Bis­[tris­(pyrazol-1-yl)­methane-κ²N,N′]­platinum(II) bis­(hexa­fluoro­phosphate) nitro­methane solvate

The title complex, [Pt(C₁₀H₁₀N₆)₂](PF₆)₂·2CH₃NO₂, crystallizes with the Pt atom located on a crystallographic center of symmetry. The asymmetric unit comprises the anion, one-half cation and a nitro­methane mol­ecule. The anions and solvent pack to form a zigzag ribbon motif, alternating with layers of cations. The extended packing consists of a network of C—H...O, C—H...N and C—H...F intermolecular interactions.

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.025
• wR factor = 0.057
• Data-to-parameter ratio = 17.5

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.85 Ratio
PLAT244_ALERT_4_C Low Solvent  U(eq) as Compared to Neighbors ....         P1
PLAT244_ALERT_4_C Low Solvent  U(eq) as Compared to Neighbors ....         N7
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          3
              C H3 N O2

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

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

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Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2002); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and DIAMOND (Crystal Impact , 1997); software used to prepare material for publication: SHELXTL.

Bis[tris(pyrazol-1-yl)methane-κ²N,N']platinum(II) bis(hexafluorophosphate) nitromethane solvate

Crystal data

[Pt(C10H10N6)2](PF6)2·2CH3NO2	F(000) = 1008
Mr = 1035.60	Dx = 1.950 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.9329 (4) Å	Cell parameters from 7038 reflections
b = 23.2431 (10) Å	θ = 1.8–28.3°
c = 9.9054 (4) Å	µ = 4.19 mm^−1
β = 105.044 (1)°	T = 150 K
V = 1763.81 (14) Å^3	Plate, colorless
Z = 2	0.12 × 0.10 × 0.05 mm

Data collection

SMART6000 CCD diffractometer	4387 independent reflections
Radiation source: fine-focus sealed tube	3090 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.047
ω scans	θmax = 28.3°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −10→10
Tmin = 0.634, Tmax = 0.818	k = −30→30
23878 measured reflections	l = −13→13

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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.057	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.017P)^2 + 3.1656P] where P = (Fo^2 + 2Fc^2)/3
4387 reflections	(Δ/σ)max = 0.001
250 parameters	Δρmax = 0.80 e Å^−3
0 restraints	Δρmin = −0.62 e Å^−3

Special details

Experimental. K₂PtCl₄ (0.162 g, 0.390 mmol) and tris(pyrazol-1-yl)methane (2 equivalents, 0.168 g, 0.784 mmol) were combined in water (15 ml). The mixture was stirred at reflux for 2 h to yield a clear, colorless solution. An aqueous solution containing excess NH₄PF₆ was added and the mixture cooled to 5 °C for 1 h. The resulting white product was isolated by vacuum filtration (0.252 g yield). Single crystals were obtained as colorless plates from CH₃NO₂—Et₂O solutions. ¹H NMR (d₆-DMSO, δ): 9.53 (2H, s, C—H), 8.88 (4H, d, bound pz), 8.05 (2H, d, unbound pz), 7.95 (4H, d, bound pz), 7.75 (2H, d, unbound pz), 6.96 (4H, t, bound pz), 6.53 (2H, t, unbound pz) p.p.m..

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	0.5000	1.0000	1.0000	0.01796 (5)
N1	0.4271 (4)	0.91776 (12)	0.9711 (3)	0.0217 (6)
C1	0.3666 (5)	0.88055 (15)	1.0494 (4)	0.0253 (8)
H1	0.3594	0.8876	1.1422	0.030*
C2	0.3152 (5)	0.82969 (16)	0.9751 (4)	0.0303 (8)
H2	0.2673	0.7965	1.0071	0.036*
N2	0.4156 (4)	0.89074 (12)	0.8465 (3)	0.0236 (6)
C3	0.3474 (5)	0.83709 (16)	0.8474 (4)	0.0284 (8)
H3	0.3262	0.8099	0.7732	0.034*
N3	0.3773 (4)	1.01406 (11)	0.7993 (3)	0.0215 (6)
N4	0.3788 (4)	0.97327 (13)	0.7004 (3)	0.0233 (6)
C4	0.2866 (5)	1.05826 (16)	0.7320 (4)	0.0285 (8)
H4	0.2625	1.0928	0.7748	0.034*
C5	0.2320 (6)	1.04646 (17)	0.5890 (4)	0.0338 (9)
H5	0.1663	1.0710	0.5179	0.041*
N5	0.6585 (4)	0.93213 (14)	0.7865 (3)	0.0279 (7)
C6	0.2923 (5)	0.99235 (18)	0.5719 (4)	0.0305 (9)
H6	0.2763	0.9721	0.4862	0.037*
N6	0.7242 (5)	0.98017 (16)	0.7412 (4)	0.0403 (9)
C7	0.4703 (5)	0.92015 (14)	0.7358 (4)	0.0231 (7)
H7	0.4486	0.8949	0.6514	0.028*
C8	0.7823 (6)	0.9014 (2)	0.8769 (6)	0.0502 (12)
H8	0.7657	0.8667	0.9226	0.060*
C9	0.9354 (7)	0.9298 (3)	0.8899 (7)	0.0659 (16)
H9	1.0475	0.9189	0.9452	0.079*
C10	0.8935 (6)	0.9785 (3)	0.8046 (5)	0.0550 (14)
H10	0.9757	1.0066	0.7935	0.066*
P1	0.19558 (14)	0.66551 (4)	0.87996 (11)	0.0302 (2)
F1	0.2842 (4)	0.70264 (10)	0.7840 (3)	0.0460 (7)
F2	0.3387 (4)	0.61572 (10)	0.8862 (3)	0.0468 (7)
F3	0.3224 (4)	0.69416 (11)	1.0157 (3)	0.0527 (7)
F4	0.0570 (3)	0.71516 (11)	0.8762 (3)	0.0512 (7)
F5	0.1145 (4)	0.62778 (12)	0.9828 (4)	0.0698 (10)
F6	0.0734 (4)	0.63496 (14)	0.7477 (3)	0.0718 (10)
O1	−0.2976 (6)	0.69773 (19)	0.6379 (6)	0.0944 (17)
O2	−0.3404 (5)	0.7746 (2)	0.7403 (4)	0.0859 (15)
N7	−0.2872 (5)	0.7485 (2)	0.6552 (5)	0.0517 (11)
C11	−0.2034 (11)	0.7802 (3)	0.5662 (7)	0.101 (3)
H11A	−0.1186	0.8070	0.6228	0.151*
H11B	−0.2913	0.8018	0.4969	0.151*
H11C	−0.1431	0.7534	0.5182	0.151*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pt	0.02210 (8)	0.01405 (8)	0.01795 (8)	−0.00105 (11)	0.00559 (6)	−0.00113 (10)
N1	0.0251 (14)	0.0178 (14)	0.0223 (15)	−0.0013 (12)	0.0066 (12)	−0.0035 (12)
C1	0.0302 (19)	0.0212 (18)	0.0245 (19)	−0.0035 (15)	0.0071 (15)	0.0033 (14)
C2	0.038 (2)	0.0175 (18)	0.034 (2)	−0.0048 (16)	0.0067 (18)	0.0024 (16)
N2	0.0287 (16)	0.0186 (15)	0.0232 (16)	−0.0016 (12)	0.0065 (13)	−0.0026 (12)
C3	0.033 (2)	0.0148 (17)	0.034 (2)	−0.0025 (15)	0.0015 (17)	−0.0035 (15)
N3	0.0296 (15)	0.0143 (16)	0.0191 (14)	−0.0012 (10)	0.0037 (12)	−0.0008 (10)
N4	0.0303 (16)	0.0191 (15)	0.0183 (16)	0.0004 (13)	0.0026 (12)	−0.0019 (12)
C4	0.030 (2)	0.0216 (19)	0.032 (2)	0.0037 (16)	0.0052 (17)	0.0023 (16)
C5	0.042 (2)	0.026 (2)	0.027 (2)	0.0035 (18)	−0.0009 (18)	0.0025 (16)
N5	0.0285 (17)	0.0274 (17)	0.0292 (18)	0.0019 (13)	0.0103 (14)	−0.0044 (13)
C6	0.040 (2)	0.027 (3)	0.0204 (16)	−0.0022 (18)	0.0016 (14)	0.0002 (16)
N6	0.040 (2)	0.053 (2)	0.0291 (18)	−0.0150 (16)	0.0099 (16)	0.0072 (16)
C7	0.036 (2)	0.0140 (16)	0.0221 (18)	−0.0023 (14)	0.0121 (16)	−0.0024 (13)
C8	0.039 (3)	0.041 (3)	0.068 (4)	0.013 (2)	0.009 (2)	0.010 (2)
C9	0.030 (3)	0.072 (4)	0.089 (5)	0.008 (3)	0.004 (3)	−0.004 (3)
C10	0.037 (3)	0.079 (4)	0.051 (3)	−0.017 (2)	0.016 (2)	0.000 (3)
P1	0.0378 (6)	0.0213 (5)	0.0343 (6)	−0.0016 (4)	0.0140 (5)	−0.0037 (4)
F1	0.0706 (18)	0.0314 (13)	0.0460 (16)	0.0003 (13)	0.0330 (14)	0.0099 (12)
F2	0.0620 (17)	0.0298 (13)	0.0577 (17)	0.0142 (12)	0.0320 (14)	0.0079 (12)
F3	0.075 (2)	0.0390 (15)	0.0341 (15)	0.0038 (14)	−0.0026 (13)	−0.0038 (12)
F4	0.0466 (15)	0.0445 (16)	0.0634 (19)	0.0171 (13)	0.0159 (14)	−0.0068 (14)
F5	0.096 (2)	0.0377 (16)	0.103 (3)	−0.0087 (16)	0.074 (2)	0.0008 (16)
F6	0.0573 (19)	0.070 (2)	0.077 (2)	−0.0129 (16)	−0.0024 (16)	−0.0431 (18)
O1	0.069 (3)	0.052 (3)	0.132 (4)	−0.013 (2)	−0.028 (3)	0.014 (3)
O2	0.055 (2)	0.153 (5)	0.055 (3)	0.004 (3)	0.023 (2)	−0.019 (3)
N7	0.042 (2)	0.058 (3)	0.050 (3)	−0.008 (2)	0.003 (2)	−0.002 (2)
C11	0.145 (7)	0.098 (6)	0.079 (5)	−0.038 (5)	0.065 (5)	−0.007 (4)

Geometric parameters (Å, º)

Pt—N1	1.996 (3)	N5—N6	1.357 (5)
Pt—N1^i	1.996 (3)	N5—C7	1.473 (5)
Pt—N3^i	2.000 (3)	C6—H6	0.9500
Pt—N3	2.000 (3)	N6—C10	1.328 (6)
N1—C1	1.332 (4)	C7—H7	1.0000
N1—N2	1.367 (4)	C8—C9	1.359 (7)
C1—C2	1.396 (5)	C8—H8	0.9500
C1—H1	0.9500	C9—C10	1.399 (8)
C2—C3	1.365 (5)	C9—H9	0.9500
C2—H2	0.9500	C10—H10	0.9500
N2—C3	1.360 (5)	P1—F1	1.578 (2)
N2—C7	1.450 (4)	P1—F6	1.581 (3)
C3—H3	0.9500	P1—F4	1.588 (3)
N3—C4	1.330 (4)	P1—F5	1.600 (3)
N3—N4	1.366 (4)	P1—F3	1.600 (3)
N4—C6	1.354 (5)	P1—F2	1.611 (3)
N4—C7	1.429 (4)	O1—N7	1.191 (6)
C4—C5	1.396 (5)	O2—N7	1.201 (5)
C4—H4	0.9500	N7—C11	1.438 (7)
C5—C6	1.372 (5)	C11—H11A	0.9800
C5—H5	0.9500	C11—H11B	0.9800
N5—C8	1.349 (5)	C11—H11C	0.9800
N1—Pt—N1^i	180.000 (1)	N4—C7—N2	111.1 (3)
N1—Pt—N3^i	91.95 (11)	N4—C7—N5	109.0 (3)
N1^i—Pt—N3^i	88.05 (11)	N2—C7—N5	107.9 (3)
N1—Pt—N3	88.05 (11)	N4—C7—H7	109.6
N1^i—Pt—N3	91.95 (11)	N2—C7—H7	109.6
N3^i—Pt—N3	180.000 (1)	N5—C7—H7	109.6
C1—N1—N2	106.1 (3)	N5—C8—C9	106.5 (5)
C1—N1—Pt	132.3 (2)	N5—C8—H8	126.7
N2—N1—Pt	121.2 (2)	C9—C8—H8	126.7
N1—C1—C2	110.1 (3)	C8—C9—C10	105.6 (5)
N1—C1—H1	125.0	C8—C9—H9	127.2
C2—C1—H1	125.0	C10—C9—H9	127.2
C3—C2—C1	106.4 (3)	N6—C10—C9	111.3 (4)
C3—C2—H2	126.8	N6—C10—H10	124.4
C1—C2—H2	126.8	C9—C10—H10	124.4
C3—N2—N1	110.4 (3)	F1—P1—F6	91.11 (18)
C3—N2—C7	129.4 (3)	F1—P1—F4	90.15 (15)
N1—N2—C7	120.2 (3)	F6—P1—F4	92.03 (17)
N2—C3—C2	107.0 (3)	F1—P1—F5	177.3 (2)
N2—C3—H3	126.5	F6—P1—F5	91.2 (2)
C2—C3—H3	126.5	F4—P1—F5	91.32 (16)
C4—N3—N4	106.3 (3)	F1—P1—F3	89.85 (16)
C4—N3—Pt	133.2 (3)	F6—P1—F3	177.88 (18)
N4—N3—Pt	120.5 (2)	F4—P1—F3	89.86 (15)
C6—N4—N3	110.5 (3)	F5—P1—F3	87.84 (18)
C6—N4—C7	128.0 (3)	F1—P1—F2	89.80 (14)
N3—N4—C7	121.5 (3)	F6—P1—F2	89.07 (17)
N3—C4—C5	110.0 (3)	F4—P1—F2	178.91 (17)
N3—C4—H4	125.0	F5—P1—F2	88.70 (15)
C5—C4—H4	125.0	F3—P1—F2	89.04 (15)
C6—C5—C4	106.2 (3)	O1—N7—O2	125.3 (6)
C6—C5—H5	126.9	O1—N7—C11	116.5 (6)
C4—C5—H5	126.9	O2—N7—C11	118.3 (5)
C8—N5—N6	112.3 (4)	N7—C11—H11A	109.5
C8—N5—C7	128.7 (4)	N7—C11—H11B	109.5
N6—N5—C7	119.0 (3)	H11A—C11—H11B	109.5
N4—C6—C5	107.0 (3)	N7—C11—H11C	109.5
N4—C6—H6	126.5	H11A—C11—H11C	109.5
C5—C6—H6	126.5	H11B—C11—H11C	109.5
C10—N6—N5	104.3 (4)
N3—Pt—N1—C1	−138.3 (3)	C7—N4—C6—C5	−177.4 (3)
N3—Pt—N1—N2	34.3 (3)	C4—C5—C6—N4	0.1 (5)
N2—N1—C1—C2	−0.3 (4)	C8—N5—N6—C10	0.6 (5)
Pt—N1—C1—C2	173.1 (3)	C7—N5—N6—C10	−179.9 (4)
N1—C1—C2—C3	0.2 (5)	C6—N4—C7—N2	−129.2 (4)
C1—N1—N2—C3	0.3 (4)	N3—N4—C7—N2	54.4 (4)
Pt—N1—N2—C3	−174.0 (2)	C6—N4—C7—N5	112.1 (4)
C1—N1—N2—C7	179.4 (3)	N3—N4—C7—N5	−64.3 (4)
Pt—N1—N2—C7	5.1 (4)	C3—N2—C7—N4	122.5 (4)
N1—N2—C3—C2	−0.2 (4)	N1—N2—C7—N4	−56.4 (4)
C7—N2—C3—C2	−179.2 (4)	C3—N2—C7—N5	−118.1 (4)
C1—C2—C3—N2	0.0 (4)	N1—N2—C7—N5	63.0 (4)
N1—Pt—N3—C4	144.4 (4)	C8—N5—C7—N4	152.2 (4)
N1—Pt—N3—N4	−36.3 (3)	N6—N5—C7—N4	−27.1 (4)
C4—N3—N4—C6	1.1 (4)	C8—N5—C7—N2	31.4 (5)
Pt—N3—N4—C6	−178.3 (2)	N6—N5—C7—N2	−147.9 (3)
C4—N3—N4—C7	178.1 (3)	N6—N5—C8—C9	−0.9 (6)
Pt—N3—N4—C7	−1.4 (4)	C7—N5—C8—C9	179.7 (4)
N4—N3—C4—C5	−1.0 (4)	N5—C8—C9—C10	0.8 (6)
Pt—N3—C4—C5	178.3 (3)	N5—N6—C10—C9	−0.1 (6)
N3—C4—C5—C6	0.6 (5)	C8—C9—C10—N6	−0.4 (7)
N3—N4—C6—C5	−0.7 (4)

Symmetry code: (i) −x+1, −y+2, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···N6^ii	0.95	2.51	3.136 (5)	123
C4—H4···O1^iii	0.95	2.58	3.481 (6)	159
C5—H5···F5^iii	0.95	2.59	3.259 (5)	128
C3—H3···F1	0.95	2.52	3.201 (4)	129
C2—H2···F3	0.95	2.42	3.174 (5)	137
C6—H6···F2^iv	0.95	2.38	3.190 (5)	144
C7—H7···F2^iv	1.00	2.56	3.450 (5)	149
C3—H3···F3^iv	0.95	2.55	3.321 (5)	139
C7—H7···F3^iv	1.00	2.53	3.444 (4)	152
C11—H11C···F4^iv	0.98	2.49	3.136 (7)	123
C1—H1···F2^v	0.95	2.47	3.402 (5)	168

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