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In the title compound, [Ni2(C2H3O2)4(C6H12N4)]n, the hexamethylenetetramine molecules, occupying a special position of mm2 symmetry, link adjacent tetraacetatodinickel units, located in a special position of 2/m symmetry, into zigzag chains that run along the b axis of the unit cell. The Ni atom in the binuclear unit is five-coordinate and has a square-pyramidal geometry. It is displaced by 0.203 (3) Å out of the basal plane of the four O atoms towards the apical N atom of the adjacent hexamethylenetetramine molecule and away from the second Ni atom of the binuclear unit. The two Ni atoms are separated by 2.622 (1) Å.
Supporting information
CCDC reference: 167790
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.004 Å
- R factor = 0.030
- wR factor = 0.076
- Data-to-parameter ratio = 12.8
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level C:
PLAT_703 Alert C Torsion Calc -133.94(5), Rep -134.00(10), Dev. 1.20 Sigma
O2 -NI1 -N1 -C3 9.555 1.555 1.555 1.555
PLAT_703 Alert C Torsion Calc 133.94(5), Rep 134.00(10), Dev. 1.20 Sigma
O2 -NI1 -N1 -C3 4.555 1.555 1.555 1.555
General Notes
ABSTM_02 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 0.902
Tmax scaled 0.462 Tmin scaled 0.364
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
2 Alert Level C = Please check
The title compound was synthesized by the reaction of nickel(II) acetate
tetrahydrate (0.50 g, 2 mmol) and hexamethylenetetramine (0.14 g, 1 mmol) (2:1
molar ratio) in a small volume of ethanol. Water was added dropwise to
dissolve the reactants. Green prismatic crystals deposited from solution in
80% yield after several weeks. Analysis calculated for
C14H24N4Ni2O8: C 34.05, H 4.86, N 11.15%; found: C 33.86, H 5.04, N
11.28%.
The H atoms of the hexamethylenetetramine entity were generated geometrically
and allowed to ride on the parent C atom; Uiso(H) =
1.2Ueq(C). The methyl H atoms were positioned by using the HFIX 137
instruction in SHELXL97.
Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; 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.
catena-µ-(
N,
N'-hexamethylenetetramine)[tetra-µ-acetatodinickel(II)]
top
Crystal data top
[Ni2(C2H3O2)4(C6H12N4)] | Dx = 1.684 Mg m−3 |
Mr = 493.79 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Cmma | Cell parameters from 1865 reflections |
a = 15.480 (1) Å | θ = 2.5–25.0° |
b = 15.638 (2) Å | µ = 1.98 mm−1 |
c = 8.048 (1) Å | T = 298 K |
V = 1948.2 (4) Å3 | Prism, green |
Z = 4 | 0.56 × 0.48 × 0.39 mm |
F(000) = 1024 | |
Data collection top
Bruker CCD area-detector diffractometer | 937 independent reflections |
Radiation source: fine-focus sealed tube | 775 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.029 |
ω scans | θmax = 25.0°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −18→16 |
Tmin = 0.403, Tmax = 0.512 | k = −18→18 |
3062 measured reflections | l = −5→9 |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.030 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.076 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0464P)2 + 0.5367P] where P = (Fo2 + 2Fc2)/3 |
937 reflections | (Δ/σ)max < 0.001 |
73 parameters | Δρmax = 0.30 e Å−3 |
0 restraints | Δρmin = −0.35 e Å−3 |
Crystal data top
[Ni2(C2H3O2)4(C6H12N4)] | V = 1948.2 (4) Å3 |
Mr = 493.79 | Z = 4 |
Orthorhombic, Cmma | Mo Kα radiation |
a = 15.480 (1) Å | µ = 1.98 mm−1 |
b = 15.638 (2) Å | T = 298 K |
c = 8.048 (1) Å | 0.56 × 0.48 × 0.39 mm |
Data collection top
Bruker CCD area-detector diffractometer | 937 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 775 reflections with I > 2σ(I) |
Tmin = 0.403, Tmax = 0.512 | Rint = 0.029 |
3062 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.076 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.30 e Å−3 |
937 reflections | Δρmin = −0.35 e Å−3 |
73 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Ni1 | 0.0000 | 0.05907 (3) | 0.11560 (5) | 0.0277 (2) | |
O1 | 0.0920 (1) | 0.1076 (1) | −0.0265 (2) | 0.046 (1) | |
O2 | 0.0903 (1) | 0.0092 (1) | −0.2250 (2) | 0.049 (1) | |
N1 | 0.0000 | 0.1718 (2) | 0.2823 (3) | 0.029 (1) | |
N2 | −0.0788 (2) | 0.2500 | 0.4975 (4) | 0.036 (1) | |
C1 | 0.1209 (2) | 0.0742 (2) | −0.1568 (3) | 0.035 (1) | |
C2 | 0.1992 (2) | 0.1155 (2) | −0.2351 (4) | 0.049 (1) | |
C3 | 0.0000 | 0.2500 | 0.1794 (6) | 0.028 (1) | |
C4 | −0.0774 (2) | 0.1736 (2) | 0.3915 (3) | 0.034 (1) | |
C5 | 0.0000 | 0.2500 | 0.5988 (6) | 0.041 (1) | |
H2a | 0.2140 | 0.0857 | −0.3354 | 0.074* | |
H2b | 0.2469 | 0.1130 | −0.1590 | 0.074* | |
H2c | 0.1865 | 0.1742 | −0.2607 | 0.074* | |
H3 | 0.0507 | 0.2500 | 0.1085 | 0.034* | |
H4a | −0.1290 | 0.1725 | 0.3234 | 0.041* | |
H4b | −0.0777 | 0.1229 | 0.4610 | 0.041* | |
H5 | 0.0000 | 0.1999 | 0.6698 | 0.049* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ni1 | 0.0280 (3) | 0.0237 (3) | 0.0314 (3) | 0.000 | 0.000 | −0.0038 (2) |
O1 | 0.045 (1) | 0.040 (1) | 0.053 (1) | −0.011 (1) | 0.015 (1) | −0.009 (1) |
O2 | 0.054 (1) | 0.047 (1) | 0.047 (1) | −0.016 (1) | 0.012 (1) | −0.008 (1) |
N1 | 0.030 (1) | 0.026 (2) | 0.030 (2) | 0.000 | 0.000 | 0.001 (1) |
N2 | 0.041 (2) | 0.029 (2) | 0.039 (2) | 0.000 | 0.010 (1) | 0.000 |
C1 | 0.028 (1) | 0.034 (2) | 0.041 (2) | 0.002 (1) | −0.001 (1) | 0.010 (1) |
C2 | 0.038 (1) | 0.053 (2) | 0.056 (2) | −0.005 (2) | 0.005 (1) | 0.01 (2) |
C3 | 0.038 (3) | 0.021 (3) | 0.026 (2) | 0.000 | 0.000 | 0.000 |
C4 | 0.032 (1) | 0.032 (2) | 0.040 (1) | −0.002 (1) | 0.004 (1) | 0.001 (1) |
C5 | 0.062 (4) | 0.037 (3) | 0.024 (3) | 0.000 | 0.000 | 0.000 |
Geometric parameters (Å, º) top
Ni1—O1 | 1.978 (2) | N2—C4 | 1.469 (3) |
Ni1—O1i | 1.978 (2) | N2—C4iv | 1.469 (3) |
Ni1—O2ii | 1.967 (2) | C1—C2 | 1.511 (4) |
Ni1—O2iii | 1.967 (2) | C3—N1v | 1.477 (4) |
Ni1—N1 | 2.215 (3) | C5—N2v | 1.467 (4) |
Ni1—Ni1iii | 2.622 (1) | C2—H2a | 0.9600 |
O1—C1 | 1.254 (3) | C2—H2b | 0.9600 |
O2—C1 | 1.248 (3) | C2—H2c | 0.9600 |
N1—C3 | 1.477 (4) | C3—H3 | 0.9700 |
N1—C4i | 1.486 (3) | C4—H4a | 0.9700 |
N1—C4 | 1.486 (3) | C4—H4b | 0.9700 |
N2—C5 | 1.467 (4) | C5—H5 | 0.9700 |
| | | |
O1—Ni1—O1i | 92.1 (1) | C5—N2—C4iv | 108.1 (2) |
O1—Ni1—O2ii | 87.5 (1) | C4—N2—C4iv | 108.9 (3) |
O1—Ni1—O2iii | 168.2 (1) | O2—C1—O1 | 124.9 (2) |
O1—Ni1—N1 | 92.6 (1) | O2—C1—C2 | 118.0 (3) |
O1—Ni1—Ni1iii | 82.0 (1) | O1—C1—C2 | 117.1 (3) |
O1i—Ni1—O2ii | 168.2 (1) | N1v—C3—N1 | 111.8 (4) |
O1i—Ni1—O2iii | 87.5 (1) | N2—C4—N1 | 111.8 (2) |
O1i—Ni1—N1 | 92.6 (1) | N2—C5—N2v | 112.5 (4) |
O1i—Ni1—Ni1iii | 82.0 (1) | C1—C2—H2a | 109.5 |
O2ii—Ni1—O2iii | 90.6 (1) | C1—C2—H2b | 109.5 |
O2ii—Ni1—N1 | 99.3 (1) | H2a—C2—H2b | 109.5 |
O2ii—Ni1—Ni1iii | 86.3 (1) | C1—C2—H2c | 109.5 |
O2iii—Ni1—N1 | 99.3 (1) | H2a—C2—H2c | 109.5 |
O2iii—Ni1—Ni1iii | 86.3 (1) | H2b—C2—H2c | 109.5 |
N1—Ni1—Ni1iii | 172.1 (1) | N1v—C3—H3 | 109.2 |
C1—O1—Ni1 | 125.4 (2) | N1—C3—H3 | 109.2 |
C1—O2—Ni1iii | 121.0 (2) | N2—C4—H4a | 109.3 |
C3—N1—C4i | 108.4 (2) | N1—C4—H4a | 109.3 |
C3—N1—C4 | 108.4 (2) | N2—C4—H4b | 109.3 |
C4i—N1—C4 | 107.4 (3) | N1—C4—H4b | 109.3 |
C3—N1—Ni1 | 108.6 (2) | H4a—C4—H4b | 107.9 |
C4i—N1—Ni1 | 111.9 (2) | N2—C5—H5 | 109.1 |
C4—N1—Ni1 | 111.9 (2) | N2v—C5—H5 | 109.1 |
C5—N2—C4 | 108.1 (2) | | |
| | | |
O2iii—Ni1—O1—C1 | 3.8 (5) | O1i—Ni1—N1—C4 | 73.6 (2) |
O2ii—Ni1—O1—C1 | 84.4 (2) | Ni1iii—O2—C1—O1 | −8.5 (4) |
O1i—Ni1—O1—C1 | −83.8 (2) | Ni1iii—O2—C1—C2 | 170.7 (2) |
N1—Ni1—O1—C1 | −176.5 (2) | Ni1—O1—C1—O2 | 7.1 (4) |
Ni1iii—Ni1—O1—C1 | −2.2 (2) | Ni1—O1—C1—C2 | −172.1 (2) |
O2iii—Ni1—N1—C3 | −134.0 (1) | C4i—N1—C3—N1v | −58.1 (2) |
O2ii—Ni1—N1—C3 | 134.0 (1) | C4—N1—C3—N1v | 58.1 (2) |
O1—Ni1—N1—C3 | 46.1 (1) | Ni1—N1—C3—N1v | 180.0 |
O1i—Ni1—N1—C3 | −46.1 (1) | C5—N2—C4—N1 | −58.9 (3) |
O2iii—Ni1—N1—C4i | 106.4 (2) | C4iv—N2—C4—N1 | 58.4 (3) |
O2ii—Ni1—N1—C4i | 14.3 (2) | C3—N1—C4—N2 | −58.1 (3) |
O1—Ni1—N1—C4i | −73.6 (2) | C4i—N1—C4—N2 | 58.9 (3) |
O1i—Ni1—N1—C4i | −165.8 (2) | Ni1—N1—C4—N2 | −177.9 (2) |
O2iii—Ni1—N1—C4 | −14.3 (2) | C4—N2—C5—N2v | 58.9 (2) |
O2ii—Ni1—N1—C4 | −106.4 (2) | C4iv—N2—C5—N2v | −58.9 (2) |
O1—Ni1—N1—C4 | 165.8 (2) | | |
Symmetry codes: (i) −x, y, z; (ii) x, −y, −z; (iii) −x, −y, −z; (iv) x, −y+1/2, z; (v) −x, −y+1/2, z. |
Experimental details
Crystal data |
Chemical formula | [Ni2(C2H3O2)4(C6H12N4)] |
Mr | 493.79 |
Crystal system, space group | Orthorhombic, Cmma |
Temperature (K) | 298 |
a, b, c (Å) | 15.480 (1), 15.638 (2), 8.048 (1) |
V (Å3) | 1948.2 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.98 |
Crystal size (mm) | 0.56 × 0.48 × 0.39 |
|
Data collection |
Diffractometer | Bruker CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.403, 0.512 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3062, 937, 775 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.076, 1.02 |
No. of reflections | 937 |
No. of parameters | 73 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.30, −0.35 |
Selected geometric parameters (Å, º) topNi1—O1 | 1.978 (2) | Ni1—N1 | 2.215 (3) |
Ni1—O2i | 1.967 (2) | Ni1—Ni1ii | 2.622 (1) |
| | | |
O1—Ni1—O1iii | 92.1 (1) | O2i—Ni1—O2ii | 90.6 (1) |
O1—Ni1—O2i | 87.5 (1) | O2i—Ni1—N1 | 99.3 (1) |
O1—Ni1—O2ii | 168.2 (1) | O2i—Ni1—Ni1ii | 86.3 (1) |
O1—Ni1—N1 | 92.6 (1) | N1—Ni1—Ni1ii | 172.1 (1) |
O1—Ni1—Ni1ii | 82.0 (1) | | |
Symmetry codes: (i) x, −y, −z; (ii) −x, −y, −z; (iii) −x, y, z. |
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Hexamethylenetetramine, a spacer molecule that has been extensively used in the crystal engineering of coordination polymers, can bridge through two (Zheng, Tong, Yu & Chen, 2001), three (Zheng, Tong, Zhu et al., 2001) or four (Tong et al., 1999) of its N atoms to furnish a variety of such polymers. To date, an enormous number of metal complexes of this kind have been reported (Zhang et al., 2000a,b); the title nickel acetate complex, (I), represents an exception, as only few acetate complexes have been studied.
The crystal structure of the title complex, which is isomorphous with its copper analog (Pickardt, 1981), is built of hexamethylenetetramine molecules and tetraacetatodinickel units, both of which occupy special positions. The hexamethylenetetramine molecule occupies the position of mm2 symmetry with one of the mirror planes passing through the N1, C3 and C5, and the other mirror plane passing through the N2, C3 and C5 atoms. The tetraacetatodinickel unit occupies the position of the 2/m symmetry with the mirror plane passing through both Ni atoms and bisecting two of the O—Ni—O angles in the coordination spheres of each of the Ni atoms; the twofold axis passes midway between the two Ni atoms but it does not pass through any of them.
The coordination geometry of the Ni atom may be described as a square pyramid, formed by four acetate O and the N atom of the adjacent hexamethylenetetramine, which is distorted towards an octahedron owing to the metal–metal interaction [2.622 (1) Å] (Fig. 1). The Ni atom is displaced out of the basal plane of the four O atoms by 0.203 (3) Å towards the apical hexamethylenetetramine N atom. The hexamethylenetetramine ligand uses only two of its four N atoms to link adjacent units to afford a zigzag chain running along the b axis of the unit cell (Fig. 2). The bonding pattern of the acetate groups in the title compound contrasts with that of tetraaquadiacetatonickel, a mononuclear compound with two monodetate acetate groups [Ni—O 2.067 (3) Å; Downie et al., 1971].