Crystal structure of di-chlorido-bis-[2-(phenyl-diazen-yl)pyridine-κN (1)]zinc.

The structure of the title complex, [ZnCl2(C11H9N3)2], comprises two 2-(phenyl-diazen-yl)pyridine ligands coordin-ating to a central Zn(II) dichloride unit via the pyridyl N-atom donors, resulting in a slightly distorted tetra-hedral geometry. The complex exhibits twofold rotation symmetry, with the rotation axis bis-ecting the zinc cation. The structure is stabilized by weak inter-molecular C-H⋯Cl inter-actions [C⋯Cl = 3.411 (2) and 3.675 (2) Å], connecting neighbouring mol-ecules into layers perpendicular to the c axis.

Related literature

For background to diazenyl­pyridine compounds, see: Krause & Krause (1980 ▸). For applications of diazenyl­pyridine complexes, see: Wong & Giandomenico (1999 ▸); Wu et al. (2006 ▸); Hotze et al. (2004 ▸); Velders et al. (2000 ▸); Barf & Sheldon (1995 ▸). For applications of zinc–diazenyl complexes, see: Saha et al. (2014 ▸); Dutta et al. (2014 ▸); Datta et al. (2014 ▸); Zhang et al. (2012 ▸). For related structures, see: Leesakul et al. (2011 ▸); Panneerselvam et al. (2000 ▸); Steffen & Palenik (1976 ▸).

Experimental

Crystal data

[ZnCl2(C11n class="Species">H9N3)2]

M = 502.69

Orthorhombic,

a = 13.7960 (4) Å

b = 10.1905 (3) Å

c = 16.1305 (5) Å

V = 2267.76 (12) Å3

Z = 4

Mo Kα radiation

μ = 1.34 mm−1

T = 298 K

0.36 × 0.32 × 0.30 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2013 ▸) T min = 0.708, T max = 0.746

65168 measured reflections

2820 independent reflections

2160 reflections with I > 2σ(I)

R int = 0.041

Refinement

R[F 2 > 2σ(F 2)] = 0.030

wR(F 2) = 0.083

S = 1.06

2820 reflections

141 parameters

H-atom parameters constrained

Δρmax = 0.35 e Å−3

Δρmin = −0.22 e Å−3

Data collection: SMART (Bruker, 2013 ▸); cell refinement: SAINT (Bruker, 2013 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ▸); molecular graphics: Mercury (Macrae et al., 2008 ▸); software used to prepare material for publication: WinGX (Farrugia, 2012 ▸) and publCIF (Westrip, 2010 ▸).

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989015019143/zl2646sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015019143/zl2646Isup2.hkl

Click here for additional data file.

11 9 3 2 2 x y -z . DOI: 10.1107/S2056989015019143/zl2646fig1.tif

Mol­ecular structure of [Zn(C11n class="Species">H9N3)2Cl2] with thermal ellipsoids plotted at the 30% probability level. Non-labelled atoms are created by the twofold symmetry axis [symmetry operator: (i) −x + 2, y, -z + 3/2].

Click here for additional data file.

11 9 3 2 2 c . DOI: 10.1107/S2056989015019143/zl2646fig2.tif

Two–dimensional inter­action sheet of [Zn(C11n class="Species">H9N3)2Cl2] plotted down c, formed through weak C–H⋯Cl inter­actions.

Click here for additional data file.

11 9 3 2 2 b . DOI: 10.1107/S2056989015019143/zl2646fig3.tif

Two–dimensional inter­action sheet of [Zn(C11n class="Species">H9N3)2Cl2] plotted down b axis, formed through weak C–H⋯Cl inter­actions.

Click here for additional data file.

a . DOI: 10.1107/S2056989015019143/zl2646fig4.tif

The arrangement of two-dimensional layers plotted down the a axis showing a lateral view of alternating C⋯Cl contact directions of adjacent sheets (A and B layers). H atoms are omitted for clarity.

CCDC reference: 1430587

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

[ZnCl2(C11H9N3)2]	Dx = 1.472 Mg m−3
Mr = 502.69	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbcn	Cell parameters from 9900 reflections
a = 13.7960 (4) Å	θ = 3.2–28.2°
b = 10.1905 (3) Å	µ = 1.34 mm−1
c = 16.1305 (5) Å	T = 298 K
V = 2267.76 (12) Å3	Block, orange
Z = 4	0.36 × 0.32 × 0.30 mm
F(000) = 1024

Bruker APEXII CCD diffractometer	2160 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.041
Absorption correction: multi-scan (SADABS; Bruker, 2013)	θmax = 28.3°, θmin = 3.5°
Tmin = 0.708, Tmax = 0.746	h = −18→18
65168 measured reflections	k = −13→13
2820 independent reflections	l = −21→21

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.030	H-atom parameters constrained
wR(F2) = 0.083	w = 1/[σ2(Fo2) + (0.0384P)2 + 0.7794P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max = 0.001
2820 reflections	Δρmax = 0.35 e Å−3
141 parameters	Δρmin = −0.22 e Å−3

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.

	x	y	z	Uiso*/Ueq
Zn1	1.0000	0.21091 (3)	0.7500	0.04573 (11)
Cl1	0.96785 (4)	0.08709 (5)	0.63805 (3)	0.06114 (15)
N1	0.86977 (11)	0.30520 (15)	0.76959 (10)	0.0468 (3)
N2	0.95560 (12)	0.45206 (15)	0.84789 (10)	0.0514 (4)
N3	0.95301 (13)	0.55766 (16)	0.88646 (11)	0.0584 (4)
C1	0.78854 (15)	0.2566 (2)	0.73676 (13)	0.0571 (5)
H1	0.7927	0.1832	0.7026	0.069*
C2	0.69884 (17)	0.3110 (2)	0.75155 (14)	0.0676 (6)
H2	0.6434	0.2755	0.7275	0.081*
C3	0.69288 (16)	0.4185 (2)	0.80247 (16)	0.0730 (6)
H3	0.6330	0.4563	0.8140	0.088*
C4	0.77541 (15)	0.4698 (2)	0.83614 (14)	0.0627 (5)
H4	0.7726	0.5429	0.8706	0.075*
C5	0.86318 (13)	0.41115 (18)	0.81815 (11)	0.0484 (4)
C6	1.04406 (15)	0.60029 (19)	0.91730 (12)	0.0555 (5)
C7	1.04401 (19)	0.7222 (2)	0.95484 (16)	0.0696 (6)
H7	0.9866	0.7696	0.9593	0.084*
C8	1.1291 (2)	0.7733 (3)	0.98561 (16)	0.0789 (7)
H8	1.1293	0.8553	1.0110	0.095*
C9	1.2132 (2)	0.7037 (3)	0.97888 (15)	0.0763 (7)
H9	1.2707	0.7390	0.9990	0.092*
C10	1.21338 (17)	0.5810 (2)	0.94239 (14)	0.0706 (6)
H10	1.2709	0.5338	0.9386	0.085*
C11	1.12915 (16)	0.5283 (2)	0.91168 (13)	0.0623 (5)
H11	1.1291	0.4455	0.8874	0.075*

	U11	U22	U33	U12	U13	U23
Zn1	0.03382 (16)	0.04842 (18)	0.05494 (19)	0.000	0.00041 (11)	0.000
Cl1	0.0475 (3)	0.0725 (3)	0.0635 (3)	0.0004 (2)	−0.0018 (2)	−0.0153 (2)
N1	0.0390 (8)	0.0491 (8)	0.0522 (8)	0.0044 (6)	0.0020 (6)	0.0048 (6)
N2	0.0533 (9)	0.0493 (8)	0.0518 (9)	0.0059 (7)	0.0038 (7)	0.0004 (7)
N3	0.0597 (11)	0.0517 (9)	0.0638 (10)	0.0067 (8)	0.0061 (8)	−0.0026 (8)
C1	0.0431 (10)	0.0613 (11)	0.0669 (13)	0.0021 (9)	−0.0025 (8)	0.0013 (9)
C2	0.0393 (10)	0.0797 (15)	0.0837 (16)	0.0077 (10)	−0.0056 (10)	0.0097 (12)
C3	0.0490 (12)	0.0840 (16)	0.0861 (16)	0.0254 (11)	0.0070 (11)	0.0133 (13)
C4	0.0602 (12)	0.0615 (12)	0.0663 (12)	0.0211 (10)	0.0057 (10)	0.0027 (10)
C5	0.0472 (10)	0.0497 (10)	0.0483 (10)	0.0089 (8)	0.0034 (8)	0.0093 (8)
C6	0.0584 (12)	0.0551 (11)	0.0530 (11)	0.0001 (9)	0.0074 (9)	0.0013 (9)
C7	0.0696 (14)	0.0602 (13)	0.0790 (15)	0.0002 (10)	0.0151 (12)	−0.0122 (11)
C8	0.0851 (18)	0.0683 (15)	0.0832 (16)	−0.0170 (13)	0.0133 (14)	−0.0153 (12)
C9	0.0742 (16)	0.0856 (17)	0.0690 (14)	−0.0211 (13)	0.0029 (12)	0.0037 (12)
C10	0.0624 (13)	0.0789 (16)	0.0704 (14)	0.0030 (11)	0.0025 (11)	0.0065 (12)
C11	0.0657 (13)	0.0609 (12)	0.0602 (12)	0.0051 (10)	0.0035 (10)	−0.0020 (10)

Zn1—N1	2.0618 (15)	C3—H3	0.9300
Zn1—N1i	2.0619 (15)	C4—C5	1.381 (3)
Zn1—Cl1i	2.2471 (5)	C4—H4	0.9300
Zn1—Cl1	2.2472 (5)	C6—C7	1.382 (3)
N1—C1	1.335 (3)	C6—C11	1.387 (3)
N1—C5	1.337 (2)	C7—C8	1.377 (3)
N2—N3	1.244 (2)	C7—H7	0.9300
N2—C5	1.425 (2)	C8—C9	1.364 (4)
N3—C6	1.419 (3)	C8—H8	0.9300
C1—C2	1.377 (3)	C9—C10	1.382 (3)
C1—H1	0.9300	C9—H9	0.9300
C2—C3	1.372 (3)	C10—C11	1.372 (3)
C2—H2	0.9300	C10—H10	0.9300
C3—C4	1.365 (3)	C11—H11	0.9300
N1—Zn1—N1i	124.45 (9)	C5—C4—H4	120.6
N1—Zn1—Cl1i	108.09 (4)	N1—C5—C4	122.15 (19)
N1i—Zn1—Cl1i	102.29 (5)	N1—C5—N2	111.89 (15)
N1—Zn1—Cl1	102.29 (5)	C4—C5—N2	125.96 (18)
N1i—Zn1—Cl1	108.09 (4)	C7—C6—C11	120.3 (2)
Cl1i—Zn1—Cl1	111.68 (3)	C7—C6—N3	115.36 (19)
C1—N1—C5	118.37 (17)	C11—C6—N3	124.36 (19)
C1—N1—Zn1	119.85 (13)	C8—C7—C6	119.8 (2)
C5—N1—Zn1	121.69 (13)	C8—C7—H7	120.1
N3—N2—C5	113.33 (16)	C6—C7—H7	120.1
N2—N3—C6	114.51 (17)	C9—C8—C7	120.0 (2)
N1—C1—C2	122.4 (2)	C9—C8—H8	120.0
N1—C1—H1	118.8	C7—C8—H8	120.0
C2—C1—H1	118.8	C8—C9—C10	120.4 (2)
C3—C2—C1	118.6 (2)	C8—C9—H9	119.8
C3—C2—H2	120.7	C10—C9—H9	119.8
C1—C2—H2	120.7	C11—C10—C9	120.4 (2)
C4—C3—C2	119.6 (2)	C11—C10—H10	119.8
C4—C3—H3	120.2	C9—C10—H10	119.8
C2—C3—H3	120.2	C10—C11—C6	119.1 (2)
C3—C4—C5	118.8 (2)	C10—C11—H11	120.5
C3—C4—H4	120.6	C6—C11—H11	120.5
C5—N2—N3—C6	179.59 (15)	N3—N2—C5—N1	173.32 (16)
C5—N1—C1—C2	−0.4 (3)	N3—N2—C5—C4	−7.2 (3)
Zn1—N1—C1—C2	176.25 (16)	N2—N3—C6—C7	175.28 (19)
N1—C1—C2—C3	−0.5 (3)	N2—N3—C6—C11	−4.7 (3)
C1—C2—C3—C4	0.9 (3)	C11—C6—C7—C8	1.0 (3)
C2—C3—C4—C5	−0.3 (3)	N3—C6—C7—C8	−179.0 (2)
C1—N1—C5—C4	1.0 (3)	C6—C7—C8—C9	0.1 (4)
Zn1—N1—C5—C4	−175.57 (14)	C7—C8—C9—C10	−1.0 (4)
C1—N1—C5—N2	−179.50 (16)	C8—C9—C10—C11	0.7 (4)
Zn1—N1—C5—N2	3.9 (2)	C9—C10—C11—C6	0.4 (3)
C3—C4—C5—N1	−0.7 (3)	C7—C6—C11—C10	−1.3 (3)
C3—C4—C5—N2	179.92 (19)	N3—C6—C11—C10	178.7 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···Cl1ii	0.93	2.75	3.675 (2)	173
C1—H1···Cl1	0.93	2.81	3.411 (2)	124

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
C3H3Cl1i	0.93	2.75	3.675(2)	173
C1H1Cl1	0.93	2.81	3.411(2)	124

Symmetry code: (i) .