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

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.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.025
• wR factor = 0.056
• Data-to-parameter ratio = 20.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT910_ALERT_3_C Missing # of FCF Reflection(s) Below Th(Min) ...          8 Report
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         11 Report

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF     Please Do !
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          2 Report
PLAT199_ALERT_1_G Reported _cell_measurement_temperature ..... (K)        293 Check
PLAT200_ALERT_1_G Reported   _diffrn_ambient_temperature ..... (K)        293 Check
PLAT794_ALERT_5_G Tentative Bond Valency for Zn1     (II)    .....       1.98 Note
PLAT899_ALERT_4_G SHELXL97   is Deprecated and Succeeded by SHELXL       2014 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600        514 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   2 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   7 ALERT level G = General information/check it is not something unexpected

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   3 ALERT type 5 Informative message, check

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Related literature

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).

S1. Experimental

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.

S2. Refinement

N and C-bound H atoms were positioned geometrically (N—H = 0.86; C—H = 0.93 Å) and allowed to ride on their parent atoms, with U_iso(H) = 1.2U_eq(N, C).

Computing details

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

	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

Crystal data

(C10H10N2)[ZnCl4]	F(000) = 728
Mr = 365.39	Dx = 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) Å^3	0.25 × 0.20 × 0.18 mm
Z = 4

Data collection

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	Rint = 0.024
ω and ϕ scans	θmax = 29.2°, θmin = 3.7°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	h = −9→9
Tmin = 0.565, Tmax = 0.654	k = −17→17
7435 measured reflections	l = −18→17

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.056	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0235P)^2 + 0.1003P] where P = (Fo^2 + 2Fc^2)/3
3115 reflections	(Δ/σ)max < 0.001
154 parameters	Δρmax = 0.49 e Å^−3
0 restraints	Δρmin = −0.51 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl4^i	0.86	2.33	3.1058 (15)	150
N2—H2A···Cl1^ii	0.86	2.26	3.0693 (15)	157
C1—H1···Cl2^iii	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.