Bis(2,2'-bipyrimidine-κ(2)N(1),N(1'))palladium(II) bis-(tetra-fluoro-borate) acetonitrile monosolvate.

The reaction of [Pd(MeCN)(4)](BF(4))(2) with 2,2'-bipyrimidine (bpm) in MeCN-CHCl(3) afforded the title compound, [Pd(C(8)H(6)N(4))(2)](BF(4))(2)·C(2)H(3)N. The asymmetric unit contains two half complexes, with the Pd(II) atoms both lying on a twofold axis. Each metal atom adopts a tetra-hedrally distorted square-planar geometry. In the crystal, [Pd(bpm)(2)] dications are linked by C-H⋯N hydrogen bonds, forming chains parallel to the b axis. The chains are further linked by C-H⋯F and C-H⋯N inter-actions involving the tetra-fluoro-borate anions and acetonitrile mol-ecules. In this way, each chain interacts with six surrounding chains to generate the observed three-dimensional structure.

Related literature

Similar Pd(bpm)2 complexes are unknown, but the subject of related dicationic adducts of PdII with 2,2′-bipyridyl (bpy) has been reviewed by Constable (1989 ▶) and McKenzie (1971 ▶), and the structures of representative analogues have been reported by Chieh (1972 ▶), Duong et al. (2011 ▶), Gao et al. (2010 ▶), Geremia et al. (1992 ▶), Hinamoto et al. (1972 ▶), Maeda et al. (1986 ▶), Milani et al. (1997 ▶), Stoccoro et al. (2002 ▶), Wehman et al. (1994 ▶) and Yue et al. (2008 ▶).

Experimental

Crystal data

[Pd(C8H6N4)2](BF4)2·C2H3N

M = 637.41

Monoclinic,

a = 18.0686 (4) Å

b = 18.1126 (4) Å

c = 14.8351 (3) Å

β = 108.613 (1)°

V = 4601.13 (17) Å3

Z = 8

Cu Kα radiation

μ = 7.38 mm−1

T = 200 K

0.20 × 0.11 × 0.10 mm

Data collection

Bruker SMART 6000 diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T min = 0.311, T max = 0.478

31076 measured reflections

4246 independent reflections

4006 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.030

wR(F 2) = 0.081

S = 1.03

4246 reflections

347 parameters

H-atom parameters constrained

Δρmax = 1.07 e Å−3

Δρmin = −0.75 e Å−3

Data collection: SMART (Bruker, 2003 ▶); cell refinement: SAINT (Bruker, 2003 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶) and Materials Studio (Accelrys, 2002 ▶); software used to prepare material for publication: UdMX (Maris, 2004 ▶) and publCIF (Westrip, 2010 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812041591/rz5009sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812041591/rz5009Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536812041591/rz5009Isup3.cdx

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Pd(C8H6N4)2](BF4)2·C2H3N	F(000) = 2512
Mr = 637.41	Dx = 1.840 Mg m−3
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -C 2yc	Cell parameters from 20829 reflections
a = 18.0686 (4) Å	θ = 3.6–68.8°
b = 18.1126 (4) Å	µ = 7.38 mm−1
c = 14.8351 (3) Å	T = 200 K
β = 108.613 (1)°	Block, yellow
V = 4601.13 (17) Å3	0.20 × 0.11 × 0.10 mm
Z = 8

Bruker SMART 6000 diffractometer	4246 independent reflections
Radiation source: Rotating anode	4006 reflections with I > 2σ(I)
Montel 200 optics monochromator	Rint = 0.031
Detector resolution: 5.5 pixels mm-1	θmax = 68.9°, θmin = 3.6°
ω scans	h = −21→21
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	k = −20→21
Tmin = 0.311, Tmax = 0.478	l = −17→17
31076 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.030	H-atom parameters constrained
wR(F2) = 0.081	w = 1/[σ2(Fo2) + (0.0458P)2 + 11.6117P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max = 0.002
4246 reflections	Δρmax = 1.07 e Å−3
347 parameters	Δρmin = −0.75 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.000355 (19)

Experimental. X-ray crystallographic data for I were collected from a single-crystal sample, which was mounted on a loop fiber. Data were collected using a Bruker Platform diffractometer, equipped with a Bruker SMART 4 K Charged-Coupled Device (CCD) Area Detector using the program APEX2 and a Nonius FR591 rotating anode equipped with Montel 200 optics. The crystal-to-detector distance was 5.0 cm, and the data collection was carried out in 512 x 512 pixel mode. The initial unit-cell parameters were determined by a least-squares fit of the angular setting of strong reflections, collected by a 10.0 degree scan in 33 frames over four different parts of the reciprocal space (132 frames total). One complete sphere of data was collected to better than 0.80 Å resolution.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l. s. planes) were estimated using the full covariance matrix. The cell e.s.d.'s were 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 were only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s was 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 and 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.

	x	y	z	Uiso*/Ueq
Pd1	0.5000	0.336135 (12)	0.2500	0.02227 (10)
N1	0.44850 (12)	0.40551 (11)	0.13874 (15)	0.0244 (4)
C1	0.46387 (15)	0.47710 (14)	0.13047 (19)	0.0294 (5)
H1	0.5006	0.5018	0.1821	0.035*
C2	0.42721 (17)	0.51534 (15)	0.0482 (2)	0.0359 (6)
H2	0.4374	0.5662	0.0422	0.043*
C3	0.37529 (18)	0.47724 (17)	−0.0249 (2)	0.0408 (7)
H3	0.3476	0.5032	−0.0812	0.049*
N3	0.36210 (15)	0.40471 (13)	−0.01994 (16)	0.0369 (5)
C4	0.39986 (14)	0.37213 (14)	0.06120 (17)	0.0277 (5)
C5	0.38836 (14)	0.29190 (14)	0.07200 (17)	0.0269 (5)
N5	0.42993 (12)	0.26406 (11)	0.15719 (15)	0.0271 (4)
C6	0.41328 (16)	0.19506 (14)	0.1769 (2)	0.0364 (6)
H6	0.4384	0.1749	0.2381	0.044*
C7	0.35997 (17)	0.15308 (15)	0.1090 (2)	0.0399 (7)
H7	0.3477	0.1041	0.1223	0.048*
C8	0.32526 (15)	0.18455 (16)	0.0217 (2)	0.0367 (6)
H8	0.2909	0.1555	−0.0272	0.044*
N8	0.33807 (13)	0.25488 (13)	0.00285 (16)	0.0340 (5)
Pd2	0.0000	0.339164 (12)	0.2500	0.02379 (10)
N9	0.06638 (12)	0.25370 (11)	0.23195 (15)	0.0278 (4)
C9	0.13999 (16)	0.25769 (15)	0.2297 (2)	0.0349 (6)
H9	0.1621	0.3045	0.2248	0.042*
C10	0.18357 (18)	0.19496 (17)	0.2344 (2)	0.0429 (7)
H10	0.2356	0.1974	0.2327	0.051*
C11	0.14925 (18)	0.12859 (16)	0.2417 (2)	0.0433 (7)
H11	0.1779	0.0844	0.2428	0.052*
N11	0.07683 (15)	0.12380 (12)	0.24733 (18)	0.0382 (5)
C12	0.03914 (15)	0.18649 (14)	0.24370 (18)	0.0287 (5)
N12	0.04299 (12)	0.42452 (11)	0.19429 (15)	0.0257 (4)
C13	0.07712 (16)	0.42029 (14)	0.12669 (19)	0.0314 (6)
H13	0.0896	0.3733	0.1070	0.038*
C14	0.09431 (17)	0.48312 (16)	0.0854 (2)	0.0364 (6)
H14	0.1184	0.4806	0.0372	0.044*
C15	0.07533 (17)	0.54960 (16)	0.1164 (2)	0.0393 (6)
H15	0.0890	0.5937	0.0909	0.047*
N15	0.03809 (14)	0.55468 (12)	0.18145 (17)	0.0349 (5)
C16	0.02226 (14)	0.49198 (13)	0.21627 (18)	0.0274 (5)
B1	0.2913 (2)	0.4231 (2)	0.2178 (3)	0.0447 (9)
F1	0.27658 (12)	0.46150 (13)	0.13349 (14)	0.0621 (5)
F2	0.36425 (10)	0.43957 (11)	0.27788 (13)	0.0496 (5)
F3	0.28788 (19)	0.34813 (14)	0.19523 (19)	0.0962 (10)
F4	0.23745 (14)	0.4387 (3)	0.26137 (17)	0.1125 (13)
B2	0.0691 (2)	0.24786 (18)	0.5158 (2)	0.0373 (7)
F5	0.09817 (13)	0.24491 (16)	0.44108 (15)	0.0749 (7)
F6	0.00661 (12)	0.29637 (11)	0.49624 (17)	0.0644 (6)
F7	0.04445 (17)	0.17898 (12)	0.5299 (2)	0.0885 (9)
F8	0.12677 (16)	0.27183 (14)	0.59487 (17)	0.0869 (8)
N16	0.35521 (18)	0.04534 (18)	0.5904 (2)	0.0563 (8)
C17	0.3079 (2)	0.08800 (18)	0.5644 (2)	0.0446 (7)
C18	0.2469 (2)	0.1432 (2)	0.5312 (4)	0.0771 (13)
H18A	0.2098	0.1274	0.4703	0.116*
H18B	0.2703	0.1905	0.5229	0.116*
H18C	0.2195	0.1489	0.5781	0.116*

	U11	U22	U33	U12	U13	U23
Pd1	0.02316 (15)	0.01678 (15)	0.02304 (15)	0.000	0.00197 (10)	0.000
N1	0.0241 (10)	0.0227 (10)	0.0262 (10)	0.0030 (8)	0.0075 (8)	0.0017 (8)
C1	0.0293 (12)	0.0249 (13)	0.0352 (14)	0.0010 (10)	0.0118 (11)	0.0013 (10)
C2	0.0417 (15)	0.0280 (14)	0.0422 (15)	0.0048 (11)	0.0193 (13)	0.0103 (11)
C3	0.0503 (17)	0.0391 (16)	0.0316 (14)	0.0103 (13)	0.0112 (12)	0.0129 (12)
N3	0.0430 (13)	0.0380 (13)	0.0259 (11)	0.0062 (10)	0.0055 (10)	0.0034 (9)
C4	0.0266 (12)	0.0297 (13)	0.0269 (12)	0.0028 (10)	0.0086 (10)	−0.0010 (10)
C5	0.0244 (12)	0.0282 (13)	0.0277 (12)	0.0023 (10)	0.0076 (10)	−0.0030 (10)
N5	0.0262 (10)	0.0215 (10)	0.0294 (10)	0.0004 (8)	0.0030 (8)	−0.0033 (8)
C6	0.0362 (14)	0.0235 (13)	0.0415 (15)	−0.0010 (11)	0.0014 (12)	0.0010 (11)
C7	0.0330 (15)	0.0244 (13)	0.0557 (18)	−0.0030 (11)	0.0050 (13)	−0.0044 (12)
C8	0.0276 (13)	0.0324 (14)	0.0448 (16)	−0.0021 (11)	0.0041 (11)	−0.0160 (12)
N8	0.0284 (11)	0.0375 (13)	0.0320 (11)	0.0020 (9)	0.0039 (9)	−0.0083 (10)
Pd2	0.02831 (16)	0.01530 (15)	0.03000 (16)	0.000	0.01245 (11)	0.000
N9	0.0341 (11)	0.0218 (10)	0.0297 (10)	0.0020 (9)	0.0133 (9)	0.0000 (8)
C9	0.0360 (14)	0.0297 (14)	0.0423 (15)	0.0015 (11)	0.0169 (12)	0.0030 (11)
C10	0.0393 (16)	0.0415 (17)	0.0533 (18)	0.0082 (13)	0.0224 (14)	0.0001 (14)
C11	0.0466 (17)	0.0298 (15)	0.0564 (18)	0.0111 (12)	0.0204 (14)	−0.0024 (13)
N11	0.0448 (13)	0.0221 (11)	0.0487 (14)	0.0042 (10)	0.0161 (11)	−0.0022 (10)
C12	0.0351 (14)	0.0219 (12)	0.0296 (13)	−0.0001 (10)	0.0109 (10)	−0.0011 (10)
N12	0.0276 (11)	0.0205 (10)	0.0288 (10)	−0.0008 (8)	0.0084 (9)	0.0008 (8)
C13	0.0348 (14)	0.0276 (13)	0.0332 (14)	0.0006 (10)	0.0129 (11)	0.0015 (10)
C14	0.0379 (14)	0.0366 (15)	0.0375 (14)	−0.0008 (12)	0.0161 (12)	0.0067 (12)
C15	0.0422 (15)	0.0306 (14)	0.0464 (16)	−0.0036 (12)	0.0161 (13)	0.0106 (12)
N15	0.0413 (13)	0.0222 (11)	0.0414 (13)	−0.0026 (9)	0.0136 (10)	0.0031 (9)
C16	0.0291 (12)	0.0197 (12)	0.0303 (12)	−0.0006 (10)	0.0049 (10)	−0.0003 (10)
B1	0.0313 (17)	0.070 (2)	0.0338 (17)	−0.0178 (16)	0.0122 (14)	−0.0100 (16)
F1	0.0564 (12)	0.0816 (15)	0.0497 (11)	0.0054 (11)	0.0191 (9)	0.0139 (10)
F2	0.0344 (9)	0.0654 (12)	0.0463 (10)	−0.0109 (8)	0.0090 (8)	−0.0200 (9)
F3	0.128 (2)	0.0692 (16)	0.0691 (16)	−0.0514 (16)	−0.0002 (15)	−0.0088 (12)
F4	0.0420 (12)	0.251 (4)	0.0502 (13)	0.0151 (18)	0.0228 (11)	−0.0055 (18)
B2	0.0413 (17)	0.0302 (16)	0.0408 (17)	0.0011 (13)	0.0135 (14)	0.0002 (13)
F5	0.0584 (13)	0.119 (2)	0.0545 (12)	0.0111 (13)	0.0274 (10)	0.0160 (13)
F6	0.0525 (12)	0.0496 (12)	0.0871 (15)	0.0149 (9)	0.0167 (11)	0.0021 (11)
F7	0.105 (2)	0.0334 (10)	0.157 (3)	−0.0061 (12)	0.084 (2)	−0.0008 (14)
F8	0.0868 (17)	0.0793 (17)	0.0655 (14)	0.0202 (13)	−0.0165 (12)	−0.0219 (12)
N16	0.0577 (18)	0.070 (2)	0.0405 (15)	0.0225 (16)	0.0146 (13)	−0.0056 (14)
C17	0.0408 (17)	0.052 (2)	0.0403 (17)	0.0031 (14)	0.0113 (14)	−0.0006 (13)
C18	0.047 (2)	0.060 (2)	0.117 (4)	0.0100 (19)	0.017 (2)	0.030 (3)

Pd1—N5i	2.022 (2)	C9—H9	0.9500
Pd1—N5	2.022 (2)	C10—C11	1.372 (5)
Pd1—N1	2.047 (2)	C10—H10	0.9500
Pd1—N1i	2.047 (2)	C11—N11	1.340 (4)
N1—C1	1.340 (3)	C11—H11	0.9500
N1—C4	1.348 (3)	N11—C12	1.316 (3)
C1—C2	1.375 (4)	C12—C12ii	1.485 (5)
C1—H1	0.9500	N12—C13	1.337 (3)
C2—C3	1.372 (4)	N12—C16	1.348 (3)
C2—H2	0.9500	C13—C14	1.374 (4)
C3—N3	1.341 (4)	C13—H13	0.9500
C3—H3	0.9500	C14—C15	1.371 (4)
N3—C4	1.318 (3)	C14—H14	0.9500
C4—C5	1.484 (4)	C15—N15	1.345 (4)
C5—N8	1.316 (3)	C15—H15	0.9500
C5—N5	1.345 (3)	N15—C16	1.316 (3)
N5—C6	1.339 (3)	C16—C16ii	1.471 (5)
C6—C7	1.378 (4)	B1—F4	1.357 (4)
C6—H6	0.9500	B1—F2	1.368 (4)
C7—C8	1.369 (4)	B1—F1	1.381 (4)
C7—H7	0.9500	B1—F3	1.396 (5)
C8—N8	1.340 (4)	B2—F7	1.363 (4)
C8—H8	0.9500	B2—F8	1.368 (4)
Pd2—N12	2.021 (2)	B2—F5	1.371 (4)
Pd2—N12ii	2.021 (2)	B2—F6	1.386 (4)
Pd2—N9	2.028 (2)	N16—C17	1.125 (4)
Pd2—N9ii	2.028 (2)	C17—C18	1.452 (5)
N9—C9	1.343 (3)	C18—H18a	0.9800
N9—C12	1.345 (3)	C18—H18b	0.9800
C9—C10	1.372 (4)	C18—H18c	0.9800
N5i—PD1—N5	99.59 (11)	N9—C9—H9	119.6
N5i—PD1—N1	165.94 (8)	C10—C9—H9	119.6
N5—PD1—N1	79.78 (8)	C9—C10—C11	117.6 (3)
N5i—PD1—N1i	79.78 (8)	C9—C10—H10	121.2
N5—PD1—N1i	165.94 (8)	C11—C10—H10	121.2
N1—PD1—N1i	104.24 (11)	N11—C11—C10	122.4 (3)
C1—N1—C4	117.0 (2)	N11—C11—H11	118.8
C1—N1—PD1	127.87 (17)	C10—C11—H11	118.8
C4—N1—PD1	114.69 (16)	C12—N11—C11	116.4 (2)
N1—C1—C2	120.9 (2)	N11—C12—N9	125.4 (2)
N1—C1—H1	119.6	N11—C12—C12ii	119.74 (16)
C2—C1—H1	119.6	N9—C12—C12ii	114.78 (14)
C3—C2—C1	117.5 (3)	C13—N12—C16	117.6 (2)
C3—C2—H2	121.2	C13—N12—PD2	126.33 (17)
C1—C2—H2	121.2	C16—N12—PD2	114.94 (17)
N3—C3—C2	122.5 (3)	N12—C13—C14	120.7 (2)
N3—C3—H3	118.7	N12—C13—H13	119.6
C2—C3—H3	118.7	C14—C13—H13	119.6
C4—N3—C3	116.1 (2)	C15—C14—C13	117.5 (3)
N3—C4—N1	125.8 (2)	C15—C14—H14	121.2
N3—C4—C5	119.2 (2)	C13—C14—H14	121.2
N1—C4—C5	115.0 (2)	N15—C15—C14	122.5 (2)
N8—C5—N5	125.5 (2)	N15—C15—H15	118.8
N8—C5—C4	120.0 (2)	C14—C15—H15	118.8
N5—C5—C4	114.4 (2)	C16—N15—C15	116.3 (2)
C6—N5—C5	117.2 (2)	N15—C16—N12	125.1 (2)
C6—N5—PD1	126.12 (18)	N15—C16—C16ii	120.10 (15)
C5—N5—PD1	115.98 (16)	N12—C16—C16ii	114.78 (14)
N5—C6—C7	120.6 (3)	F4—B1—F2	109.5 (3)
N5—C6—H6	119.7	F4—B1—F1	111.5 (3)
C7—C6—H6	119.7	F2—B1—F1	110.3 (3)
C8—C7—C6	117.6 (3)	F4—B1—F3	109.5 (3)
C8—C7—H7	121.2	F2—B1—F3	109.1 (3)
C6—C7—H7	121.2	F1—B1—F3	106.9 (3)
N8—C8—C7	122.4 (2)	F7—B2—F8	110.8 (3)
N8—C8—H8	118.8	F7—B2—F5	108.5 (3)
C7—C8—H8	118.8	F8—B2—F5	108.8 (3)
C5—N8—C8	116.3 (2)	F7—B2—F6	109.2 (3)
N12—PD2—N12ii	80.22 (12)	F8—B2—F6	109.0 (3)
N12—PD2—N9	102.08 (8)	F5—B2—F6	110.6 (3)
N12ii—PD2—N9	163.44 (9)	N16—C17—C18	179.7 (4)
N12—PD2—N9ii	163.44 (9)	C17—C18—H18A	109.5
N12ii—PD2—N9ii	102.08 (8)	C17—C18—H18B	109.5
N9—PD2—N9ii	80.47 (12)	H18A—C18—H18B	109.5
C9—N9—C12	117.3 (2)	C17—C18—H18C	109.5
C9—N9—PD2	126.46 (18)	H18A—C18—H18C	109.5
C12—N9—PD2	114.67 (17)	H18B—C18—H18C	109.5
N9—C9—C10	120.7 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···N11iii	0.95	2.62	3.460 (4)	148
C6—H6···N15iv	0.95	2.45	3.237 (4)	140
C14—H14···N16v	0.95	2.40	3.228 (4)	146
C2—H2···F7v	0.95	2.38	3.282 (3)	159
C3—H3···F2vi	0.95	2.44	3.240 (3)	142
C8—H8···F3vii	0.95	2.45	3.270 (4)	145
C13—H13···F6ii	0.95	2.37	2.982 (3)	122
C15—H15···F8vi	0.95	2.52	3.408 (4)	155
C18—H18B···F5viii	0.98	2.55	3.373 (5)	142

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯N11i	0.95	2.62	3.460 (4)	148
C6—H6⋯N15ii	0.95	2.45	3.237 (4)	140
C14—H14⋯N16iii	0.95	2.40	3.228 (4)	146
C2—H2⋯F7iii	0.95	2.38	3.282 (3)	159
C3—H3⋯F2iv	0.95	2.44	3.240 (3)	142
C8—H8⋯F3v	0.95	2.45	3.270 (4)	145
C13—H13⋯F6vi	0.95	2.37	2.982 (3)	122
C15—H15⋯F8iv	0.95	2.52	3.408 (4)	155
C18—H18B⋯F5vii	0.98	2.55	3.373 (5)	142

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .