Dichlorido(N,N-dimethyl­propane-1,3-diamine-κ²N,N′)zinc(II)

The title compound, [ZnCl₂(C₅N₂H₁₄)], crystallizes with two discrete mononuclear complex mol­ecules in the the asymmetric unit, with an inter­molecular Zn...Zn separation of 5.271 (7) Å. Each Zn^II ion is in a distorted tetra­hedral coordination geometry formed by two Cl atoms and two N atoms. In the crystal structure, mol­ecules are connected by N—H...Cl hydrogen bonds into tetra­meric clusters separated by normal van der Waals distances.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.026
• wR factor = 0.064
• Data-to-parameter ratio = 25.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT153_ALERT_1_C The su's on the Cell Axes are Equal (x 100000) .        400 Ang.
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Zn1    -   Cl1     ..       5.52 su
PLAT420_ALERT_2_C D-H Without Acceptor       N1     -   H1C    ...          ?
PLAT480_ALERT_4_C Long H...A H-Bond Reported H1C    ..  CL1     ..       2.90 Ang.

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K

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

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 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
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Fig. 1 shows the two independent molecules in the asymmetric unit of the title compound. In each molecule, a Zn^II ion is coordinated by an N,N-dimethyl-1,3-propylenediamine ligand and two Cl atoms. The average Zn—N bond length is 2.0433 Å and the average Zn—Cl length is 2.2307 Å. Each Zn^II ion displays a distorted tetrahedral coordination geometry, as observed in the structure of dichloro (N,N,N'-trimethylethylenediamine)zinc(II) (Johansson & Håkansson, 2004).

The six-membered chelate rings (Zn1/N1/C1/C2/C3/N2 and Zn2/N3/C6/C7/C8/N4) adopt chair-configurations. The dihedral angles between the N1/C1/C3/N2 plane and the C1/C2/C3 and N1/N2/Zn1 planes are 118.70 (4) and 137.46 (7)°, respectively. The dihedral angles between the N3/C6/C8/N4 plane and the C6/C7/C8 and N3/N4/Zn2/ planes are 119.89 (3) and 135.96 (7)°, respectively.

In the crystal structure, N—H···Cl hydrogen bonds link the molecules to form terameric clusters which are separated by the normal van der Waals distances (Fig. 2).

Related literature

For related literature, see: Johansson & Håkansson (2004).

S2. Experimental

To an ethanolic solution (15 ml) of biacetyl monoxime (0.101 g, 1.0 mmol), N,N-dimethylpropylenediamine (0.126 ml, 1.0 mmol) was added dropwise with stirring for 10 min. ZnCl₂ (0.136 g, 1 mmol) was then added and the mixture was refluxed for 3 h. A small amount of a precipitate appeared and this was filtered off. Colourless crystals of the title compound suitable for X-ray analysis were separated after 3 d (yield 78%).

S3. Refinement

All H atoms were positioned geometrically and refined using a riding model, with C—H = 0.97 Å and N—H = 0.90 Å, and with U_iso(H) = 1.2U_eq(C,N),

and methyl groups were allowed to rotate to fit the electron density [methyl C—H = 0.96 Å and U_iso(H) = 1.5U_eq(C)].

Computing details

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2002); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The asymmetric unit of (I), with displacement ellipsoids drawn at the 30% probability level and H atoms shown as spheres of arbitrary radii.
	Fig. 2. A partial packing plot for (I), with hydrogen bonds indicated by dashed lines.

Dichlorido(N,N-dimethylpropane-1,3-diamine-κ²N,N')zinc(II)

Crystal data

[ZnCl2(C5H14N2)]	F(000) = 976
Mr = 238.45	Dx = 1.588 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3925 reflections
a = 12.033 (4) Å	θ = 1.8–27.8°
b = 11.816 (4) Å	µ = 2.94 mm^−1
c = 15.113 (4) Å	T = 293 K
β = 111.817 (3)°	Block, colourless
V = 1995.0 (10) Å^3	0.45 × 0.38 × 0.24 mm
Z = 8

Data collection

Bruker APEXII area-detector diffractometer	4701 independent reflections
Radiation source: fine-focus sealed tube	3625 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
ω scans	θmax = 27.8°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −15→15
Tmin = 0.277, Tmax = 0.494	k = −14→15
12998 measured reflections	l = −14→19

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.064	H-atom parameters constrained
S = 0.99	w = 1/[σ^2(Fo^2) + (0.0354P)^2] where P = (Fo^2 + 2Fc^2)/3
4701 reflections	(Δ/σ)max = 0.001
185 parameters	Δρmax = 0.30 e Å^−3
0 restraints	Δρmin = −0.47 e Å^−3

Special details

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
Zn1	0.411849 (19)	0.857901 (19)	0.046947 (15)	0.03807 (7)
Zn2	0.863280 (19)	0.73098 (2)	0.201793 (15)	0.04190 (8)
N1	0.49646 (15)	0.82785 (14)	−0.04360 (12)	0.0469 (4)
H1C	0.5200	0.8940	−0.0604	0.056*
H1D	0.5623	0.7859	−0.0138	0.056*
N2	0.33563 (13)	0.70150 (13)	0.04345 (11)	0.0390 (4)
N3	0.82874 (15)	0.89004 (15)	0.23443 (12)	0.0501 (4)
H3C	0.8433	0.9395	0.1947	0.060*
H3D	0.7509	0.8957	0.2262	0.060*
N4	0.84928 (14)	0.65333 (14)	0.32039 (12)	0.0452 (4)
Cl1	0.26121 (5)	0.97769 (5)	−0.02651 (4)	0.05660 (15)
Cl2	0.52522 (4)	0.91528 (5)	0.19295 (3)	0.05169 (14)
Cl3	1.05195 (5)	0.72640 (6)	0.21087 (5)	0.06741 (17)
Cl4	0.72616 (5)	0.65413 (5)	0.07219 (4)	0.05821 (15)
C1	0.4183 (2)	0.76772 (19)	−0.13034 (15)	0.0559 (6)
H1A	0.4627	0.7532	−0.1711	0.067*
H1B	0.3508	0.8157	−0.1652	0.067*
C2	0.3727 (2)	0.65750 (19)	−0.10731 (16)	0.0580 (6)
H2A	0.4410	0.6136	−0.0672	0.070*
H2B	0.3355	0.6158	−0.1663	0.070*
C3	0.28377 (18)	0.66473 (18)	−0.05791 (15)	0.0504 (5)
H3A	0.2208	0.7173	−0.0929	0.061*
H3B	0.2472	0.5910	−0.0608	0.061*
C4	0.42189 (19)	0.61736 (19)	0.10245 (16)	0.0558 (6)
H4A	0.3843	0.5444	0.0938	0.084*
H4B	0.4478	0.6388	0.1683	0.084*
H4C	0.4898	0.6141	0.0837	0.084*
C5	0.23779 (19)	0.7116 (2)	0.07969 (17)	0.0638 (7)
H5A	0.1981	0.6399	0.0739	0.096*
H5B	0.1814	0.7675	0.0433	0.096*
H5C	0.2702	0.7339	0.1455	0.096*
C6	0.9032 (2)	0.9189 (2)	0.33350 (16)	0.0621 (6)
H6A	0.8891	0.9972	0.3457	0.075*
H6B	0.9870	0.9112	0.3427	0.075*
C7	0.8754 (3)	0.8430 (2)	0.40354 (17)	0.0717 (7)
H7A	0.9134	0.8749	0.4668	0.086*
H7B	0.7896	0.8445	0.3882	0.086*
C8	0.9139 (2)	0.7215 (2)	0.40676 (16)	0.0632 (6)
H8A	0.9986	0.7201	0.4177	0.076*
H8B	0.9039	0.6854	0.4609	0.076*
C9	0.72181 (19)	0.6399 (2)	0.30731 (18)	0.0631 (6)
H9A	0.7164	0.6092	0.3644	0.095*
H9B	0.6835	0.5895	0.2550	0.095*
H9C	0.6829	0.7123	0.2940	0.095*
C10	0.9048 (2)	0.5398 (2)	0.3337 (2)	0.0721 (7)
H10A	0.8920	0.5019	0.3853	0.108*
H10B	0.9892	0.5473	0.3482	0.108*
H10C	0.8693	0.4965	0.2763	0.108*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.04375 (13)	0.03581 (13)	0.03561 (12)	−0.00228 (9)	0.01585 (10)	−0.00326 (9)
Zn2	0.03857 (13)	0.05028 (15)	0.04007 (13)	−0.00125 (10)	0.01835 (10)	−0.00226 (10)
N1	0.0553 (10)	0.0405 (10)	0.0537 (10)	−0.0088 (8)	0.0303 (8)	−0.0044 (8)
N2	0.0353 (8)	0.0411 (9)	0.0400 (9)	−0.0024 (7)	0.0133 (7)	0.0058 (7)
N3	0.0524 (10)	0.0493 (11)	0.0555 (11)	0.0074 (8)	0.0280 (9)	0.0109 (8)
N4	0.0376 (8)	0.0502 (11)	0.0465 (9)	0.0036 (7)	0.0140 (7)	0.0114 (8)
Cl1	0.0651 (3)	0.0514 (3)	0.0478 (3)	0.0160 (3)	0.0146 (2)	0.0050 (2)
Cl2	0.0492 (3)	0.0604 (3)	0.0407 (3)	−0.0019 (2)	0.0112 (2)	−0.0115 (2)
Cl3	0.0457 (3)	0.0857 (5)	0.0820 (4)	−0.0041 (3)	0.0366 (3)	−0.0138 (3)
Cl4	0.0550 (3)	0.0658 (4)	0.0502 (3)	−0.0061 (3)	0.0153 (2)	−0.0133 (3)
C1	0.0718 (15)	0.0623 (15)	0.0411 (12)	−0.0046 (12)	0.0294 (11)	−0.0081 (10)
C2	0.0743 (16)	0.0499 (14)	0.0501 (13)	−0.0081 (11)	0.0233 (12)	−0.0179 (10)
C3	0.0482 (12)	0.0461 (13)	0.0495 (12)	−0.0150 (9)	0.0095 (10)	−0.0061 (9)
C4	0.0513 (12)	0.0487 (14)	0.0602 (14)	0.0028 (10)	0.0123 (10)	0.0165 (10)
C5	0.0463 (12)	0.0861 (19)	0.0657 (15)	−0.0035 (12)	0.0285 (11)	0.0110 (13)
C6	0.0755 (16)	0.0502 (14)	0.0658 (15)	−0.0056 (12)	0.0321 (13)	−0.0141 (11)
C7	0.095 (2)	0.081 (2)	0.0464 (13)	−0.0072 (15)	0.0353 (13)	−0.0140 (12)
C8	0.0597 (14)	0.0829 (19)	0.0405 (12)	−0.0020 (13)	0.0110 (11)	0.0093 (11)
C9	0.0443 (12)	0.0783 (18)	0.0704 (16)	−0.0019 (11)	0.0256 (11)	0.0249 (13)
C10	0.0646 (15)	0.0552 (16)	0.096 (2)	0.0122 (12)	0.0285 (14)	0.0187 (14)

Geometric parameters (Å, º)

Zn1—N1	2.0176 (16)	C2—H2A	0.9700
Zn1—N2	2.0551 (16)	C2—H2B	0.9700
Zn1—Cl2	2.2254 (7)	C3—H3A	0.9700
Zn1—Cl1	2.2419 (7)	C3—H3B	0.9700
Zn2—N3	2.0251 (18)	C4—H4A	0.9600
Zn2—N4	2.0754 (17)	C4—H4B	0.9600
Zn2—Cl3	2.2236 (9)	C4—H4C	0.9600
Zn2—Cl4	2.2319 (7)	C5—H5A	0.9600
N1—C1	1.481 (3)	C5—H5B	0.9600
N1—H1C	0.9000	C5—H5C	0.9600
N1—H1D	0.9000	C6—C7	1.516 (3)
N2—C4	1.474 (2)	C6—H6A	0.9700
N2—C5	1.476 (3)	C6—H6B	0.9700
N2—C3	1.488 (2)	C7—C8	1.504 (4)
N3—C6	1.471 (3)	C7—H7A	0.9700
N3—H3C	0.9000	C7—H7B	0.9700
N3—H3D	0.9000	C8—H8A	0.9700
N4—C10	1.479 (3)	C8—H8B	0.9700
N4—C9	1.480 (3)	C9—H9A	0.9600
N4—C8	1.485 (3)	C9—H9B	0.9600
C1—C2	1.503 (3)	C9—H9C	0.9600
C1—H1A	0.9700	C10—H10A	0.9600
C1—H1B	0.9700	C10—H10B	0.9600
C2—C3	1.518 (3)	C10—H10C	0.9600
N1—Zn1—N2	99.04 (6)	N2—C3—C2	114.85 (17)
N1—Zn1—Cl2	116.63 (5)	N2—C3—H3A	108.6
N2—Zn1—Cl2	113.75 (5)	C2—C3—H3A	108.6
N1—Zn1—Cl1	107.11 (6)	N2—C3—H3B	108.6
N2—Zn1—Cl1	106.50 (5)	C2—C3—H3B	108.6
Cl2—Zn1—Cl1	112.55 (3)	H3A—C3—H3B	107.5
N3—Zn2—N4	96.32 (7)	N2—C4—H4A	109.5
N3—Zn2—Cl3	107.75 (5)	N2—C4—H4B	109.5
N4—Zn2—Cl3	110.16 (5)	H4A—C4—H4B	109.5
N3—Zn2—Cl4	116.08 (5)	N2—C4—H4C	109.5
N4—Zn2—Cl4	107.89 (5)	H4A—C4—H4C	109.5
Cl3—Zn2—Cl4	116.68 (3)	H4B—C4—H4C	109.5
C1—N1—Zn1	111.73 (13)	N2—C5—H5A	109.5
C1—N1—H1C	109.3	N2—C5—H5B	109.5
Zn1—N1—H1C	109.3	H5A—C5—H5B	109.5
C1—N1—H1D	109.3	N2—C5—H5C	109.5
Zn1—N1—H1D	109.3	H5A—C5—H5C	109.5
H1C—N1—H1D	107.9	H5B—C5—H5C	109.5
C4—N2—C5	108.02 (16)	N3—C6—C7	111.4 (2)
C4—N2—C3	110.94 (17)	N3—C6—H6A	109.3
C5—N2—C3	108.57 (16)	C7—C6—H6A	109.3
C4—N2—Zn1	112.57 (13)	N3—C6—H6B	109.3
C5—N2—Zn1	109.13 (14)	C7—C6—H6B	109.3
C3—N2—Zn1	107.54 (11)	H6A—C6—H6B	108.0
C6—N3—Zn2	111.15 (13)	C8—C7—C6	116.2 (2)
C6—N3—H3C	109.4	C8—C7—H7A	108.2
Zn2—N3—H3C	109.4	C6—C7—H7A	108.2
C6—N3—H3D	109.4	C8—C7—H7B	108.2
Zn2—N3—H3D	109.4	C6—C7—H7B	108.2
H3C—N3—H3D	108.0	H7A—C7—H7B	107.4
C10—N4—C9	108.31 (18)	N4—C8—C7	115.82 (19)
C10—N4—C8	108.07 (17)	N4—C8—H8A	108.3
C9—N4—C8	110.72 (18)	C7—C8—H8A	108.3
C10—N4—Zn2	109.96 (14)	N4—C8—H8B	108.3
C9—N4—Zn2	110.16 (12)	C7—C8—H8B	108.3
C8—N4—Zn2	109.58 (13)	H8A—C8—H8B	107.4
N1—C1—C2	112.16 (18)	N4—C9—H9A	109.5
N1—C1—H1A	109.2	N4—C9—H9B	109.5
C2—C1—H1A	109.2	H9A—C9—H9B	109.5
N1—C1—H1B	109.2	N4—C9—H9C	109.5
C2—C1—H1B	109.2	H9A—C9—H9C	109.5
H1A—C1—H1B	107.9	H9B—C9—H9C	109.5
C1—C2—C3	116.71 (19)	N4—C10—H10A	109.5
C1—C2—H2A	108.1	N4—C10—H10B	109.5
C3—C2—H2A	108.1	H10A—C10—H10B	109.5
C1—C2—H2B	108.1	N4—C10—H10C	109.5
C3—C2—H2B	108.1	H10A—C10—H10C	109.5
H2A—C2—H2B	107.3	H10B—C10—H10C	109.5
N2—Zn1—N1—C1	45.48 (15)	N3—Zn2—N4—C9	77.48 (15)
Cl2—Zn1—N1—C1	167.90 (12)	Cl3—Zn2—N4—C9	−170.96 (13)
Cl1—Zn1—N1—C1	−65.00 (14)	Cl4—Zn2—N4—C9	−42.56 (15)
N1—Zn1—N2—C4	78.10 (15)	N3—Zn2—N4—C8	−44.57 (15)
Cl2—Zn1—N2—C4	−46.37 (14)	Cl3—Zn2—N4—C8	66.99 (14)
Cl1—Zn1—N2—C4	−170.94 (13)	Cl4—Zn2—N4—C8	−164.61 (13)
N1—Zn1—N2—C5	−161.99 (13)	Zn1—N1—C1—C2	−57.4 (2)
Cl2—Zn1—N2—C5	73.54 (13)	N1—C1—C2—C3	68.8 (3)
Cl1—Zn1—N2—C5	−51.02 (13)	C4—N2—C3—C2	−65.1 (2)
N1—Zn1—N2—C3	−44.40 (13)	C5—N2—C3—C2	176.39 (19)
Cl2—Zn1—N2—C3	−168.87 (11)	Zn1—N2—C3—C2	58.4 (2)
Cl1—Zn1—N2—C3	66.57 (12)	C1—C2—C3—N2	−71.8 (3)
N4—Zn2—N3—C6	49.49 (15)	Zn2—N3—C6—C7	−63.2 (2)
Cl3—Zn2—N3—C6	−64.07 (15)	N3—C6—C7—C8	70.0 (3)
Cl4—Zn2—N3—C6	162.96 (13)	C10—N4—C8—C7	175.9 (2)
N3—Zn2—N4—C10	−163.22 (14)	C9—N4—C8—C7	−65.6 (3)
Cl3—Zn2—N4—C10	−51.66 (15)	Zn2—N4—C8—C7	56.1 (2)
Cl4—Zn2—N4—C10	76.74 (14)	C6—C7—C8—N4	−67.7 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3C···Cl1^i	0.90	2.57	3.3106 (19)	140
N3—H3D···Cl2	0.90	2.58	3.481 (2)	177
N1—H1C···Cl1^i	0.90	2.90	3.5509 (19)	131
N1—H1D···Cl4	0.90	2.47	3.365 (2)	173

Symmetry code: (i) −x+1, −y+2, −z.