H8A	108.1
O1^i—Ni1—N1	91.43 (18)	C9—C8—H8B	108.1
O1—Ni1—N1	88.57 (18)	N1—C8—H8B	108.1
N1^i—Ni1—N1	180.000 (1)	H8A—C8—H8B	107.3
C2—O1—Ni1	125.2 (4)	C8—C9—N2	107.8 (5)
Ni1—O2—H2C	123 (6)	C8—C9—H9A	110.2
Ni1—O2—H2D	119 (6)	N2—C9—H9A	110.2
H2C—O2—H2D	109 (7)	C8—C9—H9B	110.2
C7—N1—C8	114.1 (5)	N2—C9—H9B	110.2
C7—N1—Ni1	124.5 (4)	H9A—C9—H9B	108.5
C8—N1—Ni1	121.4 (4)	C11—C10—N2	106.9 (6)
C9—N2—C10	114.2 (5)	C11—C10—C12	120.7 (6)
C9—N2—H2A	108.7	N2—C10—C12	104.4 (6)
C10—N2—H2A	108.7	C11—C10—H10	108.1
C9—N2—H2B	108.7	N2—C10—H10	108.1
C10—N2—H2B	108.7	C12—C10—H10	108.1
H2A—N2—H2B	107.6	C10—C11—H11A	109.5
C6—C1—C2	120.9 (6)	C10—C11—H11B	109.5
C6—C1—C7	114.9 (5)	H11A—C11—H11B	109.5
C2—C1—C7	124.1 (5)	C10—C11—H11C	109.5
O1—C2—C3	120.1 (5)	H11A—C11—H11C	109.5
O1—C2—C1	123.7 (5)	H11B—C11—H11C	109.5
C3—C2—C1	116.2 (6)	C10—C12—H12A	109.5
C4—C3—C2	122.2 (6)	C10—C12—H12B	109.5
C4—C3—Br1	118.4 (5)	H12A—C12—H12B	109.5
C2—C3—Br1	119.4 (5)	C10—C12—H12C	109.5
C3—C4—C5	120.4 (6)	H12A—C12—H12C	109.5
C3—C4—H4	119.8	H12B—C12—H12C	109.5
C5—C4—H4	119.8	H3A—O3—H3B	111.5

Symmetry code: (i) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···Cl1^ii	0.90	2.19	3.027 (5)	154
N2—H2A···O2^i	0.90	2.60	3.155 (7)	121
N2—H2B···O1^i	0.90	1.74	2.620 (6)	166
N2—H2B···Br1^i	0.90	2.87	3.368 (5)	117
O2—H2C···Cl1^i	0.84 (7)	2.14 (6)	2.977 (4)	174 (9)
O2—H2D···Cl1^iii	0.85 (6)	2.19 (4)	2.989 (5)	157 (9)
O3—H3A···O1^iv	0.85	2.49	3.316 (13)	163

Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x+1, −y+1, −z+1; (iii) x, y+1, z; (iv) −x+1, y−1/2, −z+1/2.