The iminodiacetate dianion in diaquaiminodiacetatonickel(II), [Ni(C
4H
5NO
4)(H
2O)
2], chelates to the Ni atom through two carboxyl O and one imino N atoms; the six-fold coordination coordination environment comprises these three atoms, the water molecules and the carbonyl O atom of an adjacent dianionic group. The dative Ni
O linkage leads to the formation of a helical chain running along the
a axis of the orthorhombic crystal; adjacent chains are held in a network motif by hydrogen bonds.
Supporting information
CCDC reference: 214799
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.008 Å
- R factor = 0.054
- wR factor = 0.105
- Data-to-parameter ratio = 13.0
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
General Notes
REFLT_03
From the CIF: _diffrn_reflns_theta_max 28.30
From the CIF: _reflns_number_total 1613
Count of symmetry unique reflns 943
Completeness (_total/calc) 171.05%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 670
Fraction of Friedel pairs measured 0.710
Are heavy atom types Z>Si present yes
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.
Nickel nitrate hexahydrate (0.29 g, 1 mmol) dissolved in water (2 ml) was reacted with iminodiacetic acid (0.13 g, 1 mmol) dissolved in ethanol (8 ml). The pH of the solution was adjusted to 5 by the addition of aqueous sodium hydroxide. The solution was then sealed in a Teflon-lined Parr stainless-steel vessel, which was heated to 433 K for 2 h. The title compound separated as plates.
The H atoms of the imino N and water O atoms were located and refined, subject to O—H = N—H = 0.85±0.01 Å; for the water H atoms, H···H = 1.39±0.01 Å. The C-bound H atoms were generated geometrically (C—H = 0.97 Å). The displacement parameters of all H atoms were set to 1.2 times those of their parent atoms.
Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.
Diaquaiminodiacetatonickel(II)
top
Crystal data top
[Ni(C4H5NO4)(H2O)2] | Dx = 2.08 Mg m−3 |
Mr = 225.83 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P21ca | Cell parameters from 1988 reflections |
a = 9.7610 (3) Å | θ = 2.9–28.3° |
b = 5.2219 (2) Å | µ = 2.68 mm−1 |
c = 14.1713 (4) Å | T = 298 K |
V = 722.32 (4) Å3 | Plate, green |
Z = 4 | 0.34 × 0.07 × 0.04 mm |
F(000) = 464 | |
Data collection top
Bruker SMART area-detector diffractometer | 1613 independent reflections |
Radiation source: fine-focus sealed tube | 1585 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.035 |
ϕ and ω scans | θmax = 28.3°, θmin = 2.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −12→12 |
Tmin = 0.728, Tmax = 0.898 | k = −6→2 |
4084 measured reflections | l = −16→18 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.054 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.105 | w = 1/[σ2(Fo2) + (0.0418P)2 + 0.7011P] where P = (Fo2 + 2Fc2)/3 |
S = 1.25 | (Δ/σ)max = 0.001 |
1613 reflections | Δρmax = 0.89 e Å−3 |
124 parameters | Δρmin = −1.03 e Å−3 |
6 restraints | Absolute structure: Flack (1983), 718 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.12 (3) |
Crystal data top
[Ni(C4H5NO4)(H2O)2] | V = 722.32 (4) Å3 |
Mr = 225.83 | Z = 4 |
Orthorhombic, P21ca | Mo Kα radiation |
a = 9.7610 (3) Å | µ = 2.68 mm−1 |
b = 5.2219 (2) Å | T = 298 K |
c = 14.1713 (4) Å | 0.34 × 0.07 × 0.04 mm |
Data collection top
Bruker SMART area-detector diffractometer | 1613 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1585 reflections with I > 2σ(I) |
Tmin = 0.728, Tmax = 0.898 | Rint = 0.035 |
4084 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.054 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.105 | Δρmax = 0.89 e Å−3 |
S = 1.25 | Δρmin = −1.03 e Å−3 |
1613 reflections | Absolute structure: Flack (1983), 718 Friedel pairs |
124 parameters | Absolute structure parameter: 0.12 (3) |
6 restraints | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Ni1 | 0.50000 (9) | 0.1153 (1) | 0.43427 (4) | 0.0168 (2) | |
O1 | 0.6934 (4) | −0.0469 (7) | 0.4677 (3) | 0.021 (1) | |
O2 | 0.9125 (4) | 0.0798 (7) | 0.4593 (3) | 0.021 (1) | |
O3 | 0.4498 (4) | −0.1789 (7) | 0.3476 (3) | 0.024 (1) | |
O4 | 0.4995 (9) | −0.3509 (7) | 0.2083 (3) | 0.035 (1) | |
O1w | 0.3319 (5) | 0.3334 (8) | 0.3915 (3) | 0.024 (1) | |
O2w | 0.5573 (5) | 0.4165 (7) | 0.5256 (3) | 0.024 (1) | |
N1 | 0.6147 (5) | 0.2352 (8) | 0.3210 (3) | 0.015 (1) | |
C1 | 0.7881 (6) | 0.088 (1) | 0.4347 (4) | 0.018 (1) | |
C2 | 0.7530 (6) | 0.279 (1) | 0.3572 (4) | 0.019 (1) | |
C3 | 0.5101 (8) | −0.1780 (9) | 0.2680 (4) | 0.022 (1) | |
C4 | 0.6093 (6) | 0.038 (1) | 0.2470 (4) | 0.022 (1) | |
H1w1 | 0.272 (5) | 0.29 (1) | 0.431 (4) | 0.028* | |
H1w2 | 0.336 (7) | 0.494 (3) | 0.382 (5) | 0.028* | |
H2w1 | 0.537 (7) | 0.574 (4) | 0.526 (5) | 0.029* | |
H2w2 | 0.540 (7) | 0.36 (1) | 0.580 (2) | 0.029* | |
H1n | 0.595 (7) | 0.382 (6) | 0.298 (4) | 0.018* | |
H2a | 0.7593 | 0.4520 | 0.3821 | 0.022* | |
H2b | 0.8185 | 0.2634 | 0.3060 | 0.022* | |
H4a | 0.7003 | −0.0341 | 0.2389 | 0.027* | |
H4b | 0.5833 | 0.1174 | 0.1879 | 0.027* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ni1 | 0.0148 (3) | 0.0174 (3) | 0.0183 (3) | −0.0020 (4) | 0.0005 (4) | 0.0024 (2) |
O1 | 0.012 (2) | 0.023 (2) | 0.028 (2) | −0.002 (2) | −0.002 (2) | 0.012 (2) |
O2 | 0.014 (2) | 0.029 (2) | 0.020 (2) | −0.001 (2) | 0.000 (2) | 0.006 (2) |
O3 | 0.033 (3) | 0.017 (2) | 0.021 (2) | −0.008 (2) | 0.004 (2) | −0.001 (2) |
O4 | 0.054 (3) | 0.025 (2) | 0.026 (2) | −0.005 (3) | −0.002 (3) | −0.001 (2) |
O1w | 0.020 (2) | 0.022 (2) | 0.028 (2) | 0.002 (2) | 0.002 (2) | 0.006 (2) |
O2w | 0.031 (2) | 0.018 (2) | 0.023 (2) | −0.001 (2) | 0.001 (2) | 0.003 (2) |
N1 | 0.013 (2) | 0.014 (2) | 0.019 (2) | −0.002 (2) | −0.001 (2) | 0.007 (2) |
C1 | 0.018 (3) | 0.019 (3) | 0.017 (3) | 0.002 (2) | 0.002 (2) | −0.009 (2) |
C2 | 0.013 (3) | 0.026 (3) | 0.016 (3) | −0.003 (2) | 0.001 (2) | 0.010 (2) |
C3 | 0.020 (3) | 0.017 (2) | 0.028 (3) | 0.006 (3) | −0.003 (3) | 0.000 (2) |
C4 | 0.015 (3) | 0.030 (3) | 0.022 (3) | −0.009 (2) | −0.003 (2) | −0.002 (2) |
Geometric parameters (Å, º) top
Ni1—O1 | 2.123 (4) | C1—C2 | 1.525 (7) |
Ni1—O2i | 2.011 (4) | C3—C4 | 1.514 (9) |
Ni1—O3 | 2.027 (4) | O1w—H1w1 | 0.85 (5) |
Ni1—O1w | 2.087 (4) | O1w—H1w2 | 0.85 (2) |
Ni1—O2w | 2.112 (4) | O2w—H2w1 | 0.85 (2) |
Ni1—N1 | 2.055 (5) | O2w—H2w2 | 0.85 (3) |
O1—C1 | 1.251 (7) | N1—H1n | 0.85 (5) |
O2—C1 | 1.264 (7) | C2—H2a | 0.97 |
O3—C3 | 1.273 (7) | C2—H2b | 0.97 |
O4—C3 | 1.242 (6) | C4—H4a | 0.97 |
N1—C2 | 1.463 (7) | C4—H4b | 0.97 |
N1—C4 | 1.472 (7) | | |
| | | |
O1—Ni1—O2i | 90.5 (2) | N1—C2—C1 | 110.9 (4) |
O1—Ni1—O3 | 92.8 (2) | O4—C3—O3 | 124.2 (6) |
O1—Ni1—O1w | 169.0 (2) | O4—C3—C4 | 117.4 (6) |
O1—Ni1—O2w | 85.7 (2) | O3—C3—C4 | 118.2 (5) |
O1—Ni1—N1 | 79.1 (2) | N1—C4—C3 | 113.8 (5) |
O2i—Ni1—O3 | 88.2 (2) | Ni1—O1w—H1w1 | 101 (5) |
O2i—Ni1—N1 | 166.4 (2) | Ni1—O1w—H1w2 | 123 (5) |
O2i—Ni1—O1w | 99.2 (2) | H1w1—O1w—H1w2 | 115 (7) |
O2i—Ni1—O2w | 91.7 (2) | Ni1—O2w—H2w1 | 132 (5) |
O3—Ni1—O1w | 92.7 (2) | Ni1—O2w—H2w2 | 104 (5) |
O3—Ni1—N1 | 83.6 (2) | H2w1—O2w—H2w2 | 107 (6) |
O3—Ni1—O2w | 178.5 (2) | C2—N1—H1n | 102 (4) |
O1w—Ni1—O2w | 88.8 (2) | C4—N1—H1n | 111 (4) |
O1w—Ni1—N1 | 92.0 (2) | Ni1—N1—H1n | 116 (4) |
O2w—Ni1—N1 | 96.2 (2) | N1—C2—H2a | 109.5 |
C1—O1—Ni1 | 110.5 (3) | C1—C2—H2a | 109.5 |
C1—O2—Ni1ii | 129.1 (4) | N1—C2—H2b | 109.5 |
C3—O3—Ni1 | 115.0 (4) | C1—C2—H2b | 109.5 |
C2—N1—C4 | 113.1 (4) | H2a—C2—H2b | 108.1 |
C2—N1—Ni1 | 106.1 (3) | N1—C4—H4a | 108.8 |
C4—N1—Ni1 | 108.8 (3) | C3—C4—H4a | 108.8 |
O1—C1—O2 | 126.0 (5) | N1—C4—H4b | 108.8 |
O1—C1—C2 | 118.1 (5) | C3—C4—H4b | 108.8 |
O2—C1—C2 | 115.8 (5) | H4a—C4—H4b | 107.7 |
| | | |
O2i—Ni1—O1—C1 | −159.1 (4) | O2w—Ni1—N1—C4 | 172.6 (4) |
O3—Ni1—O1—C1 | 112.7 (4) | O1—Ni1—N1—C4 | 88.2 (4) |
N1—Ni1—O1—C1 | 29.7 (4) | Ni1—O1—C1—O2 | 162.6 (4) |
O1w—Ni1—O1—C1 | −7.1 (11) | Ni1—O1—C1—C2 | −17.7 (6) |
O2w—Ni1—O1—C1 | −67.5 (4) | Ni1ii—O2—C1—O1 | −7.0 (8) |
O2i—Ni1—O3—C3 | −165.5 (4) | Ni1ii—O2—C1—C2 | 173.3 (3) |
N1—Ni1—O3—C3 | 3.6 (4) | C4—N1—C2—C1 | −84.7 (5) |
O1w—Ni1—O3—C3 | 95.4 (4) | Ni1—N1—C2—C1 | 34.6 (5) |
O1—Ni1—O3—C3 | −75.1 (4) | O1—C1—C2—N1 | −11.5 (7) |
O2i—Ni1—N1—C2 | −74.6 (9) | O2—C1—C2—N1 | 168.2 (5) |
O3—Ni1—N1—C2 | −127.8 (4) | Ni1—O3—C3—O4 | 175.0 (6) |
O1w—Ni1—N1—C2 | 139.6 (3) | Ni1—O3—C3—C4 | −0.4 (7) |
O2w—Ni1—N1—C2 | 50.6 (4) | C2—N1—C4—C3 | 124.8 (5) |
O1—Ni1—N1—C2 | −33.8 (3) | Ni1—N1—C4—C3 | 7.1 (6) |
O2i—Ni1—N1—C4 | 47.5 (9) | O4—C3—C4—N1 | 179.5 (6) |
O3—Ni1—N1—C4 | −5.8 (4) | O3—C3—C4—N1 | −4.8 (8) |
O1w—Ni1—N1—C4 | −98.3 (4) | | |
Symmetry codes: (i) x−1/2, −y, −z+1; (ii) x+1/2, −y, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1w—H1w1···O1i | 0.85 (5) | 2.05 (5) | 2.837 (6) | 154 (5) |
O1w—H1w2···O3iii | 0.85 (2) | 2.10 (4) | 2.863 (6) | 150 (2) |
O2w—H2w1···O2iv | 0.85 (2) | 2.19 (4) | 2.994 (6) | 159 (2) |
O2w—H2w2···O4v | 0.85 (3) | 1.86 (3) | 2.673 (6) | 160 (3) |
N1—H1n···O4iii | 0.85 (5) | 2.11 (5) | 2.913 (7) | 157 (3) |
Symmetry codes: (i) x−1/2, −y, −z+1; (iii) x, y+1, z; (iv) x−1/2, −y+1, −z+1; (v) x, −y, z+1/2. |
Experimental details
Crystal data |
Chemical formula | [Ni(C4H5NO4)(H2O)2] |
Mr | 225.83 |
Crystal system, space group | Orthorhombic, P21ca |
Temperature (K) | 298 |
a, b, c (Å) | 9.7610 (3), 5.2219 (2), 14.1713 (4) |
V (Å3) | 722.32 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.68 |
Crystal size (mm) | 0.34 × 0.07 × 0.04 |
|
Data collection |
Diffractometer | Bruker SMART area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.728, 0.898 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4084, 1613, 1585 |
Rint | 0.035 |
(sin θ/λ)max (Å−1) | 0.667 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.054, 0.105, 1.25 |
No. of reflections | 1613 |
No. of parameters | 124 |
No. of restraints | 6 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.89, −1.03 |
Absolute structure | Flack (1983), 718 Friedel pairs |
Absolute structure parameter | 0.12 (3) |
Selected geometric parameters (Å, º) topNi1—O1 | 2.123 (4) | Ni1—O1w | 2.087 (4) |
Ni1—O2i | 2.011 (4) | Ni1—O2w | 2.112 (4) |
Ni1—O3 | 2.027 (4) | Ni1—N1 | 2.055 (5) |
| | | |
O1—Ni1—O2i | 90.5 (2) | O2i—Ni1—O2w | 91.7 (2) |
O1—Ni1—O3 | 92.8 (2) | O3—Ni1—O1w | 92.7 (2) |
O1—Ni1—O1w | 169.0 (2) | O3—Ni1—N1 | 83.6 (2) |
O1—Ni1—O2w | 85.7 (2) | O3—Ni1—O2w | 178.5 (2) |
O1—Ni1—N1 | 79.1 (2) | O1w—Ni1—O2w | 88.8 (2) |
O2i—Ni1—O3 | 88.2 (2) | O1w—Ni1—N1 | 92.0 (2) |
O2i—Ni1—N1 | 166.4 (2) | O2w—Ni1—N1 | 96.2 (2) |
O2i—Ni1—O1w | 99.2 (2) | | |
Symmetry code: (i) x−1/2, −y, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1w—H1w1···O1i | 0.85 (5) | 2.05 (5) | 2.837 (6) | 154 (5) |
O1w—H1w2···O3ii | 0.85 (2) | 2.10 (4) | 2.863 (6) | 150 (2) |
O2w—H2w1···O2iii | 0.85 (2) | 2.19 (4) | 2.994 (6) | 159 (2) |
O2w—H2w2···O4iv | 0.85 (3) | 1.86 (3) | 2.673 (6) | 160 (3) |
N1—H1n···O4ii | 0.85 (5) | 2.11 (5) | 2.913 (7) | 157 (3) |
Symmetry codes: (i) x−1/2, −y, −z+1; (ii) x, y+1, z; (iii) x−1/2, −y+1, −z+1; (iv) x, −y, z+1/2. |
Unlike iminodiacetatocopper(II), a compound that forms a large number of coordination complexes, as well as complexes with metal salts (Román-Alpiste et al., 1999), the nickel(II) analog is much less studied, and even the crystal structure of iminodiacetatonickel(II) has not been reported. The limited number of derivatives of this compound comprise the trihydrated 1:1 complex of dipotassium bis(iminodiacetato)nickelate (Agre et al., 1984), caesium bis(iminodiacetato)nickelate tetrahydrate (Mammano et al., 1997), lithium bis(iminodiacetato)nickelate tetrahydrate (Kramarenko et al., 1974; Mammano et al., 1997) and the only N-heterocycle adduct, tris(imidazole)iminodiacetatonickel hydrate (Polyakova et al., 2000).
Iminodiacetatonickel crystallizes as a dihydrate, (I), in which the Ni atom exits in an octahedral environment this is comprised of the O,N,O'-chelating iminodiacetate ligand, the two water molecules and the carbonyl O atom of an adjacent molecule. The dative Ni\left arrow O linkage [2.011 (4) Å] leads to the formation of a helical chain running along the a axis of the orthorhombic crystal (Fig. 2). The other carbonyl O atom does not participate in bonding to the Ni atom but is instead engaged in hydrogen bonding with a water molecule and the imino N atom of an adjacent molecule. The extensive hydrogen bonds consolidate the structure into a tightly-held network.