Dichlorido(4'-phenyl-2,2':6',2''-ter-pyridyl)zinc.

The title compound, [ZnCl(2)(C(21)H(15)N(3))], was obtained from the reaction of ZnCl(2)·4H(2)O with 4'-phenyl-terpyridine (L) and disodium 2,6-dipicolinate. The Zn(2+) cation is ligated by the N atoms of the tridentate L ligand and two chloride anions, forming a ZnN(3)Cl(2) polyhedron with a distorted trigonal-bipyramidal coordination geometry. In the crystal, nonclassical C-H⋯Cl hydrogen bonds are observed.

Related literature

For the structures, properties and applications of MLX 2 compounds (M = transition metal, L = terpyridine, X = halogen), see: Bugarcic et al. (2004 ▶); Koo et al. (2003 ▶); Ma, Liu et al. (2009 ▶); Ma, Xing et al. (2009 ▶); Ma, Bi et al. (2010 ▶); Ma, Cao et al. (2010 ▶); Tu et al. (2004 ▶); Yam et al. (2003 ▶). For the preparation of the ligand, see: Constable et al. (1990 ▶). For standard bond lengths, see: Allen et al. (1987 ▶).

Experimental

Crystal data

[ZnCl2(C21H15N3)]

M = 445.63

Monoclinic,

a = 12.0728 (10) Å

b = 9.5640 (8) Å

c = 17.5822 (13) Å

β = 111.386 (5)°

V = 1890.3 (3) Å3

Z = 4

Mo Kα radiation

μ = 1.59 mm−1

T = 150 K

0.41 × 0.32 × 0.27 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.548, T max = 0.651

23122 measured reflections

4711 independent reflections

3809 reflections with I > 2σ(I)

R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.026

wR(F 2) = 0.066

S = 1.01

4711 reflections

244 parameters

H-atom parameters constrained

Δρmax = 0.30 e Å−3

Δρmin = −0.24 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2002 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812004862/wm2584sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812004862/wm2584Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[ZnCl2(C21H15N3)]	F(000) = 904
Mr = 445.63	Dx = 1.566 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 23122 reflections
a = 12.0728 (10) Å	θ = 2.5–28.3°
b = 9.5640 (8) Å	µ = 1.59 mm−1
c = 17.5822 (13) Å	T = 150 K
β = 111.386 (5)°	Prism, colorless
V = 1890.3 (3) Å3	0.41 × 0.32 × 0.27 mm
Z = 4

Bruker SMART CCD area-detector diffractometer	4711 independent reflections
Radiation source: fine-focus sealed tube	3809 reflections with I > 2σ(I)
Graphite Monochromator monochromator	Rint = 0.024
φ and ω scans	θmax = 28.3°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→16
Tmin = 0.548, Tmax = 0.651	k = −12→12
23122 measured reflections	l = −23→23

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.066	H-atom parameters constrained
S = 1.01	w = 1/[σ2(Fo2) + (0.0261P)2 + 0.8758P] where P = (Fo2 + 2Fc2)/3
4711 reflections	(Δ/σ)max = 0.001
244 parameters	Δρmax = 0.30 e Å−3
0 restraints	Δρmin = −0.24 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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.

	x	y	z	Uiso*/Ueq
Zn1	0.826519 (19)	0.72657 (2)	0.855588 (11)	0.04016 (7)
Cl1	0.69654 (5)	0.70715 (6)	0.72558 (3)	0.05675 (13)
Cl2	0.99013 (4)	0.85910 (5)	0.87665 (3)	0.05130 (12)
N1	0.72851 (13)	0.87880 (16)	0.90086 (8)	0.0417 (3)
N2	0.78944 (12)	0.62385 (15)	0.94908 (8)	0.0363 (3)
N3	0.90559 (13)	0.51746 (15)	0.86385 (8)	0.0408 (3)
C1	0.70079 (18)	1.0079 (2)	0.87212 (12)	0.0503 (4)
H1A	0.7176	1.0349	0.8267	0.060*
C2	0.64816 (19)	1.1033 (2)	0.90694 (13)	0.0556 (5)
H2A	0.6262	1.1914	0.8840	0.067*
C3	0.62875 (19)	1.0653 (2)	0.97635 (13)	0.0559 (5)
H3A	0.5961	1.1291	1.0023	0.067*
C4	0.65785 (18)	0.9324 (2)	1.00747 (11)	0.0492 (4)
H4A	0.6461	0.9054	1.0548	0.059*
C5	0.70490 (15)	0.83993 (19)	0.96679 (10)	0.0385 (4)
C6	0.73050 (15)	0.69077 (19)	0.98985 (9)	0.0372 (4)
C7	0.69419 (16)	0.62213 (19)	1.04596 (9)	0.0403 (4)
H7A	0.6542	0.6707	1.0740	0.048*
C8	0.71776 (15)	0.48016 (19)	1.06039 (9)	0.0390 (4)
C9	0.78203 (16)	0.41385 (19)	1.01902 (10)	0.0404 (4)
H9A	0.8017	0.3198	1.0285	0.048*
C10	0.81661 (15)	0.48883 (18)	0.96363 (9)	0.0362 (3)
C11	0.88390 (15)	0.42766 (18)	0.91567 (9)	0.0367 (3)
C12	0.92301 (17)	0.29096 (19)	0.92334 (11)	0.0445 (4)
H12A	0.9066	0.2303	0.9592	0.053*
C13	0.98702 (18)	0.2453 (2)	0.87693 (12)	0.0496 (4)
H13A	1.0140	0.1535	0.8811	0.060*
C14	1.01030 (18)	0.3371 (2)	0.82457 (11)	0.0498 (4)
H14A	1.0539	0.3091	0.7932	0.060*
C15	0.96758 (18)	0.4716 (2)	0.81954 (11)	0.0487 (4)
H15A	0.9826	0.5334	0.7836	0.058*
C16	0.67254 (16)	0.3996 (2)	1.11540 (10)	0.0415 (4)
C17	0.7271 (2)	0.2763 (2)	1.15197 (12)	0.0533 (5)
H17A	0.7972	0.2475	1.1462	0.064*
C18	0.6775 (2)	0.1954 (2)	1.19729 (12)	0.0611 (6)
H18A	0.7137	0.1121	1.2208	0.073*
C19	0.5750 (2)	0.2383 (2)	1.20741 (12)	0.0590 (6)
H19A	0.5412	0.1831	1.2367	0.071*
C20	0.52267 (18)	0.3626 (3)	1.17430 (12)	0.0563 (5)
H20A	0.4551	0.3932	1.1829	0.068*
C21	0.57041 (17)	0.4428 (2)	1.12796 (11)	0.0487 (4)
H21A	0.5338	0.5263	1.1051	0.058*

	U11	U22	U33	U12	U13	U23
Zn1	0.05320 (13)	0.04105 (12)	0.03372 (10)	−0.00062 (9)	0.02474 (9)	0.00281 (8)
Cl1	0.0724 (3)	0.0640 (3)	0.0343 (2)	0.0018 (2)	0.0199 (2)	0.0009 (2)
Cl2	0.0591 (3)	0.0462 (3)	0.0567 (3)	−0.0048 (2)	0.0307 (2)	0.0041 (2)
N1	0.0520 (9)	0.0415 (8)	0.0373 (7)	0.0009 (6)	0.0229 (6)	0.0018 (6)
N2	0.0439 (8)	0.0386 (8)	0.0305 (6)	0.0000 (6)	0.0187 (6)	0.0006 (5)
N3	0.0531 (9)	0.0403 (8)	0.0361 (7)	0.0008 (6)	0.0245 (6)	0.0013 (6)
C1	0.0650 (12)	0.0455 (11)	0.0466 (10)	0.0017 (9)	0.0276 (9)	0.0056 (8)
C2	0.0685 (13)	0.0421 (11)	0.0596 (12)	0.0074 (9)	0.0273 (10)	0.0049 (9)
C3	0.0669 (13)	0.0475 (12)	0.0613 (12)	0.0076 (10)	0.0328 (10)	−0.0058 (9)
C4	0.0605 (12)	0.0507 (11)	0.0454 (9)	0.0026 (9)	0.0301 (9)	−0.0023 (8)
C5	0.0430 (9)	0.0414 (9)	0.0338 (8)	−0.0008 (7)	0.0173 (7)	−0.0017 (7)
C6	0.0415 (9)	0.0421 (9)	0.0306 (7)	−0.0013 (7)	0.0163 (7)	−0.0022 (6)
C7	0.0462 (9)	0.0480 (10)	0.0317 (7)	−0.0009 (8)	0.0203 (7)	−0.0020 (7)
C8	0.0413 (9)	0.0492 (10)	0.0285 (7)	−0.0040 (7)	0.0148 (7)	0.0017 (7)
C9	0.0494 (10)	0.0402 (9)	0.0360 (8)	0.0000 (7)	0.0209 (7)	0.0043 (7)
C10	0.0409 (9)	0.0395 (9)	0.0303 (7)	−0.0012 (7)	0.0154 (6)	−0.0009 (6)
C11	0.0423 (9)	0.0405 (9)	0.0299 (7)	−0.0014 (7)	0.0162 (6)	−0.0016 (6)
C12	0.0553 (11)	0.0422 (10)	0.0395 (9)	0.0012 (8)	0.0216 (8)	0.0025 (7)
C13	0.0606 (12)	0.0424 (11)	0.0488 (10)	0.0062 (8)	0.0234 (9)	−0.0046 (8)
C14	0.0597 (12)	0.0547 (12)	0.0428 (9)	0.0045 (9)	0.0280 (9)	−0.0070 (8)
C15	0.0619 (12)	0.0521 (11)	0.0436 (9)	−0.0001 (9)	0.0329 (9)	0.0006 (8)
C16	0.0469 (10)	0.0504 (10)	0.0303 (7)	−0.0068 (8)	0.0175 (7)	0.0014 (7)
C17	0.0611 (12)	0.0607 (13)	0.0450 (10)	0.0034 (10)	0.0276 (9)	0.0107 (9)
C18	0.0788 (15)	0.0610 (14)	0.0476 (11)	−0.0018 (11)	0.0280 (10)	0.0156 (10)
C19	0.0674 (13)	0.0727 (15)	0.0407 (10)	−0.0248 (11)	0.0242 (9)	0.0033 (9)
C20	0.0488 (11)	0.0796 (16)	0.0468 (10)	−0.0141 (10)	0.0251 (9)	−0.0001 (10)
C21	0.0493 (10)	0.0593 (12)	0.0409 (9)	−0.0050 (9)	0.0203 (8)	0.0035 (8)

Zn1—N2	2.0987 (13)	C8—C16	1.488 (2)
Zn1—N3	2.1979 (15)	C9—C10	1.390 (2)
Zn1—N1	2.2000 (15)	C9—H9A	0.9300
Zn1—Cl1	2.2596 (5)	C10—C11	1.488 (2)
Zn1—Cl2	2.2609 (5)	C11—C12	1.380 (3)
N1—C1	1.330 (2)	C12—C13	1.383 (3)
N1—C5	1.343 (2)	C12—H12A	0.9300
N2—C10	1.334 (2)	C13—C14	1.374 (3)
N2—C6	1.342 (2)	C13—H13A	0.9300
N3—C15	1.336 (2)	C14—C15	1.376 (3)
N3—C11	1.346 (2)	C14—H14A	0.9300
C1—C2	1.376 (3)	C15—H15A	0.9300
C1—H1A	0.9300	C16—C17	1.389 (3)
C2—C3	1.373 (3)	C16—C21	1.392 (3)
C2—H2A	0.9300	C17—C18	1.393 (3)
C3—C4	1.378 (3)	C17—H17A	0.9300
C3—H3A	0.9300	C18—C19	1.375 (3)
C4—C5	1.383 (2)	C18—H18A	0.9300
C4—H4A	0.9300	C19—C20	1.372 (3)
C5—C6	1.484 (3)	C19—H19A	0.9300
C6—C7	1.383 (2)	C20—C21	1.388 (3)
C7—C8	1.392 (3)	C20—H20A	0.9300
C7—H7A	0.9300	C21—H21A	0.9300
C8—C9	1.395 (2)
N2—Zn1—N3	74.56 (5)	C7—C8—C16	121.66 (16)
N2—Zn1—N1	74.33 (5)	C9—C8—C16	120.63 (16)
N3—Zn1—N1	148.89 (5)	C10—C9—C8	119.80 (16)
N2—Zn1—Cl1	119.08 (4)	C10—C9—H9A	120.1
N3—Zn1—Cl1	96.70 (4)	C8—C9—H9A	120.1
N1—Zn1—Cl1	98.84 (4)	N2—C10—C9	121.20 (15)
N2—Zn1—Cl2	123.87 (4)	N2—C10—C11	114.77 (14)
N3—Zn1—Cl2	99.60 (4)	C9—C10—C11	124.03 (16)
N1—Zn1—Cl2	97.05 (4)	N3—C11—C12	121.80 (15)
Cl1—Zn1—Cl2	117.05 (2)	N3—C11—C10	114.47 (15)
C1—N1—C5	118.79 (16)	C12—C11—C10	123.73 (15)
C1—N1—Zn1	124.82 (12)	C11—C12—C13	119.10 (17)
C5—N1—Zn1	116.14 (12)	C11—C12—H12A	120.4
C10—N2—C6	120.02 (14)	C13—C12—H12A	120.4
C10—N2—Zn1	119.71 (11)	C14—C13—C12	119.22 (18)
C6—N2—Zn1	120.07 (11)	C14—C13—H13A	120.4
C15—N3—C11	118.29 (16)	C12—C13—H13A	120.4
C15—N3—Zn1	125.63 (12)	C13—C14—C15	118.50 (17)
C11—N3—Zn1	116.01 (11)	C13—C14—H14A	120.7
N1—C1—C2	122.63 (18)	C15—C14—H14A	120.7
N1—C1—H1A	118.7	N3—C15—C14	123.09 (17)
C2—C1—H1A	118.7	N3—C15—H15A	118.5
C3—C2—C1	118.47 (19)	C14—C15—H15A	118.5
C3—C2—H2A	120.8	C17—C16—C21	118.48 (17)
C1—C2—H2A	120.8	C17—C16—C8	121.08 (17)
C2—C3—C4	119.69 (19)	C21—C16—C8	120.36 (17)
C2—C3—H3A	120.2	C16—C17—C18	120.4 (2)
C4—C3—H3A	120.2	C16—C17—H17A	119.8
C3—C4—C5	118.55 (18)	C18—C17—H17A	119.8
C3—C4—H4A	120.7	C19—C18—C17	120.2 (2)
C5—C4—H4A	120.7	C19—C18—H18A	119.9
N1—C5—C4	121.73 (17)	C17—C18—H18A	119.9
N1—C5—C6	114.40 (14)	C20—C19—C18	120.05 (19)
C4—C5—C6	123.85 (15)	C20—C19—H19A	120.0
N2—C6—C7	121.49 (16)	C18—C19—H19A	120.0
N2—C6—C5	114.23 (14)	C19—C20—C21	120.2 (2)
C7—C6—C5	124.24 (15)	C19—C20—H20A	119.9
C6—C7—C8	119.76 (16)	C21—C20—H20A	119.9
C6—C7—H7A	120.1	C20—C21—C16	120.67 (19)
C8—C7—H7A	120.1	C20—C21—H21A	119.7
C7—C8—C9	117.67 (15)	C16—C21—H21A	119.7
N2—Zn1—N1—C1	−179.81 (17)	N1—C5—C6—C7	−168.21 (16)
N3—Zn1—N1—C1	178.96 (14)	C4—C5—C6—C7	10.2 (3)
Cl1—Zn1—N1—C1	−61.95 (16)	N2—C6—C7—C8	−0.7 (3)
Cl2—Zn1—N1—C1	56.93 (16)	C5—C6—C7—C8	176.87 (16)
N2—Zn1—N1—C5	6.05 (12)	C6—C7—C8—C9	2.4 (2)
N3—Zn1—N1—C5	4.82 (19)	C6—C7—C8—C16	−175.30 (15)
Cl1—Zn1—N1—C5	123.91 (12)	C7—C8—C9—C10	−2.1 (2)
Cl2—Zn1—N1—C5	−117.21 (12)	C16—C8—C9—C10	175.64 (15)
N3—Zn1—N2—C10	−6.33 (12)	C6—N2—C10—C9	1.8 (2)
N1—Zn1—N2—C10	174.33 (14)	Zn1—N2—C10—C9	−173.10 (12)
Cl1—Zn1—N2—C10	82.81 (13)	C6—N2—C10—C11	−178.90 (14)
Cl2—Zn1—N2—C10	−97.65 (12)	Zn1—N2—C10—C11	6.16 (19)
N3—Zn1—N2—C6	178.74 (14)	C8—C9—C10—N2	0.0 (3)
N1—Zn1—N2—C6	−0.59 (12)	C8—C9—C10—C11	−179.19 (15)
Cl1—Zn1—N2—C6	−92.12 (12)	C15—N3—C11—C12	−0.5 (3)
Cl2—Zn1—N2—C6	87.42 (13)	Zn1—N3—C11—C12	176.50 (13)
N2—Zn1—N3—C15	−177.69 (16)	C15—N3—C11—C10	178.75 (15)
N1—Zn1—N3—C15	−176.45 (14)	Zn1—N3—C11—C10	−4.23 (18)
Cl1—Zn1—N3—C15	63.93 (15)	N2—C10—C11—N3	−1.0 (2)
Cl2—Zn1—N3—C15	−55.03 (15)	C9—C10—C11—N3	178.25 (16)
N2—Zn1—N3—C11	5.53 (12)	N2—C10—C11—C12	178.27 (16)
N1—Zn1—N3—C11	6.77 (19)	C9—C10—C11—C12	−2.5 (3)
Cl1—Zn1—N3—C11	−112.85 (12)	N3—C11—C12—C13	0.5 (3)
Cl2—Zn1—N3—C11	128.19 (12)	C10—C11—C12—C13	−178.71 (17)
C5—N1—C1—C2	−0.4 (3)	C11—C12—C13—C14	0.2 (3)
Zn1—N1—C1—C2	−174.39 (16)	C12—C13—C14—C15	−0.7 (3)
N1—C1—C2—C3	3.1 (3)	C11—N3—C15—C14	−0.1 (3)
C1—C2—C3—C4	−2.5 (3)	Zn1—N3—C15—C14	−176.81 (15)
C2—C3—C4—C5	−0.7 (3)	C13—C14—C15—N3	0.7 (3)
C1—N1—C5—C4	−3.0 (3)	C7—C8—C16—C17	−157.38 (18)
Zn1—N1—C5—C4	171.47 (14)	C9—C8—C16—C17	25.0 (3)
C1—N1—C5—C6	175.42 (16)	C7—C8—C16—C21	26.0 (2)
Zn1—N1—C5—C6	−10.07 (19)	C9—C8—C16—C21	−151.68 (18)
C3—C4—C5—N1	3.6 (3)	C21—C16—C17—C18	2.6 (3)
C3—C4—C5—C6	−174.71 (18)	C8—C16—C17—C18	−174.12 (18)
C10—N2—C6—C7	−1.5 (2)	C16—C17—C18—C19	−1.2 (3)
Zn1—N2—C6—C7	173.40 (12)	C17—C18—C19—C20	−1.4 (3)
C10—N2—C6—C5	−179.26 (15)	C18—C19—C20—C21	2.4 (3)
Zn1—N2—C6—C5	−4.35 (19)	C19—C20—C21—C16	−0.9 (3)
N1—C5—C6—N2	9.5 (2)	C17—C16—C21—C20	−1.6 (3)
C4—C5—C6—N2	−172.12 (17)	C8—C16—C21—C20	175.17 (17)

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7A···Cl1i	0.93	2.78	3.546 (2)	140
C12—H12A···Cl2ii	0.93	2.83	3.583 (2)	139
C13—H13A···Cl2iii	0.93	2.83	3.694 (2)	155

Table 1

Selected bond lengths (Å)

Zn1—N2	2.0987 (13)
Zn1—N3	2.1979 (15)
Zn1—N1	2.2000 (15)
Zn1—Cl1	2.2596 (5)
Zn1—Cl2	2.2609 (5)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7A⋯Cl1i	0.93	2.78	3.546 (2)	140
C12—H12A⋯Cl2ii	0.93	2.83	3.583 (2)	139
C13—H13A⋯Cl2iii	0.93	2.83	3.694 (2)	155

Symmetry codes: (i) ; (ii) ; (iii) .