N,N′-Bis(4-chloro­benz­yl)ethane-1,2-di­ammonium dinitrate

In the title compound, C₁₆H₂₀Cl₂N₂²⁺·2NO₃⁻, the cation is located on an inversion center and links to the anions via N—H...O and C—H...O hydrogen bonding.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.056
• wR factor = 0.169
• Data-to-parameter ratio = 13.8

checkCIF/PLATON results

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Alert level C
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for         N2
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          5

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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 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

We intended to prepare a lanthanum(III) complex with N,N'-bis(4-chlorobenzyl)ethane-1,2-diamine. However, we obtained the crystal of the title compound. Here we report its structure (Fig. 1).

In the crystal, the cation is located across on an inversion center, the asymmetric unit contains one half-cation and one anion, the cation and the anion are linked by N—H···O hydrogen bonding (Table 1 and Fig. 1).

In the crystal structure, the molecules are linked by two N—H···O hydrogen bonds, the atoms N1(amine) at (x,y,z) and (1 - x,1 - y,1 - z) in the molecule centred at (1/2,1/2,1/2) act as hydrogen-bond donors to the atom O3 (nitrate) at (x,y,-1 + z) in the molecule centred at(1/2,1/2,-1/2) and the atom O3 (nitrate) at (1 - x,1 - y,2 - z) in the molecule centred at(1/2,1/2, 3/2), respectively. Propagation by translation of the two hydrogen bonds generates a chain of R₄⁴(18) rings (Bernstein et al., 1995) (Table 1 and Fig. 2).

The molecules are linked by two C—H···O and two N—H···O hydrogen bonds, so forming a [1 0 0] chain of R₄⁴(20) ring, the atoms C2 at (x,y,z) and (1 - x,1 - y,1 - z) in the molecule centred at (1/2,1/2,1/2) act as hydrogen-bond donors, via H2b, to the atom O2 (nitrate)at (1 + x,y,z) in the molecule centred at(3/2,1/2,1/2) and the atom O2 (nitrate)at (-x,1 - y,1 - z) in the molecule centred at(-1/2,1/2, 1/2), respectively, and the atoms N1(amino) at (x,y,z) and (1 - x,1 - y,1 - z) in the molecule centred at (1/2,1/2,1/2) act as hydrogen-bond donors, via H1a, to the atom O1 (nitrate) at (x,y,z) in the molecule centred at(1/2,1/2,1/2) and the atom O1 (nitrate) at (1 - x,1 - y,1 - z) in the molecule centred at(3/2,1/2,1/2), respectively. Propagation by translation of the two pairs of hydrogen bonds generates a chain of R₄⁴(20) rings along [1 0 0]direction (Table 1 and Fig. 3).

The combination of the [0 0 1] chain and the [1 0 0] chain generates a [0 1 0] stack, the stack lies in a domain of 0.260 < y < 0.740. Neighbouring stacks are linked by the intermolecular Cl···C weak interactions [Cl1···C6ⁱ = 3.441 (3) Å, symmetry codes: (i)1/2 + x,3/2 - y,-1/2 + z], resulting in a three-dimensional structure.

Related literature

For related literature, see: Bernstein et al. (1995).

S2. Experimental

To a methanol solution (30 ml) of N,N'-bis(4-chlorobenzyl)ethane-1,2-diamine (3.42 g, 10 mmol) a methanol solution (10 ml) of lanthanum nitrate (2.16 g, 10 mmol) was added, and the mixture was stirred for 3 h at 333 k. The white solid was filtered off, washed with ethanol and dried at room temperature. Colourless crystals of the title compound suitaible for X-ray structure analysis were obtained by slow evaporation of a DMF solution containing the crude solid product over a period of two months.

S3. Refinement

H atoms were placed in calculated positions with C—H = 0.93 Å (aromatic), 0.97 Å (methylene) and N—H = 0.90 Å, and refined in riding mode with U_iso(H) = 1.2U_eq(C,N).

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).

Figures

	Fig. 1. The molecular stucture of compound (I), with displacement ellipsoids drawn at the 30% probability level. Doubled lines indicate hydrogen bonds. [Symmetry codes: (*)1 - x,1 - y,1 - z]
	Fig. 2. Part of the crystal structure of (I), showing the formation of a chain of R4^4(18) rings along [0 0 1] direction. For the sake of clarity, H atoms bonded to C atoms have been omitted. Dashed lines and doubled lines indicate hydrogen bonds. [Symmetry codes: (*) 1 - x,1 - y,1 - z; (#) x,y,-1 + z; (&)1 - x,1 - y,2 - z].
	Fig. 3. Part of the crystal structure of (I), showing the formation of a chain of R4^4(20) rings along [1 0 0]direction. For the sake of clarity, H atoms bonded to C atoms have been omitted. Dashed lines and doubled lines indicate hydrogen bonds. [Symmetry codes: (*)1 - x,1 - y,1 - z; (#)1 + x,y,z; (&)-x,1 - y,1 - z].

N,N'-Bis(4-chlorobenzyl)ethane-1,2-diammonium dinitrate

Crystal data

C16H20Cl2N2^2+·2NO3^−	F(000) = 452
Mr = 435.26	Dx = 1.442 Mg m^−3
Monoclinic, P21/n	Melting point = 523–525 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 5.6168 (7) Å	Cell parameters from 2811 reflections
b = 31.132 (3) Å	θ = 2.5–27.9°
c = 5.7361 (8) Å	µ = 0.36 mm^−1
β = 91.533 (2)°	T = 298 K
V = 1002.7 (2) Å^3	Block, colourless
Z = 2	0.56 × 0.49 × 0.45 mm

Data collection

Bruker SMART CCD area-detector diffractometer	1768 independent reflections
Radiation source: fine-focus sealed tube	1486 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
φ and ω scans	θmax = 25.0°, θmin = 1.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −6→6
Tmin = 0.822, Tmax = 0.853	k = −37→19
5098 measured reflections	l = −6→6

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)] = 0.056	H-atom parameters constrained
wR(F^2) = 0.169	w = 1/[σ^2(Fo^2) + (0.0938P)^2 + 1.0094P] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max < 0.001
1768 reflections	Δρmax = 0.22 e Å^−3
128 parameters	Δρmin = −0.26 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997a), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.40 (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
Cl1	0.0520 (2)	0.73850 (3)	1.0413 (2)	0.0699 (5)
N1	0.4390 (4)	0.55809 (7)	0.5597 (4)	0.0316 (6)
H1A	0.3978	0.5555	0.7096	0.038*
H1B	0.3039	0.5588	0.4718	0.038*
N2	0.1099 (5)	0.55806 (9)	1.0499 (4)	0.0411 (7)
O1	0.3261 (4)	0.55003 (9)	1.0333 (4)	0.0567 (8)
O3	0.0322 (4)	0.56523 (10)	1.2485 (4)	0.0619 (8)
O2	−0.0175 (5)	0.55903 (12)	0.8745 (5)	0.0843 (11)
C1	0.5788 (5)	0.51959 (9)	0.4944 (5)	0.0325 (7)
H1C	0.7148	0.5163	0.6006	0.039*
H1D	0.6371	0.5230	0.3378	0.039*
C2	0.5679 (5)	0.59956 (10)	0.5305 (5)	0.0395 (8)
H2A	0.5778	0.6062	0.3659	0.047*
H2B	0.7288	0.5969	0.5947	0.047*
C3	0.4409 (5)	0.63547 (9)	0.6525 (5)	0.0357 (7)
C4	0.2310 (6)	0.65296 (10)	0.5608 (6)	0.0424 (8)
H4	0.1703	0.6433	0.4178	0.051*
C5	0.1111 (6)	0.68469 (10)	0.6801 (6)	0.0461 (8)
H5	−0.0299	0.6962	0.6189	0.055*
C6	0.2042 (6)	0.69886 (10)	0.8906 (6)	0.0437 (8)
C7	0.4130 (6)	0.68286 (11)	0.9844 (6)	0.0481 (9)
H7	0.4747	0.6934	1.1253	0.058*
C8	0.5312 (6)	0.65058 (10)	0.8650 (6)	0.0442 (8)
H8	0.6715	0.6391	0.9280	0.053*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0765 (8)	0.0546 (7)	0.0796 (8)	0.0153 (5)	0.0193 (5)	−0.0206 (5)
N1	0.0344 (13)	0.0332 (13)	0.0274 (12)	0.0030 (10)	0.0051 (9)	−0.0039 (9)
N2	0.0415 (15)	0.0510 (16)	0.0309 (14)	−0.0042 (12)	−0.0003 (11)	−0.0007 (11)
O1	0.0449 (14)	0.093 (2)	0.0330 (12)	0.0156 (13)	0.0078 (10)	0.0070 (12)
O3	0.0445 (14)	0.097 (2)	0.0453 (14)	0.0002 (13)	0.0147 (11)	−0.0157 (13)
O2	0.0629 (18)	0.138 (3)	0.0511 (17)	−0.0002 (18)	−0.0231 (14)	−0.0028 (18)
C1	0.0302 (14)	0.0373 (16)	0.0303 (15)	0.0041 (12)	0.0031 (11)	−0.0023 (11)
C2	0.0383 (16)	0.0395 (17)	0.0411 (17)	−0.0016 (13)	0.0099 (13)	−0.0036 (13)
C3	0.0379 (16)	0.0282 (15)	0.0412 (16)	−0.0001 (12)	0.0079 (12)	0.0008 (12)
C4	0.0434 (18)	0.0396 (17)	0.0440 (18)	0.0002 (13)	−0.0017 (14)	−0.0048 (13)
C5	0.0437 (18)	0.0382 (18)	0.056 (2)	0.0070 (14)	0.0019 (15)	0.0008 (14)
C6	0.0523 (19)	0.0291 (16)	0.0503 (19)	0.0004 (13)	0.0156 (15)	−0.0047 (13)
C7	0.057 (2)	0.049 (2)	0.0389 (18)	−0.0035 (16)	0.0033 (15)	−0.0092 (14)
C8	0.0450 (18)	0.0441 (18)	0.0437 (18)	0.0034 (14)	0.0030 (14)	0.0012 (14)

Geometric parameters (Å, º)

Cl1—C6	1.744 (3)	C2—H2A	0.9700
Cl1—C6^i	3.441 (3)	C2—H2B	0.9700
N1—C1	1.486 (3)	C3—C4	1.389 (4)
N1—C2	1.492 (4)	C3—C8	1.389 (5)
N1—H1A	0.9000	C4—C5	1.387 (4)
N1—H1B	0.9000	C4—H4	0.9300
N2—O2	1.219 (3)	C5—C6	1.375 (5)
N2—O1	1.246 (3)	C5—H5	0.9300
N2—O3	1.251 (3)	C6—C7	1.371 (5)
C1—C1^ii	1.509 (6)	C7—C8	1.394 (4)
C1—H1C	0.9700	C7—H7	0.9300
C1—H1D	0.9700	C8—H8	0.9300
C2—C3	1.508 (4)
C6—Cl1—C6^i	169.47 (12)	C3—C2—H2B	109.5
C1—N1—C2	114.1 (2)	H2A—C2—H2B	108.1
C1—N1—H1A	108.7	C4—C3—C8	119.1 (3)
C2—N1—H1A	108.7	C4—C3—C2	121.5 (3)
C1—N1—H1B	108.7	C8—C3—C2	119.5 (3)
C2—N1—H1B	108.7	C5—C4—C3	120.7 (3)
H1A—N1—H1B	107.6	C5—C4—H4	119.6
O2—N2—O1	119.6 (3)	C3—C4—H4	119.6
O2—N2—O3	122.4 (3)	C6—C5—C4	118.9 (3)
O1—N2—O3	118.0 (2)	C6—C5—H5	120.5
N1—C1—C1^ii	109.1 (3)	C4—C5—H5	120.5
N1—C1—H1C	109.9	C7—C6—C5	121.9 (3)
C1^ii—C1—H1C	109.9	C7—C6—Cl1	119.2 (3)
N1—C1—H1D	109.9	C5—C6—Cl1	118.8 (3)
C1^ii—C1—H1D	109.9	C6—C7—C8	118.9 (3)
H1C—C1—H1D	108.3	C6—C7—H7	120.6
N1—C2—C3	110.6 (2)	C8—C7—H7	120.6
N1—C2—H2A	109.5	C3—C8—C7	120.5 (3)
C3—C2—H2A	109.5	C3—C8—H8	119.8
N1—C2—H2B	109.5	C7—C8—H8	119.8
C2—N1—C1—C1^ii	−173.8 (3)	C4—C5—C6—Cl1	−179.5 (2)
C1—N1—C2—C3	−166.4 (2)	C6^i—Cl1—C6—C7	−86.6 (11)
N1—C2—C3—C4	−74.6 (4)	C6^i—Cl1—C6—C5	93.6 (10)
N1—C2—C3—C8	103.4 (3)	C5—C6—C7—C8	−1.5 (5)
C8—C3—C4—C5	−0.8 (5)	Cl1—C6—C7—C8	178.8 (2)
C2—C3—C4—C5	177.2 (3)	C4—C3—C8—C7	0.0 (5)
C3—C4—C5—C6	0.5 (5)	C2—C3—C8—C7	−178.1 (3)
C4—C5—C6—C7	0.7 (5)	C6—C7—C8—C3	1.1 (5)

Symmetry codes: (i) x−1/2, −y+3/2, z+1/2; (ii) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1	0.90	1.92	2.818 (3)	177
N1—H1B···O3^iii	0.90	1.98	2.870 (3)	172
C2—H2B···O2^iv	0.97	2.42	3.265 (4)	145

Symmetry codes: (iii) x, y, z−1; (iv) x+1, y, z.