catena-Poly[[[3,7-bis­(dimethyl­amino)phenothiazonium] lead(II)-tri-μ-iodo] N,N′-dimethyl­formamide]

In the title compound, {(C₁₆H₁₈N₃OS)[PbI₃]·C₃H₇NO}_n, each Pb^II atom is bonded to six I atoms to form chains of trans face-shared PbI₆ octa­hedra. In the crystal structure, the cations are stacked along the c axis, with significant π–π inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 292 K
• Mean [sigma](C-C) = 0.014 Å
• R factor = 0.037
• wR factor = 0.072
• Data-to-parameter ratio = 22.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.04
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         N3
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for         N4
PLAT342_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...         14

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           28.00
           From the CIF: _reflns_number_total               6078
           Count of symmetry unique reflns         3200
           Completeness (_total/calc)            189.94%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      2878
           Fraction of Friedel pairs measured     0.899
           Are heavy atom types Z>Si present        yes

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

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

---

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

catena-Poly[[[3,7-bis(dimethylamino)phenazathionium] lead(II)-tri-µ-iodo] N,N'-dimethylformamide]

Crystal data

(C16H18N3OS)[PbI3]·C3H7NO	F(000) = 1728
Mr = 945.38	Dx = 2.382 Mg m^−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 4580 reflections
a = 23.458 (7) Å	θ = 2.9–24.8°
b = 13.923 (4) Å	µ = 10.01 mm^−1
c = 8.228 (2) Å	T = 292 K
β = 101.163 (5)°	Block, dark blue
V = 2636.5 (13) Å^3	0.20 × 0.12 × 0.10 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	6078 independent reflections
Radiation source: fine-focus sealed tube	4912 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
φ and ω scans	θmax = 28.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)	h = −30→30
Tmin = 0.203, Tmax = 0.368	k = −18→18
14424 measured reflections	l = −10→10

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)] = 0.037	H-atom parameters constrained
wR(F^2) = 0.072	w = 1/[σ^2(Fo^2) + (0.0084P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.93	(Δ/σ)max = 0.010
6078 reflections	Δρmax = 1.47 e Å^−3
268 parameters	Δρmin = −0.72 e Å^−3
2 restraints	Absolute structure: Flack (1983); 2937 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.013 (6)

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
Pb1	0.00209 (3)	0.50434 (3)	0.38793 (7)	0.05025 (8)
I1	−0.09194 (3)	0.40461 (5)	0.07485 (6)	0.0684 (2)
I2	0.09688 (3)	0.59281 (5)	0.68068 (6)	0.06556 (19)
I3	0.00206 (3)	0.68095 (3)	0.15385 (7)	0.05880 (15)
C1	1.0042 (5)	1.0515 (7)	0.1909 (10)	0.067 (2)
C2	0.9745 (4)	0.9668 (6)	0.2283 (11)	0.063 (2)
H2	0.9892	0.9066	0.2103	0.076*
C3	0.9251 (4)	0.9740 (6)	0.2895 (10)	0.059 (2)
C4	0.8330 (4)	0.9068 (6)	0.4131 (10)	0.055 (2)
C5	0.7984 (4)	0.8388 (6)	0.4634 (10)	0.065 (2)
H5	0.8063	0.7741	0.4515	0.078*
C6	0.7514 (4)	0.8658 (7)	0.5321 (11)	0.067 (2)
C7	0.7368 (5)	0.9636 (8)	0.5405 (13)	0.078 (3)
H7	0.7033	0.9815	0.5776	0.094*
C8	0.7717 (5)	1.0308 (7)	0.4945 (13)	0.071 (3)
H8	0.7630	1.0951	0.5072	0.085*
C9	0.8220 (5)	1.0070 (6)	0.4263 (12)	0.064 (3)
C10	0.9007 (5)	1.0661 (6)	0.3270 (10)	0.061 (2)
C11	0.9324 (5)	1.1477 (7)	0.2880 (12)	0.070 (3)
H11	0.9186	1.2083	0.3085	0.084*
C12	0.9802 (5)	1.1427 (7)	0.2245 (12)	0.076 (3)
H12	0.9984	1.1991	0.2014	0.092*
C13	1.0855 (6)	1.1328 (9)	0.0956 (18)	0.113 (4)
H13A	1.0582	1.1820	0.0507	0.169*
H13B	1.1090	1.1166	0.0162	0.169*
H13C	1.1098	1.1558	0.1953	0.169*
C14	1.0810 (5)	0.9536 (7)	0.1090 (14)	0.079 (3)
H14A	1.1014	0.9300	0.2139	0.119*
H14B	1.1078	0.9619	0.0356	0.119*
H14C	1.0515	0.9084	0.0618	0.119*
C15	0.7271 (6)	0.6957 (10)	0.5618 (19)	0.119 (5)
H15A	0.7136	0.6782	0.4480	0.178*
H15B	0.7064	0.6592	0.6307	0.178*
H15C	0.7679	0.6824	0.5927	0.178*
C16	0.6668 (6)	0.8221 (11)	0.6485 (17)	0.113 (5)
H16A	0.6785	0.8531	0.7540	0.169*
H16B	0.6456	0.7645	0.6621	0.169*
H16C	0.6424	0.8646	0.5736	0.169*
C17	0.7533 (6)	0.5503 (11)	−0.078 (2)	0.116 (5)
H17	0.7766	0.5167	−0.1382	0.140*
C18	0.7420 (10)	0.6766 (18)	0.100 (3)	0.222 (13)
H18A	0.7092	0.6388	0.1147	0.333*
H18B	0.7286	0.7355	0.0446	0.333*
H18C	0.7658	0.6906	0.2055	0.333*
C19	0.8331 (7)	0.6624 (10)	0.011 (3)	0.164 (8)
H19A	0.8504	0.6324	−0.0728	0.246*
H19B	0.8562	0.6491	0.1181	0.246*
H19C	0.8312	0.7306	−0.0070	0.246*
N1	0.8530 (4)	1.0803 (5)	0.3870 (10)	0.068 (2)
N2	1.0536 (4)	1.0469 (6)	0.1331 (11)	0.075 (2)
N3	0.7169 (4)	0.7983 (7)	0.5831 (11)	0.083 (2)
S1	0.89166 (11)	0.86814 (16)	0.3311 (3)	0.0646 (6)
N4	0.7749 (4)	0.6248 (7)	0.0022 (14)	0.094 (3)
O1	0.7037 (5)	0.5203 (7)	−0.0819 (17)	0.141 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pb1	0.06264 (16)	0.04367 (14)	0.04610 (14)	0.00092 (13)	0.01467 (11)	0.00117 (12)
I1	0.0704 (5)	0.0588 (4)	0.0783 (5)	−0.0149 (3)	0.0199 (4)	0.0008 (3)
I2	0.0671 (5)	0.0570 (4)	0.0716 (4)	−0.0044 (3)	0.0109 (3)	−0.0030 (3)
I3	0.0743 (3)	0.0399 (2)	0.0642 (4)	0.0001 (3)	0.0183 (3)	0.0039 (3)
C1	0.085 (7)	0.056 (6)	0.052 (6)	−0.005 (5)	−0.005 (5)	−0.005 (4)
C2	0.081 (7)	0.044 (5)	0.055 (5)	0.003 (4)	−0.010 (5)	−0.002 (4)
C3	0.076 (6)	0.054 (5)	0.038 (4)	0.002 (4)	−0.011 (4)	0.004 (4)
C4	0.060 (5)	0.044 (5)	0.054 (5)	0.015 (4)	−0.004 (4)	−0.003 (4)
C5	0.082 (7)	0.051 (5)	0.057 (5)	0.012 (5)	0.001 (5)	−0.003 (4)
C6	0.073 (7)	0.073 (6)	0.050 (5)	0.011 (5)	0.001 (5)	−0.001 (5)
C7	0.069 (6)	0.080 (7)	0.078 (7)	0.017 (6)	−0.003 (5)	−0.001 (6)
C8	0.078 (7)	0.050 (5)	0.076 (7)	0.019 (5)	−0.006 (6)	−0.010 (5)
C9	0.081 (7)	0.049 (5)	0.052 (5)	0.011 (5)	−0.008 (5)	−0.016 (4)
C10	0.086 (7)	0.038 (5)	0.050 (5)	0.007 (4)	−0.005 (5)	−0.005 (4)
C11	0.092 (8)	0.040 (5)	0.066 (6)	0.000 (5)	−0.013 (6)	−0.009 (4)
C12	0.094 (8)	0.050 (5)	0.079 (7)	−0.017 (5)	0.001 (6)	−0.005 (5)
C13	0.102 (10)	0.088 (9)	0.146 (12)	−0.030 (7)	0.020 (9)	−0.001 (9)
C14	0.082 (7)	0.066 (6)	0.087 (8)	−0.002 (5)	0.009 (6)	−0.006 (6)
C15	0.111 (10)	0.100 (10)	0.152 (13)	0.007 (8)	0.042 (9)	0.018 (9)
C16	0.090 (9)	0.116 (11)	0.135 (11)	0.022 (8)	0.031 (8)	0.027 (9)
C17	0.080 (9)	0.101 (11)	0.164 (14)	−0.028 (8)	0.016 (9)	0.023 (10)
C18	0.22 (2)	0.25 (3)	0.23 (2)	−0.12 (2)	0.12 (2)	−0.09 (2)
C19	0.105 (11)	0.071 (9)	0.32 (2)	−0.018 (8)	0.054 (14)	0.002 (12)
N1	0.079 (6)	0.054 (5)	0.061 (5)	0.006 (4)	−0.010 (4)	−0.012 (4)
N2	0.082 (6)	0.052 (5)	0.085 (6)	−0.012 (4)	−0.002 (5)	0.003 (4)
N3	0.082 (6)	0.085 (6)	0.082 (6)	0.023 (5)	0.017 (5)	−0.002 (5)
S1	0.0824 (16)	0.0406 (11)	0.0693 (15)	0.0073 (11)	0.0110 (12)	−0.0023 (10)
N4	0.073 (6)	0.083 (7)	0.126 (9)	−0.018 (5)	0.016 (6)	0.019 (6)
O1	0.127 (9)	0.115 (8)	0.175 (12)	−0.030 (7)	0.014 (8)	0.014 (7)

Geometric parameters (Å, º)

Pb1—I3	3.1234 (9)	C11—C12	1.328 (14)
Pb1—I1^i	3.1862 (10)	C11—H11	0.93
Pb1—I2	3.1920 (11)	C12—H12	0.93
Pb1—I2^ii	3.3391 (11)	C13—N2	1.475 (13)
Pb1—I1	3.3510 (11)	C13—H13A	0.96
Pb1—I3^i	3.3827 (10)	C13—H13B	0.96
I1—Pb1^ii	3.1861 (10)	C13—H13C	0.96
I2—Pb1^i	3.3391 (11)	C14—N2	1.479 (13)
I3—Pb1^ii	3.3828 (10)	C14—H14A	0.96
C1—N2	1.336 (13)	C14—H14B	0.96
C1—C2	1.434 (13)	C14—H14C	0.96
C1—C12	1.438 (14)	C15—N3	1.465 (15)
C2—C3	1.352 (13)	C15—H15A	0.96
C2—H2	0.93	C15—H15B	0.96
C3—C10	1.462 (12)	C15—H15C	0.96
C3—S1	1.735 (10)	C16—N3	1.425 (14)
C4—C5	1.362 (12)	C16—H16A	0.96
C4—C9	1.428 (11)	C16—H16B	0.96
C4—S1	1.731 (9)	C16—H16C	0.96
C5—C6	1.385 (13)	C17—O1	1.229 (16)
C5—H5	0.93	C17—N4	1.282 (17)
C6—N3	1.357 (13)	C17—H17	0.93
C6—C7	1.409 (14)	C18—N4	1.41 (2)
C7—C8	1.345 (14)	C18—H18A	0.96
C7—H7	0.93	C18—H18B	0.96
C8—C9	1.440 (15)	C18—H18C	0.96
C8—H8	0.93	C19—N4	1.451 (16)
C9—N1	1.329 (13)	C19—H19A	0.96
C10—N1	1.322 (12)	C19—H19B	0.96
C10—C11	1.428 (14)	C19—H19C	0.96
I3—Pb1—I1^i	93.83 (3)	C11—C12—H12	119.5
I3—Pb1—I2	94.50 (3)	C1—C12—H12	119.5
I1^i—Pb1—I2	85.90 (3)	N2—C13—H13A	109.5
I3—Pb1—I2^ii	85.68 (3)	N2—C13—H13B	109.5
I1^i—Pb1—I2^ii	177.98 (3)	H13A—C13—H13B	109.5
I2—Pb1—I2^ii	96.10 (3)	N2—C13—H13C	109.5
I3—Pb1—I1	86.03 (3)	H13A—C13—H13C	109.5
I1^i—Pb1—I1	96.99 (4)	H13B—C13—H13C	109.5
I2—Pb1—I1	177.03 (3)	N2—C14—H14A	109.5
I2^ii—Pb1—I1	81.02 (3)	N2—C14—H14B	109.5
I3—Pb1—I3^i	177.76 (2)	H14A—C14—H14B	109.5
I1^i—Pb1—I3^i	84.51 (3)	N2—C14—H14C	109.5
I2—Pb1—I3^i	83.89 (3)	H14A—C14—H14C	109.5
I2^ii—Pb1—I3^i	96.02 (3)	H14B—C14—H14C	109.5
I1—Pb1—I3^i	95.66 (3)	N3—C15—H15A	109.5
Pb1^ii—I1—Pb1	77.99 (3)	N3—C15—H15B	109.5
Pb1—I2—Pb1^i	78.09 (3)	H15A—C15—H15B	109.5
Pb1—I3—Pb1^ii	78.37 (2)	N3—C15—H15C	109.5
N2—C1—C2	121.9 (9)	H15A—C15—H15C	109.5
N2—C1—C12	120.7 (10)	H15B—C15—H15C	109.5
C2—C1—C12	117.4 (11)	N3—C16—H16A	109.5
C3—C2—C1	120.4 (9)	N3—C16—H16B	109.5
C3—C2—H2	119.8	H16A—C16—H16B	109.5
C1—C2—H2	119.8	N3—C16—H16C	109.5
C2—C3—C10	122.9 (9)	H16A—C16—H16C	109.5
C2—C3—S1	117.6 (7)	H16B—C16—H16C	109.5
C10—C3—S1	119.5 (8)	O1—C17—N4	124.4 (17)
C5—C4—C9	121.9 (9)	O1—C17—H17	117.8
C5—C4—S1	117.9 (6)	N4—C17—H17	117.8
C9—C4—S1	120.2 (8)	N4—C18—H18A	109.5
C4—C5—C6	120.3 (8)	N4—C18—H18B	109.5
C4—C5—H5	119.8	H18A—C18—H18B	109.5
C6—C5—H5	119.8	N4—C18—H18C	109.5
N3—C6—C5	120.5 (9)	H18A—C18—H18C	109.5
N3—C6—C7	119.3 (10)	H18B—C18—H18C	109.5
C5—C6—C7	120.1 (10)	N4—C19—H19A	109.5
C8—C7—C6	119.5 (10)	N4—C19—H19B	109.5
C8—C7—H7	120.3	H19A—C19—H19B	109.5
C6—C7—H7	120.3	N4—C19—H19C	109.5
C7—C8—C9	122.6 (9)	H19A—C19—H19C	109.5
C7—C8—H8	118.7	H19B—C19—H19C	109.5
C9—C8—H8	118.7	C10—N1—C9	121.2 (8)
N1—C9—C4	128.1 (10)	C1—N2—C13	123.0 (10)
N1—C9—C8	116.5 (8)	C1—N2—C14	121.3 (8)
C4—C9—C8	115.3 (9)	C13—N2—C14	115.7 (10)
N1—C10—C11	118.6 (9)	C6—N3—C16	122.8 (10)
N1—C10—C3	127.3 (9)	C6—N3—C15	121.2 (9)
C11—C10—C3	114.1 (10)	C16—N3—C15	115.9 (10)
C12—C11—C10	124.3 (9)	C4—S1—C3	103.7 (5)
C12—C11—H11	117.9	C17—N4—C18	120.1 (14)
C10—C11—H11	117.9	C17—N4—C19	126.3 (14)
C11—C12—C1	121.0 (10)	C18—N4—C19	113.6 (14)
I3—Pb1—I1—Pb1^ii	43.50 (2)	C7—C8—C9—C4	−1.0 (14)
I1^i—Pb1—I1—Pb1^ii	136.89 (3)	C2—C3—C10—N1	−179.9 (9)
I2^ii—Pb1—I1—Pb1^ii	−42.748 (19)	S1—C3—C10—N1	−2.2 (12)
I3^i—Pb1—I1—Pb1^ii	−137.97 (2)	C2—C3—C10—C11	2.0 (12)
I3—Pb1—I2—Pb1^i	138.39 (2)	S1—C3—C10—C11	179.6 (6)
I1^i—Pb1—I2—Pb1^i	44.861 (19)	N1—C10—C11—C12	−178.8 (9)
I2^ii—Pb1—I2—Pb1^i	−135.48 (3)	C3—C10—C11—C12	−0.5 (13)
I3^i—Pb1—I2—Pb1^i	−40.05 (2)	C10—C11—C12—C1	−0.5 (15)
I1^i—Pb1—I3—Pb1^ii	−137.11 (2)	N2—C1—C12—C11	−177.3 (9)
I2—Pb1—I3—Pb1^ii	136.72 (2)	C2—C1—C12—C11	0.2 (13)
I2^ii—Pb1—I3—Pb1^ii	40.92 (3)	C11—C10—N1—C9	−179.6 (8)
I1—Pb1—I3—Pb1^ii	−40.35 (3)	C3—C10—N1—C9	2.4 (14)
N2—C1—C2—C3	178.8 (9)	C4—C9—N1—C10	0.1 (15)
C12—C1—C2—C3	1.3 (12)	C8—C9—N1—C10	178.5 (8)
C1—C2—C3—C10	−2.4 (13)	C2—C1—N2—C13	−179.3 (9)
C1—C2—C3—S1	179.9 (6)	C12—C1—N2—C13	−1.8 (14)
C9—C4—C5—C6	−1.0 (13)	C2—C1—N2—C14	−1.7 (13)
S1—C4—C5—C6	179.1 (7)	C12—C1—N2—C14	175.7 (8)
C4—C5—C6—N3	−179.7 (8)	C5—C6—N3—C16	−177.5 (9)
C4—C5—C6—C7	4.1 (13)	C7—C6—N3—C16	−1.3 (15)
N3—C6—C7—C8	178.1 (9)	C5—C6—N3—C15	−2.2 (15)
C5—C6—C7—C8	−5.6 (14)	C7—C6—N3—C15	174.0 (11)
C6—C7—C8—C9	4.0 (15)	C5—C4—S1—C3	−178.2 (7)
C5—C4—C9—N1	177.8 (9)	C9—C4—S1—C3	1.9 (8)
S1—C4—C9—N1	−2.3 (14)	C2—C3—S1—C4	177.8 (7)
C5—C4—C9—C8	−0.6 (13)	C10—C3—S1—C4	0.0 (7)
S1—C4—C9—C8	179.3 (7)	O1—C17—N4—C18	2 (2)
C7—C8—C9—N1	−179.6 (9)	O1—C17—N4—C19	179.5 (16)

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