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Acta Crystallogr Sect E Struct Rep Online. 2009 November 1; 65(Pt 11): m1479.
Published online 2009 October 31. doi:  10.1107/S1600536809044419
PMCID: PMC2971120

Bis{(1-methyl­imidazol-2-ylmeth­yl)[2-(2-pyridyl)eth­yl]amine-κ3 N,N′,N′′}zinc(II) bis­(hexa­fluoridophosphate)

Abstract

Two tridentate N-heterocyclic ligands chelate the ZnII atom in the title compound, [Zn(C12H16N4)2](PF6)2, conferring a fac-octa­hedral geometry. The ZnII atom lies on a center of inversion. The cation is linked to the anion by an N—H(...)F hydrogen bond.

Related literature

No crystal structure studies of metal complexes with the N-heterocyclic ligand have been reported. For the synthesis of the ligand, see: Greatti et al. (2008 [triangle]).

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Object name is e-65-m1479-scheme1.jpg

Experimental

Crystal data

  • [Zn(C12H16N4)2](PF6)2
  • M r = 787.89
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-m1479-efi1.jpg
  • a = 13.3147 (5) Å
  • b = 11.8147 (4) Å
  • c = 20.3359 (6) Å
  • V = 3199.0 (2) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.97 mm−1
  • T = 100 K
  • 0.40 × 0.38 × 0.35 mm

Data collection

  • Bruker APEXII diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.698, T max = 0.728
  • 18287 measured reflections
  • 3655 independent reflections
  • 2740 reflections with I > 2σ(I)
  • R int = 0.048

Refinement

  • R[F 2 > 2σ(F 2)] = 0.052
  • wR(F 2) = 0.147
  • S = 1.04
  • 3655 reflections
  • 219 parameters
  • 1 restraint
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 1.49 e Å−3
  • Δρmin = −0.71 e Å−3

Data collection: APEX2 (Bruker, 2005 [triangle]); cell refinement: SAINT (Bruker, 2005 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: X-SEED (Barbour, 2001 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2009 [triangle]).

Table 1
Selected bond lengths (Å)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809044419/xu2647sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809044419/xu2647Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

We thank Guangzhou University of Chinese Medicine and the University of Malaya for supporting this study.

supplementary crystallographic information

Experimental

(1-Methylimidazol-2-ylmethyl)(pyridin-2-ylethyl)amine was synthesized according to a literature method (Greatti et al., 2008).

The ligand (1 mmol, 0.26 g) dissolved in methanol (5 ml) was reacted with zinc hexafluorophosphat (1 mmol, 0.36 g) dissolved in water (5 ml). The mixture was filtered and the solution set aside for the growth of colorless block-shaped crystals that formed after several days in 60% yield. CH&N elemental analysis. Found: C 36.24, H 4.07, N 13.36%; calculated: C 36.55, H 4.06, N 14.22%.

Refinement

Carbon-bound H-atoms were placed in calculated positions (C—H 0.95 to 0.99 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2 to 1.5U(C).

The imino H-atom was located in a difference Fourier map, and was refined with a distance restraint of N–H 0.88±0.01 Å; its temperature factor was freely refined.

The final difference Fourier map had a peak in the vicinity of Zn1 but was otherwise featureless.

Figures

Fig. 1.
Thermal ellipsoid plot (Barbour, 2001) of [Zn(C12H16N4)2] 2[PF6] at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

Crystal data

[Zn(C12H16N4)2](PF6)2F(000) = 1600
Mr = 787.89Dx = 1.636 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 4790 reflections
a = 13.3147 (5) Åθ = 2.5–28.2°
b = 11.8147 (4) ŵ = 0.97 mm1
c = 20.3359 (6) ÅT = 100 K
V = 3199.0 (2) Å3Block, colorless
Z = 40.40 × 0.38 × 0.35 mm

Data collection

Bruker APEXII diffractometer3655 independent reflections
Radiation source: fine-focus sealed tube2740 reflections with I > 2σ(I)
graphiteRint = 0.048
ω scansθmax = 27.5°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −10→17
Tmin = 0.698, Tmax = 0.728k = −13→15
18287 measured reflectionsl = −22→26

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.052Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.147H atoms treated by a mixture of independent and constrained refinement
S = 1.04w = 1/[σ2(Fo2) + (0.0755P)2 + 5.7073P] where P = (Fo2 + 2Fc2)/3
3655 reflections(Δ/σ)max = 0.001
219 parametersΔρmax = 1.49 e Å3
1 restraintΔρmin = −0.71 e Å3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Zn10.50000.50000.50000.02098 (16)
P10.38657 (6)0.83958 (7)0.68434 (4)0.0251 (2)
F10.47058 (17)0.7507 (2)0.66130 (14)0.0524 (7)
F20.47025 (19)0.9039 (2)0.72513 (13)0.0563 (7)
F30.30477 (18)0.9306 (2)0.70513 (12)0.0540 (7)
F40.30581 (18)0.7775 (2)0.63902 (15)0.0586 (7)
F50.3608 (2)0.7641 (3)0.74431 (16)0.0840 (11)
F60.4135 (2)0.9157 (2)0.62167 (13)0.0588 (7)
N10.40722 (19)0.5353 (2)0.58640 (13)0.0231 (6)
H10.424 (3)0.5969 (18)0.6075 (15)0.027 (9)*
N20.48361 (19)0.3368 (2)0.53888 (14)0.0248 (6)
N30.4460 (2)0.2326 (2)0.62505 (14)0.0282 (6)
N40.3548 (2)0.4794 (2)0.44007 (14)0.0267 (6)
C10.4281 (3)0.4463 (3)0.63589 (16)0.0274 (7)
H1A0.36900.43580.66480.033*
H1B0.48610.46850.66350.033*
C20.4510 (2)0.3384 (3)0.60004 (16)0.0243 (7)
C30.4784 (3)0.1600 (3)0.57608 (19)0.0326 (8)
H30.48380.08000.57900.039*
C40.5009 (2)0.2245 (3)0.5236 (2)0.0294 (7)
H40.52480.19720.48250.035*
C50.4136 (3)0.1995 (3)0.69075 (18)0.0372 (9)
H5A0.39150.26670.71500.056*
H5B0.46970.16380.71410.056*
H5C0.35780.14570.68740.056*
C60.2980 (2)0.5415 (3)0.57167 (17)0.0254 (7)
H6A0.26210.57150.61060.031*
H6B0.27240.46430.56290.031*
C70.2758 (2)0.6170 (3)0.51236 (17)0.0292 (7)
H7A0.20920.65290.51810.035*
H7B0.32670.67780.50990.035*
C80.2766 (2)0.5506 (3)0.44925 (17)0.0277 (7)
C90.1977 (3)0.5560 (4)0.40485 (19)0.0391 (9)
H90.14480.60870.41160.047*
C100.1957 (3)0.4854 (4)0.3511 (2)0.0498 (11)
H100.14250.48950.32010.060*
C110.2727 (3)0.4086 (4)0.34328 (19)0.0449 (10)
H110.27240.35640.30780.054*
C120.3505 (3)0.4095 (3)0.38849 (17)0.0330 (8)
H120.40400.35730.38250.040*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Zn10.0169 (3)0.0213 (3)0.0247 (3)−0.00221 (18)0.00329 (19)0.00056 (19)
P10.0221 (4)0.0233 (4)0.0299 (5)0.0017 (3)−0.0017 (3)−0.0007 (3)
F10.0394 (12)0.0431 (13)0.0747 (18)0.0150 (11)−0.0061 (12)−0.0213 (12)
F20.0428 (13)0.0550 (15)0.0710 (18)0.0110 (12)−0.0256 (12)−0.0275 (13)
F30.0449 (13)0.0636 (16)0.0534 (15)0.0283 (12)−0.0118 (11)−0.0196 (12)
F40.0410 (13)0.0396 (13)0.095 (2)−0.0040 (10)−0.0220 (13)−0.0184 (13)
F50.0588 (18)0.106 (3)0.087 (2)0.0105 (17)0.0142 (15)0.069 (2)
F60.0594 (16)0.0596 (16)0.0573 (17)−0.0066 (13)−0.0012 (13)0.0243 (13)
N10.0209 (12)0.0230 (12)0.0253 (15)−0.0035 (10)0.0010 (10)−0.0006 (11)
N20.0218 (13)0.0216 (12)0.0309 (16)−0.0020 (10)0.0017 (11)0.0006 (11)
N30.0248 (13)0.0270 (14)0.0328 (16)−0.0074 (11)−0.0075 (11)0.0064 (12)
N40.0197 (13)0.0328 (14)0.0277 (15)−0.0047 (11)0.0012 (11)0.0005 (11)
C10.0271 (15)0.0277 (16)0.0273 (18)−0.0017 (13)0.0014 (13)0.0013 (13)
C20.0196 (14)0.0218 (15)0.0317 (18)−0.0034 (12)−0.0024 (12)0.0040 (13)
C30.0272 (16)0.0223 (15)0.048 (2)−0.0028 (13)−0.0097 (15)0.0008 (15)
C40.0221 (15)0.0250 (16)0.041 (2)−0.0027 (12)−0.0029 (14)−0.0050 (14)
C50.043 (2)0.0341 (18)0.035 (2)−0.0167 (16)−0.0106 (16)0.0121 (15)
C60.0171 (14)0.0282 (15)0.0310 (18)−0.0024 (12)0.0061 (12)−0.0010 (13)
C70.0164 (14)0.0285 (16)0.043 (2)0.0007 (12)0.0027 (13)0.0011 (14)
C80.0176 (14)0.0335 (17)0.0321 (19)−0.0035 (12)0.0036 (13)0.0048 (14)
C90.0227 (17)0.057 (2)0.037 (2)0.0016 (16)−0.0007 (15)0.0107 (18)
C100.0278 (19)0.087 (3)0.034 (2)−0.006 (2)−0.0050 (16)0.003 (2)
C110.0316 (19)0.076 (3)0.027 (2)−0.012 (2)0.0021 (15)−0.0128 (19)
C120.0235 (16)0.044 (2)0.031 (2)−0.0061 (15)0.0052 (13)−0.0049 (15)

Geometric parameters (Å, °)

Zn1—N12.188 (3)C1—H1A0.9900
Zn1—N1i2.188 (3)C1—H1B0.9900
Zn1—N2i2.095 (3)C3—C41.345 (5)
Zn1—N22.095 (3)C3—H30.9500
Zn1—N42.298 (3)C4—H40.9500
Zn1—N4i2.298 (3)C5—H5A0.9800
P1—F51.549 (3)C5—H5B0.9800
P1—F21.583 (2)C5—H5C0.9800
P1—F31.588 (2)C6—C71.529 (5)
P1—F41.595 (2)C6—H6A0.9900
P1—F61.601 (3)C6—H6B0.9900
P1—F11.605 (2)C7—C81.504 (5)
N1—C11.482 (4)C7—H7A0.9900
N1—C61.486 (4)C7—H7B0.9900
N1—H10.875 (10)C8—C91.386 (5)
N2—C21.317 (4)C9—C101.375 (6)
N2—C41.382 (4)C9—H90.9500
N3—C21.351 (4)C10—C111.378 (6)
N3—C31.383 (5)C10—H100.9500
N3—C51.457 (4)C11—C121.385 (5)
N4—C121.336 (4)C11—H110.9500
N4—C81.352 (4)C12—H120.9500
C1—C21.500 (4)
N2i—Zn1—N2180.00 (6)C2—C1—H1A110.1
N2i—Zn1—N1100.73 (10)N1—C1—H1B110.1
N2—Zn1—N179.27 (10)C2—C1—H1B110.1
N2i—Zn1—N1i79.27 (10)H1A—C1—H1B108.4
N2—Zn1—N1i100.73 (10)N2—C2—N3111.0 (3)
N1—Zn1—N1i180.0N2—C2—C1122.5 (3)
N2i—Zn1—N489.13 (10)N3—C2—C1126.4 (3)
N2—Zn1—N490.87 (10)C4—C3—N3106.8 (3)
N1—Zn1—N488.35 (10)C4—C3—H3126.6
N1i—Zn1—N491.65 (9)N3—C3—H3126.6
N2i—Zn1—N4i90.87 (10)C3—C4—N2109.2 (3)
N2—Zn1—N4i89.13 (10)C3—C4—H4125.4
N1—Zn1—N4i91.65 (9)N2—C4—H4125.4
N1i—Zn1—N4i88.35 (10)N3—C5—H5A109.5
N4—Zn1—N4i180.0N3—C5—H5B109.5
F5—P1—F291.12 (18)H5A—C5—H5B109.5
F5—P1—F391.64 (17)N3—C5—H5C109.5
F2—P1—F391.04 (13)H5A—C5—H5C109.5
F5—P1—F492.36 (18)H5B—C5—H5C109.5
F2—P1—F4176.28 (17)N1—C6—C7112.2 (2)
F3—P1—F490.16 (13)N1—C6—H6A109.2
F5—P1—F6179.05 (19)C7—C6—H6A109.2
F2—P1—F689.42 (16)N1—C6—H6B109.2
F3—P1—F689.12 (15)C7—C6—H6B109.2
F4—P1—F687.08 (15)H6A—C6—H6B107.9
F5—P1—F190.41 (17)C8—C7—C6111.6 (3)
F2—P1—F188.66 (13)C8—C7—H7A109.3
F3—P1—F1177.93 (16)C6—C7—H7A109.3
F4—P1—F190.02 (13)C8—C7—H7B109.3
F6—P1—F188.83 (15)C6—C7—H7B109.3
C1—N1—C6110.8 (2)H7A—C7—H7B108.0
C1—N1—Zn1107.68 (19)N4—C8—C9121.5 (3)
C6—N1—Zn1113.6 (2)N4—C8—C7116.6 (3)
C1—N1—H1102 (2)C9—C8—C7121.8 (3)
C6—N1—H1108 (2)C10—C9—C8120.3 (4)
Zn1—N1—H1114 (2)C10—C9—H9119.8
C2—N2—C4106.3 (3)C8—C9—H9119.8
C2—N2—Zn1112.2 (2)C9—C10—C11118.5 (4)
C4—N2—Zn1141.4 (2)C9—C10—H10120.8
C2—N3—C3106.7 (3)C11—C10—H10120.8
C2—N3—C5127.4 (3)C10—C11—C12118.3 (4)
C3—N3—C5125.9 (3)C10—C11—H11120.8
C12—N4—C8117.4 (3)C12—C11—H11120.8
C12—N4—Zn1121.2 (2)N4—C12—C11123.9 (4)
C8—N4—Zn1120.6 (2)N4—C12—H12118.0
N1—C1—C2108.1 (3)C11—C12—H12118.0
N1—C1—H1A110.1
N2i—Zn1—N1—C1−152.89 (19)Zn1—N2—C2—C10.5 (4)
N2—Zn1—N1—C127.11 (19)C3—N3—C2—N20.4 (4)
N4—Zn1—N1—C1118.3 (2)C5—N3—C2—N2−180.0 (3)
N4i—Zn1—N1—C1−61.7 (2)C3—N3—C2—C1−176.9 (3)
N2i—Zn1—N1—C684.0 (2)C5—N3—C2—C12.7 (5)
N2—Zn1—N1—C6−96.0 (2)N1—C1—C2—N223.2 (4)
N4—Zn1—N1—C6−4.8 (2)N1—C1—C2—N3−159.8 (3)
N4i—Zn1—N1—C6175.2 (2)C2—N3—C3—C4−0.4 (4)
N1—Zn1—N2—C2−15.5 (2)C5—N3—C3—C4179.9 (3)
N1i—Zn1—N2—C2164.5 (2)N3—C3—C4—N20.3 (4)
N4—Zn1—N2—C2−103.7 (2)C2—N2—C4—C3−0.1 (4)
N4i—Zn1—N2—C276.3 (2)Zn1—N2—C4—C3175.0 (3)
N1—Zn1—N2—C4169.6 (4)C1—N1—C6—C7−169.8 (3)
N1i—Zn1—N2—C4−10.4 (4)Zn1—N1—C6—C7−48.4 (3)
N4—Zn1—N2—C481.4 (4)N1—C6—C7—C890.1 (3)
N4i—Zn1—N2—C4−98.6 (4)C12—N4—C8—C9−3.8 (5)
N2i—Zn1—N4—C12109.5 (3)Zn1—N4—C8—C9165.9 (3)
N2—Zn1—N4—C12−70.5 (3)C12—N4—C8—C7171.8 (3)
N1—Zn1—N4—C12−149.8 (3)Zn1—N4—C8—C7−18.5 (4)
N1i—Zn1—N4—C1230.2 (3)C6—C7—C8—N4−47.0 (4)
N2i—Zn1—N4—C8−59.9 (2)C6—C7—C8—C9128.7 (3)
N2—Zn1—N4—C8120.1 (2)N4—C8—C9—C102.3 (6)
N1—Zn1—N4—C840.9 (2)C7—C8—C9—C10−173.1 (3)
N1i—Zn1—N4—C8−139.1 (2)C8—C9—C10—C111.0 (6)
C6—N1—C1—C292.0 (3)C9—C10—C11—C12−2.6 (6)
Zn1—N1—C1—C2−32.7 (3)C8—N4—C12—C112.2 (5)
C4—N2—C2—N3−0.2 (3)Zn1—N4—C12—C11−167.5 (3)
Zn1—N2—C2—N3−176.9 (2)C10—C11—C12—N41.1 (6)
C4—N2—C2—C1177.2 (3)

Symmetry codes: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···F10.88 (1)2.21 (1)3.083 (4)179 (3)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: XU2647).

References

  • Barbour, L. J. (2001). J. Supramol. Chem.1, 189–191.
  • Bruker (2005). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Greatti, A., Scarpellini, M., Peralta, R. A., Bortoluzi, A. J., Xavier, F. R., Szoganicz, B., Tomkowicz, Z., Rams, M., Haase, W. & Neves, A. (2008). Inorg. Chem.47, 1107–1119. [PubMed]
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Westrip, S. P. (2009). publCIF In preparation.

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