Syntheses and crystal structures of two hetero­metallic iodo­plumbates containing mixed-valence copper(I/II)

Mixed-valence copper(I/II) atoms have been introduced successfully into a Pb/I skeleton to obtain two heterometallic iodo­plumbates, namely poly[bis(tetra-n-butyl­ammonium) [bis­(μ₃-di­methyl­dithio­carbamato)dodeca-μ₃-iodido-hexa-μ₂-iodido-tetra­copper(I)copper(II)hexa­lead(II)]], {(C₁₆H₃₆N)₂[Cu₄^ICu^IIPb₆(C₃H₆NS₂)₂I₁₈]}_n, (I), and poly[[μ₃-iodido-tri-μ₂-iodido-iodido­[bis­(1,10-phenanthro­line)copper(I)]copper(I)copper(II)lead(II)] hemiiodine], {[Cu^ICu^IIPbI₅(C₁₂H₈N₂)₂]·0.5I₂}_n, (II), under solution and solvothermal conditions, respectively. Compound (I) contains two-dimensional anionic layers, which are built upon the linkages of Cu^II(S₂CNMe₂)₂ units and one-dimensional anionic Pb/I/Cu^I chains. Tetra-n-butyl­ammonium cations are located between the anionic layers and connected to them via C—H...I hydrogen-bonding inter­actions. Com­pound (II) exhibits a one-dimensional neutral structure, which is composed of [PbI₅] square pyramids, [Cu^II₄] tetra­hedra and [Cu^IIN₄I] trigonal bipyramids. Face-to-face aromatic π–π stacking inter­actions between adjacent 1,10-phen­anthroline ligands stabilize the structure and assemble compound (II) into a three-dimensional supra­molecular structure. I₂ mol­ecules lie in the voids of the structure.

Computing details

For both structures, data collection: CrystalClear (Rigaku, 2007); cell refinement: CrystalClear (Rigaku, 2007); data reduction: CrystalClear (Rigaku, 2007); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: XP (Sheldrick, 1998); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Poly[tetra-n-butylammonium [bis(µ₂-dimethyldithiocarbamato)dodeca-µ₃-iodido-hexa-µ₂-iodido-tetracopper(I)copper(II)hexalead(II)]] (I)

Crystal data

(C16H36N)2[Cu5Pb6(C3H6NS2)2I18]	Z = 1
Mr = 4570.37	F(000) = 1995
Triclinic, P1	Dx = 3.215 Mg m^−3
a = 13.5451 (18) Å	Mo Kα radiation, λ = 0.71073 Å
b = 13.8890 (19) Å	Cell parameters from 4164 reflections
c = 14.4514 (12) Å	θ = 3.0–27.5°
α = 94.449 (3)°	µ = 17.75 mm^−1
β = 92.316 (3)°	T = 293 K
γ = 119.009 (4)°	Prism, gray
V = 2361.0 (5) Å^3	0.2 × 0.18 × 0.06 mm

Data collection

Rigaku Mercury diffractometer	8225 independent reflections
Radiation source: fine-focus sealed tube	5419 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.042
ω scans	θmax = 25.0°, θmin = 3.0°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2007)	h = −16→16
Tmin = 0.292, Tmax = 1.000	k = −16→15
15026 measured reflections	l = −17→15

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.128	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0454P)^2 + 0.023P] where P = (Fo^2 + 2Fc^2)/3
8225 reflections	(Δ/σ)max < 0.001
340 parameters	Δρmax = 2.25 e Å^−3
1 restraint	Δρmin = −2.97 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Pb1	0.78395 (4)	0.54800 (5)	0.14198 (4)	0.04921 (17)
Pb2	0.44999 (4)	0.55866 (5)	0.13182 (4)	0.04591 (16)
Pb3	0.10823 (4)	0.54407 (5)	0.14509 (4)	0.05083 (17)
I1	0.87323 (8)	0.75541 (9)	0.28315 (7)	0.0701 (3)
I2	0.88582 (9)	0.41767 (11)	0.24340 (8)	0.0737 (4)
I3	1.00233 (7)	0.66921 (8)	0.03035 (6)	0.0508 (2)
I4	0.66799 (7)	0.33047 (8)	−0.02209 (7)	0.0533 (3)
I5	0.66716 (7)	0.66489 (8)	0.01621 (6)	0.0484 (2)
I6	0.56146 (7)	0.45017 (7)	0.25881 (6)	0.0448 (2)
I7	0.55174 (8)	0.75647 (8)	0.29859 (7)	0.0548 (3)
I8	0.22709 (7)	0.41926 (7)	0.23799 (6)	0.0438 (2)
I9	0.22479 (10)	0.71448 (9)	0.31892 (8)	0.0738 (3)
Cu1	0.5000	0.5000	0.5000	0.0432 (6)
Cu2	0.67072 (14)	0.66172 (16)	0.34186 (13)	0.0599 (5)
Cu3	0.34868 (15)	0.61775 (16)	0.34117 (13)	0.0598 (5)
S1	0.6747 (3)	0.6552 (3)	0.5045 (2)	0.0477 (8)
S2	0.6244 (3)	0.4301 (3)	0.5121 (2)	0.0476 (8)
N1	0.2781 (12)	0.0559 (11)	0.2225 (11)	0.080 (4)
N2	0.8389 (9)	0.6019 (11)	0.5184 (7)	0.058 (3)
C1	0.7289 (10)	0.5653 (12)	0.5128 (9)	0.048 (3)
C2	0.9218 (11)	0.7195 (14)	0.5339 (12)	0.088 (6)
H2A	0.8834	0.7622	0.5339	0.132*
H2B	0.9720	0.7386	0.4852	0.132*
H2C	0.9648	0.7352	0.5930	0.132*
C3	0.8793 (13)	0.5204 (15)	0.5157 (12)	0.087 (6)
H3A	0.8156	0.4468	0.5054	0.131*
H3B	0.9212	0.5293	0.5739	0.131*
H3C	0.9275	0.5320	0.4660	0.131*
C4	0.4025 (16)	0.1434 (13)	0.2611 (14)	0.095 (6)
H4A	0.4419	0.1849	0.2109	0.115*
H4B	0.3999	0.1952	0.3087	0.115*
C5	0.4693 (16)	0.094 (2)	0.302 (2)	0.145 (10)
H5A	0.4275	0.0494	0.3499	0.174*
H5B	0.4734	0.0438	0.2534	0.174*
C6	0.582 (2)	0.170 (2)	0.342 (2)	0.168 (11)
H6A	0.6255	0.2084	0.2916	0.201*
H6B	0.5783	0.2244	0.3848	0.201*
C7	0.646 (2)	0.129 (3)	0.389 (2)	0.222 (16)
H7A	0.7182	0.1905	0.4138	0.333*
H7B	0.6577	0.0800	0.3465	0.333*
H7C	0.6056	0.0905	0.4392	0.333*
C8	0.2199 (13)	−0.0153 (13)	0.2973 (12)	0.078 (5)
H8A	0.2609	−0.0535	0.3135	0.093*
H8B	0.1446	−0.0712	0.2714	0.093*
C9	0.2082 (17)	0.0426 (16)	0.3871 (15)	0.103 (7)
H9A	0.2810	0.1054	0.4104	0.124*
H9B	0.1552	0.0693	0.3751	0.124*
C10	0.1657 (17)	−0.0396 (17)	0.4582 (14)	0.103 (6)
H10A	0.0936	−0.1026	0.4335	0.124*
H10B	0.2189	−0.0664	0.4688	0.124*
C11	0.1509 (16)	0.0091 (17)	0.5492 (14)	0.113 (7)
H11A	0.1251	−0.0458	0.5921	0.170*
H11B	0.0961	0.0332	0.5396	0.170*
H11C	0.2221	0.0712	0.5742	0.170*
C12	0.2168 (18)	0.1191 (17)	0.1949 (15)	0.105 (7)
H12A	0.2140	0.1619	0.2500	0.126*
H12B	0.2602	0.1707	0.1516	0.126*
C13	0.096 (2)	0.044 (2)	0.1499 (18)	0.145 (10)
H13A	0.0999	0.0124	0.0888	0.174*
H13B	0.0575	−0.0168	0.1873	0.174*
C14	0.033 (3)	0.095 (2)	0.141 (3)	0.29 (3)
H14A	0.0851	0.1735	0.1576	0.352*
H14B	0.0116	0.0865	0.0744	0.352*
C15	−0.059 (3)	0.073 (4)	0.183 (3)	0.30 (3)
H15A	−0.0924	0.1140	0.1592	0.457*
H15B	−0.0392	0.0929	0.2484	0.457*
H15C	−0.1117	−0.0051	0.1706	0.457*
C16	0.2782 (13)	−0.0207 (12)	0.1408 (11)	0.069 (4)
H16A	0.2003	−0.0757	0.1204	0.083*
H16B	0.3164	−0.0595	0.1625	0.083*
C17	0.3364 (16)	0.0386 (14)	0.0553 (13)	0.089 (6)
H17A	0.3036	0.0830	0.0356	0.107*
H17B	0.4167	0.0874	0.0722	0.107*
C18	0.3194 (16)	−0.0474 (16)	−0.0229 (14)	0.098 (6)
H18A	0.2391	−0.0987	−0.0369	0.118*
H18B	0.3559	−0.0889	−0.0040	0.118*
C19	0.3686 (19)	0.007 (2)	−0.1086 (16)	0.151 (10)
H19A	0.3570	−0.0491	−0.1580	0.227*
H19B	0.4483	0.0567	−0.0950	0.227*
H19C	0.3318	0.0471	−0.1276	0.227*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pb1	0.0415 (3)	0.0600 (4)	0.0470 (3)	0.0260 (3)	0.0008 (2)	0.0051 (3)
Pb2	0.0434 (3)	0.0564 (4)	0.0420 (3)	0.0271 (3)	0.0016 (2)	0.0103 (3)
Pb3	0.0490 (3)	0.0646 (4)	0.0473 (3)	0.0346 (3)	−0.0018 (2)	0.0089 (3)
I1	0.0468 (6)	0.0669 (7)	0.0644 (7)	0.0049 (5)	0.0069 (5)	−0.0087 (6)
I2	0.0636 (7)	0.1042 (10)	0.0692 (7)	0.0485 (7)	0.0139 (6)	0.0400 (7)
I3	0.0459 (5)	0.0560 (6)	0.0539 (6)	0.0260 (5)	0.0059 (4)	0.0161 (5)
I4	0.0528 (6)	0.0503 (6)	0.0596 (6)	0.0271 (5)	−0.0032 (5)	0.0133 (5)
I5	0.0483 (5)	0.0506 (6)	0.0467 (5)	0.0231 (5)	0.0084 (4)	0.0138 (5)
I6	0.0442 (5)	0.0412 (5)	0.0461 (5)	0.0180 (4)	−0.0017 (4)	0.0124 (4)
I7	0.0581 (6)	0.0429 (6)	0.0611 (6)	0.0227 (5)	−0.0056 (5)	0.0124 (5)
I8	0.0460 (5)	0.0461 (5)	0.0415 (5)	0.0239 (4)	0.0036 (4)	0.0087 (4)
I9	0.0989 (8)	0.0700 (8)	0.0753 (7)	0.0636 (7)	−0.0233 (6)	−0.0081 (6)
Cu1	0.0392 (12)	0.0437 (14)	0.0476 (14)	0.0208 (11)	−0.0049 (10)	0.0106 (11)
Cu2	0.0575 (11)	0.0651 (13)	0.0581 (12)	0.0297 (10)	0.0008 (9)	0.0168 (10)
Cu3	0.0672 (12)	0.0601 (12)	0.0585 (12)	0.0353 (11)	−0.0022 (9)	0.0167 (10)
S1	0.047 (2)	0.045 (2)	0.047 (2)	0.0194 (18)	−0.0015 (16)	0.0104 (17)
S2	0.050 (2)	0.052 (2)	0.047 (2)	0.0304 (19)	−0.0065 (16)	0.0095 (17)
N1	0.099 (11)	0.047 (8)	0.106 (12)	0.041 (9)	0.029 (9)	0.029 (8)
N2	0.054 (8)	0.103 (11)	0.032 (6)	0.048 (8)	0.007 (5)	0.028 (7)
C1	0.035 (7)	0.066 (10)	0.043 (8)	0.025 (7)	−0.005 (6)	0.014 (7)
C2	0.027 (8)	0.104 (15)	0.094 (13)	−0.002 (9)	0.003 (8)	0.036 (12)
C3	0.085 (12)	0.129 (17)	0.091 (14)	0.083 (13)	0.016 (10)	0.029 (12)
C4	0.101 (15)	0.036 (10)	0.112 (16)	0.007 (11)	0.024 (13)	−0.017 (10)
C5	0.053 (13)	0.12 (2)	0.23 (3)	0.021 (14)	−0.020 (15)	−0.01 (2)
C6	0.17 (3)	0.09 (2)	0.22 (3)	0.06 (2)	−0.04 (2)	−0.02 (2)
C7	0.23 (4)	0.20 (4)	0.21 (3)	0.09 (3)	−0.12 (3)	0.00 (3)
C8	0.073 (11)	0.054 (11)	0.102 (14)	0.023 (9)	0.011 (10)	0.036 (11)
C9	0.126 (17)	0.075 (14)	0.123 (18)	0.054 (13)	0.043 (14)	0.042 (14)
C10	0.119 (17)	0.096 (16)	0.097 (16)	0.055 (14)	0.003 (13)	0.003 (13)
C11	0.104 (16)	0.099 (17)	0.109 (17)	0.030 (14)	0.028 (13)	−0.007 (13)
C12	0.144 (19)	0.085 (15)	0.121 (18)	0.075 (15)	0.051 (15)	0.051 (14)
C13	0.15 (2)	0.17 (3)	0.17 (3)	0.11 (2)	0.02 (2)	0.06 (2)
C14	0.20 (4)	0.10 (2)	0.63 (9)	0.09 (3)	0.11 (5)	0.09 (4)
C15	0.29 (5)	0.46 (7)	0.39 (6)	0.32 (5)	0.21 (4)	0.27 (5)
C16	0.068 (11)	0.036 (9)	0.091 (13)	0.014 (8)	0.006 (9)	0.012 (9)
C17	0.117 (15)	0.063 (12)	0.100 (15)	0.049 (12)	0.034 (12)	0.033 (11)
C18	0.102 (15)	0.082 (15)	0.121 (18)	0.054 (13)	0.004 (13)	0.012 (14)
C19	0.15 (2)	0.19 (3)	0.106 (19)	0.08 (2)	0.038 (17)	0.03 (2)

Geometric parameters (Å, º)

Pb1—I1	3.0714 (12)	C3—H3B	0.9600
Pb1—I2	3.1622 (11)	C3—H3C	0.9600
Pb1—I3	3.1880 (10)	C4—C5	1.51 (3)
Pb1—I6	3.2518 (10)	C4—H4A	0.9700
Pb1—I5	3.3404 (10)	C4—H4B	0.9700
Pb1—I4	3.3469 (12)	C5—C6	1.43 (3)
Pb2—I4^i	3.1623 (10)	C5—H5A	0.9700
Pb2—I5	3.1924 (10)	C5—H5B	0.9700
Pb2—I7	3.2075 (12)	C6—C7	1.42 (3)
Pb2—I6	3.2141 (9)	C6—H6A	0.9700
Pb2—I8	3.2224 (10)	C6—H6B	0.9700
Pb2—I5^i	3.2636 (12)	C7—H7A	0.9600
Pb3—I9	3.0883 (13)	C7—H7B	0.9600
Pb3—I2^ii	3.1272 (11)	C7—H7C	0.9600
Pb3—I8	3.2082 (10)	C8—C9	1.53 (2)
Pb3—I3^ii	3.2405 (10)	C8—H8A	0.9700
Pb3—I4^i	3.3431 (11)	C8—H8B	0.9700
Pb3—I3^i	3.4163 (12)	C9—C10	1.51 (2)
I1—Cu2	2.6144 (19)	C9—H9A	0.9700
I2—Pb3^iii	3.1272 (11)	C9—H9B	0.9700
I3—Pb3^iii	3.2405 (10)	C10—C11	1.50 (2)
I3—Pb3^i	3.4163 (12)	C10—H10A	0.9700
I4—Pb2^i	3.1623 (10)	C10—H10B	0.9700
I4—Pb3^i	3.3431 (11)	C11—H11A	0.9600
I5—Pb2^i	3.2636 (12)	C11—H11B	0.9600
I6—Cu2	2.712 (2)	C11—H11C	0.9600
I7—Cu2	2.6121 (19)	C12—C13	1.53 (3)
I7—Cu3	2.615 (2)	C12—H12A	0.9700
I8—Cu3	2.701 (2)	C12—H12B	0.9700
I9—Cu3	2.6333 (19)	C13—C14	1.36 (3)
Cu1—S1^iv	2.295 (3)	C13—H13A	0.9700
Cu1—S1	2.295 (3)	C13—H13B	0.9700
Cu1—S2^iv	2.324 (3)	C14—C15	1.317 (18)
Cu1—S2	2.324 (3)	C14—H14A	0.9700
Cu2—S1	2.359 (4)	C14—H14B	0.9700
Cu3—S2^iv	2.337 (4)	C15—H15A	0.9600
S1—C1	1.736 (13)	C15—H15B	0.9600
S2—C1	1.717 (14)	C15—H15C	0.9600
S2—Cu3^iv	2.337 (4)	C16—C17	1.56 (2)
N1—C8	1.500 (17)	C16—H16A	0.9700
N1—C16	1.527 (19)	C16—H16B	0.9700
N1—C12	1.53 (2)	C17—C18	1.50 (3)
N1—C4	1.57 (2)	C17—H17A	0.9700
N2—C1	1.316 (14)	C17—H17B	0.9700
N2—C2	1.457 (19)	C18—C19	1.51 (2)
N2—C3	1.477 (17)	C18—H18A	0.9700
C2—H2A	0.9600	C18—H18B	0.9700
C2—H2B	0.9600	C19—H19A	0.9600
C2—H2C	0.9600	C19—H19B	0.9600
C3—H3A	0.9600	C19—H19C	0.9600
I1—Pb1—I2	99.77 (4)	N2—C2—H2C	109.5
I1—Pb1—I3	90.32 (3)	H2A—C2—H2C	109.5
I2—Pb1—I3	92.07 (3)	H2B—C2—H2C	109.5
I1—Pb1—I6	84.85 (3)	N2—C3—H3A	109.5
I2—Pb1—I6	92.70 (3)	N2—C3—H3B	109.5
I3—Pb1—I6	173.72 (3)	H3A—C3—H3B	109.5
I1—Pb1—I5	86.19 (3)	N2—C3—H3C	109.5
I2—Pb1—I5	174.01 (4)	H3A—C3—H3C	109.5
I3—Pb1—I5	87.29 (3)	H3B—C3—H3C	109.5
I6—Pb1—I5	88.39 (2)	C5—C4—N1	114.0 (15)
I1—Pb1—I4	173.87 (3)	C5—C4—H4A	108.8
I2—Pb1—I4	86.18 (3)	N1—C4—H4A	108.8
I3—Pb1—I4	90.96 (3)	C5—C4—H4B	108.8
I6—Pb1—I4	93.43 (3)	N1—C4—H4B	108.8
I5—Pb1—I4	87.88 (3)	H4A—C4—H4B	107.7
I4^i—Pb2—I5	92.11 (3)	C6—C5—C4	117 (2)
I4^i—Pb2—I7	92.26 (3)	C6—C5—H5A	108.1
I5—Pb2—I7	95.25 (3)	C4—C5—H5A	108.1
I4^i—Pb2—I6	175.18 (3)	C6—C5—H5B	108.1
I5—Pb2—I6	91.68 (3)	C4—C5—H5B	108.1
I7—Pb2—I6	84.43 (3)	H5A—C5—H5B	107.3
I4^i—Pb2—I8	91.98 (3)	C7—C6—C5	120 (3)
I5—Pb2—I8	172.19 (3)	C7—C6—H6A	107.4
I7—Pb2—I8	91.23 (3)	C5—C6—H6A	107.4
I6—Pb2—I8	84.62 (2)	C7—C6—H6B	107.4
I4^i—Pb2—I5^i	92.45 (3)	C5—C6—H6B	107.4
I5—Pb2—I5^i	90.66 (3)	H6A—C6—H6B	106.9
I7—Pb2—I5^i	172.30 (3)	C6—C7—H7A	109.5
I6—Pb2—I5^i	90.49 (3)	C6—C7—H7B	109.5
I8—Pb2—I5^i	82.52 (3)	H7A—C7—H7B	109.5
I9—Pb3—I2^ii	91.45 (4)	C6—C7—H7C	109.5
I9—Pb3—I8	83.43 (3)	H7A—C7—H7C	109.5
I2^ii—Pb3—I8	93.52 (3)	H7B—C7—H7C	109.5
I9—Pb3—I3^ii	100.27 (3)	N1—C8—C9	117.1 (14)
I2^ii—Pb3—I3^ii	91.72 (3)	N1—C8—H8A	108.0
I8—Pb3—I3^ii	173.51 (3)	C9—C8—H8A	108.0
I9—Pb3—I4^i	93.20 (3)	N1—C8—H8B	108.0
I2^ii—Pb3—I4^i	174.95 (3)	C9—C8—H8B	108.0
I8—Pb3—I4^i	88.98 (2)	H8A—C8—H8B	107.3
I3^ii—Pb3—I4^i	85.50 (3)	C10—C9—C8	108.5 (15)
I9—Pb3—I3^i	170.34 (3)	C10—C9—H9A	110.0
I2^ii—Pb3—I3^i	88.57 (3)	C8—C9—H9A	110.0
I8—Pb3—I3^i	86.92 (3)	C10—C9—H9B	110.0
I3^ii—Pb3—I3^i	89.39 (3)	C8—C9—H9B	110.0
I4^i—Pb3—I3^i	87.18 (3)	H9A—C9—H9B	108.4
Cu2—I1—Pb1	86.15 (5)	C11—C10—C9	112.7 (18)
Pb3^iii—I2—Pb1	89.24 (3)	C11—C10—H10A	109.0
Pb1—I3—Pb3^iii	86.81 (3)	C9—C10—H10A	109.0
Pb1—I3—Pb3^i	91.64 (3)	C11—C10—H10B	109.0
Pb3^iii—I3—Pb3^i	90.61 (3)	C9—C10—H10B	109.0
Pb2^i—I4—Pb3^i	88.64 (3)	H10A—C10—H10B	107.8
Pb2^i—I4—Pb1	90.58 (3)	C10—C11—H11A	109.5
Pb3^i—I4—Pb1	90.20 (3)	C10—C11—H11B	109.5
Pb2—I5—Pb2^i	89.34 (3)	H11A—C11—H11B	109.5
Pb2—I5—Pb1	89.34 (3)	C10—C11—H11C	109.5
Pb2^i—I5—Pb1	88.96 (3)	H11A—C11—H11C	109.5
Cu2—I6—Pb2	79.95 (4)	H11B—C11—H11C	109.5
Cu2—I6—Pb1	81.07 (4)	C13—C12—N1	113.6 (17)
Pb2—I6—Pb1	90.55 (2)	C13—C12—H12A	108.8
Cu2—I7—Cu3	103.34 (6)	N1—C12—H12A	108.8
Cu2—I7—Pb2	81.53 (5)	C13—C12—H12B	108.8
Cu3—I7—Pb2	74.89 (5)	N1—C12—H12B	108.8
Cu3—I8—Pb3	82.27 (4)	H12A—C12—H12B	107.7
Cu3—I8—Pb2	73.56 (4)	C14—C13—C12	115 (3)
Pb3—I8—Pb2	90.00 (3)	C14—C13—H13A	108.6
Cu3—I9—Pb3	85.71 (5)	C12—C13—H13A	108.6
S1^iv—Cu1—S1	180.0 (2)	C14—C13—H13B	108.6
S1^iv—Cu1—S2^iv	76.84 (12)	C12—C13—H13B	108.6
S1—Cu1—S2^iv	103.16 (12)	H13A—C13—H13B	107.6
S1^iv—Cu1—S2	103.16 (12)	C15—C14—C13	125 (3)
S1—Cu1—S2	76.84 (12)	C15—C14—H14A	106.0
S2^iv—Cu1—S2	180.000 (1)	C13—C14—H14A	106.0
S1—Cu2—I7	107.69 (11)	C15—C14—H14B	106.0
S1—Cu2—I1	112.69 (11)	C13—C14—H14B	106.0
I7—Cu2—I1	113.72 (7)	H14A—C14—H14B	106.3
S1—Cu2—I6	107.76 (11)	C14—C15—H15A	109.5
I7—Cu2—I6	108.25 (7)	C14—C15—H15B	109.5
I1—Cu2—I6	106.49 (7)	H15A—C15—H15B	109.5
S2^iv—Cu3—I7	105.29 (11)	C14—C15—H15C	109.5
S2^iv—Cu3—I9	119.76 (11)	H15A—C15—H15C	109.5
I7—Cu3—I9	106.42 (7)	H15B—C15—H15C	109.5
S2^iv—Cu3—I8	103.13 (11)	N1—C16—C17	114.8 (12)
I7—Cu3—I8	119.63 (7)	N1—C16—H16A	108.6
I9—Cu3—I8	103.55 (7)	C17—C16—H16A	108.6
C1—S1—Cu1	85.6 (4)	N1—C16—H16B	108.6
C1—S1—Cu2	99.2 (4)	C17—C16—H16B	108.6
Cu1—S1—Cu2	95.14 (14)	H16A—C16—H16B	107.5
C1—S2—Cu1	85.1 (4)	C18—C17—C16	108.9 (14)
C1—S2—Cu3^iv	104.7 (4)	C18—C17—H17A	109.9
Cu1—S2—Cu3^iv	115.84 (15)	C16—C17—H17A	109.9
C8—N1—C16	107.0 (12)	C18—C17—H17B	109.9
C8—N1—C12	110.0 (12)	C16—C17—H17B	109.9
C16—N1—C12	112.2 (15)	H17A—C17—H17B	108.3
C8—N1—C4	109.1 (14)	C17—C18—C19	110.4 (17)
C16—N1—C4	110.6 (12)	C17—C18—H18A	109.6
C12—N1—C4	107.9 (14)	C19—C18—H18A	109.6
C1—N2—C2	122.5 (13)	C17—C18—H18B	109.6
C1—N2—C3	118.5 (13)	C19—C18—H18B	109.6
C2—N2—C3	118.8 (12)	H18A—C18—H18B	108.1
N2—C1—S2	126.4 (11)	C18—C19—H19A	109.5
N2—C1—S1	121.1 (11)	C18—C19—H19B	109.5
S2—C1—S1	112.4 (6)	H19A—C19—H19B	109.5
N2—C2—H2A	109.5	C18—C19—H19C	109.5
N2—C2—H2B	109.5	H19A—C19—H19C	109.5
H2A—C2—H2B	109.5	H19B—C19—H19C	109.5

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···I9^v	0.97	3.02	3.82 (2)	140

Symmetry code: (v) x, y−1, z.

Poly[[µ₃-iodido-tri-µ₂-iodido-iodido[bis(1,10-phenanthroline)copper(I)]copper(I)copper(II)lead(II)] hemiiodine] (II)

Crystal data

[Cu2PbI5(C12H8N2)2]·0.5I2	F(000) = 2584
Mr = 1456.08	Dx = 2.982 Mg m^−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
a = 17.5853 (9) Å	Cell parameters from 3122 reflections
b = 18.1041 (8) Å	θ = 3.3–28.2°
c = 13.0705 (6) Å	µ = 12.21 mm^−1
β = 128.789 (5)°	T = 293 K
V = 3243.5 (3) Å^3	Prism, gray
Z = 4	0.3 × 0.1 × 0.1 mm

Data collection

Rigaku Mercury diffractometer	3837 independent reflections
Radiation source: fine-focus sealed tube	2846 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
ω scans	θmax = 29.3°, θmin = 3.0°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2007)	h = −23→19
Tmin = 0.403, Tmax = 1.000	k = −24→22
7250 measured reflections	l = −15→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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.086	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0331P)^2 + 0.5P] where P = (Fo^2 + 2Fc^2)/3
3837 reflections	(Δ/σ)max = 0.001
187 parameters	Δρmax = 1.77 e Å^−3
1 restraint	Δρmin = −1.80 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	Occ. (<1)
Pb1	0.33381 (3)	1.0000	0.24178 (4)	0.04529 (14)
I1	0.5000	0.88817 (3)	0.5000	0.03561 (17)
I2	0.44875 (5)	1.0000	0.14749 (8)	0.0531 (2)
I3	0.19990 (4)	1.12533 (3)	0.05619 (6)	0.05326 (17)
I4	−0.08048 (6)	1.0000	−0.20893 (8)	0.0513 (2)
I5	0.01894 (7)	1.0000	0.41125 (11)	0.0718 (3)
Cu1	0.5000	0.73835 (6)	0.5000	0.0327 (3)
Cu2	0.0946 (5)	1.0000	0.0131 (6)	0.0640 (14)	0.572 (4)
Cu2'	0.0734 (8)	1.0360 (5)	0.0133 (9)	0.075 (2)	0.2141 (19)
N1	0.6309 (4)	0.6825 (3)	0.6218 (6)	0.0343 (14)
N2	0.5332 (4)	0.7359 (3)	0.3799 (6)	0.0296 (13)
C1	0.6774 (6)	0.6545 (4)	0.7410 (8)	0.047 (2)
H1A	0.6515	0.6626	0.7840	0.056*
C2	0.7613 (6)	0.6145 (5)	0.8040 (10)	0.062 (3)
H2A	0.7899	0.5949	0.8866	0.074*
C3	0.8035 (6)	0.6031 (4)	0.7460 (9)	0.053 (2)
H3A	0.8622	0.5776	0.7899	0.063*
C4	0.7564 (5)	0.6305 (4)	0.6189 (9)	0.0430 (19)
C5	0.6692 (5)	0.6706 (3)	0.5606 (7)	0.0329 (16)
C6	0.7914 (6)	0.6217 (4)	0.5450 (10)	0.052 (2)
H6A	0.8490	0.5958	0.5823	0.063*
C7	0.7432 (6)	0.6500 (4)	0.4241 (9)	0.047 (2)
H7A	0.7689	0.6444	0.3803	0.056*
C8	0.6524 (6)	0.6889 (4)	0.3608 (8)	0.0412 (18)
C9	0.6181 (5)	0.6990 (3)	0.4320 (7)	0.0318 (16)
C10	0.5990 (6)	0.7187 (4)	0.2374 (9)	0.052 (2)
H10A	0.6200	0.7128	0.1878	0.062*
C11	0.5156 (6)	0.7569 (4)	0.1869 (8)	0.0460 (19)
H11A	0.4795	0.7772	0.1032	0.055*
C12	0.4849 (5)	0.7651 (4)	0.2619 (8)	0.0390 (17)
H12A	0.4286	0.7921	0.2278	0.047*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pb1	0.0464 (3)	0.0454 (3)	0.0369 (3)	0.000	0.0225 (2)	0.000
I1	0.0414 (4)	0.0288 (3)	0.0372 (4)	0.000	0.0249 (3)	0.000
I2	0.0334 (4)	0.0648 (5)	0.0521 (5)	0.000	0.0225 (4)	0.000
I3	0.0560 (3)	0.0607 (4)	0.0533 (4)	0.0196 (3)	0.0392 (3)	0.0185 (3)
I4	0.0552 (5)	0.0543 (5)	0.0414 (5)	0.000	0.0288 (4)	0.000
I5	0.0629 (6)	0.0390 (4)	0.0936 (8)	0.000	0.0394 (6)	0.000
Cu1	0.0307 (6)	0.0391 (7)	0.0363 (7)	0.000	0.0249 (6)	0.000
Cu2	0.061 (3)	0.056 (4)	0.056 (2)	0.000	0.027 (2)	0.000
Cu2'	0.075 (6)	0.086 (8)	0.055 (4)	−0.025 (5)	0.037 (4)	−0.008 (5)
N1	0.032 (3)	0.040 (3)	0.037 (4)	0.005 (3)	0.025 (3)	0.005 (3)
N2	0.031 (3)	0.032 (3)	0.034 (3)	−0.002 (3)	0.024 (3)	−0.003 (3)
C1	0.041 (5)	0.050 (5)	0.052 (6)	0.016 (4)	0.030 (4)	0.017 (4)
C2	0.053 (5)	0.070 (6)	0.063 (7)	0.023 (5)	0.036 (5)	0.028 (5)
C3	0.036 (4)	0.047 (5)	0.063 (6)	0.012 (4)	0.025 (5)	0.013 (4)
C4	0.034 (4)	0.035 (4)	0.067 (6)	−0.002 (3)	0.035 (4)	−0.003 (4)
C5	0.025 (4)	0.029 (3)	0.046 (5)	−0.006 (3)	0.023 (4)	−0.003 (3)
C6	0.040 (5)	0.045 (5)	0.075 (7)	−0.005 (4)	0.038 (5)	−0.015 (5)
C7	0.043 (5)	0.048 (5)	0.067 (6)	−0.007 (4)	0.042 (5)	−0.017 (4)
C8	0.045 (5)	0.043 (4)	0.048 (5)	−0.005 (4)	0.035 (4)	−0.012 (4)
C9	0.037 (4)	0.025 (3)	0.041 (4)	−0.006 (3)	0.029 (4)	−0.008 (3)
C10	0.061 (6)	0.055 (5)	0.061 (6)	−0.014 (5)	0.049 (5)	−0.018 (4)
C11	0.055 (5)	0.048 (5)	0.038 (5)	−0.013 (4)	0.030 (4)	−0.006 (4)
C12	0.040 (4)	0.039 (4)	0.044 (5)	0.002 (3)	0.029 (4)	0.000 (4)

Geometric parameters (Å, º)

Pb1—I2	2.9538 (9)	Cu2'—Cu2'^iii	2.38 (2)
Pb1—I3^i	3.0693 (6)	Cu2'—I4^iv	2.565 (10)
Pb1—I3	3.0693 (6)	Cu2'—Cu2'^iv	2.71 (2)
Pb1—Cu2	3.298 (7)	Cu2'—Cu2^iv	2.827 (8)
Pb1—I1^ii	3.4165 (5)	N1—C1	1.325 (9)
Pb1—I1	3.4165 (5)	N1—C5	1.350 (8)
I1—Cu1	2.7124 (13)	N2—C12	1.319 (9)
I1—Pb1^ii	3.4165 (5)	N2—C9	1.366 (8)
I3—Cu2'	2.513 (12)	C1—C2	1.362 (10)
I3—Cu2	2.755 (4)	C1—H1A	0.9300
I4—Cu2'	2.517 (10)	C2—C3	1.368 (11)
I4—Cu2'^i	2.517 (10)	C2—H2A	0.9300
I4—Cu2'^iii	2.565 (10)	C3—C4	1.403 (11)
I4—Cu2'^iv	2.565 (10)	C3—H3A	0.9300
I4—Cu2	2.590 (6)	C4—C5	1.412 (9)
I4—Cu2^iv	2.722 (7)	C4—C6	1.442 (11)
I5—I5^v	2.786 (2)	C5—C9	1.415 (10)
Cu1—N2	1.988 (5)	C6—C7	1.342 (11)
Cu1—N2^vi	1.988 (5)	C6—H6A	0.9300
Cu1—N1^vi	2.064 (6)	C7—C8	1.441 (10)
Cu1—N1	2.064 (6)	C7—H7A	0.9300
Cu2—Cu2'	0.752 (9)	C8—C10	1.370 (11)
Cu2—Cu2'^i	0.752 (9)	C8—C9	1.402 (9)
Cu2—I4^iv	2.722 (7)	C10—C11	1.361 (11)
Cu2—Cu2'^iii	2.827 (8)	C10—H10A	0.9300
Cu2—Cu2'^iv	2.827 (8)	C11—C12	1.393 (10)
Cu2—I3^i	2.755 (4)	C11—H11A	0.9300
Cu2'—Cu2'^i	1.305 (18)	C12—H12A	0.9300
I2—Pb1—I3^i	93.270 (18)	I4—Cu2—Pb1	164.1 (3)
I2—Pb1—I3	93.270 (18)	I4^iv—Cu2—Pb1	87.93 (17)
I3^i—Pb1—I3	95.33 (3)	Cu2'^iii—Cu2—Pb1	138.83 (16)
I2—Pb1—Cu2	116.08 (13)	Cu2'^iv—Cu2—Pb1	138.83 (16)
I3^i—Pb1—Cu2	51.11 (4)	I3—Cu2—Pb1	60.15 (12)
I3—Pb1—Cu2	51.11 (4)	I3^i—Cu2—Pb1	60.15 (12)
I2—Pb1—I1^ii	91.531 (17)	Cu2—Cu2'—Cu2'^i	29.9 (13)
I3^i—Pb1—I1^ii	167.623 (18)	Cu2—Cu2'—Cu2'^iii	119.6 (13)
I3—Pb1—I1^ii	95.777 (16)	Cu2'^i—Cu2'—Cu2'^iii	90.000 (5)
Cu2—Pb1—I1^ii	135.34 (7)	Cu2—Cu2'—I4	87.0 (11)
I2—Pb1—I1	91.531 (17)	Cu2'^i—Cu2'—I4	75.0 (2)
I3^i—Pb1—I1	95.777 (16)	Cu2'^iii—Cu2'—I4	63.1 (4)
I3—Pb1—I1	167.623 (18)	Cu2—Cu2'—I3	100.8 (14)
Cu2—Pb1—I1	135.34 (7)	Cu2'^i—Cu2'—I3	130.0 (2)
I1^ii—Pb1—I1	72.680 (19)	Cu2'^iii—Cu2'—I3	139.5 (2)
Cu1—I1—Pb1^ii	126.340 (10)	I4—Cu2'—I3	125.8 (4)
Cu1—I1—Pb1	126.340 (10)	Cu2—Cu2'—I4^iv	93.9 (12)
Pb1^ii—I1—Pb1	107.320 (19)	Cu2'^i—Cu2'—I4^iv	75.27 (19)
Cu2'—I3—Cu2	15.6 (3)	Cu2'^iii—Cu2'—I4^iv	61.1 (4)
Cu2'—I3—Pb1	80.5 (2)	I4—Cu2'—I4^iv	115.5 (5)
Cu2—I3—Pb1	68.74 (12)	I3—Cu2'—I4^iv	117.3 (3)
Cu2'—I4—Cu2'^i	30.0 (4)	Cu2—Cu2'—Cu2'^iv	91.0 (14)
Cu2'—I4—Cu2'^iii	55.8 (5)	Cu2'^i—Cu2'—Cu2'^iv	61.3 (4)
Cu2'^i—I4—Cu2'^iii	64.5 (5)	Cu2'^iii—Cu2'—Cu2'^iv	28.7 (4)
Cu2'—I4—Cu2'^iv	64.5 (5)	I4—Cu2'—Cu2'^iv	58.6 (3)
Cu2'^i—I4—Cu2'^iv	55.8 (5)	I3—Cu2'—Cu2'^iv	167.5 (6)
Cu2'^iii—I4—Cu2'^iv	29.5 (4)	I4^iv—Cu2'—Cu2'^iv	56.9 (4)
Cu2'—I4—Cu2	16.9 (2)	Cu2—Cu2'—Cu2^iv	106.4 (14)
Cu2'^i—I4—Cu2	16.9 (2)	Cu2'^i—Cu2'—Cu2^iv	76.66 (19)
Cu2'^iii—I4—Cu2	66.5 (2)	Cu2'^iii—Cu2'—Cu2^iv	13.37 (18)
Cu2'^iv—I4—Cu2	66.5 (2)	I4—Cu2'—Cu2^iv	60.9 (3)
Cu2'—I4—Cu2^iv	65.2 (2)	I3—Cu2'—Cu2^iv	152.5 (4)
Cu2'^i—I4—Cu2^iv	65.2 (2)	I4^iv—Cu2'—Cu2^iv	57.2 (2)
Cu2'^iii—I4—Cu2^iv	16.0 (2)	Cu2'^iv—Cu2'—Cu2^iv	15.4 (2)
Cu2'^iv—I4—Cu2^iv	16.0 (2)	C1—N1—C5	117.7 (6)
Cu2—I4—Cu2^iv	72.0 (3)	C1—N1—Cu1	131.6 (5)
N2—Cu1—N2^vi	177.4 (3)	C5—N1—Cu1	110.6 (5)
N2—Cu1—N1^vi	96.7 (2)	C12—N2—C9	118.8 (6)
N2^vi—Cu1—N1^vi	82.0 (2)	C12—N2—Cu1	128.4 (5)
N2—Cu1—N1	82.0 (2)	C9—N2—Cu1	112.8 (5)
N2^vi—Cu1—N1	96.7 (2)	N1—C1—C2	123.5 (8)
N1^vi—Cu1—N1	121.4 (3)	N1—C1—H1A	118.2
N2—Cu1—I1	91.28 (15)	C2—C1—H1A	118.2
N2^vi—Cu1—I1	91.28 (15)	C1—C2—C3	120.2 (9)
N1^vi—Cu1—I1	119.31 (15)	C1—C2—H2A	119.9
N1—Cu1—I1	119.31 (16)	C3—C2—H2A	119.9
Cu2'—Cu2—Cu2'^i	120 (3)	C2—C3—C4	118.7 (7)
Cu2'—Cu2—I4	76.1 (11)	C2—C3—H3A	120.6
Cu2'^i—Cu2—I4	76.1 (11)	C4—C3—H3A	120.6
Cu2'—Cu2—I4^iv	70.1 (12)	C3—C4—C5	117.2 (7)
Cu2'^i—Cu2—I4^iv	70.1 (12)	C3—C4—C6	124.8 (7)
I4—Cu2—I4^iv	108.0 (3)	C5—C4—C6	118.0 (8)
Cu2'—Cu2—Cu2'^iii	47.0 (13)	N1—C5—C4	122.7 (7)
Cu2'^i—Cu2—Cu2'^iii	73.6 (14)	N1—C5—C9	117.7 (6)
I4—Cu2—Cu2'^iii	56.3 (2)	C4—C5—C9	119.7 (7)
I4^iv—Cu2—Cu2'^iii	53.9 (2)	C7—C6—C4	121.8 (7)
Cu2'—Cu2—Cu2'^iv	73.6 (14)	C7—C6—H6A	119.1
Cu2'^i—Cu2—Cu2'^iv	47.0 (13)	C4—C6—H6A	119.1
I4—Cu2—Cu2'^iv	56.3 (2)	C6—C7—C8	121.2 (7)
I4^iv—Cu2—Cu2'^iv	53.9 (2)	C6—C7—H7A	119.4
Cu2'^iii—Cu2—Cu2'^iv	26.7 (4)	C8—C7—H7A	119.4
Cu2'—Cu2—I3	63.7 (12)	C10—C8—C9	117.9 (7)
Cu2'^i—Cu2—I3	170.0 (12)	C10—C8—C7	124.3 (7)
I4—Cu2—I3	113.83 (15)	C9—C8—C7	117.8 (8)
I4^iv—Cu2—I3	104.68 (16)	N2—C9—C8	121.5 (7)
Cu2'^iii—Cu2—I3	110.62 (16)	N2—C9—C5	116.9 (6)
Cu2'^iv—Cu2—I3	137.1 (3)	C8—C9—C5	121.5 (6)
Cu2'—Cu2—I3^i	170.0 (12)	C11—C10—C8	120.4 (7)
Cu2'^i—Cu2—I3^i	63.7 (12)	C11—C10—H10A	119.8
I4—Cu2—I3^i	113.83 (15)	C8—C10—H10A	119.8
I4^iv—Cu2—I3^i	104.68 (16)	C10—C11—C12	119.3 (8)
Cu2'^iii—Cu2—I3^i	137.1 (3)	C10—C11—H11A	120.4
Cu2'^iv—Cu2—I3^i	110.62 (16)	C12—C11—H11A	120.4
I3—Cu2—I3^i	110.9 (3)	N2—C12—C11	122.0 (7)
Cu2'—Cu2—Pb1	110.5 (12)	N2—C12—H12A	119.0
Cu2'^i—Cu2—Pb1	110.5 (12)	C11—C12—H12A	119.0

Symmetry codes: (i) x, −y+2, z; (ii) −x+1, −y+2, −z+1; (iii) −x, y, −z; (iv) −x, −y+2, −z; (v) −x, −y+2, −z+1; (vi) −x+1, y, −z+1.