Crystal structure of [butane-2,3-dione bis­(4-methyl­thio­semicarbazonato)-κ⁴S,N¹,N^1′,S′](pyridine-κN)zinc(II)

The title compound was prepared by the reaction of [butane-2,3-dione bis­(4-methyl­thio­semicarbazonato)]zinc(II) with pyridine. The Zn^II atom is five-coordinate in a pseudo-square-pyramidal geometry.

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.031
• wR factor = 0.074
• Data-to-parameter ratio = 16.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      2.090 Check
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         16 Report

Alert level G
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          2 Report
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         65 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   2 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   2 ALERT level G = General information/check it is not something unexpected

   0 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
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

---

Computing details

Data collection: (CrysAlis PRO; Agilent, 2014); cell refinement: (CrysAlis PRO; Agilent, 2014); data reduction: (CrysAlis PRO; Agilent, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

[Butane-2,3-dione bis(4-methylthiosemicarbazonato)-κ⁴S,N¹,N^1',S'](pyridine-κN)zinc(II)

Crystal data

[Zn(C8H14N6S2)(C5H5N)]	F(000) = 832
Mr = 402.84	Dx = 1.535 Mg m^−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54184 Å
a = 10.1466 (2) Å	Cell parameters from 6492 reflections
b = 13.9076 (3) Å	θ = 4.8–73.0°
c = 12.7775 (3) Å	µ = 4.27 mm^−1
β = 104.756 (2)°	T = 150 K
V = 1743.64 (7) Å^3	Needle, clear yellow
Z = 4	0.26 × 0.04 × 0.02 mm

Data collection

Agilent SuperNova Dual Source diffractometer with an Atlas detector	3445 independent reflections
Radiation source: sealed X-ray tube, SuperNova (Cu) X-ray Source	3020 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.041
Detector resolution: 5.2031 pixels mm^-1	θmax = 73.6°, θmin = 4.8°
ω scans	h = −7→12
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −16→17
Tmin = 0.775, Tmax = 1.000	l = −15→15
12050 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.031	H-atom parameters constrained
wR(F^2) = 0.074	w = 1/[σ^2(Fo^2) + (0.032P)^2 + 1.1359P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
3445 reflections	Δρmax = 0.36 e Å^−3
212 parameters	Δρmin = −0.42 e Å^−3
0 restraints

Special details

Experimental. Absorption correction: CrysAlisPro, Agilent Technologies, Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET) (compiled May 22 2014,16:03:01) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Zn1	0.30020 (3)	0.73515 (2)	0.47000 (2)	0.01926 (9)
S1	0.44685 (5)	0.79566 (4)	0.36852 (4)	0.02284 (12)
S2	0.14259 (6)	0.85069 (4)	0.50133 (4)	0.02449 (13)
N1	0.68465 (19)	0.71828 (14)	0.37359 (15)	0.0248 (4)
H1	0.6813	0.7600	0.3233	0.030*
N2	0.59011 (19)	0.65189 (13)	0.50031 (15)	0.0235 (4)
N3	0.47831 (18)	0.65526 (13)	0.54215 (14)	0.0203 (4)
N4	0.26884 (18)	0.68075 (13)	0.61711 (14)	0.0213 (4)
N5	0.15519 (18)	0.70523 (13)	0.65027 (14)	0.0215 (4)
N6	−0.02309 (19)	0.80647 (14)	0.62535 (15)	0.0257 (4)
H6	−0.0411	0.7758	0.6785	0.031*
N7	0.17142 (18)	0.64416 (13)	0.35929 (14)	0.0213 (4)
C1	0.8028 (2)	0.65595 (18)	0.4039 (2)	0.0301 (5)
H1A	0.8662	0.6725	0.3624	0.045*
H1B	0.7748	0.5903	0.3898	0.045*
H1C	0.8457	0.6638	0.4796	0.045*
C2	0.5800 (2)	0.71402 (15)	0.42040 (17)	0.0214 (4)
C3	0.4771 (2)	0.60479 (15)	0.62697 (16)	0.0211 (4)
C4	0.5913 (3)	0.54130 (19)	0.6841 (2)	0.0344 (6)
H4A	0.5647	0.4752	0.6712	0.052*
H4B	0.6127	0.5542	0.7604	0.052*
H4C	0.6700	0.5537	0.6575	0.052*
C5	0.3557 (2)	0.61910 (15)	0.66955 (16)	0.0200 (4)
C6	0.3438 (2)	0.56830 (17)	0.76987 (17)	0.0251 (4)
H6A	0.4086	0.5947	0.8314	0.038*
H6B	0.3618	0.5010	0.7639	0.038*
H6C	0.2533	0.5766	0.7788	0.038*
C7	0.0907 (2)	0.78126 (15)	0.59668 (17)	0.0215 (4)
C8	−0.1183 (2)	0.88087 (17)	0.57441 (18)	0.0269 (5)
H8A	−0.1695	0.8591	0.5046	0.040*
H8B	−0.0689	0.9381	0.5662	0.040*
H8C	−0.1794	0.8946	0.6188	0.040*
C9	0.1317 (2)	0.67116 (17)	0.25522 (18)	0.0264 (5)
H9	0.1650	0.7287	0.2350	0.032*
C10	0.0434 (2)	0.61722 (18)	0.17651 (19)	0.0313 (5)
H10	0.0177	0.6381	0.1050	0.038*
C11	−0.0057 (2)	0.53150 (17)	0.2068 (2)	0.0301 (5)
H11	−0.0652	0.4937	0.1558	0.036*
C12	0.0346 (2)	0.50294 (17)	0.3136 (2)	0.0301 (5)
H12	0.0030	0.4455	0.3356	0.036*
C13	0.1226 (2)	0.56104 (16)	0.38725 (18)	0.0247 (4)
H13	0.1492	0.5417	0.4592	0.030*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.01595 (15)	0.02595 (15)	0.01686 (14)	0.00116 (10)	0.00599 (10)	0.00201 (10)
S1	0.0201 (3)	0.0283 (3)	0.0226 (2)	0.00170 (19)	0.0101 (2)	0.00528 (19)
S2	0.0234 (3)	0.0268 (3)	0.0264 (3)	0.0057 (2)	0.0122 (2)	0.0057 (2)
N1	0.0194 (9)	0.0345 (10)	0.0227 (9)	0.0000 (7)	0.0097 (7)	0.0049 (7)
N2	0.0193 (9)	0.0316 (10)	0.0219 (8)	0.0020 (7)	0.0095 (7)	0.0024 (7)
N3	0.0158 (9)	0.0268 (9)	0.0191 (8)	0.0023 (7)	0.0060 (7)	0.0020 (7)
N4	0.0202 (9)	0.0270 (9)	0.0186 (8)	0.0011 (7)	0.0081 (7)	0.0002 (7)
N5	0.0149 (9)	0.0318 (9)	0.0201 (8)	0.0022 (7)	0.0088 (7)	0.0010 (7)
N6	0.0182 (9)	0.0365 (10)	0.0246 (9)	0.0064 (8)	0.0098 (7)	0.0051 (8)
N7	0.0159 (9)	0.0259 (9)	0.0221 (8)	0.0001 (7)	0.0050 (7)	−0.0005 (7)
C1	0.0169 (11)	0.0405 (13)	0.0358 (12)	0.0037 (9)	0.0118 (9)	0.0010 (10)
C2	0.0176 (10)	0.0268 (10)	0.0209 (10)	−0.0029 (8)	0.0069 (8)	−0.0028 (8)
C3	0.0178 (10)	0.0270 (10)	0.0192 (9)	0.0017 (8)	0.0060 (8)	0.0019 (8)
C4	0.0292 (13)	0.0448 (14)	0.0331 (12)	0.0165 (11)	0.0149 (10)	0.0157 (11)
C5	0.0179 (10)	0.0257 (10)	0.0165 (9)	−0.0013 (8)	0.0047 (8)	−0.0002 (8)
C6	0.0185 (11)	0.0355 (12)	0.0210 (10)	0.0003 (9)	0.0047 (8)	0.0051 (9)
C7	0.0183 (11)	0.0295 (11)	0.0171 (9)	−0.0006 (8)	0.0055 (8)	−0.0036 (8)
C8	0.0209 (11)	0.0346 (12)	0.0263 (11)	0.0062 (9)	0.0077 (9)	−0.0014 (9)
C9	0.0230 (12)	0.0300 (11)	0.0247 (11)	−0.0010 (9)	0.0034 (9)	0.0025 (9)
C10	0.0255 (12)	0.0408 (13)	0.0242 (11)	0.0011 (10)	0.0004 (9)	0.0004 (9)
C11	0.0203 (11)	0.0334 (12)	0.0346 (12)	−0.0013 (9)	0.0032 (9)	−0.0096 (10)
C12	0.0240 (12)	0.0258 (11)	0.0410 (13)	−0.0018 (9)	0.0094 (10)	−0.0021 (10)
C13	0.0197 (11)	0.0274 (11)	0.0280 (11)	0.0017 (9)	0.0080 (8)	0.0037 (9)

Geometric parameters (Å, º)

Zn1—S1	2.3635 (6)	C1—H1C	0.9600
Zn1—S2	2.3718 (6)	C3—C4	1.491 (3)
Zn1—N3	2.1218 (18)	C3—C5	1.482 (3)
Zn1—N4	2.1241 (17)	C4—H4A	0.9600
Zn1—N7	2.0900 (18)	C4—H4B	0.9600
S1—C2	1.760 (2)	C4—H4C	0.9600
S2—C7	1.738 (2)	C5—C6	1.495 (3)
N1—H1	0.8600	C6—H6A	0.9600
N1—C1	1.450 (3)	C6—H6B	0.9600
N1—C2	1.347 (3)	C6—H6C	0.9600
N2—N3	1.372 (3)	C8—H8A	0.9600
N2—C2	1.321 (3)	C8—H8B	0.9600
N3—C3	1.294 (3)	C8—H8C	0.9600
N4—N5	1.369 (2)	C9—H9	0.9300
N4—C5	1.288 (3)	C9—C10	1.385 (3)
N5—C7	1.337 (3)	C10—H10	0.9300
N6—H6	0.8600	C10—C11	1.385 (4)
N6—C7	1.344 (3)	C11—H11	0.9300
N6—C8	1.452 (3)	C11—C12	1.379 (4)
N7—C9	1.341 (3)	C12—H12	0.9300
N7—C13	1.341 (3)	C12—C13	1.382 (3)
C1—H1A	0.9600	C13—H13	0.9300
C1—H1B	0.9600
S1—Zn1—S2	113.40 (2)	C5—C3—C4	120.98 (18)
N3—Zn1—S1	80.75 (5)	C3—C4—H4A	109.5
N3—Zn1—S2	144.85 (5)	C3—C4—H4B	109.5
N3—Zn1—N4	74.45 (7)	C3—C4—H4C	109.5
N4—Zn1—S1	150.39 (5)	H4A—C4—H4B	109.5
N4—Zn1—S2	80.36 (5)	H4A—C4—H4C	109.5
N7—Zn1—S1	102.52 (5)	H4B—C4—H4C	109.5
N7—Zn1—S2	101.09 (5)	N4—C5—C3	114.89 (18)
N7—Zn1—N3	107.07 (7)	N4—C5—C6	124.51 (19)
N7—Zn1—N4	100.05 (7)	C3—C5—C6	120.51 (18)
C2—S1—Zn1	95.38 (7)	C5—C6—H6A	109.5
C7—S2—Zn1	94.57 (7)	C5—C6—H6B	109.5
C1—N1—H1	118.4	C5—C6—H6C	109.5
C2—N1—H1	118.4	H6A—C6—H6B	109.5
C2—N1—C1	123.16 (19)	H6A—C6—H6C	109.5
C2—N2—N3	111.67 (18)	H6B—C6—H6C	109.5
N2—N3—Zn1	123.07 (13)	N5—C7—S2	127.03 (16)
C3—N3—Zn1	117.35 (14)	N5—C7—N6	114.16 (19)
C3—N3—N2	119.53 (18)	N6—C7—S2	118.75 (17)
N5—N4—Zn1	120.87 (13)	N6—C8—H8A	109.5
C5—N4—Zn1	117.43 (14)	N6—C8—H8B	109.5
C5—N4—N5	121.53 (18)	N6—C8—H8C	109.5
C7—N5—N4	112.29 (17)	H8A—C8—H8B	109.5
C7—N6—H6	117.1	H8A—C8—H8C	109.5
C7—N6—C8	125.71 (19)	H8B—C8—H8C	109.5
C8—N6—H6	117.1	N7—C9—H9	118.5
C9—N7—Zn1	118.66 (15)	N7—C9—C10	122.9 (2)
C13—N7—Zn1	123.45 (15)	C10—C9—H9	118.5
C13—N7—C9	117.86 (19)	C9—C10—H10	120.8
N1—C1—H1A	109.5	C11—C10—C9	118.4 (2)
N1—C1—H1B	109.5	C11—C10—H10	120.8
N1—C1—H1C	109.5	C10—C11—H11	120.4
H1A—C1—H1B	109.5	C12—C11—C10	119.1 (2)
H1A—C1—H1C	109.5	C12—C11—H11	120.4
H1B—C1—H1C	109.5	C11—C12—H12	120.6
N1—C2—S1	114.89 (16)	C11—C12—C13	118.9 (2)
N2—C2—S1	127.89 (17)	C13—C12—H12	120.6
N2—C2—N1	117.2 (2)	N7—C13—C12	122.8 (2)
N3—C3—C4	124.0 (2)	N7—C13—H13	118.6
N3—C3—C5	114.89 (18)	C12—C13—H13	118.6
Zn1—S1—C2—N1	173.89 (15)	N4—N5—C7—N6	178.74 (18)
Zn1—S1—C2—N2	−7.9 (2)	N5—N4—C5—C3	−176.54 (18)
Zn1—S2—C7—N5	17.1 (2)	N5—N4—C5—C6	−0.1 (3)
Zn1—S2—C7—N6	−165.88 (16)	N7—C9—C10—C11	−0.1 (4)
Zn1—N3—C3—C4	177.10 (18)	C1—N1—C2—S1	−179.04 (17)
Zn1—N3—C3—C5	−6.8 (2)	C1—N1—C2—N2	2.6 (3)
Zn1—N4—N5—C7	−15.4 (2)	C2—N2—N3—Zn1	8.8 (2)
Zn1—N4—C5—C3	8.2 (2)	C2—N2—N3—C3	−174.17 (19)
Zn1—N4—C5—C6	−175.37 (16)	C4—C3—C5—N4	175.3 (2)
Zn1—N7—C9—C10	−178.02 (18)	C4—C3—C5—C6	−1.3 (3)
Zn1—N7—C13—C12	178.17 (17)	C5—N4—N5—C7	169.43 (19)
N2—N3—C3—C4	−0.1 (3)	C8—N6—C7—S2	7.9 (3)
N2—N3—C3—C5	175.95 (18)	C8—N6—C7—N5	−174.7 (2)
N3—N2—C2—S1	1.0 (3)	C9—N7—C13—C12	0.2 (3)
N3—N2—C2—N1	179.17 (18)	C9—C10—C11—C12	0.0 (4)
N3—C3—C5—N4	−0.9 (3)	C10—C11—C12—C13	0.2 (3)
N3—C3—C5—C6	−177.50 (19)	C11—C12—C13—N7	−0.4 (3)
N4—N5—C7—S2	−4.1 (3)	C13—N7—C9—C10	0.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N5^i	0.86	2.21	2.988 (3)	150
N6—H6···S1^ii	0.86	2.65	3.500 (2)	167

Symmetry codes: (i) x+1/2, −y+3/2, z−1/2; (ii) x−3/2, −y+1/2, z−1/2.