Bis{4-bromo-2-[(2-hy­droxy­eth­yl)imino­meth­yl]phenolato}nickel(II) monohydrate

The title mononuclear nickel complex, [Ni(C₉H₉BrNO₂)₂]·H₂O, was obtained by the reaction of 5-bromo­salicyl­aldehyde, 2-amino­ethanol and nickel nitrate in methanol. The Ni^II atom is six-coordinated by two phenolate O, two imine N and two hy­droxy O atoms from two crystallographically different Schiff base ligands, forming an octa­hedral geometry. In the crystal, mol­ecules are linked by inter­molecular O—H...O and O—H...Br hydrogen bonds, forming a three-dimensional network.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.012 Å
• R factor = 0.048
• wR factor = 0.128
• Data-to-parameter ratio = 17.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT234_ALERT_4_C Large Hirshfeld Difference N2     --  C17     ..       0.16 Ang.
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C14
PLAT341_ALERT_3_C Low Bond Precision on  C-C Bonds ...............     0.0124 Ang
PLAT732_ALERT_1_C Angle   Calc      106(7), Rep      106(3) ......       2.33 su-Ra
              H5A  -O5   -H5B     1.555   1.555   1.555      #         24
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          1
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600          5

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.00
           From the CIF: _reflns_number_total               4474
           Count of symmetry unique reflns         2551
           Completeness (_total/calc)            175.38%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1923
           Fraction of Friedel pairs measured     0.754
           Are heavy atom types Z>Si present        yes
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          3
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          3

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

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 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
   1 ALERT type 5 Informative message, check

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S1. Comment

As part of our investigations into novel urease inhibitors (Wang & Ye, 2011; Wang, 2009), we have synthesized the title compound, a new mononuclear nickel(II) complex, Fig. 1. The compound contains a mononuclear nickel(II) complex molecule and a water molecule of crystallization. The Ni atom in the complex is six-coordinated by two phenolate O, two imine N, and two hydroxy O atoms from two Schiff base ligands, forming an octahedral geometry. The trans angles at the Ni atom are in the range 173.1 (3)–174.0 (2)°; the other angles are close to 90°, ranging from 80.4 (3) to 94.8 (2)°, indicating a slightly distorted octahedral coordination. The Ni—O and Ni—N bond lengths (Table 1) are typical and are comparable to those observed in other similar nickel(II) complexes (Arıcı et al., 2005; Liu et al., 2006; Li & Wang, 2007; Ali et al., 2006).

In the crystal structure of the compound, molecules are linked through intermolecular O—H···O and O—H···Br hydrogen bonds (Table 2), to form a three-dimensional network (Fig. 2).

Related literature

For urease inhibitors, see: Wang (2009); Wang & Ye (2011). For related nickel(II) complexes, see: Arıcı et al. (2005); Liu et al. (2006); Li & Wang (2007); Ali et al. (2006).

S2. Experimental

5-Bromosalicylaldehyde (1.0 mmol, 0.201 g), 2-aminoethanol (1.0 mmol, 0.061 g), and nickel nitrate hexahydrate (0.5 mmol, 0.146 g) were dissolved in MeOH (30 ml). The mixture was stirred at room temperature for 10 min to give a clear green solution. After keeping the solution in air for a week, green block-shaped crystals were formed at the bottom of the vessel.

S3. Refinement

The water H atoms were located in a difference Fourier map and refined isotropically, with O–H and H···H distances restrained to 0.85 (1) and 1.37 (2) Å, respectively. The remaining H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C–H distances in the range 0.93–0.97 Å, O—H distance of 0.93 Å, and with U_iso(H) set at 1.2U_eq(C and O).

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); 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 the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. The dashed line indicates a hydrogen bond.
	Fig. 2. The crystal packing of the title compound. Hydrogen bonds are shown as dashed lines.

Bis{4-bromo-2-[(2-hydroxyethyl)iminomethyl]phenolato}nickel(II) monohydrate

Crystal data

[Ni(C9H9BrNO2)2]·H2O	F(000) = 1120
Mr = 562.89	Dx = 1.823 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2063 reflections
a = 9.835 (3) Å	θ = 2.5–25.3°
b = 12.851 (2) Å	µ = 4.87 mm^−1
c = 16.226 (3) Å	T = 298 K
V = 2050.8 (8) Å^3	BlocK, green
Z = 4	0.21 × 0.20 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer	4474 independent reflections
Radiation source: fine-focus sealed tube	2310 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.099
ω scans	θmax = 27.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→12
Tmin = 0.428, Tmax = 0.442	k = −16→16
13318 measured reflections	l = −20→15

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.048	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.128	w = 1/[σ^2(Fo^2) + (0.0374P)^2 + 1.9512P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.001
4474 reflections	Δρmax = 0.60 e Å^−3
259 parameters	Δρmin = −0.95 e Å^−3
3 restraints	Absolute structure: Flack (1983), 1930 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.013 (19)

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
Br1	1.08191 (9)	−0.02277 (7)	0.25079 (7)	0.0550 (3)
Br2	0.5363 (2)	0.81053 (8)	0.47258 (10)	0.1150 (7)
Ni1	0.45998 (10)	0.24321 (8)	0.40117 (7)	0.0323 (3)
O1	0.6019 (5)	0.2555 (4)	0.3127 (4)	0.0425 (15)
O2	0.3198 (5)	0.2157 (4)	0.4990 (3)	0.0364 (16)
H2A	0.2280	0.2329	0.4989	0.044*
O3	0.5614 (6)	0.3443 (4)	0.4733 (4)	0.0366 (15)
O4	0.3367 (6)	0.1508 (4)	0.3188 (4)	0.0451 (17)
H4A	0.3131	0.0812	0.3251	0.054*
O5	0.5810 (10)	0.4431 (5)	0.2144 (5)	0.074 (2)
N1	0.5494 (7)	0.1225 (5)	0.4536 (4)	0.0307 (17)
N2	0.3496 (7)	0.3550 (5)	0.3502 (5)	0.0371 (19)
C1	0.7389 (8)	0.1086 (6)	0.3572 (5)	0.029 (2)
C2	0.7047 (8)	0.1925 (6)	0.3039 (5)	0.032 (2)
C3	0.7945 (8)	0.2085 (6)	0.2369 (6)	0.040 (2)
H3	0.7772	0.2640	0.2016	0.048*
C4	0.9041 (9)	0.1480 (7)	0.2209 (6)	0.042 (2)
H4	0.9582	0.1617	0.1752	0.051*
C5	0.9358 (9)	0.0658 (7)	0.2726 (6)	0.042 (2)
C6	0.8539 (8)	0.0483 (6)	0.3384 (6)	0.038 (2)
H6	0.8751	−0.0070	0.3732	0.046*
C7	0.6629 (8)	0.0814 (6)	0.4292 (5)	0.028 (2)
H7	0.6986	0.0286	0.4620	0.033*
C8	0.4827 (8)	0.0827 (6)	0.5276 (5)	0.040 (2)
H8A	0.5507	0.0620	0.5676	0.047*
H8B	0.4287	0.0220	0.5138	0.047*
C9	0.3914 (9)	0.1664 (7)	0.5646 (6)	0.045 (3)
H9A	0.3276	0.1353	0.6030	0.054*
H9B	0.4458	0.2171	0.5941	0.054*
C10	0.4558 (9)	0.5003 (6)	0.4176 (5)	0.041 (2)
C11	0.5478 (8)	0.4458 (6)	0.4704 (5)	0.033 (2)
C12	0.6275 (8)	0.5055 (6)	0.5233 (6)	0.045 (2)
H12	0.6845	0.4714	0.5602	0.055*
C13	0.6258 (10)	0.6126 (7)	0.5234 (6)	0.051 (3)
H13	0.6819	0.6502	0.5586	0.061*
C14	0.5408 (13)	0.6614 (7)	0.4712 (7)	0.060 (3)
C15	0.4569 (12)	0.6097 (7)	0.4200 (7)	0.062 (3)
H15	0.3987	0.6469	0.3857	0.075*
C16	0.3650 (8)	0.4525 (6)	0.3608 (6)	0.041 (2)
H16	0.3121	0.4964	0.3285	0.049*
C17	0.2488 (9)	0.3159 (7)	0.2904 (6)	0.051 (3)
H17A	0.2340	0.3675	0.2477	0.061*
H17B	0.1628	0.3033	0.3180	0.061*
C18	0.2992 (9)	0.2178 (6)	0.2530 (7)	0.051 (3)
H18A	0.2286	0.1858	0.2198	0.062*
H18B	0.3771	0.2316	0.2180	0.062*
H5A	0.584 (12)	0.395 (5)	0.178 (4)	0.080*
H5B	0.605 (11)	0.415 (6)	0.260 (3)	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0343 (4)	0.0641 (6)	0.0666 (7)	0.0118 (5)	0.0052 (6)	−0.0190 (6)
Br2	0.2030 (18)	0.0286 (5)	0.1133 (12)	0.0049 (9)	−0.0640 (13)	−0.0095 (7)
Ni1	0.0245 (5)	0.0278 (5)	0.0446 (7)	0.0024 (5)	0.0003 (5)	0.0031 (5)
O1	0.032 (3)	0.036 (3)	0.059 (4)	0.013 (3)	0.003 (3)	0.011 (3)
O2	0.026 (3)	0.038 (4)	0.045 (4)	0.015 (3)	−0.003 (3)	0.004 (3)
O3	0.030 (4)	0.032 (3)	0.048 (4)	0.001 (3)	−0.006 (3)	0.009 (3)
O4	0.051 (4)	0.035 (3)	0.050 (5)	−0.003 (3)	−0.012 (4)	0.001 (3)
O5	0.076 (5)	0.062 (4)	0.083 (6)	−0.010 (5)	0.002 (5)	0.017 (4)
N1	0.031 (4)	0.025 (3)	0.036 (5)	−0.005 (3)	0.008 (4)	0.000 (3)
N2	0.027 (4)	0.034 (4)	0.050 (5)	−0.005 (3)	−0.002 (4)	−0.005 (4)
C1	0.026 (5)	0.031 (5)	0.029 (6)	0.008 (4)	0.001 (4)	−0.012 (4)
C2	0.030 (5)	0.024 (4)	0.041 (6)	0.000 (4)	−0.006 (5)	−0.002 (4)
C3	0.043 (5)	0.034 (5)	0.044 (7)	−0.002 (4)	0.000 (5)	0.004 (5)
C4	0.029 (5)	0.060 (6)	0.037 (6)	−0.011 (5)	0.013 (4)	−0.006 (5)
C5	0.034 (5)	0.045 (5)	0.046 (7)	−0.007 (4)	0.001 (5)	−0.022 (5)
C6	0.027 (5)	0.033 (5)	0.055 (7)	0.006 (4)	0.007 (5)	−0.012 (5)
C7	0.026 (5)	0.019 (4)	0.038 (6)	0.007 (3)	−0.005 (4)	−0.006 (4)
C8	0.036 (5)	0.043 (5)	0.039 (6)	0.001 (4)	0.002 (5)	0.012 (5)
C9	0.031 (5)	0.058 (6)	0.045 (7)	0.013 (4)	0.007 (5)	−0.008 (5)
C10	0.043 (5)	0.034 (4)	0.048 (6)	0.004 (4)	−0.008 (5)	0.000 (4)
C11	0.027 (5)	0.035 (5)	0.036 (6)	−0.001 (4)	−0.008 (5)	0.001 (4)
C12	0.046 (6)	0.038 (5)	0.052 (7)	0.007 (4)	−0.009 (5)	−0.001 (5)
C13	0.057 (7)	0.037 (5)	0.059 (8)	−0.001 (5)	−0.009 (6)	−0.016 (5)
C14	0.080 (8)	0.031 (5)	0.067 (8)	−0.001 (6)	−0.008 (8)	0.001 (5)
C15	0.077 (7)	0.037 (5)	0.073 (8)	0.013 (6)	−0.018 (7)	−0.004 (5)
C16	0.036 (5)	0.029 (5)	0.057 (7)	0.004 (4)	−0.018 (5)	0.002 (5)
C17	0.040 (6)	0.040 (5)	0.072 (8)	0.012 (5)	−0.008 (5)	0.011 (5)
C18	0.048 (5)	0.053 (6)	0.053 (7)	−0.002 (4)	−0.020 (6)	0.000 (6)

Geometric parameters (Å, º)

Ni1—N1	1.976 (7)	C4—C5	1.385 (12)
Ni1—N2	1.981 (7)	C4—H4	0.93
Ni1—O1	2.008 (6)	C5—C6	1.356 (11)
Ni1—O3	2.014 (6)	C6—H6	0.93
Ni1—O2	2.132 (5)	C7—H7	0.93
Ni1—O4	2.160 (6)	C8—C9	1.523 (11)
Br1—C5	1.867 (9)	C8—H8A	0.97
Br2—C14	1.917 (8)	C8—H8B	0.97
O1—C2	1.303 (9)	C9—H9A	0.97
O2—C9	1.424 (10)	C9—H9B	0.97
O2—H2A	0.9298	C10—C15	1.407 (12)
O3—C11	1.312 (8)	C10—C16	1.423 (11)
O4—C18	1.420 (10)	C10—C11	1.430 (11)
O4—H4A	0.9298	C11—C12	1.392 (11)
O5—H5A	0.853 (10)	C12—C13	1.377 (11)
O5—H5B	0.854 (10)	C12—H12	0.93
N1—C7	1.297 (10)	C13—C14	1.346 (13)
N1—C8	1.461 (10)	C13—H13	0.93
N2—C16	1.274 (10)	C14—C15	1.346 (14)
N2—C17	1.476 (11)	C15—H15	0.93
C1—C6	1.405 (10)	C16—H16	0.93
C1—C2	1.422 (11)	C17—C18	1.485 (12)
C1—C7	1.431 (11)	C17—H17A	0.97
C2—C3	1.416 (12)	C17—H17B	0.97
C3—C4	1.354 (11)	C18—H18A	0.97
C3—H3	0.93	C18—H18B	0.97
N1—Ni1—N2	173.1 (3)	N1—C7—C1	126.8 (8)
N1—Ni1—O1	93.4 (2)	N1—C7—H7	116.6
N2—Ni1—O1	91.5 (3)	C1—C7—H7	116.6
N1—Ni1—O3	92.1 (2)	N1—C8—C9	110.0 (7)
N2—Ni1—O3	92.6 (2)	N1—C8—H8A	109.7
O1—Ni1—O3	91.2 (2)	C9—C8—H8A	109.7
N1—Ni1—O2	80.6 (2)	N1—C8—H8B	109.7
N2—Ni1—O2	94.4 (3)	C9—C8—H8B	109.7
O1—Ni1—O2	174.0 (2)	H8A—C8—H8B	108.2
O3—Ni1—O2	89.7 (2)	O2—C9—C8	108.1 (7)
N1—Ni1—O4	94.8 (2)	O2—C9—H9A	110.1
N2—Ni1—O4	80.4 (3)	C8—C9—H9A	110.1
O1—Ni1—O4	89.5 (2)	O2—C9—H9B	110.1
O3—Ni1—O4	173.0 (2)	C8—C9—H9B	110.1
O2—Ni1—O4	90.4 (2)	H9A—C9—H9B	108.4
C2—O1—Ni1	124.7 (5)	C15—C10—C16	117.0 (8)
C9—O2—Ni1	108.1 (5)	C15—C10—C11	117.9 (8)
C9—O2—H2A	126.0	C16—C10—C11	125.0 (7)
Ni1—O2—H2A	125.9	O3—C11—C12	117.9 (7)
C11—O3—Ni1	124.8 (5)	O3—C11—C10	125.0 (7)
C18—O4—Ni1	106.1 (5)	C12—C11—C10	117.1 (7)
C18—O4—H4A	126.9	C13—C12—C11	123.0 (8)
Ni1—O4—H4A	126.9	C13—C12—H12	118.5
H5A—O5—H5B	106 (3)	C11—C12—H12	118.5
C7—N1—C8	119.7 (7)	C14—C13—C12	118.2 (9)
C7—N1—Ni1	124.9 (6)	C14—C13—H13	120.9
C8—N1—Ni1	115.4 (5)	C12—C13—H13	120.9
C16—N2—C17	120.2 (8)	C13—C14—C15	122.6 (9)
C16—N2—Ni1	126.3 (6)	C13—C14—Br2	118.3 (8)
C17—N2—Ni1	113.3 (5)	C15—C14—Br2	119.1 (8)
C6—C1—C2	118.5 (8)	C14—C15—C10	121.0 (9)
C6—C1—C7	117.5 (8)	C14—C15—H15	119.5
C2—C1—C7	123.9 (7)	C10—C15—H15	119.5
O1—C2—C3	118.5 (7)	N2—C16—C10	125.9 (8)
O1—C2—C1	126.0 (8)	N2—C16—H16	117.0
C3—C2—C1	115.4 (7)	C10—C16—H16	117.0
C4—C3—C2	124.0 (8)	N2—C17—C18	109.5 (7)
C4—C3—H3	118.0	N2—C17—H17A	109.8
C2—C3—H3	118.0	C18—C17—H17A	109.8
C3—C4—C5	120.1 (9)	N2—C17—H17B	109.8
C3—C4—H4	119.9	C18—C17—H17B	109.8
C5—C4—H4	119.9	H17A—C17—H17B	108.2
C6—C5—C4	118.0 (8)	O4—C18—C17	107.1 (8)
C6—C5—Br1	120.3 (7)	O4—C18—H18A	110.3
C4—C5—Br1	121.6 (7)	C17—C18—H18A	110.3
C5—C6—C1	123.8 (9)	O4—C18—H18B	110.3
C5—C6—H6	118.1	C17—C18—H18B	110.3
C1—C6—H6	118.1	H18A—C18—H18B	108.6

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5B···O1	0.85 (1)	2.22 (7)	2.898 (8)	136 (8)
O5—H5A···Br2^i	0.85 (1)	2.92 (5)	3.666 (9)	146 (8)
O4—H4A···Br1^ii	0.93	2.90	3.532 (6)	126
O4—H4A···O5^i	0.93	2.16	2.841 (9)	130
O2—H2A···O3^iii	0.93	1.97	2.694 (7)	133

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