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Acta Cryst. (2009). E65, m1479    [ doi:10.1107/S1600536809044419 ]

Bis{(1-methylimidazol-2-ylmethyl)[2-(2-pyridyl)ethyl]amine-[kappa]3N,N',N''}zinc(II) bis(hexafluoridophosphate)

A.-Z. Wu and S. W. Ng

Abstract top

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 top

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).

Experimental top

(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 top

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.

Computing details top

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

Figures top
[Figure 1] 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.
Bis{(1-methylimidazol-2-ylmethyl)[2-(2-pyridyl)ethyl]amine- κ3N,N',N''}zinc(II) bis(hexafluoridophosphate) top
Crystal data top
[Zn(C12H16N4)2](PF6)2F(000) = 1600
Mr = 787.89Dx = 1.636 Mg m−3
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 mm−1
c = 20.3359 (6) ÅT = 100 K
V = 3199.0 (2) Å3Block, colorless
Z = 40.40 × 0.38 × 0.35 mm
Data collection top
Bruker APEXII
diffractometer		3655 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 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)] = 0.052Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.147H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 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 Å−3
1 restraintΔρmin = −0.71 e Å−3
Crystal data top
[Zn(C12H16N4)2](PF6)2V = 3199.0 (2) Å3
Mr = 787.89Z = 4
Orthorhombic, PbcaMo Kα radiation
a = 13.3147 (5) ŵ = 0.97 mm−1
b = 11.8147 (4) ÅT = 100 K
c = 20.3359 (6) Å0.40 × 0.38 × 0.35 mm
Data collection top
Bruker APEXII
diffractometer		2740 reflections with I > 2σ(I)
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		Rint = 0.048
Tmin = 0.698, Tmax = 0.728θmax = 27.5°
18287 measured reflectionsStandard reflections: 0
3655 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.052H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.147Δρmax = 1.49 e Å−3
S = 1.04Δρmin = −0.71 e Å−3
3655 reflectionsAbsolute structure: ?
219 parametersFlack parameter: ?
1 restraintRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
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) top
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, °) top
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, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···F10.88 (1)2.21 (1)3.083 (4)179 (3)
Table 1
Selected geometric parameters (Å) top
Zn1—N12.188 (3)Zn1—N42.298 (3)
Zn1—N22.095 (3)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···F10.88 (1)2.21 (1)3.083 (4)179 (3)
Acknowledgements top

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

references
References top

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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Westrip, S. P. (2009). publCIF. In preparation.