Crystal structure of di-chlorido-(2,2':6',2''-terpyridine-κ(3) N,N',N'')zinc: a redeter-min-ation.

The crystal structure of the title compound, [ZnCl2(C15H11N3)], was redetermined based on modern CCD data. In comparison with the previous determination from photographic film data [Corbridge & Cox (1956 ▶). J. Chem. Soc. 159, 594-603; Einstein & Penfold (1966 ▶). Acta Cryst. 20, 924-926], all non-H atoms were refined with anisotropic displacement parameters, leading to a much higher precision in terms of bond lengths and angles [e.g. Zn-Cl = 2.2684 (8) and 2.2883 (11) compared to 2.25 (1) and 2.27 (1) Å]. In the title mol-ecule, the Zn(II) atom is five-coordinated in a distorted square-pyramidal mode by two Cl atoms and by the three N atoms from the 2,2':6',2''-terpyridine ligand. The latter is not planar and shows dihedral angles between the least-squares planes of the central pyridine ring and the terminal rings of 3.18 (8) and 6.36 (9)°. The mol-ecules in the crystal structure pack with π-π inter-actions [centroid-centroid distance = 3.655 (2) Å] between pyridine rings of neighbouring terpyridine moieties. These, together with inter-molecular C-H⋯Cl inter-actions, stablize the three-dimensional structure.

Related literature

The title compound is dimorphic, with one polymorph (form I) crystallizing in space group No. 15, and the second polymorph (type II) crystallizing in space group No. 14 (Corbridge & Cox, 1956 ▶). The crystal structure of the title compound was originally determined by Corbridge & Cox (1956 ▶) from photographic data (final R value = 0.24) and was later re-refined by Einstein & Penfold (1966 ▶) based on the original intensity data but using more advanced least-squares procedures (R = 0.14). In both reports, the setting in P21/a of space group No. 14 was used. For background to terpyridine-based materials, see: Fermi et al. (2014 ▶); Song et al. (2014 ▶). For the biocompatibility of zinc compounds, see: Gao et al. (2009 ▶).

Experimental

Crystal data

[ZnCl2(C15H11N3)]

M = 369.54

Monoclinic,

a = 10.950 (5) Å

b = 8.250 (5) Å

c = 16.216 (5) Å

β = 93.911 (5)°

V = 1461.5 (12) Å3

Z = 4

Mo Kα radiation

μ = 2.04 mm−1

T = 298 K

0.30 × 0.20 × 0.20 mm

Data collection

Bruker SMART CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2002 ▶) T min = 0.580, T max = 0.686

9990 measured reflections

2564 independent reflections

2404 reflections with I > 2σ(I)

R int = 0.017

Refinement

R[F 2 > 2σ(F 2)] = 0.020

wR(F 2) = 0.056

S = 1.05

2564 reflections

190 parameters

H-atom parameters constrained

Δρmax = 0.24 e Å−3

Δρmin = −0.24 e Å−3

Data collection: SMART (Bruker, 2002 ▶); 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 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Crystal structure: contains datablock(s) I, Global. DOI: 10.1107/S1600536814023605/wm5082sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814023605/wm5082Isup2.hkl

Click here for additional data file.

. DOI: 10.1107/S1600536814023605/wm5082fig1.tif

The mol­ecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

Click here for additional data file.

. DOI: 10.1107/S1600536814023605/wm5082fig2.tif

The arrangement of the mol­ecules in the crystal structure of (I), showing π—π inter­actions (dashed red lines) and C—H⋯Cl hydrogen bonds (dashed green and turquoise lines).

Click here for additional data file.

. DOI: 10.1107/S1600536814023605/wm5082fig3.tif

Packing diagram of (I). All H atoms have been omitted for clarity.

CCDC reference: 1029855

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

[ZnCl2(C15H11N3)]	F(000) = 744
Mr = 369.54	Dx = 1.679 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ybc	Cell parameters from 6593 reflections
a = 10.950 (5) Å	θ = 2.8–26.9°
b = 8.250 (5) Å	µ = 2.04 mm−1
c = 16.216 (5) Å	T = 298 K
β = 93.911 (5)°	Block, colorless
V = 1461.5 (12) Å3	0.30 × 0.20 × 0.20 mm
Z = 4

Bruker SMART CCD diffractometer	2564 independent reflections
Radiation source: fine-focus sealed tube	2404 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.017
φ and ω scans	θmax = 25.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −13→12
Tmin = 0.580, Tmax = 0.686	k = −9→9
9990 measured reflections	l = −18→19

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)] = 0.020	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.056	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0322P)2 + 0.4083P] where P = (Fo2 + 2Fc2)/3
2564 reflections	(Δ/σ)max < 0.001
190 parameters	Δρmax = 0.24 e Å−3
0 restraints	Δρmin = −0.24 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.

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.

	x	y	z	Uiso*/Ueq
Zn1	0.217983 (18)	0.40487 (2)	0.117728 (11)	0.03587 (8)
Cl2	0.33535 (4)	0.17571 (5)	0.13148 (3)	0.04477 (12)
Cl3	0.13940 (5)	0.47642 (7)	0.23837 (3)	0.06000 (15)
N1	0.35875 (14)	0.59791 (17)	0.11822 (9)	0.0384 (3)
N2	0.22895 (12)	0.47354 (16)	−0.00704 (8)	0.0324 (3)
N3	0.05709 (13)	0.29671 (17)	0.05158 (9)	0.0385 (3)
C4	0.48010 (17)	0.7621 (2)	0.03495 (12)	0.0471 (4)
H4	0.5007	0.7944	−0.0173	0.057*
C5	0.39054 (15)	0.6462 (2)	0.04352 (10)	0.0353 (4)
C10	0.15500 (16)	0.40050 (19)	−0.06497 (11)	0.0352 (4)
C9	0.17350 (19)	0.4201 (2)	−0.14845 (11)	0.0462 (5)
H9	0.1228	0.3690	−0.1888	0.055*
C12	−0.03366 (17)	0.2236 (2)	−0.08134 (13)	0.0463 (4)
H12	−0.0337	0.2290	−0.1386	0.056*
C2	0.5060 (2)	0.7802 (2)	0.18111 (14)	0.0564 (5)
H2	0.5441	0.8240	0.2291	0.068*
C8	0.26887 (19)	0.5170 (3)	−0.16981 (11)	0.0497 (5)
H8	0.2832	0.5304	−0.2253	0.060*
C15	−0.02974 (17)	0.2127 (2)	0.08669 (13)	0.0459 (4)
H15	−0.0286	0.2094	0.1441	0.055*
C6	0.32011 (15)	0.56916 (19)	−0.02768 (10)	0.0336 (4)
C11	0.05559 (15)	0.3024 (2)	−0.03164 (11)	0.0369 (4)
C1	0.41594 (19)	0.6650 (2)	0.18517 (12)	0.0485 (5)
H1	0.3938	0.6323	0.2370	0.058*
C14	−0.12109 (18)	0.1307 (2)	0.04107 (15)	0.0522 (5)
H14	−0.1802	0.0728	0.0673	0.063*
C13	−0.12326 (18)	0.1362 (2)	−0.04368 (15)	0.0542 (5)
H13	−0.1841	0.0819	−0.0756	0.065*
C3	0.53854 (19)	0.8291 (3)	0.10520 (14)	0.0560 (5)
H3	0.5994	0.9067	0.1008	0.067*
C7	0.34327 (18)	0.5944 (2)	−0.11007 (11)	0.0430 (4)
H7	0.4068	0.6613	−0.1244	0.052*

	U11	U22	U33	U12	U13	U23
Zn1	0.04271 (14)	0.03704 (13)	0.02811 (12)	0.00301 (8)	0.00414 (9)	0.00265 (7)
Cl2	0.0482 (3)	0.0413 (2)	0.0446 (3)	0.00621 (19)	0.00184 (19)	0.00566 (19)
Cl3	0.0765 (4)	0.0645 (3)	0.0410 (3)	0.0083 (3)	0.0181 (2)	−0.0013 (2)
N1	0.0457 (8)	0.0353 (8)	0.0339 (8)	0.0016 (6)	0.0007 (6)	0.0008 (6)
N2	0.0369 (7)	0.0307 (7)	0.0296 (7)	0.0045 (6)	0.0023 (6)	0.0007 (5)
N3	0.0390 (8)	0.0358 (8)	0.0410 (8)	0.0042 (6)	0.0045 (6)	0.0028 (6)
C4	0.0467 (11)	0.0434 (10)	0.0518 (11)	−0.0007 (8)	0.0073 (9)	0.0049 (8)
C5	0.0361 (9)	0.0319 (8)	0.0381 (9)	0.0066 (7)	0.0039 (7)	0.0012 (7)
C10	0.0390 (9)	0.0332 (9)	0.0330 (9)	0.0083 (7)	0.0005 (7)	−0.0021 (7)
C9	0.0546 (11)	0.0507 (11)	0.0328 (10)	0.0051 (9)	−0.0013 (8)	−0.0075 (8)
C12	0.0454 (10)	0.0379 (10)	0.0541 (11)	0.0058 (8)	−0.0071 (8)	−0.0063 (8)
C2	0.0657 (13)	0.0434 (11)	0.0571 (13)	−0.0012 (10)	−0.0170 (10)	−0.0062 (10)
C8	0.0623 (12)	0.0595 (12)	0.0284 (9)	0.0057 (10)	0.0120 (8)	0.0005 (8)
C15	0.0426 (10)	0.0410 (10)	0.0549 (11)	0.0047 (8)	0.0101 (8)	0.0073 (8)
C6	0.0359 (9)	0.0315 (8)	0.0335 (9)	0.0073 (7)	0.0045 (7)	0.0014 (7)
C11	0.0370 (9)	0.0304 (8)	0.0429 (10)	0.0077 (7)	−0.0015 (7)	−0.0017 (7)
C1	0.0646 (12)	0.0426 (11)	0.0370 (10)	0.0025 (9)	−0.0063 (9)	−0.0023 (8)
C14	0.0384 (10)	0.0358 (10)	0.0831 (16)	0.0036 (8)	0.0102 (10)	0.0056 (10)
C13	0.0402 (10)	0.0361 (10)	0.0844 (16)	0.0035 (8)	−0.0091 (10)	−0.0081 (10)
C3	0.0493 (11)	0.0444 (11)	0.0731 (15)	−0.0086 (9)	−0.0050 (10)	−0.0010 (10)
C7	0.0477 (11)	0.0461 (11)	0.0365 (10)	0.0045 (8)	0.0132 (8)	0.0037 (8)

Zn1—N2	2.1123 (14)	C9—H9	0.9300
Zn1—N3	2.1893 (16)	C12—C11	1.386 (3)
Zn1—N1	2.2160 (17)	C12—C13	1.392 (3)
Zn1—Cl3	2.2684 (8)	C12—H12	0.9300
Zn1—Cl2	2.2883 (11)	C2—C3	1.365 (3)
N1—C1	1.336 (2)	C2—C1	1.375 (3)
N1—C5	1.343 (2)	C2—H2	0.9300
N2—C6	1.333 (2)	C8—C7	1.379 (3)
N2—C10	1.341 (2)	C8—H8	0.9300
N3—C15	1.335 (2)	C15—C14	1.380 (3)
N3—C11	1.349 (2)	C15—H15	0.9300
C4—C5	1.383 (3)	C6—C7	1.393 (2)
C4—C3	1.384 (3)	C1—H1	0.9300
C4—H4	0.9300	C14—C13	1.374 (3)
C5—C6	1.487 (2)	C14—H14	0.9300
C10—C9	1.392 (3)	C13—H13	0.9300
C10—C11	1.487 (2)	C3—H3	0.9300
C9—C8	1.378 (3)	C7—H7	0.9300
N2—Zn1—N3	74.72 (6)	C11—C12—H12	120.7
N2—Zn1—N1	74.08 (5)	C13—C12—H12	120.7
N3—Zn1—N1	146.20 (6)	C3—C2—C1	118.67 (19)
N2—Zn1—Cl3	143.70 (4)	C3—C2—H2	120.7
N3—Zn1—Cl3	100.88 (5)	C1—C2—H2	120.7
N1—Zn1—Cl3	96.58 (5)	C7—C8—C9	120.90 (17)
N2—Zn1—Cl2	104.28 (4)	C7—C8—H8	119.5
N3—Zn1—Cl2	97.98 (5)	C9—C8—H8	119.5
N1—Zn1—Cl2	101.98 (6)	N3—C15—C14	122.48 (19)
Cl3—Zn1—Cl2	111.99 (2)	N3—C15—H15	118.8
C1—N1—C5	118.30 (16)	C14—C15—H15	118.8
C1—N1—Zn1	126.03 (13)	N2—C6—C7	121.20 (16)
C5—N1—Zn1	115.64 (11)	N2—C6—C5	114.56 (14)
C6—N2—C10	121.12 (14)	C7—C6—C5	124.22 (16)
C6—N2—Zn1	119.46 (11)	N3—C11—C12	121.68 (17)
C10—N2—Zn1	118.66 (11)	N3—C11—C10	115.04 (15)
C15—N3—C11	118.97 (16)	C12—C11—C10	123.27 (17)
C15—N3—Zn1	125.12 (13)	N1—C1—C2	123.08 (19)
C11—N3—Zn1	115.48 (11)	N1—C1—H1	118.5
C5—C4—C3	119.01 (18)	C2—C1—H1	118.5
C5—C4—H4	120.5	C13—C14—C15	118.87 (19)
C3—C4—H4	120.5	C13—C14—H14	120.6
N1—C5—C4	121.64 (17)	C15—C14—H14	120.6
N1—C5—C6	114.90 (15)	C14—C13—C12	119.42 (19)
C4—C5—C6	123.44 (16)	C14—C13—H13	120.3
N2—C10—C9	120.56 (17)	C12—C13—H13	120.3
N2—C10—C11	114.32 (15)	C2—C3—C4	119.32 (19)
C9—C10—C11	125.12 (16)	C2—C3—H3	120.3
C8—C9—C10	118.35 (18)	C4—C3—H3	120.3
C8—C9—H9	120.8	C8—C7—C6	117.84 (17)
C10—C9—H9	120.8	C8—C7—H7	121.1
C11—C12—C13	118.6 (2)	C6—C7—H7	121.1
N2—Zn1—N1—C1	174.74 (16)	N2—C10—C9—C8	−0.5 (3)
N3—Zn1—N1—C1	151.48 (14)	C11—C10—C9—C8	179.05 (16)
Cl3—Zn1—N1—C1	30.57 (15)	C10—C9—C8—C7	−0.8 (3)
Cl2—Zn1—N1—C1	−83.62 (15)	C11—N3—C15—C14	0.2 (3)
N2—Zn1—N1—C5	−7.44 (11)	Zn1—N3—C15—C14	−171.91 (14)
N3—Zn1—N1—C5	−30.69 (17)	C10—N2—C6—C7	−1.2 (2)
Cl3—Zn1—N1—C5	−151.60 (11)	Zn1—N2—C6—C7	168.70 (12)
Cl2—Zn1—N1—C5	94.20 (11)	C10—N2—C6—C5	177.68 (14)
N3—Zn1—N2—C6	177.72 (13)	Zn1—N2—C6—C5	−12.46 (18)
N1—Zn1—N2—C6	10.88 (11)	N1—C5—C6—N2	5.3 (2)
Cl3—Zn1—N2—C6	90.10 (13)	C4—C5—C6—N2	−173.10 (16)
Cl2—Zn1—N2—C6	−87.75 (12)	N1—C5—C6—C7	−175.93 (16)
N3—Zn1—N2—C10	−12.17 (11)	C4—C5—C6—C7	5.7 (3)
N1—Zn1—N2—C10	−179.01 (13)	C15—N3—C11—C12	0.0 (2)
Cl3—Zn1—N2—C10	−99.79 (13)	Zn1—N3—C11—C12	172.94 (13)
Cl2—Zn1—N2—C10	82.36 (12)	C15—N3—C11—C10	179.28 (14)
N2—Zn1—N3—C15	−177.15 (15)	Zn1—N3—C11—C10	−7.83 (18)
N1—Zn1—N3—C15	−153.97 (13)	C13—C12—C11—N3	−0.2 (3)
Cl3—Zn1—N3—C15	−34.18 (14)	C13—C12—C11—C10	−179.42 (16)
Cl2—Zn1—N3—C15	80.15 (14)	N2—C10—C11—N3	−2.3 (2)
N2—Zn1—N3—C11	10.46 (11)	C9—C10—C11—N3	178.21 (16)
N1—Zn1—N3—C11	33.64 (17)	N2—C10—C11—C12	176.96 (15)
Cl3—Zn1—N3—C11	153.42 (11)	C9—C10—C11—C12	−2.6 (3)
Cl2—Zn1—N3—C11	−92.24 (11)	C5—N1—C1—C2	−0.4 (3)
C1—N1—C5—C4	0.1 (2)	Zn1—N1—C1—C2	177.41 (15)
Zn1—N1—C5—C4	−177.91 (13)	C3—C2—C1—N1	0.2 (3)
C1—N1—C5—C6	−178.31 (15)	N3—C15—C14—C13	−0.3 (3)
Zn1—N1—C5—C6	3.69 (18)	C15—C14—C13—C12	0.1 (3)
C3—C4—C5—N1	0.3 (3)	C11—C12—C13—C14	0.2 (3)
C3—C4—C5—C6	178.53 (17)	C1—C2—C3—C4	0.1 (3)
C6—N2—C10—C9	1.4 (2)	C5—C4—C3—C2	−0.4 (3)
Zn1—N2—C10—C9	−168.50 (13)	C9—C8—C7—C6	1.1 (3)
C6—N2—C10—C11	−178.11 (14)	N2—C6—C7—C8	−0.1 (3)
Zn1—N2—C10—C11	11.94 (18)	C5—C6—C7—C8	−178.83 (16)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···Cl2i	0.93	2.68	3.518 (2)	151
C13—H13···Cl2ii	0.93	2.81	3.686 (2)	158

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
C4H4Cl2i	0.93	2.68	3.518(2)	151
C13H13Cl2ii	0.93	2.81	3.686(2)	158

Symmetry codes: (i) ; (ii) .