Crystal structure of 2,2′-bi­pyridine-1,1′-diium tetra­chlorido­zincate

Govindaraj, J.; Thirumurugan, S.; Clara, A.S.; Anbalagan, K.; SubbiahPandi, A.

doi:10.1107/S2056989015003175

metal-organic compounds

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Volume 71| Part 3| March 2015| Pages m67-m68

doi:10.1107/S2056989015003175

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Crystal structure of 2,2′-bipyridine-1,1′-diium tetrachloridozincate

Jeyaraman Govindaraj,^a Subramani Thirumurugan,^b Antoni Samy Clara,^b Krishnamoorthy Anbalagan ^b and Arunachalathevar SubbiahPandi ^c ^*

^aDepartment of Physics, Pachaiyappa's College for Men, Kanchipuram 631 501, India, ^bDepartment of Chemistry, Pondicherry University, Pondicherry 605 014, India, and ^cDepartment of Physics, Presidency College (Autonomous), Chennai 600 005, India
^*Correspondence e-mail: aspandian59@gmail.com

Edited by M. Weil, Vienna University of Technology, Austria (Received 4 February 2015; accepted 14 February 2015; online 21 February 2015)

In the crystal structure of the title salt, (C₁₀H₁₀N₂)[ZnCl₄], the bipyridinediium dication is not planar, with a dihedral angle of 37.21 (9)° between the planes of the two pyridine rings. In the crystal, the slightly distorted [ZnCl₄]²⁻ anions are packed into rods parallel to [001], with the organic cations arranged in corrugated layers parallel to (100). Cations and anions are linked through N—H⋯Cl hydrogen bonds, forming chains parallel to [20-1]. Additional C—H⋯Cl interactions consolidate the crystal packing.

Keywords: crystal structure; 2,2′-bipyridine-1,1′-diium; tetrachloridozincate; hydrogen bonding.

CCDC reference: 1049571

1. Related literature

For the crystal structure of 4,4′-bipyridine-1,1′-diium tetrachloridozincate, see: Gillon et al. (2000 ). For other bipyridine derivatives with a [ZnCl₄]²⁻ counter-anion, see: Rice et al. (2002 ).

2. Experimental

2.1. Crystal data

(C₁₀H₁₀N₂)[ZnCl₄]
M_r = 365.39
Monoclinic, P 2₁ /c
a = 7.1059 (4) Å
b = 13.6075 (6) Å
c = 14.2631 (7) Å
β = 100.816 (5)°
V = 1354.65 (12) Å³
Z = 4
Mo Kα radiation
μ = 2.58 mm⁻¹
T = 293 K
0.25 × 0.20 × 0.18 mm

2.2. Data collection

Oxford Diffraction Xcalibur diffractometer with an Eos detector
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD, CrysAlis RED and CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ) T_min = 0.565, T_max = 0.654
7435 measured reflections
3115 independent reflections
2717 reflections with I > 2σ(I)
R_int = 0.024

2.3. Refinement

R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.056
S = 1.05
3115 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.51 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl4ⁱ	0.86	2.33	3.1058 (15)	150
N2—H2A⋯Cl1ⁱⁱ	0.86	2.26	3.0693 (15)	157
C1—H1⋯Cl2ⁱⁱⁱ	0.93	2.74	3.4842 (19)	137
C3—H3⋯Cl4^iv	0.93	2.83	3.664 (2)	150
C10—H10⋯Cl2^v	0.93	2.67	3.570 (2)	162
Symmetry codes: (i) x+1, y, z; (ii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) -x+1, -y, -z+1; (iv) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (v) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD, CrysAlis RED and CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD, CrysAlis RED and CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ); 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: 1049571

Crystal structure: contains datablocks global, I. DOI: 10.1107/S2056989015003175/wm5125sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015003175/wm5125Isup2.hkl

checkCIF report

Related literature top

For the crystal structure of 4,4'-bipyridine-4,4'-diium tetrachloridozincate, see: Gillon et al. (2000). For other bipyridine derivatives with a [ZnCl₄]^2- counter-anion, see: Rice et al. (2002).

Experimental top

Zinc chloride (136 mg, 1 mmol) was dissolved in 20 ml of water. To this solution was added dropwise 2,2'-bipyridine (156 mg, 1 mmol) in 20 ml of an EtOH/HCl mixture (1:9 v/v). The mixture was heated to 333 K for 2–3 hrs and allowed to stand until colorless crystals separated. The crystals were filtered and repeatedly recrystallized by using acidified water.

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 components of the title salt with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. The crystal packing of the title compound viewed along [100].

2,2'-Bipyridine-1,1'-diium tetrachloridozincate top

Crystal data top

(C₁₀H₁₀N₂)[ZnCl₄]	F(000) = 728
M_r = 365.39	D_x = 1.791 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -p 2ybc	Cell parameters from 2717 reflections
a = 7.1059 (4) Å	θ = 3.7–29.2°
b = 13.6075 (6) Å	µ = 2.58 mm⁻¹
c = 14.2631 (7) Å	T = 293 K
β = 100.816 (5)°	Block, colourless
V = 1354.65 (12) Å³	0.25 × 0.20 × 0.18 mm
Z = 4

Data collection top

Oxford Diffraction Xcalibur diffractometer with an Eos detector	3115 independent reflections
Radiation source: fine-focus sealed tube	2717 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ω and ϕ scans	θ_max = 29.2°, θ_min = 3.7°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	h = −9→9
T_min = 0.565, T_max = 0.654	k = −17→17
7435 measured reflections	l = −18→17

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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.056	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0235P)² + 0.1003P] where P = (F_o² + 2F_c²)/3
3115 reflections	(Δ/σ)_max < 0.001
154 parameters	Δρ_max = 0.49 e Å⁻³
0 restraints	Δρ_min = −0.51 e Å⁻³

Crystal data top

(C₁₀H₁₀N₂)[ZnCl₄]	V = 1354.65 (12) Å³
M_r = 365.39	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.1059 (4) Å	µ = 2.58 mm⁻¹
b = 13.6075 (6) Å	T = 293 K
c = 14.2631 (7) Å	0.25 × 0.20 × 0.18 mm
β = 100.816 (5)°

Data collection top

Oxford Diffraction Xcalibur diffractometer with an Eos detector	3115 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	2717 reflections with I > 2σ(I)
T_min = 0.565, T_max = 0.654	R_int = 0.024
7435 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	0 restraints
wR(F²) = 0.056	H-atom parameters constrained
S = 1.05	Δρ_max = 0.49 e Å⁻³
3115 reflections	Δρ_min = −0.51 e Å⁻³
154 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
C1	0.6920 (3)	0.07397 (14)	0.51855 (13)	0.0181 (4)
H1	0.6776	0.0453	0.5759	0.022*
C2	0.7677 (3)	0.02053 (14)	0.45317 (14)	0.0200 (4)
H2	0.8001	−0.0452	0.4643	0.024*
C3	0.7947 (3)	0.06655 (14)	0.37010 (14)	0.0192 (4)
H3	0.8492	0.0321	0.3256	0.023*
C4	0.7409 (3)	0.16360 (14)	0.35321 (13)	0.0164 (4)
H4	0.7598	0.1947	0.2977	0.020*
C5	0.6590 (3)	0.21376 (13)	0.41919 (12)	0.0130 (4)
C6	0.5805 (3)	0.31365 (14)	0.40546 (12)	0.0132 (4)
C7	0.4136 (3)	0.34390 (14)	0.43280 (12)	0.0159 (4)
H7	0.3465	0.3010	0.4652	0.019*
C8	0.3461 (3)	0.43815 (15)	0.41188 (13)	0.0205 (4)
H8	0.2330	0.4586	0.4297	0.025*
C9	0.4473 (3)	0.50196 (14)	0.36437 (13)	0.0234 (4)
H9	0.4041	0.5658	0.3506	0.028*
C10	0.6122 (3)	0.46959 (14)	0.33786 (13)	0.0225 (4)
H10	0.6811	0.5114	0.3052	0.027*
N1	0.6743 (2)	0.37817 (11)	0.35883 (10)	0.0163 (3)
H1A	0.7786	0.3595	0.3419	0.020*
N2	0.6388 (2)	0.16722 (11)	0.50012 (10)	0.0147 (3)
H2A	0.5896	0.1990	0.5417	0.018*
Zn1	0.14622 (3)	0.224086 (15)	0.198218 (14)	0.01454 (7)
Cl1	0.43041 (7)	0.28035 (4)	0.16341 (3)	0.02205 (12)
Cl2	0.22538 (7)	0.12838 (3)	0.32961 (3)	0.01744 (10)
Cl3	−0.01698 (8)	0.14035 (4)	0.07333 (4)	0.03026 (13)
Cl4	−0.01829 (7)	0.35933 (3)	0.23116 (3)	0.02098 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0177 (10)	0.0151 (9)	0.0199 (10)	−0.0006 (8)	−0.0003 (8)	0.0045 (7)
C2	0.0127 (10)	0.0140 (9)	0.0310 (11)	0.0012 (8)	−0.0017 (8)	−0.0010 (8)
C3	0.0121 (10)	0.0210 (10)	0.0250 (10)	0.0014 (8)	0.0050 (8)	−0.0068 (8)
C4	0.0136 (10)	0.0189 (10)	0.0174 (9)	−0.0007 (8)	0.0047 (7)	−0.0003 (7)
C5	0.0104 (9)	0.0139 (9)	0.0138 (9)	−0.0023 (7)	−0.0002 (7)	0.0003 (7)
C6	0.0160 (10)	0.0146 (9)	0.0081 (8)	−0.0026 (7)	0.0002 (7)	−0.0004 (7)
C7	0.0175 (10)	0.0158 (9)	0.0141 (9)	−0.0002 (8)	0.0027 (7)	−0.0009 (7)
C8	0.0213 (11)	0.0214 (10)	0.0172 (10)	0.0039 (8)	−0.0007 (8)	−0.0045 (8)
C9	0.0370 (13)	0.0130 (9)	0.0170 (10)	0.0050 (9)	−0.0032 (8)	0.0000 (8)
C10	0.0350 (12)	0.0164 (10)	0.0148 (10)	−0.0064 (9)	0.0015 (8)	0.0023 (7)
N1	0.0186 (9)	0.0158 (8)	0.0151 (8)	−0.0026 (7)	0.0044 (6)	−0.0005 (6)
N2	0.0171 (8)	0.0141 (8)	0.0132 (8)	0.0017 (6)	0.0035 (6)	−0.0009 (6)
Zn1	0.01358 (12)	0.01320 (12)	0.01649 (12)	−0.00066 (8)	0.00192 (8)	0.00128 (8)
Cl1	0.0188 (3)	0.0326 (3)	0.0162 (2)	−0.0072 (2)	0.00697 (18)	−0.00060 (19)
Cl2	0.0193 (2)	0.0146 (2)	0.0184 (2)	0.00016 (18)	0.00339 (17)	0.00387 (17)
Cl3	0.0305 (3)	0.0245 (3)	0.0295 (3)	−0.0056 (2)	−0.0106 (2)	−0.0036 (2)
Cl4	0.0207 (3)	0.0164 (2)	0.0278 (3)	0.00419 (19)	0.0097 (2)	0.00458 (19)

Geometric parameters (Å, º) top

C1—N2	1.336 (2)	C7—H7	0.9300
C1—C2	1.370 (3)	C8—C9	1.383 (3)
C1—H1	0.9300	C8—H8	0.9300
C2—C3	1.385 (3)	C9—C10	1.370 (3)
C2—H2	0.9300	C9—H9	0.9300
C3—C4	1.383 (3)	C10—N1	1.335 (2)
C3—H3	0.9300	C10—H10	0.9300
C4—C5	1.377 (2)	N1—H1A	0.8600
C4—H4	0.9300	N2—H2A	0.8600
C5—N2	1.348 (2)	Zn1—Cl3	2.2452 (5)
C5—C6	1.468 (2)	Zn1—Cl2	2.2647 (5)
C6—N1	1.350 (2)	Zn1—Cl4	2.2760 (5)
C6—C7	1.379 (2)	Zn1—Cl1	2.2994 (5)
C7—C8	1.382 (3)

N2—C1—C2	120.20 (17)	C7—C8—C9	119.83 (18)
N2—C1—H1	119.9	C7—C8—H8	120.1
C2—C1—H1	119.9	C9—C8—H8	120.1
C1—C2—C3	118.53 (18)	C10—C9—C8	118.92 (18)
C1—C2—H2	120.7	C10—C9—H9	120.5
C3—C2—H2	120.7	C8—C9—H9	120.5
C4—C3—C2	120.15 (17)	N1—C10—C9	120.09 (18)
C4—C3—H3	119.9	N1—C10—H10	120.0
C2—C3—H3	119.9	C9—C10—H10	120.0
C5—C4—C3	119.53 (17)	C10—N1—C6	122.94 (17)
C5—C4—H4	120.2	C10—N1—H1A	118.5
C3—C4—H4	120.2	C6—N1—H1A	118.5
N2—C5—C4	118.61 (16)	C1—N2—C5	122.91 (16)
N2—C5—C6	116.77 (15)	C1—N2—H2A	118.5
C4—C5—C6	124.51 (16)	C5—N2—H2A	118.5
N1—C6—C7	118.37 (17)	Cl3—Zn1—Cl2	112.08 (2)
N1—C6—C5	117.22 (16)	Cl3—Zn1—Cl4	111.43 (2)
C7—C6—C5	124.33 (16)	Cl2—Zn1—Cl4	110.585 (18)
C6—C7—C8	119.84 (18)	Cl3—Zn1—Cl1	109.97 (2)
C6—C7—H7	120.1	Cl2—Zn1—Cl1	106.16 (2)
C8—C7—H7	120.1	Cl4—Zn1—Cl1	106.33 (2)

N2—C1—C2—C3	2.6 (3)	C5—C6—C7—C8	−176.39 (17)
C1—C2—C3—C4	−1.8 (3)	C6—C7—C8—C9	−0.6 (3)
C2—C3—C4—C5	−0.5 (3)	C7—C8—C9—C10	0.8 (3)
C3—C4—C5—N2	1.9 (3)	C8—C9—C10—N1	−0.7 (3)
C3—C4—C5—C6	−174.26 (18)	C9—C10—N1—C6	0.5 (3)
N2—C5—C6—N1	146.62 (17)	C7—C6—N1—C10	−0.2 (3)
C4—C5—C6—N1	−37.1 (3)	C5—C6—N1—C10	176.69 (16)
N2—C5—C6—C7	−36.7 (3)	C2—C1—N2—C5	−1.2 (3)
C4—C5—C6—C7	139.56 (19)	C4—C5—N2—C1	−1.1 (3)
N1—C6—C7—C8	0.3 (3)	C6—C5—N2—C1	175.37 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl4ⁱ	0.86	2.33	3.1058 (15)	150
N2—H2A···Cl1ⁱⁱ	0.86	2.26	3.0693 (15)	157
C1—H1···Cl2ⁱⁱⁱ	0.93	2.74	3.4842 (19)	137
C3—H3···Cl4^iv	0.93	2.83	3.664 (2)	150
C10—H10···Cl2^v	0.93	2.67	3.570 (2)	162

Symmetry codes: (i) x+1, y, z; (ii) x, −y+1/2, z+1/2; (iii) −x+1, −y, −z+1; (iv) −x+1, y−1/2, −z+1/2; (v) −x+1, y+1/2, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl4ⁱ	0.86	2.33	3.1058 (15)	150
N2—H2A···Cl1ⁱⁱ	0.86	2.26	3.0693 (15)	157
C1—H1···Cl2ⁱⁱⁱ	0.93	2.74	3.4842 (19)	137
C3—H3···Cl4^iv	0.93	2.83	3.664 (2)	150
C10—H10···Cl2^v	0.93	2.67	3.570 (2)	162

Symmetry codes: (i) x+1, y, z; (ii) x, −y+1/2, z+1/2; (iii) −x+1, −y, −z+1; (iv) −x+1, y−1/2, −z+1/2; (v) −x+1, y+1/2, −z+1/2.

Acknowledgements

KA is 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 acknowledge the Department of Chemistry, Pondicherry University, for the single-crystal XRD instrumentation facility.

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