Literature DB >> 23794983

catena-Poly[[[di-aqua-bis-[1,2-bis-(pyridin-4-yl)diazene]copper(II)]-μ-1,2-bis-(pyridin-4-yl)diazene] bis-(perchlorate)].

Ernesto Ballestero-Martínez¹, Cristian Saul Campos-Fernández, Victor Hugo Soto-Tellini, Simplicio Gonzalez-Montiel, Diego Martínez-Otero.

Abstract

In the title compound, {[Cu(C10H8N4)3(H2O)2](ClO4)2} n , the coordination environment of the cationic Cu(II) atom is distorted octa-hedral, formed by pairs of symmetry-equivalent 1,2-bis-(pyridin-4-yl)diazene ligands, bridging 1,2-bis-(pyridin-4-yl)diazene ligands and two non-equivalent water mol-ecules. The 1,2-bis-(pyridin-4-yl)diazene mol-ecules form polymeric chains parallel to [-101] via azo bonds which are situated about inversion centres. Since the Cu(II) atom is situated on a twofold rotation axis, the monomeric unit has point symmetry 2. The perchlorate anions are disordered in a 0.536 (9):0.464 (9) ratio and are acceptors of water H atoms in medium-strong O-H⋯O hydrogen bonds with graph set R 4 (4)(12). The water mol-ecules, which are coordinated to the Cu(II) atom and are hydrogen-bonded to the perchlorate anions, form columns parallel to [010]. A π-π inter-action [centroid-centroid distance = 3.913 (2) Å] occurs between pyridine rings, and weak C-H⋯O inter-actions also occur.

Entities: Chemical Disease Species

Year: 2013 PMID： 23794983 PMCID： PMC3684881 DOI： 10.1107/S1600536813012269

Source DB: PubMed Journal: Acta Crystallogr Sect E Struct Rep Online ISSN： 1600-5368

Related literature

For the synthesis of trans-4,4′-azobispyridine, see: Brown & Granneman (1975 ▶). For the synthesis and structures of other polymers with CuI or CuII and trans-4,4′-azobispyridine, see: He et al. (2000 ▶); Kondo et al. (2006 ▶); Marinescu et al. (2010 ▶). For compounds with trans-4,4′-azobispyridine with other cations, including one with ZnII, see: Noro et al. (2005 ▶). For categorization of hydrogen bonds, see: Gilli & Gilli (2009 ▶). For a description of the Cambridge Crystallographic Database, see: Allen (2002 ▶). For the Hirshfeld test, see: Hirshfeld (1976 ▶); Spek (2009 ▶).

Experimental

Crystal data

[Cu(C10H8N4)3(H2O)2](ClO4)2 M = 851.29 Monoclinic, a = 20.5028 (6) Å b = 9.5882 (4) Å c = 18.7797 (6) Å β = 96.629 (3)° V = 3667.1 (2) Å3 Z = 4 Mo Kα radiation μ = 0.81 mm−1 T = 293 K 0.38 × 0.37 × 0.29 mm

Data collection

Oxford Diffraction Xcalibur Gemini diffractometer Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2009 ▶) and Clark & Reid (1995 ▶)] T min = 0.951, T max = 0.965 27735 measured reflections 3738 independent reflections 2902 reflections with I > 3σ(I) R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.043 wR(F 2) = 0.106 S = 2.67 3738 reflections 373 parameters 22 restraints H atoms treated by a mixture of independent and constrained refinement Δρmax = 0.76 e Å−3 Δρmin = −0.47 e Å−3 Data collection: CrysAlis PRO (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: JANA2006 (Petříček et al., 2006 ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▶) and DIAMOND (Brandenburg, 2010 ▶).; software used to prepare material for publication: JANA2006 and PLATON (Spek, 2009 ▶). Click here for additional data file. Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813012269/fb2274sup1.cif Click here for additional data file. Supplementary material file. DOI: 10.1107/S1600536813012269/fb2274Isup2.mol Click here for additional data file. Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813012269/fb2274Isup3.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Cu(C₁₀H₈N₄)₃(H₂O)₂](ClO₄)₂	F(000) = 1740
M_r = 851.29	D_x = 1.541 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 10880 reflections
a = 20.5028 (6) Å	θ = 3.1–26.3°
b = 9.5882 (4) Å	µ = 0.81 mm⁻¹
c = 18.7797 (6) Å	T = 293 K
β = 96.629 (3)°	Prism, violet
V = 3667.1 (2) Å³	0.38 × 0.37 × 0.29 mm
Z = 4

Oxford Diffraction Xcalibur Gemini diffractometer	3738 independent reflections
Radiation source: X-ray tube	2902 reflections with I > 3σ(I)
Graphite monochromator	R_int = 0.026
ω scans	θ_max = 26.4°, θ_min = 3.1°
Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2009) and Clark & Reid (1995)]	h = −25→25
T_min = 0.951, T_max = 0.965	k = −11→11
27735 measured reflections	l = −23→23

Refinement on F²	Primary atom site location: structure-invariant direct methods
R[F² > 2σ(F²)] = 0.043	Secondary atom site location: difference Fourier map
wR(F²) = 0.106	Hydrogen site location: difference Fourier map
S = 2.67	H atoms treated by a mixture of independent and constrained refinement
3738 reflections	Weighting scheme based on measured s.u.'s w = 1/(σ²(I) + 0.0004I²)
373 parameters	(Δ/σ)_max = 0.044
22 restraints	Δρ_max = 0.76 e Å⁻³
57 constraints	Δρ_min = −0.47 e Å⁻³

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cu1	0.5	0.24717 (4)	0.75	0.03398 (14)
Cl	0.54953 (8)	0.75644 (13)	0.60764 (6)	0.0956 (5)
N2	0.56205 (9)	0.25720 (18)	0.67295 (10)	0.0359 (6)
N1	0.57826 (9)	0.24420 (19)	0.82723 (10)	0.0378 (6)
C15	0.68446 (12)	0.2241 (3)	0.93132 (15)	0.0513 (9)
C1	0.58515 (12)	0.3335 (3)	0.88204 (12)	0.0457 (8)
H1c1	0.553612	0.402415	0.884613	0.0548*
C2	0.63800 (13)	0.3267 (3)	0.93548 (13)	0.0531 (9)
H1c2	0.641896	0.390084	0.973213	0.0637*
N3	0.67222 (12)	0.3481 (3)	0.50343 (13)	0.0614 (9)
C5	0.55314 (11)	0.1796 (3)	0.61320 (12)	0.0431 (8)
H1c5	0.521918	0.108841	0.610531	0.0517*
N6	0.74448 (13)	0.2009 (3)	0.98199 (13)	0.0652 (10)
C6	0.58805 (13)	0.1996 (3)	0.55559 (14)	0.0503 (9)
H1c6	0.580747	0.144085	0.514857	0.0604*
C9	0.60886 (11)	0.3549 (3)	0.67708 (13)	0.0463 (9)
H1c9	0.61685	0.406885	0.718993	0.0556*
C4	0.62437 (11)	0.1462 (3)	0.82472 (13)	0.0525 (9)
H1c4	0.620345	0.084669	0.7862	0.063*
N4	0.66166 (12)	0.2783 (3)	0.44975 (14)	0.0626 (9)
C11	0.74683 (13)	0.4261 (3)	0.39990 (14)	0.0571 (10)
H1c11	0.762209	0.46114	0.444894	0.0685*
C7	0.63456 (12)	0.3057 (3)	0.56043 (14)	0.0485 (9)
C10	0.69675 (13)	0.3311 (3)	0.39178 (14)	0.0525 (10)
C8	0.64559 (12)	0.3817 (3)	0.62202 (14)	0.0534 (10)
H1c8	0.677626	0.450758	0.626648	0.064*
C3	0.67725 (12)	0.1318 (3)	0.87591 (14)	0.0605 (11)
H1c3	0.707548	0.060508	0.872858	0.0726*
N5	0.75455 (13)	0.4230 (3)	0.27360 (13)	0.0724 (11)
C12	0.77402 (15)	0.4687 (3)	0.33930 (17)	0.0666 (12)
H1c12	0.80804	0.533335	0.345032	0.0799*
C13	0.70650 (17)	0.3312 (4)	0.26799 (16)	0.0761 (13)
H1c13	0.69199	0.29756	0.222456	0.0913*
C14	0.67590 (16)	0.2808 (3)	0.32486 (16)	0.0681 (12)
H1c14	0.642393	0.215145	0.317754	0.0817*
O2	0.5	−0.0034 (3)	0.75	0.0688 (12)
O1	0.5	0.5102 (3)	0.75	0.0725 (12)
H1o2	0.4866 (17)	−0.055 (3)	0.7829 (14)	0.1033*
H1o1	0.4862 (18)	0.567 (3)	0.7805 (16)	0.1088*
O1a	0.5232 (6)	0.8609 (9)	0.5573 (5)	0.161 (7)	0.464 (9)
O2a	0.5038 (5)	0.6425 (9)	0.6076 (7)	0.238 (11)	0.464 (9)
O3a	0.5602 (4)	0.8164 (12)	0.6783 (3)	0.195 (5)	0.464 (9)
O4a	0.6109 (2)	0.7059 (14)	0.5874 (5)	0.188 (6)	0.464 (9)
O1b	0.4963 (4)	0.8525 (11)	0.6130 (6)	0.148 (4)	0.536 (9)
O2b	0.5246 (5)	0.6320 (6)	0.5712 (6)	0.115 (4)	0.536 (9)
O3b	0.5796 (6)	0.7209 (11)	0.6784 (3)	0.195 (6)	0.536 (9)
O4b	0.5976 (5)	0.8204 (13)	0.5679 (6)	0.314 (13)	0.536 (9)

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0240 (2)	0.0517 (3)	0.0246 (2)	0	−0.00415 (14)	0
Cl	0.1544 (12)	0.0710 (8)	0.0605 (6)	−0.0011 (9)	0.0092 (7)	0.0064 (6)
N2	0.0294 (9)	0.0468 (12)	0.0306 (10)	−0.0027 (8)	−0.0006 (8)	0.0010 (9)
N1	0.0280 (9)	0.0549 (12)	0.0288 (10)	0.0006 (9)	−0.0047 (8)	−0.0017 (9)
C15	0.0304 (13)	0.074 (2)	0.0460 (15)	−0.0075 (12)	−0.0122 (11)	0.0231 (14)
C1	0.0436 (14)	0.0534 (16)	0.0369 (13)	−0.0036 (12)	−0.0084 (11)	−0.0011 (12)
C2	0.0629 (17)	0.0571 (17)	0.0352 (14)	−0.0217 (14)	−0.0115 (12)	−0.0011 (12)
N3	0.0730 (16)	0.0581 (15)	0.0559 (15)	−0.0015 (12)	0.0198 (13)	0.0023 (12)
C5	0.0411 (13)	0.0502 (15)	0.0374 (14)	−0.0062 (11)	0.0025 (11)	−0.0021 (12)
N6	0.0789 (17)	0.0660 (18)	0.0487 (15)	−0.0019 (15)	−0.0011 (13)	0.0060 (11)
C6	0.0518 (15)	0.0614 (17)	0.0381 (14)	0.0020 (13)	0.0065 (12)	−0.0049 (13)
C9	0.0402 (13)	0.0532 (16)	0.0455 (15)	−0.0074 (12)	0.0049 (11)	−0.0033 (12)
C4	0.0367 (13)	0.079 (2)	0.0399 (14)	0.0137 (13)	−0.0047 (11)	−0.0051 (13)
N4	0.0620 (16)	0.0761 (18)	0.0512 (15)	−0.0010 (12)	0.0131 (12)	0.0004 (13)
C11	0.0693 (18)	0.0577 (17)	0.0465 (16)	0.0105 (15)	0.0160 (14)	−0.0007 (13)
C7	0.0470 (15)	0.0539 (15)	0.0472 (16)	0.0044 (13)	0.0167 (12)	0.0134 (13)
C10	0.0548 (16)	0.0570 (18)	0.0488 (16)	0.0103 (13)	0.0197 (13)	0.0080 (13)
C8	0.0500 (15)	0.0526 (17)	0.0596 (17)	−0.0114 (12)	0.0149 (13)	0.0005 (13)
C3	0.0384 (14)	0.090 (2)	0.0498 (16)	0.0141 (14)	−0.0076 (12)	0.0025 (16)
N5	0.0883 (19)	0.0797 (19)	0.0543 (16)	0.0033 (16)	0.0298 (14)	0.0107 (14)
C12	0.0715 (19)	0.0575 (19)	0.075 (2)	0.0012 (15)	0.0260 (17)	0.0043 (16)
C13	0.092 (2)	0.093 (3)	0.0451 (18)	0.001 (2)	0.0146 (17)	0.0001 (17)
C14	0.068 (2)	0.084 (2)	0.0537 (19)	−0.0058 (16)	0.0123 (15)	0.0019 (16)
O2	0.093 (2)	0.0504 (18)	0.065 (2)	0	0.0167 (17)	0
O1	0.089 (2)	0.0526 (19)	0.078 (2)	0	0.0163 (17)	0
O1a	0.281 (17)	0.078 (7)	0.097 (9)	−0.032 (9)	−0.083 (10)	0.037 (7)
O2a	0.35 (2)	0.111 (12)	0.283 (19)	0.030 (12)	0.177 (17)	0.059 (10)
O3a	0.328 (12)	0.178 (10)	0.077 (6)	0.159 (9)	0.012 (6)	−0.026 (6)
O4a	0.253 (8)	0.214 (14)	0.116 (7)	0.122 (9)	0.096 (7)	0.020 (6)
O1b	0.232 (9)	0.091 (5)	0.095 (7)	0.042 (6)	−0.086 (6)	−0.032 (5)
O2b	0.112 (5)	0.066 (5)	0.177 (10)	−0.016 (4)	0.051 (7)	−0.032 (6)
O3b	0.309 (15)	0.148 (9)	0.115 (7)	0.023 (9)	−0.029 (8)	−0.006 (6)
O4b	0.57 (3)	0.157 (13)	0.270 (19)	−0.102 (17)	0.26 (2)	−0.088 (12)

Cu1—N2	2.0364 (19)	N4—C10	1.463 (4)
Cu1—N2ⁱ	2.0364 (19)	C11—H1c11	0.93
Cu1—N1	2.0350 (17)	C11—C10	1.368 (4)
Cu1—N1ⁱ	2.0350 (17)	C11—C12	1.385 (4)
Cu1—O2	2.403 (3)	C7—C8	1.363 (4)
Cu1—O1	2.522 (3)	C10—C14	1.368 (4)
N2—C5	1.341 (3)	C8—H1c8	0.93
N2—C9	1.337 (3)	C3—H1c3	0.93
N1—C1	1.334 (3)	N5—C12	1.327 (4)
N1—C4	1.337 (3)	N5—C13	1.316 (5)
C15—C2	1.378 (4)	C12—H1c12	0.93
C15—N6	1.483 (3)	C13—H1c13	0.93
C15—C3	1.361 (4)	C13—C14	1.386 (5)
C1—H1c1	0.93	C14—H1c14	0.93
C1—C2	1.391 (3)	O2—H1o2	0.86 (3)
C2—H1c2	0.93	O2—H1o2ⁱ	0.86 (3)
N3—N4	1.209 (4)	O1—H1o1	0.86 (3)
N3—C7	1.448 (4)	O1—H1o1ⁱ	0.86 (3)
C5—H1c5	0.93	Cl—O1a	1.439 (9)
C5—C6	1.378 (4)	Cl—O2a	1.440 (10)
N6—N6ⁱⁱ	1.166 (4)	Cl—O3a	1.439 (7)
C6—H1c6	0.93	Cl—O4a	1.440 (7)
C6—C7	1.390 (4)	Cl—O1b	1.440 (10)
C9—H1c9	0.93	Cl—O2b	1.440 (8)
C9—C8	1.372 (4)	Cl—O3b	1.440 (6)
C4—H1c4	0.93	Cl—O4b	1.440 (11)
C4—C3	1.370 (3)

N2—Cu1—N2ⁱ	174.58 (7)	N3—N4—C10	111.9 (2)
N2—Cu1—N1	90.07 (7)	H1c11—C11—C10	120.8874
N2—Cu1—N1ⁱ	90.01 (7)	H1c11—C11—C12	120.8893
N2—Cu1—O2	92.71 (5)	C10—C11—C12	118.2 (3)
N2—Cu1—O1	87.29 (5)	N3—C7—C6	125.3 (2)
N2ⁱ—Cu1—N1	90.01 (7)	N3—C7—C8	115.3 (2)
N2ⁱ—Cu1—N1ⁱ	90.07 (7)	C6—C7—C8	119.4 (3)
N2ⁱ—Cu1—O2	92.71 (5)	N4—C10—C11	125.1 (2)
N2ⁱ—Cu1—O1	87.29 (5)	N4—C10—C14	115.7 (3)
N1—Cu1—N1ⁱ	178.40 (8)	C11—C10—C14	119.2 (3)
N1—Cu1—O2	89.20 (5)	C9—C8—C7	119.2 (2)
N1—Cu1—O1	90.80 (5)	C9—C8—H1c8	120.3901
N1ⁱ—Cu1—O2	89.20 (5)	C7—C8—H1c8	120.3912
N1ⁱ—Cu1—O1	90.80 (5)	C15—C3—C4	118.6 (3)
O2—Cu1—O1	180.0 (5)	C15—C3—H1c3	120.7243
C5—N2—C9	117.7 (2)	C4—C3—H1c3	120.7229
C1—N1—C4	117.74 (19)	C12—N5—C13	115.9 (3)
C2—C15—N6	126.8 (2)	C11—C12—N5	124.1 (3)
C2—C15—C3	119.5 (2)	C11—C12—H1c12	117.969
N6—C15—C3	113.7 (2)	N5—C12—H1c12	117.9667
N1—C1—H1c1	118.9506	N5—C13—H1c13	117.5416
N1—C1—C2	122.1 (2)	N5—C13—C14	124.9 (3)
H1c1—C1—C2	118.9493	H1c13—C13—C14	117.5406
C15—C2—C1	118.6 (2)	C10—C14—C13	117.6 (3)
C15—C2—H1c2	120.7066	C10—C14—H1c14	121.1841
C1—C2—H1c2	120.7056	C13—C14—H1c14	121.1852
N4—N3—C7	113.7 (2)	H1o2—O2—H1o2ⁱ	110 (3)
N2—C5—H1c5	118.4381	H1o1—O1—H1o1ⁱ	102 (3)
N2—C5—C6	123.1 (2)	O1a—Cl—O2a	109.5 (6)
H1c5—C5—C6	118.4384	O1a—Cl—O3a	109.5 (6)
C15—N6—N6ⁱⁱ	110.0 (2)	O1a—Cl—O4a	109.5 (7)
C5—C6—H1c6	121.132	O2a—Cl—O3a	109.5 (6)
C5—C6—C7	117.7 (2)	O2a—Cl—O4a	109.5 (6)
H1c6—C6—C7	121.1303	O3a—Cl—O4a	109.5 (5)
N2—C9—H1c9	118.6589	O1b—Cl—O2b	109.5 (6)
N2—C9—C8	122.7 (2)	O1b—Cl—O3b	109.5 (6)
H1c9—C9—C8	118.6588	O1b—Cl—O4b	109.5 (6)
N1—C4—H1c4	118.2663	O2b—Cl—O3b	109.5 (6)
N1—C4—C3	123.5 (2)	O2b—Cl—O4b	109.5 (7)
H1c4—C4—C3	118.2675	O3b—Cl—O4b	109.5 (6)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H1o2···O1bⁱⁱⁱ	0.86 (3)	2.14 (3)	2.913 (12)	150 (3)
O2—H1o2···O3aⁱⁱⁱ	0.86 (3)	1.77 (3)	2.589 (10)	158 (3)
O1—H1o1···O2aⁱ	0.86 (3)	2.21 (3)	2.969 (13)	147 (3)
O1—H1o1···O3bⁱ	0.86 (3)	2.20 (3)	3.010 (11)	157 (3)
C5—H1C5···O1b^iv	0.93	2.51	3.346 (11)	149
C13—H1c13···O3b^v	0.93	2.36	2.973 (11)	123

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H1o2⋯O1b ⁱ	0.86 (3)	2.14 (3)	2.913 (12)	150 (3)
O2—H1o2⋯O3a ⁱ	0.86 (3)	1.77 (3)	2.589 (10)	158 (3)
O1—H1o1⋯O2a ⁱⁱ	0.86 (3)	2.21 (3)	2.969 (13)	147 (3)
O1—H1o1⋯O3b ⁱⁱ	0.86 (3)	2.20 (3)	3.010 (11)	157 (3)
C5—H1C5⋯O1b ⁱⁱⁱ	0.93	2.51	3.346 (11)	149
C13—H1c13⋯O3b ^iv	0.93	2.36	2.973 (11)	123

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

5 in total

1. The Cambridge Structural Database: a quarter of a million crystal structures and rising.

Authors: Frank H Allen
Journal: Acta Crystallogr B Date: 2002-05-29

2. Synthesis and crystallographic characterization of low-dimensional and porous coordination compounds capable of supramolecular aromatic interaction using the 4,4'-azobis(pyridine) ligand.

Authors: Shin-ichiro Noro; Susumu Kitagawa; Takayoshi Nakamura; Tatsuo Wada
Journal: Inorg Chem Date: 2005-05-30 Impact factor: 5.165