Poly[μ(2)-chlorido-dichlorido[μ(2)-4'-(4-pyrid-yl)-2,2':6',2''-terpyridine]-copper(I)copper(II)].

In the mixed-valence Cu(I)/Cu(II) coordination polymer, [Cu(2)Cl(3)(C(20)H(14)N(4))](n), the two Cu atoms are bridged to a pair of Cl atoms across a centre of inversion. The monovalent metal atoms is coordinated by a pyridine N atom as well as by three Cl atoms in a tetra-hedral CuNCl(3) geometry. The divalent metal atom is N,N',N''-chelated by the heterocycle, and it exists in a square-pyramidal CuN(3)Cl(2) geometry; the apical site is occupied by the second bridging Cl atom. The bridging modes of the Cl atoms and the heterocycle give rise to the formation of a layered arrangement parallel to (001).

Related literature

For related structures, see: Hou et al. (2005 ▶); Zhang et al. (2007 ▶)

Experimental

Crystal data

[Cu2Cl3(C20H14N4)]

M = 543.78

Triclinic,

a = 8.1389 (8) Å

b = 9.8161 (10) Å

c = 12.4823 (13) Å

α = 79.512 (2)°

β = 85.036 (2)°

γ = 88.202 (2)°

V = 976.78 (17) Å3

Z = 2

Mo Kα radiation

μ = 2.60 mm−1

T = 294 K

0.15 × 0.12 × 0.10 mm

Data collection

Bruker SMART diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.694, T max = 0.771

7840 measured reflections

3778 independent reflections

3391 reflections with I > 2σ(I)

R int = 0.014

Refinement

R[F 2 > 2σ(F 2)] = 0.027

wR(F 2) = 0.072

S = 1.06

3778 reflections

262 parameters

H-atom parameters constrained

Δρmax = 0.40 e Å−3

Δρmin = −0.34 e Å−3

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1998 ▶); 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.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811014759/ng5143sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811014759/ng5143Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Cu2Cl3(C20H14N4)]	Z = 2
Mr = 543.78	F(000) = 542
Triclinic, P1	Dx = 1.849 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.1389 (8) Å	Cell parameters from 1056 reflections
b = 9.8161 (10) Å	θ = 2.4–26.0°
c = 12.4823 (13) Å	µ = 2.60 mm−1
α = 79.512 (2)°	T = 294 K
β = 85.036 (2)°	Block, black
γ = 88.202 (2)°	0.15 × 0.12 × 0.10 mm
V = 976.78 (17) Å3

Bruker SMART diffractometer	3778 independent reflections
Radiation source: fine-focus sealed tube	3391 reflections with I > 2σ(I)
graphite	Rint = 0.014
φ and ω scans	θmax = 26.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→9
Tmin = 0.694, Tmax = 0.771	k = −12→12
7840 measured reflections	l = −15→15

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.072	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0383P)2 + 0.3983P] where P = (Fo2 + 2Fc2)/3
3778 reflections	(Δ/σ)max = 0.002
262 parameters	Δρmax = 0.40 e Å−3
0 restraints	Δρmin = −0.34 e Å−3

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.

	x	y	z	Uiso*/Ueq
Cu1	1.55686 (3)	0.36696 (3)	−0.35707 (2)	0.02849 (9)
Cu2	1.49349 (3)	0.14312 (3)	−0.05428 (3)	0.04087 (10)
Cl1	1.36557 (7)	−0.05058 (6)	−0.10452 (5)	0.03600 (14)
Cl3	1.68201 (7)	0.25884 (6)	−0.18347 (5)	0.03968 (15)
Cl2	1.73952 (7)	0.30031 (7)	−0.48213 (5)	0.04485 (16)
C16	0.4539 (2)	0.3584 (2)	0.30399 (17)	0.0271 (4)
N2	0.6324 (2)	0.54582 (18)	0.28869 (14)	0.0266 (4)
N4	1.2937 (2)	0.24557 (19)	0.00438 (16)	0.0332 (4)
N3	0.3521 (2)	0.43980 (19)	0.35802 (14)	0.0299 (4)
N1	0.6210 (2)	0.77686 (18)	0.35354 (14)	0.0288 (4)
C11	1.3087 (3)	0.3651 (2)	0.03817 (19)	0.0333 (5)
H11	1.4103	0.4084	0.0239	0.040*
C15	0.6150 (2)	0.4212 (2)	0.26284 (17)	0.0265 (4)
C14	0.7417 (2)	0.3610 (2)	0.20518 (17)	0.0282 (4)
H14	0.7274	0.2755	0.1854	0.034*
C9	1.0297 (2)	0.3681 (2)	0.11560 (17)	0.0273 (4)
C8	0.8918 (2)	0.4302 (2)	0.17696 (17)	0.0260 (4)
C6	0.7742 (2)	0.6135 (2)	0.26509 (17)	0.0270 (4)
C7	0.9077 (2)	0.5576 (2)	0.20962 (17)	0.0286 (4)
H7	1.0068	0.6047	0.1944	0.034*
C10	1.1832 (3)	0.4291 (2)	0.09312 (19)	0.0324 (5)
H10	1.2014	0.5126	0.1150	0.039*
C1	0.6025 (3)	0.8956 (2)	0.39099 (19)	0.0355 (5)
H1	0.5002	0.9170	0.4237	0.043*
C3	0.8787 (3)	0.9570 (3)	0.3336 (2)	0.0464 (6)
H3	0.9655	1.0182	0.3272	0.056*
C18	0.2576 (3)	0.1787 (3)	0.3369 (2)	0.0415 (6)
H18	0.2260	0.0904	0.3308	0.050*
C4	0.9006 (3)	0.8347 (2)	0.2933 (2)	0.0404 (6)
H4	1.0018	0.8122	0.2598	0.049*
C5	0.7688 (3)	0.7472 (2)	0.30392 (17)	0.0286 (4)
C17	0.4102 (3)	0.2284 (2)	0.29147 (19)	0.0335 (5)
H17	0.4816	0.1749	0.2532	0.040*
C2	0.7283 (3)	0.9875 (3)	0.3832 (2)	0.0411 (6)
H2	0.7120	1.0691	0.4109	0.049*
C13	1.0125 (3)	0.2455 (3)	0.0776 (2)	0.0465 (7)
H13	0.9113	0.2014	0.0886	0.056*
C20	0.2040 (3)	0.3911 (3)	0.40001 (19)	0.0368 (5)
H20	0.1330	0.4468	0.4364	0.044*
C19	0.1529 (3)	0.2610 (3)	0.3913 (2)	0.0420 (6)
H19	0.0496	0.2296	0.4216	0.050*
C12	1.1452 (3)	0.1887 (3)	0.0232 (2)	0.0480 (7)
H12	1.1300	0.1065	−0.0014	0.058*

	U11	U22	U33	U12	U13	U23
Cu1	0.02035 (14)	0.03193 (16)	0.03487 (16)	0.00211 (10)	0.00583 (10)	−0.01466 (11)
Cu2	0.02869 (16)	0.04265 (18)	0.0509 (2)	0.00035 (12)	0.01106 (13)	−0.01440 (14)
Cl1	0.0362 (3)	0.0355 (3)	0.0399 (3)	−0.0021 (2)	−0.0025 (2)	−0.0165 (2)
Cl3	0.0261 (3)	0.0494 (3)	0.0401 (3)	−0.0083 (2)	0.0011 (2)	0.0003 (3)
Cl2	0.0350 (3)	0.0568 (4)	0.0461 (3)	0.0020 (3)	0.0134 (2)	−0.0265 (3)
C16	0.0199 (10)	0.0300 (11)	0.0308 (11)	0.0016 (8)	0.0031 (8)	−0.0069 (9)
N2	0.0191 (8)	0.0270 (9)	0.0340 (9)	0.0018 (7)	0.0035 (7)	−0.0092 (7)
N4	0.0229 (9)	0.0345 (10)	0.0428 (11)	0.0016 (7)	0.0081 (8)	−0.0140 (8)
N3	0.0234 (9)	0.0323 (10)	0.0334 (10)	0.0012 (7)	0.0061 (7)	−0.0085 (8)
N1	0.0244 (9)	0.0311 (9)	0.0335 (9)	0.0033 (7)	−0.0003 (7)	−0.0143 (8)
C11	0.0208 (10)	0.0339 (12)	0.0455 (13)	−0.0020 (9)	0.0067 (9)	−0.0120 (10)
C15	0.0211 (10)	0.0263 (10)	0.0319 (11)	0.0001 (8)	0.0028 (8)	−0.0073 (8)
C14	0.0228 (10)	0.0270 (10)	0.0359 (11)	−0.0002 (8)	0.0051 (8)	−0.0121 (9)
C9	0.0217 (10)	0.0289 (11)	0.0315 (11)	0.0030 (8)	0.0033 (8)	−0.0092 (9)
C8	0.0211 (10)	0.0285 (11)	0.0291 (10)	0.0023 (8)	0.0016 (8)	−0.0094 (8)
C6	0.0203 (10)	0.0284 (11)	0.0331 (11)	0.0024 (8)	0.0015 (8)	−0.0099 (9)
C7	0.0199 (10)	0.0309 (11)	0.0365 (12)	−0.0011 (8)	0.0035 (8)	−0.0125 (9)
C10	0.0235 (11)	0.0306 (11)	0.0452 (13)	−0.0013 (9)	0.0034 (9)	−0.0149 (10)
C1	0.0316 (12)	0.0363 (12)	0.0416 (13)	0.0062 (10)	0.0012 (10)	−0.0184 (10)
C3	0.0365 (13)	0.0401 (14)	0.0682 (18)	−0.0090 (11)	−0.0012 (12)	−0.0244 (13)
C18	0.0294 (12)	0.0366 (13)	0.0583 (16)	−0.0068 (10)	0.0024 (11)	−0.0096 (11)
C4	0.0261 (11)	0.0393 (13)	0.0595 (15)	−0.0017 (10)	0.0031 (10)	−0.0213 (12)
C5	0.0238 (10)	0.0294 (11)	0.0342 (11)	0.0038 (8)	−0.0005 (8)	−0.0117 (9)
C17	0.0232 (11)	0.0334 (12)	0.0444 (13)	−0.0002 (9)	0.0043 (9)	−0.0115 (10)
C2	0.0433 (14)	0.0348 (13)	0.0504 (14)	0.0015 (10)	−0.0019 (11)	−0.0231 (11)
C13	0.0246 (11)	0.0452 (14)	0.0749 (18)	−0.0108 (10)	0.0186 (11)	−0.0334 (13)
C20	0.0240 (11)	0.0434 (13)	0.0411 (13)	0.0019 (10)	0.0092 (9)	−0.0087 (10)
C19	0.0225 (11)	0.0462 (14)	0.0538 (15)	−0.0075 (10)	0.0082 (10)	−0.0044 (12)
C12	0.0326 (13)	0.0413 (14)	0.0762 (19)	−0.0075 (11)	0.0179 (12)	−0.0361 (13)

Cu1—N2i	1.9466 (16)	C14—H14	0.9300
Cu1—N1i	2.0455 (18)	C9—C10	1.387 (3)
Cu1—N3i	2.0557 (18)	C9—C13	1.387 (3)
Cu1—Cl2	2.2325 (6)	C9—C8	1.483 (3)
Cu1—Cl3	2.5172 (6)	C8—C7	1.397 (3)
Cu2—N4	2.0374 (18)	C6—C7	1.390 (3)
Cu2—Cl3	2.2933 (6)	C6—C5	1.478 (3)
Cu2—Cl1ii	2.3964 (7)	C7—H7	0.9300
Cu2—Cl1	2.4007 (6)	C10—H10	0.9300
Cu2—Cu2ii	2.8917 (7)	C1—C2	1.371 (3)
Cl1—Cu2ii	2.3964 (7)	C1—H1	0.9300
C16—N3	1.355 (3)	C3—C2	1.373 (3)
C16—C17	1.375 (3)	C3—C4	1.385 (3)
C16—C15	1.477 (3)	C3—H3	0.9300
N2—C6	1.333 (3)	C18—C19	1.377 (3)
N2—C15	1.335 (3)	C18—C17	1.385 (3)
N2—Cu1i	1.9466 (16)	C18—H18	0.9300
N4—C11	1.330 (3)	C4—C5	1.377 (3)
N4—C12	1.332 (3)	C4—H4	0.9300
N3—C20	1.339 (3)	C17—H17	0.9300
N3—Cu1i	2.0557 (18)	C2—H2	0.9300
N1—C1	1.332 (3)	C13—C12	1.382 (3)
N1—C5	1.353 (3)	C13—H13	0.9300
N1—Cu1i	2.0455 (18)	C20—C19	1.381 (3)
C11—C10	1.380 (3)	C20—H20	0.9300
C11—H11	0.9300	C19—H19	0.9300
C15—C14	1.385 (3)	C12—H12	0.9300
C14—C8	1.403 (3)
N2i—Cu1—N1i	78.97 (7)	C10—C9—C8	121.92 (19)
N2i—Cu1—N3i	79.19 (7)	C13—C9—C8	121.8 (2)
N1i—Cu1—N3i	156.19 (7)	C7—C8—C14	118.17 (18)
N2i—Cu1—Cl2	162.20 (6)	C7—C8—C9	121.33 (19)
N1i—Cu1—Cl2	99.27 (5)	C14—C8—C9	120.49 (19)
N3i—Cu1—Cl2	98.61 (5)	N2—C6—C7	120.70 (19)
N2i—Cu1—Cl3	96.91 (5)	N2—C6—C5	112.78 (17)
N1i—Cu1—Cl3	97.93 (5)	C7—C6—C5	126.51 (19)
N3i—Cu1—Cl3	93.99 (5)	C6—C7—C8	119.42 (19)
Cl2—Cu1—Cl3	100.87 (2)	C6—C7—H7	120.3
N4—Cu2—Cl3	120.37 (6)	C8—C7—H7	120.3
N4—Cu2—Cl1ii	104.34 (6)	C11—C10—C9	119.6 (2)
Cl3—Cu2—Cl1ii	107.93 (2)	C11—C10—H10	120.2
N4—Cu2—Cl1	101.32 (6)	C9—C10—H10	120.2
Cl3—Cu2—Cl1	115.66 (2)	N1—C1—C2	122.6 (2)
Cl1ii—Cu2—Cl1	105.86 (2)	N1—C1—H1	118.7
N4—Cu2—Cu2ii	111.61 (6)	C2—C1—H1	118.7
Cl3—Cu2—Cu2ii	127.92 (2)	C2—C3—C4	119.6 (2)
Cl1ii—Cu2—Cu2ii	52.998 (16)	C2—C3—H3	120.2
Cl1—Cu2—Cu2ii	52.861 (18)	C4—C3—H3	120.2
Cu2ii—Cl1—Cu2	74.14 (2)	C19—C18—C17	119.5 (2)
Cu2—Cl3—Cu1	112.90 (2)	C19—C18—H18	120.2
N3—C16—C17	122.26 (19)	C17—C18—H18	120.2
N3—C16—C15	113.85 (18)	C5—C4—C3	118.4 (2)
C17—C16—C15	123.88 (18)	C5—C4—H4	120.8
C6—N2—C15	121.47 (17)	C3—C4—H4	120.8
C6—N2—Cu1i	119.54 (14)	N1—C5—C4	121.9 (2)
C15—N2—Cu1i	118.95 (14)	N1—C5—C6	113.76 (18)
C11—N4—C12	116.29 (19)	C4—C5—C6	124.37 (19)
C11—N4—Cu2	121.51 (15)	C16—C17—C18	118.6 (2)
C12—N4—Cu2	121.71 (15)	C16—C17—H17	120.7
C20—N3—C16	118.36 (19)	C18—C17—H17	120.7
C20—N3—Cu1i	127.42 (15)	C1—C2—C3	118.8 (2)
C16—N3—Cu1i	114.11 (14)	C1—C2—H2	120.6
C1—N1—C5	118.65 (19)	C3—C2—H2	120.6
C1—N1—Cu1i	126.56 (15)	C12—C13—C9	120.2 (2)
C5—N1—Cu1i	114.75 (14)	C12—C13—H13	119.9
N4—C11—C10	124.2 (2)	C9—C13—H13	119.9
N4—C11—H11	117.9	N3—C20—C19	122.4 (2)
C10—C11—H11	117.9	N3—C20—H20	118.8
N2—C15—C14	120.84 (19)	C19—C20—H20	118.8
N2—C15—C16	113.24 (17)	C18—C19—C20	118.9 (2)
C14—C15—C16	125.90 (19)	C18—C19—H19	120.6
C15—C14—C8	119.30 (19)	C20—C19—H19	120.6
C15—C14—H14	120.4	N4—C12—C13	123.4 (2)
C8—C14—H14	120.4	N4—C12—H12	118.3
C10—C9—C13	116.26 (19)	C13—C12—H12	118.3