[Bis(2-pyridylmethyl)amine]dichloridozinc(II) chloro­form solvate

Kim, Y.-I.; Lee, Y.-S.; Seo, H.-J.; Lee, J.-Y.; Kang, S.K.

doi:10.1107/S1600536807051422

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[Bis(2-pyridylmethyl)amine]dichloridozinc(II) chloroform solvate

Y.-I. Kim, Y.-S. Lee, H.-J. Seo, J.-Y. Lee and S. K. Kang

The Zn atom in the title complex, [ZnCl₂(C₁₂H₁₃N₃)]·CHCl₃, adopts a distorted square-pyramidal geometry, being coordinated by three N atoms of the tridentate dipicolylamine ligand and two Cl atoms. Intermolecular N—H

Cl hydrogen-bonding interactions link the molecules into centrosymmetric dimers.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807051422/tk2200sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807051422/tk2200Isup2.hkl Contains datablock I

CCDC reference: 667218

checkCIF report

Key indicators

Single-crystal X-ray study
T = 295 K
Mean (C-C) = 0.007 Å
R factor = 0.046
wR factor = 0.132
Data-to-parameter ratio = 23.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       1.02
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        C16
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          7

Alert level G
PLAT793_ALERT_1_G Check the Absolute Configuration of N8     = ...          S
PLAT794_ALERT_5_G Check Predicted Bond Valency for Zn          (2)       1.89

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   1 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
   1 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

Comment top

Transition metal complexes with di(2-picolyl)amine (dpa) or substituted-dpa ligands continue to be of interest in many fields in chemistry (Kirin et al., 2005; Storr et al., 2005; Tamamura et al., 2006 & Lee et al., 2007). Among them, Zn(II) complexes exhibit fluorescence and can be applied as fluorescent chemosensors (Ojida et al., 2004). The Zn(II) center in the title [Zn(dpa)Cl₂] complex, characterized as a monochloroform solvate, (I), is five-coordinated by the three N atoms of the dpa ligand and two Cl atoms (Fig. 1 & Table 1). The coordination pattern of the three N atoms of the dpa ligand is meridional and forms a planar ZnN₃ arrangement and the overall coordination geometry is based on a square pyramid. The calculated trigonality index, τ, for Zn(dpa)Cl₂ in (I), of 0.21, is consistent with this conclusion (τ = 0 for a square pyramid and τ = 1 for a trigonal bipyramid (Addison et al., 1984)). Hydrogen bonding interactions of the type N—H···Cl link molecules into centrosymmetric dimeric aggregates (Table 2). Upon excitation at 400 nm, complex (I) exhibits an intense blue emission at 426 nm in DMF solution.

Related literature top

For general background see: Kirin et al. (2005); Storr et al. (2005); Tamamura et al. (2006); Lee et al. (2007) & Ojida et al. (2004). For related literature, see: Addison et al. (1984).

Experimental top

All reagents and solvents were purchased from Aldrich and used without further purification. A mixture of ZnCl₂ (0.66 g, 5 mmol) and di(2-picolyl)amine (0.99 g, 5 mmol) in ethanol (20 ml) was stirred at room temperature under an nitrogen atmosphere. The precipitates were filtered off and recrystallized from chloroform to yield (I). ¹H NMR for dpa in (I) (d₆-DMSO, p.p.m.): δ: 8.76 (d, 2H), 8.00 (m, 2H), 7.55 (t, 4H), 4.90 (t, 1H), 4.13 (s, 4H).

Structure description top

For general background see: Kirin et al. (2005); Storr et al. (2005); Tamamura et al. (2006); Lee et al. (2007) & Ojida et al. (2004). For related literature, see: Addison et al. (1984).

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. Molecular structure of (I), showing the atom-numbering scheme and 30% probability ellipsoids.

(I) top

Crystal data top

[ZnCl₂(C₁₂H₁₃N₃)]·CHCl₃	F(000) = 912
M_r = 454.89	D_x = 1.611 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5802 reflections
a = 6.9650 (6) Å	θ = 2.5–23.5°
b = 12.8654 (12) Å	µ = 2.02 mm⁻¹
c = 20.9341 (18) Å	T = 295 K
β = 90.335 (5)°	Block, colourless
V = 1875.8 (3) Å³	0.20 × 0.18 × 0.17 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	3104 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.055
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	θ_max = 28.4°, θ_min = 1.9°
T_min = 0.661, T_max = 0.697	h = −9→9
36984 measured reflections	k = −17→17
4676 independent reflections	l = −27→27

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.046	w = 1/[σ²(F_o²) + (0.0612P)² + 1.569P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.132	(Δ/σ)_max < 0.001
S = 1.03	Δρ_max = 0.85 e Å⁻³
4676 reflections	Δρ_min = −0.76 e Å⁻³
203 parameters

Crystal data top

[ZnCl₂(C₁₂H₁₃N₃)]·CHCl₃	V = 1875.8 (3) Å³
M_r = 454.89	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.9650 (6) Å	µ = 2.02 mm⁻¹
b = 12.8654 (12) Å	T = 295 K
c = 20.9341 (18) Å	0.20 × 0.18 × 0.17 mm
β = 90.335 (5)°

Data collection top

Bruker SMART CCD area-detector diffractometer	4676 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	3104 reflections with I > 2σ(I)
T_min = 0.661, T_max = 0.697	R_int = 0.055
36984 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.132	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.85 e Å⁻³
4676 reflections	Δρ_min = −0.76 e Å⁻³
203 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Zn	0.58918 (5)	0.97733 (3)	0.110162 (18)	0.04221 (14)
Cl1	0.69504 (13)	0.90035 (8)	0.20260 (4)	0.0528 (2)
Cl2	0.80351 (14)	1.08035 (8)	0.05874 (4)	0.0566 (3)
N1	0.4222 (4)	1.1003 (3)	0.15276 (15)	0.0514 (7)
C2	0.4828 (7)	1.1957 (4)	0.1677 (2)	0.0665 (11)
H2	0.6083	1.2144	0.1581	0.08*
C3	0.3661 (8)	1.2674 (4)	0.1968 (2)	0.0819 (15)
H3	0.4118	1.3332	0.207	0.098*
C4	0.1807 (8)	1.2396 (5)	0.2105 (2)	0.0817 (15)
H4	0.0986	1.2869	0.2299	0.098*
C5	0.1169 (6)	1.1420 (4)	0.1956 (2)	0.0722 (13)
H5	−0.0084	1.1222	0.2047	0.087*
C6	0.2417 (5)	1.0731 (3)	0.16676 (16)	0.0521 (9)
C7	0.1865 (5)	0.9624 (3)	0.1518 (2)	0.0577 (10)
H7A	0.2079	0.9192	0.1892	0.069*
H7B	0.0512	0.9592	0.1408	0.069*
N8	0.3013 (4)	0.9232 (3)	0.09836 (15)	0.0462 (7)
H8	0.252 (5)	0.947 (3)	0.0644 (19)	0.045 (11)*
C9	0.3055 (6)	0.8096 (3)	0.0925 (2)	0.0553 (10)
H9A	0.185	0.7851	0.0745	0.066*
H9B	0.3218	0.7785	0.1344	0.066*
C10	0.4691 (6)	0.7776 (3)	0.04990 (17)	0.0517 (9)
C11	0.4684 (8)	0.6857 (3)	0.0160 (2)	0.0721 (13)
H11	0.3635	0.6411	0.0176	0.087*
C12	0.6275 (9)	0.6612 (4)	−0.0206 (2)	0.0844 (15)
H12	0.6321	0.599	−0.0431	0.101*
C13	0.7771 (8)	0.7294 (4)	−0.0231 (2)	0.0775 (14)
H13	0.884	0.7148	−0.048	0.093*
C14	0.7680 (6)	0.8190 (4)	0.01125 (19)	0.0597 (10)
H14	0.8708	0.865	0.0094	0.072*
N15	0.6173 (4)	0.8437 (2)	0.04767 (14)	0.0482 (7)
C16	0.9172 (9)	0.5298 (4)	0.1609 (2)	0.0859 (16)
H16	0.8947	0.4975	0.2026	0.103*
Cl3	1.1706 (3)	0.53673 (14)	0.14969 (12)	0.1342 (7)
Cl4	0.8241 (3)	0.65527 (13)	0.16368 (8)	0.1098 (5)
Cl5	0.8131 (5)	0.4523 (2)	0.10431 (13)	0.1840 (12)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn	0.0364 (2)	0.0507 (2)	0.0396 (2)	−0.00151 (17)	0.00611 (15)	−0.00004 (18)
Cl1	0.0524 (5)	0.0634 (6)	0.0426 (5)	0.0039 (4)	0.0040 (4)	0.0078 (4)
Cl2	0.0553 (5)	0.0690 (6)	0.0458 (5)	−0.0137 (5)	0.0094 (4)	0.0064 (4)
N1	0.0486 (17)	0.057 (2)	0.0483 (17)	0.0100 (14)	0.0022 (13)	0.0002 (15)
C2	0.071 (3)	0.063 (3)	0.066 (3)	0.008 (2)	0.001 (2)	−0.010 (2)
C3	0.104 (4)	0.068 (3)	0.074 (3)	0.025 (3)	−0.009 (3)	−0.023 (3)
C4	0.086 (4)	0.098 (4)	0.062 (3)	0.043 (3)	−0.002 (2)	−0.022 (3)
C5	0.055 (2)	0.106 (4)	0.056 (3)	0.025 (3)	0.0048 (19)	−0.009 (3)
C6	0.045 (2)	0.074 (3)	0.0372 (18)	0.0155 (18)	0.0046 (15)	0.0008 (18)
C7	0.0410 (19)	0.074 (3)	0.058 (2)	0.0064 (18)	0.0086 (17)	0.008 (2)
N8	0.0393 (15)	0.058 (2)	0.0408 (16)	−0.0017 (14)	0.0009 (13)	0.0050 (15)
C9	0.053 (2)	0.055 (2)	0.059 (2)	−0.0118 (18)	0.0001 (18)	0.0050 (18)
C10	0.059 (2)	0.053 (2)	0.043 (2)	−0.0036 (18)	−0.0042 (16)	0.0019 (17)
C11	0.097 (4)	0.055 (3)	0.064 (3)	−0.005 (2)	−0.008 (3)	−0.009 (2)
C12	0.117 (5)	0.069 (3)	0.067 (3)	0.011 (3)	−0.001 (3)	−0.023 (3)
C13	0.089 (3)	0.082 (3)	0.061 (3)	0.016 (3)	0.013 (2)	−0.014 (3)
C14	0.059 (2)	0.070 (3)	0.050 (2)	0.010 (2)	0.0101 (18)	−0.003 (2)
N15	0.0487 (17)	0.0533 (18)	0.0426 (16)	−0.0011 (14)	0.0044 (13)	−0.0029 (14)
C16	0.128 (5)	0.071 (3)	0.059 (3)	0.006 (3)	0.009 (3)	−0.001 (2)
Cl3	0.1399 (17)	0.0955 (12)	0.168 (2)	0.0094 (11)	0.0342 (14)	0.0047 (12)
Cl4	0.1519 (15)	0.0851 (10)	0.0925 (10)	0.0336 (10)	0.0029 (10)	0.0020 (8)
Cl5	0.245 (3)	0.141 (2)	0.165 (2)	0.0070 (19)	−0.077 (2)	−0.0631 (17)

Geometric parameters (Å, º) top

Zn—N1	2.159 (3)	C7—H7B	0.97
Zn—N8	2.136 (3)	N8—H8	0.85 (4)
Zn—N15	2.170 (3)	C9—C10	1.508 (5)
Zn—Cl1	2.2919 (10)	C9—H9A	0.97
Zn—Cl2	2.2722 (9)	C9—H9B	0.97
N1—C2	1.335 (5)	C10—N15	1.338 (5)
N1—C6	1.339 (5)	C10—C11	1.380 (6)
C2—C3	1.374 (6)	C11—C12	1.386 (7)
C2—H2	0.93	C11—H11	0.93
C3—C4	1.372 (8)	C12—C13	1.364 (7)
C3—H3	0.93	C12—H12	0.93
C4—C5	1.367 (7)	C13—C14	1.360 (6)
C4—H4	0.93	C13—H13	0.93
C5—C6	1.382 (6)	C14—N15	1.340 (5)
C5—H5	0.93	C14—H14	0.93
C6—C7	1.507 (6)	C16—Cl5	1.706 (6)
N8—C9	1.467 (5)	C16—Cl4	1.741 (5)
C7—N8	1.468 (5)	C16—Cl3	1.784 (7)
C7—H7A	0.97	C16—H16	0.98

N1—Zn—N8	77.23 (12)	C9—N8—Zn	108.4 (2)
N1—Zn—N15	151.65 (12)	C7—N8—Zn	108.3 (2)
N1—Zn—Cl1	98.01 (9)	C9—N8—H8	108 (3)
N1—Zn—Cl2	97.20 (9)	C7—N8—H8	107 (3)
N8—Zn—N15	76.11 (12)	Zn—N8—H8	111 (3)
N8—Zn—Cl1	104.71 (9)	N8—C9—C10	109.7 (3)
N8—Zn—Cl2	138.97 (9)	N8—C9—H9A	109.7
N15—Zn—Cl1	97.87 (9)	C10—C9—H9A	109.7
N15—Zn—Cl2	96.59 (8)	N8—C9—H9B	109.7
Cl1—Zn—Cl2	116.30 (4)	C10—C9—H9B	109.7
C2—N1—C6	119.0 (4)	H9A—C9—H9B	108.2
C2—N1—Zn	126.9 (3)	N15—C10—C11	121.8 (4)
C6—N1—Zn	114.1 (3)	N15—C10—C9	115.7 (3)
N1—C2—C3	122.3 (5)	C11—C10—C9	122.5 (4)
N1—C2—H2	118.9	C10—C11—C12	118.6 (5)
C3—C2—H2	118.9	C10—C11—H11	120.7
C4—C3—C2	118.6 (5)	C12—C11—H11	120.7
C4—C3—H3	120.7	C13—C12—C11	119.3 (5)
C2—C3—H3	120.7	C13—C12—H12	120.3
C5—C4—C3	119.8 (4)	C11—C12—H12	120.3
C5—C4—H4	120.1	C14—C13—C12	119.1 (5)
C3—C4—H4	120.1	C14—C13—H13	120.5
C4—C5—C6	119.0 (5)	C12—C13—H13	120.5
C4—C5—H5	120.5	N15—C14—C13	122.8 (4)
C6—C5—H5	120.5	N15—C14—H14	118.6
N1—C6—C5	121.4 (4)	C13—C14—H14	118.6
N1—C6—C7	116.1 (3)	C10—N15—C14	118.4 (3)
C5—C6—C7	122.4 (4)	C10—N15—Zn	114.2 (2)
N8—C7—C6	110.1 (3)	C14—N15—Zn	127.2 (3)
N8—C7—H7A	109.6	Cl5—C16—Cl4	114.1 (4)
C6—C7—H7A	109.6	Cl5—C16—Cl3	110.8 (3)
N8—C7—H7B	109.6	Cl4—C16—Cl3	109.1 (3)
C6—C7—H7B	109.6	Cl5—C16—H16	107.5
H7A—C7—H7B	108.2	Cl4—C16—H16	107.5
C9—N8—C7	114.7 (3)	Cl3—C16—H16	107.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N8—H8···Cl2ⁱ	0.85 (4)	2.63 (4)	3.365 (3)	146 (3)

Symmetry code: (i) −x+1, −y+2, −z.

Experimental details

Crystal data
Chemical formula	[ZnCl₂(C₁₂H₁₃N₃)]·CHCl₃
M_r	454.89
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	295
a, b, c (Å)	6.9650 (6), 12.8654 (12), 20.9341 (18)
β (°)	90.335 (5)
V (Å³)	1875.8 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.02
Crystal size (mm)	0.20 × 0.18 × 0.17

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 2002)
T_min, T_max	0.661, 0.697
No. of measured, independent and observed [I > 2σ(I)] reflections	36984, 4676, 3104
R_int	0.055
(sin θ/λ)_max (Å⁻¹)	0.669

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.132, 1.03
No. of reflections	4676
No. of parameters	203
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.85, −0.76

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) top

Zn—N1	2.159 (3)	Zn—Cl1	2.2919 (10)
Zn—N8	2.136 (3)	Zn—Cl2	2.2722 (9)
Zn—N15	2.170 (3)

N1—Zn—N8	77.23 (12)	N8—Zn—Cl1	104.71 (9)
N1—Zn—N15	151.65 (12)	N8—Zn—Cl2	138.97 (9)
N1—Zn—Cl1	98.01 (9)	N15—Zn—Cl1	97.87 (9)
N1—Zn—Cl2	97.20 (9)	N15—Zn—Cl2	96.59 (8)
N8—Zn—N15	76.11 (12)	Cl1—Zn—Cl2	116.30 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N8—H8···Cl2ⁱ	0.85 (4)	2.63 (4)	3.365 (3)	146 (3)

Symmetry code: (i) −x+1, −y+2, −z.

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