Buy article online - an online subscription or single-article purchase is required to access this article.
Download citation
Download citation
link to html
The title compound, [ZnCl2(bpp)]n (where bpp is 1,3-di-4-pyridyl­propane, C13H14N2), has been prepared by the hydro­thermal reaction of ZnCl2 and bpp at 433 K. The Zn, Cl and central propyl C atom lie on the mirrors of the P21/m space group. The molecular structure shows a weave-like polymeric chain. Each Zn atom is coordinated by two N atoms and two Cl atoms in a distorted tetrahedral geometry, with the Zn—N distance being 2.055 (5) Å and the Zn—Cl distances being 2.239 (3) and 2.247 (2) Å.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104003592/na1639sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270104003592/na1639Isup2.hkl
Contains datablock I

CCDC reference: 237912

Comment top

A large amount of investigation has involved linear pyridyl-donor ligands, including pyrazine (Real et al., 1991; Kitagawa et al., 1992; Carlucci et al., 1995), 4,4'-bipyridine (bipy; Blake et al., 1997; Yaghi & Li, 1996; Tong et al., 1998) and longer bridges (Fujita et al., 1995; Withersby et al., 1997). The commercially available compound bpp is a bipyridine-type ligand with a flexible CH2CH2CH2– spacer, and a number of metal-bpp coordination polymers have been reported (Pan et al., 2001; Fu et al., 2001; Carlucci et al., 2002). However, to our knowledge, only a few structures of Zn-bpp coordination polymers have been reported (Plater et al., 2000). Here, we report a new zinc(II) polymeric compound, [Zn(bpp)Cl2]n, (I), with a weave-like polymeric chain structure, obtained via hydrothermal synthesis. \sch

In the title compound, (I), each Zn atom is coordinated by two N atoms from two bpp ligands and two Cl atoms to form a distorted tetrahedral geometry, with the Zn—N distance being 2.055 (5) Å and the Zn—Cl distances being 2.239 (3) and 2.247 (2) Å. As the result of this coordination, the molecular structure shows a weave-like polymeric chain, as shown in Fig.1. The chains have a repeat length (`wavelength') of 12.937 Å, which is approximately one half of the value of 24.6 Å in [Ag(bpp)](CF3SO3)·EtOH and 23.98 Å in [Ag(bpp)](NO3) (Batten et al., 1999). This result is due to the different coordination mode [N1—Zn—N1' = 111.7 (3), N1—Zn1—Cl1 = 104.5 (1), N1—Zn1—Cl2 = 105.1 (1) and Cl1—Zn1—Cl2 = 126.0 (1)°] of the two-coordinate Ag+ ions (N—Ag—N = 180°) in [Ag(bpp)](NO3). In addition, this molecule-polymer transition is linked to the capacity of the bidentate ligand (bpp) to span two metal centres (Zn). The pyridine rings in the same bpp ligand are not coplanar] dihedral angle of two planes 66.66 (18)°].

Experimental top

A mixture of ZnCl2 (0.259 g, 1.9 mmol), bpp (0.255 g, 1.3 mmol), CH3CH2OH (3 ml) and H2O (13 ml) was sealed in a 25 ml Teflon-lined stainless-steel reactor, heated to 443 K for 60 h, and then slowly cooled to room temperature. Block-shaped colourless crystals of (I), suitable for X-ray analysis, were obtained by filtration (yield 41.8%). Analysis calculated for C13H14Cl2N2Zn (%): C 46.67, H 4.22, N 8.37; found: C 46.46, H 3.84, N 8.35. IR spectroscopic analysis (KBr disc, ν, cm−1): 1620 (s), 1433 (s), 1221 (m), 1072 (m), 1032 (s), 823 (s), 621 (m), 519 (s).

Refinement top

All H atoms were located theoretically and refined as riding atoms, with C—H distances in the range 0.93–0.97 Å and with Uiso(H) = 1.2Ueq(C). Is added text OK?

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SMART and SAINT (Siemens, 1996); data reduction: XPREP in SHELXTL (Siemens, 1996); program(s) used to solve structure: SHELXTL (Siemens, 1996); program(s) used to refine structure: SHELXTL (Siemens, 1996); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL (Bruker, 2001).

Figures top
[Figure 1] Fig. 1. A view of the repeat unit of (I). Displacement ellipsoids are plotted at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
catena-Poly[[dichloro-zinc(II)]-µ-1,3-di-4-pyridylpropane-κ2N:N'] top
Crystal data top
[ZnCl2(C13H14N2)]F(000) = 340
Mr = 334.53Dx = 1.563 Mg m3
Monoclinic, P21/mMo Kα radiation, λ = 0.71073 Å
a = 5.2254 (4) ÅCell parameters from 1292 reflections
b = 12.9371 (9) Åθ = 1.9–25.0°
c = 10.5425 (6) ŵ = 2.09 mm1
β = 94.247 (3)°T = 293 K
V = 710.73 (8) Å3Block, colourless
Z = 20.80 × 0.26 × 0.20 mm
Data collection top
CCD area detector
diffractometer
1311 independent reflections
Radiation source: fine-focus sealed tube1091 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.034
ϕ and ω scansθmax = 25.0°, θmin = 1.9°
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
h = 56
Tmin = 0.486, Tmax = 0.659k = 1515
2313 measured reflectionsl = 124
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)] = 0.060Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.153H-atom parameters constrained
S = 1.08 w = 1/[σ2(Fo2) + (0.0526P)2 + 3.0106P]
where P = (Fo2 + 2Fc2)/3
1311 reflections(Δ/σ)max < 0.001
88 parametersΔρmax = 0.64 e Å3
0 restraintsΔρmin = 0.48 e Å3
Crystal data top
[ZnCl2(C13H14N2)]V = 710.73 (8) Å3
Mr = 334.53Z = 2
Monoclinic, P21/mMo Kα radiation
a = 5.2254 (4) ŵ = 2.09 mm1
b = 12.9371 (9) ÅT = 293 K
c = 10.5425 (6) Å0.80 × 0.26 × 0.20 mm
β = 94.247 (3)°
Data collection top
CCD area detector
diffractometer
1311 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
1091 reflections with I > 2σ(I)
Tmin = 0.486, Tmax = 0.659Rint = 0.034
2313 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0600 restraints
wR(F2) = 0.153H-atom parameters constrained
S = 1.08Δρmax = 0.64 e Å3
1311 reflectionsΔρmin = 0.48 e Å3
88 parameters
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
Zn10.4591 (2)0.25000.72070 (9)0.0464 (4)
N10.2451 (9)0.3815 (4)0.7407 (5)0.0450 (12)
C10.2886 (12)0.4433 (5)0.8416 (6)0.0514 (15)
H1A0.42190.42680.90160.062*
C20.1447 (12)0.5299 (5)0.8605 (6)0.0525 (15)
H2A0.18290.57110.93160.063*
C30.0574 (11)0.5563 (4)0.7739 (6)0.0474 (14)
C40.1016 (12)0.4919 (5)0.6701 (6)0.0539 (16)
H4A0.23520.50580.60930.065*
C50.0522 (12)0.4074 (5)0.6573 (6)0.0544 (16)
H5A0.01990.36570.58610.065*
C60.2131 (12)0.6524 (4)0.7918 (6)0.0513 (15)
H6A0.26410.65440.87840.062*
H6B0.36770.64990.73500.062*
C70.0646 (17)0.75000.7657 (9)0.048 (2)
H7A0.02340.75000.67750.057*
H7B0.09560.75000.81840.057*
Cl10.7497 (5)0.25000.8888 (2)0.0557 (6)
Cl20.5460 (5)0.25000.5159 (2)0.0631 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0583 (7)0.0359 (5)0.0446 (6)0.0000.0010 (4)0.000
N10.050 (3)0.035 (3)0.049 (3)0.007 (2)0.002 (2)0.003 (2)
C10.056 (4)0.043 (3)0.053 (4)0.005 (3)0.008 (3)0.001 (3)
C20.062 (4)0.043 (3)0.051 (4)0.008 (3)0.002 (3)0.010 (3)
C30.051 (3)0.032 (3)0.060 (4)0.008 (3)0.011 (3)0.007 (3)
C40.059 (4)0.046 (4)0.054 (4)0.002 (3)0.009 (3)0.003 (3)
C50.065 (4)0.047 (4)0.050 (4)0.004 (3)0.003 (3)0.005 (3)
C60.050 (3)0.035 (3)0.069 (4)0.000 (3)0.005 (3)0.006 (3)
C70.046 (5)0.041 (5)0.055 (5)0.0000.000 (4)0.000
Cl10.0640 (14)0.0469 (12)0.0547 (13)0.0000.0064 (11)0.000
Cl20.0680 (15)0.0736 (16)0.0469 (13)0.0000.0003 (11)0.000
Geometric parameters (Å, º) top
Zn1—N1i2.055 (5)C3—C61.505 (8)
Zn1—N12.055 (5)C4—C51.369 (9)
Zn1—Cl22.239 (3)C4—H4A0.9300
Zn1—Cl12.247 (2)C5—H5A0.9300
N1—C51.330 (8)C6—C71.518 (7)
N1—C11.337 (8)C6—H6A0.9700
C1—C21.373 (9)C6—H6B0.9700
C1—H1A0.9300C7—C6ii1.518 (7)
C2—C31.386 (9)C7—H7A0.9700
C2—H2A0.9300C7—H7B0.9700
C3—C41.381 (9)
N1i—Zn1—N1111.7 (3)C5—C4—C3119.7 (6)
N1i—Zn1—Cl2104.45 (14)C5—C4—H4A120.2
N1—Zn1—Cl2104.45 (14)C3—C4—H4A120.2
N1i—Zn1—Cl1105.09 (14)N1—C5—C4123.9 (6)
N1—Zn1—Cl1105.09 (14)N1—C5—H5A118.0
Cl2—Zn1—Cl1125.95 (10)C4—C5—H5A118.0
C5—N1—C1116.8 (5)C3—C6—C7112.1 (5)
C5—N1—Zn1122.2 (4)C3—C6—H6A109.2
C1—N1—Zn1121.0 (4)C7—C6—H6A109.2
N1—C1—C2122.8 (6)C3—C6—H6B109.2
N1—C1—H1A118.6C7—C6—H6B109.2
C2—C1—H1A118.6H6A—C6—H6B107.9
C1—C2—C3120.3 (6)C6—C7—C6ii112.6 (7)
C1—C2—H2A119.8C6—C7—H7A109.1
C3—C2—H2A119.8C6ii—C7—H7A109.1
C4—C3—C2116.6 (6)C6—C7—H7B109.1
C4—C3—C6122.5 (6)C6ii—C7—H7B109.1
C2—C3—C6120.9 (6)H7A—C7—H7B107.8
Symmetry codes: (i) x, y+1/2, z; (ii) x, y+3/2, z.

Experimental details

Crystal data
Chemical formula[ZnCl2(C13H14N2)]
Mr334.53
Crystal system, space groupMonoclinic, P21/m
Temperature (K)293
a, b, c (Å)5.2254 (4), 12.9371 (9), 10.5425 (6)
β (°) 94.247 (3)
V3)710.73 (8)
Z2
Radiation typeMo Kα
µ (mm1)2.09
Crystal size (mm)0.80 × 0.26 × 0.20
Data collection
DiffractometerCCD area detector
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.486, 0.659
No. of measured, independent and
observed [I > 2σ(I)] reflections
2313, 1311, 1091
Rint0.034
(sin θ/λ)max1)0.596
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.060, 0.153, 1.08
No. of reflections1311
No. of parameters88
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.64, 0.48

Computer programs: SMART (Siemens, 1996), SMART and SAINT (Siemens, 1996), XPREP in SHELXTL (Siemens, 1996), SHELXTL (Siemens, 1996), SHELXTL (Bruker, 2001).

Selected geometric parameters (Å, º) top
Zn1—N12.055 (5)C2—C31.386 (9)
Zn1—Cl22.239 (3)C3—C41.381 (9)
Zn1—Cl12.247 (2)C3—C61.505 (8)
N1—C51.330 (8)C4—C51.369 (9)
N1—C11.337 (8)C6—C71.518 (7)
C1—C21.373 (9)
N1i—Zn1—N1111.7 (3)C1—C2—C3120.3 (6)
N1—Zn1—Cl2104.45 (14)C4—C3—C2116.6 (6)
N1—Zn1—Cl1105.09 (14)C4—C3—C6122.5 (6)
Cl2—Zn1—Cl1125.95 (10)C2—C3—C6120.9 (6)
C5—N1—C1116.8 (5)C5—C4—C3119.7 (6)
C5—N1—Zn1122.2 (4)N1—C5—C4123.9 (6)
C1—N1—Zn1121.0 (4)C3—C6—C7112.1 (5)
N1—C1—C2122.8 (6)C6—C7—C6ii112.6 (7)
Symmetry codes: (i) x, y+1/2, z; (ii) x, y+3/2, z.
 

Subscribe to Acta Crystallographica Section C: Structural Chemistry

The full text of this article is available to subscribers to the journal.

If you have already registered and are using a computer listed in your registration details, please email support@iucr.org for assistance.

Buy online

You may purchase this article in PDF and/or HTML formats. For purchasers in the European Community who do not have a VAT number, VAT will be added at the local rate. Payments to the IUCr are handled by WorldPay, who will accept payment by credit card in several currencies. To purchase the article, please complete the form below (fields marked * are required), and then click on `Continue'.
E-mail address* 
Repeat e-mail address* 
(for error checking) 

Format*   PDF (US $40)
   HTML (US $40)
   PDF+HTML (US $50)
In order for VAT to be shown for your country javascript needs to be enabled.

VAT number 
(non-UK EC countries only) 
Country* 
 

Terms and conditions of use
Contact us

Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds