(4,7-Dimethyl-1,10-phenanthroline)(ethyl­enediamine)platinum(II) dichloride tris­(deuterium oxide) solvate

In the mol­ecule of the title compound, [Pt(C₁₄H₁₂N₂)(C₂H₄D₄N₂)]Cl₂·3D₂O, the complex dication has square-planar coordination to the Pt^II atom from N-donor atoms. A small tilt of 4.34 (6)° is observed between the plane of the phenanthroline (phen) ligand and the coordination plane. The phen ligands are assembled along [010], with π–π stacking inter­actions between phen ligands of inter­leaved complexes. The structure also reveals hydrogen-bond inter­actions between the complex ion, its counter-ions and the solvent mol­ecules. The introduction of methyl residues onto the phen ligand at positions 4 and 7 does not appear to alter the geometry of the complex significantly.

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.018
• wR factor = 0.038
• Data-to-parameter ratio = 17.0

checkCIF/PLATON results

No syntax errors found



Alert level B
CHEMS01_ALERT_1_B  The sum formula contains elements in the wrong order.
            D  precedes Cl
            Sequence must be C, H, then alphabetical.

Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.97
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       3.54
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........         10
PLAT731_ALERT_1_C Bond    Calc     0.87(4), Rep   0.864(18) ......       2.22 su-Ra
              O1   -D1OA    1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.87(4), Rep   0.864(18) ......       2.22 su-Ra
              O1   -D1#     1.555   1.555

Alert level G
CHEMS02_ALERT_1_G  Please check that you have entered the correct
            _publ_requested_category classification of your compound;
            FI or CI or EI for inorganic; FM or CM or EM for metal-organic;
            FO or CO or EO for organic.
            From the CIF: _publ_requested_category   FI
            From the CIF: _chemical_formula_sum:C16 H16 Cl2 D10 N4 O3 Pt1

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

   5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT and XPREP (Siemens, 1995); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Xtal3.6 (Hall et al., 1999), ORTEPII (Johnson, 1976) and WinGX (Farrugia, 1999); software used to prepare material for publication: Please provide details.

(4,7-Dimethyl-1,10-phenanthroline)(ethylenediamine)platinum(II) dichloride tris(deuterium oxide) solvate

Crystal data

[Pt(C14H12N2)(C2H4D4N2)]Cl2·3D2O	F(000) = 1144
Mr = 598.41	Dx = 2.022 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 998 reflections
a = 11.3986 (16) Å	θ = 3.4–28.2°
b = 7.1092 (10) Å	µ = 7.44 mm^−1
c = 24.761 (4) Å	T = 150 K
β = 101.623 (2)°	Acicular, pale yellow
V = 1965.4 (5) Å^3	0.44 × 0.06 × 0.05 mm
Z = 4

Data collection

Bruker SMART 1000 CCD area-detector diffractometer	4717 independent reflections
Radiation source: sealed tube	4126 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
ω scans	θmax = 28.3°, θmin = 1.7°
Absorption correction: gaussian [GAUSSIAN (Coppens et al., 1965) and XPREP (Siemens, 1995)]	h = −15→14
Tmin = 0.212, Tmax = 0.720	k = −9→9
19380 measured reflections	l = −32→32

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)] = 0.018	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.038	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.02P)^2] where P = (Fo^2 + 2Fc^2)/3
4717 reflections	(Δ/σ)max = 0.007
277 parameters	Δρmax = 1.63 e Å^−3
6 restraints	Δρmin = −0.46 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
Pt1	0.165236 (8)	0.283357 (14)	0.134989 (4)	0.01609 (3)
Cl1	0.50565 (6)	1.01946 (9)	0.13521 (3)	0.02524 (14)
Cl2	0.09978 (6)	0.83682 (10)	0.23482 (3)	0.02766 (15)
O1	0.3207 (2)	0.7443 (3)	0.17359 (10)	0.0334 (5)
D1OA	0.264 (3)	0.790 (5)	0.1885 (16)	0.066 (13)*
D1OB	0.368 (3)	0.836 (4)	0.1691 (13)	0.045 (10)*
O2	0.51405 (19)	0.5763 (3)	0.09879 (9)	0.0317 (5)
D2OA	0.510 (3)	0.697 (3)	0.1065 (15)	0.053 (11)*
D2OB	0.561 (3)	0.529 (5)	0.1268 (11)	0.066 (13)*
O3	0.63999 (19)	0.3840 (3)	0.19053 (9)	0.0338 (5)
D3OA	0.613 (3)	0.273 (3)	0.1812 (12)	0.025 (8)*
D3OB	0.710 (2)	0.363 (5)	0.2103 (12)	0.053 (11)*
N1	0.33826 (19)	0.3469 (4)	0.16913 (9)	0.0194 (4)
D1NA	0.388 (3)	0.285 (4)	0.1552 (13)	0.032 (9)*
D1NB	0.346 (3)	0.474 (5)	0.1626 (12)	0.040 (9)*
N2	0.1488 (2)	0.2748 (3)	0.21565 (9)	0.0207 (5)
D2NA	0.143 (2)	0.147 (4)	0.2273 (11)	0.030 (8)*
D2NB	0.089 (3)	0.331 (4)	0.2206 (13)	0.033 (9)*
N3	−0.00611 (19)	0.2224 (3)	0.09975 (9)	0.0185 (4)
N4	0.17890 (19)	0.2942 (3)	0.05470 (9)	0.0187 (4)
C1	0.3637 (2)	0.2989 (4)	0.22920 (11)	0.0254 (6)
H1A	0.4361	0.3662	0.2485	0.030*
H1B	0.3776	0.1620	0.2343	0.030*
C2	0.2564 (2)	0.3578 (4)	0.25192 (10)	0.0234 (6)
H2A	0.2637	0.3116	0.2902	0.028*
H2B	0.2500	0.4967	0.2522	0.028*
C3	−0.0970 (2)	0.1828 (3)	0.12430 (11)	0.0215 (6)
H3	−0.0824	0.1727	0.1633	0.026*
C4	−0.2130 (2)	0.1559 (4)	0.09420 (11)	0.0230 (6)
H4	−0.2753	0.1279	0.1133	0.028*
C5	−0.2399 (2)	0.1686 (3)	0.03758 (11)	0.0201 (5)
C6	−0.1425 (2)	0.2031 (3)	0.01076 (11)	0.0191 (5)
C7	−0.1544 (2)	0.2145 (4)	−0.04820 (11)	0.0226 (5)
H7	−0.2310	0.1974	−0.0713	0.027*
C8	−0.0587 (3)	0.2491 (3)	−0.07146 (11)	0.0222 (6)
H8	−0.0696	0.2542	−0.1105	0.027*
C9	0.0589 (2)	0.2783 (3)	−0.03854 (10)	0.0185 (5)
C10	0.1630 (2)	0.3159 (3)	−0.06028 (11)	0.0210 (6)
C11	0.2694 (2)	0.3410 (4)	−0.02327 (11)	0.0231 (6)
H11	0.3403	0.3659	−0.0367	0.028*
C12	0.2755 (2)	0.3307 (4)	0.03368 (11)	0.0219 (6)
H12	0.3503	0.3501	0.0580	0.026*
C13	0.0720 (2)	0.2678 (3)	0.01880 (10)	0.0172 (5)
C14	−0.0288 (2)	0.2301 (3)	0.04330 (10)	0.0163 (5)
C15	−0.3659 (2)	0.1499 (4)	0.00638 (11)	0.0278 (6)
H15A	−0.4172	0.1088	0.0315	0.042*
H15B	−0.3691	0.0570	−0.0231	0.042*
H15C	−0.3940	0.2718	−0.0097	0.042*
C16	0.1564 (3)	0.3297 (4)	−0.12116 (11)	0.0295 (7)
H16A	0.2342	0.3698	−0.1282	0.044*
H16B	0.0951	0.4217	−0.1370	0.044*
H16C	0.1356	0.2065	−0.1382	0.044*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pt1	0.01361 (5)	0.02056 (5)	0.01443 (5)	−0.00102 (4)	0.00359 (4)	−0.00121 (4)
Cl1	0.0238 (3)	0.0265 (3)	0.0265 (3)	−0.0024 (3)	0.0077 (3)	0.0002 (3)
Cl2	0.0206 (3)	0.0358 (4)	0.0273 (4)	−0.0011 (3)	0.0065 (3)	0.0042 (3)
O1	0.0347 (13)	0.0304 (12)	0.0397 (13)	−0.0050 (9)	0.0188 (10)	−0.0023 (9)
O2	0.0319 (12)	0.0308 (12)	0.0312 (12)	0.0015 (10)	0.0034 (9)	0.0021 (10)
O3	0.0316 (13)	0.0282 (13)	0.0366 (13)	0.0002 (10)	−0.0049 (10)	−0.0006 (9)
N1	0.0144 (11)	0.0260 (12)	0.0178 (11)	−0.0023 (9)	0.0033 (9)	−0.0004 (10)
N2	0.0153 (12)	0.0283 (12)	0.0191 (11)	−0.0004 (10)	0.0050 (9)	−0.0015 (10)
N3	0.0156 (11)	0.0228 (10)	0.0177 (11)	−0.0019 (9)	0.0051 (8)	−0.0017 (9)
N4	0.0198 (11)	0.0192 (11)	0.0185 (11)	−0.0012 (9)	0.0069 (9)	−0.0018 (9)
C1	0.0205 (14)	0.0360 (16)	0.0188 (13)	−0.0013 (11)	0.0015 (11)	0.0013 (11)
C2	0.0226 (14)	0.0328 (14)	0.0148 (13)	−0.0029 (12)	0.0036 (10)	−0.0012 (11)
C3	0.0213 (14)	0.0241 (15)	0.0205 (13)	−0.0033 (10)	0.0076 (11)	−0.0023 (10)
C4	0.0183 (13)	0.0257 (13)	0.0261 (14)	−0.0048 (11)	0.0068 (11)	−0.0010 (11)
C5	0.0186 (13)	0.0181 (13)	0.0231 (13)	−0.0031 (10)	0.0034 (11)	−0.0013 (10)
C6	0.0210 (13)	0.0149 (12)	0.0215 (13)	0.0002 (10)	0.0042 (10)	−0.0006 (10)
C7	0.0213 (14)	0.0234 (13)	0.0208 (13)	−0.0016 (11)	−0.0012 (11)	−0.0006 (11)
C8	0.0283 (15)	0.0196 (14)	0.0176 (13)	0.0002 (10)	0.0023 (11)	0.0004 (10)
C9	0.0236 (13)	0.0155 (11)	0.0168 (12)	0.0005 (10)	0.0053 (10)	−0.0002 (10)
C10	0.0299 (15)	0.0161 (14)	0.0193 (13)	0.0011 (10)	0.0105 (11)	0.0010 (10)
C11	0.0225 (14)	0.0250 (14)	0.0248 (14)	−0.0022 (11)	0.0121 (11)	−0.0008 (11)
C12	0.0169 (13)	0.0252 (14)	0.0253 (14)	−0.0006 (10)	0.0079 (11)	−0.0002 (11)
C13	0.0177 (13)	0.0144 (12)	0.0196 (13)	0.0015 (9)	0.0042 (10)	0.0003 (9)
C14	0.0188 (13)	0.0124 (11)	0.0181 (12)	0.0000 (9)	0.0048 (10)	−0.0005 (9)
C15	0.0182 (14)	0.0362 (15)	0.0282 (15)	−0.0041 (12)	0.0025 (11)	0.0011 (12)
C16	0.0358 (18)	0.0355 (17)	0.0188 (14)	−0.0067 (12)	0.0096 (12)	0.0003 (11)

Geometric parameters (Å, º)

Pt1—N3	2.019 (2)	C3—H3	0.9500
Pt1—N4	2.027 (2)	C4—C5	1.376 (4)
Pt1—N1	2.034 (2)	C4—H4	0.9500
Pt1—N2	2.044 (2)	C5—C6	1.425 (3)
O1—D1OA	0.864 (18)	C5—C15	1.493 (3)
O1—D1OB	0.868 (18)	C6—C14	1.395 (3)
O2—D2OA	0.881 (18)	C6—C7	1.441 (4)
O2—D2OB	0.856 (18)	C7—C8	1.355 (4)
O3—D3OA	0.857 (17)	C7—H7	0.9500
O3—D3OB	0.861 (18)	C8—C9	1.436 (4)
N1—C1	1.497 (3)	C8—H8	0.9500
N1—D1NA	0.84 (3)	C9—C13	1.400 (3)
N1—D1NB	0.93 (3)	C9—C10	1.424 (4)
N2—C2	1.488 (3)	C10—C11	1.376 (4)
N2—D2NA	0.96 (3)	C10—C16	1.497 (3)
N2—D2NB	0.82 (3)	C11—C12	1.400 (4)
N3—C3	1.332 (3)	C11—H11	0.9500
N3—C14	1.370 (3)	C12—H12	0.9500
N4—C12	1.334 (3)	C13—C14	1.429 (3)
N4—C13	1.368 (3)	C15—H15A	0.9800
C1—C2	1.505 (4)	C15—H15B	0.9800
C1—H1A	0.9900	C15—H15C	0.9800
C1—H1B	0.9900	C16—H16A	0.9800
C2—H2A	0.9900	C16—H16B	0.9800
C2—H2B	0.9900	C16—H16C	0.9800
C3—C4	1.394 (4)
N3—Pt1—N4	80.97 (8)	C3—C4—H4	119.1
N3—Pt1—N1	178.93 (8)	C4—C5—C6	116.8 (2)
N4—Pt1—N1	98.02 (9)	C4—C5—C15	121.0 (2)
N3—Pt1—N2	98.33 (9)	C6—C5—C15	122.2 (2)
N4—Pt1—N2	179.05 (9)	C14—C6—C5	118.4 (2)
N1—Pt1—N2	82.67 (9)	C14—C6—C7	117.7 (2)
D1OA—O1—D1OB	108 (3)	C5—C6—C7	124.0 (2)
D2OA—O2—D2OB	105 (3)	C8—C7—C6	121.4 (2)
D3OA—O3—D3OB	103 (3)	C8—C7—H7	119.3
C1—N1—Pt1	109.89 (16)	C6—C7—H7	119.3
C1—N1—D1NA	106 (2)	C7—C8—C9	121.6 (2)
Pt1—N1—D1NA	113 (2)	C7—C8—H8	119.2
C1—N1—D1NB	112.9 (19)	C9—C8—H8	119.2
Pt1—N1—D1NB	105.4 (19)	C13—C9—C10	117.8 (2)
D1NA—N1—D1NB	110 (3)	C13—C9—C8	117.7 (2)
C2—N2—Pt1	110.58 (16)	C10—C9—C8	124.5 (2)
C2—N2—D2NA	106.8 (16)	C11—C10—C9	117.5 (2)
Pt1—N2—D2NA	110.3 (17)	C11—C10—C16	121.4 (2)
C2—N2—D2NB	109 (2)	C9—C10—C16	121.1 (2)
Pt1—N2—D2NB	112 (2)	C10—C11—C12	121.5 (2)
D2NA—N2—D2NB	108 (3)	C10—C11—H11	119.3
C3—N3—C14	118.0 (2)	C12—C11—H11	119.3
C3—N3—Pt1	128.42 (18)	N4—C12—C11	121.7 (2)
C14—N3—Pt1	113.55 (16)	N4—C12—H12	119.1
C12—N4—C13	118.0 (2)	C11—C12—H12	119.1
C12—N4—Pt1	128.49 (19)	N4—C13—C9	123.4 (2)
C13—N4—Pt1	113.43 (16)	N4—C13—C14	115.9 (2)
N1—C1—C2	107.4 (2)	C9—C13—C14	120.7 (2)
N1—C1—H1A	110.2	N3—C14—C6	123.1 (2)
C2—C1—H1A	110.2	N3—C14—C13	116.0 (2)
N1—C1—H1B	110.2	C6—C14—C13	120.9 (2)
C2—C1—H1B	110.2	C5—C15—H15A	109.5
H1A—C1—H1B	108.5	C5—C15—H15B	109.5
N2—C2—C1	107.3 (2)	H15A—C15—H15B	109.5
N2—C2—H2A	110.3	C5—C15—H15C	109.5
C1—C2—H2A	110.3	H15A—C15—H15C	109.5
N2—C2—H2B	110.3	H15B—C15—H15C	109.5
C1—C2—H2B	110.3	C10—C16—H16A	109.5
H2A—C2—H2B	108.5	C10—C16—H16B	109.5
N3—C3—C4	121.7 (2)	H16A—C16—H16B	109.5
N3—C3—H3	119.1	C10—C16—H16C	109.5
C4—C3—H3	119.1	H16A—C16—H16C	109.5
C5—C4—C3	121.9 (2)	H16B—C16—H16C	109.5
C5—C4—H4	119.1
N4—Pt1—N1—C1	−164.76 (18)	C13—C9—C10—C11	−0.5 (3)
N2—Pt1—N1—C1	15.90 (18)	C8—C9—C10—C11	179.9 (2)
N3—Pt1—N2—C2	−167.02 (18)	C13—C9—C10—C16	−179.9 (2)
N1—Pt1—N2—C2	12.61 (19)	C8—C9—C10—C16	0.5 (4)
N4—Pt1—N3—C3	178.5 (2)	C9—C10—C11—C12	−0.2 (4)
N2—Pt1—N3—C3	−2.2 (2)	C16—C10—C11—C12	179.1 (2)
N4—Pt1—N3—C14	−3.84 (16)	C13—N4—C12—C11	−0.4 (4)
N2—Pt1—N3—C14	175.50 (17)	Pt1—N4—C12—C11	−177.21 (19)
N3—Pt1—N4—C12	−179.7 (2)	C10—C11—C12—N4	0.7 (4)
N1—Pt1—N4—C12	0.7 (2)	C12—N4—C13—C9	−0.4 (4)
N3—Pt1—N4—C13	3.36 (16)	Pt1—N4—C13—C9	176.87 (18)
N1—Pt1—N4—C13	−176.28 (17)	C12—N4—C13—C14	−179.7 (2)
Pt1—N1—C1—C2	−41.0 (3)	Pt1—N4—C13—C14	−2.4 (3)
Pt1—N2—C2—C1	−38.2 (3)	C10—C9—C13—N4	0.9 (4)
N1—C1—C2—N2	51.3 (3)	C8—C9—C13—N4	−179.5 (2)
C14—N3—C3—C4	−2.1 (4)	C10—C9—C13—C14	−179.9 (2)
Pt1—N3—C3—C4	175.55 (18)	C8—C9—C13—C14	−0.3 (3)
N3—C3—C4—C5	0.0 (4)	C3—N3—C14—C6	1.5 (4)
C3—C4—C5—C6	2.6 (4)	Pt1—N3—C14—C6	−176.42 (18)
C3—C4—C5—C15	−176.5 (2)	C3—N3—C14—C13	−178.3 (2)
C4—C5—C6—C14	−3.0 (4)	Pt1—N3—C14—C13	3.7 (3)
C15—C5—C6—C14	176.1 (2)	C5—C6—C14—N3	1.0 (4)
C4—C5—C6—C7	178.0 (2)	C7—C6—C14—N3	−179.9 (2)
C15—C5—C6—C7	−2.9 (4)	C5—C6—C14—C13	−179.1 (2)
C14—C6—C7—C8	0.4 (4)	C7—C6—C14—C13	0.0 (3)
C5—C6—C7—C8	179.5 (2)	N4—C13—C14—N3	−0.9 (3)
C6—C7—C8—C9	−0.7 (4)	C9—C13—C14—N3	179.8 (2)
C7—C8—C9—C13	0.7 (4)	N4—C13—C14—C6	179.2 (2)
C7—C8—C9—C10	−179.7 (2)	C9—C13—C14—C6	0.0 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—D1OA···Cl2	0.86 (2)	2.41 (2)	3.257 (2)	166 (3)
O1—D1OB···Cl1	0.87 (2)	2.32 (2)	3.160 (2)	162 (3)
O2—D2OA···Cl1	0.88 (2)	2.41 (2)	3.284 (2)	175 (3)
O2—D2OB···O3	0.86 (2)	1.95 (2)	2.788 (3)	168 (4)
O3—D3OA···Cl1^i	0.86 (2)	2.35 (2)	3.177 (2)	164 (3)
O3—D3OB···Cl2^ii	0.86 (2)	2.32 (2)	3.181 (2)	174 (3)
N1—D1NA···Cl1^i	0.84 (3)	2.43 (3)	3.226 (3)	159 (3)
N1—D1NB···O1	0.93 (3)	1.97 (3)	2.836 (3)	155 (3)
N2—D2NA···Cl2^i	0.96 (3)	2.27 (3)	3.216 (3)	166 (2)
N2—D2NB···Cl2^iii	0.82 (3)	2.61 (3)	3.336 (2)	149 (3)

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