Redetermination of poly[di-μ3-iodido-[μ-1,2-trans-(pyridin-4-yl)ethene-κ2N:N′]dicopper(I)]

Neal, H.C.; Tamtam, H.; Smucker, B.W.; Nesterov, V.V.

doi:10.1107/S2414314619001226

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 4| Part 1| January 2019| x190122

https://doi.org/10.1107/S2414314619001226

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Redetermination of poly[di-μ₃-iodido-[μ-1,2-trans-(pyridin-4-yl)ethene-κ²N:N′]dicopper(I)]

Henry C. Neal,^a Harsha Tamtam,^a Bradley W. Smucker ^a ^* and Volodymyr V. Nesterov ^b

^aAustin College, 900 N Grand, Sherman, TX 75090, USA, and ^bDepartment of Chemistry, University of North Texas, 1508 W. Mulberry, Denton, TX 76201, USA
^*Correspondence e-mail: bsmucker@austincollege.edu

Edited by S. Bernès, Benemérita Universidad Autónoma de Puebla, México (Received 21 December 2018; accepted 22 January 2019; online 29 January 2019)

The re-investigated structure of the title compound, [Cu₂I₂(C₁₂H₁₀N₂)]_n, a two-dimensional coordination polymer crystallizing with monoclinic (P2₁/n) symmetry, is based on data collected at 100 K, while the previously reported structure was obtained with data collected at 203 K [Blake et al. (1999 ). Cryst. Eng. 2, 181–195]. The refinement of the crystal structure is greatly improved; for example, the wR₂ residual converges to 0.047 for 1532 independent data, versus wR₂ = 0.179 for 992 independent data in the 1999 study.

Keywords: X-ray analysis; crystal structure; coordination polymer; redetermination.

CCDC reference: 1892770

Structure description

The previously reported structure for the title compound (Blake et al., 1999) at 203 K with R₁ = 6.48% [I > 2σ(I)] was re-investigated at 100 K (Fig. 1), producing a much more accurate refinement for the crystal structure. We were able to achieve R₁ = 1.78% and wR₂ = 4.74% (as compared with R₁ = 6.48% and wR₂ = 17.86% for the structure reported by Blake et al.) after collecting 1532 independent reflections for 83 refined parameters (as compared with 992 independent reflections for 82 parameters in the previously reported structure). Our completeness is 100%, a vast improvement over the reported 76.6%, and our goodness of fit is 1.073 (as compared with 1.109). We were able to achieve an R_int of 2.19% after collecting experimental data up to 2θ_max angle of 54° as compared with an R_int of 13.48% after collecting experimental data up to 2θ_max angle of 48°. A comparison of the improved resolution of select bond lengths between this refinement and that reported by Blake et al. is given in Table 1.

Table 1
Comparison of some bond lengths (Å) in the reported refinement and the refinement published by Blake et al. (1999)

Bond	This structure	Structure of Blake et al.
Cu1—I1	2.6200 (4)	2.6314 (16)
Cu1⋯Cu1ⁱ	2.7852 (4)	2.8182 (17)
Cu1—N1	2.039 (2)	2.055 (8)
C6=C6ⁱⁱ	1.329 (5)	1.31 (2)
N1—C1	1.344 (4)	1.360 (14)
N1—C5	1.343 (4)	1.331 (15)
Symmetry codes: (i) $[{3\over 2}]$ − x, y − $[{1\over 2}]$ , $[{3\over 2}]$ − z; (ii) −x, 1 − y, 1 − z.

Figure 1
Ellipsoid plot (50% probability level for all non-hydrogen atoms) of the title compound with additional Cu–I fragments included to indicate the directionality of the two-dimensional coordination polymer.

Analysis of the crystal packing shows that molecules in the crystal form staggered sheets (Fig. 2). Equidistant intermolecular contacts Cu1⋯Cu1 [2.7852 (4) Å] and I1⋯I1 [4.0743 (1) Å] link these sheets along the b-axis direction and form stacks (Fig. 3).

Figure 2
Fragment of the crystal packing along the b-axis direction.

Figure 3
Fragment of the crystal packing along the a-axis direction. Dashed lines indicate intermolecular Cu⋯Cu and I⋯I contacts.

Synthesis and crystallization

Following the general procedure for making copper(I)-pyridine-iodide clusters (Parmeggiani & Sacchetti, 2012 ), an acetonitrile solution of copper(I) iodide, ascorbic acid, and potassium iodide was added to a thin tube and layered first with acetonitrile then with an acetonitrile solution of 1,2-di(pyridin-4-yl)ethylene. Large yello–orange crystals were present after 1 week.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Single crystal X-ray data were collected using a Rigaku XtaLAB Synergy-S diffractometer equipped with a HyPix-6000HE Hybrid Photon Counting (HPC) detector and dual Mo and Cu microfocus sealed X-ray source as well as a low-temperature Oxford Cryostream 800 liquid nitrogen cooling system at 100 (2) K. The data collection strategy was calculated within CrysAlis PRO (Rigaku OD, 2018 $[Rigaku, OD (2018). CrysAlis PRO. Rigaku Oxford Diffraction Ltd, Yarnton, England.]$ ) to ensure desired data redundancy and percent completeness.

Table 2
Experimental details

Crystal data
Chemical formula	[Cu₂I₂(C₁₂H₁₀N₂)]
M_r	563.1
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	9.4695 (3), 4.0743 (1), 18.6048 (6)
β (°)	102.878 (4)
V (Å³)	699.75 (4)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	7.43
Crystal size (mm)	0.09 × 0.03 × 0.02

Data collection
Diffractometer	Rigaku XtaLAB Synergy, Dualflex, HyPix
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2018 $[Rigaku, OD (2018). CrysAlis PRO. Rigaku Oxford Diffraction Ltd, Yarnton, England.]$ )
T_min, T_max	0.604, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	4364, 1532, 1435
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.641

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.018, 0.047, 1.07
No. of reflections	1532
No. of parameters	83
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.70
Computer programs: CrysAlis PRO (Rigaku OD, 2018 $[Rigaku, OD (2018). CrysAlis PRO. Rigaku Oxford Diffraction Ltd, Yarnton, England.]$ ), SHELXT2018 (Sheldrick, 2015a ), SHELXL2018 (Sheldrick, 2015b ), OLEX2 (Dolomanov et al., 2009 ) and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1892770

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314619001226/bh4044sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314619001226/bh4044Isup2.hkl

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2018); cell refinement: CrysAlis PRO (Rigaku OD, 2018); data reduction: CrysAlis PRO (Rigaku OD, 2018); program(s) used to solve structure: SHELXT2018 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009) and PLATON (Spek, 2009).

Poly[di-µ₃-iodido-[µ-1,2-trans-(pyridin-4-yl)ethene-κ²N:N']dicopper(I)] top

Crystal data top

[Cu₂I₂(C₁₂H₁₀N₂)]	F(000) = 520
M_r = 563.1	D_x = 2.673 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.4695 (3) Å	Cell parameters from 3630 reflections
b = 4.0743 (1) Å	θ = 2.3–31.1°
c = 18.6048 (6) Å	µ = 7.43 mm⁻¹
β = 102.878 (4)°	T = 100 K
V = 699.75 (4) Å³	Plate, clear light yellow
Z = 2	0.09 × 0.03 × 0.02 mm

Data collection top

Rigaku XtaLAB Synergy, Dualflex, HyPix diffractometer	1532 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet X-ray Source	1435 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.022
ω scans	θ_max = 27.1°, θ_min = 2.2°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2018)	h = −12→12
T_min = 0.604, T_max = 1.000	k = −5→5
4364 measured reflections	l = −23→23

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.018	H-atom parameters constrained
wR(F²) = 0.047	w = 1/[σ²(F_o²) + (0.023P)² + 0.7134P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.002
1532 reflections	Δρ_max = 0.46 e Å⁻³
83 parameters	Δρ_min = −0.70 e Å⁻³
0 restraints	Extinction correction: SHELXL2018 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: dual	Extinction coefficient: 0.0016 (3)

Special details top

Refinement. Single crystal X-ray data were collected using a Rigaku XtaLAB Synergy-S diffractometer equipped with a HyPix-6000HE Hybrid Photon Counting (HPC) detector and dual Mo and Cu microfocus sealed X-ray source as well as a low-temperature Oxford Cryostream 800 liquid nitrogen cooling system at 100 (2) K. The data collection strategy was calculated within CrysAlis PRO (Rigaku OD, 2018; Table 2) to ensure desired data redundancy and percent completeness. All non-hydrogen atoms were refined anisotropically using SHELXL (Sheldrick, 2015b) and the space group was unambiguously verified by PLATON (Spek, 2009). All H atoms were attached via the riding model at calculated positions, with calculated isotropic displacement parameters.

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

	x	y	z	U_iso*/U_eq
I1	0.68604 (2)	0.62004 (4)	0.84525 (2)	0.01014 (9)
Cu1	0.68200 (4)	0.62033 (8)	0.70399 (2)	0.01281 (10)
N1	0.4696 (2)	0.5974 (5)	0.65013 (12)	0.0123 (5)
C1	0.3630 (3)	0.7307 (7)	0.67755 (14)	0.0141 (5)
H1	0.387165	0.831271	0.723539	0.017*
C2	0.2186 (3)	0.7258 (7)	0.64066 (15)	0.0149 (6)
H2	0.148556	0.821387	0.661890	0.018*
C3	0.1788 (3)	0.5767 (7)	0.57138 (14)	0.0115 (5)
C4	0.2899 (3)	0.4386 (7)	0.54285 (14)	0.0139 (5)
H4	0.269163	0.338118	0.496805	0.017*
C5	0.4311 (3)	0.4528 (7)	0.58375 (14)	0.0138 (5)
H5	0.503348	0.356747	0.564167	0.017*
C6	0.0256 (3)	0.5728 (7)	0.53223 (15)	0.0122 (5)
H6	−0.040426	0.680460	0.554244	0.015*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.01214 (11)	0.00854 (12)	0.01046 (11)	−0.00082 (6)	0.00406 (7)	0.00027 (6)
Cu1	0.01037 (17)	0.0149 (2)	0.01267 (17)	−0.00004 (12)	0.00152 (13)	−0.00116 (13)
N1	0.0103 (10)	0.0145 (12)	0.0116 (10)	−0.0003 (9)	0.0013 (8)	−0.0003 (9)
C1	0.0137 (13)	0.0161 (14)	0.0116 (12)	0.0018 (11)	0.0011 (10)	−0.0024 (11)
C2	0.0136 (13)	0.0155 (14)	0.0166 (13)	0.0020 (11)	0.0053 (10)	−0.0017 (11)
C3	0.0099 (12)	0.0129 (13)	0.0117 (12)	−0.0014 (10)	0.0021 (10)	0.0024 (10)
C4	0.0137 (13)	0.0178 (14)	0.0095 (11)	−0.0012 (11)	0.0013 (10)	−0.0023 (11)
C5	0.0115 (12)	0.0168 (14)	0.0132 (12)	0.0013 (11)	0.0028 (10)	−0.0010 (11)
C6	0.0109 (12)	0.0130 (13)	0.0135 (12)	0.0008 (10)	0.0042 (9)	0.0017 (10)

Geometric parameters (Å, º) top

I1—Cu1	2.6200 (4)	C2—H2	0.9300
I1—Cu1ⁱ	2.6563 (4)	C2—C3	1.399 (4)
I1—Cu1ⁱⁱ	2.6582 (4)	C3—C4	1.398 (4)
Cu1—Cu1ⁱ	2.7852 (4)	C3—C6	1.472 (4)
Cu1—Cu1ⁱⁱ	2.7852 (4)	C4—H4	0.9300
Cu1—N1	2.039 (2)	C4—C5	1.384 (4)
N1—C1	1.344 (4)	C5—H5	0.9300
N1—C5	1.343 (4)	C6—C6ⁱⁱⁱ	1.329 (5)
C1—H1	0.9300	C6—H6	0.9300
C1—C2	1.386 (4)

Cu1—I1—Cu1ⁱ	63.719 (10)	C5—N1—C1	117.0 (2)
Cu1—I1—Cu1ⁱⁱ	63.694 (10)	N1—C1—H1	118.4
Cu1ⁱ—I1—Cu1ⁱⁱ	100.106 (12)	N1—C1—C2	123.2 (2)
I1—Cu1—I1ⁱⁱ	116.327 (13)	C2—C1—H1	118.4
I1—Cu1—I1ⁱ	116.263 (13)	C1—C2—H2	120.1
I1ⁱⁱ—Cu1—I1ⁱ	100.105 (13)	C1—C2—C3	119.7 (3)
I1—Cu1—Cu1ⁱ	58.776 (13)	C3—C2—H2	120.1
I1ⁱ—Cu1—Cu1ⁱⁱ	125.749 (19)	C2—C3—C6	119.6 (2)
I1ⁱⁱ—Cu1—Cu1ⁱⁱ	57.506 (9)	C4—C3—C2	117.0 (2)
I1ⁱⁱ—Cu1—Cu1ⁱ	125.731 (19)	C4—C3—C6	123.4 (2)
I1—Cu1—Cu1ⁱⁱ	58.820 (13)	C3—C4—H4	120.3
I1ⁱ—Cu1—Cu1ⁱ	57.487 (9)	C5—C4—C3	119.4 (2)
Cu1ⁱ—Cu1—Cu1ⁱⁱ	94.010 (19)	C5—C4—H4	120.3
N1—Cu1—I1ⁱⁱ	110.72 (7)	N1—C5—C4	123.7 (3)
N1—Cu1—I1	106.57 (6)	N1—C5—H5	118.2
N1—Cu1—I1ⁱ	106.46 (6)	C4—C5—H5	118.2
N1—Cu1—Cu1ⁱⁱ	127.29 (7)	C3—C6—H6	117.5
N1—Cu1—Cu1ⁱ	122.60 (7)	C6ⁱⁱⁱ—C6—C3	124.9 (3)
C1—N1—Cu1	122.50 (18)	C6ⁱⁱⁱ—C6—H6	117.5
C5—N1—Cu1	120.53 (18)

Cu1—N1—C1—C2	178.0 (2)	C2—C3—C4—C5	0.5 (4)
Cu1—N1—C5—C4	−177.6 (2)	C2—C3—C6—C6ⁱⁱⁱ	−177.1 (3)
N1—C1—C2—C3	0.0 (5)	C3—C4—C5—N1	−0.9 (5)
C1—N1—C5—C4	0.8 (4)	C4—C3—C6—C6ⁱⁱⁱ	3.2 (5)
C1—C2—C3—C4	−0.1 (4)	C5—N1—C1—C2	−0.3 (4)
C1—C2—C3—C6	−179.8 (3)	C6—C3—C4—C5	−179.8 (3)

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

Comparison of some bond lengths (Å) in the reported refinement and the refinement published by Blake et al. (1999) top

Bond	This structure	Structure of Blake et al.
Cu1—I1	2.6200 (4)	2.6314 (16)
Cu1···Cu1ⁱ	2.7852 (4)	2.8182 (17)
Cu1—N1	2.039 (2)	2.055 (8)
C6═C6ⁱⁱ	1.329 (5)	1.31 (2)
N1—C1	1.344 (4)	1.360 (14)
N1—C5	1.343 (4)	1.331 (15)

Symmetry codes: (i) 3/2 - x, y - 1/2, 3/2 - z; (ii) -x, 1 - y, 1 - z.

Acknowledgements

We acknowledge the NSF MRI Program (CHE-1726652) and the UNT for supporting the acquisition of the Rigaku XtaLAB Synergy-S X-ray diffractometer.

Funding information

Funding for this research was provided by: National Science Foundation.

References

Blake, A. J., Brooks, N. R., Champness, N. R., Cooke, P. A., Crew, M., Deveson, A. M., Hanton, L. R., Hubberstey, P., Fenske, D. & Schröder, M. (1999). Cryst. Eng. 2, 181–195. CrossRef CAS Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Parmeggiani, F. & Sacchetti, A. (2012). J. Chem. Educ. 89, 946–949. CrossRef CAS Google Scholar
Rigaku, OD (2018). CrysAlis PRO. Rigaku Oxford Diffraction Ltd, Yarnton, England. Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar

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