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Acta Cryst. (2007). E63, m1715-m1716    [ doi:10.1107/S1600536807024518 ]

Triaqua(5-formyl-N-salicylidene-DL-alaninato-[kappa]3N,O,O')nickel(II) monohydrate

J.-H. Cai, J.-M. Li and S. W. Ng

Abstract top

The deprotonated Schiff-base dianion in the title compound, [Ni(C11H9NO4)(H2O)3]·H2O, occupies the meridional sites of the NiO5N octahedron. The neutral complex molecule interacts with the uncoordinated water molecule by way of O-H...O hydrogen bonds to give rise to a three-dimensional network. The ethylidene part of the molecule is disordered over two positions in a 0.74:0.26 ratio.

Comment top

The salicylidene-glycine carboxylic acid when doubly deprotonated generally chelates to metal centers through its N,O,O' atoms. The planar ligand chelates to nickel in this manner in, for example, the tripyridinenickel complex for which it occupies the meridional sites (Cui et al., 1992). The 3-methoxy analog also affords a six-coordinate tripyridine complex, but it also contains ethanol as the solvate molecule (Cui et al., 1993). The N-(5-bromosalicylidene)tryptophanate complex is a triaqua complex that crystallizes with two uncoordinated water molecules (Rodríguez et al., 1990).

This chelating feature is also found in the title compound, (I), (Table 1) which has a formyl group as substituent in the aromatic ring. The formyl substitutent in involved in hydrogen bonding interactions with the water molecules to give rise to a three-dimenional network architecture (Table 2).

Related literature top

For the structures of other salicylidene-glycine-nickel complexes, see Cui et al. (1992, 1993); Rodríguez et al. (1990).

Experimental top

5-Formylsalicylaldehyde (0.2 mmol, 0.27 g), D,L-alanine (0.2 mmol, 0.18 g) and potassium hydroxide (0.2 mmol, 0.11 g) were dissolved in 80% aqueous methanol (15 ml). The mixture was stirred for 1 h to give a clear yellow solution. To the solution was added an aqueous solution (15 ml) of nickel(II) acetate hexahydrate (0.2 mmol, 0.57 g). The mixture heated at 323 K for 3 h. Green crystals of (I) were obtained in about 50% yield.

Refinement top

The ethylidene part of the molecule is disordered over two positions; the disorder refined to a 0.737 (11):0.263 (11) ratio. Pairs of equivalent carbon-carbon distances were restrained to within 0.01 Å of each other, and the disordered atoms were restrained to vibrate in a nearly isotropic manner.

The carbon-bound H atoms were placed in calculated positions (C—H 0.93 Å), and were included in the refinement in the riding model approximation, with Uiso(H) = 1.2Ueq(C).

The water H-atoms were located in a difference Fourier map, and were refined with a distance restraint of O–H = 0.85±0.01 Å; Uiso was freely varied for each H atom.

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2006).

Figures top
[Figure 1] Fig. 1. View of (I) as a displacement ellipsoid plot (50% probability). Hydrogen atoms are drawn as spheres of arbitrary radii; the minor disorder component is not shown.
Triaqua(5-formyl-N-salicylidene-D,L-alaninato-κ3N,\ O,O')nickel(II) monohydrate top
Crystal data top
[Ni(C11H9NO4)(H2O)3].H2OZ = 2
Mr = 349.97F(000) = 364
Triclinic, P1Dx = 1.647 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.861 (2) ÅCell parameters from 2418 reflections
b = 8.664 (2) Åθ = 2.3–27.1°
c = 12.363 (3) ŵ = 1.41 mm−1
α = 82.967 (3)°T = 295 K
β = 80.639 (3)°Block, green
γ = 77.706 (3)°0.20 × 0.10 × 0.05 mm
V = 705.5 (3) Å3
Data collection top
Bruker SMART CCD
diffractometer		2966 independent reflections
Radiation source: fine-focus sealed tube2635 reflections with I > 2σ(I)
graphiteRint = 0.020
φ and ω scansθmax = 27.1°, θmin = 1.7°
Absorption correction: multi-scan
SADABS (Sheldrick, 1996)		h = −5→8
Tmin = 0.870, Tmax = 0.933k = −9→11
4072 measured reflectionsl = −14→15
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)] = 0.036Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.099H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.059P)2 + 0.1949P]
where P = (Fo2 + 2Fc2)/3
2966 reflections(Δ/σ)max = 0.001
241 parametersΔρmax = 0.55 e Å−3
35 restraintsΔρmin = −0.43 e Å−3
Crystal data top
[Ni(C11H9NO4)(H2O)3].H2Oγ = 77.706 (3)°
Mr = 349.97V = 705.5 (3) Å3
Triclinic, P1Z = 2
a = 6.861 (2) ÅMo Kα radiation
b = 8.664 (2) ŵ = 1.41 mm−1
c = 12.363 (3) ÅT = 295 K
α = 82.967 (3)°0.20 × 0.10 × 0.05 mm
β = 80.639 (3)°
Data collection top
Bruker SMART CCD
diffractometer		2966 independent reflections
Absorption correction: multi-scan
SADABS (Sheldrick, 1996)		2635 reflections with I > 2σ(I)
Tmin = 0.870, Tmax = 0.933Rint = 0.020
4072 measured reflectionsθmax = 27.1°
Refinement top
R[F2 > 2σ(F2)] = 0.036H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.099Δρmax = 0.55 e Å−3
S = 1.04Δρmin = −0.43 e Å−3
2966 reflectionsAbsolute structure: ?
241 parametersFlack parameter: ?
35 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Ni10.62546 (4)0.75271 (3)0.39426 (2)0.02769 (12)
O10.7525 (3)0.52716 (18)0.44937 (13)0.0347 (4)
O20.9267 (3)0.3003 (2)0.39286 (16)0.0463 (5)
O30.5195 (3)0.96942 (18)0.32259 (13)0.0315 (4)
O40.6313 (4)1.3584 (2)−0.14612 (15)0.0495 (5)
O1W0.3722 (3)0.6685 (2)0.36805 (15)0.0396 (4)
O2W0.4613 (3)0.8013 (2)0.54397 (15)0.0382 (4)
O3W0.8478 (3)0.8416 (2)0.44387 (17)0.0445 (5)
O4W1.0881 (3)0.0138 (2)0.31021 (19)0.0474 (5)
N10.7874 (3)0.6852 (2)0.25235 (17)0.0356 (5)
C10.8554 (4)0.4445 (3)0.3764 (2)0.0355 (5)
C20.9180 (6)0.5251 (4)0.2619 (3)0.0302 (10)0.737 (11)
H21.05980.53420.25350.036*0.737 (11)
C30.8859 (14)0.4276 (7)0.1736 (6)0.065 (2)0.737 (11)
H3A0.92250.31670.19670.097*0.737 (11)
H3B0.96840.45200.10580.097*0.737 (11)
H3C0.74680.45290.16300.097*0.737 (11)
C2'0.817 (2)0.5062 (9)0.2564 (6)0.045 (4)0.263 (11)
H2'0.68950.48030.24570.054*0.263 (11)
C3'0.980 (2)0.430 (2)0.1702 (14)0.049 (4)0.263 (11)
H3'10.95420.47860.09850.073*0.263 (11)
H3'20.98050.31900.17440.073*0.263 (11)
H3'31.10850.44560.18310.073*0.263 (11)
C40.8019 (4)0.7699 (3)0.1609 (2)0.0361 (5)
H40.88340.72220.10150.043*
C50.7030 (3)0.9339 (3)0.14088 (18)0.0284 (5)
C60.7401 (4)1.0054 (3)0.03400 (19)0.0320 (5)
H60.82490.9459−0.01900.038*
C70.6553 (4)1.1611 (3)0.00411 (19)0.0326 (5)
C80.5282 (4)1.2502 (3)0.0832 (2)0.0372 (5)
H80.47121.35550.06430.045*
C90.4865 (4)1.1843 (3)0.1885 (2)0.0375 (6)
H90.40051.24580.24000.045*
C100.5710 (3)1.0242 (3)0.22144 (18)0.0279 (4)
C110.6961 (4)1.2240 (3)−0.1101 (2)0.0386 (6)
H110.77791.1560−0.15900.046*
H1W10.336 (5)0.601 (3)0.418 (2)0.058 (10)*
H1W20.369 (6)0.640 (4)0.3058 (16)0.066 (11)*
H2W10.473 (6)0.875 (3)0.580 (3)0.065 (11)*
H2W20.3354 (18)0.810 (4)0.548 (3)0.069 (12)*
H3W10.933 (4)0.787 (3)0.482 (2)0.046 (9)*
H3W20.930 (4)0.886 (4)0.399 (2)0.061 (11)*
H4W11.048 (5)0.1082 (18)0.326 (3)0.052 (9)*
H4W21.207 (3)−0.009 (4)0.325 (3)0.071 (12)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.03501 (19)0.02257 (17)0.02212 (17)−0.00216 (12)−0.00137 (12)0.00139 (11)
O10.0449 (10)0.0265 (8)0.0270 (8)−0.0007 (7)0.0002 (7)0.0024 (6)
O20.0660 (13)0.0256 (8)0.0379 (10)0.0062 (8)−0.0041 (9)0.0025 (7)
O30.0409 (9)0.0247 (7)0.0234 (8)−0.0008 (7)0.0009 (7)0.0012 (6)
O40.0741 (14)0.0393 (10)0.0324 (10)−0.0108 (9)−0.0107 (9)0.0109 (8)
O1W0.0515 (11)0.0420 (10)0.0285 (9)−0.0172 (8)−0.0077 (8)0.0020 (8)
O2W0.0443 (11)0.0399 (10)0.0305 (9)−0.0111 (8)0.0032 (8)−0.0105 (7)
O3W0.0438 (11)0.0461 (11)0.0454 (11)−0.0136 (9)−0.0159 (9)0.0105 (9)
O4W0.0417 (11)0.0376 (10)0.0598 (13)−0.0030 (9)−0.0008 (10)−0.0093 (9)
N10.0460 (12)0.0244 (9)0.0283 (10)0.0029 (8)0.0019 (9)0.0024 (7)
C10.0442 (14)0.0258 (11)0.0322 (13)−0.0020 (10)−0.0042 (10)0.0034 (9)
C20.0248 (19)0.0265 (16)0.0328 (18)0.0014 (13)0.0023 (14)0.0028 (12)
C30.112 (6)0.033 (2)0.042 (3)0.013 (3)−0.020 (4)−0.0076 (19)
C2'0.049 (7)0.036 (5)0.038 (5)0.004 (5)0.011 (5)0.004 (4)
C3'0.057 (7)0.037 (6)0.036 (6)0.007 (6)0.007 (6)0.010 (4)
C40.0437 (14)0.0333 (12)0.0236 (11)0.0018 (10)0.0034 (10)−0.0006 (9)
C50.0312 (11)0.0268 (10)0.0257 (11)−0.0058 (9)−0.0038 (9)0.0032 (8)
C60.0356 (12)0.0342 (12)0.0249 (11)−0.0065 (10)−0.0016 (9)−0.0012 (9)
C70.0414 (13)0.0326 (12)0.0241 (11)−0.0100 (10)−0.0075 (10)0.0047 (9)
C80.0507 (15)0.0253 (11)0.0326 (13)−0.0046 (10)−0.0068 (11)0.0051 (9)
C90.0520 (15)0.0263 (11)0.0288 (12)−0.0002 (10)−0.0018 (11)−0.0005 (9)
C100.0313 (11)0.0268 (10)0.0248 (11)−0.0050 (9)−0.0052 (9)0.0008 (8)
C110.0500 (15)0.0383 (13)0.0281 (12)−0.0132 (11)−0.0068 (10)0.0045 (10)
Geometric parameters (Å, °) top
Ni1—N11.999 (2)C2—C31.528 (6)
Ni1—O32.0149 (16)C2—H20.9800
Ni1—O2W2.0450 (19)C3—H3A0.9600
Ni1—O12.0455 (16)C3—H3B0.9600
Ni1—O3W2.053 (2)C3—H3C0.9600
Ni1—O1W2.1063 (19)C2'—C3'1.512 (9)
C1—O11.250 (3)C2'—H2'0.9800
C1—O21.245 (3)C3'—H3'10.9600
O3—C101.302 (3)C3'—H3'20.9600
O4—C111.212 (3)C3'—H3'30.9600
O1W—H1W10.845 (10)C4—C51.449 (3)
O1W—H1W20.842 (10)C4—H40.9300
O2W—H2W10.845 (10)C5—C61.397 (3)
O2W—H2W20.845 (10)C5—C101.421 (3)
O3W—H3W10.840 (10)C6—C71.382 (3)
O3W—H3W20.847 (10)C6—H60.9300
O4W—H4W10.841 (10)C7—C81.390 (4)
O4W—H4W20.844 (10)C7—C111.454 (3)
N1—C41.272 (3)C8—C91.368 (3)
N1—C21.485 (4)C8—H80.9300
N1—C2'1.516 (8)C9—C101.422 (3)
C1—C21.538 (4)C9—H90.9300
C1—C2'1.558 (8)C11—H110.9300
N1—Ni1—O391.55 (7)C1—C2—H2110.1
N1—Ni1—O2W175.02 (7)C2—C3—H3A109.5
O3—Ni1—O2W93.10 (7)C2—C3—H3B109.5
N1—Ni1—O181.70 (7)H3A—C3—H3B109.5
O3—Ni1—O1173.25 (6)C2—C3—H3C109.5
O2W—Ni1—O193.65 (7)H3A—C3—H3C109.5
N1—Ni1—O3W95.22 (9)H3B—C3—H3C109.5
O3—Ni1—O3W89.33 (8)C3'—C2'—N1114.9 (11)
O2W—Ni1—O3W86.63 (8)C3'—C2'—C1113.1 (11)
O1—Ni1—O3W91.04 (8)N1—C2'—C1105.0 (6)
N1—Ni1—O1W93.73 (9)C3'—C2'—H2'107.8
O3—Ni1—O1W91.45 (7)N1—C2'—H2'107.8
O2W—Ni1—O1W84.37 (8)C1—C2'—H2'107.8
O1—Ni1—O1W89.24 (7)C2'—C3'—H3'1109.5
O3W—Ni1—O1W170.99 (8)C2'—C3'—H3'2109.5
C1—O1—Ni1114.98 (14)H3'1—C3'—H3'2109.5
C10—O3—Ni1126.69 (14)C2'—C3'—H3'3109.5
Ni1—O1W—H1W1114 (2)H3'1—C3'—H3'3109.5
Ni1—O1W—H1W2119 (3)H3'2—C3'—H3'3109.5
H1W1—O1W—H1W2110 (3)N1—C4—C5125.9 (2)
Ni1—O2W—H2W1124 (3)N1—C4—H4117.0
Ni1—O2W—H2W2116 (3)C5—C4—H4117.0
H2W1—O2W—H2W2104 (4)C6—C5—C10118.8 (2)
Ni1—O3W—H3W1123 (2)C6—C5—C4116.7 (2)
Ni1—O3W—H3W2122 (2)C10—C5—C4124.6 (2)
H3W1—O3W—H3W296 (3)C7—C6—C5122.4 (2)
H4W1—O4W—H4W2103 (3)C7—C6—H6118.8
C4—N1—C2118.8 (2)C5—C6—H6118.8
C4—N1—C2'121.0 (3)C6—C7—C8118.9 (2)
C2—N1—C2'29.3 (5)C6—C7—C11118.7 (2)
C4—N1—Ni1126.63 (17)C8—C7—C11122.3 (2)
C2—N1—Ni1114.18 (17)C9—C8—C7120.5 (2)
C2'—N1—Ni1107.9 (4)C9—C8—H8119.8
O2—C1—O1123.8 (2)C7—C8—H8119.8
O2—C1—C2116.6 (2)C8—C9—C10121.8 (2)
O1—C1—C2119.3 (2)C8—C9—H9119.1
O2—C1—C2'116.3 (3)C10—C9—H9119.1
O1—C1—C2'115.2 (4)O3—C10—C5124.49 (19)
C2—C1—C2'28.4 (5)O3—C10—C9117.9 (2)
N1—C2—C3109.6 (4)C5—C10—C9117.6 (2)
N1—C2—C1107.6 (2)O4—C11—C7124.9 (3)
C3—C2—C1109.3 (4)O4—C11—H11117.6
N1—C2—H2110.1C7—C11—H11117.6
C3—C2—H2110.1
N1—Ni1—O1—C1−5.22 (18)C4—N1—C2'—C3'37.6 (17)
O2W—Ni1—O1—C1172.96 (19)C2—N1—C2'—C3'−57.0 (15)
O3W—Ni1—O1—C1−100.35 (19)Ni1—N1—C2'—C3'−164.6 (12)
O1W—Ni1—O1—C188.66 (19)C4—N1—C2'—C1162.6 (5)
N1—Ni1—O3—C10−4.48 (19)C2—N1—C2'—C168.0 (8)
O2W—Ni1—O3—C10177.31 (19)Ni1—N1—C2'—C1−39.7 (9)
O3W—Ni1—O3—C1090.72 (19)O2—C1—C2'—C3'−38.8 (16)
O1W—Ni1—O3—C10−98.26 (19)O1—C1—C2'—C3'164.5 (11)
O3—Ni1—N1—C42.1 (2)C2—C1—C2'—C3'58.9 (15)
O1—Ni1—N1—C4−177.6 (3)O2—C1—C2'—N1−164.9 (5)
O3W—Ni1—N1—C4−87.3 (2)O1—C1—C2'—N138.4 (10)
O1W—Ni1—N1—C493.7 (2)C2—C1—C2'—N1−67.1 (8)
O3—Ni1—N1—C2175.2 (2)C2—N1—C4—C5−172.8 (3)
O1—Ni1—N1—C2−4.6 (2)C2'—N1—C4—C5153.3 (7)
O3W—Ni1—N1—C285.7 (2)Ni1—N1—C4—C50.0 (4)
O1W—Ni1—N1—C2−93.3 (2)N1—C4—C5—C6179.8 (3)
O3—Ni1—N1—C2'−154.0 (6)N1—C4—C5—C10−1.1 (4)
O1—Ni1—N1—C2'26.2 (6)C10—C5—C6—C70.9 (4)
O3W—Ni1—N1—C2'116.5 (6)C4—C5—C6—C7−179.9 (2)
O1W—Ni1—N1—C2'−62.5 (6)C5—C6—C7—C8−0.1 (4)
Ni1—O1—C1—O2−172.5 (2)C5—C6—C7—C11−177.7 (2)
Ni1—O1—C1—C214.0 (3)C6—C7—C8—C9−0.6 (4)
Ni1—O1—C1—C2'−17.7 (7)C11—C7—C8—C9176.9 (2)
C4—N1—C2—C3−56.1 (6)C7—C8—C9—C100.4 (4)
C2'—N1—C2—C346.6 (8)Ni1—O3—C10—C54.8 (3)
Ni1—N1—C2—C3130.3 (4)Ni1—O3—C10—C9−176.50 (17)
C4—N1—C2—C1−174.9 (3)C6—C5—C10—O3177.6 (2)
C2'—N1—C2—C1−72.2 (6)C4—C5—C10—O3−1.5 (4)
Ni1—N1—C2—C111.5 (4)C6—C5—C10—C9−1.1 (3)
O2—C1—C2—N1169.1 (3)C4—C5—C10—C9179.8 (2)
O1—C1—C2—N1−16.9 (4)C8—C9—C10—O3−178.3 (2)
C2'—C1—C2—N172.4 (6)C8—C9—C10—C50.5 (4)
O2—C1—C2—C350.2 (5)C6—C7—C11—O4−179.7 (3)
O1—C1—C2—C3−135.9 (4)C8—C7—C11—O42.8 (4)
C2'—C1—C2—C3−46.5 (8)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1w—H1w1···O1i0.85 (1)1.95 (1)2.784 (2)170 (3)
O1w—H1w2···O4ii0.84 (1)1.97 (2)2.786 (3)162 (4)
O2w—H2w1···O3iii0.85 (1)1.93 (1)2.769 (2)173 (4)
O2w—H2w2···O2i0.85 (1)2.19 (2)2.937 (3)147 (3)
O3w—H3w1···O2iv0.84 (1)1.95 (1)2.753 (3)161 (3)
O3w—H3w2···O4wv0.85 (1)1.85 (1)2.689 (3)171 (4)
O4w—H4w1···O20.84 (1)1.92 (1)2.741 (3)166 (3)
O4w—H4w2···O3vi0.84 (1)2.11 (2)2.929 (3)165 (4)
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+2, −z; (iii) −x+1, −y+2, −z+1; (iv) −x+2, −y+1, −z+1; (v) x, y+1, z; (vi) x+1, y−1, z.
Table 1
Selected geometric parameters (Å) top
Ni1—N11.999 (2)Ni1—O12.0455 (16)
Ni1—O32.0149 (16)Ni1—O3W2.053 (2)
Ni1—O2W2.0450 (19)Ni1—O1W2.1063 (19)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1w—H1w1···O1i0.85 (1)1.95 (1)2.784 (2)170 (3)
O1w—H1w2···O4ii0.84 (1)1.97 (2)2.786 (3)162 (4)
O2w—H2w1···O3iii0.85 (1)1.93 (1)2.769 (2)173 (4)
O2w—H2w2···O2i0.85 (1)2.19 (2)2.937 (3)147 (3)
O3w—H3w1···O2iv0.84 (1)1.95 (1)2.753 (3)161 (3)
O3w—H3w2···O4wv0.85 (1)1.85 (1)2.689 (3)171 (4)
O4w—H4w1···O20.84 (1)1.92 (1)2.741 (3)166 (3)
O4w—H4w2···O3vi0.84 (1)2.11 (2)2.929 (3)165 (4)
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+2, −z; (iii) −x+1, −y+2, −z+1; (iv) −x+2, −y+1, −z+1; (v) x, y+1, z; (vi) x+1, y−1, z.
Acknowledgements top

We are grateful to the Ministry of Education Foundation of the Guangxi Zhuang Autonomous Region for funding this study. We thank Hechi University and the University of Malaya for supporting this study.

references
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