Iodidobis(1,10-phenanthroline)copper(II) perchlorate

The title compound, [CuI(C₁₂H₈N₂)₂]ClO₄, was prepared by a hydro­thermal reaction at 453 K. The Cu atom has a slightly distorted trigonal–bipyramidal coordination geometry, penta­coordinated by four N atoms of two chelating 1,10-phenanthroline ligands and one I atom. There are supra­molecular π–π inter­actions between neighbouring parallel pyridine rings, with a face-to-face distance of 3.51 (1) Å.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.061
• wR factor = 0.164
• Data-to-parameter ratio = 17.4

checkCIF/PLATON results

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Alert level C
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        Cl1

Alert level G
PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1         (2)       2.12

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S1. Comment

In recent years, bivalent copper complexes with 1,10-phenanthroline ligand have attracted much attention for their biochemical, optical and electromagnetic applications (Marta et al., 2006; Yu et al., 2004; Bencini et al., 1989). Many complexes have been synthesized and their structure have been reported, such as [Cu(phen)₂Cl]ClO₄ (Boys et al., 1981) and [Cu(phen)₂Br]ClO₄ (Parker et al., 1994) as representative examples. We report here the crystal structure of the title compound.

The structure of the title compound(I), is illustrated in Fig.1. Selected geometric parameters are listed in Table 1. The copper atom exhibits a slightly distorted trigonal-bipyramidal stereochemistry, which is five-coordinated by four nitrogen atoms from two cis-related chelating 1,10-phenanthroline ligands and one iodine atom.

There are supramolecular π—π interactions between neighbouring parallel pyridine rings, which help to stabilize the crystal structure of (I), and link the molecules into two-dimensional layers, with a face-to-face distance of 3.51 (1) Å (Fig. 2). The similar interactions were observed in the structures of [Ag(phen)(CN)] compound (Huang et al., 2004) and [Ag(phen)–(PPh₃)] ClO₄ 0.5CH₃CN (Khalaji et al., 2007).

Related literature

For related literature, see: Bencini et al. (1989); Boys et al. (1981); Huang et al. (2004); Khalaji et al. (2007); Marta et al. (2006); Parker et al. (1994); Yu et al. (2004).

S2. Experimental

For the synthesis of complex(I), a mixture of copper(II) perchlorate hexahydrate (0.4 mmol, 146 mg), 1,10-phenanthroline (0.4 mmol, 79.2 mg), KI (0.6 mmol, 99.6 mg) and H₂O (20.0 ml) was sealed in a 40 ml stainless steel reactor with a Teflon liner and heated directly to 453 K. After maintaining this temperature for 72 h, the mixture was cooled slowly to room temperature at a rate of 3 K/h(kept at 383 K for 12 h and kept at 363 K for 72 h respectively). Black long strip crystals of the title complex were collected by filtration and were obtained in 35% yield. Analysis calculated for C₂₄H₁₆ClCuIN₄O₄(%): C 44.33, H 2.48, N 8.62; found: C 44.36, H 2.46, N 8.68.

S3. Refinement

All H atoms were placed in geometrically idealized positions and were refined isotropically in the riding-model approximation. The bond lengths of C—H were fixed at 0.93 Å. The U_iso(H) values were set equal to 1.2 times the U_eq value of the C parent atoms. O atoms of the perchlorate group are slightly disordered; it was not split into two positions as its U_eq values are normally.

Computing details

Data collection: RAPID-AUTO (Rigaku, 2004); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 199); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The structure of complex (I), with displacement ellipsoids drawn at the 30% probability level and H atoms shown as small spheres of arbitrary radii.
	Fig. 2. Part of the crystal structure of the title compound, showing the π—π stacking interactions as dashed lines between the pyridine rings. H atoms have been omitted for clarity.

Iodidobis(1,10-phenanthroline)copper(II) perchlorate

Crystal data

[CuI(C12H8N2)2]ClO4	F(000) = 1276
Mr = 650.30	Dx = 1.897 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 8209 reflections
a = 16.740 (3) Å	θ = 3.1–25.6°
b = 11.796 (2) Å	µ = 2.47 mm^−1
c = 12.558 (3) Å	T = 295 K
β = 113.30 (3)°	Prism, blue
V = 2277.5 (9) Å^3	0.46 × 0.13 × 0.12 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID IP area-detector diffractometer	2617 independent reflections
Radiation source: rotating anode	2296 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.064
oscillation scans	θmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −21→20
Tmin = 0.370, Tmax = 0.743	k = −15→15
10929 measured reflections	l = −16→16

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.165	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0551P)^2 + 30.844P] where P = (Fo^2 + 2Fc^2)/3
2617 reflections	(Δ/σ)max = 0.011
150 parameters	Δρmax = 3.88 e Å^−3
0 restraints	Δρmin = −2.86 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
I1	0.5000	0.51742 (3)	0.2500	0.05310 (10)
Cu1	0.5000	0.74631 (7)	0.2500	0.05310 (10)
Cl1	0.5000	0.12606 (12)	0.2500	0.0489 (3)
O1	0.5620 (3)	0.0559 (5)	0.2329 (5)	0.1297 (16)
O2	0.4631 (5)	0.1929 (6)	0.1527 (5)	0.174 (3)
N1	0.5935 (2)	0.7470 (3)	0.1910 (3)	0.05310 (10)
N2	0.59261 (19)	0.8369 (3)	0.3854 (3)	0.0435 (7)
C1	0.5919 (3)	0.6988 (4)	0.0937 (4)	0.0598 (12)
H1A	0.5398	0.6690	0.0410	0.072*
C2	0.6658 (3)	0.6919 (4)	0.0691 (4)	0.0637 (12)
H2A	0.6627	0.6576	0.0009	0.076*
C3	0.7419 (3)	0.7350 (4)	0.1440 (4)	0.0636 (12)
H3A	0.7918	0.7281	0.1290	0.076*
C4	0.7455 (2)	0.7909 (4)	0.2461 (4)	0.0532 (10)
C5	0.8213 (3)	0.8429 (4)	0.3292 (5)	0.0669 (13)
H5A	0.8727	0.8418	0.3175	0.080*
C6	0.8198 (3)	0.8937 (4)	0.4247 (5)	0.0638 (14)
H6A	0.8701	0.9282	0.4766	0.077*
C7	0.7429 (3)	0.8958 (4)	0.4482 (4)	0.0519 (11)
C8	0.7376 (3)	0.9452 (4)	0.5476 (4)	0.0616 (13)
H8A	0.7859	0.9803	0.6030	0.074*
C9	0.6613 (3)	0.9409 (4)	0.5616 (4)	0.0608 (12)
H9A	0.6566	0.9747	0.6258	0.073*
C10	0.5901 (3)	0.8856 (4)	0.4793 (3)	0.0516 (10)
H10A	0.5385	0.8827	0.4906	0.062*
C11	0.6678 (2)	0.8436 (3)	0.3694 (3)	0.0423 (9)
C12	0.6686 (2)	0.7934 (3)	0.2658 (3)	0.0420 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.04444 (14)	0.05585 (19)	0.06436 (17)	0.000	0.02721 (12)	0.000
Cu1	0.04444 (14)	0.05585 (19)	0.06436 (17)	0.000	0.02721 (12)	0.000
Cl1	0.0505 (6)	0.0512 (7)	0.0480 (6)	0.000	0.0226 (5)	0.000
O1	0.130 (2)	0.127 (4)	0.188 (3)	0.052 (2)	0.123 (2)	0.048 (3)
O2	0.193 (5)	0.213 (6)	0.118 (3)	0.096 (5)	0.064 (3)	0.093 (4)
N1	0.04444 (14)	0.05585 (19)	0.06436 (17)	0.000	0.02721 (12)	0.000
N2	0.0431 (12)	0.0451 (16)	0.0467 (13)	0.0017 (12)	0.0226 (11)	0.0062 (12)
C1	0.0636 (19)	0.068 (3)	0.0604 (19)	0.0010 (19)	0.0381 (15)	0.0009 (18)
C2	0.077 (2)	0.072 (3)	0.0629 (18)	0.012 (2)	0.0492 (15)	0.0108 (18)
C3	0.0593 (17)	0.071 (3)	0.080 (2)	0.0142 (18)	0.0480 (15)	0.0219 (19)
C4	0.0454 (15)	0.052 (2)	0.0714 (19)	0.0105 (15)	0.0327 (14)	0.0229 (17)
C5	0.0410 (16)	0.072 (3)	0.092 (3)	0.0059 (18)	0.0314 (18)	0.025 (2)
C6	0.0391 (17)	0.065 (3)	0.083 (3)	−0.0040 (18)	0.0193 (18)	0.012 (2)
C7	0.0446 (17)	0.046 (2)	0.059 (2)	−0.0006 (16)	0.0140 (16)	0.0133 (17)
C8	0.061 (2)	0.055 (2)	0.062 (2)	−0.009 (2)	0.0169 (19)	0.0028 (19)
C9	0.077 (2)	0.055 (2)	0.0520 (19)	−0.007 (2)	0.0283 (18)	−0.0033 (17)
C10	0.0552 (18)	0.053 (2)	0.0527 (18)	−0.0005 (16)	0.0274 (15)	0.0029 (16)
C11	0.0392 (14)	0.0412 (17)	0.0479 (16)	0.0027 (13)	0.0186 (12)	0.0122 (13)
C12	0.0396 (13)	0.0438 (18)	0.0487 (15)	0.0063 (13)	0.0240 (12)	0.0145 (13)

Geometric parameters (Å, º)

I1—Cu1	2.7000 (10)	C3—C4	1.422 (7)
Cu1—N1^i	1.978 (4)	C3—H3A	0.9300
Cu1—N1	1.978 (4)	C4—C12	1.404 (6)
Cu1—N2	2.086 (3)	C4—C5	1.424 (6)
Cu1—N2^i	2.086 (3)	C5—C6	1.349 (8)
Cl1—O2^i	1.378 (6)	C5—H5A	0.9300
Cl1—O2	1.378 (6)	C6—C7	1.430 (7)
Cl1—O1^i	1.408 (5)	C6—H6A	0.9300
Cl1—O1	1.408 (5)	C7—C11	1.398 (5)
N1—C1	1.338 (6)	C7—C8	1.411 (7)
N1—C12	1.352 (5)	C8—C9	1.357 (7)
N2—C10	1.327 (5)	C8—H8A	0.9300
N2—C11	1.354 (5)	C9—C10	1.393 (6)
C1—C2	1.392 (6)	C9—H9A	0.9300
C1—H1A	0.9300	C10—H10A	0.9300
C2—C3	1.348 (6)	C11—C12	1.434 (6)
C2—H2A	0.9300
N1^i—Cu1—N1	179.6 (2)	C2—C3—H3A	120.1
N1^i—Cu1—N2	97.80 (14)	C4—C3—H3A	120.1
N1—Cu1—N2	81.97 (14)	C12—C4—C3	117.0 (3)
N1^i—Cu1—N2^i	81.97 (14)	C12—C4—C5	118.4 (4)
N1—Cu1—N2^i	97.80 (14)	C3—C4—C5	124.6 (4)
N2—Cu1—N2^i	118.35 (18)	C6—C5—C4	121.2 (4)
N1^i—Cu1—I1	90.22 (11)	C6—C5—H5A	119.4
N1—Cu1—I1	90.22 (11)	C4—C5—H5A	119.4
N2—Cu1—I1	120.82 (9)	C5—C6—C7	121.7 (4)
N2^i—Cu1—I1	120.82 (9)	C5—C6—H6A	119.2
O2^i—Cl1—O2	110.2 (6)	C7—C6—H6A	119.2
O2^i—Cl1—O1^i	107.5 (4)	C11—C7—C8	117.0 (4)
O2—Cl1—O1^i	111.9 (4)	C11—C7—C6	118.5 (4)
O2^i—Cl1—O1	111.9 (4)	C8—C7—C6	124.5 (4)
O2—Cl1—O1	107.5 (4)	C9—C8—C7	119.5 (4)
O1^i—Cl1—O1	108.0 (5)	C9—C8—H8A	120.3
C1—N1—C12	118.9 (4)	C7—C8—H8A	120.3
C1—N1—Cu1	127.4 (3)	C8—C9—C10	119.6 (5)
C12—N1—Cu1	113.4 (3)	C8—C9—H9A	120.2
C10—N2—C11	117.7 (3)	C10—C9—H9A	120.2
C10—N2—Cu1	132.2 (3)	N2—C10—C9	122.9 (4)
C11—N2—Cu1	110.1 (2)	N2—C10—H10A	118.5
N1—C1—C2	121.9 (4)	C9—C10—H10A	118.5
N1—C1—H1A	119.0	N2—C11—C7	123.3 (4)
C2—C1—H1A	119.0	N2—C11—C12	116.9 (3)
C3—C2—C1	120.0 (4)	C7—C11—C12	119.8 (4)
C3—C2—H2A	120.0	N1—C12—C4	122.3 (4)
C1—C2—H2A	120.0	N1—C12—C11	117.3 (3)
C2—C3—C4	119.7 (4)	C4—C12—C11	120.4 (3)
N2—Cu1—N1—C1	178.6 (4)	C6—C7—C8—C9	−179.2 (4)
N2^i—Cu1—N1—C1	−63.7 (4)	C7—C8—C9—C10	1.6 (7)
I1—Cu1—N1—C1	57.5 (4)	C11—N2—C10—C9	−1.0 (6)
N2—Cu1—N1—C12	5.0 (3)	Cu1—N2—C10—C9	178.6 (3)
N2^i—Cu1—N1—C12	122.7 (3)	C8—C9—C10—N2	−0.7 (7)
I1—Cu1—N1—C12	−116.1 (3)	C10—N2—C11—C7	2.0 (5)
N1^i—Cu1—N2—C10	−3.1 (4)	Cu1—N2—C11—C7	−177.6 (3)
N1—Cu1—N2—C10	176.6 (4)	C10—N2—C11—C12	−178.3 (3)
N2^i—Cu1—N2—C10	82.0 (3)	Cu1—N2—C11—C12	2.1 (4)
I1—Cu1—N2—C10	−98.0 (3)	C8—C7—C11—N2	−1.2 (6)
N1^i—Cu1—N2—C11	176.5 (2)	C6—C7—C11—N2	177.4 (4)
N1—Cu1—N2—C11	−3.8 (2)	C8—C7—C11—C12	179.1 (4)
N2^i—Cu1—N2—C11	−98.4 (2)	C6—C7—C11—C12	−2.3 (6)
I1—Cu1—N2—C11	81.6 (2)	C1—N1—C12—C4	−1.3 (6)
C12—N1—C1—C2	2.1 (7)	Cu1—N1—C12—C4	172.9 (3)
Cu1—N1—C1—C2	−171.2 (4)	C1—N1—C12—C11	−179.7 (4)
N1—C1—C2—C3	−0.3 (7)	Cu1—N1—C12—C11	−5.5 (4)
C1—C2—C3—C4	−2.2 (7)	C3—C4—C12—N1	−1.2 (6)
C2—C3—C4—C12	2.9 (6)	C5—C4—C12—N1	179.4 (4)
C2—C3—C4—C5	−177.8 (5)	C3—C4—C12—C11	177.2 (4)
C12—C4—C5—C6	−0.1 (7)	C5—C4—C12—C11	−2.2 (6)
C3—C4—C5—C6	−179.5 (5)	N2—C11—C12—N1	2.2 (5)
C4—C5—C6—C7	1.3 (7)	C7—C11—C12—N1	−178.1 (4)
C5—C6—C7—C11	0.0 (7)	N2—C11—C12—C4	−176.3 (3)
C5—C6—C7—C8	178.5 (5)	C7—C11—C12—C4	3.5 (5)
C11—C7—C8—C9	−0.6 (6)

Symmetry code: (i) −x+1, y, −z+1/2.