Bis(1,10-phenanthrolin-1-ium) tetra­chlorido­zincate monohydrate

E Govindan; Subramani Thirumurugan; Ayyakannu Sundaram Ganeshraja; Krishnamoorthy Anbalagan; A SubbiahPandi

doi:10.1107/S1600536814000208

. 2014 Jan 18;70(Pt 2):m53. doi: 10.1107/S1600536814000208

Bis(1,10-phenanthrolin-1-ium) tetrachloridozincate monohydrate

E Govindan ^a, Subramani Thirumurugan ^b, Ayyakannu Sundaram Ganeshraja ^b, Krishnamoorthy Anbalagan ^b, A SubbiahPandi ^a,^*

PMCID: PMC3998259 PMID: 24764820

Abstract

In the crystal structure of the title compound, (C₁₂H₉N₂)₂[ZnCl₄]·H₂O, the two independent 1,10-phenanthrolinium cations are bridged by the water molecule and the tetrahedral tetrachloridozincate anion via N—H⋯O, O—H⋯Cl and N—H⋯Cl hydrogen bonds, forming chains along [100]. The chains are linked via C—H⋯Cl hydrogen bonds and a number of π–π interactions [centroid–centroid distances vary from 3.5594 (14) to 3.7057 (13) Å], forming a three-dimensional network. In each 1,10-phenanthrolinium cation, there is a short N—H⋯N interaction.

Related literature

For an example of the crystal structure of a hybrid compound combining an organic cation and the tetrachloridozincate anion, see: Dong & Liu (2012 ▶). For details of the Cambridge Structural Database, see: Allen (2002 ▶). graphic file with name e-70-00m53-scheme1.jpg

Experimental

Crystal data

(C₁₂H₉N₂)₂[ZnCl₄]·H₂O
M _r = 587.61
Monoclinic,
a = 14.6046 (5) Å
b = 10.8008 (3) Å
c = 16.3151 (6) Å
β = 107.390 (4)°
V = 2455.93 (14) Å³
Z = 4
Mo Kα radiation
μ = 1.46 mm⁻¹
T = 293 K
0.21 × 0.18 × 0.15 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with Eos detector
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T _min = 0.743, T _max = 0.803
10373 measured reflections
4293 independent reflections
3414 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.031
wR(F ²) = 0.068
S = 1.05
4293 reflections
324 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2009 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008 ▶) and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814000208/su2681sup1.cif

e-70-00m53-sup1.cif^{(24.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814000208/su2681Isup2.hkl

e-70-00m53-Isup2.hkl^{(210.4KB, hkl)}

CCDC reference: http://scripts.iucr.org/cgi-bin/cr.cgi?rm=csd&csdid=979772

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.74 (3)	2.01 (3)	2.711 (4)	158 (2)
O1—H1A⋯Cl1	0.80 (4)	2.44 (4)	3.231 (3)	172 (3)
O1—H1B⋯Cl2ⁱⁱ	0.73 (3)	2.82 (4)	3.317 (3)	128 (4)
N15—H15⋯Cl3	0.83 (3)	2.50 (2)	3.225 (2)	146 (2)
C3—H3⋯Cl2ⁱⁱⁱ	0.93	2.80	3.728 (3)	172
C24—H24⋯Cl2^iv	0.93	2.74	3.629 (3)	160
N1—H1⋯N12	0.74 (3)	2.42 (2)	2.737 (3)	107 (2)
N15—H15⋯N26	0.83 (3)	2.41 (2)	2.731 (3)	104 (2)

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) .

Acknowledgments

EG and KA thank the CSIR, New Delhi (Lr: No. 01 (2570)/12/EMR-II/3.4.2012) for financial support through a major research project. The authors also thank the Department of Chemistry, Pondicherry University, for the single-crystal XRD instrumentation facility.

supplementary crystallographic information

1. Comment

As part of an ongoing investigation of the structures of and non-covalent interactions present in self-assembling organic and inorganic hybrid materials prepared by the combination of an organic cation and the tetrachloridozincate anion we synthesized the title compound. There are only a small number of structures of materials containing bis(1,10-phenanthrolinium) cations and perhalometallate anions in the Cambridge Structural Database (CSD; V5.35, last update Nov. 2013; Allen, 2002), and none of them involve the tetrachloridozincate anion.

The molecule structure of the title compound is shown in Fig. 1. The asymmetric unit contains one inorganic tetrachloridozincate anion and two 1,10-phenanthrolinium organic cations. The compound crystallized as a monohydrate. The tetrachlorozincate anion has a perfect tetrahedral coordination environment. The bond lengths Zn—Cl [2.556 (7) - 2.3085 (7) Å] and C—N [1.320 (3) - 1.362 (3) Å] are comparable with the values reported for Bis(10-methoxybenzo[h]quinolinium) tetrachloridozinc [Dong & Liu, 2012]. The sum of the bond angles around atoms N1 and N15 (360°) in the 1,10-phenanthrolinium cations indicates sp² hybridization states. The two 1,10-phenanthrolinium ring systems (N1/N12/C2-C11/C13/C14) and (N15/N26/C16-C25/C27/C28) are planar with r.m.s values of 0.029 (3) and 0.022 (2) Å, respectively. In each 1,10-phenanthrolinium cation there is a short N-H···N interaction (Table 1).

In the crystal, the two independent 1,10-phenanthrolinium cations are bridged by the water molecule and the tetrachloridozinc anion via N-H···O, O-H···Cl and N-H···Cl hydrogen bonds (Table 1 and Fig. 2) forming chains along [100]. The chains are linked via C-H···Cl hydrogen bonds (Table 1) and a number of π-π interactions forming a three-dimensional network.

The centroid-centroid distances are 3.5594 (14) Å for Cg1···Cg2ⁱ [Cg1 and Cg2 and the centroids of rings N1/C2-C5/C14 and N12/C8-C11/C13, respectively; symmetry code: (i) = -x, -y+2, -z+1 ], 3.6501 (15) Å for Cg1···Cg3ⁱ [Cg3 is the centroid of ring C5-C8/C13/C14] and 3.7057 (13) Å for Cg8···Cg9ⁱⁱ [Cg8 and Cg9 are the centroids of rings N26/C22-C25/C27 and C19-C22/C27/C28, respectively; symmetry code: (ii) -x, -y, -z+2].

2. Experimental

Zinc chloride (136 mg, 1 mmol) was dissolved in 10 mL of water. To this 1,10-phenanthroline (396 mg, 2 mmol) in 20 ml of an EtOH/HCl mixture (1:9 v/v) was added drop wise. The mixture was heated to 323 K for 2–3 hrs and then allowed to stand. On slow evaporation colourless crystals separated out. They were filtered off and recrystallized using acidified water.