Bis­(pyridine-2-carb­aldehyde thio­semicarbazonato)­cobalt(III) perchlorate

In the crystal structure of the title complex, [Co(C₇H₇N₄S₂)₂]ClO₄, which was synthesized solvothermally from cobalt diperchlorate and pyridine-2-carb­aldehyde thio­semicarbazone, the two planar thio­semicarbazone ligands are aligned perpendicular to each other. The Co atom is octahedrally coordinated by the S, imino N and pyridinyl N atoms of each ligand. The cation interacts with the perchlorate counterion via hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.035
• wR factor = 0.092
• Data-to-parameter ratio = 13.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT031_ALERT_4_C Refined Extinction Parameter within Range ......       3.22 Sigma
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT244_ALERT_4_C Low Solvent  U(eq) as Compared to Neighbors ....         Cl
PLAT432_ALERT_2_C Short Inter X...Y Contact  O1     ..  C1      ..       3.00 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H6     ..  S2      ..       2.89 Ang.
PLAT731_ALERT_1_C Bond    Calc     0.86(3), Rep   0.863(10) ......       3.00 su-Rat
              N4   -H4A     1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.87(3), Rep   0.862(10) ......       3.00 su-Rat
              N8   -H8B     1.555   1.555
PLAT745_ALERT_1_C D-H     Calc     0.86(2), Rep     0.86000 ......    Missing su
              N4   -H4B     1.555   1.555
PLAT745_ALERT_1_C D-H     Calc     0.86(3), Rep     0.86000 ......    Missing su
              N4   -H4A     1.555   1.555
PLAT745_ALERT_1_C D-H     Calc   0.855(15), Rep     0.86000 ......    Missing su
              N8   -H8A     1.555   1.555
PLAT746_ALERT_1_C H...A   Calc     2.11(2), Rep     2.11000 ......    Missing su
              H4B  -N3      1.555   2.766
PLAT746_ALERT_1_C H...A   Calc     2.24(3), Rep     2.24000 ......    Missing su
              H4A  -O4      1.555   1.655
PLAT746_ALERT_1_C H...A   Calc   2.168(16), Rep     2.17000 ......    Missing su
              H8A  -O1      1.555   2.677

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

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

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Computing details

Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1994); software used to prepare material for publication: SHELXTL.

(I)

Crystal data

[Co(C7H7N4S2)2]ClO4	Z = 2
Mr = 516.83	F(000) = 524
Triclinic, P1	Dx = 1.689 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.568 (1) Å	Cell parameters from 30 reflections
b = 10.352 (1) Å	θ = 3.6–14.4°
c = 12.440 (2) Å	µ = 1.22 mm^−1
α = 103.73 (1)°	T = 296 K
β = 102.42 (1)°	Block, red
γ = 100.16 (1)°	0.30 × 0.26 × 0.20 mm
V = 1016.3 (3) Å^3

Data collection

Siemens P4 diffractometer	2937 reflections with I > 2σ(I)
Radiation source: normal-focus sealed tube	Rint = 0.015
Graphite monochromator	θmax = 25.5°, θmin = 1.8°
ω scans	h = 0→10
Absorption correction: empirical (using intensity measurements) via ψ scan (North et al., 1968)	k = −11→11
Tmin = 0.690, Tmax = 0.783	l = −15→14
4144 measured reflections	3 standard reflections every 97 reflections
3735 independent reflections	intensity decay: 3.5%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.035	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.092	w = 1/[σ^2(Fo^2) + (0.0507P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
3735 reflections	Δρmax = 0.77 e Å^−3
288 parameters	Δρmin = −0.53 e Å^−3
4 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0029 (9)

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

	x	y	z	Uiso*/Ueq
Co	0.68779 (5)	0.46030 (4)	0.76128 (3)	0.02765 (13)
S1	0.95285 (10)	0.56451 (9)	0.81132 (6)	0.0407 (2)
S2	0.61861 (11)	0.65927 (8)	0.77203 (6)	0.0391 (2)
N1	0.4574 (3)	0.3644 (2)	0.68615 (19)	0.0293 (5)
N2	0.7029 (3)	0.4277 (2)	0.60847 (19)	0.0315 (5)
N3	0.8455 (3)	0.4674 (3)	0.5800 (2)	0.0361 (6)
N4	1.1143 (4)	0.5859 (3)	0.6557 (3)	0.0475 (7)
N5	0.7388 (3)	0.2886 (2)	0.7824 (2)	0.0329 (6)
N6	0.6828 (3)	0.4930 (2)	0.91582 (18)	0.0290 (5)
N7	0.6536 (3)	0.6090 (3)	0.97911 (19)	0.0355 (6)
N8	0.5939 (4)	0.8122 (3)	0.9673 (3)	0.0547 (8)
C1	0.3340 (4)	0.3375 (3)	0.7336 (3)	0.0364 (7)
H1	0.3554	0.3627	0.8132	0.044*
C2	0.1765 (4)	0.2735 (4)	0.6676 (3)	0.0477 (8)
H2	0.0929	0.2556	0.7028	0.057*
C3	0.1420 (4)	0.2357 (4)	0.5499 (3)	0.0499 (9)
H3	0.0355	0.1922	0.5046	0.060*
C4	0.2683 (4)	0.2636 (3)	0.5000 (3)	0.0440 (8)
H4	0.2479	0.2403	0.4205	0.053*
C5	0.4256 (4)	0.3264 (3)	0.5696 (2)	0.0340 (7)
C6	0.5693 (4)	0.3625 (3)	0.5289 (2)	0.0368 (7)
H6	0.5654	0.3404	0.4513	0.044*
C7	0.9689 (4)	0.5370 (3)	0.6716 (3)	0.0360 (7)
C8	0.7643 (4)	0.1846 (3)	0.7071 (3)	0.0431 (8)
H8	0.7529	0.1868	0.6315	0.052*
C9	0.8072 (5)	0.0739 (4)	0.7382 (4)	0.0594 (10)
H9	0.8269	0.0036	0.6846	0.071*
C10	0.8207 (5)	0.0675 (4)	0.8487 (4)	0.0601 (10)
H10	0.8502	−0.0066	0.8706	0.072*
C11	0.7899 (4)	0.1727 (3)	0.9272 (3)	0.0492 (9)
H11	0.7968	0.1700	1.0022	0.059*
C12	0.7486 (4)	0.2824 (3)	0.8914 (3)	0.0353 (7)
C13	0.7147 (4)	0.3990 (3)	0.9636 (2)	0.0343 (7)
H13	0.7156	0.4064	1.0398	0.041*
C14	0.6228 (4)	0.6931 (3)	0.9163 (2)	0.0355 (7)
Cl	0.29258 (12)	0.94574 (9)	0.73021 (8)	0.0559 (3)
O1	0.3974 (4)	1.0790 (3)	0.7832 (3)	0.0771 (9)
O2	0.1282 (4)	0.9484 (4)	0.7168 (4)	0.1216 (15)
O3	0.3106 (6)	0.8861 (5)	0.6251 (4)	0.154 (2)
O4	0.3295 (5)	0.8620 (4)	0.8041 (4)	0.1254 (16)
H4A	1.185 (3)	0.646 (3)	0.7142 (19)	0.053 (11)*
H4B	1.124 (5)	0.579 (4)	0.5874 (16)	0.088 (15)*
H8A	0.598 (4)	0.838 (3)	1.0386 (11)	0.044 (10)*
H8B	0.550 (4)	0.860 (3)	0.926 (2)	0.050 (11)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co	0.0300 (2)	0.0314 (2)	0.0208 (2)	0.00657 (16)	0.00929 (15)	0.00454 (15)
S1	0.0342 (4)	0.0514 (5)	0.0286 (4)	−0.0012 (4)	0.0096 (3)	0.0043 (3)
S2	0.0574 (5)	0.0362 (4)	0.0262 (4)	0.0156 (4)	0.0117 (3)	0.0098 (3)
N1	0.0322 (13)	0.0308 (13)	0.0250 (11)	0.0090 (11)	0.0091 (10)	0.0058 (10)
N2	0.0366 (14)	0.0338 (13)	0.0229 (11)	0.0065 (11)	0.0127 (11)	0.0033 (10)
N3	0.0379 (14)	0.0412 (15)	0.0291 (13)	0.0027 (12)	0.0179 (11)	0.0064 (11)
N4	0.0424 (17)	0.0529 (19)	0.0399 (16)	−0.0046 (14)	0.0180 (14)	0.0051 (15)
N5	0.0286 (13)	0.0321 (14)	0.0354 (13)	0.0056 (11)	0.0101 (11)	0.0047 (11)
N6	0.0284 (12)	0.0346 (14)	0.0224 (11)	0.0067 (11)	0.0063 (10)	0.0063 (10)
N7	0.0487 (16)	0.0359 (14)	0.0245 (12)	0.0143 (12)	0.0153 (11)	0.0055 (11)
N8	0.086 (2)	0.0433 (18)	0.0387 (17)	0.0298 (17)	0.0191 (17)	0.0070 (14)
C1	0.0353 (17)	0.0408 (18)	0.0360 (16)	0.0101 (14)	0.0149 (14)	0.0110 (14)
C2	0.0337 (18)	0.055 (2)	0.058 (2)	0.0085 (16)	0.0172 (16)	0.0192 (18)
C3	0.0340 (18)	0.050 (2)	0.054 (2)	0.0006 (16)	−0.0011 (16)	0.0099 (17)
C4	0.0430 (19)	0.0444 (19)	0.0337 (16)	0.0054 (16)	0.0005 (14)	0.0034 (14)
C5	0.0384 (17)	0.0333 (16)	0.0257 (14)	0.0070 (13)	0.0060 (13)	0.0035 (12)
C6	0.0447 (18)	0.0404 (17)	0.0224 (14)	0.0086 (15)	0.0115 (13)	0.0029 (13)
C7	0.0388 (17)	0.0361 (17)	0.0371 (16)	0.0080 (14)	0.0200 (14)	0.0102 (14)
C8	0.0440 (19)	0.0378 (18)	0.0476 (19)	0.0106 (15)	0.0197 (16)	0.0049 (15)
C9	0.061 (2)	0.035 (2)	0.082 (3)	0.0161 (18)	0.029 (2)	0.0025 (19)
C10	0.064 (3)	0.044 (2)	0.079 (3)	0.0234 (19)	0.018 (2)	0.022 (2)
C11	0.050 (2)	0.042 (2)	0.055 (2)	0.0111 (16)	0.0066 (17)	0.0203 (17)
C12	0.0303 (16)	0.0366 (17)	0.0388 (16)	0.0086 (13)	0.0062 (13)	0.0127 (14)
C13	0.0358 (17)	0.0414 (18)	0.0279 (14)	0.0107 (14)	0.0083 (13)	0.0131 (13)
C14	0.0392 (17)	0.0348 (17)	0.0300 (15)	0.0094 (14)	0.0106 (13)	0.0031 (13)
Cl	0.0549 (6)	0.0403 (5)	0.0579 (6)	0.0161 (4)	−0.0021 (4)	−0.0008 (4)
O1	0.086 (2)	0.0473 (16)	0.076 (2)	−0.0029 (15)	0.0116 (16)	−0.0004 (14)
O2	0.058 (2)	0.115 (3)	0.176 (4)	0.033 (2)	0.006 (2)	0.027 (3)
O3	0.175 (5)	0.145 (4)	0.100 (3)	0.005 (3)	0.062 (3)	−0.043 (3)
O4	0.120 (3)	0.078 (2)	0.143 (3)	0.009 (2)	−0.048 (3)	0.050 (2)

Geometric parameters (Å, º)

Co—N1	1.957 (2)	C1—C2	1.373 (4)
Co—N2	1.887 (2)	C1—H1	0.9300
Co—N5	1.966 (2)	C2—C3	1.374 (5)
Co—N6	1.883 (2)	C2—H2	0.9300
Co—S1	2.2176 (10)	C3—C4	1.379 (5)
Co—S2	2.2239 (10)	C3—H3	0.9300
N1—C1	1.336 (4)	C4—C5	1.382 (4)
N1—C5	1.362 (3)	C4—H4	0.9300
N2—C6	1.292 (4)	C5—C6	1.451 (4)
N6—C13	1.294 (4)	C6—H6	0.9300
S2—C14	1.736 (3)	C8—C9	1.377 (5)
S1—C7	1.733 (3)	C8—H8	0.9300
N2—N3	1.366 (3)	C9—C10	1.373 (5)
N3—C7	1.326 (4)	C9—H9	0.9300
N4—C7	1.334 (4)	C10—C11	1.384 (5)
N4—H4A	0.863 (10)	C10—H10	0.9300
N4—H4B	0.858 (10)	C11—C12	1.389 (4)
N5—C8	1.334 (4)	C11—H11	0.9300
N5—C12	1.357 (4)	C12—C13	1.439 (4)
N6—N7	1.366 (3)	C13—H13	0.9300
N7—C14	1.324 (4)	Cl—O3	1.360 (4)
N8—C14	1.337 (4)	Cl—O2	1.388 (3)
N8—H8A	0.857 (10)	Cl—O1	1.422 (3)
N8—H8B	0.862 (10)	Cl—O4	1.431 (3)
N1—Co—N2	82.90 (10)	C2—C3—C4	118.7 (3)
N1—Co—N5	90.29 (10)	C2—C3—H3	120.7
N1—Co—N6	99.41 (10)	C4—C3—H3	120.7
N1—Co—S1	168.68 (7)	C3—C4—C5	119.3 (3)
N1—Co—S2	89.46 (7)	C3—C4—H4	120.4
N2—Co—N5	95.99 (10)	C5—C4—H4	120.4
N2—Co—N6	177.43 (10)	N1—C5—C4	121.2 (3)
N2—Co—S1	85.81 (8)	N1—C5—C6	113.6 (3)
N2—Co—S2	95.66 (8)	C4—C5—C6	125.1 (3)
N5—Co—N6	82.91 (10)	N2—C6—C5	115.1 (2)
N5—Co—S1	91.64 (7)	N2—C6—H6	122.4
N5—Co—S2	168.23 (7)	C5—C6—H6	122.4
N6—Co—S1	91.89 (7)	N3—C7—N4	118.4 (3)
N6—Co—S2	85.52 (8)	N3—C7—S1	123.5 (2)
S1—Co—S2	90.90 (4)	N4—C7—S1	118.1 (2)
C7—S1—Co	94.90 (11)	N5—C8—C9	121.7 (3)
C14—S2—Co	94.50 (11)	N5—C8—H8	119.2
C1—N1—C5	119.0 (3)	C9—C8—H8	119.2
C1—N1—Co	129.0 (2)	C10—C9—C8	119.8 (3)
C5—N1—Co	112.00 (19)	C10—C9—H9	120.1
C6—N2—N3	120.1 (2)	C8—C9—H9	120.1
C6—N2—Co	116.4 (2)	C9—C10—C11	119.2 (3)
N3—N2—Co	123.53 (18)	C9—C10—H10	120.4
C7—N3—N2	112.1 (2)	C11—C10—H10	120.4
C7—N4—H4A	116 (2)	C10—C11—C12	118.5 (3)
C7—N4—H4B	120 (3)	C10—C11—H11	120.7
H4A—N4—H4B	121 (4)	C12—C11—H11	120.7
C8—N5—C12	119.1 (3)	N5—C12—C11	121.6 (3)
C8—N5—Co	129.3 (2)	N5—C12—C13	113.8 (3)
C12—N5—Co	111.59 (19)	C11—C12—C13	124.6 (3)
C13—N6—N7	119.5 (2)	N6—C13—C12	115.7 (3)
C13—N6—Co	116.0 (2)	N6—C13—H13	122.2
N7—N6—Co	124.45 (18)	C12—C13—H13	122.2
C14—N7—N6	111.2 (2)	N7—C14—N8	118.0 (3)
C14—N8—H8A	124 (2)	N7—C14—S2	124.2 (2)
C14—N8—H8B	120 (2)	N8—C14—S2	117.7 (2)
H8A—N8—H8B	115 (3)	O3—Cl—O2	107.8 (3)
N1—C1—C2	121.6 (3)	O3—Cl—O1	113.1 (3)
N1—C1—H1	119.2	O2—Cl—O1	111.3 (2)
C2—C1—H1	119.2	O3—Cl—O4	109.0 (3)
C1—C2—C3	120.2 (3)	O2—Cl—O4	107.3 (3)
C1—C2—H2	119.9	O1—Cl—O4	108.2 (2)
C3—C2—H2	119.9
N6—Co—S1—C7	179.34 (13)	N1—Co—N6—N7	−92.0 (2)
N2—Co—S1—C7	0.49 (13)	N5—Co—N6—N7	178.9 (2)
N1—Co—S1—C7	−3.3 (4)	S1—Co—N6—N7	87.5 (2)
N5—Co—S1—C7	96.38 (13)	S2—Co—N6—N7	−3.3 (2)
S2—Co—S1—C7	−95.12 (11)	C13—N6—N7—C14	−179.8 (3)
N6—Co—S2—C14	2.44 (12)	Co—N6—N7—C14	2.5 (3)
N2—Co—S2—C14	−175.26 (13)	C5—N1—C1—C2	−0.5 (4)
N1—Co—S2—C14	101.92 (13)	Co—N1—C1—C2	177.2 (2)
N5—Co—S2—C14	13.1 (4)	N1—C1—C2—C3	−0.2 (5)
S1—Co—S2—C14	−89.39 (11)	C1—C2—C3—C4	−0.1 (5)
N6—Co—N1—C1	2.7 (3)	C2—C3—C4—C5	1.0 (5)
N2—Co—N1—C1	−178.5 (3)	C1—N1—C5—C4	1.4 (4)
N5—Co—N1—C1	85.5 (3)	Co—N1—C5—C4	−176.7 (2)
S1—Co—N1—C1	−174.6 (3)	C1—N1—C5—C6	179.5 (3)
S2—Co—N1—C1	−82.7 (3)	Co—N1—C5—C6	1.4 (3)
N6—Co—N1—C5	−179.49 (19)	C3—C4—C5—N1	−1.7 (5)
N2—Co—N1—C5	−0.6 (2)	C3—C4—C5—C6	−179.5 (3)
N5—Co—N1—C5	−96.6 (2)	N3—N2—C6—C5	−179.7 (2)
S1—Co—N1—C5	3.2 (5)	Co—N2—C6—C5	1.2 (4)
S2—Co—N1—C5	95.14 (19)	N1—C5—C6—N2	−1.8 (4)
N1—Co—N2—C6	−0.4 (2)	C4—C5—C6—N2	176.2 (3)
N5—Co—N2—C6	89.2 (2)	N2—N3—C7—N4	−177.8 (3)
S1—Co—N2—C6	−179.6 (2)	N2—N3—C7—S1	3.7 (4)
S2—Co—N2—C6	−89.1 (2)	Co—S1—C7—N3	−2.5 (3)
N1—Co—N2—N3	−179.4 (2)	Co—S1—C7—N4	179.0 (3)
N5—Co—N2—N3	−89.9 (2)	C12—N5—C8—C9	−2.8 (5)
S1—Co—N2—N3	1.3 (2)	Co—N5—C8—C9	176.7 (2)
S2—Co—N2—N3	91.8 (2)	N5—C8—C9—C10	1.6 (5)
C6—N2—N3—C7	177.8 (3)	C8—C9—C10—C11	0.3 (6)
Co—N2—N3—C7	−3.1 (3)	C9—C10—C11—C12	−0.9 (6)
N6—Co—N5—C8	178.9 (3)	C8—N5—C12—C11	2.2 (4)
N2—Co—N5—C8	−3.5 (3)	Co—N5—C12—C11	−177.4 (2)
N1—Co—N5—C8	79.4 (3)	C8—N5—C12—C13	−178.6 (3)
S1—Co—N5—C8	−89.4 (3)	Co—N5—C12—C13	1.9 (3)
S2—Co—N5—C8	168.2 (3)	C10—C11—C12—N5	−0.4 (5)
N6—Co—N5—C12	−1.62 (19)	C10—C11—C12—C13	−179.5 (3)
N2—Co—N5—C12	176.04 (19)	N7—N6—C13—C12	−178.2 (2)
N1—Co—N5—C12	−101.1 (2)	Co—N6—C13—C12	−0.3 (3)
S1—Co—N5—C12	90.08 (19)	N5—C12—C13—N6	−1.1 (4)
S2—Co—N5—C12	−12.3 (5)	C11—C12—C13—N6	178.1 (3)
N1—Co—N6—C13	90.2 (2)	N6—N7—C14—N8	−179.1 (3)
N5—Co—N6—C13	1.1 (2)	N6—N7—C14—S2	0.5 (4)
S1—Co—N6—C13	−90.3 (2)	Co—S2—C14—N7	−2.3 (3)
S2—Co—N6—C13	178.9 (2)	Co—S2—C14—N8	177.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4B···N3^i	0.86 (1)	2.11 (1)	2.959 (4)	171 (4)
N4—H4A···O4^ii	0.86 (1)	2.24 (2)	3.024 (5)	151 (3)
N8—H8A···O1^iii	0.86 (1)	2.17 (1)	3.021 (4)	175 (3)
C1—H1···N7^iv	0.93	2.55	3.460 (4)	166
C6—H6···S2^v	0.93	2.89	3.679 (3)	144

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