In the title complex, (C
6H
8N)
2[Zn(dmit)
2] (dmit is 2-thioxo-1,3-dithiole-4,5-dithiolate, C
3S
5), each Zn atom is coordinated by four dmit S atoms that define a distorted tetrahedral arrangement. The crystal structure is stabilized by C—H
S hydrogen bonding and S
S contacts.
Supporting information
CCDC reference: 289908
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (C-C) = 0.012 Å
- R factor = 0.053
- wR factor = 0.138
- Data-to-parameter ratio = 19.1
checkCIF/PLATON results
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Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for N1
PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for N2
PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 12
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety C7
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
5 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
1 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
1 ALERT type 3 Indicator that the structure quality may be low
3 ALERT type 4 Improvement, methodology, query or suggestion
checkCIF publication errors
Alert level A
PUBL024_ALERT_1_A The number of authors is greater than 5.
Please specify the role of each of the co-authors
for your paper.
| Author Response: The role of authors
Wang, Yan Ling: the first author
Yu, Wen Tao: determinate the structure
Xu, Dong: synthesis
Wang, Xin Qiang: synthesis
Guo, Wen Feng: synthesis
Zhang, Guang Hui: determinate the optical properties
|
1 ALERT level A = Data missing that is essential or data in wrong format
0 ALERT level G = General alerts. Data that may be required is missing
Data collection: XSCANS (Bruker, 1996); cell refinement: XSCANS; data reduction: SHELXTL (Bruker, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: WinGX (Farrugia, 1999).
Bis(
N-methylpyridinium)
bis(2-thioxo-1,3-dithiole-4,5-dithiolato)zincate(II)
top
Crystal data top
(C6H8N)2[Zn(C3S5)2] | F(000) = 1312 |
Mr = 646.30 | Dx = 1.657 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 30 reflections |
a = 14.1687 (19) Å | θ = 5.3–12.3° |
b = 13.6246 (16) Å | µ = 1.77 mm−1 |
c = 14.024 (2) Å | T = 296 K |
β = 106.865 (11)° | Block, red |
V = 2590.8 (6) Å3 | 0.40 × 0.36 × 0.31 mm |
Z = 4 | |
Data collection top
Bruker P4 diffractometer | 3269 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.030 |
Graphite monochromator | θmax = 26.5°, θmin = 2.1° |
ω scans | h = −17→17 |
Absorption correction: ψ scan (XSCANS; Bruker, 1996) | k = −17→1 |
Tmin = 0.552, Tmax = 0.587 | l = −1→17 |
6564 measured reflections | 3 standard reflections every 97 reflections |
5378 independent reflections | intensity decay: none |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.053 | H-atom parameters constrained |
wR(F2) = 0.138 | w = 1/[σ2(Fo2) + (0.0624P)2 + 1.3186P] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max < 0.001 |
5378 reflections | Δρmax = 0.66 e Å−3 |
281 parameters | Δρmin = −0.49 e Å−3 |
54 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0039 (4) |
Special details top
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 (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 1.0686 (3) | 0.7684 (4) | 0.4058 (4) | 0.0615 (15) | |
C2 | 0.8766 (3) | 0.7526 (4) | 0.3750 (4) | 0.0489 (12) | |
C3 | 0.9091 (3) | 0.6587 (4) | 0.3788 (4) | 0.0532 (13) | |
C4 | 0.4747 (4) | 0.5893 (4) | 0.3157 (4) | 0.0547 (13) | |
C5 | 0.4747 (4) | 0.5881 (4) | 0.2193 (4) | 0.0528 (12) | |
C6 | 0.2875 (4) | 0.5701 (4) | 0.2129 (5) | 0.0672 (16) | |
C7 | 0.8538 (8) | 0.9181 (7) | 0.6049 (8) | 0.166 (4) | |
H7A | 0.7852 | 0.9329 | 0.5942 | 0.249* | |
H7B | 0.8736 | 0.9393 | 0.5483 | 0.249* | |
H7C | 0.8924 | 0.9517 | 0.6634 | 0.249* | |
C8 | 0.9591 (5) | 0.7747 (7) | 0.6340 (5) | 0.101 (2) | |
H8A | 1.0141 | 0.8145 | 0.6411 | 0.121* | |
C9 | 0.9686 (7) | 0.6772 (8) | 0.6398 (6) | 0.121 (3) | |
H9A | 1.0307 | 0.6494 | 0.6510 | 0.145* | |
C10 | 0.8891 (7) | 0.6178 (7) | 0.6297 (6) | 0.133 (3) | |
H10A | 0.8958 | 0.5499 | 0.6306 | 0.159* | |
C11 | 0.8001 (7) | 0.6603 (7) | 0.6183 (6) | 0.119 (3) | |
H11A | 0.7453 | 0.6219 | 0.6163 | 0.142* | |
C12 | 0.7916 (6) | 0.7597 (7) | 0.6098 (5) | 0.103 (3) | |
H12A | 0.7299 | 0.7888 | 0.5981 | 0.123* | |
C13 | 0.5429 (7) | 0.3466 (6) | 0.0910 (6) | 0.130 (3) | |
H13A | 0.4724 | 0.3517 | 0.0666 | 0.195* | |
H13B | 0.5641 | 0.2878 | 0.0655 | 0.195* | |
H13C | 0.5725 | 0.4026 | 0.0694 | 0.195* | |
C14 | 0.5058 (5) | 0.3492 (5) | 0.2492 (7) | 0.090 (2) | |
H14A | 0.4391 | 0.3535 | 0.2150 | 0.108* | |
C15 | 0.5364 (6) | 0.3490 (5) | 0.3506 (7) | 0.098 (2) | |
H15A | 0.4906 | 0.3525 | 0.3864 | 0.117* | |
C16 | 0.6348 (6) | 0.3437 (6) | 0.3993 (6) | 0.111 (3) | |
H16A | 0.6567 | 0.3456 | 0.4686 | 0.133* | |
C17 | 0.6988 (6) | 0.3359 (6) | 0.3473 (7) | 0.103 (2) | |
H17A | 0.7656 | 0.3299 | 0.3806 | 0.124* | |
C18 | 0.6699 (5) | 0.3364 (5) | 0.2497 (6) | 0.0839 (19) | |
H18A | 0.7162 | 0.3323 | 0.2146 | 0.101* | |
N1 | 0.8689 (5) | 0.8147 (5) | 0.6179 (4) | 0.0916 (17) | |
N2 | 0.5731 (5) | 0.3430 (3) | 0.1997 (4) | 0.0755 (14) | |
S1 | 1.18119 (11) | 0.80862 (15) | 0.42218 (15) | 0.0903 (6) | |
S2 | 0.96808 (9) | 0.84290 (10) | 0.39239 (10) | 0.0576 (4) | |
S3 | 1.03617 (10) | 0.64565 (12) | 0.40077 (12) | 0.0679 (4) | |
S4 | 0.75521 (9) | 0.79096 (10) | 0.35236 (12) | 0.0639 (4) | |
S5 | 0.83913 (11) | 0.55215 (11) | 0.36545 (12) | 0.0679 (4) | |
S6 | 0.57550 (11) | 0.60265 (12) | 0.42015 (11) | 0.0677 (4) | |
S7 | 0.57637 (10) | 0.60064 (12) | 0.17480 (11) | 0.0619 (4) | |
S8 | 0.35874 (11) | 0.57555 (12) | 0.33468 (13) | 0.0718 (4) | |
S9 | 0.35934 (10) | 0.57362 (11) | 0.13191 (12) | 0.0668 (4) | |
S10 | 0.16741 (11) | 0.55873 (15) | 0.17715 (17) | 0.0998 (7) | |
Zn1 | 0.68832 (4) | 0.63263 (5) | 0.33119 (5) | 0.0574 (2) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.046 (3) | 0.082 (4) | 0.052 (3) | 0.004 (3) | 0.007 (2) | 0.010 (3) |
C2 | 0.044 (3) | 0.051 (3) | 0.050 (3) | −0.002 (2) | 0.010 (2) | 0.001 (2) |
C3 | 0.043 (3) | 0.061 (3) | 0.052 (3) | 0.006 (2) | 0.009 (2) | −0.002 (3) |
C4 | 0.051 (3) | 0.048 (3) | 0.069 (4) | −0.005 (2) | 0.023 (3) | −0.002 (3) |
C5 | 0.047 (3) | 0.046 (3) | 0.063 (3) | −0.003 (2) | 0.012 (2) | 0.002 (3) |
C6 | 0.057 (3) | 0.043 (3) | 0.103 (5) | −0.002 (3) | 0.025 (3) | 0.005 (3) |
C7 | 0.228 (7) | 0.114 (5) | 0.161 (7) | 0.010 (5) | 0.065 (6) | −0.001 (5) |
C8 | 0.097 (4) | 0.139 (6) | 0.074 (4) | −0.029 (4) | 0.036 (4) | −0.007 (4) |
C9 | 0.115 (5) | 0.164 (6) | 0.088 (5) | 0.034 (5) | 0.035 (4) | 0.009 (5) |
C10 | 0.185 (7) | 0.113 (6) | 0.100 (5) | 0.023 (5) | 0.043 (5) | −0.005 (4) |
C11 | 0.133 (6) | 0.123 (6) | 0.089 (5) | −0.030 (5) | 0.014 (4) | −0.003 (5) |
C12 | 0.080 (5) | 0.148 (8) | 0.077 (5) | −0.009 (5) | 0.016 (4) | 0.011 (5) |
C13 | 0.166 (6) | 0.109 (5) | 0.102 (5) | −0.005 (5) | 0.018 (5) | −0.004 (4) |
C14 | 0.070 (4) | 0.051 (4) | 0.152 (8) | −0.001 (3) | 0.036 (5) | 0.003 (4) |
C15 | 0.120 (5) | 0.073 (4) | 0.122 (5) | 0.007 (4) | 0.070 (4) | 0.002 (4) |
C16 | 0.146 (6) | 0.087 (5) | 0.097 (5) | 0.006 (4) | 0.032 (5) | 0.000 (4) |
C17 | 0.098 (6) | 0.090 (6) | 0.118 (7) | −0.004 (4) | 0.025 (6) | 0.012 (5) |
C18 | 0.075 (4) | 0.076 (5) | 0.108 (6) | 0.003 (4) | 0.039 (4) | 0.010 (4) |
N1 | 0.137 (6) | 0.087 (4) | 0.060 (3) | −0.008 (4) | 0.044 (4) | −0.010 (3) |
N2 | 0.100 (4) | 0.050 (3) | 0.075 (4) | −0.007 (3) | 0.023 (3) | −0.004 (3) |
S1 | 0.0467 (8) | 0.1119 (15) | 0.1105 (14) | −0.0052 (9) | 0.0202 (9) | 0.0056 (12) |
S2 | 0.0460 (7) | 0.0604 (9) | 0.0637 (8) | −0.0020 (6) | 0.0119 (6) | 0.0041 (7) |
S3 | 0.0487 (7) | 0.0717 (10) | 0.0798 (10) | 0.0122 (7) | 0.0132 (7) | 0.0013 (8) |
S4 | 0.0432 (7) | 0.0521 (8) | 0.0940 (11) | 0.0015 (6) | 0.0160 (7) | 0.0003 (8) |
S5 | 0.0607 (8) | 0.0509 (8) | 0.0885 (11) | 0.0037 (7) | 0.0159 (8) | −0.0030 (8) |
S6 | 0.0629 (9) | 0.0822 (11) | 0.0595 (9) | −0.0110 (8) | 0.0201 (7) | −0.0069 (8) |
S7 | 0.0525 (7) | 0.0736 (10) | 0.0594 (8) | −0.0086 (7) | 0.0162 (6) | −0.0028 (7) |
S8 | 0.0601 (8) | 0.0708 (10) | 0.0916 (11) | −0.0094 (7) | 0.0332 (8) | −0.0057 (9) |
S9 | 0.0497 (7) | 0.0653 (9) | 0.0785 (10) | −0.0049 (7) | 0.0074 (7) | 0.0014 (8) |
S10 | 0.0481 (8) | 0.0897 (13) | 0.1583 (19) | −0.0030 (8) | 0.0250 (10) | 0.0019 (13) |
Zn1 | 0.0492 (3) | 0.0568 (4) | 0.0648 (4) | −0.0039 (3) | 0.0144 (3) | −0.0028 (3) |
Geometric parameters (Å, º) top
Zn1—S4 | 2.3401 (15) | C8—N1 | 1.347 (11) |
Zn1—S5 | 2.3245 (16) | C8—H8A | 0.9300 |
Zn1—S6 | 2.3315 (16) | C9—C10 | 1.360 (14) |
Zn1—S7 | 2.3447 (15) | C9—H9A | 0.9300 |
S1—C1 | 1.639 (5) | C10—C11 | 1.355 (14) |
S2—C1 | 1.714 (5) | C10—H10A | 0.9300 |
S3—C1 | 1.731 (6) | C11—C12 | 1.362 (13) |
C2—C3 | 1.355 (7) | C11—H11A | 0.9300 |
S4—C2 | 1.737 (5) | C12—N1 | 1.304 (9) |
S2—C2 | 1.753 (5) | C12—H12A | 0.9300 |
S5—C3 | 1.737 (5) | C13—N2 | 1.460 (9) |
S3—C3 | 1.746 (5) | C13—H13A | 0.9600 |
C4—C5 | 1.352 (7) | C13—H13B | 0.9600 |
S6—C4 | 1.734 (5) | C13—H13C | 0.9600 |
S8—C4 | 1.749 (5) | C14—N2 | 1.335 (8) |
S7—C5 | 1.737 (5) | C14—C15 | 1.360 (10) |
S9—C5 | 1.746 (5) | C14—H14A | 0.9300 |
S10—C6 | 1.635 (5) | C15—C16 | 1.366 (13) |
S8—C6 | 1.714 (6) | C15—H15A | 0.9300 |
S9—C6 | 1.732 (6) | C16—C17 | 1.323 (10) |
C7—N1 | 1.429 (11) | C16—H16A | 0.9300 |
C7—H7A | 0.9600 | C17—C18 | 1.310 (10) |
C7—H7B | 0.9600 | C17—H17A | 0.9300 |
C7—H7C | 0.9600 | C18—N2 | 1.349 (8) |
C8—C9 | 1.335 (11) | C18—H18A | 0.9300 |
| | | |
S1—C1—S2 | 124.2 (4) | N2—C13—H13B | 109.5 |
S1—C1—S3 | 124.4 (3) | H13A—C13—H13B | 109.5 |
S2—C1—S3 | 111.4 (3) | N2—C13—H13C | 109.5 |
C3—C2—S4 | 126.8 (4) | H13A—C13—H13C | 109.5 |
C3—C2—S2 | 115.4 (4) | H13B—C13—H13C | 109.5 |
S4—C2—S2 | 117.8 (3) | N2—C14—C15 | 119.0 (7) |
C2—C3—S5 | 127.4 (4) | N2—C14—H14A | 120.5 |
C2—C3—S3 | 115.1 (4) | C15—C14—H14A | 120.5 |
S5—C3—S3 | 117.4 (3) | C14—C15—C16 | 119.5 (7) |
C5—C4—S6 | 127.4 (4) | C14—C15—H15A | 120.3 |
C5—C4—S8 | 115.1 (4) | C16—C15—H15A | 120.3 |
S6—C4—S8 | 117.6 (3) | C17—C16—C15 | 119.5 (8) |
C4—C5—S7 | 126.8 (4) | C17—C16—H16A | 120.3 |
C4—C5—S9 | 115.6 (4) | C15—C16—H16A | 120.3 |
S7—C5—S9 | 117.6 (3) | C18—C17—C16 | 121.3 (8) |
S10—C6—S8 | 124.7 (4) | C18—C17—H17A | 119.4 |
S10—C6—S9 | 123.9 (4) | C16—C17—H17A | 119.4 |
S8—C6—S9 | 111.3 (3) | C17—C18—N2 | 120.4 (7) |
N1—C7—H7A | 109.5 | C17—C18—H18A | 119.8 |
N1—C7—H7B | 109.5 | N2—C18—H18A | 119.8 |
H7A—C7—H7B | 109.5 | C12—N1—C8 | 120.9 (7) |
N1—C7—H7C | 109.5 | C12—N1—C7 | 117.7 (8) |
H7A—C7—H7C | 109.5 | C8—N1—C7 | 121.3 (8) |
H7B—C7—H7C | 109.5 | C14—N2—C18 | 120.4 (6) |
C9—C8—N1 | 119.1 (8) | C14—N2—C13 | 120.3 (7) |
C9—C8—H8A | 120.5 | C18—N2—C13 | 119.3 (7) |
N1—C8—H8A | 120.5 | C1—S2—C2 | 99.0 (3) |
C8—C9—C10 | 121.4 (9) | C1—S3—C3 | 99.0 (2) |
C8—C9—H9A | 119.3 | C2—S4—Zn1 | 95.08 (17) |
C10—C9—H9A | 119.3 | C3—S5—Zn1 | 95.13 (17) |
C11—C10—C9 | 118.2 (9) | C4—S6—Zn1 | 95.22 (18) |
C11—C10—H10A | 120.9 | C5—S7—Zn1 | 95.09 (18) |
C9—C10—H10A | 120.9 | C6—S8—C4 | 99.3 (3) |
C10—C11—C12 | 119.4 (9) | C6—S9—C5 | 98.7 (3) |
C10—C11—H11A | 120.3 | S4—Zn1—S5 | 95.42 (5) |
C12—C11—H11A | 120.3 | S4—Zn1—S6 | 114.14 (6) |
N1—C12—C11 | 120.9 (8) | S4—Zn1—S7 | 115.42 (6) |
N1—C12—H12A | 119.5 | S5—Zn1—S6 | 122.58 (6) |
C11—C12—H12A | 119.5 | S5—Zn1—S7 | 115.94 (6) |
N2—C13—H13A | 109.5 | S6—Zn1—S7 | 94.89 (5) |
| | | |
S4—C2—C3—S5 | −1.8 (8) | C2—C3—S3—C1 | −1.5 (5) |
S2—C2—C3—S5 | 179.6 (3) | S5—C3—S3—C1 | 179.1 (3) |
S4—C2—C3—S3 | 178.8 (3) | C3—C2—S4—Zn1 | −1.3 (5) |
S2—C2—C3—S3 | 0.2 (6) | S2—C2—S4—Zn1 | 177.2 (3) |
S6—C4—C5—S7 | −0.6 (8) | C2—C3—S5—Zn1 | 3.7 (5) |
S8—C4—C5—S7 | 179.5 (3) | S3—C3—S5—Zn1 | −177.0 (3) |
S6—C4—C5—S9 | −179.8 (3) | C5—C4—S6—Zn1 | 6.0 (5) |
S8—C4—C5—S9 | 0.3 (6) | S8—C4—S6—Zn1 | −174.2 (3) |
N1—C8—C9—C10 | 0.0 (13) | C4—C5—S7—Zn1 | −5.1 (5) |
C8—C9—C10—C11 | −3.1 (15) | S9—C5—S7—Zn1 | 174.1 (3) |
C9—C10—C11—C12 | 4.9 (14) | S10—C6—S8—C4 | −179.0 (4) |
C10—C11—C12—N1 | −3.7 (13) | S9—C6—S8—C4 | 3.2 (3) |
N2—C14—C15—C16 | 0.7 (11) | C5—C4—S8—C6 | −2.2 (5) |
C14—C15—C16—C17 | −2.0 (12) | S6—C4—S8—C6 | 178.0 (3) |
C15—C16—C17—C18 | 2.3 (13) | S10—C6—S9—C5 | 179.2 (4) |
C16—C17—C18—N2 | −1.4 (12) | S8—C6—S9—C5 | −3.0 (3) |
C11—C12—N1—C8 | 0.6 (11) | C4—C5—S9—C6 | 1.7 (5) |
C11—C12—N1—C7 | 178.0 (8) | S7—C5—S9—C6 | −177.6 (3) |
C9—C8—N1—C12 | 1.3 (11) | C3—S5—Zn1—S6 | −126.49 (18) |
C9—C8—N1—C7 | −176.1 (8) | C3—S5—Zn1—S4 | −3.25 (18) |
C15—C14—N2—C18 | 0.2 (9) | C3—S5—Zn1—S7 | 118.46 (18) |
C15—C14—N2—C13 | −177.8 (7) | C4—S6—Zn1—S5 | −131.77 (19) |
C17—C18—N2—C14 | 0.1 (10) | C4—S6—Zn1—S4 | 114.06 (19) |
C17—C18—N2—C13 | 178.1 (7) | C4—S6—Zn1—S7 | −6.62 (19) |
S1—C1—S2—C2 | 178.4 (4) | C2—S4—Zn1—S5 | 2.68 (18) |
S3—C1—S2—C2 | −2.0 (3) | C2—S4—Zn1—S6 | 132.13 (17) |
C3—C2—S2—C1 | 1.2 (5) | C2—S4—Zn1—S7 | −119.44 (17) |
S4—C2—S2—C1 | −177.6 (3) | C5—S7—Zn1—S5 | 136.43 (18) |
S1—C1—S3—C3 | −178.3 (4) | C5—S7—Zn1—S6 | 6.44 (18) |
S2—C1—S3—C3 | 2.1 (3) | C5—S7—Zn1—S4 | −113.24 (18) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8A···S10i | 0.93 | 2.71 | 3.632 (8) | 174 |
C14—H14A···S4ii | 0.93 | 2.77 | 3.644 (7) | 157 |
C18—H18A···S1iii | 0.93 | 2.74 | 3.655 (8) | 168 |
Symmetry codes: (i) x+1, −y+3/2, z+1/2; (ii) −x+1, y−1/2, −z+1/2; (iii) −x+2, y−1/2, −z+1/2. |