Dichloridobis(4-pyridylmethyl 1H-pyrrole-2-carboxyl­ate-κN)zinc

Li, C.; Zhang, G.; Yin, Z.

doi:10.1107/S1600536812001353

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Page m323

doi:10.1107/S1600536812001353

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Dichloridobis(4-pyridylmethyl 1H-pyrrole-2-carboxylate-κN)zinc

Can Li,^a Guilong Zhang ^b and Zhenming Yin ^a ^*

^aTianjin Key Laboratory of Structure and Performance for Functional Molecules, College of Chemistry, Tianjin Normal University, Tianjin 300387, People's Republic of China, and ^bAgro-Environmental Protection Institute, Ministry of Agriculture, Tianjin 300191, People's Republic of China
^*Correspondence e-mail: tjyinzm@yahoo.com.cn

(Received 19 December 2011; accepted 11 January 2012; online 24 February 2012)

In the title molecule, [ZnCl₂(C₁₁H₁₀N₂O₂)₂], the Zn^II ion, situated on a twofold axis, is in a distorted tetrahedral coordination environment formed by two chloride anions and two pyridine N atoms of the two organic ligands. In the pyrrole-2-carboxylate unit, the pyrrole N—H group and the carbonyl group point approximately in the same direction. The dihedral angle between the two pyridine rings is 54.8 (3)°. The complex molecules are connected into chains extending along [101] by N—H⋯Cl hydrogen bonds. The chains are further assembled into (-101) layers by C—H⋯O and C—H⋯Cl interactions.

Related literature

For the hydrogen-bonded assemblies of pyrrole-based structures, see: Wang & Yin (2007 ); Yin & Li (2006 ); Cui et al. (2009 ).

Experimental

Crystal data

[ZnCl₂(C₁₁H₁₀N₂O₂)₂]
M_r = 540.69
Monoclinic, C 2/c
a = 27.604 (14) Å
b = 6.205 (3) Å
c = 16.087 (8) Å
β = 120.309 (6)°
V = 2379 (2) Å³
Z = 4
Mo Kα radiation
μ = 1.29 mm⁻¹
T = 296 K
0.26 × 0.20 × 0.14 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ) T_min = 0.727, T_max = 1.000
6100 measured reflections
2098 independent reflections
1823 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.024
wR(F²) = 0.069
S = 1.06
2098 reflections
150 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯Cl1ⁱ	0.86	2.57	3.306 (3)	144
C3—H3⋯Cl1ⁱⁱ	0.93	2.75	3.495 (3)	138
C4—H4⋯O1ⁱⁱⁱ	0.93	2.54	3.354 (3)	146
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (ii) x, y+1, z; (iii) $[-x+{\script{1\over 2}}, -y+{\script{5\over 2}}, -z+1]$ .

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); 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: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812001353/gk2445sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812001353/gk2445Isup2.hkl

checkCIF report

Comment top

In our earlier works, we have reported the hydrogen-bonded assemblies of 4-pyridylmethyl 1H-pyrrole-2-carboxylate (Wang & Yin, 2007) and some other pyrrole-based compounds (Yin & Li, 2006; Cui et al. 2009) in the solid state. Combination of coordination bonding and hydrogen bonding is an effective strategy for the generation of supramolecular networks. Continuing our study, herein we report the crystal structure of the complex obtained with 4-pyridylmethyl-1H-pyrrole-2-carboxylate and ZnCl₂.

A perspective view of the title compound with atomic labeling is shown in Fig. 1. The complex consists of one ZnCl₂ and two ligand molecules, in which both the pyrrole-2-carboxylate moieties adopted syn conformation with the carbonyl group arranged in the same direction as the adjacent pyrrole N—H group. In the complex, the dihedral angle between the two pyridine rings is 54.8 (3)°. The complex molecules assemble into layer structrue through N—H···Cl, C—H···O and C—H···Cl hydrogen bonds (Fig. 2).

Related literature top

For the hydrogen- bonded assemblies of pyrrole-based compounds, see: Wang & Yin (2007); Yin &Li (2006); Cui et al. (2009).

Experimental top

The methanol solution of ZnCl₂ (0.1 M, 5 mL) was layered on CHCl₃ solution of 4-pyridylmethyl 1H-pyrrole-2-carboxylate (0.1 M, 10 mL) and then evaporated to give colorless crystals of the title compound in about 70% yield.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SMART (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with displacement ellipsoids shown at the 30% probability level. The atom with the 'A' label were generated by the symmetry operation -x,y,1/2-z.
	Fig. 2. The layer of the title molecules assembled by intermolecular hydrogen bonds (hydrogen bonds are shown as dashed lines).

Dichloridobis(pyridin-4-ylmethyl 1H-pyrrole-2-carboxylate-κN)zinc top

Crystal data top

[ZnCl₂(C₁₁H₁₀N₂O₂)₂]	F(000) = 1104
M_r = 540.69	D_x = 1.510 Mg m⁻³
Monoclinic, C2/c	Melting point: 438 K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 27.604 (14) Å	Cell parameters from 2747 reflections
b = 6.205 (3) Å	θ = 2.5–26.8°
c = 16.087 (8) Å	µ = 1.29 mm⁻¹
β = 120.309 (6)°	T = 296 K
V = 2379 (2) Å³	Block, colourless
Z = 4	0.26 × 0.20 × 0.14 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2098 independent reflections
Radiation source: fine-focus sealed tube	1823 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
phi and ω scans	θ_max = 25.0°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −32→32
T_min = 0.727, T_max = 1.000	k = −7→5
6100 measured reflections	l = −17→19

Refinement top

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)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.069	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0441P)² + 0.3857P] where P = (F_o² + 2F_c²)/3
2098 reflections	(Δ/σ)_max < 0.001
150 parameters	Δρ_max = 0.17 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

[ZnCl₂(C₁₁H₁₀N₂O₂)₂]	V = 2379 (2) Å³
M_r = 540.69	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 27.604 (14) Å	µ = 1.29 mm⁻¹
b = 6.205 (3) Å	T = 296 K
c = 16.087 (8) Å	0.26 × 0.20 × 0.14 mm
β = 120.309 (6)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2098 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	1823 reflections with I > 2σ(I)
T_min = 0.727, T_max = 1.000	R_int = 0.018
6100 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	0 restraints
wR(F²) = 0.069	H-atom parameters constrained
S = 1.06	Δρ_max = 0.17 e Å⁻³
2098 reflections	Δρ_min = −0.27 e Å⁻³
150 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.

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 (Å²) top

	x	y	z	U_iso*/U_eq
Zn1	0.0000	0.41749 (4)	0.2500	0.03878 (12)
Cl1	0.01743 (2)	0.23365 (8)	0.14847 (3)	0.05019 (15)
O1	0.30330 (6)	1.1722 (3)	0.65205 (11)	0.0654 (4)
O2	0.24547 (5)	0.8880 (2)	0.60656 (9)	0.0495 (3)
N1	0.06598 (6)	0.6110 (2)	0.33725 (10)	0.0395 (3)
N2	0.37959 (7)	0.9421 (3)	0.81985 (12)	0.0555 (5)
H2	0.3931	1.0663	0.8187	0.067*
C1	0.15031 (8)	0.6615 (3)	0.48714 (13)	0.0481 (5)
H1	0.1754	0.6095	0.5483	0.058*
C2	0.10377 (8)	0.5440 (3)	0.42633 (14)	0.0470 (5)
H2A	0.0980	0.4122	0.4475	0.056*
C3	0.07520 (7)	0.8013 (3)	0.30828 (13)	0.0405 (4)
H3	0.0494	0.8502	0.2469	0.049*
C4	0.12083 (8)	0.9263 (3)	0.36502 (14)	0.0427 (4)
H4	0.1258	1.0569	0.3420	0.051*
C5	0.15987 (7)	0.8576 (3)	0.45746 (13)	0.0394 (4)
C6	0.20924 (8)	0.9974 (3)	0.51816 (14)	0.0501 (5)
H6A	0.2293	1.0285	0.4844	0.060*
H6B	0.1968	1.1328	0.5313	0.060*
C7	0.29241 (8)	0.9944 (4)	0.66858 (13)	0.0444 (4)
C8	0.32739 (8)	0.8683 (3)	0.75342 (13)	0.0460 (4)
C9	0.40637 (10)	0.7894 (5)	0.88712 (16)	0.0712 (7)
H9	0.4427	0.7994	0.9392	0.085*
C10	0.37168 (12)	0.6193 (5)	0.86637 (18)	0.0767 (8)
H10	0.3796	0.4930	0.9020	0.092*
C11	0.32176 (10)	0.6672 (4)	0.78171 (16)	0.0607 (5)
H11	0.2904	0.5784	0.7504	0.073*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.03178 (17)	0.03411 (18)	0.03693 (18)	0.000	0.00734 (13)	0.000
Cl1	0.0473 (3)	0.0494 (3)	0.0450 (3)	0.0092 (2)	0.0167 (2)	−0.0014 (2)
O1	0.0573 (9)	0.0543 (9)	0.0588 (9)	−0.0232 (8)	0.0102 (8)	0.0022 (8)
O2	0.0393 (7)	0.0473 (8)	0.0451 (7)	−0.0124 (6)	0.0089 (6)	0.0012 (6)
N1	0.0343 (8)	0.0366 (8)	0.0373 (8)	−0.0042 (6)	0.0104 (7)	0.0007 (6)
N2	0.0416 (9)	0.0756 (13)	0.0404 (9)	−0.0067 (9)	0.0142 (8)	−0.0053 (8)
C1	0.0428 (10)	0.0460 (11)	0.0378 (10)	−0.0054 (9)	0.0071 (9)	0.0065 (9)
C2	0.0450 (11)	0.0395 (11)	0.0426 (10)	−0.0090 (8)	0.0118 (9)	0.0066 (8)
C3	0.0382 (10)	0.0378 (10)	0.0368 (9)	0.0010 (8)	0.0124 (8)	0.0037 (8)
C4	0.0404 (10)	0.0370 (10)	0.0457 (10)	−0.0039 (8)	0.0181 (9)	0.0047 (8)
C5	0.0341 (9)	0.0381 (9)	0.0416 (10)	−0.0050 (8)	0.0159 (8)	−0.0028 (8)
C6	0.0425 (11)	0.0455 (11)	0.0460 (11)	−0.0106 (9)	0.0103 (9)	0.0023 (9)
C7	0.0357 (10)	0.0500 (11)	0.0417 (10)	−0.0097 (9)	0.0152 (9)	−0.0063 (9)
C8	0.0386 (10)	0.0565 (12)	0.0412 (10)	−0.0040 (9)	0.0190 (9)	−0.0036 (9)
C9	0.0527 (13)	0.112 (2)	0.0409 (12)	0.0165 (15)	0.0176 (11)	0.0113 (13)
C10	0.0786 (18)	0.092 (2)	0.0623 (15)	0.0227 (16)	0.0379 (14)	0.0292 (14)
C11	0.0610 (13)	0.0659 (14)	0.0588 (13)	−0.0012 (12)	0.0328 (12)	0.0075 (11)

Geometric parameters (Å, º) top

Zn1—N1	2.0367 (15)	C2—H2A	0.9300
Zn1—N1ⁱ	2.0367 (15)	C3—C4	1.364 (3)
Zn1—Cl1ⁱ	2.2347 (9)	C3—H3	0.9300
Zn1—Cl1	2.2347 (9)	C4—C5	1.392 (3)
O1—C7	1.208 (3)	C4—H4	0.9300
O2—C7	1.344 (2)	C5—C6	1.490 (3)
O2—C6	1.431 (2)	C6—H6A	0.9700
N1—C3	1.340 (2)	C6—H6B	0.9700
N1—C2	1.344 (2)	C7—C8	1.441 (3)
N2—C9	1.345 (3)	C8—C11	1.364 (3)
N2—C8	1.369 (3)	C9—C10	1.349 (4)
N2—H2	0.8600	C9—H9	0.9300
C1—C2	1.368 (3)	C10—C11	1.396 (3)
C1—C5	1.380 (3)	C10—H10	0.9300
C1—H1	0.9300	C11—H11	0.9300

N1—Zn1—N1ⁱ	107.76 (9)	C1—C5—C4	117.34 (17)
N1—Zn1—Cl1ⁱ	104.16 (6)	C1—C5—C6	123.90 (17)
N1ⁱ—Zn1—Cl1ⁱ	110.92 (6)	C4—C5—C6	118.76 (17)
N1—Zn1—Cl1	110.92 (6)	O2—C6—C5	108.94 (16)
N1ⁱ—Zn1—Cl1	104.16 (6)	O2—C6—H6A	109.9
Cl1ⁱ—Zn1—Cl1	118.61 (4)	C5—C6—H6A	109.9
C7—O2—C6	115.69 (15)	O2—C6—H6B	109.9
C3—N1—C2	117.51 (15)	C5—C6—H6B	109.9
C3—N1—Zn1	122.71 (12)	H6A—C6—H6B	108.3
C2—N1—Zn1	119.71 (12)	O1—C7—O2	122.62 (18)
C9—N2—C8	109.1 (2)	O1—C7—C8	125.59 (17)
C9—N2—H2	125.4	O2—C7—C8	111.77 (17)
C8—N2—H2	125.4	C11—C8—N2	107.33 (19)
C2—C1—C5	119.81 (18)	C11—C8—C7	132.68 (19)
C2—C1—H1	120.1	N2—C8—C7	119.74 (18)
C5—C1—H1	120.1	N2—C9—C10	108.6 (2)
N1—C2—C1	122.78 (17)	N2—C9—H9	125.7
N1—C2—H2A	118.6	C10—C9—H9	125.7
C1—C2—H2A	118.6	C9—C10—C11	107.6 (2)
N1—C3—C4	122.79 (17)	C9—C10—H10	126.2
N1—C3—H3	118.6	C11—C10—H10	126.2
C4—C3—H3	118.6	C8—C11—C10	107.3 (2)
C3—C4—C5	119.77 (17)	C8—C11—H11	126.3
C3—C4—H4	120.1	C10—C11—H11	126.3
C5—C4—H4	120.1

N1ⁱ—Zn1—N1—C3	−34.15 (12)	C7—O2—C6—C5	179.31 (16)
Cl1ⁱ—Zn1—N1—C3	−152.03 (13)	C1—C5—C6—O2	4.0 (3)
Cl1—Zn1—N1—C3	79.27 (15)	C4—C5—C6—O2	−175.71 (16)
N1ⁱ—Zn1—N1—C2	149.00 (17)	C6—O2—C7—O1	1.0 (3)
Cl1ⁱ—Zn1—N1—C2	31.12 (15)	C6—O2—C7—C8	−177.45 (16)
Cl1—Zn1—N1—C2	−97.58 (15)	C9—N2—C8—C11	1.1 (2)
C3—N1—C2—C1	0.1 (3)	C9—N2—C8—C7	−173.90 (18)
Zn1—N1—C2—C1	177.12 (16)	O1—C7—C8—C11	−178.6 (2)
C5—C1—C2—N1	−0.1 (3)	O2—C7—C8—C11	−0.2 (3)
C2—N1—C3—C4	0.2 (3)	O1—C7—C8—N2	−5.1 (3)
Zn1—N1—C3—C4	−176.75 (14)	O2—C7—C8—N2	173.28 (17)
N1—C3—C4—C5	−0.5 (3)	C8—N2—C9—C10	−1.4 (3)
C2—C1—C5—C4	−0.2 (3)	N2—C9—C10—C11	1.2 (3)
C2—C1—C5—C6	−179.95 (19)	N2—C8—C11—C10	−0.4 (2)
C3—C4—C5—C1	0.5 (3)	C7—C8—C11—C10	173.7 (2)
C3—C4—C5—C6	−179.77 (18)	C9—C10—C11—C8	−0.5 (3)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···Cl1ⁱⁱ	0.86	2.57	3.306 (3)	144
C3—H3···Cl1ⁱⁱⁱ	0.93	2.75	3.495 (3)	138
C4—H4···O1^iv	0.93	2.54	3.354 (3)	146

Symmetry codes: (ii) −x+1/2, −y+3/2, −z+1; (iii) x, y+1, z; (iv) −x+1/2, −y+5/2, −z+1.

Experimental details

Crystal data
Chemical formula	[ZnCl₂(C₁₁H₁₀N₂O₂)₂]
M_r	540.69
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	27.604 (14), 6.205 (3), 16.087 (8)
β (°)	120.309 (6)
V (Å³)	2379 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.29
Crystal size (mm)	0.26 × 0.20 × 0.14

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.727, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	6100, 2098, 1823
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.069, 1.06
No. of reflections	2098
No. of parameters	150
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.27

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···Cl1ⁱ	0.86	2.57	3.306 (3)	144
C3—H3···Cl1ⁱⁱ	0.93	2.75	3.495 (3)	138
C4—H4···O1ⁱⁱⁱ	0.93	2.54	3.354 (3)	146

Symmetry codes: (i) −x+1/2, −y+3/2, −z+1; (ii) x, y+1, z; (iii) −x+1/2, −y+5/2, −z+1.

Acknowledgements

We sincerely thank the Natural Science Foundation of China for financial support (NSFC Nos. 20702038 and 21172174)

References

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