Bis(4,4'-bipyridinium) hexa­cyano­platinate(IV) bis­(4,4'-bipyridine)

In the title compound, (C₁₀H₉N₂)₂[Pt(CN)₆]·2C₁₀H₈N₂ or [(Hbpy)⁺]₂[Pt(CN)₆]^2-·2bpy, where bpy is 4,4'-bipyridine, the Hbpy⁺ cations and bpy mol­ecules form a hydrogen-bonded two-dimensional cationic approximately square grid parallel to the (110) plane. The [Pt(CN)₆]^2- dianions reside in the cavities within this grid, with the nitrile N atoms forming weak hydrogen bonds with the CH groups in the cationic lattice.

S1. Comment

The 4,4'-bipyridine (bpy) ligand has commonly been used as a bidentate bridging ligand for the construction of both metal-organic frameworks (Noro et al., 2000; Noro et al., 2002; Xu et al., 2004) and hydrogen-bound networks. (Sharma & Zaworotko, 1996) In the course of our efforts to prepare such frameworks, the (Hbpy)₂Pt(CN)₆.2bpy salt, (I), was obtained, and its crystal structure is described here.

Over 100 crystal structures that contain bpy have been reported. The two amine positions allow for the formation of both the mono- (Hbpy⁺) and the dication (H₂bpy²⁺). Only nine crystal structures have been reported that contain both bpy and Hbpy⁺. Four of these, with the formula (Hbpy)[Ln(NO₃)₄(H₂O)₂(bpy)] (Ln = Nd, Pr, Ce and La), have a neutral bpy molecule coordinated to a lanthanide metal (Bukowska-Strzyzewska & Tosik, 1978; Al-Rasoul & Weakley, 1982; Sharma & Rogers, 1999). Similar to (I), four complexes have been reported to possess both uncoordinated neutral bpy and the Hbpy⁺ monocation, viz. (Hbpy)₂[(bpy)Nd₂(NO₃)₈(H₂O)₄](bpy)₃ (Weakley, 1984), (Hbpy)₂(HQS)₂(bpy)(H₂O)₅ (HQS is 8-hydroxyquinoline-5-sulfonate; Raj et al., 2003), [H_0.72(bpy)]^0.72+[(H_0.5O)₃PCH₂CH₂COOH_0.78]^0.72− (Bowes et al., 2003) and [Tm(pic)(H₂O)₆][Tm(pic)₂(H₂O)₄]₂(Hbpy)₂(bpy)₅(pic)₆ (pic is picrate; Liang et al., 2001). The remaining complex, [Fe(SCN)₆][(Hbpy)(H₂bpy)(bpy)], reportedly contains all three of these species (Wei et al., 2002).

The asymmetric unit of (I) contains two Hbpy⁺ cations, one [Pt(CN)₆]²⁻ dianion and two neutral bpy molecules. The atom-numbering scheme is shown in Fig. 1. The bond lengths in the bpy and Hbpy⁺ species are essentially identical. The average ring-linking C—C bond length is 1.487 (4) Å, which is 0.11 Å longer than the average observed bond length for the ring C—C bonds, of 1.380 (6) Å. The average C—N bond length in bpy and Hbpy⁺ is 1.325 (6) Å. For the non-protonated N atoms, the C—N—C angles range from 115.2 (3)° to 117.7 (2)°, which is in good agreement with the average C—N—C angle observed in neutral bpy [115.6 (2)°; Boag et al., 1999] and the average value reported in the Cambridge Structural Database (CSD; Version 5.24; Allen, 2002) for neutral bpy molecules (116.5°; Raj et al., 2003). The protonated C—NH—C angles in (I) are both 120.2 (2)°, in agreement with the analogous angle in (Hbpy)Br(H₂O) of 121.9 (2)° (Iyere et al., 2002) and the average value of 121.5° reported for Hbpy⁺ in the CSD (Raj et al., 2003). The internal angles at the C atoms adjacent to N atoms are also affected by protonation of the amide. As the C—N—C angle is increased upon protonation, the average C—C—N angle is decreased from 123.9 (7) to 121.1 (2)° for C—C—NH. Similarly, but to a lesser extent, the angle about the C atom β to the N atom is increased upon protonation of the N atom from 119.6 (3) to 120.3 (2)°. The C—C—C angle at the ring-connecting C atom is essentially identical in both the protonated and the non-protonated rings, with an average value of 116.7 (3)°. All pyridyl rings are essentially planar, the greatest r.m.s. deviation from planarity (0.0076 Å) occurring for the ring associated with N30. The dihedral angles between the two pyridyl planes in (I) are 2.47 (13) and 15.22 (12)° for the bpy molecules, and 13.71 (10) and 9.82 (13)° for the Hbpy⁺ cations. This dihedral angle is probably determined from crystal-packing forces. For example, in neutral bpy, this dihedral angle is 18.50 (12) and 34.85 (10)° (Boag et al., 1999), and it is 29.6 (4)° in the monoprotonated (Hbpy)Br(H₂O) complex. (Iyere et al., 2002) Coplanar pyridyl rings have been observed for bpy in Y(H₂O)₃(NO₃)(bpy)₂ (Weakley, 1982) and for H₂bpy in (H₂bpy)(ClO₄) (Ng, 1999).

Only a handful of crystal structures containing the hexacyanoplatinate(IV) anion have been reported. The geometry of the [Pt(CN)₆]²⁻ anion in (I) is essentially identical to the previously reported geometries in [Pt(dienH)(CN)₂][Pt(CN)₆] (dienH is 2,2'-diaminodiethylamine; Yanovskii et al., 1984) and [Cd(tren)][Pt(CN)₆] [tren is tris(2-aminoethyl)amine; Zhang et al., 2002]. The Pt—C bond lengths, which range from 2.015 (3) to 2.026 (3) Å, and the C—N bond lengths, which average 1.133 (4) Å, are also nearly identical to those found in Pt(CN)₄²⁻ (Ouahab et al., 1989, 1993) and partially oxidized tetracyanoplatinates (Williams et al., 1978; Johnson et al., 1978).

As illustrated in Fig. 2, the crystal structure of (I) is characterized by two-dimensional grids of hydrogen-bound bpy and Hbpy⁺ molecules that lie parallel to the (110) plane. The bpy and Hbpy⁺ molecules form a square network that is templated by the [Pt(CN)₆]²⁻ anion. The strongest hydrogen bonding between the amine H atoms of the Hbpy⁺ cations and the N atoms of the neutral bpy molecules leads to end-to-end dimers. Secondary hydrogen bonding occurs between the H atoms on the α-C atoms and the N atoms of bpy. Additional weak hydrogen bonding is present between the H atoms on the C atoms and the nitrile N atoms of the [Pt(CN)₆]²⁻ anion. These weak hydrogen bonds organize orthogonal sets of dimers into a loose approximately square grid.

S2. Experimental

Single crystals of (I) were prepared as a byproduct of a solvothermal reaction designed to grow CuPt(CN)₆(bpy)₂, which was expected to be analogous to CuSiF₆(bpy) (Noro et al., 2000). Copper(II) tetrafluoroborate hydrate (1 mmol, 237 mg; Aldrich), potassium hexacyanoplatinate(IV) (1 mmol, 429 mg; Aldrich) and 4,4'-dipyridyl (2 mmol, 312 mg; Aldrich) were placed in a 23 ml Teflon liner for a Parr acid digestion bomb along with ethanol (4 ml; Aaper) and water (6 ml). The bomb was sealed and heated at 413 K for 16 h. The temperature was then lowered at the rate of 10 K h⁻¹. Pale-pink crystals suitable for single-crystal X-ray diffraction were separated from a blue powder.

S3. Refinement

The acidic H atoms located on the amine N atoms of the Hbpy⁺ cations were located in a Fourier difference map. The H atoms on the aromatic C atoms were postioned geometrically (C—H = 0.93 Å). All H atoms were refined with a riding model and with U_iso(H) constrained to be 1.2 times U_eq of the carrier atom.

Computing details

Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. A vew of the molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level, and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. A packing diagram for (I), illustrating the two-dimensional approximately square network in the (110) plane. Displacement ellipsoids are drawn at the 50% probability level, with H atoms shown as small spheres of arbitrary radii. Hydrogen bonds are depicted as dashed lines.

Bis(4,4'-bipyridinium) hexacyanoplatinate(IV) bis(4,4'-bipyridine)

Crystal data

(C10H9N2)2[Pt(CN)6]·2C10H8N2	Z = 2
Mr = 977.96	F(000) = 972
Triclinic, P1	Dx = 1.573 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.4954 (4) Å	Cell parameters from 1792 reflections
b = 16.3529 (8) Å	θ = 2.4–29.6°
c = 16.9711 (8) Å	µ = 3.45 mm^−1
α = 93.024 (2)°	T = 298 K
β = 96.132 (2)°	Rod, pink
γ = 90.623 (2)°	0.44 × 0.18 × 0.16 mm
V = 2065.11 (18) Å^3

Data collection

Siemens SMART CCD area-detector diffractometer	11361 independent reflections
Radiation source: fine-focus sealed tube	9009 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
ω scans	θmax = 29.6°, θmin = 1.2°
Absorption correction: integration (Sheldrick, 2001)	h = −10→10
Tmin = 0.287, Tmax = 0.636	k = −22→22
24138 measured reflections	l = −23→23

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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.065	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0258P)^2 + 0.1P] where P = (Fo^2 + 2Fc^2)/3
11361 reflections	(Δ/σ)max = 0.070
550 parameters	Δρmax = 0.84 e Å^−3
0 restraints	Δρmin = −0.68 e Å^−3

Special details

Experimental. The data collection nominally covered over a hemisphere of reciprocal space, by a combination of four sets of exposures; each set had a different ϕ angle for the crystal and each exposure covered 0.3° in ω. The crystal-to-detector distance was 4.508 cm. Coverage of the unique set was 97.8% complete to at least 29.5° in θ and greater than 99% complete to at least 28.2° in θ. Crystal decay was monitored by repeating the initial 50 frames at the end of data collection and analyzing the duplicate reflections. Decay was found to be less than 1%, and no decay correction was therefore applied.

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
Pt	0.744051 (14)	0.749508 (6)	0.253010 (5)	0.04075 (4)
N1	0.9006 (5)	0.5725 (2)	0.2323 (2)	0.0893 (11)
N2	0.4146 (4)	0.6702 (2)	0.32342 (19)	0.0765 (9)
N3	0.9004 (4)	0.7767 (2)	0.43267 (16)	0.0750 (8)
N4	0.5871 (5)	0.92657 (18)	0.26915 (19)	0.0741 (9)
N5	1.0824 (5)	0.8270 (2)	0.1874 (2)	0.0823 (9)
N6	0.5740 (5)	0.7334 (2)	0.07494 (16)	0.0769 (9)
C1	0.8471 (5)	0.63631 (19)	0.24143 (18)	0.0588 (8)
C2	0.5274 (4)	0.69964 (18)	0.29504 (16)	0.0508 (7)
C3	0.8517 (4)	0.76481 (18)	0.36733 (16)	0.0514 (7)
C4	0.6410 (4)	0.86243 (17)	0.26349 (16)	0.0504 (7)
C5	0.9642 (4)	0.79842 (18)	0.21261 (17)	0.0529 (7)
C6	0.6322 (4)	0.73782 (18)	0.13954 (16)	0.0534 (7)
N10	0.0789 (3)	0.14901 (13)	0.25301 (12)	0.0459 (5)
H10	0.0494	0.1839	0.2179	0.055*
N11	0.3660 (4)	−0.13081 (16)	0.54075 (15)	0.0602 (7)
C10	0.1755 (3)	0.03744 (16)	0.36579 (14)	0.0385 (5)
C11	0.2357 (3)	−0.02139 (16)	0.42650 (14)	0.0404 (6)
C12	0.1896 (4)	0.01993 (18)	0.28594 (15)	0.0563 (8)
H12	0.2321	−0.0306	0.2694	0.068*
C13	0.1092 (4)	0.11357 (17)	0.38634 (15)	0.0506 (7)
H13	0.0967	0.1280	0.4392	0.061*
C14	0.2747 (4)	−0.10149 (17)	0.40565 (16)	0.0506 (7)
H14	0.2577	−0.1206	0.3528	0.061*
C15	0.2607 (4)	0.00215 (18)	0.50688 (15)	0.0500 (7)
H15	0.2346	0.0551	0.5244	0.060*
C16	0.1414 (4)	0.07662 (18)	0.23119 (16)	0.0571 (8)
H16	0.1527	0.0641	0.1779	0.068*
C17	0.0618 (4)	0.16774 (17)	0.32871 (16)	0.0524 (7)
H17	0.0169	0.2185	0.3432	0.063*
C18	0.3391 (5)	−0.15317 (19)	0.46390 (17)	0.0604 (8)
H18	0.3650	−0.2067	0.4483	0.072*
C19	0.3251 (4)	−0.05429 (19)	0.56054 (16)	0.0578 (8)
H19	0.3407	−0.0374	0.6141	0.069*
N20	0.4888 (3)	0.24189 (13)	0.24307 (12)	0.0453 (5)
H20	0.4504	0.2759	0.2775	0.054*
N21	0.7967 (3)	−0.04009 (15)	−0.04015 (14)	0.0517 (6)
C20	0.6091 (3)	0.13204 (15)	0.13234 (14)	0.0359 (5)
C21	0.6753 (3)	0.07279 (15)	0.07266 (14)	0.0371 (5)
C22	0.6270 (4)	0.11749 (16)	0.21239 (14)	0.0491 (7)
H22	0.6805	0.0697	0.2298	0.059*
C23	0.5288 (4)	0.20408 (17)	0.11014 (15)	0.0504 (7)
H23	0.5138	0.2161	0.0569	0.061*
C24	0.7312 (4)	−0.00442 (17)	0.09251 (16)	0.0505 (7)
H24	0.7296	−0.0205	0.1442	0.061*
C25	0.6830 (4)	0.09238 (18)	−0.00567 (15)	0.0504 (7)
H25	0.6476	0.1436	−0.0223	0.060*
C26	0.5659 (4)	0.17338 (17)	0.26620 (15)	0.0525 (7)
H26	0.5789	0.1629	0.3198	0.063*
C27	0.4705 (4)	0.25824 (17)	0.16666 (15)	0.0520 (7)
H27	0.4178	0.3069	0.1511	0.062*
C28	0.7899 (4)	−0.05793 (18)	0.03470 (16)	0.0556 (8)
H28	0.8266	−0.1096	0.0495	0.067*
C29	0.7437 (4)	0.03478 (19)	−0.05845 (16)	0.0558 (8)
H29	0.7479	0.0492	−0.1105	0.067*
N30	0.6349 (3)	0.65470 (14)	0.64970 (13)	0.0534 (6)
N31	0.8485 (4)	0.34964 (15)	0.36498 (15)	0.0605 (7)
C30	0.7263 (4)	0.53527 (16)	0.53918 (15)	0.0412 (6)
C31	0.7696 (3)	0.47131 (16)	0.47878 (14)	0.0417 (6)
C32	0.7290 (6)	0.51996 (19)	0.61819 (18)	0.0897 (14)
H32	0.7615	0.4687	0.6357	0.108*
C33	0.6805 (4)	0.61265 (16)	0.51785 (15)	0.0495 (7)
H33	0.6800	0.6264	0.4653	0.059*
C34	0.8111 (4)	0.39258 (17)	0.49870 (16)	0.0484 (7)
H34	0.8132	0.3781	0.5511	0.058*
C35	0.7690 (7)	0.4870 (2)	0.40055 (19)	0.0914 (14)
H35	0.7424	0.5391	0.3836	0.110*
C36	0.6833 (6)	0.5810 (2)	0.67140 (19)	0.0902 (14)
H36	0.6868	0.5698	0.7247	0.108*
C37	0.6353 (4)	0.66998 (17)	0.57456 (16)	0.0541 (7)
H37	0.6036	0.7220	0.5588	0.065*
C38	0.8495 (4)	0.33521 (17)	0.44037 (17)	0.0540 (7)
H38	0.8780	0.2827	0.4556	0.065*
C39	0.8082 (7)	0.4252 (2)	0.3466 (2)	0.1001 (16)
H39	0.8059	0.4376	0.2936	0.120*
N40	0.6418 (4)	0.54643 (17)	−0.12729 (16)	0.0677 (8)
N41	0.9940 (3)	0.25781 (14)	0.14268 (13)	0.0482 (5)
C40	0.7844 (3)	0.43163 (16)	−0.02085 (15)	0.0409 (6)
C41	0.8585 (3)	0.37137 (16)	0.03579 (15)	0.0396 (5)
C42	0.7461 (5)	0.4116 (2)	−0.10077 (17)	0.0650 (9)
H42	0.7676	0.3590	−0.1209	0.078*
C43	0.7464 (4)	0.51109 (17)	0.00431 (17)	0.0491 (7)
H43	0.7684	0.5280	0.0577	0.059*
C44	0.9324 (4)	0.29879 (17)	0.01038 (16)	0.0531 (7)
H44	0.9369	0.2866	−0.0435	0.064*
C45	0.8560 (5)	0.38485 (18)	0.11676 (16)	0.0616 (9)
H45	0.8085	0.4329	0.1369	0.074*
C46	0.6761 (6)	0.4695 (2)	−0.15047 (19)	0.0815 (12)
H46	0.6508	0.4540	−0.2041	0.098*
C47	0.6760 (4)	0.56464 (18)	−0.05019 (18)	0.0564 (7)
H47	0.6506	0.6173	−0.0316	0.068*
C48	0.9990 (4)	0.24480 (18)	0.06497 (17)	0.0575 (8)
H48	1.0500	0.1968	0.0467	0.069*
C49	0.9241 (5)	0.32700 (19)	0.16759 (17)	0.0654 (9)
H49	0.9206	0.3372	0.2218	0.079*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pt	0.06689 (8)	0.02910 (5)	0.02670 (5)	0.00193 (4)	0.00569 (4)	0.00412 (3)
N1	0.137 (3)	0.0484 (18)	0.089 (2)	0.0268 (19)	0.037 (2)	0.0115 (16)
N2	0.094 (2)	0.071 (2)	0.0679 (19)	−0.0167 (17)	0.0227 (17)	0.0082 (15)
N3	0.101 (2)	0.081 (2)	0.0406 (14)	−0.0043 (18)	−0.0029 (14)	0.0026 (14)
N4	0.113 (2)	0.0442 (16)	0.0714 (19)	0.0175 (16)	0.0330 (17)	0.0124 (13)
N5	0.094 (2)	0.081 (2)	0.077 (2)	−0.0117 (19)	0.0294 (18)	0.0168 (17)
N6	0.122 (3)	0.069 (2)	0.0370 (14)	0.0010 (18)	−0.0059 (15)	0.0058 (13)
C1	0.094 (2)	0.0369 (16)	0.0478 (16)	0.0061 (16)	0.0153 (16)	0.0085 (12)
C2	0.074 (2)	0.0411 (16)	0.0375 (14)	−0.0032 (14)	0.0077 (13)	0.0051 (11)
C3	0.072 (2)	0.0464 (16)	0.0355 (14)	−0.0038 (14)	0.0057 (13)	0.0044 (12)
C4	0.079 (2)	0.0335 (15)	0.0410 (14)	0.0090 (14)	0.0158 (14)	0.0069 (11)
C5	0.075 (2)	0.0444 (16)	0.0407 (14)	−0.0001 (15)	0.0113 (14)	0.0061 (12)
C6	0.085 (2)	0.0427 (16)	0.0326 (13)	0.0008 (15)	0.0032 (13)	0.0047 (11)
N10	0.0584 (14)	0.0417 (13)	0.0377 (11)	0.0144 (11)	0.0019 (10)	0.0067 (9)
N11	0.0873 (19)	0.0512 (16)	0.0425 (13)	0.0002 (14)	0.0031 (12)	0.0131 (11)
C10	0.0455 (14)	0.0373 (14)	0.0328 (12)	0.0039 (11)	0.0044 (10)	0.0014 (10)
C11	0.0483 (15)	0.0397 (14)	0.0335 (12)	0.0011 (12)	0.0044 (11)	0.0039 (10)
C12	0.087 (2)	0.0481 (17)	0.0343 (13)	0.0283 (16)	0.0069 (14)	0.0012 (12)
C13	0.0719 (19)	0.0470 (17)	0.0329 (13)	0.0125 (14)	0.0075 (12)	−0.0034 (11)
C14	0.076 (2)	0.0391 (15)	0.0361 (14)	0.0009 (14)	0.0044 (13)	0.0004 (11)
C15	0.0693 (19)	0.0466 (16)	0.0341 (13)	0.0056 (14)	0.0061 (12)	0.0013 (11)
C16	0.084 (2)	0.0520 (18)	0.0356 (14)	0.0277 (16)	0.0067 (14)	0.0008 (12)
C17	0.0730 (19)	0.0423 (16)	0.0414 (15)	0.0164 (14)	0.0046 (13)	−0.0028 (12)
C18	0.094 (2)	0.0417 (17)	0.0457 (16)	0.0063 (16)	0.0055 (16)	0.0090 (13)
C19	0.082 (2)	0.059 (2)	0.0326 (14)	−0.0039 (17)	0.0028 (14)	0.0075 (13)
N20	0.0645 (14)	0.0375 (12)	0.0346 (11)	0.0109 (11)	0.0094 (10)	−0.0020 (9)
N21	0.0645 (15)	0.0490 (15)	0.0432 (13)	0.0043 (12)	0.0172 (11)	−0.0077 (10)
C20	0.0457 (14)	0.0324 (13)	0.0299 (11)	0.0035 (10)	0.0059 (10)	0.0010 (9)
C21	0.0448 (14)	0.0352 (13)	0.0314 (12)	0.0020 (11)	0.0063 (10)	−0.0003 (10)
C22	0.081 (2)	0.0343 (14)	0.0335 (13)	0.0173 (13)	0.0075 (13)	0.0058 (10)
C23	0.0736 (19)	0.0478 (17)	0.0305 (12)	0.0176 (14)	0.0038 (12)	0.0082 (11)
C24	0.075 (2)	0.0405 (16)	0.0389 (14)	0.0123 (14)	0.0186 (13)	0.0059 (11)
C25	0.077 (2)	0.0413 (16)	0.0343 (13)	0.0083 (14)	0.0095 (13)	0.0032 (11)
C26	0.087 (2)	0.0405 (16)	0.0312 (13)	0.0112 (15)	0.0095 (13)	0.0017 (11)
C27	0.0725 (19)	0.0441 (16)	0.0402 (14)	0.0199 (14)	0.0061 (13)	0.0068 (12)
C28	0.078 (2)	0.0427 (16)	0.0490 (16)	0.0137 (15)	0.0209 (15)	−0.0001 (12)
C29	0.080 (2)	0.0562 (19)	0.0327 (13)	0.0064 (16)	0.0132 (13)	−0.0018 (12)
N30	0.0779 (17)	0.0398 (13)	0.0444 (13)	0.0127 (12)	0.0171 (12)	−0.0020 (10)
N31	0.091 (2)	0.0441 (15)	0.0483 (14)	0.0136 (14)	0.0199 (13)	−0.0049 (11)
C30	0.0515 (15)	0.0341 (13)	0.0399 (13)	0.0057 (11)	0.0135 (11)	0.0005 (10)
C31	0.0542 (15)	0.0358 (14)	0.0367 (13)	0.0075 (12)	0.0116 (11)	0.0028 (10)
C32	0.190 (4)	0.0407 (18)	0.0468 (18)	0.038 (2)	0.043 (2)	0.0133 (14)
C33	0.0722 (19)	0.0397 (16)	0.0375 (14)	0.0129 (14)	0.0070 (13)	0.0063 (11)
C34	0.0674 (18)	0.0389 (15)	0.0403 (14)	0.0108 (13)	0.0098 (13)	0.0048 (11)
C35	0.190 (4)	0.046 (2)	0.0467 (18)	0.039 (2)	0.043 (2)	0.0116 (15)
C36	0.184 (4)	0.050 (2)	0.0448 (18)	0.027 (2)	0.045 (2)	0.0086 (15)
C37	0.078 (2)	0.0377 (16)	0.0462 (16)	0.0111 (14)	0.0061 (14)	0.0006 (12)
C38	0.075 (2)	0.0344 (15)	0.0546 (17)	0.0115 (14)	0.0140 (15)	0.0031 (12)
C39	0.205 (5)	0.058 (2)	0.0455 (19)	0.047 (3)	0.042 (2)	0.0100 (16)
N40	0.103 (2)	0.0446 (16)	0.0530 (16)	0.0088 (15)	−0.0067 (15)	0.0113 (12)
N41	0.0598 (14)	0.0413 (13)	0.0431 (12)	0.0143 (11)	0.0018 (10)	0.0036 (10)
C40	0.0511 (15)	0.0342 (14)	0.0379 (13)	0.0034 (11)	0.0052 (11)	0.0044 (10)
C41	0.0471 (14)	0.0351 (14)	0.0367 (13)	0.0038 (11)	0.0043 (11)	0.0030 (10)
C42	0.114 (3)	0.0416 (17)	0.0380 (15)	0.0094 (18)	−0.0005 (16)	0.0015 (12)
C43	0.0652 (18)	0.0396 (15)	0.0424 (15)	0.0068 (13)	0.0054 (13)	0.0008 (11)
C44	0.079 (2)	0.0455 (17)	0.0354 (13)	0.0169 (15)	0.0099 (13)	−0.0021 (12)
C45	0.101 (2)	0.0427 (17)	0.0415 (15)	0.0297 (17)	0.0074 (15)	−0.0011 (12)
C46	0.144 (4)	0.052 (2)	0.0447 (18)	0.011 (2)	−0.012 (2)	0.0055 (15)
C47	0.075 (2)	0.0373 (16)	0.0577 (18)	0.0094 (14)	0.0060 (15)	0.0071 (13)
C48	0.079 (2)	0.0450 (17)	0.0491 (16)	0.0223 (15)	0.0097 (15)	−0.0036 (13)
C49	0.101 (3)	0.059 (2)	0.0373 (15)	0.0331 (18)	0.0070 (16)	0.0025 (13)

Geometric parameters (Å, º)

Pt—C6	2.015 (3)	C24—H24	0.9300
Pt—C4	2.016 (3)	C25—C29	1.380 (4)
Pt—C1	2.022 (3)	C25—H25	0.9300
Pt—C3	2.022 (3)	C26—H26	0.9300
Pt—C2	2.023 (3)	C27—H27	0.9300
Pt—C5	2.026 (3)	C28—H28	0.9300
N1—C1	1.131 (4)	C29—H29	0.9300
N2—C2	1.132 (4)	N30—C37	1.313 (3)
N3—C3	1.136 (4)	N30—C36	1.322 (4)
N4—C4	1.131 (4)	N31—C38	1.312 (3)
N5—C5	1.132 (4)	N31—C39	1.320 (4)
N6—C6	1.134 (4)	C30—C33	1.372 (4)
N10—C17	1.325 (3)	C30—C32	1.375 (4)
N10—C16	1.327 (3)	C30—C31	1.489 (3)
N10—H10	0.8600	C31—C35	1.365 (4)
N11—C19	1.326 (4)	C31—C34	1.379 (4)
N11—C18	1.329 (4)	C32—C36	1.381 (4)
C10—C12	1.386 (3)	C32—H32	0.9300
C10—C13	1.387 (4)	C33—C37	1.379 (3)
C10—C11	1.485 (3)	C33—H33	0.9300
C11—C14	1.381 (4)	C34—C38	1.383 (3)
C11—C15	1.390 (3)	C34—H34	0.9300
C12—C16	1.371 (4)	C35—C39	1.384 (4)
C12—H12	0.9300	C35—H35	0.9300
C13—C17	1.375 (4)	C36—H36	0.9300
C13—H13	0.9300	C37—H37	0.9300
C14—C18	1.385 (4)	C38—H38	0.9300
C14—H14	0.9300	C39—H39	0.9300
C15—C19	1.385 (4)	N40—C47	1.324 (4)
C15—H15	0.9300	N40—C46	1.335 (4)
C16—H16	0.9300	N41—C49	1.320 (3)
C17—H17	0.9300	N41—C48	1.329 (3)
C18—H18	0.9300	C40—C42	1.377 (4)
C19—H19	0.9300	C40—C43	1.388 (4)
N20—C26	1.325 (3)	C40—C41	1.484 (4)
N20—C27	1.331 (3)	C41—C45	1.382 (4)
N20—H20	0.8600	C41—C44	1.383 (4)
N21—C28	1.325 (3)	C42—C46	1.373 (4)
N21—C29	1.333 (4)	C42—H42	0.9300
C20—C23	1.381 (4)	C43—C47	1.376 (4)
C20—C22	1.384 (3)	C43—H43	0.9300
C20—C21	1.492 (3)	C44—C48	1.373 (4)
C21—C24	1.382 (4)	C44—H44	0.9300
C21—C25	1.391 (3)	C45—C49	1.379 (4)
C22—C26	1.375 (3)	C45—H45	0.9300
C22—H22	0.9300	C46—H46	0.9300
C23—C27	1.380 (3)	C47—H47	0.9300
C23—H23	0.9300	C48—H48	0.9300
C24—C28	1.390 (3)	C49—H49	0.9300
C6—Pt—C4	89.80 (12)	N20—C26—C22	121.2 (2)
C6—Pt—C1	89.72 (12)	N20—C26—H26	119.4
C4—Pt—C1	179.49 (9)	C22—C26—H26	119.4
C6—Pt—C3	178.05 (10)	N20—C27—C23	120.9 (2)
C4—Pt—C3	88.27 (12)	N20—C27—H27	119.5
C1—Pt—C3	92.22 (13)	C23—C27—H27	119.5
C6—Pt—C2	92.98 (12)	N21—C28—C24	124.2 (3)
C4—Pt—C2	91.00 (12)	N21—C28—H28	117.9
C1—Pt—C2	89.20 (13)	C24—C28—H28	117.9
C3—Pt—C2	86.78 (12)	N21—C29—C25	124.7 (3)
C6—Pt—C5	87.95 (12)	N21—C29—H29	117.7
C4—Pt—C5	89.64 (12)	C25—C29—H29	117.7
C1—Pt—C5	90.16 (13)	C37—N30—C36	117.7 (2)
C3—Pt—C5	92.32 (12)	C38—N31—C39	115.3 (2)
C2—Pt—C5	178.87 (11)	C33—C30—C32	117.0 (2)
N1—C1—Pt	177.4 (4)	C33—C30—C31	120.9 (2)
N2—C2—Pt	174.8 (3)	C32—C30—C31	122.1 (2)
N3—C3—Pt	174.6 (3)	C35—C31—C34	116.2 (2)
N4—C4—Pt	178.4 (3)	C35—C31—C30	122.0 (3)
N5—C5—Pt	177.0 (3)	C34—C31—C30	121.8 (2)
N6—C6—Pt	177.3 (3)	C30—C32—C36	119.7 (3)
C17—N10—C16	120.2 (2)	C30—C32—H32	120.1
C17—N10—H10	119.9	C36—C32—H32	120.1
C16—N10—H10	119.9	C30—C33—C37	119.7 (2)
C19—N11—C18	116.1 (3)	C30—C33—H33	120.1
C12—C10—C13	116.8 (2)	C37—C33—H33	120.1
C12—C10—C11	121.3 (2)	C31—C34—C38	119.6 (3)
C13—C10—C11	121.8 (2)	C31—C34—H34	120.2
C14—C11—C15	116.8 (3)	C38—C34—H34	120.2
C14—C11—C10	121.6 (2)	C31—C35—C39	119.8 (3)
C15—C11—C10	121.6 (2)	C31—C35—H35	120.1
C16—C12—C10	120.5 (3)	C39—C35—H35	120.1
C16—C12—H12	119.8	N30—C36—C32	122.7 (3)
C10—C12—H12	119.8	N30—C36—H36	118.6
C17—C13—C10	120.1 (2)	C32—C36—H36	118.6
C17—C13—H13	119.9	N30—C37—C33	123.1 (3)
C10—C13—H13	119.9	N30—C37—H37	118.4
C11—C14—C18	119.7 (3)	C33—C37—H37	118.4
C11—C14—H14	120.2	N31—C38—C34	124.6 (3)
C18—C14—H14	120.2	N31—C38—H38	117.7
C19—C15—C11	119.1 (3)	C34—C38—H38	117.7
C19—C15—H15	120.4	N31—C39—C35	124.5 (3)
C11—C15—H15	120.4	N31—C39—H39	117.7
N10—C16—C12	121.1 (2)	C35—C39—H39	117.7
N10—C16—H16	119.5	C47—N40—C46	115.2 (3)
C12—C16—H16	119.5	C49—N41—C48	117.5 (2)
N10—C17—C13	121.3 (2)	C42—C40—C43	116.4 (3)
N10—C17—H17	119.4	C42—C40—C41	122.0 (2)
C13—C17—H17	119.4	C43—C40—C41	121.6 (2)
N11—C18—C14	123.9 (3)	C45—C41—C44	116.6 (2)
N11—C18—H18	118.0	C45—C41—C40	121.5 (2)
C14—C18—H18	118.0	C44—C41—C40	121.8 (2)
N11—C19—C15	124.4 (3)	C46—C42—C40	119.7 (3)
N11—C19—H19	117.8	C46—C42—H42	120.2
C15—C19—H19	117.8	C40—C42—H42	120.2
C26—N20—C27	120.2 (2)	C47—C43—C40	119.6 (3)
C26—N20—H20	119.9	C47—C43—H43	120.2
C27—N20—H20	119.9	C40—C43—H43	120.2
C28—N21—C29	115.7 (2)	C48—C44—C41	119.8 (2)
C23—C20—C22	117.1 (2)	C48—C44—H44	120.1
C23—C20—C21	121.4 (2)	C41—C44—H44	120.1
C22—C20—C21	121.4 (2)	C49—C45—C41	119.9 (3)
C24—C21—C25	116.8 (2)	C49—C45—H45	120.0
C24—C21—C20	121.6 (2)	C41—C45—H45	120.0
C25—C21—C20	121.7 (2)	N40—C46—C42	124.6 (3)
C26—C22—C20	120.3 (2)	N40—C46—H46	117.7
C26—C22—H22	119.9	C42—C46—H46	117.7
C20—C22—H22	119.9	N40—C47—C43	124.5 (3)
C27—C23—C20	120.2 (2)	N40—C47—H47	117.7
C27—C23—H23	119.9	C43—C47—H47	117.7
C20—C23—H23	119.9	N41—C48—C44	123.2 (2)
C21—C24—C28	119.5 (3)	N41—C48—H48	118.4
C21—C24—H24	120.2	C44—C48—H48	118.4
C28—C24—H24	120.2	N41—C49—C45	122.9 (3)
C29—C25—C21	119.1 (3)	N41—C49—H49	118.5
C29—C25—H25	120.5	C45—C49—H49	118.5
C21—C25—H25	120.5
C12—C10—C11—C14	−13.0 (4)	C33—C30—C31—C35	1.2 (5)
C13—C10—C11—C14	169.6 (3)	C32—C30—C31—C35	−179.1 (4)
C12—C10—C11—C15	165.1 (3)	C33—C30—C31—C34	−178.2 (3)
C13—C10—C11—C15	−12.3 (4)	C32—C30—C31—C34	1.5 (5)
C13—C10—C12—C16	0.7 (4)	C33—C30—C32—C36	1.3 (6)
C11—C10—C12—C16	−176.8 (3)	C31—C30—C32—C36	−178.4 (4)
C12—C10—C13—C17	−0.3 (4)	C32—C30—C33—C37	−1.8 (5)
C11—C10—C13—C17	177.2 (3)	C31—C30—C33—C37	177.9 (3)
C15—C11—C14—C18	−1.4 (4)	C35—C31—C34—C38	0.3 (5)
C10—C11—C14—C18	176.8 (3)	C30—C31—C34—C38	179.7 (3)
C14—C11—C15—C19	1.2 (4)	C34—C31—C35—C39	0.2 (6)
C10—C11—C15—C19	−177.0 (3)	C30—C31—C35—C39	−179.2 (4)
C17—N10—C16—C12	−0.1 (5)	C37—N30—C36—C32	−1.7 (6)
C10—C12—C16—N10	−0.6 (5)	C30—C32—C36—N30	0.5 (7)
C16—N10—C17—C13	0.5 (5)	C36—N30—C37—C33	1.2 (5)
C10—C13—C17—N10	−0.3 (5)	C30—C33—C37—N30	0.6 (5)
C19—N11—C18—C14	0.8 (5)	C39—N31—C38—C34	0.4 (5)
C11—C14—C18—N11	0.4 (5)	C31—C34—C38—N31	−0.6 (5)
C18—N11—C19—C15	−1.1 (5)	C38—N31—C39—C35	0.1 (7)
C11—C15—C19—N11	0.1 (5)	C31—C35—C39—N31	−0.4 (8)
C23—C20—C21—C24	−170.2 (3)	C42—C40—C41—C45	−164.1 (3)
C22—C20—C21—C24	10.3 (4)	C43—C40—C41—C45	14.6 (4)
C23—C20—C21—C25	9.4 (4)	C42—C40—C41—C44	15.5 (4)
C22—C20—C21—C25	−170.0 (3)	C43—C40—C41—C44	−165.8 (3)
C23—C20—C22—C26	0.1 (4)	C43—C40—C42—C46	0.7 (5)
C21—C20—C22—C26	179.6 (3)	C41—C40—C42—C46	179.4 (3)
C22—C20—C23—C27	0.2 (4)	C42—C40—C43—C47	−0.5 (4)
C21—C20—C23—C27	−179.3 (3)	C41—C40—C43—C47	−179.3 (3)
C25—C21—C24—C28	−0.5 (4)	C45—C41—C44—C48	−0.3 (4)
C20—C21—C24—C28	179.2 (3)	C40—C41—C44—C48	−179.9 (3)
C24—C21—C25—C29	0.4 (4)	C44—C41—C45—C49	−0.4 (5)
C20—C21—C25—C29	−179.3 (3)	C40—C41—C45—C49	179.2 (3)
C27—N20—C26—C22	−0.6 (5)	C47—N40—C46—C42	−1.7 (6)
C20—C22—C26—N20	0.1 (5)	C40—C42—C46—N40	0.5 (7)
C26—N20—C27—C23	0.9 (4)	C46—N40—C47—C43	1.8 (5)
C20—C23—C27—N20	−0.7 (5)	C40—C43—C47—N40	−0.7 (5)
C29—N21—C28—C24	0.4 (5)	C49—N41—C48—C44	−1.2 (5)
C21—C24—C28—N21	0.1 (5)	C41—C44—C48—N41	1.1 (5)
C28—N21—C29—C25	−0.5 (5)	C48—N41—C49—C45	0.5 (5)
C21—C25—C29—N21	0.1 (5)	C41—C45—C49—N41	0.3 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N20—H20···N30^i	0.86	1.80	2.665 (3)	178
N10—H10···N41^ii	0.86	1.82	2.683 (3)	178
C16—H16···N21^iii	0.93	2.42	3.347 (3)	175
C26—H26···N11^iv	0.93	2.44	3.372 (4)	176
C27—H27···N40^v	0.93	2.49	3.394 (4)	164
C17—H17···N31^ii	0.93	2.53	3.450 (4)	170
C49—H49···N31	0.93	2.54	3.458 (4)	168
C36—H36···N40^vi	0.93	2.62	3.538 (4)	171
C23—H23···N6^v	0.93	2.45	3.368 (4)	168
C22—H22···N4^vii	0.93	2.58	3.335 (4)	139
C13—H13···N3^i	0.93	2.61	3.483 (4)	157
C39—H39···N1	0.93	2.61	3.284 (5)	130
C38—H38···N3^viii	0.93	2.62	3.337 (4)	135

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