catena-Poly[[[diaqua­(nitrato-κ2O,O′)(2,2′:6′,2′′-terpyridine-κ3N,N′,N′′)neodymium(III)]-μ-cyanido-κ2N:C-[dicyanidoplatinum(II)]-μ-cyanido-κ2C:N] acetonitrile solvate 2,2′:6′,2′′-terpyridine hemisolvate]

Maynard, B.A.; Smith, P.A.; Sykora, R.E.

doi:10.1107/S160053680903325X

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 9| September 2009| Pages m1132-m1133

doi:10.1107/S160053680903325X

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catena-Poly[[[diaqua(nitrato-κ²O,O′)(2,2′:6′,2′′-terpyridine-κ³N,N′,N′′)neodymium(III)]-μ-cyanido-κ²N:C-[dicyanidoplatinum(II)]-μ-cyanido-κ²C:N] acetonitrile solvate 2,2′:6′,2′′-terpyridine hemisolvate]

Branson A. Maynard,^a Philip A. Smith ^a and Richard E. Sykora ^a ^*

^aDepartment of Chemistry, University of South Alabama, Mobile, AL 36688-0002, USA
^*Correspondence e-mail: rsykora@jaguar1.usouthal.edu

(Received 24 July 2009; accepted 20 August 2009; online 26 August 2009)

The title compound, {[NdPt(CN)₄(NO₃)(C₁₅H₁₁N₃)(H₂O)₂]·CH₃CN·0.5C₁₅H₁₁N₃}_n, was isolated from solution as a one-dimensional coordination polymer. The Nd³⁺ site in the structure has a ninefold coordination with a distorted tricapped trigonal-prismatic geometry, while the Pt^II ion is coordinated by four cyanide groups in an almost regular square-planar geometry. Cis-bridging by the tetracyanidoplatinate anions links the Nd³⁺ cations, forming the one-dimensional chains. Additionally, each Nd³⁺ contains coordination by two water molecules, one tridentate 2,2′:6′,2′′-terpyridine molecule, and one bidentate nitrate anion. 2,2′:6′,2′′-Terpyridine and acetonitrile solvent molecules are incorporated between the chains, the former form π-stacking interactions (average interplanar distance 3.33 Å) with terpyridine molecules located in the chains. Relatively long Pt⋯Pt interactions [3.847 (1) Å] are observed in the structure. O—H⋯N and O—H⋯O hydrogen bonding interactions between the consituents consolidates the crystal packing.

Related literature

For related lanthanide tetracyanidoplatinate structures containing 2,2′:6′,2′′-terpyridine, see: Maynard et al. (2008 ); Maynard, Smith, Ladner et al. (2009 ); Maynard, Smith, Jaleel et al. (2009 ). For structural and spectroscopic information on simpler lanthanide tetracyanidoplatinates, see: Gliemann & Yersin (1985 ); Holzapfel et al. (1981 ). For luminescence data on lanthanide terpyridine systems, see: Mukkala et al. (1995 ).

Experimental

Crystal data

[NdPt(CN)₄(NO₃)(C₁₅H₁₁N₃)(H₂O)₂]·C₂H₃N·0.5C₁₅H₁₁N₃
M_r = 932.4
Monoclinic, C 2/c
a = 33.231 (6) Å
b = 14.3642 (17) Å
c = 13.823 (3) Å
β = 108.931 (16)°
V = 6241.5 (19) Å³
Z = 8
Mo Kα radiation
μ = 6.18 mm⁻¹
T = 290 K
0.45 × 0.17 × 0.08 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: analytical (XPREP; Bruker, 1998 ) T_min = 0.308, T_max = 0.632
5824 measured reflections
5722 independent reflections
4089 reflections with I > 2σ(I)
R_int = 0.031
3 standard reflections frequency: 120 min intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.087
S = 1.00
5722 reflections
420 parameters
H-atom parameters constrained
Δρ_max = 0.86 e Å⁻³
Δρ_min = −0.84 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4A⋯N4ⁱ	0.85	2.00	2.760 (9)	149.1
O4—H4B⋯N3ⁱⁱ	0.85	2.00	2.814 (10)	160.5
O5—H5B⋯N9ⁱⁱⁱ	0.85	2.16	2.993 (9)	167.4
O5—H5C⋯O1^iv	0.85	1.99	2.770 (8)	152.2
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z-{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z]$ ; (iii) -x+1, -y+1, -z; (iv) $[x, -y+1, z-{\script{1\over 2}}]$ .

Data collection: CAD-4-PC Software (Enraf–Nonius, 1993 ); cell refinement: CAD-4-PC Software; data reduction: XCAD4 (Harms & Wocadlo, 1996 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680903325X/nc2153sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680903325X/nc2153Isup2.hkl

checkCIF report

Comment top

One of our research goals is to prepare systems where the generally weak Ln³⁺ emissions are enhanced through the use of sensitizing ligands coordinated directly to Ln³⁺ cations. Recent efforts in our lab have focused on the novel lanthanide compounds that incorporate two ligand groups simultaneously to achieve this goal. The effort has focused on preparing lanthanide compounds that contain both tetracyanoplatinate(II) anions (TCP) and 2,2':6',2''-terpyridine (tpy) ligands, since each of these ligands have been shown to act as sensitizers for various Ln³⁺ cations (Gliemann & Yersin, 1985; Mukkala et al., 1995). We recently communicated some of our findings in this area (Maynard et al., 2008; Maynard, Smith, Ladner et al., 2009). Through our efforts we have prepared a number of novel compounds incorporating various Ln³⁺ cations, terpyridine, and TCP anions and have also recently reported on these structures (Maynard et al., 2008; Maynard, Smith, Ladner et al., 2009; Maynard, Smith, Jaleel, et al., 2009).

The title compound, (I), is similar to several previously reported compounds in that it contains one-dimensional [Nd(C₁₅H₁₁N₃)(H₂O)₂(NO₃)(Pt(CN)₄)] chains reminiscent of those found in Ln(C₁₅H₁₁N₃)(H₂O)₂(NO₃)[Pt(CN)₄].CH₃CN (Ln = Eu (Maynard et al., 2008; Maynard, Smith, Ladner et al., 2009) or Ln = Ho (Maynard, Smith, Jaleel, et al., 2009)) and Yb(C₁₅H₁₁N₃)(H₂O)₂(NO₃)[Pt(CN)₄].0.5CH₃CN.1.5H₂O (Maynard, Smith, Jaleel, et al., 2009). The major structural differences between these related structure types can be attributed in part to the crystallization of various solvent or guest molecules between the one-dimensional chains.

The neutral, one-dimensional [Nd(C₁₅H₁₁N₃)(H₂O)₂(NO₃)(Pt(CN)₄)] chains in the structure of (I) are illustrated in Figure 1 and a thermal ellipsoid plot of the asymmetric unit is illustrated in Figure 2. The chains are formed by the linkage of the Nd³⁺ cations by cis-bridging tetracyanoplatinate anions. The coordination of the Nd site is ninefold and can be described as a distorted [NdO₄N₅] tri-capped trigonal prism. The five nitrogen atoms in the inner sphere of the Nd³⁺ cations result from the coordination of one tridentate terpyridine ligand and two N-bound TCP anions while the four oxygen atoms are a result of one bidentate nitrate anion and two coordinated water molecules. The two longest Nd—O bond distances for each compound are those to the nitrate anion. The Nd—N bonds to the cyano groups are shorter by an average of ~0.08 Å than the Nd—N bonds to the tpy molecule. The Pt—C distances have an average of 1.984 (8) Å.

The packing diagram of (I) viewed along the c axis is shown in Figure 3. The predominant inter-chain feature is the existence of Pt—Pt interactions. These interactions in (I) are quite long (3.847 (1) Å), but are otherwise reminiscent of those observed in earlier reported lanthanide TCP compounds in that they form dimeric groups (Maynard, Smith, Ladner et al., 2009; Maynard, Smith, Jaleel, et al., 2009). This is in contrast to many reported lanthanide TCP compounds where there exist pseudo-1-D columnar stacks (Gliemann & Yersin, 1985; Holzapfel et al., 1981) containing planar TCP anions parallel to one another. Additional features found in the packing diagram for (I) include porous channels along the c axis that contain acetonitrile solvate molecules, numerous inter-chain hydrogen bonding interactions, and also the presence of π-stacking interactions. These latter interactions (3.33 Å average distance between planes) are between the coordinated tpy and the guest tpy molecule that is co-crystallized between the one-dimensional chains. Also worth noting is the orientation of the coordinated tpy molecules in the one-dimensional chains; viewing along the c axis reveals that these molecules are located on either side of the chains. A similar situation also occurs in Eu(C₁₅H₁₁N₃)(H₂O)₂(NO₃)[Pt(CN)₄].CH₃CN (Maynard et al., 2008; Maynard, Smith, Ladner et al., 2009) while Yb(C₁₅H₁₁N₃)(H₂O)₂(NO₃)[Pt(CN)₄].0.5CH₃CN.1.5H₂O (Maynard, Smith, Jaleel, et al., 2009) contains one-dimensional chains where all of the terpyridine molecules reside on a single side of the chain.

Related literature top

For related lanthanide tetracyanoplatinate structures containing 2,2':6',2''-terpyridine see: Maynard et al. (2008); Maynard, Smith, Ladner et al. (2009); Maynard, Smith, Jaleel et al. (2009). For structural and spectroscopic information on simpler lanthanide tetracyanoplatinates, see: Gliemann & Yersin, (1985); Holzapfel et al. (1981). For luminescence data on lanthanide terpyridine systems, see: Mukkala et al. (1995).

Experimental top

The title compound was synthesized by reacting Nd(NO₃).6H₂O (Strem, 99.9%), K₂Pt(CN)₄.3H₂O (Alfa Aesar, 99.9%), and 2,2':6',2''-terpyridine (Aldrich, 98%) in a 1:1:1 molar ratio. The reaction proceeded by adding 1 ml of a 0.10 M solution of potassium tetracyanoplatinate in 20%:80% water:acetonitrile mixture to 1 ml of a 0.10 M solution of neodymium nitrate in acetonitrile. Next, 1 ml of a 0.10 M solution of 2,2':6',2''-terpyridine in acetonitrile was layered on the former mixture. Purple crystals were harvested from the reaction tube after several days.

Computing details top

Data collection: CAD-4-PC Software (Enraf–Nonius, 1993); cell refinement: CAD-4-PC Software (Enraf–Nonius, 1993); data reduction: XCAD4 (Harms & Wocadlo, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top

	Fig. 1. A representation of the one-dimensional chains that extend along the c axis in (I).
	Fig. 2. A thermal ellipsoid plot of (I) with the atom-numbering scheme. Displacement ellipsoids for non-hydrogen atoms are drawn at the 50% probability level. H-atoms are shown as spheres of arbitrary size. Symmetry codes: (i) x, -y + 1, z - 1/2; (ii) -x + 1, y, -z + 1/2.
	Fig. 3. A packing diagram for (I) viewed along the c axis, the direction parallel to the 1-D chains. Pt—Pt and hydrogen-bonding interactions are shown by the dashed lines and one of the 1-D chains is circled for clarity.

catena-Poly[[[diaqua(nitrato-κ²O,O')(2,2':6',2''- terpyridine-κ³N,N',N'')neodymium(III)]-µ-cyanido- κ²N:C-[dicyanidoplatinum(II)]-µ-cyanido- κ²C:N] acetonitrile solvate 2,2':6',2''-terpyridine hemisolvate] top

Crystal data top

[NdPt(CN)₄(NO₃)(C₁₅H₁₁N₃)(H₂O)₂]·C₂H₃N·0.5C₁₅H₁₁N₃	F(000) = 3568
M_r = 932.4	D_x = 1.985 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 25 reflections
a = 33.231 (6) Å	θ = 8.5–15.4°
b = 14.3642 (17) Å	µ = 6.18 mm⁻¹
c = 13.823 (3) Å	T = 290 K
β = 108.931 (16)°	Plate, purple
V = 6241.5 (19) Å³	0.45 × 0.17 × 0.08 mm
Z = 8

Data collection top

Enraf–Nonius CAD-4 diffractometer	4089 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.031
Graphite monochromator	θ_max = 25.4°, θ_min = 2.1°
θ/2θ scans	h = 0→40
Absorption correction: analytical (SADABS; Bruker, 1998)	k = 0→17
T_min = 0.308, T_max = 0.632	l = −16→15
5824 measured reflections	3 standard reflections every 120 min
5722 independent reflections	intensity decay: none

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.036	Hydrogen site location: mixed
wR(F²) = 0.087	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0283P)²] where P = (F_o² + 2F_c²)/3
5722 reflections	(Δ/σ)_max = 0.001
420 parameters	Δρ_max = 0.86 e Å⁻³
0 restraints	Δρ_min = −0.84 e Å⁻³
44 constraints

Crystal data top

[NdPt(CN)₄(NO₃)(C₁₅H₁₁N₃)(H₂O)₂]·C₂H₃N·0.5C₁₅H₁₁N₃	V = 6241.5 (19) Å³
M_r = 932.4	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 33.231 (6) Å	µ = 6.18 mm⁻¹
b = 14.3642 (17) Å	T = 290 K
c = 13.823 (3) Å	0.45 × 0.17 × 0.08 mm
β = 108.931 (16)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	4089 reflections with I > 2σ(I)
Absorption correction: analytical (SADABS; Bruker, 1998)	R_int = 0.031
T_min = 0.308, T_max = 0.632	3 standard reflections every 120 min
5824 measured reflections	intensity decay: none
5722 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.087	H-atom parameters constrained
S = 1.00	Δρ_max = 0.86 e Å⁻³
5722 reflections	Δρ_min = −0.84 e Å⁻³
420 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Nd1	0.349783 (14)	0.43585 (3)	−0.06095 (3)	0.02261 (11)
Pt1	0.308541 (10)	0.775186 (19)	0.07657 (2)	0.02355 (9)
C1	0.3149 (3)	0.6590 (6)	0.0072 (6)	0.0287 (18)
C2	0.3302 (3)	0.7125 (5)	0.2122 (6)	0.0277 (17)
C3	0.3023 (3)	0.8936 (6)	0.1443 (6)	0.0330 (19)
C4	0.2851 (3)	0.8356 (5)	−0.0596 (6)	0.0302 (18)
C5	0.2743 (3)	0.4274 (6)	0.0670 (7)	0.039 (2)
H5A	0.2704	0.4877	0.0410	0.046*
C6	0.2505 (3)	0.3991 (6)	0.1269 (7)	0.044 (2)
H6A	0.2307	0.4391	0.1391	0.053*
C7	0.2562 (3)	0.3117 (7)	0.1679 (7)	0.052 (3)
H7A	0.2411	0.2918	0.2102	0.062*
C8	0.2849 (3)	0.2537 (7)	0.1451 (7)	0.042 (2)
H8A	0.2891	0.1934	0.1709	0.051*
C9	0.3075 (3)	0.2860 (5)	0.0832 (6)	0.0329 (19)
C10	0.3394 (3)	0.2280 (6)	0.0592 (6)	0.035 (2)
C11	0.3405 (3)	0.1306 (7)	0.0718 (7)	0.050 (3)
H11A	0.3202	0.1003	0.0936	0.060*
C12	0.3719 (4)	0.0820 (7)	0.0512 (9)	0.068 (3)
H12A	0.3729	0.0176	0.0582	0.082*
C13	0.4015 (4)	0.1255 (7)	0.0211 (8)	0.057 (3)
H13A	0.4231	0.0914	0.0087	0.069*
C14	0.4000 (3)	0.2214 (6)	0.0084 (7)	0.039 (2)
C15	0.4318 (3)	0.2724 (6)	−0.0214 (6)	0.035 (2)
C16	0.4697 (3)	0.2336 (8)	−0.0204 (8)	0.056 (3)
H16A	0.4750	0.1711	−0.0036	0.067*
C17	0.4999 (3)	0.2866 (10)	−0.0443 (9)	0.069 (4)
H17A	0.5255	0.2604	−0.0442	0.083*
C18	0.4915 (3)	0.3766 (9)	−0.0677 (7)	0.058 (3)
H18A	0.5112	0.4140	−0.0841	0.069*
C19	0.4530 (3)	0.4133 (7)	−0.0669 (7)	0.045 (2)
H19A	0.4472	0.4757	−0.0837	0.054*
C20	0.5895 (4)	0.0801 (8)	0.1679 (10)	0.073 (4)
H20A	0.5883	0.0154	0.1653	0.088*
C21	0.6217 (3)	0.1261 (8)	0.1448 (8)	0.060 (3)
H21A	0.6423	0.0937	0.1265	0.072*
C22	0.6220 (3)	0.2221 (8)	0.1500 (8)	0.055 (3)
H22A	0.6435	0.2536	0.1340	0.066*
C23	0.5593 (3)	0.1288 (7)	0.1946 (8)	0.056 (3)
H23A	0.5373	0.0984	0.2094	0.068*
C24	0.5627 (3)	0.2254 (6)	0.1988 (6)	0.039 (2)
C25	0.5303 (3)	0.2810 (6)	0.2270 (6)	0.038 (2)
C26	0.5314 (3)	0.3784 (7)	0.2262 (7)	0.048 (2)
H26A	0.5527	0.4102	0.2100	0.058*
C27	0.5000	0.4252 (10)	0.2500	0.053 (4)
H27A	0.5000	0.4899	0.2500	0.063*
C28	0.4505 (6)	0.8941 (11)	0.1457 (17)	0.109 (7)
C29	0.4263 (8)	0.8338 (13)	0.1910 (18)	0.134 (7)
H29A	0.3967	0.8499	0.1644	0.4 (2)*
H29B	0.4362	0.8416	0.2639	0.12 (7)*
H29C	0.4300	0.7701	0.1745	0.09 (4)*
N1	0.3189 (2)	0.5906 (5)	−0.0313 (5)	0.0376 (17)
N2	0.3413 (2)	0.6737 (5)	0.2886 (5)	0.0378 (18)
N3	0.2968 (3)	0.9628 (5)	0.1791 (7)	0.055 (2)
N4	0.2716 (3)	0.8690 (5)	−0.1384 (6)	0.046 (2)
N5	0.4061 (2)	0.5440 (5)	0.1161 (5)	0.0326 (16)
N6	0.3027 (2)	0.3734 (5)	0.0445 (5)	0.0327 (16)
N7	0.3677 (2)	0.2706 (4)	0.0232 (5)	0.0304 (15)
N8	0.4242 (2)	0.3633 (5)	−0.0434 (5)	0.0358 (17)
N9	0.5936 (2)	0.2724 (5)	0.1765 (6)	0.0447 (19)
N10	0.5000	0.2344 (7)	0.2500	0.039 (2)
N11	0.4708 (5)	0.9406 (10)	0.1179 (14)	0.130 (6)
O1	0.38212 (18)	0.4789 (4)	0.1277 (4)	0.0366 (14)
O2	0.40884 (19)	0.5548 (4)	0.0286 (4)	0.0418 (15)
O3	0.4259 (2)	0.5928 (5)	0.1889 (5)	0.058 (2)
O4	0.27728 (18)	0.4401 (4)	−0.1750 (4)	0.0374 (14)
H4A	0.2716	0.4145	−0.2333	0.045*
H4B	0.2556	0.4753	−0.1890	0.045*
O5	0.3686 (2)	0.5374 (4)	−0.1855 (4)	0.0402 (15)
H5B	0.3769	0.5937	−0.1773	0.048*
H5C	0.3765	0.5152	−0.2334	0.048*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Nd1	0.0283 (2)	0.0236 (2)	0.0168 (2)	−0.00194 (17)	0.00833 (17)	−0.00252 (16)
Pt1	0.03025 (17)	0.02168 (15)	0.02051 (15)	0.00316 (14)	0.01069 (12)	0.00322 (12)
C1	0.032 (5)	0.031 (4)	0.027 (4)	0.000 (4)	0.015 (4)	0.007 (4)
C2	0.037 (5)	0.024 (4)	0.025 (4)	0.001 (4)	0.015 (4)	−0.001 (3)
C3	0.048 (5)	0.027 (4)	0.027 (4)	0.005 (4)	0.017 (4)	0.005 (4)
C4	0.036 (5)	0.030 (4)	0.027 (4)	0.005 (4)	0.013 (4)	0.004 (4)
C5	0.037 (5)	0.033 (5)	0.047 (5)	−0.003 (4)	0.016 (4)	−0.001 (4)
C6	0.045 (6)	0.048 (5)	0.047 (5)	−0.017 (5)	0.026 (5)	−0.010 (5)
C7	0.055 (7)	0.071 (7)	0.035 (5)	−0.016 (6)	0.021 (5)	0.010 (5)
C8	0.036 (5)	0.051 (5)	0.050 (6)	−0.006 (4)	0.027 (5)	0.020 (5)
C9	0.039 (5)	0.034 (4)	0.025 (4)	−0.006 (4)	0.009 (4)	−0.005 (4)
C10	0.043 (5)	0.038 (5)	0.019 (4)	−0.005 (4)	0.004 (4)	0.010 (4)
C11	0.058 (7)	0.043 (6)	0.052 (6)	−0.001 (5)	0.021 (5)	0.013 (5)
C12	0.081 (9)	0.029 (5)	0.090 (9)	0.016 (6)	0.021 (7)	0.015 (5)
C13	0.063 (7)	0.045 (6)	0.067 (7)	0.019 (5)	0.025 (6)	0.009 (5)
C14	0.039 (5)	0.041 (5)	0.037 (5)	0.013 (4)	0.012 (4)	0.003 (4)
C15	0.036 (5)	0.048 (5)	0.020 (4)	0.007 (4)	0.007 (4)	−0.004 (4)
C16	0.050 (6)	0.065 (7)	0.053 (6)	0.024 (6)	0.019 (5)	0.010 (5)
C17	0.032 (6)	0.116 (11)	0.062 (7)	0.017 (7)	0.018 (5)	−0.004 (8)
C18	0.044 (6)	0.095 (9)	0.032 (5)	−0.015 (6)	0.012 (5)	0.008 (6)
C19	0.034 (5)	0.064 (6)	0.038 (5)	−0.001 (5)	0.015 (4)	0.002 (5)
C20	0.076 (9)	0.050 (6)	0.105 (10)	0.005 (6)	0.047 (8)	−0.004 (7)
C21	0.060 (7)	0.068 (7)	0.069 (7)	0.007 (6)	0.045 (6)	−0.008 (6)
C22	0.055 (7)	0.071 (7)	0.047 (6)	0.004 (6)	0.026 (5)	−0.004 (6)
C23	0.067 (7)	0.041 (5)	0.077 (8)	0.007 (5)	0.046 (6)	0.004 (5)
C24	0.038 (5)	0.050 (5)	0.031 (5)	0.005 (5)	0.014 (4)	−0.001 (4)
C25	0.036 (5)	0.057 (6)	0.024 (4)	0.002 (5)	0.014 (4)	0.000 (4)
C26	0.046 (6)	0.050 (6)	0.050 (6)	−0.016 (5)	0.018 (5)	0.000 (5)
C27	0.039 (8)	0.042 (8)	0.074 (11)	0.000	0.016 (8)	0.000
C28	0.080 (12)	0.061 (10)	0.17 (2)	−0.003 (8)	0.019 (12)	−0.024 (11)
C29	0.14 (2)	0.103 (15)	0.16 (2)	−0.002 (13)	0.052 (16)	−0.022 (13)
N1	0.048 (5)	0.030 (4)	0.038 (4)	−0.002 (3)	0.018 (4)	−0.003 (3)
N2	0.040 (5)	0.040 (4)	0.031 (4)	0.003 (3)	0.009 (3)	0.008 (3)
N3	0.070 (6)	0.036 (4)	0.070 (6)	0.008 (4)	0.039 (5)	−0.004 (4)
N4	0.052 (5)	0.048 (5)	0.036 (4)	0.008 (4)	0.011 (4)	0.007 (4)
N5	0.031 (4)	0.038 (4)	0.028 (4)	−0.002 (3)	0.009 (3)	−0.004 (3)
N6	0.036 (4)	0.032 (4)	0.029 (4)	−0.005 (3)	0.008 (3)	−0.001 (3)
N7	0.039 (4)	0.028 (3)	0.022 (3)	0.001 (3)	0.008 (3)	0.008 (3)
N8	0.036 (4)	0.049 (4)	0.024 (4)	0.001 (4)	0.012 (3)	0.001 (3)
N9	0.041 (5)	0.056 (5)	0.043 (4)	−0.008 (4)	0.020 (4)	−0.008 (4)
N10	0.040 (6)	0.047 (6)	0.031 (5)	0.000	0.012 (5)	0.000
N11	0.122 (14)	0.102 (12)	0.173 (16)	0.015 (10)	0.060 (12)	−0.002 (11)
O1	0.043 (4)	0.041 (3)	0.024 (3)	−0.005 (3)	0.010 (3)	−0.002 (3)
O2	0.046 (4)	0.051 (4)	0.033 (3)	−0.018 (3)	0.020 (3)	−0.007 (3)
O3	0.055 (5)	0.070 (5)	0.040 (4)	−0.015 (4)	0.001 (3)	−0.026 (4)
O4	0.032 (3)	0.048 (3)	0.027 (3)	0.007 (3)	0.002 (3)	−0.012 (3)
O5	0.063 (4)	0.033 (3)	0.032 (3)	−0.006 (3)	0.026 (3)	−0.002 (3)

Geometric parameters (Å, º) top

Nd1—O4	2.414 (5)	C15—C16	1.374 (12)
Nd1—O5	2.486 (5)	C16—C17	1.383 (15)
Nd1—N1	2.536 (7)	C16—H16A	0.9300
Nd1—N2ⁱ	2.550 (7)	C17—C18	1.339 (16)
Nd1—O1	2.554 (5)	C17—H17A	0.9300
Nd1—O2	2.594 (6)	C18—C19	1.389 (14)
Nd1—N6	2.619 (7)	C18—H18A	0.9300
Nd1—N8	2.623 (7)	C19—N8	1.317 (11)
Nd1—N7	2.625 (6)	C19—H19A	0.9300
Nd1—N5	2.989 (7)	C20—C23	1.367 (14)
Pt1—C1	1.970 (8)	C20—C21	1.380 (14)
Pt1—C3	1.985 (8)	C20—H20A	0.9300
Pt1—C4	1.988 (8)	C21—C22	1.380 (14)
Pt1—C2	1.992 (8)	C21—H21A	0.9300
C1—N1	1.146 (10)	C22—N9	1.331 (12)
C2—N2	1.144 (9)	C22—H22A	0.9300
C3—N3	1.144 (10)	C23—C24	1.392 (12)
C4—N4	1.140 (10)	C23—H23A	0.9300
C5—N6	1.334 (11)	C24—N9	1.347 (11)
C5—C6	1.379 (12)	C24—C25	1.491 (12)
C5—H5A	0.9300	C25—N10	1.329 (10)
C6—C7	1.365 (13)	C25—C26	1.400 (12)
C6—H6A	0.9300	C26—C27	1.367 (11)
C7—C8	1.378 (14)	C26—H26A	0.9300
C7—H7A	0.9300	C27—C26ⁱⁱ	1.367 (11)
C8—C9	1.388 (11)	C27—H27A	0.9300
C8—H8A	0.9300	C28—N11	1.10 (2)
C9—N6	1.355 (10)	C28—C29	1.46 (2)
C9—C10	1.469 (12)	C29—H29A	0.9600
C10—N7	1.344 (10)	C29—H29B	0.9600
C10—C11	1.410 (12)	C29—H29C	0.9600
C11—C12	1.360 (14)	N2—Nd1ⁱⁱⁱ	2.550 (7)
C11—H11A	0.9300	N5—O3	1.227 (8)
C12—C13	1.340 (15)	N5—O2	1.252 (8)
C12—H12A	0.9300	N5—O1	1.273 (8)
C13—C14	1.387 (13)	N10—C25ⁱⁱ	1.329 (10)
C13—H13A	0.9300	O4—H4A	0.8500
C14—N7	1.356 (10)	O4—H4B	0.8499
C14—C15	1.449 (12)	O5—H5B	0.8500
C15—N8	1.344 (11)	O5—H5C	0.8499

O4—Nd1—O5	87.4 (2)	C12—C13—C14	120.2 (10)
O4—Nd1—N1	73.3 (2)	C12—C13—H13A	119.9
O5—Nd1—N1	78.7 (2)	C14—C13—H13A	119.9
O4—Nd1—N2ⁱ	70.1 (2)	N7—C14—C13	119.7 (9)
O5—Nd1—N2ⁱ	77.5 (2)	N7—C14—C15	117.7 (7)
N1—Nd1—N2ⁱ	136.8 (2)	C13—C14—C15	122.6 (9)
O4—Nd1—O1	131.37 (19)	N8—C15—C16	119.9 (9)
O5—Nd1—O1	116.64 (18)	N8—C15—C14	117.1 (8)
N1—Nd1—O1	71.4 (2)	C16—C15—C14	122.8 (9)
N2ⁱ—Nd1—O1	151.8 (2)	C15—C16—C17	120.6 (10)
O4—Nd1—O2	137.3 (2)	C15—C16—H16A	119.7
O5—Nd1—O2	67.83 (18)	C17—C16—H16A	119.7
N1—Nd1—O2	68.2 (2)	C18—C17—C16	118.6 (10)
N2ⁱ—Nd1—O2	131.5 (2)	C18—C17—H17A	120.7
O1—Nd1—O2	49.51 (17)	C16—C17—H17A	120.7
O4—Nd1—N6	73.9 (2)	C17—C18—C19	119.0 (10)
O5—Nd1—N6	156.4 (2)	C17—C18—H18A	120.5
N1—Nd1—N6	82.2 (2)	C19—C18—H18A	120.5
N2ⁱ—Nd1—N6	108.3 (2)	N8—C19—C18	122.6 (10)
O1—Nd1—N6	69.15 (19)	N8—C19—H19A	118.7
O2—Nd1—N6	117.16 (19)	C18—C19—H19A	118.7
O4—Nd1—N8	141.46 (19)	C23—C20—C21	120.5 (10)
O5—Nd1—N8	81.7 (2)	C23—C20—H20A	119.7
N1—Nd1—N8	138.8 (2)	C21—C20—H20A	119.7
N2ⁱ—Nd1—N8	71.4 (2)	C20—C21—C22	117.4 (10)
O1—Nd1—N8	85.98 (19)	C20—C21—H21A	121.3
O2—Nd1—N8	70.9 (2)	C22—C21—H21A	121.3
N6—Nd1—N8	121.9 (2)	N9—C22—C21	124.2 (10)
O4—Nd1—N7	110.3 (2)	N9—C22—H22A	117.9
O5—Nd1—N7	140.0 (2)	C21—C22—H22A	117.9
N1—Nd1—N7	140.0 (2)	C20—C23—C24	117.8 (10)
N2ⁱ—Nd1—N7	75.7 (2)	C20—C23—H23A	121.1
O1—Nd1—N7	78.85 (18)	C24—C23—H23A	121.1
O2—Nd1—N7	110.9 (2)	N9—C24—C23	123.1 (9)
N6—Nd1—N7	62.3 (2)	N9—C24—C25	117.5 (8)
N8—Nd1—N7	61.8 (2)	C23—C24—C25	119.4 (9)
O4—Nd1—N5	138.48 (18)	N10—C25—C26	121.9 (9)
O5—Nd1—N5	91.78 (19)	N10—C25—C24	117.4 (8)
N1—Nd1—N5	65.9 (2)	C26—C25—C24	120.7 (8)
N2ⁱ—Nd1—N5	149.6 (2)	C27—C26—C25	117.7 (10)
O1—Nd1—N5	24.99 (17)	C27—C26—H26A	121.2
O2—Nd1—N5	24.64 (17)	C25—C26—H26A	121.2
N6—Nd1—N5	92.92 (19)	C26—C27—C26ⁱⁱ	121.2 (13)
N8—Nd1—N5	79.0 (2)	C26—C27—H27A	119.4
N7—Nd1—N5	96.63 (19)	C26ⁱⁱ—C27—H27A	119.4
C1—Pt1—C3	178.9 (3)	N11—C28—C29	175 (3)
C1—Pt1—C4	88.8 (3)	C28—C29—H29A	109.5
C3—Pt1—C4	90.2 (3)	C28—C29—H29B	109.5
C1—Pt1—C2	90.7 (3)	H29A—C29—H29B	109.5
C3—Pt1—C2	90.3 (3)	C28—C29—H29C	109.5
C4—Pt1—C2	178.1 (3)	H29A—C29—H29C	109.5
N1—C1—Pt1	178.6 (8)	H29B—C29—H29C	109.5
N2—C2—Pt1	177.1 (8)	C1—N1—Nd1	160.2 (7)
N3—C3—Pt1	176.4 (9)	C2—N2—Nd1ⁱⁱⁱ	166.1 (7)
N4—C4—Pt1	179.0 (7)	O3—N5—O2	122.3 (7)
N6—C5—C6	123.8 (8)	O3—N5—O1	120.4 (7)
N6—C5—H5A	118.1	O2—N5—O1	117.3 (6)
C6—C5—H5A	118.1	O3—N5—Nd1	173.9 (6)
C7—C6—C5	119.4 (10)	O2—N5—Nd1	59.7 (4)
C7—C6—H6A	120.3	O1—N5—Nd1	58.0 (3)
C5—C6—H6A	120.3	C5—N6—C9	116.7 (8)
C6—C7—C8	118.4 (9)	C5—N6—Nd1	121.8 (5)
C6—C7—H7A	120.8	C9—N6—Nd1	121.5 (6)
C8—C7—H7A	120.8	C10—N7—C14	120.1 (7)
C7—C8—C9	119.4 (9)	C10—N7—Nd1	119.4 (5)
C7—C8—H8A	120.3	C14—N7—Nd1	118.8 (5)
C9—C8—H8A	120.3	C19—N8—C15	119.3 (8)
N6—C9—C8	122.4 (8)	C19—N8—Nd1	119.8 (6)
N6—C9—C10	116.0 (7)	C15—N8—Nd1	120.5 (6)
C8—C9—C10	121.6 (8)	C22—N9—C24	116.9 (8)
N7—C10—C11	120.4 (9)	C25—N10—C25ⁱⁱ	119.6 (11)
N7—C10—C9	117.9 (7)	N5—O1—Nd1	97.0 (4)
C11—C10—C9	121.7 (8)	N5—O2—Nd1	95.6 (4)
C12—C11—C10	118.3 (10)	Nd1—O4—H4A	118.3
C12—C11—H11A	120.9	Nd1—O4—H4B	139.2
C10—C11—H11A	120.9	H4A—O4—H4B	97.6
C13—C12—C11	121.0 (9)	Nd1—O5—H5B	127.5
C13—C12—H12A	119.5	Nd1—O5—H5C	122.0
C11—C12—H12A	119.5	H5B—O5—H5C	107.0

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···N4^iv	0.85	2.00	2.760 (9)	149.1
O4—H4B···N3^v	0.85	2.00	2.814 (10)	160.5
O5—H5B···N9^vi	0.85	2.16	2.993 (9)	167.4
O5—H5C···O1ⁱ	0.85	1.99	2.770 (8)	152.2

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

Experimental details

Crystal data
Chemical formula	[NdPt(CN)₄(NO₃)(C₁₅H₁₁N₃)(H₂O)₂]·C₂H₃N·0.5C₁₅H₁₁N₃
M_r	932.4
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	290
a, b, c (Å)	33.231 (6), 14.3642 (17), 13.823 (3)
β (°)	108.931 (16)
V (Å³)	6241.5 (19)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	6.18
Crystal size (mm)	0.45 × 0.17 × 0.08

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	Analytical (SADABS; Bruker, 1998)
T_min, T_max	0.308, 0.632
No. of measured, independent and observed [I > 2σ(I)] reflections	5824, 5722, 4089
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.087, 1.00
No. of reflections	5722
No. of parameters	420
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.86, −0.84

Computer programs: CAD-4-PC Software (Enraf–Nonius, 1993), XCAD4 (Harms & Wocadlo, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···N4ⁱ	0.85	2.00	2.760 (9)	149.1
O4—H4B···N3ⁱⁱ	0.85	2.00	2.814 (10)	160.5
O5—H5B···N9ⁱⁱⁱ	0.85	2.16	2.993 (9)	167.4
O5—H5C···O1^iv	0.85	1.99	2.770 (8)	152.2

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

Acknowledgements

The authors gratefully acknowledge the National Science Foundation for their generous support (NSF-CAREER grant to RES, CHE-0846680).

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