Diacridinium hexa­chloridoplatinate(IV) dihydrate

The asymmetric unit of the title compound, (C₁₃H₁₀N)₂[PtCl₆]·2H₂O, contains a protonated acridine cation, one half of a [PtCl₆]²⁻ dianionic complex and a solvent water mol­ecule. The octa­hedral [PtCl₆]²⁻ dianion is located on an inversion centre. π–π inter­actions between neighboring acridinium cations produce stacks along the a axis; the shortest distance between the centroids of the six-membered rings within the cations is 3.553 (9) Å. In the crystal, two independent inter­molecular O—H...Cl hydrogen bonds, both involving the same Cl atom of the anion as acceptor, give rise to chains also running along the a axis; in addition each water mol­ecule, as a hydrogen-bond acceptor, is linked to the acridinium N—H group.

Key indicators

• Single-crystal X-ray study
• T = 200 K
• Mean [sigma](C-C) = 0.020 Å
• R factor = 0.059
• wR factor = 0.174
• Data-to-parameter ratio = 16.1

checkCIF/PLATON results

No syntax errors found



Alert level C
SHFSU01_ALERT_2_C  Test not performed. _refine_ls_shift/su_max and
            _refine_ls_shift/esd_max not present.
            Absolute value of the parameter shift to su ratio given   0.001
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Pt1    --  Cl1     ..       8.05 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Pt1    --  Cl2     ..       8.12 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Pt1    --  Cl3     ..       8.01 su
PLAT342_ALERT_3_C Low Bond Precision on  C-C Bonds (x 1000) Ang ..         20
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         34
PLAT971_ALERT_2_C Large Calcd. Non-Metal Positive Residual Density       1.90 eA-3
PLAT971_ALERT_2_C Large Calcd. Non-Metal Positive Residual Density       1.90 eA-3
PLAT971_ALERT_2_C Large Calcd. Non-Metal Positive Residual Density       1.79 eA-3
PLAT971_ALERT_2_C Large Calcd. Non-Metal Positive Residual Density       1.69 eA-3
PLAT971_ALERT_2_C Large Calcd. Non-Metal Positive Residual Density       1.63 eA-3
PLAT234_ALERT_4_C Large Hirshfeld Difference C1     --  C6      ..       0.17 Ang.
PLAT234_ALERT_4_C Large Hirshfeld Difference C2     --  C3      ..       0.16 Ang.
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600         11
PLAT925_ALERT_1_C The Reported and Calculated Rho(max) Differ by .       1.37 eA-3

Alert level G
PLAT083_ALERT_2_G SHELXL Second Parameter in WGHT Unusually Large.      22.36
PLAT154_ALERT_1_G The su's on the Cell Angles are Equal  (x 10000)        200 Deg.

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

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
  10 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
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

The asymmetric unit of the title compound, (C₁₃H₁₀N)₂[PtCl₆].2H₂O, contains a protonated acridine cation, one half of a [PtCl₆]^2- dianionic complex and a solvent water molecule (Fig. 1). The anion occupies a special position in the inversion centre; the Pt—Cl bond lengths, 2.370 (3), 2.377 (3) and 2.379 (3) Å, are similar to those found in other PtCl₆ salts, i.e. (C₁₃H₁₀N)₂[PtCl₆].2C₂H₆OS (Karaca et al., 2009), (C₁₄H₁₃N₂)₂[PtCl₆] (Yousefi et al., 2007) and (HPyX-3)₂[PtCl₆].2H₂O (X = Br or I) (Zordan & Brammer, 2004).

The essentially planar acridinium cations [maximum deviation from the least-squares plane is equal to 0.025 (17) Å], are stacked in columns along the a-axis (Fig. 2); the shortest distance between the centroids of the six-membered rings in neighboring cations in the stack is equal to 3.553 (9) Å. Two independent O-H···Cl bonds, both involving atom Cl1 of the anion as acceptor (Table 1), give rise to the chains also running along the a-axis; in addition each water molecule, as an H-bond acceptor is linked to the acridinium N-H group (Fig. 2).

Related literature

For related acridinium salts, see: Hafiz (2006); Veldhuizen et al. (1997). For the crystal structures of [PtCl₆]^2- complexes, see: Karaca et al. (2009); Yousefi et al. (2007); Zordan & Brammer (2004).

S2. Experimental

To a solution of K₂PtCl₆ (0.1999 g, 0.411 mmol) in H₂O (20 ml) was added acridine (0.1548 g, 0.864 mmol) and the mixture was refluxed for 7 h. The precipitate was then separated by filtration, washed with water and acetone, and dried at 50 °C, to give an orange powder (0.2198 g). Crystals suitable for X-ray analysis were obtained by slow evaporation from a CH₃CN solution.

S3. Refinement

H atoms were positioned geometrically and allowed to ride on their parent atoms [C—H = 0.95 Å, N—H = 0.88 Å and U_iso(H) = 1.2U_eq(C, N)]. The H atoms of the solvent water molecule were located from difference maps then allowed to ride on their parent O atom in the final cycles of refinement [O—H = 0.84 Å; U_iso(H)= 1.5U_eq(O)]. The highest peak (1.99 e Å^-3) and the deepest hole (-2.96 e Å^-3) in the difference Fourier map are located 0.60 and 0.84 Å from the Cl3 and Pt1 atoms, respectively.

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The structure of the title compound, with displacement ellipsoids drawn at the 50% probability level; H atoms are shown as small circles of arbitrary radius. Unlabelled atoms are related to the reference atoms by the (1-x, 1-y, -z) symmetry transformation.
	Fig. 2. Packing diagram for the crystal of the title compound viewed down the c-axis; H-bonds are drawn as dashed lines.

Diacridinium hexachloridoplatinate(IV) dihydrate

Crystal data

(C13H10N)2[PtCl6]·2H2O	Z = 1
Mr = 804.26	F(000) = 390
Triclinic, P1	Dx = 1.894 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.4781 (8) Å	Cell parameters from 2945 reflections
b = 9.8973 (10) Å	θ = 2.6–26.0°
c = 10.7226 (12) Å	µ = 5.57 mm^−1
α = 70.675 (2)°	T = 200 K
β = 71.505 (2)°	Plate, orange
γ = 77.862 (2)°	0.24 × 0.20 × 0.06 mm
V = 705.29 (13) Å^3

Data collection

Bruker SMART 1000 CCD diffractometer	2725 independent reflections
Radiation source: fine-focus sealed tube	2536 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
ϕ and ω scans	θmax = 26.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −9→8
Tmin = 0.577, Tmax = 1.000	k = −12→12
4295 measured reflections	l = −13→9

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.174	H-atom parameters constrained
S = 1.21	w = 1/[σ^2(Fo^2) + (0.0248P)^2 + 22.3646P] where P = (Fo^2 + 2Fc^2)/3
2725 reflections	(Δ/σ)max < 0.001
169 parameters	Δρmax = 1.99 e Å^−3
0 restraints	Δρmin = −2.96 e Å^−3

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. 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 > 2sigma(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
Pt1	0.5000	0.5000	0.0000	0.0289 (2)
Cl1	0.1916 (4)	0.4938 (3)	0.1558 (3)	0.0282 (7)
Cl2	0.3696 (4)	0.5171 (3)	−0.1801 (3)	0.0289 (7)
Cl3	0.5401 (5)	0.2446 (3)	0.0506 (3)	0.0315 (7)
N1	0.8227 (15)	0.1042 (13)	0.3453 (12)	0.035 (3)
H1	0.8630	0.1656	0.2645	0.042*
C1	0.8023 (17)	0.1451 (13)	0.4598 (13)	0.027 (3)
C2	0.842 (2)	0.2841 (15)	0.4478 (15)	0.035 (3)
H2	0.8838	0.3500	0.3600	0.043*
C3	0.820 (2)	0.3208 (17)	0.5619 (18)	0.047 (4)
H3	0.8465	0.4130	0.5553	0.056*
C4	0.758 (2)	0.2231 (18)	0.6908 (16)	0.046 (4)
H4	0.7445	0.2515	0.7699	0.055*
C5	0.716 (2)	0.0926 (16)	0.7086 (16)	0.040 (3)
H5	0.6727	0.0301	0.7982	0.048*
C6	0.7368 (19)	0.0490 (15)	0.5907 (16)	0.037 (3)
C7	0.694 (2)	−0.0880 (15)	0.6011 (14)	0.036 (3)
H7	0.6495	−0.1540	0.6883	0.043*
C8	0.7195 (18)	−0.1244 (15)	0.4794 (14)	0.032 (3)
C9	0.678 (2)	−0.2605 (15)	0.4860 (15)	0.038 (3)
H9	0.6376	−0.3289	0.5724	0.045*
C10	0.698 (2)	−0.2930 (16)	0.3666 (16)	0.040 (3)
H10	0.6665	−0.3824	0.3696	0.049*
C11	0.765 (2)	−0.1910 (17)	0.2399 (17)	0.047 (4)
H11	0.7788	−0.2149	0.1582	0.057*
C12	0.810 (2)	−0.0609 (17)	0.2278 (15)	0.040 (3)
H12	0.8583	0.0039	0.1405	0.048*
C13	0.784 (2)	−0.0259 (14)	0.3493 (16)	0.037 (3)
O1	0.0214 (17)	0.2503 (13)	0.0838 (11)	0.054 (3)
H1A	−0.0687	0.3001	0.0522	0.081*
H1B	0.1071	0.2824	0.0970	0.081*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pt1	0.0362 (4)	0.0291 (4)	0.0234 (4)	−0.0105 (3)	−0.0078 (3)	−0.0060 (3)
Cl1	0.0281 (16)	0.0351 (17)	0.0217 (14)	−0.0124 (13)	0.0031 (12)	−0.0124 (13)
Cl2	0.0365 (17)	0.0379 (17)	0.0221 (15)	−0.0061 (13)	−0.0158 (13)	−0.0125 (13)
Cl3	0.049 (2)	0.0154 (14)	0.0234 (15)	−0.0030 (13)	−0.0029 (13)	−0.0041 (12)
N1	0.024 (6)	0.043 (7)	0.039 (7)	−0.006 (5)	−0.008 (5)	−0.012 (5)
C1	0.023 (6)	0.027 (6)	0.028 (7)	−0.013 (5)	0.003 (5)	−0.007 (5)
C2	0.036 (8)	0.036 (8)	0.038 (8)	0.004 (6)	−0.018 (6)	−0.012 (6)
C3	0.042 (9)	0.035 (8)	0.072 (12)	−0.001 (7)	−0.024 (8)	−0.018 (8)
C4	0.049 (9)	0.055 (10)	0.046 (9)	0.014 (8)	−0.017 (7)	−0.036 (8)
C5	0.038 (8)	0.042 (8)	0.040 (8)	−0.001 (6)	−0.008 (6)	−0.016 (7)
C6	0.028 (7)	0.034 (7)	0.052 (9)	0.010 (6)	−0.017 (6)	−0.017 (7)
C7	0.036 (8)	0.035 (7)	0.032 (7)	0.003 (6)	−0.012 (6)	−0.006 (6)
C8	0.024 (7)	0.039 (8)	0.039 (8)	0.002 (5)	−0.015 (6)	−0.019 (6)
C9	0.040 (8)	0.027 (7)	0.042 (8)	−0.003 (6)	−0.016 (7)	0.000 (6)
C10	0.043 (8)	0.037 (8)	0.051 (9)	−0.006 (6)	−0.019 (7)	−0.017 (7)
C11	0.056 (10)	0.048 (9)	0.051 (10)	0.015 (8)	−0.027 (8)	−0.031 (8)
C12	0.032 (8)	0.047 (9)	0.039 (8)	0.010 (6)	−0.007 (6)	−0.020 (7)
C13	0.034 (8)	0.024 (7)	0.053 (9)	0.012 (6)	−0.018 (7)	−0.012 (6)
O1	0.052 (7)	0.064 (8)	0.039 (6)	−0.005 (6)	−0.008 (5)	−0.012 (6)

Geometric parameters (Å, º)

Pt1—Cl2^i	2.370 (3)	C5—C6	1.42 (2)
Pt1—Cl2	2.370 (3)	C5—H5	0.9500
Pt1—Cl3^i	2.377 (3)	C6—C7	1.42 (2)
Pt1—Cl3	2.377 (3)	C7—C8	1.412 (19)
Pt1—Cl1^i	2.379 (3)	C7—H7	0.9500
Pt1—Cl1	2.379 (3)	C8—C13	1.42 (2)
N1—C13	1.362 (18)	C8—C9	1.418 (19)
N1—C1	1.370 (17)	C9—C10	1.38 (2)
N1—H1	0.8800	C9—H9	0.9500
C1—C6	1.411 (19)	C10—C11	1.41 (2)
C1—C2	1.424 (18)	C10—H10	0.9500
C2—C3	1.34 (2)	C11—C12	1.36 (2)
C2—H2	0.9500	C11—H11	0.9500
C3—C4	1.40 (2)	C12—C13	1.40 (2)
C3—H3	0.9500	C12—H12	0.9500
C4—C5	1.33 (2)	O1—H1A	0.8400
C4—H4	0.9500	O1—H1B	0.8400
Cl2^i—Pt1—Cl2	180.0	C3—C4—H4	118.2
Cl2^i—Pt1—Cl3^i	89.44 (11)	C4—C5—C6	118.4 (15)
Cl2—Pt1—Cl3^i	90.56 (11)	C4—C5—H5	120.8
Cl2^i—Pt1—Cl3	90.56 (11)	C6—C5—H5	120.8
Cl2—Pt1—Cl3	89.44 (11)	C1—C6—C7	119.4 (13)
Cl3^i—Pt1—Cl3	180.00 (16)	C1—C6—C5	118.8 (13)
Cl2^i—Pt1—Cl1^i	90.27 (11)	C7—C6—C5	121.8 (14)
Cl2—Pt1—Cl1^i	89.73 (11)	C8—C7—C6	118.7 (13)
Cl3^i—Pt1—Cl1^i	90.55 (11)	C8—C7—H7	120.6
Cl3—Pt1—Cl1^i	89.45 (11)	C6—C7—H7	120.6
Cl2^i—Pt1—Cl1	89.73 (11)	C7—C8—C13	120.8 (13)
Cl2—Pt1—Cl1	90.27 (11)	C7—C8—C9	120.3 (13)
Cl3^i—Pt1—Cl1	89.45 (11)	C13—C8—C9	118.9 (12)
Cl3—Pt1—Cl1	90.55 (11)	C10—C9—C8	119.7 (13)
Cl1^i—Pt1—Cl1	180.00 (10)	C10—C9—H9	120.1
C13—N1—C1	123.9 (12)	C8—C9—H9	120.1
C13—N1—H1	118.0	C9—C10—C11	118.7 (13)
C1—N1—H1	118.0	C9—C10—H10	120.6
N1—C1—C6	119.2 (11)	C11—C10—H10	120.6
N1—C1—C2	120.8 (12)	C12—C11—C10	123.9 (14)
C6—C1—C2	119.9 (12)	C12—C11—H11	118.1
C3—C2—C1	119.3 (14)	C10—C11—H11	118.1
C3—C2—H2	120.4	C11—C12—C13	117.3 (15)
C1—C2—H2	120.4	C11—C12—H12	121.4
C2—C3—C4	119.9 (14)	C13—C12—H12	121.4
C2—C3—H3	120.0	N1—C13—C12	120.7 (14)
C4—C3—H3	120.0	N1—C13—C8	117.9 (13)
C5—C4—C3	123.7 (14)	C12—C13—C8	121.4 (13)
C5—C4—H4	118.2	H1A—O1—H1B	125.9
C13—N1—C1—C6	−0.4 (19)	C6—C7—C8—C13	−1 (2)
C13—N1—C1—C2	−178.9 (12)	C6—C7—C8—C9	180.0 (12)
N1—C1—C2—C3	179.7 (13)	C7—C8—C9—C10	177.9 (13)
C6—C1—C2—C3	1 (2)	C13—C8—C9—C10	−1 (2)
C1—C2—C3—C4	0 (2)	C8—C9—C10—C11	2 (2)
C2—C3—C4—C5	−1 (2)	C9—C10—C11—C12	−1 (2)
C3—C4—C5—C6	1 (2)	C10—C11—C12—C13	−2 (2)
N1—C1—C6—C7	0.3 (19)	C1—N1—C13—C12	−179.3 (12)
C2—C1—C6—C7	178.8 (12)	C1—N1—C13—C8	−0.1 (19)
N1—C1—C6—C5	−179.8 (12)	C11—C12—C13—N1	−178.5 (13)
C2—C1—C6—C5	−1.3 (19)	C11—C12—C13—C8	2 (2)
C4—C5—C6—C1	0 (2)	C7—C8—C13—N1	0.6 (19)
C4—C5—C6—C7	−179.7 (14)	C9—C8—C13—N1	179.9 (12)
C1—C6—C7—C8	0.2 (19)	C7—C8—C13—C12	179.8 (13)
C5—C6—C7—C8	−179.7 (13)	C9—C8—C13—C12	−1 (2)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1^ii	0.88	1.94	2.782 (16)	161
O1—H1A···Cl1^iii	0.84	2.74	3.485 (12)	149
O1—H1B···Cl1	0.84	2.62	3.342 (12)	145

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