Bis(acetyl­acetonato-κ²O,O′)(4-hydroxy­benzaldehyde thio­semicarbazone-κS)zinc(II)

In the title compound, [Zn(C₅H₇O₂)₂(C₈H₉N₃OS)], the Zn atom has a square-pyramidal coordination formed by four O atoms belonging to two acetylacetonates in the basal square plane and the S atom of the ligand at the apex. The occurrence of N—H...O, N—H...S and O—H...O hydrogen-bonding inter­actions results in the formation of a layered structure parallel to the (100) plane.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.036
• wR factor = 0.095
• Data-to-parameter ratio = 16.5

checkCIF/PLATON results

No syntax errors found



Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K

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

   2 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
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2003); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Bruker, 2005); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Bis(acetylacetonato-κ²O,O')(4-Hydroxybenzaldehyde thiosemicarbazone-κS)zinc(II)

Crystal data

[Zn(C5H7O2)2(C8H9N3OS)]	F(000) = 1904
Mr = 458.82	Dx = 1.409 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 5656 reflections
a = 14.3048 (7) Å	θ = 2.5–26.2°
b = 10.1746 (5) Å	µ = 1.26 mm^−1
c = 29.7259 (15) Å	T = 293 K
V = 4326.5 (4) Å^3	Block, colorless
Z = 8	0.48 × 0.41 × 0.39 mm

Data collection

Bruker SMART 1000 CCD diffractometer	4266 independent reflections
Radiation source: fine-focus sealed tube	2782 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.042
ω scans	θmax = 26.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→17
Tmin = 0.559, Tmax = 0.613	k = −10→12
20382 measured reflections	l = −36→36

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.095	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0356P)^2 + 3.1381P] where P = (Fo^2 + 2Fc^2)/3
4265 reflections	(Δ/σ)max = 0.005
258 parameters	Δρmax = 0.49 e Å^−3
0 restraints	Δρmin = −0.25 e Å^−3

Special details

Experimental. Spectroscopic analysis: ¹H NMR (DMSO-d₆, δ, p.p.m.): 1.8 (s, 12H), 5.2 (s, 2H), 6.7–6.8 (d, 2H), 7.5–7.6 (d, 2H), 7.7 (s, 1H), 7.9 (s, 2H), 9.8 (s, 1H), 11.2 (s, 1H).

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
Zn1	0.98209 (2)	0.16333 (3)	0.400700 (11)	0.03916 (12)
S1	0.97474 (7)	0.33683 (8)	0.45550 (3)	0.0515 (2)
C1	0.7296 (3)	0.1490 (5)	0.31846 (14)	0.0865 (14)
H1A	0.7079	0.2370	0.3236	0.130*
H1B	0.6774	0.0896	0.3190	0.130*
H1C	0.7598	0.1441	0.2897	0.130*
C2	0.7980 (2)	0.1114 (4)	0.35475 (11)	0.0538 (9)
C3	0.7782 (2)	0.0054 (3)	0.38237 (12)	0.0576 (9)
H3	0.7234	−0.0408	0.3766	0.069*
C4	0.8326 (2)	−0.0378 (3)	0.41775 (11)	0.0480 (8)
C5	0.8009 (3)	−0.1533 (4)	0.44530 (14)	0.0762 (12)
H5A	0.8313	−0.2316	0.4347	0.114*
H5B	0.7344	−0.1632	0.4425	0.114*
H5C	0.8168	−0.1391	0.4763	0.114*
C6	1.1756 (3)	0.3033 (5)	0.30153 (13)	0.0833 (13)
H6A	1.1269	0.3082	0.2794	0.125*
H6B	1.2286	0.2582	0.2891	0.125*
H6C	1.1937	0.3905	0.3103	0.125*
C7	1.1405 (2)	0.2297 (4)	0.34206 (11)	0.0527 (9)
C8	1.2008 (2)	0.1493 (3)	0.36572 (12)	0.0578 (9)
H8	1.2626	0.1471	0.3561	0.069*
C9	1.1782 (2)	0.0718 (3)	0.40244 (12)	0.0517 (8)
C10	1.2527 (3)	−0.0123 (4)	0.42372 (15)	0.0854 (13)
H10A	1.2598	0.0117	0.4548	0.128*
H10B	1.3109	0.0008	0.4083	0.128*
H10C	1.2350	−0.1032	0.4217	0.128*
C11	0.9629 (2)	0.2615 (3)	0.50688 (10)	0.0412 (7)
C12	0.9780 (2)	0.3454 (3)	0.62000 (10)	0.0457 (7)
H12	0.9979	0.4319	0.6170	0.055*
C13	0.9627 (2)	0.2905 (3)	0.66452 (10)	0.0399 (7)
C14	0.9644 (2)	0.3710 (3)	0.70207 (11)	0.0489 (8)
H14	0.9794	0.4594	0.6987	0.059*
C15	0.9443 (2)	0.3227 (3)	0.74430 (10)	0.0458 (8)
H15	0.9453	0.3786	0.7690	0.055*
C16	0.9226 (2)	0.1910 (3)	0.74996 (10)	0.0428 (7)
C17	0.9231 (2)	0.1091 (3)	0.71270 (10)	0.0475 (8)
H17	0.9099	0.0202	0.7161	0.057*
C18	0.9429 (2)	0.1581 (3)	0.67090 (10)	0.0474 (8)
H18	0.9431	0.1017	0.6463	0.057*
N1	0.9404 (2)	0.1382 (2)	0.51184 (9)	0.0517 (7)
H1D	0.9354	0.1052	0.5384	0.062*
H1E	0.9306	0.0899	0.4886	0.062*
N2	0.97760 (19)	0.3336 (2)	0.54381 (8)	0.0487 (7)
H2	0.9950	0.4143	0.5418	0.058*
N3	0.96418 (18)	0.2755 (3)	0.58509 (8)	0.0467 (7)
O1	0.87147 (15)	0.1814 (2)	0.35723 (7)	0.0493 (5)
O2	0.91004 (14)	0.0128 (2)	0.42909 (7)	0.0488 (5)
O3	1.05534 (16)	0.2477 (2)	0.35139 (7)	0.0605 (6)
O4	1.09751 (14)	0.0617 (2)	0.41977 (7)	0.0489 (5)
O5	0.89982 (18)	0.1382 (2)	0.79007 (7)	0.0556 (6)
H5	0.9040	0.1945	0.8097	0.083*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.03879 (19)	0.0460 (2)	0.03265 (19)	−0.00508 (16)	0.00074 (15)	−0.00055 (16)
S1	0.0827 (6)	0.0380 (4)	0.0340 (4)	−0.0068 (4)	0.0029 (4)	0.0006 (4)
C1	0.064 (3)	0.111 (4)	0.085 (3)	−0.025 (2)	−0.033 (2)	0.025 (3)
C2	0.046 (2)	0.069 (2)	0.047 (2)	−0.0063 (18)	−0.0047 (16)	−0.0037 (17)
C3	0.046 (2)	0.063 (2)	0.064 (2)	−0.0197 (18)	−0.0083 (17)	0.0032 (19)
C4	0.0467 (19)	0.0450 (18)	0.052 (2)	−0.0059 (16)	0.0055 (16)	−0.0033 (16)
C5	0.065 (2)	0.070 (3)	0.094 (3)	−0.023 (2)	−0.005 (2)	0.022 (2)
C6	0.065 (3)	0.119 (4)	0.066 (3)	−0.016 (3)	0.020 (2)	0.020 (3)
C7	0.048 (2)	0.068 (2)	0.0427 (19)	−0.0161 (18)	0.0087 (16)	−0.0043 (17)
C8	0.0410 (19)	0.062 (2)	0.070 (2)	−0.0061 (18)	0.0112 (17)	0.000 (2)
C9	0.0429 (19)	0.0453 (19)	0.067 (2)	−0.0010 (15)	−0.0030 (17)	−0.0068 (18)
C10	0.054 (2)	0.086 (3)	0.116 (4)	0.014 (2)	0.004 (2)	0.020 (3)
C11	0.0473 (19)	0.0420 (17)	0.0343 (17)	0.0013 (14)	0.0015 (13)	−0.0004 (14)
C12	0.0508 (19)	0.0467 (18)	0.0395 (17)	−0.0012 (16)	−0.0030 (15)	−0.0035 (15)
C13	0.0433 (18)	0.0421 (17)	0.0344 (16)	−0.0006 (13)	−0.0015 (13)	−0.0046 (13)
C14	0.060 (2)	0.0388 (17)	0.048 (2)	−0.0073 (15)	−0.0041 (16)	−0.0049 (15)
C15	0.061 (2)	0.0440 (18)	0.0321 (16)	−0.0040 (16)	−0.0004 (14)	−0.0113 (14)
C16	0.0432 (18)	0.0501 (19)	0.0352 (17)	0.0028 (15)	−0.0068 (13)	−0.0018 (14)
C17	0.062 (2)	0.0357 (16)	0.0448 (19)	0.0022 (16)	−0.0065 (16)	−0.0042 (15)
C18	0.060 (2)	0.0433 (18)	0.0387 (18)	0.0047 (16)	−0.0078 (15)	−0.0153 (15)
N1	0.080 (2)	0.0421 (15)	0.0333 (14)	−0.0085 (14)	−0.0002 (13)	−0.0009 (12)
N2	0.0734 (18)	0.0401 (14)	0.0324 (14)	−0.0035 (14)	0.0023 (13)	−0.0002 (12)
N3	0.0613 (18)	0.0463 (15)	0.0325 (14)	0.0034 (13)	0.0008 (12)	0.0003 (12)
O1	0.0441 (12)	0.0635 (15)	0.0402 (12)	−0.0136 (11)	−0.0077 (9)	0.0070 (11)
O2	0.0475 (13)	0.0539 (13)	0.0450 (13)	−0.0163 (11)	−0.0059 (10)	0.0032 (10)
O3	0.0439 (13)	0.0914 (18)	0.0463 (14)	−0.0020 (13)	0.0074 (11)	0.0198 (13)
O4	0.0420 (13)	0.0496 (13)	0.0550 (14)	−0.0009 (10)	0.0040 (10)	0.0045 (11)
O5	0.0774 (17)	0.0496 (13)	0.0397 (13)	−0.0032 (12)	0.0000 (12)	0.0022 (10)

Geometric parameters (Å, º)

Zn1—O3	1.996 (2)	C9—O4	1.268 (4)
Zn1—O4	2.029 (2)	C9—C10	1.507 (5)
Zn1—O2	2.029 (2)	C10—H10A	0.9600
Zn1—O1	2.051 (2)	C10—H10B	0.9600
Zn1—S1	2.4044 (9)	C10—H10C	0.9600
S1—C11	1.717 (3)	C11—N1	1.303 (4)
C1—C2	1.506 (5)	C11—N2	1.337 (4)
C1—H1A	0.9600	C12—N3	1.273 (4)
C1—H1B	0.9600	C12—C13	1.453 (4)
C1—H1C	0.9600	C12—H12	0.9300
C2—O1	1.272 (4)	C13—C14	1.385 (4)
C2—C3	1.385 (5)	C13—C18	1.389 (4)
C3—C4	1.380 (5)	C14—C15	1.378 (4)
C3—H3	0.9300	C14—H14	0.9300
C4—O2	1.267 (4)	C15—C16	1.385 (4)
C4—C5	1.503 (4)	C15—H15	0.9300
C5—H5A	0.9600	C16—O5	1.348 (4)
C5—H5B	0.9600	C16—C17	1.386 (4)
C5—H5C	0.9600	C17—C18	1.368 (4)
C6—C7	1.505 (5)	C17—H17	0.9300
C6—H6A	0.9600	C18—H18	0.9300
C6—H6B	0.9600	N1—H1D	0.8600
C6—H6C	0.9600	N1—H1E	0.8600
C7—O3	1.263 (4)	N2—N3	1.376 (3)
C7—C8	1.380 (5)	N2—H2	0.8600
C8—C9	1.385 (5)	O5—H5	0.8200
C8—H8	0.9300
O3—Zn1—O4	89.85 (9)	O4—C9—C10	115.3 (3)
O3—Zn1—O2	153.71 (10)	C8—C9—C10	119.3 (3)
O4—Zn1—O2	84.98 (9)	C9—C10—H10A	109.5
O3—Zn1—O1	84.47 (9)	C9—C10—H10B	109.5
O4—Zn1—O1	148.15 (9)	H10A—C10—H10B	109.5
O2—Zn1—O1	86.44 (8)	C9—C10—H10C	109.5
O3—Zn1—S1	101.80 (8)	H10A—C10—H10C	109.5
O4—Zn1—S1	102.74 (7)	H10B—C10—H10C	109.5
O2—Zn1—S1	104.48 (6)	N1—C11—N2	118.3 (3)
O1—Zn1—S1	109.10 (7)	N1—C11—S1	123.7 (2)
C11—S1—Zn1	106.22 (11)	N2—C11—S1	118.0 (2)
C2—C1—H1A	109.5	N3—C12—C13	120.3 (3)
C2—C1—H1B	109.5	N3—C12—H12	119.9
H1A—C1—H1B	109.5	C13—C12—H12	119.9
C2—C1—H1C	109.5	C14—C13—C18	117.8 (3)
H1A—C1—H1C	109.5	C14—C13—C12	120.3 (3)
H1B—C1—H1C	109.5	C18—C13—C12	121.9 (3)
O1—C2—C3	124.8 (3)	C15—C14—C13	121.3 (3)
O1—C2—C1	115.9 (3)	C15—C14—H14	119.4
C3—C2—C1	119.3 (3)	C13—C14—H14	119.4
C4—C3—C2	125.7 (3)	C14—C15—C16	120.1 (3)
C4—C3—H3	117.1	C14—C15—H15	119.9
C2—C3—H3	117.1	C16—C15—H15	119.9
O2—C4—C3	124.5 (3)	O5—C16—C15	123.2 (3)
O2—C4—C5	115.9 (3)	O5—C16—C17	117.9 (3)
C3—C4—C5	119.6 (3)	C15—C16—C17	118.9 (3)
C4—C5—H5A	109.5	C18—C17—C16	120.5 (3)
C4—C5—H5B	109.5	C18—C17—H17	119.8
H5A—C5—H5B	109.5	C16—C17—H17	119.8
C4—C5—H5C	109.5	C17—C18—C13	121.3 (3)
H5A—C5—H5C	109.5	C17—C18—H18	119.4
H5B—C5—H5C	109.5	C13—C18—H18	119.4
C7—C6—H6A	109.5	C11—N1—H1D	120.0
C7—C6—H6B	109.5	C11—N1—H1E	120.0
H6A—C6—H6B	109.5	H1D—N1—H1E	120.0
C7—C6—H6C	109.5	C11—N2—N3	118.3 (3)
H6A—C6—H6C	109.5	C11—N2—H2	120.8
H6B—C6—H6C	109.5	N3—N2—H2	120.8
O3—C7—C8	125.2 (3)	C12—N3—N2	117.7 (3)
O3—C7—C6	115.1 (3)	C2—O1—Zn1	128.6 (2)
C8—C7—C6	119.6 (3)	C4—O2—Zn1	129.8 (2)
C7—C8—C9	126.3 (3)	C7—O3—Zn1	127.2 (2)
C7—C8—H8	116.8	C9—O4—Zn1	125.9 (2)
C9—C8—H8	116.8	C16—O5—H5	109.5
O4—C9—C8	125.4 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5···O1^i	0.82	1.95	2.742 (3)	162
N2—H2···S1^ii	0.86	2.57	3.422 (3)	171
N1—H1E···O2	0.86	1.96	2.805 (3)	169
N1—H1D···O4^iii	0.86	2.16	2.926 (3)	149

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