A new mixed-valence Cu^II/Cu^I complex: chloro­bis(1,10-phenanthroline)copper(II) di­chloro­cuprate(I)

A new mixed-valence Cu^II/Cu^I complex, dark-green [CuCl(phen)₂][CuCl₂] (phen = phenanthroline, C₁₂H₈N₂), consisting of isolated [Cu(phen)₂Cl]⁺ cations and [CuCl₂]^- anions, has been synthesized under hydro­thermal conditions. The [Cu(phen)₂Cl]⁺ cation contains a five-coordinated Cu²⁺ ion, coordinated by two bidentate phenanthroline ligands and a Cl atom. Each di­chloro­cuprate counter-ion contains a monovalent Cu⁺ ion, which occupies a special position on a twofold axis.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.035
• wR factor = 0.110
• Data-to-parameter ratio = 16.9

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT031_ALERT_4_C Refined Extinction Parameter within Range ......       3.00 Sigma
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: TEXRAY (Molecular Structure Corporation, 1999); cell refinement: TEXRAY; data reduction: TEXSAN (Molecular Structure Corporation, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEX (McArdle, 1995); software used to prepare material for publication: SHELXL97.

chlorobis(1,10-phenanthroline)copper(II) dichlorocuprate(I)

Crystal data

[CuCl(C12H8N2)2][CuCl2]	F(000) = 1188
Mr = 593.86	Dx = 1.748 Mg m^−3
Monoclinic, P2/c	Mo Kα radiation, λ = 0.71069 Å
a = 14.4063 (5) Å	Cell parameters from 25 reflections
b = 12.6196 (6) Å	θ = 12–18°
c = 13.3400 (5) Å	µ = 2.26 mm^−1
β = 111.480 (3)°	T = 298 K
V = 2256.79 (16) Å^3	Block, green
Z = 4	0.20 × 0.20 × 0.20 mm

Data collection

Rigaku Weissenberg IP diffractometer	3786 reflections with I > 2σ(I)
Radiation source: rotor target	Rint = 0.000
Graphite monochromator	θmax = 27.5°, θmin = 1.5°
Detector resolution: none pixels mm^-1	h = −18→17
scintillation counter scans	k = −16→0
5081 measured reflections	l = 0→17
5081 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.035	H-atom parameters constrained
wR(F^2) = 0.110	w = 1/[σ^2(Fo^2) + (0.0676P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max = 0.001
5081 reflections	Δρmax = 0.60 e Å^−3
300 parameters	Δρmin = −0.44 e Å^−3
0 restraints	Extinction correction: SHELXL97
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0012 (4)

Special details

Experimental. Information about the range of hkl for the original data set is missing, because the authors received only the averaged data and the original data in the machine has been deleted (R_int=0.0351).

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
Cu1	0.25883 (2)	0.22733 (3)	0.51218 (2)	0.03846 (12)
Cu2	0.0000	0.18091 (4)	0.7500	0.05902 (18)
Cu3	0.5000	0.63526 (5)	0.7500	0.06134 (18)
Cl1	0.16355 (6)	0.22794 (7)	0.61706 (6)	0.0535 (2)
Cl2	0.12348 (6)	0.17720 (6)	0.89434 (6)	0.0553 (2)
Cl3	0.35601 (9)	0.64043 (12)	0.74871 (14)	0.1164 (5)
N1	0.17978 (16)	0.17912 (17)	0.34962 (16)	0.0370 (5)
N2	0.21024 (17)	0.36749 (18)	0.44526 (18)	0.0410 (5)
N3	0.41216 (17)	0.27198 (18)	0.56550 (18)	0.0439 (5)
N4	0.32272 (16)	0.08647 (17)	0.56185 (16)	0.0363 (5)
C1	0.1576 (2)	0.0842 (2)	0.3048 (2)	0.0440 (6)
H1	0.1803	0.0248	0.3482	0.053*
C2	0.1015 (2)	0.0691 (3)	0.1954 (2)	0.0517 (7)
H2	0.0868	0.0010	0.1672	0.062*
C3	0.0688 (2)	0.1550 (3)	0.1307 (2)	0.0509 (7)
H3	0.0321	0.1462	0.0576	0.061*
C4	0.0906 (2)	0.2570 (2)	0.1746 (2)	0.0445 (7)
C5	0.14566 (19)	0.2647 (2)	0.2857 (2)	0.0370 (6)
C6	0.16397 (19)	0.3656 (2)	0.3364 (2)	0.0384 (6)
C7	0.1316 (2)	0.4576 (2)	0.2749 (2)	0.0467 (7)
C8	0.1485 (2)	0.5542 (2)	0.3300 (3)	0.0556 (8)
H8	0.1299	0.6175	0.2921	0.067*
C9	0.1928 (2)	0.5555 (2)	0.4404 (3)	0.0579 (8)
H9	0.2033	0.6193	0.4778	0.070*
C10	0.2218 (2)	0.4597 (2)	0.4957 (3)	0.0520 (7)
H10	0.2502	0.4608	0.5705	0.062*
C11	0.0606 (2)	0.3525 (3)	0.1134 (2)	0.0541 (8)
H11	0.0264	0.3482	0.0393	0.065*
C12	0.0805 (2)	0.4475 (3)	0.1602 (3)	0.0565 (8)
H12	0.0612	0.5082	0.1181	0.068*
C13	0.4563 (3)	0.3646 (3)	0.5725 (3)	0.0622 (9)
H13	0.4166	0.4248	0.5512	0.075*
C14	0.5611 (3)	0.3770 (3)	0.6107 (3)	0.0698 (10)
H14	0.5892	0.4441	0.6159	0.084*
C15	0.6202 (2)	0.2903 (3)	0.6397 (2)	0.0591 (9)
H15	0.6892	0.2973	0.6640	0.071*
C16	0.5766 (2)	0.1892 (2)	0.6329 (2)	0.0443 (6)
C17	0.47148 (19)	0.1847 (2)	0.59576 (18)	0.0371 (6)
C18	0.42361 (18)	0.0853 (2)	0.59197 (17)	0.0347 (5)
C19	0.4805 (2)	−0.0082 (2)	0.61974 (17)	0.0385 (6)
C20	0.4285 (2)	−0.1029 (2)	0.61735 (19)	0.0453 (7)
H20	0.4627	−0.1669	0.6339	0.054*
C21	0.3275 (2)	−0.1008 (2)	0.5907 (2)	0.0461 (7)
H21	0.2929	−0.1630	0.5908	0.055*
C22	0.2767 (2)	−0.0047 (2)	0.56342 (19)	0.0427 (6)
H22	0.2080	−0.0042	0.5456	0.051*
C23	0.6328 (2)	0.0931 (3)	0.6610 (2)	0.0471 (7)
H23	0.7021	0.0959	0.6852	0.056*
C24	0.5875 (2)	−0.0008 (3)	0.65325 (19)	0.0446 (6)
H24	0.6257	−0.0623	0.6697	0.054*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.03923 (19)	0.0354 (2)	0.04006 (18)	0.00276 (14)	0.01377 (14)	0.00480 (13)
Cu2	0.0612 (4)	0.0380 (3)	0.0557 (3)	0.000	−0.0047 (3)	0.000
Cu3	0.0530 (3)	0.0517 (3)	0.0860 (4)	0.000	0.0332 (3)	0.000
Cl1	0.0504 (4)	0.0679 (5)	0.0473 (4)	0.0075 (4)	0.0238 (3)	0.0088 (3)
Cl2	0.0545 (4)	0.0504 (4)	0.0479 (4)	0.0036 (3)	0.0033 (3)	0.0040 (3)
Cl3	0.0680 (7)	0.1121 (10)	0.1903 (15)	0.0163 (7)	0.0723 (8)	0.0418 (10)
N1	0.0353 (11)	0.0375 (12)	0.0376 (10)	0.0036 (9)	0.0127 (9)	0.0048 (9)
N2	0.0433 (12)	0.0354 (12)	0.0472 (12)	0.0039 (10)	0.0200 (10)	0.0032 (10)
N3	0.0404 (13)	0.0391 (13)	0.0486 (12)	−0.0029 (10)	0.0120 (10)	0.0043 (10)
N4	0.0351 (11)	0.0376 (12)	0.0329 (10)	−0.0013 (9)	0.0087 (9)	0.0035 (9)
C1	0.0465 (16)	0.0434 (16)	0.0422 (14)	0.0011 (13)	0.0163 (12)	0.0024 (12)
C2	0.0536 (17)	0.0555 (19)	0.0462 (15)	−0.0063 (15)	0.0184 (14)	−0.0069 (13)
C3	0.0471 (16)	0.068 (2)	0.0370 (13)	−0.0026 (15)	0.0149 (12)	−0.0009 (13)
C4	0.0354 (14)	0.0578 (18)	0.0420 (14)	0.0054 (13)	0.0162 (12)	0.0091 (13)
C5	0.0306 (12)	0.0432 (15)	0.0403 (13)	0.0057 (11)	0.0166 (11)	0.0064 (11)
C6	0.0344 (13)	0.0403 (14)	0.0447 (13)	0.0060 (11)	0.0194 (11)	0.0089 (11)
C7	0.0417 (15)	0.0437 (16)	0.0613 (17)	0.0113 (13)	0.0268 (14)	0.0176 (13)
C8	0.0549 (18)	0.0418 (17)	0.078 (2)	0.0114 (14)	0.0341 (17)	0.0193 (15)
C9	0.063 (2)	0.0353 (16)	0.084 (2)	0.0043 (15)	0.0366 (19)	−0.0007 (15)
C10	0.0582 (18)	0.0461 (18)	0.0565 (17)	0.0030 (15)	0.0267 (15)	−0.0012 (13)
C11	0.0487 (17)	0.069 (2)	0.0432 (14)	0.0111 (16)	0.0155 (14)	0.0185 (15)
C12	0.0502 (17)	0.064 (2)	0.0592 (18)	0.0180 (16)	0.0250 (15)	0.0295 (16)
C13	0.057 (2)	0.0409 (17)	0.083 (2)	−0.0071 (16)	0.0191 (18)	0.0081 (16)
C14	0.056 (2)	0.054 (2)	0.090 (2)	−0.0178 (17)	0.0156 (19)	0.0077 (18)
C15	0.0412 (16)	0.070 (2)	0.0599 (19)	−0.0139 (16)	0.0113 (15)	0.0049 (16)
C16	0.0377 (14)	0.0586 (18)	0.0348 (12)	−0.0024 (13)	0.0110 (11)	0.0009 (12)
C17	0.0367 (13)	0.0430 (15)	0.0293 (11)	−0.0012 (12)	0.0093 (10)	0.0017 (10)
C18	0.0382 (13)	0.0391 (14)	0.0245 (10)	−0.0013 (11)	0.0089 (10)	0.0005 (9)
C19	0.0453 (15)	0.0441 (15)	0.0228 (10)	0.0055 (12)	0.0086 (10)	0.0010 (10)
C20	0.0579 (18)	0.0369 (15)	0.0307 (11)	0.0060 (13)	0.0039 (12)	0.0008 (10)
C21	0.0537 (17)	0.0396 (15)	0.0365 (13)	−0.0068 (13)	0.0065 (12)	0.0031 (11)
C22	0.0405 (14)	0.0451 (16)	0.0370 (13)	−0.0052 (12)	0.0078 (12)	0.0034 (11)
C23	0.0366 (14)	0.065 (2)	0.0369 (13)	0.0056 (14)	0.0106 (12)	0.0013 (13)
C24	0.0419 (15)	0.0561 (18)	0.0314 (12)	0.0117 (14)	0.0083 (11)	0.0026 (11)

Geometric parameters (Å, º)

Cu1—N1	2.136 (2)	C8—C9	1.373 (5)
Cu1—N2	1.989 (2)	C8—H8	0.9300
Cu1—N3	2.133 (2)	C9—C10	1.398 (4)
Cu1—N4	2.000 (2)	C9—H9	0.9300
Cu1—Cl1	2.2909 (8)	C10—H10	0.9300
Cu2—Cl2	2.0894 (7)	C11—C12	1.333 (5)
Cu2—Cl2^i	2.0894 (7)	C11—H11	0.9300
Cu3—Cl3	2.0692 (10)	C12—H12	0.9300
Cu3—Cl3^ii	2.0692 (10)	C13—C14	1.415 (5)
N1—C1	1.325 (3)	C13—H13	0.9300
N1—C5	1.353 (3)	C14—C15	1.353 (5)
N2—C10	1.324 (4)	C14—H14	0.9300
N2—C6	1.359 (3)	C15—C16	1.410 (4)
N3—C13	1.318 (4)	C15—H15	0.9300
N3—C17	1.361 (3)	C16—C17	1.412 (4)
N4—C22	1.331 (3)	C16—C23	1.430 (4)
N4—C18	1.359 (3)	C17—C18	1.424 (4)
C1—C2	1.399 (4)	C18—C19	1.407 (4)
C1—H1	0.9300	C19—C20	1.405 (4)
C2—C3	1.358 (4)	C19—C24	1.442 (4)
C2—H2	0.9300	C20—C21	1.365 (4)
C3—C4	1.402 (4)	C20—H20	0.9300
C3—H3	0.9300	C21—C22	1.395 (4)
C4—C5	1.405 (4)	C21—H21	0.9300
C4—C11	1.431 (4)	C22—H22	0.9300
C5—C6	1.419 (4)	C23—C24	1.338 (4)
C6—C7	1.400 (4)	C23—H23	0.9300
C7—C8	1.398 (4)	C24—H24	0.9300
C7—C12	1.440 (4)
N1—Cu1—N2	80.12 (9)	C8—C9—C10	119.2 (3)
N1—Cu1—N3	121.05 (9)	C8—C9—H9	120.4
N1—Cu1—N4	95.32 (8)	C10—C9—H9	120.4
N2—Cu1—N3	93.79 (9)	N2—C10—C9	122.3 (3)
N2—Cu1—N4	169.29 (9)	N2—C10—H10	118.9
N3—Cu1—N4	80.19 (9)	C9—C10—H10	118.9
N1—Cu1—Cl1	113.90 (6)	C12—C11—C4	121.4 (3)
N2—Cu1—Cl1	94.59 (7)	C12—C11—H11	119.3
N3—Cu1—Cl1	125.05 (7)	C4—C11—H11	119.3
N4—Cu1—Cl1	96.12 (6)	C11—C12—C7	121.1 (3)
Cl2—Cu2—Cl2^i	177.44 (5)	C11—C12—H12	119.5
Cl3—Cu3—Cl3^ii	176.38 (9)	C7—C12—H12	119.5
C1—N1—C5	117.8 (2)	N3—C13—C14	123.2 (3)
C1—N1—Cu1	131.81 (17)	N3—C13—H13	118.4
C5—N1—Cu1	110.38 (17)	C14—C13—H13	118.4
C10—N2—C6	118.7 (2)	C15—C14—C13	119.4 (3)
C10—N2—Cu1	126.5 (2)	C15—C14—H14	120.3
C6—N2—Cu1	114.71 (18)	C13—C14—H14	120.3
C13—N3—C17	117.6 (3)	C14—C15—C16	119.7 (3)
C13—N3—Cu1	132.2 (2)	C14—C15—H15	120.2
C17—N3—Cu1	110.26 (17)	C16—C15—H15	120.2
C22—N4—C18	118.1 (2)	C15—C16—C17	117.0 (3)
C22—N4—Cu1	126.98 (18)	C15—C16—C23	123.7 (3)
C18—N4—Cu1	114.85 (17)	C17—C16—C23	119.3 (3)
N1—C1—C2	123.1 (3)	N3—C17—C16	123.2 (3)
N1—C1—H1	118.5	N3—C17—C18	117.3 (2)
C2—C1—H1	118.5	C16—C17—C18	119.4 (2)
C3—C2—C1	119.2 (3)	N4—C18—C19	123.0 (2)
C3—C2—H2	120.4	N4—C18—C17	116.9 (2)
C1—C2—H2	120.4	C19—C18—C17	120.1 (2)
C2—C3—C4	119.7 (3)	C20—C19—C18	116.9 (2)
C2—C3—H3	120.2	C20—C19—C24	124.3 (3)
C4—C3—H3	120.2	C18—C19—C24	118.7 (3)
C3—C4—C5	117.3 (3)	C21—C20—C19	119.9 (3)
C3—C4—C11	124.1 (3)	C21—C20—H20	120.1
C5—C4—C11	118.6 (3)	C19—C20—H20	120.1
N1—C5—C4	123.0 (3)	C20—C21—C22	119.5 (3)
N1—C5—C6	117.0 (2)	C20—C21—H21	120.3
C4—C5—C6	120.0 (2)	C22—C21—H21	120.3
N2—C6—C7	122.6 (3)	N4—C22—C21	122.6 (3)
N2—C6—C5	117.3 (2)	N4—C22—H22	118.7
C7—C6—C5	120.1 (2)	C21—C22—H22	118.7
C8—C7—C6	117.3 (3)	C24—C23—C16	121.1 (3)
C8—C7—C12	124.0 (3)	C24—C23—H23	119.4
C6—C7—C12	118.6 (3)	C16—C23—H23	119.4
C9—C8—C7	119.8 (3)	C23—C24—C19	121.2 (3)
C9—C8—H8	120.1	C23—C24—H24	119.4
C7—C8—H8	120.1	C19—C24—H24	119.4

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