(Nitrato-κO)(2,2′:6′,2′′-terpyridine-κ³N,N′,N′′)palladium(II) nitrate

The title complex, [Pd(NO₃)(C₁₅H₁₁N₃)]NO₃, comprises a cationic Pd^II complex and a nitrate anion. In the complex, the Pd^II cation is four-coordinated in a distorted square-planar coordination geometry defined by the three N atoms of the tridentate 2,2′:6′,2′′-terpyridine ligand and one O atom from the NO₃⁻ anion. In the crystal, the complex mol­ecules are stacked in columns along the a axis being connected by π–π stacking [closest inter-centroid separation between pyridyl rings = 3.878 (3) Å]. The connections between columns and anions to sustain a three-dimensional architecture are C—H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 223 K
• Mean [sigma](C-C) = 0.008 Å
• R factor = 0.027
• wR factor = 0.048
• Data-to-parameter ratio = 12.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT090_ALERT_3_C Poor Data / Parameter Ratio (Zmax > 18) ........       6.91 Note
PLAT978_ALERT_2_C Number C-C Bonds with Positive Residual Density.          0 Info

Alert level G
PLAT794_ALERT_5_G Tentative Bond Valency for Pd1       (II)      .       2.39 Info
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          1 Note
PLAT933_ALERT_2_G Number of OMIT Records in Embedded .res File ...          1 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
   3 ALERT level G = General information/check it is not something unexpected

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

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Computing details

Data collection: APEX2 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT2014/7 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL2014/7 (Sheldrick, 2015b).

(Nitrato-κO)(2,2':6',2''-terpyridine-κ³N,N',N'')palladium(II) nitrate

Crystal data

[Pd(C15H11N3)(NO3)]NO3	Dx = 1.948 Mg m^−3
Mr = 463.69	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna21	Cell parameters from 9942 reflections
a = 6.2190 (2) Å	θ = 2.4–27.7°
b = 33.9728 (15) Å	µ = 1.22 mm^−1
c = 7.4819 (3) Å	T = 223 K
V = 1580.75 (11) Å^3	Plate, yellow
Z = 4	0.21 × 0.14 × 0.06 mm
F(000) = 920

Data collection

PHOTON 100 CMOS detector diffractometer	2745 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.084
φ and ω scans	θmax = 26.1°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2016)	h = −7→7
Tmin = 0.688, Tmax = 0.745	k = −41→42
41749 measured reflections	l = −9→9
3116 independent reflections

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)] = 0.027	H-atom parameters constrained
wR(F^2) = 0.048	w = 1/[σ^2(Fo^2) + (0.0152P)^2 + 0.8349P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max = 0.001
3116 reflections	Δρmax = 0.34 e Å^−3
244 parameters	Δρmin = −0.43 e Å^−3
1 restraint	Absolute structure: Flack x determined using 1141 quotients [(I^+)-(I^-)]/[(I^+)+(I^-)] Parsons et al. (2013).
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.006 (16)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Hydrogen atoms on C atoms were positioned geometrically and allowed to ride on their respective parent atoms: C—H = 0.94 Å and U_iso(H) = 1.2U_eq(C). The Flack parameter = 0.006 (16) after the final cycles of refinement.

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

	x	y	z	Uiso*/Ueq
Pd1	0.22807 (4)	0.15784 (2)	0.48682 (9)	0.02233 (10)
O1	0.1702 (6)	0.21529 (10)	0.4313 (4)	0.0343 (10)
O2	0.2291 (7)	0.19950 (12)	0.1521 (6)	0.0463 (10)
O3	0.1758 (7)	0.26017 (11)	0.2256 (6)	0.0540 (13)
N1	0.4977 (6)	0.16769 (12)	0.6321 (6)	0.0261 (10)
N2	0.2920 (6)	0.10452 (11)	0.5520 (5)	0.0220 (9)
N3	−0.0259 (6)	0.13077 (12)	0.3685 (5)	0.0214 (9)
N4	0.1927 (7)	0.22538 (14)	0.2626 (7)	0.0364 (12)
C1	0.5913 (9)	0.20210 (16)	0.6668 (8)	0.0344 (13)
H1	0.5322	0.2252	0.6180	0.041*
C2	0.7726 (9)	0.2048 (2)	0.7722 (8)	0.0450 (16)
H2	0.8307	0.2295	0.8015	0.054*
C3	0.8672 (9)	0.17072 (19)	0.8340 (8)	0.0415 (15)
H3	0.9939	0.1719	0.9023	0.050*
C4	0.7740 (9)	0.13467 (19)	0.7944 (8)	0.0323 (13)
H4	0.8378	0.1112	0.8343	0.039*
C5	0.5864 (9)	0.13370 (17)	0.6959 (7)	0.0232 (12)
C6	0.4710 (8)	0.09759 (15)	0.6481 (6)	0.0232 (11)
C7	0.5267 (8)	0.05923 (15)	0.6877 (7)	0.0293 (13)
H7	0.6493	0.0536	0.7566	0.035*
C8	0.3979 (8)	0.02930 (15)	0.6235 (7)	0.0308 (13)
H8	0.4354	0.0031	0.6481	0.037*
C9	0.2163 (7)	0.03682 (14)	0.5247 (7)	0.0282 (16)
H9	0.1295	0.0161	0.4828	0.034*
C10	0.1642 (6)	0.07567 (11)	0.4881 (12)	0.0219 (8)
C11	−0.0190 (8)	0.09089 (14)	0.3876 (7)	0.0222 (11)
C12	−0.1803 (8)	0.06726 (16)	0.3173 (7)	0.0285 (12)
H12	−0.1745	0.0398	0.3300	0.034*
C13	−0.3493 (8)	0.08484 (17)	0.2285 (7)	0.0302 (13)
H13	−0.4597	0.0694	0.1793	0.036*
C14	−0.3552 (9)	0.12527 (18)	0.2122 (8)	0.0266 (14)
H14	−0.4706	0.1376	0.1535	0.032*
C15	−0.1895 (8)	0.14736 (16)	0.2831 (8)	0.0269 (12)
H15	−0.1927	0.1749	0.2705	0.032*
O4	0.1900 (5)	0.09192 (10)	1.0047 (10)	0.0396 (10)
O5	0.2336 (6)	0.03043 (12)	1.0689 (6)	0.0505 (11)
O6	−0.0235 (6)	0.04770 (11)	0.8974 (5)	0.0425 (10)
N5	0.1345 (5)	0.05686 (11)	0.9909 (9)	0.0287 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pd1	0.02599 (16)	0.01582 (15)	0.02517 (16)	0.00131 (14)	−0.0033 (4)	−0.0007 (3)
O1	0.049 (2)	0.0166 (18)	0.037 (3)	0.0048 (15)	−0.0099 (16)	0.0013 (15)
O2	0.064 (3)	0.036 (2)	0.040 (2)	−0.010 (2)	−0.010 (2)	0.000 (2)
O3	0.059 (3)	0.020 (2)	0.083 (3)	−0.003 (2)	−0.020 (2)	0.021 (2)
N1	0.030 (2)	0.025 (3)	0.023 (2)	−0.0059 (18)	−0.0040 (19)	−0.0003 (19)
N2	0.0229 (19)	0.019 (2)	0.024 (2)	0.0028 (17)	0.0051 (17)	0.0003 (16)
N3	0.025 (2)	0.019 (2)	0.020 (2)	−0.0004 (17)	0.0018 (18)	−0.0021 (19)
N4	0.030 (2)	0.026 (3)	0.054 (3)	−0.007 (2)	−0.016 (2)	0.011 (3)
C1	0.042 (3)	0.024 (3)	0.037 (3)	−0.002 (3)	−0.004 (3)	0.000 (3)
C2	0.051 (4)	0.047 (4)	0.038 (3)	−0.021 (3)	−0.008 (3)	−0.002 (3)
C3	0.035 (3)	0.063 (4)	0.027 (3)	−0.014 (3)	−0.009 (3)	0.003 (3)
C4	0.029 (3)	0.044 (4)	0.025 (3)	0.003 (3)	0.001 (3)	0.006 (3)
C5	0.026 (3)	0.026 (3)	0.018 (3)	0.000 (2)	0.000 (2)	0.003 (2)
C6	0.025 (3)	0.027 (3)	0.018 (3)	0.003 (2)	0.003 (2)	0.005 (2)
C7	0.027 (3)	0.029 (3)	0.031 (3)	0.003 (2)	0.002 (2)	0.009 (3)
C8	0.034 (3)	0.020 (3)	0.039 (3)	0.008 (2)	0.007 (3)	0.012 (2)
C9	0.029 (2)	0.019 (2)	0.037 (5)	−0.0034 (19)	0.008 (2)	0.000 (2)
C10	0.0234 (19)	0.018 (2)	0.024 (2)	0.0004 (15)	0.000 (5)	−0.001 (4)
C11	0.026 (3)	0.018 (3)	0.022 (3)	0.002 (2)	0.006 (2)	0.000 (2)
C12	0.028 (3)	0.024 (3)	0.033 (3)	−0.006 (2)	0.007 (2)	−0.004 (2)
C13	0.024 (3)	0.037 (4)	0.030 (3)	−0.004 (2)	0.003 (2)	−0.009 (3)
C14	0.021 (3)	0.034 (4)	0.024 (4)	0.006 (3)	0.004 (3)	0.001 (3)
C15	0.029 (3)	0.024 (3)	0.027 (3)	0.007 (2)	0.003 (3)	−0.002 (2)
O4	0.0415 (17)	0.0291 (18)	0.048 (3)	−0.0045 (14)	−0.002 (3)	−0.003 (3)
O5	0.041 (2)	0.042 (3)	0.068 (3)	0.011 (2)	−0.020 (2)	0.013 (2)
O6	0.039 (2)	0.039 (2)	0.050 (2)	−0.0026 (18)	−0.0192 (19)	0.002 (2)
N5	0.0249 (17)	0.035 (2)	0.027 (2)	0.0011 (16)	0.004 (4)	−0.007 (4)

Geometric parameters (Å, º)

Pd1—N2	1.917 (4)	C5—C6	1.466 (8)
Pd1—N1	2.026 (4)	C6—C7	1.381 (7)
Pd1—O1	2.028 (3)	C7—C8	1.380 (7)
Pd1—N3	2.030 (4)	C7—H7	0.9400
O1—N4	1.315 (6)	C8—C9	1.374 (7)
O2—N4	1.228 (6)	C8—H8	0.9400
O3—N4	1.218 (6)	C9—C10	1.386 (6)
N1—C1	1.332 (6)	C9—H9	0.9400
N1—C5	1.366 (7)	C10—C11	1.460 (7)
N2—C6	1.346 (6)	C11—C12	1.388 (7)
N2—C10	1.349 (6)	C12—C13	1.379 (7)
N3—C15	1.328 (6)	C12—H12	0.9400
N3—C11	1.363 (6)	C13—C14	1.379 (8)
C1—C2	1.379 (7)	C13—H13	0.9400
C1—H1	0.9400	C14—C15	1.381 (8)
C2—C3	1.379 (9)	C14—H14	0.9400
C2—H2	0.9400	C15—H15	0.9400
C3—C4	1.387 (8)	O4—N5	1.245 (5)
C3—H3	0.9400	O5—N5	1.236 (6)
C4—C5	1.380 (7)	O6—N5	1.245 (5)
C4—H4	0.9400
N2—Pd1—N1	81.26 (17)	N2—C6—C7	119.1 (5)
N2—Pd1—O1	176.54 (15)	N2—C6—C5	112.9 (4)
N1—Pd1—O1	95.62 (15)	C7—C6—C5	128.0 (5)
N2—Pd1—N3	81.03 (16)	C8—C7—C6	118.4 (5)
N1—Pd1—N3	162.23 (16)	C8—C7—H7	120.8
O1—Pd1—N3	102.04 (15)	C6—C7—H7	120.8
N4—O1—Pd1	115.4 (3)	C9—C8—C7	121.8 (5)
C1—N1—C5	119.8 (5)	C9—C8—H8	119.1
C1—N1—Pd1	127.7 (4)	C7—C8—H8	119.1
C5—N1—Pd1	112.5 (4)	C8—C9—C10	118.4 (5)
C6—N2—C10	123.3 (4)	C8—C9—H9	120.8
C6—N2—Pd1	118.2 (3)	C10—C9—H9	120.8
C10—N2—Pd1	118.3 (3)	N2—C10—C9	118.9 (5)
C15—N3—C11	119.8 (4)	N2—C10—C11	112.6 (4)
C15—N3—Pd1	127.9 (3)	C9—C10—C11	128.4 (4)
C11—N3—Pd1	112.4 (3)	N3—C11—C12	120.8 (5)
O3—N4—O2	123.9 (5)	N3—C11—C10	115.5 (4)
O3—N4—O1	117.5 (5)	C12—C11—C10	123.7 (4)
O2—N4—O1	118.6 (4)	C13—C12—C11	118.9 (5)
N1—C1—C2	121.9 (6)	C13—C12—H12	120.6
N1—C1—H1	119.1	C11—C12—H12	120.6
C2—C1—H1	119.1	C12—C13—C14	119.6 (5)
C1—C2—C3	118.9 (6)	C12—C13—H13	120.2
C1—C2—H2	120.5	C14—C13—H13	120.2
C3—C2—H2	120.5	C13—C14—C15	119.1 (5)
C2—C3—C4	119.5 (5)	C13—C14—H14	120.4
C2—C3—H3	120.3	C15—C14—H14	120.4
C4—C3—H3	120.3	N3—C15—C14	121.8 (5)
C5—C4—C3	119.2 (6)	N3—C15—H15	119.1
C5—C4—H4	120.4	C14—C15—H15	119.1
C3—C4—H4	120.4	O5—N5—O4	121.2 (5)
N1—C5—C4	120.5 (5)	O5—N5—O6	118.5 (4)
N1—C5—C6	115.1 (5)	O4—N5—O6	120.3 (5)
C4—C5—C6	124.3 (5)
Pd1—O1—N4—O3	−174.4 (3)	C6—C7—C8—C9	−0.9 (8)
Pd1—O1—N4—O2	5.6 (6)	C7—C8—C9—C10	0.6 (8)
C5—N1—C1—C2	−2.6 (8)	C6—N2—C10—C9	1.0 (9)
Pd1—N1—C1—C2	178.2 (4)	Pd1—N2—C10—C9	175.9 (5)
N1—C1—C2—C3	4.2 (9)	C6—N2—C10—C11	−179.7 (4)
C1—C2—C3—C4	−2.4 (9)	Pd1—N2—C10—C11	−4.8 (7)
C2—C3—C4—C5	−0.9 (8)	C8—C9—C10—N2	−0.6 (9)
C1—N1—C5—C4	−0.8 (8)	C8—C9—C10—C11	−179.7 (6)
Pd1—N1—C5—C4	178.5 (4)	C15—N3—C11—C12	0.5 (7)
C1—N1—C5—C6	−179.4 (5)	Pd1—N3—C11—C12	179.3 (4)
Pd1—N1—C5—C6	−0.2 (5)	C15—N3—C11—C10	−178.3 (5)
C3—C4—C5—N1	2.5 (8)	Pd1—N3—C11—C10	0.5 (6)
C3—C4—C5—C6	−179.0 (5)	N2—C10—C11—N3	2.6 (8)
C10—N2—C6—C7	−1.4 (8)	C9—C10—C11—N3	−178.2 (6)
Pd1—N2—C6—C7	−176.3 (4)	N2—C10—C11—C12	−176.1 (5)
C10—N2—C6—C5	177.7 (5)	C9—C10—C11—C12	3.0 (11)
Pd1—N2—C6—C5	2.8 (5)	N3—C11—C12—C13	−0.4 (8)
N1—C5—C6—N2	−1.6 (6)	C10—C11—C12—C13	178.3 (5)
C4—C5—C6—N2	179.8 (5)	C11—C12—C13—C14	−0.3 (8)
N1—C5—C6—C7	177.4 (5)	C12—C13—C14—C15	1.0 (8)
C4—C5—C6—C7	−1.2 (8)	C11—N3—C15—C14	0.1 (8)
N2—C6—C7—C8	1.3 (7)	Pd1—N3—C15—C14	−178.4 (4)
C5—C6—C7—C8	−177.7 (5)	C13—C14—C15—N3	−0.9 (9)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O2^i	0.94	2.55	3.419 (7)	153
C4—H4···O6^ii	0.94	2.37	3.303 (7)	172
C7—H7···O6^ii	0.94	2.30	3.231 (6)	171
C8—H8···O5^iii	0.94	2.43	3.088 (6)	127
C9—H9···O6^iv	0.94	2.35	3.254 (6)	160
C13—H13···O5^v	0.94	2.46	3.402 (7)	176
C15—H15···O3^vi	0.94	2.38	3.280 (7)	161

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