{Bis­[2-(3,5-dimethyl­pyrazol-1-yl)eth­yl]amine-κ³N,N′,N′′}chloro­palladium(II) chloride dihydrate

The title compound, [PdCl(C₁₄H₂₃N₅)]Cl·2H₂O, contains a four-coordinate palladium complex, in which the planes of the pyrazole rings are almost perpendicular. This is mainly a consequence of the close steric contacts between the methyl groups which would occur in the case of mirror symmetry, which are avoided by adopting a quasi-twofold rotation symmetry.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.027
• wR factor = 0.072
• Data-to-parameter ratio = 17.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Pd1    -   Cl1     ..       5.17 su
PLAT731_ALERT_1_C Bond    Calc     0.86(3), Rep   0.853(10) ......       3.00 su-Ra
              O1   -H12     1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.82(4), Rep   0.827(10) ......       4.00 su-Ra
              O2   -H21     1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.83(4), Rep   0.823(10) ......       4.00 su-Ra
              O2   -H22     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.86(3), Rep   0.853(10) ......       3.00 su-Ra
              O1   -H12     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.82(4), Rep   0.827(10) ......       4.00 su-Ra
              O2   -H21     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.83(4), Rep   0.823(10) ......       4.00 su-Ra
              O2   -H22     1.555   1.555
PLAT736_ALERT_1_C H...A   Calc     2.27(3), Rep   2.267(14) ......       2.14 su-Ra
              H11  -CL2     1.555   3.656

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

   8 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
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXTL-Plus (Sheldrick, 1998); program(s) used to refine structure: SHELXTL-Plus; molecular graphics: SHELXTL-Plus, Mercury (Version 1.4.1; Macrae et al., 2006); software used to prepare material for publication: SHELXTL-Plus.

Chloro{bis[2-(3,5-dimethylpyrazol-1-yl)ethyl]amine-κ³N,N',N''}palladium(II) chloride dihydrate

Crystal data

[PdCl(C14H23N5)]Cl·2H2O	F(000) = 968
Mr = 474.71	Dx = 1.562 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 79 reflections
a = 8.0061 (10) Å	θ = 4.6–12.5°
b = 22.6390 (19) Å	µ = 1.20 mm^−1
c = 11.8202 (8) Å	T = 298 K
β = 109.607 (7)°	Prism, yellow
V = 2018.2 (3) Å^3	0.48 × 0.24 × 0.22 mm
Z = 4

Data collection

Bruker P4 diffractometer	3591 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube, FN4	Rint = 0.018
Graphite monochromator	θmax = 26.3°, θmin = 2.0°
2θ/ω scans	h = −9→4
Absorption correction: ψ scan (XSCANS; Siemens, 1996)	k = −1→28
Tmin = 0.666, Tmax = 0.768	l = −14→14
6611 measured reflections	3 standard reflections every 97 reflections
4070 independent reflections	intensity decay: 1.5%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.027	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.072	w = 1/[σ^2(Fo^2) + (0.039P)^2 + 1.5198P] where P = (Fo^2 + 2Fc^2)/3
S = 0.94	(Δ/σ)max < 0.001
4070 reflections	Δρmax = 0.54 e Å^−3
234 parameters	Δρmin = −0.47 e Å^−3
4 restraints	Extinction correction: SHELXTL-Plus, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0016 (3)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Pd1	0.29119 (2)	0.173806 (7)	0.810261 (15)	0.03237 (8)
Cl1	0.48644 (10)	0.22414 (3)	0.96993 (6)	0.05195 (18)
Cl2	0.24351 (15)	0.01245 (5)	0.34113 (8)	0.0822 (3)
N1	0.3939 (3)	0.20946 (9)	0.69025 (18)	0.0393 (5)
N2	0.4188 (3)	0.17384 (9)	0.6037 (2)	0.0411 (5)
C3	0.4893 (4)	0.20473 (12)	0.5328 (2)	0.0438 (6)
C4	0.5156 (4)	0.26090 (13)	0.5780 (3)	0.0495 (7)
H4A	0.5674	0.2919	0.5500	0.059*
C5	0.4509 (4)	0.26326 (11)	0.6733 (2)	0.0441 (6)
C6	0.5204 (5)	0.17903 (15)	0.4256 (3)	0.0584 (8)
H6A	0.5708	0.1403	0.4447	0.088*
H6B	0.6007	0.2038	0.4024	0.088*
H6C	0.4099	0.1764	0.3605	0.088*
C7	0.4322 (6)	0.31662 (13)	0.7420 (3)	0.0639 (9)
H7A	0.3362	0.3109	0.7724	0.096*
H7B	0.4081	0.3505	0.6901	0.096*
H7C	0.5402	0.3229	0.8078	0.096*
C8	0.3455 (4)	0.11426 (12)	0.5860 (2)	0.0455 (6)
H8A	0.4040	0.0904	0.6564	0.055*
H8B	0.3665	0.0962	0.5176	0.055*
C9	0.1492 (4)	0.11613 (13)	0.5646 (2)	0.0474 (7)
H9A	0.0963	0.1485	0.5109	0.057*
H9B	0.0950	0.0797	0.5265	0.057*
N10	0.1136 (3)	0.12394 (9)	0.67930 (18)	0.0387 (5)
H10A	0.1235	0.0870	0.7112	0.046*
N11	0.1762 (3)	0.13362 (9)	0.91793 (18)	0.0365 (4)
N12	−0.0055 (3)	0.12909 (9)	0.87468 (19)	0.0395 (5)
C13	−0.0634 (4)	0.09367 (12)	0.9452 (2)	0.0422 (6)
C14	0.0846 (4)	0.07452 (12)	1.0359 (2)	0.0450 (6)
H14A	0.0865	0.0496	1.0988	0.054*
C15	0.2310 (3)	0.09955 (11)	1.0158 (2)	0.0389 (5)
C16	−0.2542 (4)	0.08136 (15)	0.9217 (3)	0.0601 (8)
H16A	−0.3164	0.1179	0.9187	0.090*
H16B	−0.2670	0.0571	0.9849	0.090*
H16C	−0.3027	0.0611	0.8463	0.090*
C17	0.4214 (4)	0.08978 (16)	1.0871 (3)	0.0594 (8)
H17A	0.4858	0.1260	1.0917	0.089*
H17B	0.4694	0.0600	1.0489	0.089*
H17C	0.4317	0.0770	1.1666	0.089*
C18	−0.1028 (4)	0.16328 (12)	0.7692 (3)	0.0456 (6)
H18A	−0.0653	0.2042	0.7819	0.055*
H18B	−0.2283	0.1618	0.7585	0.055*
C19	−0.0745 (4)	0.14071 (13)	0.6564 (2)	0.0474 (6)
H19A	−0.1497	0.1066	0.6265	0.057*
H19B	−0.1085	0.1711	0.5951	0.057*
O1	0.6531 (4)	0.03563 (13)	0.3981 (3)	0.0792 (7)
H11	0.692 (7)	0.025 (2)	0.4708 (17)	0.119*
H12	0.542 (2)	0.029 (2)	0.366 (5)	0.119*
O2	0.1649 (4)	0.00023 (11)	0.7621 (2)	0.0640 (6)
H21	0.066 (3)	−0.010 (2)	0.718 (4)	0.096*
H22	0.235 (5)	−0.004 (2)	0.725 (4)	0.096*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pd1	0.03664 (12)	0.02954 (11)	0.03010 (11)	−0.00247 (7)	0.01010 (8)	0.00017 (7)
Cl1	0.0591 (4)	0.0459 (4)	0.0416 (3)	−0.0105 (3)	0.0048 (3)	−0.0068 (3)
Cl2	0.0909 (7)	0.0954 (7)	0.0578 (5)	−0.0127 (6)	0.0216 (5)	−0.0095 (5)
N1	0.0484 (13)	0.0337 (10)	0.0369 (10)	−0.0043 (9)	0.0158 (9)	−0.0007 (8)
N2	0.0532 (14)	0.0356 (11)	0.0376 (11)	−0.0024 (9)	0.0191 (10)	0.0002 (8)
C3	0.0460 (15)	0.0474 (15)	0.0395 (13)	0.0026 (12)	0.0162 (11)	0.0100 (11)
C4	0.0575 (17)	0.0438 (15)	0.0502 (15)	−0.0066 (13)	0.0219 (13)	0.0104 (12)
C5	0.0513 (15)	0.0359 (13)	0.0447 (14)	−0.0078 (12)	0.0156 (12)	0.0030 (11)
C6	0.068 (2)	0.064 (2)	0.0514 (17)	0.0080 (16)	0.0307 (16)	0.0078 (14)
C7	0.101 (3)	0.0365 (15)	0.0589 (19)	−0.0117 (16)	0.0329 (19)	−0.0035 (13)
C8	0.0631 (18)	0.0353 (13)	0.0418 (13)	−0.0036 (12)	0.0225 (13)	−0.0039 (11)
C9	0.0627 (18)	0.0450 (14)	0.0313 (12)	−0.0132 (13)	0.0116 (12)	−0.0057 (11)
N10	0.0432 (12)	0.0358 (11)	0.0351 (10)	−0.0047 (9)	0.0106 (9)	0.0009 (8)
N11	0.0359 (11)	0.0389 (11)	0.0364 (10)	0.0012 (9)	0.0143 (9)	0.0006 (8)
N12	0.0384 (11)	0.0387 (11)	0.0427 (11)	0.0007 (9)	0.0155 (9)	−0.0006 (9)
C13	0.0468 (15)	0.0374 (13)	0.0516 (14)	0.0001 (11)	0.0285 (12)	−0.0044 (11)
C14	0.0567 (17)	0.0401 (13)	0.0470 (14)	0.0035 (12)	0.0290 (13)	0.0058 (11)
C15	0.0443 (14)	0.0403 (13)	0.0360 (12)	0.0072 (11)	0.0188 (11)	0.0042 (10)
C16	0.0497 (17)	0.0592 (19)	0.083 (2)	−0.0020 (15)	0.0375 (16)	−0.0012 (17)
C17	0.0487 (17)	0.077 (2)	0.0523 (16)	0.0110 (15)	0.0163 (13)	0.0257 (16)
C18	0.0371 (14)	0.0413 (14)	0.0549 (16)	0.0060 (11)	0.0107 (12)	0.0031 (12)
C19	0.0397 (14)	0.0525 (16)	0.0419 (14)	−0.0061 (12)	0.0031 (11)	0.0067 (12)
O1	0.0864 (19)	0.0690 (17)	0.0886 (19)	0.0100 (15)	0.0380 (17)	0.0141 (15)
O2	0.0799 (17)	0.0601 (13)	0.0612 (14)	0.0288 (13)	0.0358 (12)	0.0175 (11)

Geometric parameters (Å, º)

Pd1—N11	2.021 (2)	N10—H10A	0.9100
Pd1—N1	2.030 (2)	N11—C15	1.336 (3)
Pd1—N10	2.053 (2)	N11—N12	1.374 (3)
Pd1—Cl1	2.3073 (7)	N12—C13	1.346 (3)
N1—C5	1.339 (3)	N12—C18	1.452 (3)
N1—N2	1.369 (3)	C13—C14	1.374 (4)
N2—C3	1.351 (3)	C13—C16	1.484 (4)
N2—C8	1.458 (3)	C14—C15	1.392 (4)
C3—C4	1.368 (4)	C14—H14A	0.9300
C3—C6	1.490 (4)	C15—C17	1.490 (4)
C4—C5	1.391 (4)	C16—H16A	0.9600
C4—H4A	0.9300	C16—H16B	0.9600
C5—C7	1.491 (4)	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	1.515 (4)
C7—H7B	0.9600	C18—H18A	0.9700
C7—H7C	0.9600	C18—H18B	0.9700
C8—C9	1.506 (4)	C19—H19A	0.9700
C8—H8A	0.9700	C19—H19B	0.9700
C8—H8B	0.9700	O1—H11	0.848 (10)
C9—N10	1.486 (3)	O1—H12	0.853 (10)
C9—H9A	0.9700	O2—H21	0.827 (10)
C9—H9B	0.9700	O2—H22	0.823 (10)
N10—C19	1.487 (3)
N11—Pd1—N1	174.95 (8)	C9—N10—Pd1	117.20 (16)
N11—Pd1—N10	83.15 (8)	C19—N10—Pd1	113.55 (17)
N1—Pd1—N10	91.84 (8)	C9—N10—H10A	104.6
N11—Pd1—Cl1	91.95 (6)	C19—N10—H10A	104.6
N1—Pd1—Cl1	93.05 (6)	Pd1—N10—H10A	104.6
N10—Pd1—Cl1	174.85 (6)	C15—N11—N12	106.2 (2)
C5—N1—N2	106.3 (2)	C15—N11—Pd1	135.94 (18)
C5—N1—Pd1	134.77 (18)	N12—N11—Pd1	116.65 (15)
N2—N1—Pd1	118.88 (15)	C13—N12—N11	110.8 (2)
C3—N2—N1	110.8 (2)	C13—N12—C18	130.7 (2)
C3—N2—C8	128.4 (2)	N11—N12—C18	118.4 (2)
N1—N2—C8	119.9 (2)	N12—C13—C14	106.6 (2)
N2—C3—C4	106.3 (2)	N12—C13—C16	122.9 (3)
N2—C3—C6	123.3 (3)	C14—C13—C16	130.6 (3)
C4—C3—C6	130.3 (3)	C13—C14—C15	107.1 (2)
C3—C4—C5	107.6 (2)	C13—C14—H14A	126.5
C3—C4—H4A	126.2	C15—C14—H14A	126.5
C5—C4—H4A	126.2	N11—C15—C14	109.4 (2)
N1—C5—C4	108.9 (2)	N11—C15—C17	123.5 (2)
N1—C5—C7	123.6 (3)	C14—C15—C17	127.1 (2)
C4—C5—C7	127.3 (3)	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	112.4 (2)
N2—C8—C9	110.2 (2)	N12—C18—H18A	109.1
N2—C8—H8A	109.6	C19—C18—H18A	109.1
C9—C8—H8A	109.6	N12—C18—H18B	109.1
N2—C8—H8B	109.6	C19—C18—H18B	109.1
C9—C8—H8B	109.6	H18A—C18—H18B	107.9
H8A—C8—H8B	108.1	N10—C19—C18	111.6 (2)
N10—C9—C8	111.0 (2)	N10—C19—H19A	109.3
N10—C9—H9A	109.4	C18—C19—H19A	109.3
C8—C9—H9A	109.4	N10—C19—H19B	109.3
N10—C9—H9B	109.4	C18—C19—H19B	109.3
C8—C9—H9B	109.4	H19A—C19—H19B	108.0
H9A—C9—H9B	108.0	H11—O1—H12	111 (5)
C9—N10—C19	110.9 (2)	H21—O2—H22	108 (5)
**N11—Pd1—N1—C5	147.1 (9)	N11—Pd1—N10—C19	65.97 (17)
N10—Pd1—N1—C5	140.7 (3)	N1—Pd1—N10—C19	−114.59 (17)
Cl1—Pd1—N1—C5	−40.9 (3)	**Cl1—Pd1—N10—C19	84.1 (8)
**N11—Pd1—N1—N2	−34.2 (11)	**N1—Pd1—N11—C15	115.5 (9)
N10—Pd1—N1—N2	−40.5 (2)	N10—Pd1—N11—C15	121.9 (3)
Cl1—Pd1—N1—N2	137.81 (18)	Cl1—Pd1—N11—C15	−56.5 (2)
C5—N1—N2—C3	−0.4 (3)	**N1—Pd1—N11—N12	−49.6 (10)
Pd1—N1—N2—C3	−179.47 (17)	N10—Pd1—N11—N12	−43.22 (17)
C5—N1—N2—C8	−170.8 (2)	Cl1—Pd1—N11—N12	138.39 (16)
Pd1—N1—N2—C8	10.2 (3)	C15—N11—N12—C13	1.0 (3)
N1—N2—C3—C4	2.1 (3)	Pd1—N11—N12—C13	170.25 (16)
C8—N2—C3—C4	171.4 (3)	C15—N11—N12—C18	178.2 (2)
N1—N2—C3—C6	−175.8 (3)	Pd1—N11—N12—C18	−12.5 (3)
C8—N2—C3—C6	−6.5 (5)	N11—N12—C13—C14	−0.4 (3)
N2—C3—C4—C5	−3.0 (3)	C18—N12—C13—C14	−177.2 (3)
C6—C3—C4—C5	174.8 (3)	N11—N12—C13—C16	179.0 (2)
N2—N1—C5—C4	−1.5 (3)	C18—N12—C13—C16	2.2 (4)
Pd1—N1—C5—C4	177.4 (2)	N12—C13—C14—C15	−0.4 (3)
N2—N1—C5—C7	174.3 (3)	C16—C13—C14—C15	−179.6 (3)
Pd1—N1—C5—C7	−6.9 (5)	N12—N11—C15—C14	−1.2 (3)
C3—C4—C5—N1	2.8 (3)	Pd1—N11—C15—C14	−167.34 (19)
C3—C4—C5—C7	−172.8 (3)	N12—N11—C15—C17	177.0 (3)
C3—N2—C8—C9	−113.7 (3)	Pd1—N11—C15—C17	10.9 (4)
N1—N2—C8—C9	54.7 (3)	C13—C14—C15—N11	1.0 (3)
N2—C8—C9—N10	−78.6 (3)	C13—C14—C15—C17	−177.1 (3)
C8—C9—N10—C19	165.8 (2)	C13—N12—C18—C19	−113.6 (3)
C8—C9—N10—Pd1	33.2 (3)	N11—N12—C18—C19	69.8 (3)
N11—Pd1—N10—C9	−162.6 (2)	C9—N10—C19—C18	−166.1 (2)
N1—Pd1—N10—C9	16.8 (2)	Pd1—N10—C19—C18	−31.6 (3)
**Cl1—Pd1—N10—C9	−144.5 (6)	N12—C18—C19—N10	−40.8 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H11···Cl2^i	0.85 (1)	2.27 (1)	3.108 (3)	171 (5)
O1—H12···Cl2	0.85 (1)	2.34 (2)	3.162 (3)	162 (5)
O2—H21···Cl2^ii	0.83 (1)	2.34 (2)	3.096 (3)	153 (5)
O2—H22···O1^i	0.82 (1)	2.08 (2)	2.867 (4)	160 (5)
N10—H10A···O2	0.91	2.05	2.950 (3)	171

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