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Acta Cryst. (2009). E65, m537    [ doi:10.1107/S1600536809013877 ]

catena-Poly[[dichloridozinc(II)]-[mu]-1,4-bis(3-pyridylmethyl)piperazine]

A. M. Hardy and R. L. LaDuca

Abstract top

In the title compound, [ZnCl2(C16H20N4)]n, tetrahedrally coordinated divalent Zn atoms are ligated by two Cl atoms and two N-donor atoms from two 1,4-bis(3-pyridylmethyl)piperazine (3-bpmp) ligands. The tethering 3-bpmp ligands promote the formation of [ZnCl2(3-bpmp)]n chains situated parallel to (\overline{1}02). These chains aggregate via C-H...Cl interactions to form supramolecular layers, which in turn stack to construct the three-dimensional crystal structure.

Comment top

In comparison to coordination polymers based on the rigid rod tether 4,4'- bipyridine, extended solids based on the hydrogen-bonding capable bis(3-pyridylmethyl)piperazine (3-bpmp) ligand are much less common (Johnston et al., 2008). The title compound was obtained during an attempt to prepare a zinc azide 3-bpmp coordination polymer.

The asymmetric unit of the title compound consists of a divalent Zn atom, two Cl atoms, and two halves of two crystallographically distinct 3-bpmp molecules. The coordination environment at Zn is a slightly distorted {ZnCl2N2} tetrahedron, with two chloro ligands and two N donor atoms from crystallographically distinct bis(3-pyridylmethyl)piperazine (3-bpmp) ligands (Figure 1).

Neighboring Zn atoms are bridged by tethering 3-bpmp ligands to construct neutral [ZnCl2(3-bpmp)]n coordination polymer chains, that are oriented parallel to the (1 0 2) crystal direction. There are crystallographic inversion centres at the centroids of the piperazinyl rings within the 3-bpmp ligands. The through-ligand Zn···Zn distances within the chain motifs are 14.218 (4) and 14.259 (4) Å. These chains aggregate by C—H···Cl interactions to construct a supramolecular layer that is oriented parallel to the ac crystal planes (Figure 2). In turn these layer motifs stack by means of crystal packing forces to establish the three-dimensional crystal structure of the title compound (Figure 3).

Related literature top

The structure is a non-merohedral twin; for the generation of reflection data from the major twin component, see: Sheldrick (2007). For 1,4-bis(3-pyridylmethyl)piperazine coordination polymers of copper arylcarboxylates, see: Johnston et al. (2008). For the synthesis of the ligand, see: Pocic et al. (2005).

Experimental top

Zinc chloride dihydrate and sodium azide were obtained commercially. Bis(3-pyridylmethyl)piperazine (3-bpmp) was prepared via a published procedure (Pocic et al., 2005). Zinc chloride dihydrate (0.082 g, 0.48 mmol) was dissolved in 6 ml water in a glass vial. A 2 ml aliquot of tetrahydrofuran was carefully layered on the top of the zinc chloride solution. Above the tetrahydrofuran layer was gently placed a mixture of sodium azide (0.065 g, 1.0 mmol) and 3-bpmp (134 mg, 0.500 mmol) taken up in 5.5 ml of a 10:1 methanol:water mixture. Colourless blocks of the title compound deposited after standing at 25 °C for one week.

Refinement top

All H atoms bound to C atoms were placed in calculated positions, with C—H = 0.95 Å and refined in riding mode with Uiso = 1.2Ueq(C).

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Crystal Maker (Palmer, 2007); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The asymmetric unit of the title compound, showing 50% probability ellipsoids and atom numbering scheme. Hydrogen atom positions are shown as sticks. Colour codes: gray Zn, green Cl, blue N, black C.
[Figure 2] Fig. 2. A layer of [ZnCl2(3-bpmp)]n chains in the title compound. C—H···Cl interactions are shown as dashed lines.
[Figure 3] Fig. 3. Stacking of layer motifs in the title compound.
catena-Poly[[dichloridozinc(II)]-µ-1,4-bis(3-pyridylmethyl)piperazine] top
Crystal data top
[ZnCl2(C16H20N4)]F(000) = 832
Mr = 404.63Dx = 1.461 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 6035 reflections
a = 11.4474 (4) Åθ = 2.3–32.2°
b = 13.0007 (4) ŵ = 1.63 mm−1
c = 12.4234 (4) ÅT = 173 K
β = 95.909 (2)°Block, colourless
V = 1839.08 (10) Å30.38 × 0.21 × 0.13 mm
Z = 4
Data collection top
Bruker APEXII CCD area-detector
diffractometer		6035 independent reflections
Radiation source: fine-focus sealed tube3366 reflections with I > 2σ(I)
graphiteRint = 0.059
ω–ψ scansθmax = 32.2°, θmin = 2.3°
Absorption correction: multi-scan
(TWINABS; Sheldrick, 2007)		h = −17→16
Tmin = 0.568, Tmax = 0.813k = 0→19
21222 measured reflectionsl = 0→17
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)] = 0.047Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.132H-atom parameters constrained
S = 1.10 w = 1/[σ2(Fo2) + (0.0539P)2 + 0.1746P]
where P = (Fo2 + 2Fc2)/3
6035 reflections(Δ/σ)max < 0.001
208 parametersΔρmax = 0.58 e Å−3
0 restraintsΔρmin = −0.60 e Å−3
Crystal data top
[ZnCl2(C16H20N4)]V = 1839.08 (10) Å3
Mr = 404.63Z = 4
Monoclinic, P21/nMo Kα radiation
a = 11.4474 (4) ŵ = 1.63 mm−1
b = 13.0007 (4) ÅT = 173 K
c = 12.4234 (4) Å0.38 × 0.21 × 0.13 mm
β = 95.909 (2)°
Data collection top
Bruker APEXII CCD area-detector
diffractometer		6035 independent reflections
Absorption correction: multi-scan
(TWINABS; Sheldrick, 2007)		3366 reflections with I > 2σ(I)
Tmin = 0.568, Tmax = 0.813Rint = 0.059
21222 measured reflectionsθmax = 32.2°
Refinement top
R[F2 > 2σ(F2)] = 0.047H-atom parameters constrained
wR(F2) = 0.132Δρmax = 0.58 e Å−3
S = 1.10Δρmin = −0.60 e Å−3
6035 reflectionsAbsolute structure: ?
208 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Experimental. Reflection data were collected on a non-merohedrally twinned crystal. The twin law was determined with CELLNOW (Sheldrick, 2003). The structure was solved and refined using reflections from only the major twin component, whose reflection file was generated using TWINABS (Sheldrick, 2007). Composite reflections belonging to both twin domains were omitted from the reflection list, causing the loss of 246 reflections from the major twin component data. The data set was still 99.9% complete to 2θ of 50°.

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
Zn10.25226 (2)0.03824 (2)0.00021 (2)0.02591 (10)
Cl10.41393 (5)0.13442 (5)0.00653 (5)0.03268 (16)
Cl20.08858 (5)0.13279 (5)−0.00242 (5)0.03181 (16)
N10.25698 (18)−0.06042 (15)−0.12735 (16)0.0271 (4)
N20.48104 (17)−0.04111 (15)−0.39476 (16)0.0268 (5)
N30.24771 (17)−0.05999 (15)0.12836 (16)0.0261 (4)
N40.04009 (17)−0.07296 (15)0.42481 (16)0.0252 (4)
C10.3501 (2)−0.05974 (18)−0.18528 (19)0.0266 (5)
H10.4074−0.0074−0.17060.032*
C20.3670 (2)−0.13096 (18)−0.26506 (19)0.0262 (5)
C30.2813 (2)−0.2056 (2)−0.2866 (2)0.0344 (6)
H30.2886−0.2556−0.34130.041*
C40.1844 (2)−0.2069 (2)−0.2272 (2)0.0401 (7)
H40.1249−0.2575−0.24130.048*
C50.1758 (2)−0.13440 (19)−0.1481 (2)0.0331 (6)
H50.1104−0.1366−0.10680.040*
C60.4782 (2)−0.12722 (18)−0.31972 (19)0.0284 (5)
H6A0.5461−0.1218−0.26380.034*
H6B0.4863−0.1923−0.35970.034*
C70.3966 (2)−0.05658 (19)−0.49056 (19)0.0293 (6)
H7A0.3164−0.0624−0.46800.035*
H7B0.4149−0.1215−0.52680.035*
C80.5991 (2)−0.03190 (19)−0.4310 (2)0.0292 (6)
H8A0.6196−0.0966−0.46660.035*
H8B0.6575−0.0205−0.36770.035*
C110.1506 (2)−0.06356 (18)0.18122 (18)0.0252 (5)
H110.0869−0.01930.15810.030*
C120.1394 (2)−0.12847 (17)0.26723 (19)0.0242 (5)
C130.2323 (2)−0.19399 (18)0.3005 (2)0.0284 (5)
H130.2279−0.23910.36010.034*
C140.3317 (2)−0.1922 (2)0.2450 (2)0.0337 (6)
H140.3956−0.23710.26540.040*
C150.3364 (2)−0.12444 (19)0.1598 (2)0.0311 (6)
H150.4047−0.12340.12230.037*
C160.0267 (2)−0.12896 (19)0.32236 (19)0.0271 (5)
H16A−0.0371−0.09720.27360.032*
H16B0.0040−0.20090.33580.032*
C17−0.0598 (2)−0.09447 (19)0.4855 (2)0.0301 (6)
H17A−0.0649−0.16940.49830.036*
H17B−0.1332−0.07260.44250.036*
C180.0478 (2)0.03892 (18)0.4078 (2)0.0309 (6)
H18A−0.02370.06310.36340.037*
H18B0.11640.05450.36820.037*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.02662 (16)0.03010 (17)0.02220 (16)−0.00085 (13)0.00820 (11)0.00006 (13)
Cl10.0279 (3)0.0348 (3)0.0370 (4)−0.0033 (2)0.0115 (3)−0.0063 (3)
Cl20.0271 (3)0.0334 (3)0.0361 (4)0.0018 (2)0.0088 (3)0.0044 (3)
N10.0284 (11)0.0316 (11)0.0219 (10)0.0012 (9)0.0055 (8)−0.0017 (9)
N20.0242 (10)0.0342 (12)0.0226 (11)0.0022 (8)0.0049 (8)0.0021 (9)
N30.0262 (10)0.0323 (11)0.0206 (10)0.0014 (8)0.0062 (8)−0.0006 (9)
N40.0259 (10)0.0263 (10)0.0252 (11)−0.0019 (8)0.0112 (8)0.0008 (9)
C10.0290 (12)0.0280 (13)0.0232 (13)−0.0012 (10)0.0048 (10)0.0008 (10)
C20.0261 (12)0.0305 (13)0.0225 (13)0.0047 (10)0.0046 (10)0.0014 (10)
C30.0325 (14)0.0361 (15)0.0352 (15)0.0007 (11)0.0067 (12)−0.0090 (12)
C40.0343 (15)0.0385 (16)0.0487 (18)−0.0093 (12)0.0100 (13)−0.0132 (14)
C50.0253 (13)0.0404 (15)0.0348 (15)−0.0037 (11)0.0093 (11)−0.0030 (12)
C60.0302 (13)0.0336 (14)0.0219 (13)0.0029 (10)0.0059 (10)0.0014 (11)
C70.0255 (12)0.0366 (14)0.0254 (13)−0.0027 (10)0.0006 (10)−0.0002 (11)
C80.0247 (12)0.0383 (15)0.0247 (13)0.0002 (10)0.0026 (10)0.0016 (11)
C110.0236 (12)0.0328 (13)0.0196 (12)0.0001 (10)0.0045 (9)−0.0017 (10)
C120.0257 (12)0.0272 (12)0.0205 (12)−0.0013 (10)0.0059 (10)−0.0042 (10)
C130.0293 (13)0.0315 (13)0.0247 (13)−0.0008 (10)0.0048 (10)0.0023 (11)
C140.0270 (13)0.0382 (15)0.0361 (15)0.0078 (11)0.0039 (11)0.0042 (12)
C150.0258 (13)0.0391 (15)0.0301 (14)0.0008 (11)0.0117 (11)−0.0005 (12)
C160.0243 (12)0.0335 (14)0.0247 (13)−0.0057 (10)0.0093 (10)−0.0017 (11)
C170.0339 (13)0.0275 (13)0.0314 (14)−0.0038 (10)0.0158 (11)−0.0007 (11)
C180.0367 (14)0.0285 (14)0.0299 (14)−0.0033 (11)0.0146 (11)0.0032 (11)
Geometric parameters (Å, °) top
Zn1—N12.044 (2)C6—H6B0.9900
Zn1—N32.046 (2)C7—C8i1.511 (3)
Zn1—Cl12.2282 (6)C7—H7A0.9900
Zn1—Cl22.2383 (6)C7—H7B0.9900
N1—C51.344 (3)C8—C7i1.511 (3)
N1—C11.346 (3)C8—H8A0.9900
N2—C61.459 (3)C8—H8B0.9900
N2—C71.468 (3)C11—C121.378 (3)
N2—C81.473 (3)C11—H110.9500
N3—C151.343 (3)C12—C131.392 (3)
N3—C111.349 (3)C12—C161.522 (3)
N4—C171.460 (3)C13—C141.389 (3)
N4—C161.461 (3)C13—H130.9500
N4—C181.474 (3)C14—C151.382 (3)
C1—C21.384 (3)C14—H140.9500
C1—H10.9500C15—H150.9500
C2—C31.386 (3)C16—H16A0.9900
C2—C61.505 (3)C16—H16B0.9900
C3—C41.394 (4)C17—C18ii1.503 (3)
C3—H30.9500C17—H17A0.9900
C4—C51.372 (4)C17—H17B0.9900
C4—H40.9500C18—C17ii1.503 (3)
C5—H50.9500C18—H18A0.9900
C6—H6A0.9900C18—H18B0.9900
N1—Zn1—N3102.50 (8)N2—C7—H7B109.5
N1—Zn1—Cl1106.94 (6)C8i—C7—H7B109.5
N3—Zn1—Cl1114.23 (6)H7A—C7—H7B108.1
N1—Zn1—Cl2114.98 (6)N2—C8—C7i110.5 (2)
N3—Zn1—Cl2105.42 (6)N2—C8—H8A109.5
Cl1—Zn1—Cl2112.54 (2)C7i—C8—H8A109.5
C5—N1—C1118.2 (2)N2—C8—H8B109.5
C5—N1—Zn1121.65 (17)C7i—C8—H8B109.5
C1—N1—Zn1119.74 (16)H8A—C8—H8B108.1
C6—N2—C7110.91 (19)N3—C11—C12123.1 (2)
C6—N2—C8109.81 (19)N3—C11—H11118.5
C7—N2—C8108.15 (19)C12—C11—H11118.5
C15—N3—C11118.2 (2)C11—C12—C13118.4 (2)
C15—N3—Zn1122.47 (17)C11—C12—C16120.1 (2)
C11—N3—Zn1119.25 (16)C13—C12—C16121.4 (2)
C17—N4—C16109.71 (18)C14—C13—C12118.8 (2)
C17—N4—C18108.93 (18)C14—C13—H13120.6
C16—N4—C18111.69 (19)C12—C13—H13120.6
N1—C1—C2123.7 (2)C15—C14—C13119.3 (2)
N1—C1—H1118.1C15—C14—H14120.4
C2—C1—H1118.1C13—C14—H14120.4
C1—C2—C3117.3 (2)N3—C15—C14122.1 (2)
C1—C2—C6119.2 (2)N3—C15—H15118.9
C3—C2—C6123.4 (2)C14—C15—H15118.9
C2—C3—C4119.5 (2)N4—C16—C12111.88 (19)
C2—C3—H3120.3N4—C16—H16A109.2
C4—C3—H3120.3C12—C16—H16A109.2
C5—C4—C3119.4 (3)N4—C16—H16B109.2
C5—C4—H4120.3C12—C16—H16B109.2
C3—C4—H4120.3H16A—C16—H16B107.9
N1—C5—C4122.0 (2)N4—C17—C18ii111.0 (2)
N1—C5—H5119.0N4—C17—H17A109.4
C4—C5—H5119.0C18ii—C17—H17A109.4
N2—C6—C2112.85 (19)N4—C17—H17B109.4
N2—C6—H6A109.0C18ii—C17—H17B109.4
C2—C6—H6A109.0H17A—C17—H17B108.0
N2—C6—H6B109.0N4—C18—C17ii110.45 (19)
C2—C6—H6B109.0N4—C18—H18A109.6
H6A—C6—H6B107.8C17ii—C18—H18A109.6
N2—C7—C8i110.8 (2)N4—C18—H18B109.6
N2—C7—H7A109.5C17ii—C18—H18B109.6
C8i—C7—H7A109.5H18A—C18—H18B108.1
N3—Zn1—N1—C554.4 (2)C1—C2—C6—N2−73.3 (3)
Cl1—Zn1—N1—C5174.89 (18)C3—C2—C6—N2109.9 (3)
Cl2—Zn1—N1—C5−59.4 (2)C6—N2—C7—C8i−179.14 (19)
N3—Zn1—N1—C1−117.99 (18)C8—N2—C7—C8i−58.7 (3)
Cl1—Zn1—N1—C12.48 (19)C6—N2—C8—C7i179.64 (19)
Cl2—Zn1—N1—C1128.20 (16)C7—N2—C8—C7i58.5 (3)
N1—Zn1—N3—C1563.97 (19)C15—N3—C11—C121.5 (3)
Cl1—Zn1—N3—C15−51.3 (2)Zn1—N3—C11—C12179.02 (17)
Cl2—Zn1—N3—C15−175.38 (18)N3—C11—C12—C13−0.6 (4)
N1—Zn1—N3—C11−113.45 (18)N3—C11—C12—C16−179.5 (2)
Cl1—Zn1—N3—C11131.27 (16)C11—C12—C13—C14−0.8 (3)
Cl2—Zn1—N3—C117.20 (18)C16—C12—C13—C14178.1 (2)
C5—N1—C1—C20.0 (4)C12—C13—C14—C151.1 (4)
Zn1—N1—C1—C2172.65 (18)C11—N3—C15—C14−1.1 (4)
N1—C1—C2—C31.1 (4)Zn1—N3—C15—C14−178.54 (19)
N1—C1—C2—C6−176.0 (2)C13—C14—C15—N3−0.2 (4)
C1—C2—C3—C4−0.9 (4)C17—N4—C16—C12−167.5 (2)
C6—C2—C3—C4176.0 (2)C18—N4—C16—C1271.6 (3)
C2—C3—C4—C5−0.3 (4)C11—C12—C16—N4−102.5 (2)
C1—N1—C5—C4−1.2 (4)C13—C12—C16—N478.6 (3)
Zn1—N1—C5—C4−173.8 (2)C16—N4—C17—C18ii179.2 (2)
C3—C4—C5—N11.4 (4)C18—N4—C17—C18ii−58.2 (3)
C7—N2—C6—C2−70.0 (3)C17—N4—C18—C17ii57.9 (3)
C8—N2—C6—C2170.5 (2)C16—N4—C18—C17ii179.2 (2)
Symmetry codes: (i) −x+1, −y, −z−1; (ii) −x, −y, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C5—H5···Cl2iii0.952.773.718 (2)176
C15—H15···Cl1iv0.952.753.698 (2)173
Symmetry codes: (iii) −x, −y, −z; (iv) −x+1, −y, −z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C5—H5···Cl2i0.952.773.718 (2)176
C15—H15···Cl1ii0.952.753.698 (2)173
Symmetry codes: (i) −x, −y, −z; (ii) −x+1, −y, −z.
Acknowledgements top

We gratefully acknowledge the American Chemical Society Petroleum Research Fund for funding this work.

references
References top

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