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Acta Cryst. (2009). E65, m723    [ doi:10.1107/S1600536809020042 ]

cis-[(7R,14R)-5,5,7,12,12,14-Hexamethyl-1,4,8,11-tetraazacyclotetradecane-[kappa]4N](oxalato-[kappa]2O,O')nickel(II) oxalic acid solvate

G.-C. Ou, Y.-Q. Dai and M.-S. Tang

Abstract top

Both molecules of the title compound, [Ni(C2O4)(C16H36N4)]·C2H2O4, are located on a crystallographic twofold rotation axis. The NiII atom shows a distorted octahedral geometry. The crystal packing is stabilized by N-H...O and O-H...O hydrogen bonds.

Comment top

Recently, many helical structures have been constructed through the coordination interactions of the organic ligand with suitable metal ions. Helical polymers constructed via hydrogen bonding, which is a versatile and efficient strategy, are still rare, and only a few cases have been reported. Then we employ chiral macrocyclic ligand L and oxalic acid as building blocks to construct helical structure, and unfortunately the helical structure is not obtained.

As illustrated in Fig.1, the six-coordinated Ni centre displays a distorted octahedral geometry. Neighbouring molecules are connected through intermolecular N-H···O and O-H···O hydrogen bonds (Fig. 2).

Related literature top

For general background, see: Tait et al. (1976); Curtis (1965). For a related crystal structure, see: Tang et al. (2002).

Experimental top

Oxalic acid (0.5 g, 4 mmol) and NaOH (0.08 g, 2 mmol) were dissolved in 15 ml of water. To this solution was added [Ni(C16H36N4)](ClO4)2 (0.54 g, 1 mmol) dissolved in 2 ml of CH3CN. The solution was left to stand at room temperature and violet crystals formed after several weeks.

Refinement top

All H atoms were placed in calculated positions (O—H = 0.84Å, N—H = 0.93Å, C—H 0.98 to 1.00 Å) and were included in the refinement in the riding model approximation, with Uiso (H) set to 1.2 Ueq(C,N) or 1.5 Ueq(Cmethyl,O).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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 top
[Figure 1] Fig. 1. The molecular structure of the title compound, showing displacement ellipsoids at the 50% probability level; symmetry codes for the generated atoms: A(1 - x, 2 - y, z), B(2 - x, -y, z). H-atoms have been excluded for clarity.
[Figure 2] Fig. 2. The hydrogen bond pattern in the title compound.
cis-[(7R,14R)-5,5,7,12,12,14-Hexamethyl-1,4,8,11- tetraazacyclotetradecane-κ4N](oxalato- κ2O,O')nickel(II) oxalic acid solvate top
Crystal data top
[Ni(C2O4)(C16H36N4)]·C2H2O4F(000) = 556
Mr = 521.25Dx = 1.369 Mg m−3
Orthorhombic, P21212Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2 2abCell parameters from 3630 reflections
a = 10.1261 (15) Åθ = 2.4–26.9°
b = 15.515 (2) ŵ = 0.82 mm−1
c = 8.0467 (11) ÅT = 173 K
V = 1264.2 (3) Å3Prism, violet
Z = 20.48 × 0.21 × 0.15 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		2740 independent reflections
Radiation source: fine-focus sealed tube2435 reflections with I > 2σ(I)
graphiteRint = 0.022
φ and ω scansθmax = 27.1°, θmin = 2.4°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −12→12
Tmin = 0.695, Tmax = 0.887k = −19→8
5665 measured reflectionsl = −10→8
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.028H-atom parameters constrained
wR(F2) = 0.064 w = 1/[σ2(Fo2) + (0.0267P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max = 0.001
2740 reflectionsΔρmax = 0.40 e Å−3
154 parametersΔρmin = −0.19 e Å−3
0 restraintsAbsolute structure: Flack (1983), 1131 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.027 (13)
Crystal data top
[Ni(C2O4)(C16H36N4)]·C2H2O4V = 1264.2 (3) Å3
Mr = 521.25Z = 2
Orthorhombic, P21212Mo Kα radiation
a = 10.1261 (15) ŵ = 0.82 mm−1
b = 15.515 (2) ÅT = 173 K
c = 8.0467 (11) Å0.48 × 0.21 × 0.15 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		2740 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2435 reflections with I > 2σ(I)
Tmin = 0.695, Tmax = 0.887Rint = 0.022
5665 measured reflectionsθmax = 27.1°
Refinement top
R[F2 > 2σ(F2)] = 0.028H-atom parameters constrained
wR(F2) = 0.064Δρmax = 0.40 e Å−3
S = 1.08Δρmin = −0.19 e Å−3
2740 reflectionsAbsolute structure: Flack (1983), 1131 Friedel pairs
154 parametersFlack parameter: 0.027 (13)
0 restraints
Special details top

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 (Å2) top
xyzUiso*/Ueq
Ni11.00000.00000.60729 (3)0.02079 (9)
C100.57461 (18)1.00225 (19)0.2451 (2)0.0304 (4)
O11.09484 (13)0.05954 (8)0.40383 (17)0.0245 (3)
N10.81963 (17)0.07108 (10)0.6220 (2)0.0256 (4)
H1C0.77590.05970.52270.031*
C31.0605 (3)0.17864 (15)0.7602 (3)0.0338 (6)
H31.08870.19910.64780.041*
C50.9146 (3)0.19508 (15)0.7775 (3)0.0366 (6)
H5A0.90250.25770.79500.044*
H5B0.88460.16590.88010.044*
N21.09305 (18)0.08487 (10)0.7733 (2)0.0271 (4)
H2C1.07180.06720.88040.032*
O21.12362 (14)0.03860 (10)0.13153 (16)0.0360 (4)
O30.62920 (15)0.94107 (11)0.1583 (2)0.0423 (4)
H3A0.71170.94670.16090.064*
O40.63195 (17)1.05745 (11)0.3227 (2)0.0520 (5)
C21.2350 (2)0.06808 (14)0.7481 (3)0.0331 (5)
H2A1.28690.09640.83690.040*
H2B1.26360.09200.63990.040*
C91.0624 (2)0.02855 (12)0.2656 (2)0.0249 (4)
C10.7410 (2)0.02740 (14)0.7515 (3)0.0334 (5)
H1A0.64600.03900.73290.040*
H1B0.76520.05050.86200.040*
C60.8215 (2)0.16770 (13)0.6365 (2)0.0301 (5)
C41.1353 (3)0.23189 (14)0.8912 (3)0.0486 (7)
H4A1.11310.29300.87820.073*
H4B1.23060.22400.87640.073*
H4C1.10970.21261.00270.073*
C80.6827 (3)0.20270 (16)0.6697 (3)0.0452 (6)
H8A0.62090.17820.58880.068*
H8B0.68330.26560.65940.068*
H8C0.65510.18660.78230.068*
C70.8682 (2)0.20360 (14)0.4693 (3)0.0343 (5)
H7A0.95570.18030.44320.051*
H7B0.87310.26660.47560.051*
H7C0.80570.18690.38210.051*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.02928 (17)0.02073 (15)0.01236 (14)−0.00015 (18)0.0000.000
C100.0352 (10)0.0320 (10)0.0240 (9)−0.0018 (13)−0.0030 (8)0.0069 (14)
O10.0311 (7)0.0263 (7)0.0160 (7)0.0006 (6)−0.0020 (6)0.0021 (6)
N10.0341 (9)0.0269 (8)0.0159 (8)0.0017 (7)0.0010 (8)−0.0023 (7)
C30.0562 (15)0.0247 (11)0.0205 (11)−0.0054 (11)−0.0064 (11)−0.0006 (9)
C50.0602 (18)0.0221 (11)0.0277 (13)0.0046 (11)−0.0021 (12)−0.0058 (10)
N20.0421 (11)0.0249 (9)0.0142 (8)−0.0023 (8)−0.0032 (7)0.0006 (7)
O20.0294 (8)0.0628 (10)0.0158 (7)−0.0010 (7)0.0028 (6)0.0070 (7)
O30.0281 (8)0.0581 (11)0.0408 (9)−0.0047 (8)0.0026 (7)−0.0161 (8)
O40.0439 (10)0.0474 (10)0.0647 (12)0.0033 (8)−0.0190 (9)−0.0187 (9)
C20.0385 (13)0.0368 (13)0.0239 (11)−0.0086 (11)−0.0034 (10)−0.0029 (10)
C90.0278 (10)0.0297 (10)0.0170 (9)0.0073 (8)−0.0008 (8)0.0048 (8)
C10.0356 (12)0.0391 (13)0.0255 (11)0.0041 (10)0.0104 (10)−0.0003 (9)
C60.0404 (13)0.0262 (10)0.0238 (11)0.0077 (9)−0.0002 (10)−0.0034 (9)
C40.0816 (19)0.0296 (11)0.0346 (13)−0.0077 (12)−0.0185 (15)−0.0059 (12)
C80.0556 (16)0.0412 (13)0.0388 (13)0.0170 (12)0.0040 (12)−0.0066 (11)
C70.0477 (14)0.0283 (11)0.0269 (11)0.0057 (10)−0.0066 (11)0.0049 (9)
Geometric parameters (Å, °) top
Ni1—N22.0990 (17)N2—H2C0.9300
Ni1—N2i2.0990 (17)O2—C91.254 (2)
Ni1—O1i2.1110 (13)O3—H3A0.8400
Ni1—O12.1110 (13)C2—C1i1.501 (3)
Ni1—N12.1368 (16)C2—H2A0.9900
Ni1—N1i2.1368 (16)C2—H2B0.9900
C10—O41.209 (3)C9—C9i1.543 (4)
C10—O31.302 (3)C1—C2i1.501 (3)
C10—C10ii1.513 (4)C1—H1A0.9900
O1—C91.255 (2)C1—H1B0.9900
N1—C11.477 (3)C6—C81.530 (3)
N1—C61.504 (2)C6—C71.531 (3)
N1—H1C0.9300C4—H4A0.9800
C3—N21.495 (3)C4—H4B0.9800
C3—C51.506 (3)C4—H4C0.9800
C3—C41.539 (3)C8—H8A0.9800
C3—H31.0000C8—H8B0.9800
C5—C61.535 (3)C8—H8C0.9800
C5—H5A0.9900C7—H7A0.9800
C5—H5B0.9900C7—H7B0.9800
N2—C21.475 (3)C7—H7C0.9800
N2—Ni1—N2i100.97 (9)Ni1—N2—H2C107.5
N2—Ni1—O1i166.48 (6)C10—O3—H3A109.5
N2i—Ni1—O1i90.84 (6)N2—C2—C1i109.25 (19)
N2—Ni1—O190.84 (6)N2—C2—H2A109.8
N2i—Ni1—O1166.48 (6)C1i—C2—H2A109.8
O1i—Ni1—O178.29 (7)N2—C2—H2B109.8
N2—Ni1—N191.42 (7)C1i—C2—H2B109.8
N2i—Ni1—N184.55 (6)H2A—C2—H2B108.3
O1i—Ni1—N183.10 (6)O2—C9—O1125.80 (19)
O1—Ni1—N1101.88 (5)O2—C9—C9i118.43 (12)
N2—Ni1—N1i84.55 (6)O1—C9—C9i115.74 (11)
N2i—Ni1—N1i91.42 (7)N1—C1—C2i110.65 (19)
O1i—Ni1—N1i101.88 (5)N1—C1—H1A109.5
O1—Ni1—N1i83.10 (6)C2i—C1—H1A109.5
N1—Ni1—N1i173.67 (9)N1—C1—H1B109.5
O4—C10—O3126.15 (19)C2i—C1—H1B109.5
O4—C10—C10ii120.8 (3)H1A—C1—H1B108.1
O3—C10—C10ii113.0 (3)N1—C6—C8110.86 (18)
C9—O1—Ni1113.59 (12)N1—C6—C7107.34 (15)
C1—N1—C6114.16 (15)C8—C6—C7107.94 (18)
C1—N1—Ni1105.25 (12)N1—C6—C5109.95 (17)
C6—N1—Ni1120.54 (13)C8—C6—C5109.69 (18)
C1—N1—H1C105.2C7—C6—C5111.02 (19)
C6—N1—H1C105.2C3—C4—H4A109.5
Ni1—N1—H1C105.2C3—C4—H4B109.5
N2—C3—C5112.0 (2)H4A—C4—H4B109.5
N2—C3—C4111.46 (19)C3—C4—H4C109.5
C5—C3—C4109.2 (2)H4A—C4—H4C109.5
N2—C3—H3108.0H4B—C4—H4C109.5
C5—C3—H3108.0C6—C8—H8A109.5
C4—C3—H3108.0C6—C8—H8B109.5
C3—C5—C6119.2 (2)H8A—C8—H8B109.5
C3—C5—H5A107.5C6—C8—H8C109.5
C6—C5—H5A107.5H8A—C8—H8C109.5
C3—C5—H5B107.5H8B—C8—H8C109.5
C6—C5—H5B107.5C6—C7—H7A109.5
H5A—C5—H5B107.0C6—C7—H7B109.5
C2—N2—C3112.13 (17)H7A—C7—H7B109.5
C2—N2—Ni1103.84 (12)C6—C7—H7C109.5
C3—N2—Ni1117.82 (13)H7A—C7—H7C109.5
C2—N2—H2C107.5H7B—C7—H7C109.5
C3—N2—H2C107.5
N2—Ni1—O1—C9−177.81 (13)O1—Ni1—N2—C2−60.63 (12)
N2i—Ni1—O1—C931.2 (3)N1—Ni1—N2—C2−162.53 (13)
O1i—Ni1—O1—C9−5.92 (10)N1i—Ni1—N2—C222.36 (12)
N1—Ni1—O1—C9−86.19 (13)N2i—Ni1—N2—C3−122.59 (18)
N1i—Ni1—O1—C997.78 (13)O1i—Ni1—N2—C327.8 (4)
N2—Ni1—N1—C1−94.43 (13)O1—Ni1—N2—C364.03 (16)
N2i—Ni1—N1—C16.46 (13)N1—Ni1—N2—C3−37.87 (16)
O1i—Ni1—N1—C197.97 (13)N1i—Ni1—N2—C3147.02 (16)
O1—Ni1—N1—C1174.42 (12)C3—N2—C2—C1i−176.24 (19)
N1i—Ni1—N1—C1−44.13 (12)Ni1—N2—C2—C1i−48.0 (2)
N2—Ni1—N1—C636.38 (14)Ni1—O1—C9—O2−163.44 (16)
N2i—Ni1—N1—C6137.26 (14)Ni1—O1—C9—C9i14.9 (2)
O1i—Ni1—N1—C6−131.22 (14)C6—N1—C1—C2i−169.19 (19)
O1—Ni1—N1—C6−54.78 (14)Ni1—N1—C1—C2i−34.8 (2)
N1i—Ni1—N1—C686.67 (13)C1—N1—C6—C8−45.1 (2)
N2—C3—C5—C6−70.9 (3)Ni1—N1—C6—C8−171.97 (14)
C4—C3—C5—C6165.16 (19)C1—N1—C6—C7−162.80 (18)
C5—C3—N2—C2177.2 (2)Ni1—N1—C6—C770.36 (19)
C4—C3—N2—C2−60.2 (2)C1—N1—C6—C576.3 (2)
C5—C3—N2—Ni156.7 (2)Ni1—N1—C6—C5−50.5 (2)
C4—C3—N2—Ni1179.33 (16)C3—C5—C6—N166.3 (3)
N2i—Ni1—N2—C2112.75 (13)C3—C5—C6—C8−171.6 (2)
O1i—Ni1—N2—C2−96.8 (3)C3—C5—C6—C7−52.4 (3)
Symmetry codes: (i) −x+2, −y, z; (ii) −x+1, −y+2, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1C···O4iii0.932.173.075 (2)164
N2—H2C···O2iv0.932.132.987 (2)152
O3—H3A···O2v0.841.702.532 (2)170
Symmetry codes: (iii) x, y−1, z; (iv) x, y, z+1; (v) −x+2, −y+1, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1C···O4i0.932.173.075 (2)164
N2—H2C···O2ii0.932.132.987 (2)152
O3—H3A···O2iii0.841.702.532 (2)170
Symmetry codes: (i) x, y−1, z; (ii) x, y, z+1; (iii) −x+2, −y+1, z.
Acknowledgements top

This work was supported financially by the Foundation for University Key Teachers by the Education Department of Hunan Province and the Key Subject Construction Project of Hunan Province (No. 2006–180).

references
References top

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Tait, A. M. & Busch, D. H. (1976). Inorg. Synth. 18, 4–7.

Tang, J. K., Gao, E. Q., Zhang, L., Liao, D. Z., Jiang, Z. H. & Yan, S. P. (2002). J. Coord. Chem. 55, 527–535.