cis-Bis(thio­semicarbazide-κ²N¹,S)palladium(II) dinitrate

In the title compound, cis-[Pd(CH₅N₃S)](NO₃)₂, the Pd^II atom is in a distorted square-planar geometry, with two thio­semicarbazides, coordinated cis relative to each other, acting as bidentate ligands coordinated through the S and the hydrazine N atoms. The complex cations and the nitrate anions are linked by N—H...O hydrogen bonds into a three-dimensional network.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](O-N) = 0.002 Å
• R factor = 0.019
• wR factor = 0.046
• Data-to-parameter ratio = 12.9

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Pd1    -   S1      ..       7.03 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Pd1    -   S2      ..       9.05 su

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

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 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, 1999); cell refinement: SMART; data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 2000); software used to prepare material for publication: publCIF (Westrip, 2007).

cis-Bis(thiosemicarbazide-κ²N¹,S)palladium(II) dinitrate

Crystal data

[Pd(CH5N3S)](NO3)2	F(000) = 816
Mr = 412.70	Dx = 2.262 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8014 reflections
a = 9.0540 (5) Å	θ = 2.3–25.4°
b = 8.8997 (5) Å	µ = 1.92 mm^−1
c = 15.0991 (9) Å	T = 298 K
β = 95.129 (1)°	Prism, orange
V = 1211.78 (12) Å^3	0.36 × 0.29 × 0.26 mm
Z = 4

Data collection

Bruker SMART APEX CCD area-detector diffractometer	2215 independent reflections
Radiation source: fine-focus sealed tube	2094 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
Detector resolution: 0.83 pixels mm^-1	θmax = 25.4°, θmin = 2.7°
ω scans	h = −10→10
Absorption correction: integration (Sheldrick, 2000)	k = −10→10
Tmin = 0.545, Tmax = 0.636	l = −18→18
9854 measured reflections

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)] = 0.019	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.046	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0221P)^2 + 0.4048P] where P = (Fo^2 + 2Fc^2)/3
2215 reflections	(Δ/σ)max = 0.002
172 parameters	Δρmax = 0.25 e Å^−3
0 restraints	Δρmin = −0.47 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
Pd1	0.749137 (16)	0.489779 (16)	0.511140 (10)	0.02227 (7)
S1	0.62827 (6)	0.42910 (6)	0.37817 (3)	0.02786 (13)
S2	0.87784 (6)	0.68175 (6)	0.45651 (3)	0.02746 (13)
N1	0.62789 (19)	0.31931 (19)	0.56212 (11)	0.0270 (4)
H1A	0.6910	0.2484	0.5852	0.032*
H1B	0.5796	0.3566	0.6069	0.032*
N2	0.52323 (19)	0.2507 (2)	0.49940 (10)	0.0281 (4)
H2	0.4645	0.1828	0.5166	0.034*
N3	0.4166 (2)	0.2243 (2)	0.35833 (12)	0.0331 (4)
H3A	0.3585	0.1565	0.3764	0.040*
H3B	0.4104	0.2493	0.3031	0.040*
N4	0.86491 (19)	0.5395 (2)	0.63200 (11)	0.0272 (4)
H4A	0.7995	0.5561	0.6724	0.033*
H4B	0.9199	0.4591	0.6502	0.033*
N5	0.9592 (2)	0.6660 (2)	0.62972 (11)	0.0311 (4)
H5	1.0052	0.6985	0.6783	0.037*
N6	1.0739 (2)	0.8456 (2)	0.55428 (13)	0.0342 (4)
H6A	1.1233	0.8721	0.6031	0.041*
H6B	1.0873	0.8916	0.5055	0.041*
C1	0.5150 (2)	0.2899 (2)	0.41538 (14)	0.0252 (4)
C2	0.9776 (2)	0.7344 (2)	0.55420 (13)	0.0259 (4)
N7	0.6510 (2)	0.5695 (2)	0.84624 (12)	0.0300 (4)
O1	0.64373 (19)	0.52488 (17)	0.92373 (11)	0.0352 (4)
O2	0.7310 (2)	0.50128 (19)	0.79659 (13)	0.0499 (5)
O3	0.5803 (2)	0.6835 (2)	0.81967 (10)	0.0462 (4)
N8	0.8466 (2)	0.0635 (2)	0.68309 (12)	0.0296 (4)
O4	0.8780 (2)	0.19709 (18)	0.70365 (11)	0.0437 (4)
O5	0.8831 (2)	−0.04067 (19)	0.73405 (12)	0.0464 (5)
O6	0.77488 (19)	0.03800 (19)	0.60922 (11)	0.0383 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pd1	0.02191 (10)	0.02459 (11)	0.02037 (10)	0.00211 (6)	0.00231 (7)	0.00177 (6)
S1	0.0305 (3)	0.0308 (3)	0.0221 (3)	−0.0044 (2)	0.0017 (2)	0.0037 (2)
S2	0.0290 (3)	0.0306 (3)	0.0223 (3)	−0.0019 (2)	−0.0004 (2)	0.0035 (2)
N1	0.0279 (9)	0.0302 (10)	0.0231 (9)	0.0013 (7)	0.0037 (7)	0.0051 (7)
N2	0.0315 (10)	0.0260 (10)	0.0271 (10)	−0.0061 (7)	0.0052 (8)	0.0018 (7)
N3	0.0367 (11)	0.0328 (10)	0.0291 (10)	−0.0073 (8)	−0.0004 (8)	0.0021 (8)
N4	0.0262 (9)	0.0347 (10)	0.0209 (9)	0.0018 (8)	0.0040 (7)	0.0028 (7)
N5	0.0368 (10)	0.0323 (10)	0.0232 (9)	−0.0037 (8)	−0.0035 (8)	−0.0032 (8)
N6	0.0354 (10)	0.0322 (10)	0.0341 (10)	−0.0054 (8)	−0.0024 (8)	0.0016 (8)
C1	0.0261 (11)	0.0211 (10)	0.0291 (11)	0.0053 (8)	0.0057 (9)	0.0005 (8)
C2	0.0242 (10)	0.0252 (11)	0.0279 (11)	0.0061 (8)	0.0012 (8)	−0.0020 (9)
N7	0.0317 (10)	0.0316 (10)	0.0270 (10)	0.0006 (8)	0.0044 (8)	−0.0024 (8)
O1	0.0477 (10)	0.0319 (8)	0.0274 (9)	0.0031 (7)	0.0105 (7)	0.0048 (6)
O2	0.0634 (13)	0.0511 (12)	0.0387 (11)	0.0213 (8)	0.0247 (10)	0.0034 (8)
O3	0.0610 (11)	0.0472 (11)	0.0303 (9)	0.0247 (9)	0.0040 (8)	0.0066 (7)
N8	0.0300 (10)	0.0339 (11)	0.0247 (9)	0.0016 (8)	0.0002 (8)	0.0015 (8)
O4	0.0616 (11)	0.0290 (9)	0.0376 (9)	−0.0087 (8)	−0.0111 (8)	0.0025 (7)
O5	0.0656 (12)	0.0318 (9)	0.0383 (10)	0.0097 (8)	−0.0146 (9)	0.0049 (8)
O6	0.0444 (10)	0.0416 (9)	0.0264 (8)	−0.0032 (8)	−0.0106 (7)	−0.0008 (7)

Geometric parameters (Å, º)

Pd1—N1	2.0616 (17)	N4—N5	1.415 (2)
Pd1—N4	2.0695 (17)	N4—H4A	0.9000
Pd1—S1	2.2644 (5)	N4—H4B	0.9000
Pd1—S2	2.2647 (5)	N5—C2	1.316 (3)
S1—C1	1.734 (2)	N5—H5	0.8600
S2—C2	1.724 (2)	N6—C2	1.319 (3)
N1—N2	1.417 (2)	N6—H6A	0.8600
N1—H1A	0.9000	N6—H6B	0.8600
N1—H1B	0.9000	N7—O1	1.243 (2)
N2—C1	1.311 (2)	N7—O2	1.246 (2)
N2—H2	0.8600	N7—O3	1.246 (2)
N3—C1	1.319 (3)	N8—O5	1.231 (2)
N3—H3A	0.8600	N8—O4	1.255 (2)
N3—H3B	0.8600	N8—O6	1.260 (2)
N1—Pd1—N4	94.17 (7)	Pd1—N4—H4A	108.7
N1—Pd1—S1	85.66 (5)	N5—N4—H4B	108.7
N4—Pd1—S1	178.02 (5)	Pd1—N4—H4B	108.7
N1—Pd1—S2	178.40 (5)	H4A—N4—H4B	107.6
N4—Pd1—S2	85.60 (5)	C2—N5—N4	120.80 (17)
S1—Pd1—S2	94.622 (19)	C2—N5—H5	119.6
C1—S1—Pd1	97.82 (7)	N4—N5—H5	119.6
C2—S2—Pd1	98.07 (7)	C2—N6—H6A	120.0
N2—N1—Pd1	114.46 (12)	C2—N6—H6B	120.0
N2—N1—H1A	108.6	H6A—N6—H6B	120.0
Pd1—N1—H1A	108.6	N2—C1—N3	119.40 (19)
N2—N1—H1B	108.6	N2—C1—S1	121.29 (16)
Pd1—N1—H1B	108.6	N3—C1—S1	119.30 (16)
H1A—N1—H1B	107.6	N5—C2—N6	118.75 (19)
C1—N2—N1	120.60 (17)	N5—C2—S2	121.24 (16)
C1—N2—H2	119.7	N6—C2—S2	120.01 (16)
N1—N2—H2	119.7	O1—N7—O2	119.54 (19)
C1—N3—H3A	120.0	O1—N7—O3	119.63 (18)
C1—N3—H3B	120.0	O2—N7—O3	120.82 (18)
H3A—N3—H3B	120.0	O5—N8—O4	121.12 (18)
N5—N4—Pd1	114.07 (12)	O5—N8—O6	120.37 (19)
N5—N4—H4A	108.7	O4—N8—O6	118.50 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O6	0.90	2.04	2.894 (2)	158
N1—H1A···O4	0.90	2.39	3.164 (2)	144
N1—H1B···O3^i	0.90	2.45	2.967 (2)	117
N1—H1B···S1^ii	0.90	2.70	3.4027 (19)	135
N2—H2···O1^i	0.86	1.98	2.826 (2)	169
N2—H2···O3^i	0.86	2.54	3.026 (2)	117
N3—H3A···O6^iii	0.86	2.13	2.974 (3)	166
N3—H3B···O3^ii	0.86	1.96	2.813 (2)	173
N4—H4A···O2	0.90	2.08	2.881 (2)	147
N4—H4B···O5^iv	0.90	2.38	2.996 (3)	125
N4—H4B···O4	0.90	2.51	3.232 (2)	138
N4—H4B···S2^v	0.90	2.84	3.4124 (19)	123
N5—H5···O4^iv	0.86	1.99	2.813 (2)	160
N6—H6A···O2^iv	0.86	2.24	3.066 (3)	162
N6—H6A···O1^iv	0.86	2.57	3.007 (2)	112
N6—H6B···O6^v	0.86	2.31	3.106 (3)	154

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