Bis(isoquinolin-2-ium) tetra­chlorido­zincate dihydrate

Govindan, E.; Thirumurugan, S.; Rajkumar, K.; Anbalagan, K.; SubbiahPandi, A.

doi:10.1107/S1600536814015682

metal-organic compounds

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ISSN: 2056-9890

Volume 70| Part 8| August 2014| Page m303

doi:10.1107/S1600536814015682

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Bis(isoquinolin-2-ium) tetrachloridozincate dihydrate

Elumalai Govindan,^a Subramani Thirumurugan,^b Kanniah Rajkumar,^b Krishnamoorthy Anbalagan ^b and Arunachalam SubbiahPandi ^a ^*

^aDepartment of Physics, Presidency College, Chennai 600 005, India, and ^bDepartment of Chemistry, Pondicherry University, Pondicherry 605 014, India
^*Correspondence e-mail: a_sp59@yahoo.in

Edited by M. Bolte, Goethe-Universität Frankfurt, Germany (Received 6 April 2014; accepted 5 July 2014; online 23 July 2014)

In the title compound, (C₉H₈N)₂[ZnCl₄]·2H₂O, the tetrachloridozincate ion is located on a twofold rotation axis with the Zn atom on a special position. The crystal packing is stabilized by N—H⋯O and O—H⋯Cl interactions.

Keywords: crystal structure.

CCDC reference: 1012416

Related literature

For the synthesis of the title compound, see: Anbalagan & Lydia (2011 ). For applications of isoquinoline derivatives, see: Katritsky & Pozharskii (2000 ). For a related structure, see: Harrison (2005 ). For a description of the Cambridge Crystallographic Database, see: Allen (2002 ).

Experimental

Crystal data

2(C₉H₈N)·Cl₄Zn·2(H₂O)
M_r = 503.53
Monoclinic, C 2/c
a = 11.4337 (5) Å
b = 9.9160 (5) Å
c = 19.1544 (11) Å
β = 100.120 (6)°
V = 2137.87 (19) Å³
Z = 4
Mo Kα radiation
μ = 1.66 mm⁻¹
T = 293 K
0.45 × 0.35 × 0.35 mm

Data collection

Xcalibur, Eos diffractometer
Absorption correction: multi-scan CrysAlis PRO (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD, CrysAlis RED and CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.502, T_max = 0.559
5345 measured reflections
1857 independent reflections
1578 reflections with I > 2σ(I)
R_int = 0.024
Standard reflections: 0

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.088
S = 1.04
1857 reflections
129 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.61 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1	0.86	1.92	2.747 (4)	161
O1—H1B⋯Cl1ⁱ	0.85 (1)	2.47 (2)	3.270 (3)	157 (4)
Symmetry code: (i) $[-x+{\script{3\over 2}}, -y+{\script{3\over 2}}, -z+1]$ .

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD, CrysAlis RED and CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD, CrysAlis RED and CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); data reduction: CrysAlis RED); 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 and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1012416

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536814015682/bt6974sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814015682/bt6974Isup2.hkl

checkCIF report

Comment top

Isoquinoline derivatives are of interest in synthesizing new fungicides, insecticides, textile assistants, corrosion inhibitors, dye stabilizers, and pharmaceuticals (Katritsky & Pozharskii, 2000) Against this background and to ascertain the molecular structure and conformation of the title compound, the crystal structure determination has been carried out.

The ORTEP plot of the molecule is shown in Fig. 1. The tetrachlorozincate ion is located on a two-fold rotation axis with the Zn atom on the special position. The bond lengths and angles in the title compound are within normal ranges (Allen, 2002) and are comparable with those in related structures (Harrison, 2005).

The crystal packing is stabilized by intermolecular N—H···O and O—H···Cl interactions, which are linking the molecules to a three dimensional network.

Related literature top

For the synthesis of the title compound, see: Anbalagan & Lydia (2011). For applications of isoquinoline derivatives, see: Katritsky & Pozharskii (2000). For a related structure, see: Harrison (2005). For a description of the Cambridge Crystallographic Database, see: Allen (2002).

Experimental top

Zinc(II) chloride was dissolved in 10 mL(1 mmol) of distilled water. To this isoquinoline in 20 ml of EtOH/HCl mixture (1:5 v/v) 1 mmol was added in drops. The mixture was heated to 70°C for 2 h and allowed to stand, colorless crystals separated out were filtered and recrystallized using acidified water. X-ray quality crystals were obtained by repeated recrystallization from hot acidified distilled water. Microcrystalline pink color crystal was obtained for analysis.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis RED (Oxford Diffraction, 2009); 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).

Figures top

	Fig. 1. The molecular structure of the title compound, showing the atomic numbering and displacement ellipsoids drawn at 30% probability level.
	Fig. 2. The packing of the molecules viewed down a-axis.

Bis(isoquinolin-2-ium) tetrachloridozincate dihydrate top

Crystal data top

2(C₉H₈N)·Cl₄Zn·2(H₂O)	F(000) = 1024
M_r = 503.53	D_x = 1.564 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1578 reflections
a = 11.4337 (5) Å	θ = 3.9–25.0°
b = 9.9160 (5) Å	µ = 1.66 mm⁻¹
c = 19.1544 (11) Å	T = 293 K
β = 100.120 (6)°	Block, pink
V = 2137.87 (19) Å³	0.45 × 0.35 × 0.35 mm
Z = 4

Data collection top

Xcalibur, Eos diffractometer	1857 independent reflections
Radiation source: fine-focus sealed tube	1578 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ω scans	θ_max = 25.0°, θ_min = 3.9°
Absorption correction: multi-scan CrysAlis PRO (Oxford Diffraction, 2009)	h = −13→13
T_min = 0.502, T_max = 0.559	k = −11→11
5345 measured reflections	l = −15→22

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.088	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0445P)² + 1.8258P] where P = (F_o² + 2F_c²)/3
1857 reflections	(Δ/σ)_max < 0.001
129 parameters	Δρ_max = 0.61 e Å⁻³
4 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

2(C₉H₈N)·Cl₄Zn·2(H₂O)	V = 2137.87 (19) Å³
M_r = 503.53	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 11.4337 (5) Å	µ = 1.66 mm⁻¹
b = 9.9160 (5) Å	T = 293 K
c = 19.1544 (11) Å	0.45 × 0.35 × 0.35 mm
β = 100.120 (6)°

Data collection top

Xcalibur, Eos diffractometer	1857 independent reflections
Absorption correction: multi-scan CrysAlis PRO (Oxford Diffraction, 2009)	1578 reflections with I > 2σ(I)
T_min = 0.502, T_max = 0.559	R_int = 0.024
5345 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	4 restraints
wR(F²) = 0.088	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.61 e Å⁻³
1857 reflections	Δρ_min = −0.32 e Å⁻³
129 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

	x	y	z	U_iso*/U_eq
C2	0.5564 (3)	0.7834 (3)	0.5659 (2)	0.0638 (9)
H2	0.6310	0.7446	0.5797	0.077*
C3	0.5124 (3)	0.8013 (3)	0.49629 (19)	0.0547 (8)
H3	0.5563	0.7748	0.4621	0.066*
C4	0.3988 (3)	0.8607 (3)	0.47563 (15)	0.0426 (6)
C5	0.3464 (3)	0.8850 (3)	0.40473 (16)	0.0551 (8)
H5	0.3858	0.8605	0.3681	0.066*
C6	0.2388 (3)	0.9441 (3)	0.39003 (18)	0.0663 (10)
H6	0.2053	0.9605	0.3430	0.080*
C7	0.1760 (3)	0.9815 (3)	0.4434 (2)	0.0630 (9)
H7	0.1018	1.0220	0.4314	0.076*
C8	0.2223 (3)	0.9590 (3)	0.51179 (18)	0.0543 (8)
H8	0.1800	0.9832	0.5471	0.065*
C9	0.3354 (3)	0.8986 (3)	0.52987 (14)	0.0434 (6)
C10	0.3869 (3)	0.8765 (3)	0.59995 (16)	0.0537 (8)
H10	0.3462	0.9008	0.6360	0.064*
Cl1	0.63080 (8)	0.80565 (9)	0.32392 (5)	0.0717 (3)
N1	0.4918 (3)	0.8221 (2)	0.61579 (15)	0.0630 (8)
H1	0.5217	0.8100	0.6598	0.076*
Zn1	0.5000	0.67743 (4)	0.2500	0.04026 (17)
Cl2	0.39409 (7)	0.54525 (9)	0.31295 (4)	0.0624 (3)
O1	0.6337 (2)	0.7676 (4)	0.74389 (14)	0.0902 (9)
H1A	0.647 (3)	0.8552 (12)	0.7531 (15)	0.108*
H1B	0.7009 (18)	0.737 (3)	0.738 (2)	0.108*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C2	0.0525 (18)	0.0463 (17)	0.086 (3)	0.0002 (15)	−0.0053 (19)	0.0048 (18)
C3	0.0550 (18)	0.0445 (16)	0.067 (2)	−0.0010 (14)	0.0165 (16)	−0.0013 (15)
C4	0.0547 (16)	0.0303 (12)	0.0429 (15)	−0.0075 (12)	0.0092 (13)	−0.0024 (11)
C5	0.079 (2)	0.0473 (16)	0.0403 (16)	−0.0048 (17)	0.0133 (16)	−0.0035 (14)
C6	0.091 (3)	0.0501 (18)	0.0491 (19)	−0.0068 (19)	−0.0103 (19)	0.0034 (15)
C7	0.0583 (19)	0.0479 (18)	0.078 (2)	0.0025 (15)	−0.0020 (18)	0.0034 (17)
C8	0.0575 (18)	0.0441 (16)	0.065 (2)	0.0015 (15)	0.0193 (16)	0.0013 (15)
C9	0.0560 (16)	0.0329 (13)	0.0423 (15)	−0.0078 (13)	0.0112 (13)	−0.0001 (12)
C10	0.073 (2)	0.0450 (15)	0.0430 (16)	−0.0059 (16)	0.0110 (15)	0.0021 (14)
Cl1	0.0560 (5)	0.0770 (6)	0.0835 (6)	−0.0228 (4)	0.0165 (5)	−0.0287 (5)
N1	0.085 (2)	0.0496 (15)	0.0473 (15)	−0.0087 (15)	−0.0087 (15)	0.0038 (12)
Zn1	0.0361 (3)	0.0450 (3)	0.0418 (3)	0.000	0.01239 (19)	0.000
Cl2	0.0637 (5)	0.0713 (5)	0.0561 (5)	−0.0201 (4)	0.0216 (4)	0.0066 (4)
O1	0.0648 (15)	0.149 (3)	0.0565 (15)	0.0270 (18)	0.0102 (13)	0.0027 (17)

Geometric parameters (Å, º) top

C2—C3	1.351 (5)	C8—C9	1.412 (4)
C2—N1	1.362 (5)	C8—H8	0.9300
C2—H2	0.9300	C9—C10	1.385 (4)
C3—C4	1.417 (4)	C10—N1	1.302 (4)
C3—H3	0.9300	C10—H10	0.9300
C4—C5	1.406 (4)	Cl1—Zn1	2.2614 (9)
C4—C9	1.418 (4)	N1—H1	0.8600
C5—C6	1.347 (5)	Zn1—Cl1ⁱ	2.2614 (9)
C5—H5	0.9300	Zn1—Cl2	2.2697 (7)
C6—C7	1.399 (5)	Zn1—Cl2ⁱ	2.2697 (7)
C6—H6	0.9300	O1—H1A	0.894 (10)
C7—C8	1.343 (5)	O1—H1B	0.850 (10)
C7—H7	0.9300

C3—C2—N1	120.1 (3)	C7—C8—H8	120.1
C3—C2—H2	119.9	C9—C8—H8	120.1
N1—C2—H2	119.9	C10—C9—C8	121.3 (3)
C2—C3—C4	119.6 (3)	C10—C9—C4	118.9 (3)
C2—C3—H3	120.2	C8—C9—C4	119.8 (3)
C4—C3—H3	120.2	N1—C10—C9	120.6 (3)
C5—C4—C3	123.7 (3)	N1—C10—H10	119.7
C5—C4—C9	118.4 (3)	C9—C10—H10	119.7
C3—C4—C9	117.8 (3)	C10—N1—C2	123.0 (3)
C6—C5—C4	119.7 (3)	C10—N1—H1	118.5
C6—C5—H5	120.2	C2—N1—H1	118.5
C4—C5—H5	120.2	Cl1—Zn1—Cl1ⁱ	111.58 (6)
C5—C6—C7	122.0 (3)	Cl1—Zn1—Cl2	110.36 (3)
C5—C6—H6	119.0	Cl1ⁱ—Zn1—Cl2	107.54 (3)
C7—C6—H6	119.0	Cl1—Zn1—Cl2ⁱ	107.55 (3)
C8—C7—C6	120.3 (3)	Cl1ⁱ—Zn1—Cl2ⁱ	110.36 (3)
C8—C7—H7	119.9	Cl2—Zn1—Cl2ⁱ	109.45 (5)
C6—C7—H7	119.9	H1A—O1—H1B	104.4 (16)
C7—C8—C9	119.8 (3)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.86	1.92	2.747 (4)	161
O1—H1B···Cl1ⁱⁱ	0.85 (1)	2.47 (2)	3.270 (3)	157 (4)

Symmetry code: (ii) −x+3/2, −y+3/2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.86	1.92	2.747 (4)	160.7
O1—H1B···Cl1ⁱ	0.850 (10)	2.47 (2)	3.270 (3)	157 (4)

Symmetry code: (i) −x+3/2, −y+3/2, −z+1.

Acknowledgements

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

References

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