cis-Dichlorido[2-(3,5-dimethyl-1H-pyrazol-1-yl-κN(2))ethanamine-κN]palladium(II) dichloro-methane monosolvate.

In the title compound, [PdCl(2)(C(7)H(13)N(3))]·CH(2)Cl(2), the 2-(3,5-dimethyl-1H-pyrazol-1-yl)ethanamine ligand chelates the Pd(II) atom via two N atoms forming a six-membered ring resulting in a distorted square-planar metal coordination environment, highlighted by N-Pd-Cl angles of 172.63 (8) and 174.98 (9)°. In addition to N-H⋯Cl hydrogen bonds creating infinite chains along [001], several C-H⋯Cl inter-actions are observed in the crystal structure.

Related literature

For the synthesis and catalytic applications of Schiff base complexes, see: Connor et al. (2003 ▶); Wang et al. (1998 ▶). For catalytic hydrolysis of free and bound imines, see: Nolan & Hay (1974 ▶); Satchell & Satchell (1979 ▶); Hay (1987 ▶); Bähr & Thämlitz (1955 ▶); Bähr & Döge (1957 ▶).

Experimental

Crystal data

[PdCl2(C7H13N3)]·CH2Cl2

M = 401.43

Monoclinic,

a = 11.9415 (11) Å

b = 11.432 (1) Å

c = 10.5901 (10) Å

β = 97.087 (2)°

V = 1434.7 (2) Å3

Z = 4

Mo Kα radiation

μ = 2.02 mm−1

T = 100 K

0.31 × 0.27 × 0.26 mm

Data collection

Bruker X8 APEXII 4K KappaCCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T min = 0.574, T max = 0.622

18522 measured reflections

3582 independent reflections

3373 reflections with I > 2σ(I)

R int = 0.021

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.085

S = 1.11

3582 reflections

155 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 2.28 e Å−3

Δρmin = −1.12 e Å−3

Data collection: APEX2 (Bruker, 2011 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT and XPREP (Bruker, 2008 ▶); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812032308/bt5968sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812032308/bt5968Isup2.hkl

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

[PdCl2(C7H13N3)]·CH2Cl2	F(000) = 792
Mr = 401.43	Dx = 1.859 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9923 reflections
a = 11.9415 (11) Å	θ = 2.5–28.4°
b = 11.432 (1) Å	µ = 2.02 mm−1
c = 10.5901 (10) Å	T = 100 K
β = 97.087 (2)°	Cube, orange
V = 1434.7 (2) Å3	0.31 × 0.27 × 0.26 mm
Z = 4

Bruker X8 APEXII 4K KappaCCD diffractometer	3582 independent reflections
Graphite monochromator	3373 reflections with I > 2σ(I)
Detector resolution: 8.4 pixels mm-1	Rint = 0.021
ω & φ scans	θmax = 28.4°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −15→15
Tmin = 0.574, Tmax = 0.622	k = −15→14
18522 measured reflections	l = −14→14

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.085	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ2(Fo2) + (0.0378P)2 + 4.6095P] where P = (Fo2 + 2Fc2)/3
3582 reflections	(Δ/σ)max < 0.001
155 parameters	Δρmax = 2.28 e Å−3
2 restraints	Δρmin = −1.12 e Å−3

Experimental. The intensity data was collected on a Bruker X8 Apex II 4 K Kappa CCD diffractometer using an exposure time of 10 s/frame. A total of 1491 frames were collected with a frame width of 0.5° covering up to θ = 28.40° with 99.5% completeness accomplished.

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.

	x	y	z	Uiso*/Ueq
Pd1	0.560565 (18)	0.158108 (19)	0.080787 (19)	0.01469 (8)
Cl1	0.64115 (6)	0.16169 (7)	−0.10627 (7)	0.02358 (16)
Cl2	0.38953 (6)	0.22298 (6)	−0.01819 (6)	0.01848 (14)
Cl3	0.18032 (8)	0.10624 (10)	0.19406 (9)	0.0377 (2)
Cl4	0.07255 (8)	0.14275 (8)	−0.06665 (10)	0.0362 (2)
N1	0.7084 (2)	0.1182 (2)	0.1833 (2)	0.0174 (5)
N2	0.7127 (2)	0.0281 (2)	0.2683 (2)	0.0187 (5)
N3	0.4849 (2)	0.1402 (3)	0.2426 (2)	0.0211 (5)
C1	0.8094 (3)	0.1697 (3)	0.1996 (3)	0.0190 (6)
C2	0.8790 (3)	0.1109 (3)	0.2939 (3)	0.0241 (6)
H2	0.9555	0.1286	0.3233	0.029*
C3	0.8152 (3)	0.0221 (3)	0.3364 (3)	0.0243 (6)
C4	0.6096 (3)	−0.0357 (3)	0.2823 (3)	0.0209 (6)
H4A	0.6271	−0.1015	0.3424	0.025*
H4B	0.5782	−0.0688	0.199	0.025*
C5	0.5224 (3)	0.0435 (3)	0.3313 (3)	0.0242 (6)
H5A	0.456	−0.004	0.3463	0.029*
H5B	0.5548	0.0771	0.414	0.029*
C6	0.8449 (4)	−0.0700 (4)	0.4360 (4)	0.0400 (9)
H6A	0.803	−0.0556	0.5084	0.06*
H6B	0.9261	−0.0671	0.4647	0.06*
H6C	0.8251	−0.1473	0.4	0.06*
C7	0.8348 (3)	0.2783 (3)	0.1295 (3)	0.0270 (7)
H7A	0.822	0.2636	0.0377	0.041*
H7B	0.9137	0.3008	0.1539	0.041*
H7C	0.7852	0.3417	0.1511	0.041*
C8	0.1640 (3)	0.0524 (3)	0.0354 (4)	0.0302 (7)
H8A	0.2387	0.0491	0.0041	0.036*
H8B	0.133	−0.0279	0.0341	0.036*
H3A	0.4137 (17)	0.137 (4)	0.220 (4)	0.033 (12)*
H3B	0.492 (5)	0.204 (3)	0.287 (5)	0.067 (19)*

	U11	U22	U33	U12	U13	U23
Pd1	0.01967 (12)	0.01323 (12)	0.01177 (11)	−0.00021 (7)	0.00431 (8)	0.00061 (7)
Cl1	0.0239 (3)	0.0321 (4)	0.0162 (3)	0.0084 (3)	0.0083 (3)	0.0089 (3)
Cl2	0.0209 (3)	0.0198 (3)	0.0152 (3)	0.0011 (2)	0.0042 (2)	−0.0005 (2)
Cl3	0.0388 (5)	0.0452 (6)	0.0314 (4)	0.0025 (4)	0.0136 (4)	0.0040 (4)
Cl4	0.0366 (5)	0.0254 (4)	0.0442 (5)	0.0005 (3)	−0.0050 (4)	−0.0017 (4)
N1	0.0235 (12)	0.0153 (12)	0.0141 (11)	−0.0003 (9)	0.0049 (9)	0.0015 (9)
N2	0.0282 (13)	0.0138 (12)	0.0140 (11)	−0.0024 (9)	0.0015 (9)	0.0015 (9)
N3	0.0184 (12)	0.0343 (16)	0.0110 (11)	0.0007 (10)	0.0033 (9)	0.0009 (10)
C1	0.0225 (14)	0.0177 (14)	0.0172 (13)	−0.0002 (11)	0.0042 (10)	0.0007 (11)
C2	0.0259 (15)	0.0223 (16)	0.0229 (14)	−0.0006 (12)	−0.0020 (11)	0.0023 (12)
C3	0.0333 (16)	0.0184 (15)	0.0195 (14)	0.0001 (12)	−0.0031 (12)	0.0015 (11)
C4	0.0334 (16)	0.0126 (13)	0.0174 (13)	−0.0052 (11)	0.0060 (11)	−0.0001 (10)
C5	0.0375 (17)	0.0193 (15)	0.0179 (13)	−0.0045 (13)	0.0110 (12)	0.0002 (11)
C6	0.049 (2)	0.031 (2)	0.036 (2)	−0.0079 (17)	−0.0139 (17)	0.0140 (16)
C7	0.0290 (16)	0.0234 (17)	0.0293 (16)	−0.0047 (13)	0.0062 (12)	0.0081 (13)
C8	0.0289 (16)	0.0224 (16)	0.0400 (19)	0.0001 (13)	0.0066 (14)	0.0009 (14)

Pd1—N1	2.007 (3)	C2—H2	0.95
Pd1—N3	2.044 (3)	C3—C6	1.501 (5)
Pd1—Cl2	2.3004 (7)	C4—C5	1.519 (4)
Pd1—Cl1	2.3070 (7)	C4—H4A	0.99
Cl3—C8	1.777 (4)	C4—H4B	0.99
Cl4—C8	1.770 (4)	C5—H5A	0.99
N1—C1	1.335 (4)	C5—H5B	0.99
N1—N2	1.365 (3)	C6—H6A	0.98
N2—C3	1.344 (4)	C6—H6B	0.98
N2—C4	1.454 (4)	C6—H6C	0.98
N3—C5	1.484 (4)	C7—H7A	0.98
N3—H3A	0.855 (19)	C7—H7B	0.98
N3—H3B	0.87 (2)	C7—H7C	0.98
C1—C2	1.391 (4)	C8—H8A	0.99
C1—C7	1.496 (4)	C8—H8B	0.99
C2—C3	1.378 (5)
N1—Pd1—N3	88.52 (10)	C5—C4—H4A	109.4
N1—Pd1—Cl2	172.63 (8)	N2—C4—H4B	109.4
N3—Pd1—Cl2	87.40 (8)	C5—C4—H4B	109.4
N1—Pd1—Cl1	92.08 (7)	H4A—C4—H4B	108
N3—Pd1—Cl1	174.98 (9)	N3—C5—C4	113.2 (2)
Cl2—Pd1—Cl1	92.52 (3)	N3—C5—H5A	108.9
C1—N1—N2	106.7 (2)	C4—C5—H5A	108.9
C1—N1—Pd1	133.7 (2)	N3—C5—H5B	108.9
N2—N1—Pd1	119.16 (19)	C4—C5—H5B	108.9
C3—N2—N1	110.5 (3)	H5A—C5—H5B	107.7
C3—N2—C4	130.2 (3)	C3—C6—H6A	109.5
N1—N2—C4	118.9 (2)	C3—C6—H6B	109.5
C5—N3—Pd1	118.4 (2)	H6A—C6—H6B	109.5
C5—N3—H3A	111 (3)	C3—C6—H6C	109.5
Pd1—N3—H3A	107 (3)	H6A—C6—H6C	109.5
C5—N3—H3B	106 (4)	H6B—C6—H6C	109.5
Pd1—N3—H3B	110 (4)	C1—C7—H7A	109.5
H3A—N3—H3B	103 (5)	C1—C7—H7B	109.5
N1—C1—C2	109.3 (3)	H7A—C7—H7B	109.5
N1—C1—C7	122.5 (3)	C1—C7—H7C	109.5
C2—C1—C7	128.1 (3)	H7A—C7—H7C	109.5
C3—C2—C1	106.6 (3)	H7B—C7—H7C	109.5
C3—C2—H2	126.7	Cl4—C8—Cl3	111.3 (2)
C1—C2—H2	126.7	Cl4—C8—H8A	109.4
N2—C3—C2	106.9 (3)	Cl3—C8—H8A	109.4
N2—C3—C6	122.3 (3)	Cl4—C8—H8B	109.4
C2—C3—C6	130.8 (3)	Cl3—C8—H8B	109.4
N2—C4—C5	111.1 (3)	H8A—C8—H8B	108
N2—C4—H4A	109.4
N3—Pd1—N1—C1	−127.5 (3)	Pd1—N1—C1—C7	−3.4 (5)
Cl1—Pd1—N1—C1	57.5 (3)	N1—C1—C2—C3	−1.0 (4)
N3—Pd1—N1—N2	43.7 (2)	C7—C1—C2—C3	175.0 (3)
Cl1—Pd1—N1—N2	−131.3 (2)	N1—N2—C3—C2	−0.1 (4)
C1—N1—N2—C3	−0.5 (3)	C4—N2—C3—C2	−172.6 (3)
Pd1—N1—N2—C3	−173.9 (2)	N1—N2—C3—C6	−179.1 (3)
C1—N1—N2—C4	173.0 (3)	C4—N2—C3—C6	8.4 (5)
Pd1—N1—N2—C4	−0.4 (3)	C1—C2—C3—N2	0.7 (4)
N1—Pd1—N3—C5	−39.8 (2)	C1—C2—C3—C6	179.5 (4)
Cl2—Pd1—N3—C5	146.4 (2)	C3—N2—C4—C5	109.0 (4)
N2—N1—C1—C2	1.0 (3)	N1—N2—C4—C5	−63.0 (3)
Pd1—N1—C1—C2	172.9 (2)	Pd1—N3—C5—C4	−3.9 (4)
N2—N1—C1—C7	−175.4 (3)	N2—C4—C5—N3	63.1 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3B···Cl1i	0.87 (2)	2.51 (4)	3.230 (3)	141 (5)
N3—H3B···Cl2i	0.87 (2)	2.66 (5)	3.297 (3)	131 (5)
N3—H3A···Cl3	0.86 (2)	2.79 (2)	3.631 (3)	169 (4)
C4—H4A···Cl2ii	0.99	2.76	3.720 (3)	163
C4—H4A···Cl2ii	0.99	2.76	3.720 (3)	163
C7—H7A···Cl1	0.98	2.74	3.455 (4)	130
C8—H8A···Cl2	0.99	2.71	3.428 (4)	130

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3B⋯Cl1i	0.87 (2)	2.51 (4)	3.230 (3)	141 (5)
N3—H3B⋯Cl2i	0.87 (2)	2.66 (5)	3.297 (3)	131 (5)
N3—H3A⋯Cl3	0.86 (2)	2.79 (2)	3.631 (3)	169 (4)
C4—H4A⋯Cl2ii	0.99	2.76	3.720 (3)	163
C4—H4A⋯Cl2ii	0.99	2.76	3.720 (3)	163
C7—H7A⋯Cl1	0.98	2.74	3.455 (4)	130
C8—H8A⋯Cl2	0.99	2.71	3.428 (4)	130

Symmetry codes: (i) ; (ii) .