Di­chloro­bis­(thio­urea)­zinc(II) bis(4,5-di­aza­fluoren-9-one)

Wu, Z.-Y.; Xu, D.-J.; Yin, K.-L.

doi:10.1107/S1600536804006403

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Dichlorobis(thiourea)zinc(II) bis(4,5-diazafluoren-9-one)

Z.-Y. Wu, D.-J. Xu and K.-L. Yin

The title compound, [ZnCl₂(CH₄N₂S)₂]·2C₁₁H₆N₂O, consists of the tetrahedral ZnCl₂–thiourea complex and hydrogen-bonded 4,5-diazafluoren-9-one (dafone). The N

N distance in dafone when not involved in metal coordination is significantly larger than when it is metal chelating. Neighboring zinc(II) complex molecules hydrogen bond to each other, forming supramolecular chains. π–π stacking is observed between neighboring dafone rings.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536804006403/na6304sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536804006403/na6304Isup2.hkl Contains datablock I

CCDC reference: 238688

checkCIF report

Key indicators

Single-crystal X-ray study
T = 295 K
Mean (C-C) = 0.004 Å
R factor = 0.033
wR factor = 0.103
Data-to-parameter ratio = 15.7

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT052_ALERT_1_A (Proper) Absorption Correction Method Missing ..          ?
PLAT057_ALERT_3_A Correction for Absorption Required   RT(exp) ...       1.51

Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT241_ALERT_2_C Check High   U(eq) as Compared to Neighbors ....         S1
PLAT242_ALERT_2_C Check Low    U(eq) as Compared to Neighbors ....         Zn
PLAT242_ALERT_2_C Check Low    U(eq) as Compared to Neighbors ....         C1
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          2
              C11 H6 N2 O

   2 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

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 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
   1 ALERT type 4 Improvement, methodology, query or suggestion

Computing details top

Data collection: MSC/AFC (Molecular Structure Corporation, 1992); cell refinement: MSC/AFC; data reduction: TEXSAN (Molecular Structure Corporation, 1985); program(s) used to solve structure: SIR92 (Altomare, 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

(I) top

Crystal data top

[ZnCl₂(CH₄N₂S)₂]·2C₁₁H₆N₂O	Z = 2
M_r = 652.86	F(000) = 664
Triclinic, P1	D_x = 1.542 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.4059 (17) Å	Cell parameters from 20 reflections
b = 12.973 (2) Å	θ = 4.5–8.1°
c = 15.184 (3) Å	µ = 1.25 mm⁻¹
α = 89.167 (17)°	T = 295 K
β = 78.006 (16)°	Prism, colorless
γ = 80.220 (16)°	0.52 × 0.44 × 0.18 mm
V = 1405.9 (5) Å³

Data collection top

Rigaku AFC-7S diffractometer	R_int = 0.050
ω/2θ scans	θ_max = 26.0°, θ_min = 2.1°
Absorption correction: ψ scan (North et al., 1968)	h = −9→9
T_min = 0.535, T_max = 0.802	k = −15→0
5774 measured reflections	l = −18→18
5520 independent reflections	3 standard reflections every 150 reflections
4070 reflections with I > \2s(I)	intensity decay: 0.6%

Refinement top

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.103	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0568P)² + 0.4107P] where P = (F_o² + 2F_c²)/3
5520 reflections	(Δ/σ)_max = 0.001
352 parameters	Δρ_max = 0.62 e Å⁻³
0 restraints	Δρ_min = −0.39 e Å⁻³

Special details top

Experimental. The C, H and N content was analysed using a Carlo-Erba 1160 instrument.

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	U_iso*/U_eq
Zn	0.48952 (4)	0.23743 (2)	0.361449 (19)	0.04786 (11)
Cl1	0.72134 (12)	0.23922 (7)	0.43600 (6)	0.0698 (2)
Cl2	0.59406 (13)	0.24517 (6)	0.21048 (5)	0.0736 (2)
S1	0.22983 (12)	0.36849 (6)	0.41841 (5)	0.0707 (3)
S2	0.35100 (11)	0.09079 (5)	0.40682 (5)	0.0598 (2)
N1	0.1710 (4)	0.57087 (18)	0.39842 (17)	0.0623 (6)
N2	0.3406 (3)	0.47875 (17)	0.27474 (15)	0.0547 (6)
N3	0.4838 (4)	−0.10875 (17)	0.37778 (15)	0.0552 (6)
N4	0.5800 (3)	−0.00517 (17)	0.26228 (15)	0.0553 (6)
C1	0.2517 (4)	0.4806 (2)	0.35874 (18)	0.0466 (6)
C2	0.4846 (3)	−0.01488 (19)	0.34406 (16)	0.0434 (5)
O1	0.2660 (4)	1.02964 (17)	0.10364 (15)	0.0755 (6)
N5	0.1193 (3)	0.77754 (16)	0.32434 (14)	0.0483 (5)
N6	0.3872 (3)	0.66567 (16)	0.15929 (14)	0.0470 (5)
C3	0.0036 (4)	0.8441 (2)	0.38721 (19)	0.0568 (7)
H3	−0.0498	0.8164	0.4413	0.068*
C4	−0.0405 (4)	0.9502 (2)	0.3765 (2)	0.0585 (7)
H4	−0.1218	0.9918	0.4224	0.070*
C5	0.0360 (4)	0.9951 (2)	0.2974 (2)	0.0535 (6)
H5	0.0082	1.0666	0.2883	0.064*
C6	0.1558 (3)	0.92839 (19)	0.23273 (17)	0.0445 (5)
C7	0.2633 (4)	0.9469 (2)	0.14143 (18)	0.0507 (6)
C8	0.3629 (4)	0.8422 (2)	0.10497 (17)	0.0470 (6)
C9	0.4796 (4)	0.8108 (2)	0.02281 (18)	0.0552 (7)
H9	0.5097	0.8585	−0.0219	0.066*
C10	0.5487 (4)	0.7057 (2)	0.01047 (19)	0.0570 (7)
H10	0.6270	0.6807	−0.0437	0.068*
C11	0.5019 (4)	0.6372 (2)	0.07870 (19)	0.0541 (7)
H11	0.5528	0.5667	0.0685	0.065*
C12	0.3220 (3)	0.76765 (19)	0.16966 (16)	0.0414 (5)
C13	0.1917 (3)	0.82161 (19)	0.24930 (16)	0.0415 (5)
O2	1.1359 (4)	−0.52084 (18)	0.07231 (18)	0.0820 (7)
N7	0.6924 (3)	−0.31099 (18)	0.29936 (16)	0.0529 (5)
N8	0.8189 (3)	−0.17293 (17)	0.14077 (15)	0.0503 (5)
C14	0.6588 (5)	−0.3876 (2)	0.3580 (2)	0.0626 (7)
H14	0.5746	−0.3696	0.4122	0.075*
C15	0.7412 (5)	−0.4911 (3)	0.3429 (2)	0.0690 (8)
H15	0.7116	−0.5404	0.3862	0.083*
C16	0.8685 (5)	−0.5217 (2)	0.2629 (2)	0.0670 (8)
H16	0.9258	−0.5910	0.2509	0.080*
C17	0.9053 (4)	−0.4443 (2)	0.2025 (2)	0.0542 (7)
C18	1.0302 (4)	−0.4466 (2)	0.1115 (2)	0.0594 (7)
C19	0.9994 (4)	−0.3379 (2)	0.07860 (19)	0.0525 (6)
C20	1.0691 (4)	−0.2942 (3)	−0.0012 (2)	0.0609 (7)
H20	1.1524	−0.3341	−0.0475	0.073*
C21	1.0107 (4)	−0.1887 (3)	−0.0099 (2)	0.0626 (8)
H21	1.0524	−0.1557	−0.0632	0.075*
C22	0.8893 (4)	−0.1322 (2)	0.0616 (2)	0.0584 (7)
H22	0.8536	−0.0609	0.0543	0.070*
C23	0.8742 (3)	−0.2751 (2)	0.14668 (17)	0.0454 (6)
C24	0.8157 (4)	−0.3417 (2)	0.22321 (18)	0.0476 (6)
H3A	0.5544	−0.1697	0.3438	0.080*
H4B	0.5697	0.0606	0.2388	0.080*
H4A	0.6467	−0.0610	0.2264	0.080*
H2B	0.4051	0.4131	0.2521	0.080*
H2A	0.3496	0.5380	0.2452	0.080*
H1A	0.1573	0.6285	0.3678	0.080*
H1B	0.1166	0.5699	0.4599	0.080*
H3B	0.4187	−0.1127	0.4373	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn	0.0621 (2)	0.03741 (17)	0.03755 (17)	−0.00421 (13)	0.00092 (13)	0.00184 (11)
Cl1	0.0710 (5)	0.0672 (5)	0.0748 (5)	−0.0175 (4)	−0.0192 (4)	0.0081 (4)
Cl2	0.1051 (6)	0.0607 (4)	0.0391 (4)	−0.0052 (4)	0.0135 (4)	0.0047 (3)
S1	0.0806 (5)	0.0469 (4)	0.0604 (5)	0.0108 (4)	0.0215 (4)	0.0159 (3)
S2	0.0716 (5)	0.0422 (4)	0.0533 (4)	−0.0133 (3)	0.0186 (3)	−0.0094 (3)
N1	0.0768 (16)	0.0406 (12)	0.0572 (14)	−0.0003 (11)	0.0055 (12)	0.0040 (10)
N2	0.0641 (14)	0.0449 (12)	0.0478 (13)	−0.0024 (10)	−0.0016 (11)	0.0086 (10)
N3	0.0689 (15)	0.0419 (12)	0.0493 (13)	−0.0050 (10)	−0.0033 (11)	0.0006 (10)
N4	0.0675 (15)	0.0429 (12)	0.0454 (13)	−0.0033 (10)	0.0065 (11)	−0.0043 (9)
C1	0.0439 (13)	0.0452 (14)	0.0489 (15)	−0.0056 (11)	−0.0076 (11)	0.0060 (11)
C2	0.0440 (13)	0.0440 (13)	0.0406 (13)	−0.0082 (10)	−0.0039 (10)	−0.0046 (10)
O1	0.0960 (17)	0.0532 (12)	0.0677 (14)	−0.0058 (11)	−0.0022 (12)	0.0227 (11)
N5	0.0522 (12)	0.0432 (12)	0.0438 (12)	−0.0089 (9)	0.0035 (9)	0.0028 (9)
N6	0.0489 (12)	0.0453 (12)	0.0431 (11)	−0.0040 (9)	−0.0044 (9)	−0.0005 (9)
C3	0.0616 (17)	0.0538 (16)	0.0470 (15)	−0.0118 (13)	0.0088 (12)	0.0001 (12)
C4	0.0579 (17)	0.0544 (16)	0.0544 (17)	−0.0037 (13)	0.0042 (13)	−0.0072 (13)
C5	0.0543 (15)	0.0419 (14)	0.0612 (17)	−0.0031 (11)	−0.0088 (13)	−0.0011 (12)
C6	0.0440 (13)	0.0433 (13)	0.0465 (14)	−0.0085 (10)	−0.0098 (11)	0.0042 (11)
C7	0.0554 (15)	0.0493 (15)	0.0473 (15)	−0.0091 (12)	−0.0110 (12)	0.0087 (12)
C8	0.0457 (14)	0.0533 (15)	0.0414 (13)	−0.0096 (11)	−0.0074 (11)	0.0077 (11)
C9	0.0531 (15)	0.0681 (18)	0.0415 (14)	−0.0101 (13)	−0.0037 (12)	0.0093 (12)
C10	0.0499 (15)	0.0726 (19)	0.0420 (14)	−0.0030 (13)	−0.0006 (12)	−0.0024 (13)
C11	0.0519 (15)	0.0551 (16)	0.0501 (15)	0.0008 (12)	−0.0059 (12)	−0.0072 (12)
C12	0.0393 (12)	0.0466 (13)	0.0387 (13)	−0.0090 (10)	−0.0075 (10)	0.0025 (10)
C13	0.0400 (12)	0.0424 (13)	0.0417 (13)	−0.0091 (10)	−0.0062 (10)	0.0013 (10)
O2	0.0832 (16)	0.0609 (14)	0.0884 (17)	0.0182 (12)	−0.0104 (13)	−0.0264 (12)
N7	0.0557 (13)	0.0506 (13)	0.0513 (13)	−0.0071 (10)	−0.0101 (11)	−0.0019 (10)
N8	0.0521 (12)	0.0472 (12)	0.0480 (12)	−0.0018 (10)	−0.0072 (10)	−0.0076 (10)
C14	0.0673 (18)	0.0655 (19)	0.0570 (18)	−0.0176 (15)	−0.0124 (14)	0.0063 (14)
C15	0.080 (2)	0.0553 (18)	0.077 (2)	−0.0203 (16)	−0.0243 (18)	0.0119 (16)
C16	0.072 (2)	0.0458 (16)	0.088 (2)	−0.0062 (14)	−0.0298 (18)	−0.0032 (15)
C17	0.0567 (16)	0.0447 (14)	0.0644 (18)	−0.0038 (12)	−0.0232 (14)	−0.0083 (13)
C18	0.0536 (16)	0.0555 (17)	0.0688 (19)	0.0028 (13)	−0.0204 (14)	−0.0183 (14)
C19	0.0453 (14)	0.0548 (16)	0.0564 (16)	−0.0005 (12)	−0.0136 (12)	−0.0152 (13)
C20	0.0477 (15)	0.076 (2)	0.0532 (17)	−0.0035 (14)	−0.0024 (13)	−0.0154 (14)
C21	0.0579 (17)	0.073 (2)	0.0509 (17)	−0.0092 (15)	−0.0002 (13)	0.0000 (14)
C22	0.0622 (17)	0.0564 (17)	0.0541 (17)	−0.0073 (13)	−0.0088 (13)	0.0018 (13)
C23	0.0415 (13)	0.0484 (14)	0.0463 (14)	−0.0037 (11)	−0.0114 (11)	−0.0102 (11)
C24	0.0445 (13)	0.0482 (14)	0.0514 (15)	−0.0054 (11)	−0.0146 (11)	−0.0076 (11)

Geometric parameters (Å, º) top

Zn—Cl1	2.2475 (10)	C7—C8	1.486 (4)
Zn—Cl2	2.2685 (9)	C8—C9	1.384 (4)
Zn—S2	2.3403 (9)	C8—C12	1.393 (3)
Zn—S1	2.3619 (10)	C9—C10	1.373 (4)
S1—C1	1.715 (3)	C9—H9	0.9300
S2—C2	1.718 (3)	C10—C11	1.383 (4)
N1—C1	1.314 (3)	C10—H10	0.9300
N1—H1A	0.877	C11—H11	0.9300
N1—H1B	0.938	C12—C13	1.481 (3)
N2—C1	1.307 (3)	O2—C18	1.209 (3)
N2—H2B	0.935	N7—C24	1.334 (3)
N2—H2A	0.890	N7—C14	1.345 (4)
N3—C2	1.315 (3)	N8—C23	1.327 (3)
N3—H3A	0.961	N8—C22	1.346 (4)
N3—H3B	0.937	C14—C15	1.379 (4)
N4—C2	1.311 (3)	C14—H14	0.9300
N4—H4B	0.917	C15—C16	1.391 (5)
N4—H4A	0.918	C15—H15	0.9300
O1—C7	1.211 (3)	C16—C17	1.373 (4)
N5—C13	1.321 (3)	C16—H16	0.9300
N5—C3	1.351 (3)	C17—C24	1.391 (4)
N6—C12	1.329 (3)	C17—C18	1.492 (4)
N6—C11	1.353 (3)	C18—C19	1.485 (4)
C3—C4	1.375 (4)	C19—C20	1.369 (4)
C3—H3	0.9300	C19—C23	1.401 (4)
C4—C5	1.382 (4)	C20—C21	1.377 (4)
C4—H4	0.9300	C20—H20	0.9300
C5—C6	1.379 (4)	C21—C22	1.384 (4)
C5—H5	0.9300	C21—H21	0.9300
C6—C13	1.395 (3)	C22—H22	0.9300
C6—C7	1.486 (4)	C23—C24	1.474 (4)

Cl1—Zn—Cl2	111.46 (4)	C8—C9—H9	121.6
Cl1—Zn—S2	107.84 (4)	C9—C10—C11	120.0 (3)
Cl2—Zn—S2	114.11 (3)	C9—C10—H10	120.0
Cl1—Zn—S1	111.10 (4)	C11—C10—H10	120.0
Cl2—Zn—S1	113.19 (4)	N6—C11—C10	124.4 (3)
S2—Zn—S1	98.40 (3)	N6—C11—H11	117.8
C1—S1—Zn	109.26 (9)	C10—C11—H11	117.8
C2—S2—Zn	107.56 (9)	N6—C12—C8	124.9 (2)
C1—N1—H1A	121.6	N6—C12—C13	126.9 (2)
C1—N1—H1B	117.0	C8—C12—C13	108.2 (2)
H1A—N1—H1B	121.0	N5—C13—C6	124.6 (2)
C1—N2—H2B	115.1	N5—C13—C12	126.5 (2)
C1—N2—H2A	120.5	C6—C13—C12	108.9 (2)
H2B—N2—H2A	123.9	C24—N7—C14	115.0 (3)
C2—N3—H3A	120.8	C23—N8—C22	114.6 (2)
C2—N3—H3B	117.0	N7—C14—C15	124.3 (3)
H3A—N3—H3B	122.0	N7—C14—H14	117.9
C2—N4—H4B	117.1	C15—C14—H14	117.9
C2—N4—H4A	123.4	C14—C15—C16	119.9 (3)
H4B—N4—H4A	119.2	C14—C15—H15	120.1
N2—C1—N1	119.2 (2)	C16—C15—H15	120.1
N2—C1—S1	122.3 (2)	C17—C16—C15	116.6 (3)
N1—C1—S1	118.5 (2)	C17—C16—H16	121.7
N4—C2—N3	119.2 (2)	C15—C16—H16	121.7
N4—C2—S2	122.0 (2)	C16—C17—C24	119.6 (3)
N3—C2—S2	118.73 (19)	C16—C17—C18	132.1 (3)
C13—N5—C3	115.0 (2)	C24—C17—C18	108.3 (3)
C12—N6—C11	114.5 (2)	O2—C18—C19	126.7 (3)
N5—C3—C4	124.3 (3)	O2—C18—C17	127.5 (3)
N5—C3—H3	117.9	C19—C18—C17	105.7 (2)
C4—C3—H3	117.9	C20—C19—C23	119.6 (3)
C3—C4—C5	120.0 (3)	C20—C19—C18	132.1 (3)
C3—C4—H4	120.0	C23—C19—C18	108.3 (3)
C5—C4—H4	120.0	C19—C20—C21	117.2 (3)
C6—C5—C4	116.6 (3)	C19—C20—H20	121.4
C6—C5—H5	121.7	C21—C20—H20	121.4
C4—C5—H5	121.7	C20—C21—C22	119.3 (3)
C5—C6—C13	119.5 (2)	C20—C21—H21	120.4
C5—C6—C7	132.1 (2)	C22—C21—H21	120.4
C13—C6—C7	108.3 (2)	N8—C22—C21	124.9 (3)
O1—C7—C6	127.3 (3)	N8—C22—H22	117.6
O1—C7—C8	127.0 (3)	C21—C22—H22	117.6
C6—C7—C8	105.7 (2)	N8—C23—C19	124.4 (3)
C9—C8—C12	119.4 (3)	N8—C23—C24	127.0 (2)
C9—C8—C7	131.7 (2)	C19—C23—C24	108.6 (2)
C12—C8—C7	108.9 (2)	N7—C24—C17	124.6 (3)
C10—C9—C8	116.8 (3)	N7—C24—C23	126.4 (2)
C10—C9—H9	121.6	C17—C24—C23	109.0 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N5	0.88	2.03	2.888 (3)	167
N1—H1B···S1ⁱ	0.94	2.83	3.606 (3)	141
N2—H2A···N6	0.89	2.11	2.997 (3)	172
N2—H2B···Cl2	0.93	2.40	3.324 (2)	172
N3—H3A···N7	0.96	1.99	2.939 (3)	167
N3—H3B···Cl1ⁱⁱ	0.94	2.67	3.481 (3)	145
N4—H4A···N8	0.92	2.04	2.953 (3)	173
N4—H4B···Cl2	0.92	2.46	3.344 (2)	163

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

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