Crystal structure of {bis-[2-(3,5-di-methyl-pyrazol-1-yl-κN (2))eth-yl]amine-κN}chlorido-platinum(II) chloride dihydrate.

The title complex, [PtCl(C14H23N5)]Cl·2H2O, is isomorphous with the Pd(II) compound characterized previously [Mendoza, Bernès & Mendoza-Díaz (2006 ▶). Acta Cryst. E62, m2934-m2936]. The angle between pyrazole mean planes in the main ligand is 88.3 (4)°, similar to that observed in the Pd(II) analogue [87.62 (11)°]. This tridentate ligand adopts a conformation approximating a twofold symmetry, allowing its coordination to the metal atom, together with a chloride ligand, in an almost perfect square-planar geometry. A chloride anion and two water mol-ecules in the asymmetric unit form a hydrogen-bonded network connected to the complex mol-ecules in the crystal via the NH amine groups, forming chains along [100].

Related literature

For the isomorphous PdII structure, see: Mendoza et al. (2006 ▸). For a pseudopolymorph of the PdII complex, see: Guzei et al. (2010 ▸). For other PdII and NiII complexes bearing the same bis­(pyrazol-1-yl)amine ligand, see: Mendoza et al. (2015 ▸); Ajellal et al. (2006 ▸); Massoud et al. (2012 ▸, 2013 ▸).

Experimental

Crystal data

[PtCl(C14H23N5)]Cl·2H2O

M = 563.39

Monoclinic,

a = 7.944 (4) Å

b = 22.523 (4) Å

c = 11.783 (2) Å

β = 109.34 (2)°

V = 1989.1 (11) Å3

Z = 4

Mo Kα radiation

μ = 7.34 mm−1

T = 291 K

0.60 × 0.40 × 0.18 mm

Data collection

Bruker P4 diffractometer

Absorption correction: part of the refinement model (ΔF) (Walker & Stuart, 1983 ▸) T min = 0.024, T max = 0.111

4492 measured reflections

3482 independent reflections

3032 reflections with I > 2σ(I)

R int = 0.057

3 standard reflections every 97 reflections intensity decay: 1%

Refinement

R[F 2 > 2σ(F 2)] = 0.052

wR(F 2) = 0.138

S = 1.05

3482 reflections

233 parameters

4 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 2.96 e Å−3

Δρmin = −1.26 e Å−3

Data collection: XSCANS (Siemens, 1996 ▸); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ▸); molecular graphics: SHELXTL (Sheldrick, 2008 ▸) and Mercury (Macrae et al., 2008 ▸)’; software used to prepare material for publication: SHELXL2014.

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989015005307/hp2070sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015005307/hp2070Isup2.hkl

Click here for additional data file.

. DOI: 10.1107/S2056989015005307/hp2070fig1.tif

View of the title complex, with displacement ellipsoids for non-H atoms at the 30% probability level.

Click here for additional data file.

. DOI: 10.1107/S2056989015005307/hp2070fig2.tif

Part of the crystal structure of the title complex, emphasizing the hydrogen-bond network (dashed bonds). H atoms not involved in hydrogen bonds are omitted.

CCDC reference: 1054111

Additional supporting information: crystallographic information; 3D view; checkCIF report

[PtCl(C14H23N5)]Cl·2H2O	F(000) = 1096
Mr = 563.39	Dx = 1.881 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.944 (4) Å	Cell parameters from 74 reflections
b = 22.523 (4) Å	θ = 4.6–12.5°
c = 11.783 (2) Å	µ = 7.34 mm−1
β = 109.34 (2)°	T = 291 K
V = 1989.1 (11) Å3	Irregular, yellow
Z = 4	0.60 × 0.40 × 0.18 mm

Bruker P4 diffractometer	3032 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube, FN4	Rint = 0.057
Graphite monochromator	θmax = 25.0°, θmin = 1.8°
2θ/ω scans	h = −9→1
Absorption correction: part of the refinement model (ΔF) (Walker & Stuart, 1983)	k = −26→1
Tmin = 0.024, Tmax = 0.111	l = −13→14
4492 measured reflections	3 standard reflections every 97 reflections
3482 independent reflections	intensity decay: 1%

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.138	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0808P)2 + 10.4703P] where P = (Fo2 + 2Fc2)/3
3482 reflections	(Δ/σ)max = 0.001
233 parameters	Δρmax = 2.96 e Å−3
4 restraints	Δρmin = −1.26 e Å−3
0 constraints

	x	y	z	Uiso*/Ueq
Pt1	0.29461 (4)	0.17362 (2)	0.81174 (3)	0.04691 (17)
Cl1	0.4903 (3)	0.22408 (12)	0.9706 (2)	0.0666 (6)
Cl2	0.2473 (5)	0.01323 (18)	0.3417 (3)	0.0959 (10)
N1	0.3971 (10)	0.2093 (3)	0.6922 (7)	0.0529 (17)
N2	0.4257 (12)	0.1738 (3)	0.6053 (8)	0.0557 (19)
C3	0.4939 (12)	0.2055 (5)	0.5363 (9)	0.057 (2)
C4	0.5163 (14)	0.2619 (5)	0.5808 (9)	0.064 (2)
H4A	0.5659	0.2935	0.5522	0.077*
C5	0.4526 (13)	0.2634 (4)	0.6751 (9)	0.059 (2)
C6	0.5244 (18)	0.1798 (5)	0.4275 (11)	0.074 (3)
H6A	0.5841	0.1423	0.4478	0.111*
H6B	0.5968	0.2065	0.3999	0.111*
H6C	0.4118	0.1742	0.3650	0.111*
C7	0.431 (2)	0.3173 (5)	0.7433 (12)	0.080 (4)
H7A	0.3608	0.3075	0.7930	0.121*
H7B	0.3725	0.3480	0.6877	0.121*
H7C	0.5465	0.3310	0.7930	0.121*
C8	0.3519 (13)	0.1130 (5)	0.5867 (10)	0.060 (2)
H8A	0.4091	0.0888	0.6570	0.073*
H8B	0.3729	0.0949	0.5179	0.073*
C9	0.1509 (12)	0.1172 (4)	0.5650 (9)	0.055 (2)
H9A	0.1014	0.1508	0.5134	0.066*
H9B	0.0923	0.0815	0.5247	0.066*
N10	0.1180 (10)	0.1241 (3)	0.6811 (7)	0.0542 (18)
H10A	0.1296	0.0876	0.7115	0.065*
N11	0.1783 (9)	0.1329 (3)	0.9188 (7)	0.0512 (17)
N12	−0.0039 (10)	0.1288 (3)	0.8745 (7)	0.0530 (17)
C13	−0.0607 (13)	0.0933 (4)	0.9487 (10)	0.060 (2)
C14	0.0871 (13)	0.0748 (5)	1.0375 (10)	0.064 (3)
H14A	0.0893	0.0502	1.1013	0.077*
C15	0.2331 (12)	0.0988 (4)	1.0167 (8)	0.053 (2)
C16	−0.2500 (13)	0.0794 (5)	0.9250 (11)	0.071 (3)
H16A	−0.3143	0.1154	0.9261	0.107*
H16B	−0.2613	0.0529	0.9860	0.107*
H16C	−0.2982	0.0609	0.8476	0.107*
C17	0.4253 (14)	0.0902 (6)	1.0886 (10)	0.071 (3)
H17A	0.4955	0.1200	1.0669	0.106*
H17B	0.4632	0.0516	1.0724	0.106*
H17C	0.4409	0.0935	1.1727	0.106*
C18	−0.1019 (13)	0.1636 (4)	0.7703 (10)	0.060 (2)
H18A	−0.0629	0.2047	0.7823	0.072*
H18B	−0.2283	0.1624	0.7596	0.072*
C19	−0.0704 (12)	0.1391 (5)	0.6588 (9)	0.064 (3)
H19A	−0.1426	0.1038	0.6322	0.077*
H19B	−0.1081	0.1683	0.5948	0.077*
O1	0.6546 (14)	0.0365 (5)	0.3986 (10)	0.093 (3)
H11	0.68 (2)	0.026 (8)	0.471 (6)	0.139*
H12	0.543 (5)	0.030 (8)	0.373 (17)	0.139*
O2	0.1596 (12)	−0.0015 (4)	0.7589 (8)	0.076 (2)
H21	0.049 (5)	−0.001 (7)	0.722 (13)	0.114*
H22	0.205 (17)	−0.016 (7)	0.710 (10)	0.114*

	U11	U22	U33	U12	U13	U23
Pt1	0.0457 (2)	0.0476 (2)	0.0468 (3)	−0.00155 (12)	0.01444 (16)	0.00047 (13)
Cl1	0.0658 (14)	0.0665 (15)	0.0609 (14)	−0.0101 (12)	0.0120 (11)	−0.0062 (12)
Cl2	0.099 (2)	0.111 (3)	0.0747 (19)	−0.0099 (19)	0.0257 (17)	−0.0069 (18)
N1	0.054 (4)	0.055 (4)	0.052 (4)	−0.006 (3)	0.020 (3)	−0.003 (3)
N2	0.062 (5)	0.055 (5)	0.052 (5)	−0.001 (3)	0.022 (4)	−0.002 (3)
C3	0.050 (5)	0.067 (6)	0.056 (5)	−0.004 (4)	0.021 (4)	0.006 (5)
C4	0.067 (6)	0.067 (6)	0.061 (6)	−0.004 (5)	0.023 (5)	0.013 (5)
C5	0.059 (5)	0.059 (6)	0.058 (6)	−0.006 (4)	0.016 (4)	−0.003 (4)
C6	0.079 (7)	0.083 (8)	0.069 (7)	0.001 (6)	0.037 (6)	0.004 (6)
C7	0.126 (11)	0.046 (6)	0.078 (8)	−0.017 (6)	0.044 (8)	0.000 (5)
C8	0.068 (6)	0.060 (6)	0.058 (6)	0.002 (5)	0.027 (5)	−0.009 (5)
C9	0.061 (5)	0.048 (5)	0.053 (5)	−0.007 (4)	0.014 (4)	−0.002 (4)
N10	0.063 (5)	0.042 (4)	0.054 (5)	−0.002 (3)	0.014 (3)	−0.005 (3)
N11	0.045 (4)	0.048 (4)	0.063 (5)	−0.001 (3)	0.022 (3)	−0.002 (3)
N12	0.047 (4)	0.056 (4)	0.057 (5)	−0.002 (3)	0.019 (3)	0.000 (4)
C13	0.055 (5)	0.052 (5)	0.083 (7)	0.001 (4)	0.035 (5)	−0.004 (5)
C14	0.064 (6)	0.074 (7)	0.067 (6)	0.002 (5)	0.039 (5)	0.008 (5)
C15	0.055 (5)	0.061 (6)	0.047 (5)	0.006 (4)	0.021 (4)	0.007 (4)
C16	0.057 (6)	0.073 (7)	0.092 (8)	0.006 (5)	0.037 (6)	0.005 (6)
C17	0.059 (6)	0.089 (8)	0.063 (6)	0.008 (5)	0.019 (5)	0.016 (6)
C18	0.047 (5)	0.056 (5)	0.071 (7)	0.003 (4)	0.011 (5)	0.000 (5)
C19	0.045 (5)	0.081 (7)	0.058 (6)	−0.004 (5)	0.005 (4)	0.007 (5)
O1	0.095 (6)	0.083 (6)	0.104 (7)	0.008 (5)	0.037 (6)	0.015 (5)
O2	0.085 (5)	0.084 (5)	0.069 (5)	0.028 (4)	0.042 (4)	0.025 (4)

Pt1—N1	2.013 (7)	N10—H10A	0.8900
Pt1—N11	2.015 (7)	N11—C15	1.332 (12)
Pt1—N10	2.037 (7)	N11—N12	1.370 (10)
Pt1—Cl1	2.298 (3)	N12—C13	1.366 (12)
N1—C5	1.334 (12)	N12—C18	1.448 (13)
N1—N2	1.375 (11)	C13—C14	1.354 (15)
N2—C3	1.325 (12)	C13—C16	1.470 (14)
N2—C8	1.477 (13)	C14—C15	1.373 (13)
C3—C4	1.364 (15)	C14—H14A	0.9300
C3—C6	1.497 (15)	C15—C17	1.493 (14)
C4—C5	1.365 (14)	C16—H16A	0.9600
C4—H4A	0.9300	C16—H16B	0.9600
C5—C7	1.497 (15)	C16—H16C	0.9600
C6—H6A	0.9600	C17—H17A	0.9600
C6—H6B	0.9600	C17—H17B	0.9600
C6—H6C	0.9600	C17—H17C	0.9600
C7—H7A	0.9600	C18—C19	1.520 (16)
C7—H7B	0.9600	C18—H18A	0.9700
C7—H7C	0.9600	C18—H18B	0.9700
C8—C9	1.534 (13)	C19—H19A	0.9700
C8—H8A	0.9700	C19—H19B	0.9700
C8—H8B	0.9700	O1—H11	0.85 (2)
C9—N10	1.483 (12)	O1—H12	0.85 (2)
C9—H9A	0.9700	O2—H21	0.84 (2)
C9—H9B	0.9700	O2—H22	0.84 (2)
N10—C19	1.470 (12)
N1—Pt1—N11	174.6 (3)	C19—N10—Pt1	114.5 (6)
N1—Pt1—N10	91.5 (3)	C9—N10—Pt1	117.9 (6)
N11—Pt1—N10	83.1 (3)	C19—N10—H10A	104.3
N1—Pt1—Cl1	92.9 (2)	C9—N10—H10A	104.3
N11—Pt1—Cl1	92.4 (2)	Pt1—N10—H10A	104.3
N10—Pt1—Cl1	175.3 (2)	C15—N11—N12	107.0 (7)
C5—N1—N2	105.9 (7)	C15—N11—Pt1	135.9 (6)
C5—N1—Pt1	134.5 (7)	N12—N11—Pt1	116.0 (6)
N2—N1—Pt1	119.6 (6)	C13—N12—N11	109.1 (8)
C3—N2—N1	110.2 (7)	C13—N12—C18	131.4 (8)
C3—N2—C8	129.1 (9)	N11—N12—C18	119.3 (7)
N1—N2—C8	119.6 (8)	C14—C13—N12	106.8 (8)
N2—C3—C4	107.0 (9)	C14—C13—C16	130.7 (10)
N2—C3—C6	122.2 (9)	N12—C13—C16	122.5 (10)
C4—C3—C6	130.6 (9)	C13—C14—C15	108.0 (9)
C3—C4—C5	107.5 (9)	C13—C14—H14A	126.0
C3—C4—H4A	126.3	C15—C14—H14A	126.0
C5—C4—H4A	126.3	N11—C15—C14	109.1 (9)
N1—C5—C4	109.3 (9)	N11—C15—C17	123.0 (8)
N1—C5—C7	123.9 (9)	C14—C15—C17	127.8 (9)
C4—C5—C7	126.6 (10)	C13—C16—H16A	109.5
C3—C6—H6A	109.5	C13—C16—H16B	109.5
C3—C6—H6B	109.5	H16A—C16—H16B	109.5
H6A—C6—H6B	109.5	C13—C16—H16C	109.5
C3—C6—H6C	109.5	H16A—C16—H16C	109.5
H6A—C6—H6C	109.5	H16B—C16—H16C	109.5
H6B—C6—H6C	109.5	C15—C17—H17A	109.5
C5—C7—H7A	109.5	C15—C17—H17B	109.5
C5—C7—H7B	109.5	H17A—C17—H17B	109.5
H7A—C7—H7B	109.5	C15—C17—H17C	109.5
C5—C7—H7C	109.5	H17A—C17—H17C	109.5
H7A—C7—H7C	109.5	H17B—C17—H17C	109.5
H7B—C7—H7C	109.5	N12—C18—C19	109.9 (8)
N2—C8—C9	108.0 (8)	N12—C18—H18A	109.7
N2—C8—H8A	110.1	C19—C18—H18A	109.7
C9—C8—H8A	110.1	N12—C18—H18B	109.7
N2—C8—H8B	110.1	C19—C18—H18B	109.7
C9—C8—H8B	110.1	H18A—C18—H18B	108.2
H8A—C8—H8B	108.4	N10—C19—C18	112.2 (8)
N10—C9—C8	110.1 (8)	N10—C19—H19A	109.2
N10—C9—H9A	109.6	C18—C19—H19A	109.2
C8—C9—H9A	109.6	N10—C19—H19B	109.2
N10—C9—H9B	109.6	C18—C19—H19B	109.2
C8—C9—H9B	109.6	H19A—C19—H19B	107.9
H9A—C9—H9B	108.2	H11—O1—H12	101 (10)
C19—N10—C9	109.8 (7)	H21—O2—H22	106 (10)
C5—N1—N2—C3	−1.0 (11)	C15—N11—N12—C13	2.0 (10)
Pt1—N1—N2—C3	−179.8 (6)	Pt1—N11—N12—C13	171.7 (6)
C5—N1—N2—C8	−170.2 (9)	C15—N11—N12—C18	177.2 (8)
Pt1—N1—N2—C8	10.9 (11)	Pt1—N11—N12—C18	−13.1 (10)
N1—N2—C3—C4	2.2 (11)	N11—N12—C13—C14	−1.1 (11)
C8—N2—C3—C4	170.1 (10)	C18—N12—C13—C14	−175.5 (10)
N1—N2—C3—C6	−174.6 (9)	N11—N12—C13—C16	−179.3 (9)
C8—N2—C3—C6	−6.7 (17)	C18—N12—C13—C16	6.3 (16)
N2—C3—C4—C5	−2.5 (12)	N12—C13—C14—C15	−0.3 (12)
C6—C3—C4—C5	173.9 (11)	C16—C13—C14—C15	177.7 (11)
N2—N1—C5—C4	−0.6 (11)	N12—N11—C15—C14	−2.2 (11)
Pt1—N1—C5—C4	177.9 (7)	Pt1—N11—C15—C14	−168.8 (7)
N2—N1—C5—C7	174.4 (11)	N12—N11—C15—C17	178.0 (9)
Pt1—N1—C5—C7	−7.0 (16)	Pt1—N11—C15—C17	11.4 (16)
C3—C4—C5—N1	1.9 (12)	C13—C14—C15—N11	1.6 (12)
C3—C4—C5—C7	−172.9 (11)	C13—C14—C15—C17	−178.7 (11)
C3—N2—C8—C9	−112.7 (11)	C13—N12—C18—C19	−115.1 (11)
N1—N2—C8—C9	54.3 (11)	N11—N12—C18—C19	71.0 (11)
N2—C8—C9—N10	−79.8 (10)	C9—N10—C19—C18	−163.9 (8)
C8—C9—N10—C19	169.6 (8)	Pt1—N10—C19—C18	−28.6 (11)
C8—C9—N10—Pt1	36.0 (10)	N12—C18—C19—N10	−43.4 (12)

D—H···A	D—H	H···A	D···A	D—H···A
N10—H10A···O2	0.89	2.08	2.960 (11)	172
O1—H11···Cl2i	0.85 (2)	2.26 (3)	3.105 (11)	174
O1—H12···Cl2	0.85 (2)	2.28 (5)	3.123 (11)	169
O2—H21···Cl2ii	0.84 (2)	2.24 (4)	3.063 (10)	166
O2—H22···O1i	0.84 (2)	2.01 (4)	2.839 (13)	169

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
N10H10AO2	0.89	2.08	2.960(11)	172
O1H11Cl2i	0.85(2)	2.26(3)	3.105(11)	174
O1H12Cl2	0.85(2)	2.28(5)	3.123(11)	169
O2H21Cl2ii	0.84(2)	2.24(4)	3.063(10)	166
O2H22O1i	0.84(2)	2.01(4)	2.839(13)	169

Symmetry codes: (i) ; (ii) .