(5-Methoxy-2-oxidoacetophenone 4-methyl­thio­semicarbazonato-κ³O,N,S)pyridinenickel(II)

In the title compound, [Ni(C₁₁H₁₃N₃O₂S)(C₅H₅N)], the Ni^II ion is in a distorted square-planar geometry, with the C₁₁H₁₃N₃O₂S ligand coordinated in a dianionic tridentate fashion; the pyridine mol­ecule occupies the fourth position. The mol­ecules are linked by N—H...S inter­actions about an inversion center.

Key indicators

• Single-crystal X-ray study
• T = 291 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.047
• wR factor = 0.083
• Data-to-parameter ratio = 17.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       3.90
PLAT230_ALERT_2_C Hirshfeld Test Diff for    O2     -   C10     ..       5.10 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C1     -   C2      ..       5.37 su
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         S1
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         O1
PLAT731_ALERT_1_C Bond    Calc     0.85(3), Rep   0.849(10) ......       3.00 su-Ra
              N3   -H3A     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.85(3), Rep   0.849(10) ......       3.00 su-Ra
              N3   -H3A     1.555   1.555
PLAT736_ALERT_1_C H...A   Calc     2.73(3), Rep   2.728(11) ......       2.73 su-Ra
              H3A  -S1      1.555   3.666

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

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   5 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, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: enCIFer (Allen et al., 2004).

Pyridine(2-hydroxy-5-methoxy-1-benzaldehyde 4-methylthiosemicarbazonato-κ³S,N,O)nickel(II)

Crystal data

[Ni(C11H13N3O2S)(C5H5N)]	F(000) = 808
Mr = 389.11	Dx = 1.499 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4130 reflections
a = 13.9017 (12) Å	θ = 3.0–31.0°
b = 6.2419 (6) Å	µ = 1.26 mm^−1
c = 20.3533 (18) Å	T = 291 K
β = 102.453 (2)°	Prism, red
V = 1724.6 (3) Å^3	0.40 × 0.12 × 0.08 mm
Z = 4

Data collection

Bruker Smart Apex AXS CCD area-detector diffractometer	3952 independent reflections
Radiation source: fine-focus sealed tube	2311 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.049
ω scans	θmax = 27.5°, θmin = 2.1°
Absorption correction: analytical (Program??; Sheldrick, 1997b)	h = −18→18
Tmin = 0.691, Tmax = 0.909	k = −8→8
16339 measured reflections	l = −26→26

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.083	H atoms treated by a mixture of independent and constrained refinement
S = 0.88	w = 1/[σ^2(Fo^2) + (0.030P)^2] where P = (Fo^2 + 2Fc^2)/3
3952 reflections	(Δ/σ)max = 0.001
223 parameters	Δρmax = 0.78 e Å^−3
1 restraint	Δρmin = −0.20 e Å^−3

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
Ni1	0.19550 (3)	0.52512 (6)	0.410017 (18)	0.05214 (14)
S1	0.34866 (5)	0.50869 (14)	0.45760 (4)	0.0718 (3)
O1	0.06574 (15)	0.5604 (3)	0.37123 (10)	0.0753 (7)
O2	−0.18666 (14)	0.1333 (3)	0.17074 (10)	0.0672 (6)
N1	0.21494 (16)	0.2948 (3)	0.35568 (10)	0.0476 (6)
N2	0.30834 (16)	0.1989 (4)	0.36543 (11)	0.0519 (6)
N3	0.46598 (19)	0.2086 (5)	0.42599 (14)	0.0732 (8)
H3A	0.5076 (18)	0.268 (5)	0.4575 (11)	0.088*
N4	0.17554 (16)	0.7409 (4)	0.47298 (11)	0.0501 (6)
C1	0.0471 (2)	0.2734 (4)	0.29139 (13)	0.0471 (7)
C2	0.0134 (2)	0.4517 (5)	0.32146 (14)	0.0579 (8)
C3	−0.0854 (2)	0.5161 (5)	0.29809 (16)	0.0714 (9)
H3	−0.1082	0.6365	0.3170	0.086*
C4	−0.1480 (2)	0.4081 (5)	0.24906 (15)	0.0641 (9)
H4	−0.2127	0.4550	0.2349	0.077*
C5	−0.1168 (2)	0.2302 (5)	0.22004 (14)	0.0519 (7)
C6	−0.0213 (2)	0.1642 (5)	0.24041 (13)	0.0515 (7)
H6	−0.0005	0.0441	0.2203	0.062*
C7	0.1481 (2)	0.1970 (5)	0.31010 (14)	0.0502 (7)
C8	0.3736 (2)	0.2902 (5)	0.41155 (14)	0.0559 (8)
C9	0.1769 (2)	0.0042 (5)	0.27495 (16)	0.0793 (10)
H9A	0.2474	−0.0095	0.2852	0.095*
H9B	0.1537	0.0202	0.2273	0.095*
H9C	0.1482	−0.1216	0.2899	0.095*
C10	−0.1604 (2)	−0.0588 (5)	0.14449 (17)	0.0843 (11)
H10A	−0.1061	−0.0344	0.1232	0.101*
H10B	−0.2155	−0.1133	0.1120	0.101*
H10C	−0.1415	−0.1610	0.1802	0.101*
C11	0.2260 (2)	0.9224 (5)	0.48522 (16)	0.0679 (9)
H11	0.2736	0.9528	0.4607	0.082*
C12	0.2108 (3)	1.0647 (6)	0.5321 (2)	0.0905 (12)
H12	0.2482	1.1894	0.5397	0.109*
C13	0.1411 (3)	1.0257 (7)	0.56812 (18)	0.0881 (12)
H13	0.1296	1.1230	0.6001	0.106*
C14	0.0887 (3)	0.8408 (7)	0.55624 (17)	0.0804 (10)
H14	0.0404	0.8090	0.5801	0.096*
C15	0.1078 (2)	0.7029 (5)	0.50888 (16)	0.0648 (9)
H15	0.0718	0.5763	0.5012	0.078*
C16	0.4937 (2)	0.0253 (5)	0.39101 (17)	0.0786 (10)
H16A	0.4565	−0.0974	0.3995	0.094*
H16B	0.5627	−0.0026	0.4067	0.094*
H16C	0.4802	0.0540	0.3436	0.094*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0458 (2)	0.0603 (3)	0.0491 (2)	−0.0048 (2)	0.00760 (16)	−0.0099 (2)
S1	0.0447 (5)	0.0904 (7)	0.0781 (6)	−0.0091 (4)	0.0081 (4)	−0.0338 (5)
O1	0.0610 (14)	0.0843 (16)	0.0699 (14)	0.0170 (11)	−0.0094 (11)	−0.0344 (12)
O2	0.0482 (13)	0.0769 (15)	0.0683 (14)	−0.0074 (11)	−0.0055 (11)	−0.0131 (12)
N1	0.0424 (14)	0.0557 (15)	0.0444 (14)	−0.0015 (12)	0.0084 (11)	−0.0003 (12)
N2	0.0405 (15)	0.0639 (16)	0.0505 (15)	−0.0020 (12)	0.0084 (12)	−0.0058 (13)
N3	0.0399 (17)	0.096 (2)	0.080 (2)	−0.0027 (15)	0.0044 (14)	−0.0295 (18)
N4	0.0473 (15)	0.0553 (16)	0.0464 (14)	−0.0051 (12)	0.0072 (12)	−0.0048 (12)
C1	0.0477 (18)	0.0526 (18)	0.0397 (16)	0.0006 (14)	0.0064 (13)	−0.0067 (14)
C2	0.0494 (19)	0.070 (2)	0.0514 (18)	0.0004 (16)	0.0054 (15)	−0.0081 (17)
C3	0.062 (2)	0.079 (2)	0.068 (2)	0.0193 (18)	0.0022 (17)	−0.0238 (19)
C4	0.0431 (19)	0.089 (2)	0.057 (2)	0.0090 (17)	0.0018 (15)	−0.0082 (18)
C5	0.0468 (19)	0.063 (2)	0.0437 (17)	−0.0067 (16)	0.0060 (14)	−0.0004 (16)
C6	0.0500 (19)	0.0554 (18)	0.0492 (17)	−0.0047 (15)	0.0108 (14)	−0.0057 (15)
C7	0.0485 (19)	0.0551 (18)	0.0459 (17)	−0.0002 (15)	0.0076 (14)	−0.0042 (15)
C8	0.0426 (19)	0.069 (2)	0.0584 (19)	−0.0047 (15)	0.0153 (15)	−0.0034 (17)
C9	0.058 (2)	0.083 (2)	0.087 (2)	0.0068 (18)	−0.0055 (17)	−0.036 (2)
C10	0.072 (2)	0.091 (3)	0.077 (2)	−0.011 (2)	−0.0110 (19)	−0.020 (2)
C11	0.080 (3)	0.056 (2)	0.071 (2)	−0.0141 (18)	0.0233 (19)	−0.0036 (18)
C12	0.105 (3)	0.058 (2)	0.101 (3)	−0.006 (2)	0.008 (3)	−0.024 (2)
C13	0.101 (3)	0.091 (3)	0.069 (2)	0.027 (3)	0.011 (2)	−0.029 (2)
C14	0.073 (3)	0.107 (3)	0.067 (2)	0.016 (2)	0.026 (2)	−0.005 (2)
C15	0.054 (2)	0.072 (2)	0.070 (2)	−0.0073 (17)	0.0158 (17)	−0.0107 (19)
C16	0.053 (2)	0.087 (3)	0.096 (3)	0.0024 (19)	0.0156 (18)	−0.015 (2)

Geometric parameters (Å, º)

Ni1—O1	1.820 (2)	C4—H4	0.9300
Ni1—N1	1.869 (2)	C5—C6	1.366 (4)
Ni1—N4	1.920 (2)	C6—H6	0.9300
Ni1—S1	2.1429 (8)	C7—C9	1.498 (4)
S1—C8	1.731 (3)	C9—H9A	0.9600
O1—C2	1.303 (3)	C9—H9B	0.9600
O2—C5	1.377 (3)	C9—H9C	0.9600
O2—C10	1.393 (3)	C10—H10A	0.9600
N1—C7	1.313 (3)	C10—H10B	0.9600
N1—N2	1.404 (3)	C10—H10C	0.9600
N2—C8	1.289 (3)	C11—C12	1.353 (4)
N3—C8	1.354 (4)	C11—H11	0.9300
N3—C16	1.443 (4)	C12—C13	1.357 (5)
N3—H3A	0.849 (10)	C12—H12	0.9300
N4—C11	1.327 (3)	C13—C14	1.359 (5)
N4—C15	1.332 (3)	C13—H13	0.9300
C1—C2	1.399 (4)	C14—C15	1.360 (4)
C1—C6	1.421 (3)	C14—H14	0.9300
C1—C7	1.454 (4)	C15—H15	0.9300
C2—C3	1.412 (4)	C16—H16A	0.9600
C3—C4	1.354 (4)	C16—H16B	0.9600
C3—H3	0.9300	C16—H16C	0.9600
C4—C5	1.372 (4)
O1—Ni1—N1	95.32 (9)	N1—C7—C9	119.3 (3)
O1—Ni1—N4	86.12 (9)	C1—C7—C9	118.7 (2)
N1—Ni1—N4	174.18 (9)	N2—C8—N3	118.5 (3)
O1—Ni1—S1	175.69 (7)	N2—C8—S1	123.4 (2)
N1—Ni1—S1	88.52 (7)	N3—C8—S1	118.0 (2)
N4—Ni1—S1	90.25 (7)	C7—C9—H9A	109.5
C8—S1—Ni1	95.07 (10)	C7—C9—H9B	109.5
C2—O1—Ni1	127.56 (19)	H9A—C9—H9B	109.5
C5—O2—C10	117.1 (2)	C7—C9—H9C	109.5
C7—N1—N2	113.2 (2)	H9A—C9—H9C	109.5
C7—N1—Ni1	127.2 (2)	H9B—C9—H9C	109.5
N2—N1—Ni1	119.44 (17)	O2—C10—H10A	109.5
C8—N2—N1	113.5 (2)	O2—C10—H10B	109.5
C8—N3—C16	122.2 (3)	H10A—C10—H10B	109.5
C8—N3—H3A	117 (2)	O2—C10—H10C	109.5
C16—N3—H3A	120 (2)	H10A—C10—H10C	109.5
C11—N4—C15	117.2 (3)	H10B—C10—H10C	109.5
C11—N4—Ni1	125.2 (2)	N4—C11—C12	122.4 (3)
C15—N4—Ni1	117.5 (2)	N4—C11—H11	118.8
C2—C1—C6	117.8 (3)	C12—C11—H11	118.8
C2—C1—C7	122.8 (2)	C11—C12—C13	120.1 (4)
C6—C1—C7	119.4 (3)	C11—C12—H12	120.0
O1—C2—C1	124.8 (3)	C13—C12—H12	120.0
O1—C2—C3	117.0 (3)	C12—C13—C14	118.3 (3)
C1—C2—C3	118.2 (3)	C12—C13—H13	120.8
C4—C3—C2	122.0 (3)	C14—C13—H13	120.8
C4—C3—H3	119.0	C13—C14—C15	118.9 (3)
C2—C3—H3	119.0	C13—C14—H14	120.5
C3—C4—C5	120.5 (3)	C15—C14—H14	120.5
C3—C4—H4	119.7	N4—C15—C14	123.1 (3)
C5—C4—H4	119.7	N4—C15—H15	118.5
C6—C5—C4	119.4 (3)	C14—C15—H15	118.5
C6—C5—O2	125.1 (3)	N3—C16—H16A	109.5
C4—C5—O2	115.5 (3)	N3—C16—H16B	109.5
C5—C6—C1	122.0 (3)	H16A—C16—H16B	109.5
C5—C6—H6	119.0	N3—C16—H16C	109.5
C1—C6—H6	119.0	H16A—C16—H16C	109.5
N1—C7—C1	121.9 (3)	H16B—C16—H16C	109.5
N1—Ni1—S1—C8	−1.65 (12)	C4—C5—C6—C1	0.5 (4)
N4—Ni1—S1—C8	172.66 (12)	O2—C5—C6—C1	179.5 (2)
N1—Ni1—O1—C2	−1.1 (3)	C2—C1—C6—C5	0.9 (4)
N4—Ni1—O1—C2	−175.4 (3)	C7—C1—C6—C5	−179.1 (3)
O1—Ni1—N1—C7	−4.4 (2)	N2—N1—C7—C1	−178.7 (2)
S1—Ni1—N1—C7	177.6 (2)	Ni1—N1—C7—C1	6.0 (4)
O1—Ni1—N1—N2	−179.52 (18)	N2—N1—C7—C9	−0.2 (4)
S1—Ni1—N1—N2	2.44 (17)	Ni1—N1—C7—C9	−175.6 (2)
C7—N1—N2—C8	−178.0 (2)	C2—C1—C7—N1	−1.6 (4)
Ni1—N1—N2—C8	−2.2 (3)	C6—C1—C7—N1	178.3 (2)
O1—Ni1—N4—C11	−123.7 (2)	C2—C1—C7—C9	179.9 (3)
S1—Ni1—N4—C11	54.0 (2)	C6—C1—C7—C9	−0.1 (4)
O1—Ni1—N4—C15	58.5 (2)	N1—N2—C8—N3	178.9 (2)
S1—Ni1—N4—C15	−123.8 (2)	N1—N2—C8—S1	0.5 (3)
Ni1—O1—C2—C1	5.0 (4)	C16—N3—C8—N2	0.7 (5)
Ni1—O1—C2—C3	−177.1 (2)	C16—N3—C8—S1	179.2 (2)
C6—C1—C2—O1	176.0 (3)	Ni1—S1—C8—N2	1.1 (3)
C7—C1—C2—O1	−4.0 (5)	Ni1—S1—C8—N3	−177.3 (2)
C6—C1—C2—C3	−1.8 (4)	C15—N4—C11—C12	0.3 (5)
C7—C1—C2—C3	178.1 (3)	Ni1—N4—C11—C12	−177.5 (3)
O1—C2—C3—C4	−176.5 (3)	N4—C11—C12—C13	−0.8 (6)
C1—C2—C3—C4	1.5 (5)	C11—C12—C13—C14	0.7 (6)
C2—C3—C4—C5	−0.1 (5)	C12—C13—C14—C15	−0.1 (6)
C3—C4—C5—C6	−0.9 (5)	C11—N4—C15—C14	0.3 (4)
C3—C4—C5—O2	−180.0 (3)	Ni1—N4—C15—C14	178.3 (2)
C10—O2—C5—C6	6.7 (4)	C13—C14—C15—N4	−0.4 (5)
C10—O2—C5—C4	−174.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···S1^i	0.85 (1)	2.73 (1)	3.569 (3)	171 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.