Bis(benzyl­trimethyl­ammonium) dichromate(VI)

Jin, L.; Liu, N.

doi:10.1107/S1600536811043091

metal-organic compounds

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Volume 67| Part 11| November 2011| Page m1586

doi:10.1107/S1600536811043091

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Bis(benzyltrimethylammonium) dichromate(VI)

Lei Jin ^a ^* and Ning Liu ^a

^aCollege of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: jinlei8812@163.com

(Received 3 October 2011; accepted 18 October 2011; online 22 October 2011)

The asymmetric part of the title compound, (C₁₀H₁₆N)₂[Cr₂O₇], contains one cation and a half of the dichromate dianion, which has a staggered conformation and exhibits disorder of the bridging O atom around the inversion center over two positions in a 1:1 ratio. Weak intermolecular C—H⋯O hydrogen bonds link cations and anions into a three-dimensional structure.

Related literature

For related structure, see: Jin et al. (2011 ).

Experimental

Crystal data

(C₁₀H₁₆N)₂[Cr₂O₇]
M_r = 516.48
Monoclinic, P 2₁ /n
a = 8.8550 (18) Å
b = 12.442 (3) Å
c = 10.919 (2) Å
β = 91.75 (3)°
V = 1202.4 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.94 mm⁻¹
T = 291 K
0.28 × 0.24 × 0.20 mm

Data collection

Rigaku Mercury2 (2x2 bin mode) diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.778, T_max = 0.834
10940 measured reflections
2356 independent reflections
2070 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.108
S = 1.07
2356 reflections
148 parameters
60 restraints
H-atom parameters constrained
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.50 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯O4ⁱ	0.96	2.58	3.308 (4)	133
C2—H2A⋯O1ⁱⁱ	0.96	2.59	3.467 (4)	153
C2—H2B⋯O2	0.96	2.53	3.416 (5)	154
C2—H2C⋯O4ⁱⁱⁱ	0.96	2.42	3.294 (4)	152
C4—H4B⋯O4ⁱⁱⁱ	0.97	2.52	3.393 (4)	149
Symmetry codes: (i) x+1, y, z; (ii) -x+1, -y+2, -z+1; (iii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811043091/cv5168sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811043091/cv5168Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811043091/cv5168Isup3.cml

checkCIF report

Comment top

In continuation of our structural study of organic-inorganic salts with benzyltrimethylammonium cations (Jin et al., 2011), we present here the title compound, (I).

The asymmetric unit of (I) consists of one half dichromate dianion and one benzyltrimethylammonium cation (Fig 1). The dichromate anion exhibits disorder of the bridging O3 atom around the invesion center over two positions in a ratio 1:1. The terminal bond distances of Cr–O are in the range 1.595 (3) - 1.610 (2) Å, and the bond angles of O–Cr–O vary in the range of 108.37 (17)–110.92 (14)°. The bridging Cr–O are in the range 1.754 (6) - 1.766 (6) Å, and the bond angles of O–Cr–O vary from 94.7 (2) to 120.51 (19) °. Atom O3 is disordered over two positions (separated by 0.794 (9) Å) in a ratio 1:1.

There are no classical hydrogen bonds in (I). The benzyltriethylammonium cations interact with the Cr₂O₇^2- anions through the weak intermolecular C–H···O hydrogen-bonded interactions (Table 1).

Related literature top

For related structure, see: Jin et al. (2011).

Experimental top

At room temperature, benzyltriethylammoniumchlorine (10 mmol, 2.28 g) was dissolved in 30 ml water, then a solution with (NH₄)₂Cr₂O₇ (5 mmol, 1.26 g) was dropped slowly into the solution with proper sirring. Yellow solid blocks appeared after several days (yield 75%). Single crystals suitable for X-ray structure analysis were obtained by the slow evaporation of the above solution after two weeks in air.

The dielectric constant of the compound as a function of temperature indicates that the permittivity is basically temperature-independent (ε = C/(T–T₀)), suggesting that this compound is not ferroelectric or there may be no distinct phase transition occurring within the measured temperature (below the melting point).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. View of (I) showing the atomic numbering and 30% probability displacement ellipsoids. Unlabelled atoms are related to the labelled atoms by the (-x, 2 - y, 1 - z) symmetry transformation.

Bis(benzyltrimethylammonium) dichromate(VI) top

Crystal data top

(C₁₀H₁₆N)₂[Cr₂O₇]	Z = 2
M_r = 516.48	F(000) = 540
Monoclinic, P2₁/n	D_x = 1.427 Mg m⁻³
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 8.8550 (18) Å	θ = 3.0–26.0°
b = 12.442 (3) Å	µ = 0.94 mm⁻¹
c = 10.919 (2) Å	T = 291 K
β = 91.75 (3)°	Block, orange
V = 1202.4 (4) Å³	0.28 × 0.24 × 0.20 mm

Data collection top

Rigaku Mercury2 (2x2 bin mode) diffractometer	2356 independent reflections
Radiation source: fine-focus sealed tube	2070 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
Detector resolution: 13.6612 pixels mm^-1	θ_max = 26.0°, θ_min = 3.0°
CCD_Profile_fitting scans	h = −10→10
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −15→15
T_min = 0.778, T_max = 0.834	l = −13→13
10940 measured reflections

Refinement top

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.108	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.057P)² + 0.6088P] where P = (F_o² + 2F_c²)/3
2356 reflections	(Δ/σ)_max = 0.001
148 parameters	Δρ_max = 0.42 e Å⁻³
60 restraints	Δρ_min = −0.50 e Å⁻³

Crystal data top

(C₁₀H₁₆N)₂[Cr₂O₇]	V = 1202.4 (4) Å³
M_r = 516.48	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.8550 (18) Å	µ = 0.94 mm⁻¹
b = 12.442 (3) Å	T = 291 K
c = 10.919 (2) Å	0.28 × 0.24 × 0.20 mm
β = 91.75 (3)°

Data collection top

Rigaku Mercury2 (2x2 bin mode) diffractometer	2356 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2070 reflections with I > 2σ(I)
T_min = 0.778, T_max = 0.834	R_int = 0.035
10940 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	60 restraints
wR(F²) = 0.108	H-atom parameters constrained
S = 1.07	Δρ_max = 0.42 e Å⁻³
2356 reflections	Δρ_min = −0.50 e Å⁻³
148 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.6409 (4)	0.8457 (3)	0.5418 (3)	0.0524 (7)
H1A	0.7118	0.8025	0.5884	0.079*
H1B	0.5473	0.8493	0.5838	0.079*
H1C	0.6809	0.9168	0.5326	0.079*
C2	0.5041 (4)	0.8658 (3)	0.3458 (3)	0.0558 (8)
H2A	0.5448	0.9370	0.3392	0.084*
H2B	0.4100	0.8687	0.3869	0.084*
H2C	0.4877	0.8361	0.2653	0.084*
C3	0.7592 (3)	0.7905 (2)	0.3526 (3)	0.0486 (7)
H3A	0.7981	0.8618	0.3418	0.073*
H3B	0.7423	0.7574	0.2739	0.073*
H3C	0.8308	0.7487	0.4001	0.073*
C4	0.5429 (3)	0.6849 (2)	0.4291 (3)	0.0470 (7)
H4A	0.4491	0.6919	0.4721	0.056*
H4B	0.5179	0.6583	0.3475	0.056*
C5	0.6397 (3)	0.6029 (2)	0.4944 (3)	0.0456 (7)
C6	0.6318 (4)	0.5878 (3)	0.6211 (3)	0.0541 (8)
H6	0.5700	0.6321	0.6664	0.065*
C7	0.7141 (4)	0.5085 (3)	0.6794 (3)	0.0649 (9)
H7	0.7074	0.4997	0.7636	0.078*
C8	0.8061 (4)	0.4422 (3)	0.6148 (4)	0.0681 (10)
H8	0.8624	0.3890	0.6549	0.082*
C9	0.8143 (4)	0.4550 (3)	0.4892 (4)	0.0670 (9)
H9	0.8755	0.4096	0.4447	0.080*
C10	0.7327 (4)	0.5344 (3)	0.4300 (3)	0.0537 (7)
H10	0.7397	0.5424	0.3457	0.064*
Cr1	0.10047 (4)	0.88613 (3)	0.53692 (4)	0.03659 (18)
N1	0.6137 (2)	0.79616 (18)	0.4177 (2)	0.0407 (5)
O1	0.2580 (3)	0.9159 (2)	0.6062 (2)	0.0755 (7)
O2	0.1341 (4)	0.8252 (3)	0.4124 (2)	0.0863 (8)
O3	0.0066 (8)	0.9953 (5)	0.4646 (4)	0.0720 (13)	0.50
O4	0.0014 (3)	0.8091 (2)	0.6192 (2)	0.0753 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0550 (17)	0.0549 (18)	0.0474 (16)	−0.0100 (15)	0.0024 (13)	−0.0200 (14)
C2	0.0458 (17)	0.0575 (19)	0.064 (2)	0.0067 (14)	−0.0047 (14)	−0.0065 (15)
C3	0.0398 (14)	0.0510 (16)	0.0555 (17)	−0.0065 (13)	0.0098 (12)	−0.0085 (13)
C4	0.0387 (14)	0.0534 (17)	0.0487 (15)	−0.0164 (12)	−0.0005 (12)	−0.0095 (13)
C5	0.0472 (15)	0.0467 (16)	0.0428 (14)	−0.0196 (12)	0.0002 (12)	−0.0070 (12)
C6	0.0624 (19)	0.0548 (18)	0.0452 (16)	−0.0195 (15)	0.0041 (14)	−0.0092 (14)
C7	0.085 (2)	0.062 (2)	0.0471 (17)	−0.0263 (19)	−0.0090 (17)	0.0004 (15)
C8	0.076 (2)	0.053 (2)	0.075 (2)	−0.0156 (18)	−0.0153 (19)	0.0049 (17)
C9	0.071 (2)	0.0492 (19)	0.082 (2)	−0.0072 (16)	0.0116 (18)	−0.0101 (17)
C10	0.0634 (19)	0.0508 (17)	0.0474 (16)	−0.0124 (15)	0.0093 (14)	−0.0062 (14)
Cr1	0.0359 (3)	0.0317 (3)	0.0421 (3)	0.00047 (16)	−0.00114 (18)	0.00768 (16)
N1	0.0331 (11)	0.0450 (12)	0.0439 (12)	−0.0033 (9)	0.0015 (9)	−0.0107 (10)
O1	0.0554 (14)	0.0929 (18)	0.0772 (16)	−0.0188 (13)	−0.0147 (12)	0.0001 (14)
O2	0.0880 (18)	0.104 (2)	0.0677 (16)	−0.0161 (16)	0.0182 (14)	−0.0238 (15)
O3	0.090 (3)	0.056 (2)	0.070 (3)	0.030 (2)	0.003 (3)	0.015 (3)
O4	0.0664 (14)	0.0954 (18)	0.0642 (14)	−0.0221 (13)	0.0029 (12)	0.0330 (13)

Geometric parameters (Å, º) top

C1—N1	1.501 (3)	C5—C6	1.400 (4)
C1—H1A	0.9600	C6—C7	1.371 (5)
C1—H1B	0.9600	C6—H6	0.9300
C1—H1C	0.9600	C7—C8	1.370 (5)
C2—N1	1.504 (4)	C7—H7	0.9300
C2—H2A	0.9600	C8—C9	1.384 (5)
C2—H2B	0.9600	C8—H8	0.9300
C2—H2C	0.9600	C9—C10	1.373 (5)
C3—N1	1.492 (3)	C9—H9	0.9300
C3—H3A	0.9600	C10—H10	0.9300
C3—H3B	0.9600	Cr1—O2	1.593 (3)
C3—H3C	0.9600	Cr1—O4	1.595 (2)
C4—C5	1.498 (4)	Cr1—O1	1.610 (2)
C4—N1	1.527 (4)	Cr1—O3ⁱ	1.754 (6)
C4—H4A	0.9700	Cr1—O3	1.766 (6)
C4—H4B	0.9700	O3—O3ⁱ	0.794 (9)
C5—C10	1.392 (4)	O3—Cr1ⁱ	1.754 (6)

N1—C1—H1A	109.5	C8—C7—H7	119.7
N1—C1—H1B	109.5	C6—C7—H7	119.7
H1A—C1—H1B	109.5	C7—C8—C9	119.4 (4)
N1—C1—H1C	109.5	C7—C8—H8	120.3
H1A—C1—H1C	109.5	C9—C8—H8	120.3
H1B—C1—H1C	109.5	C10—C9—C8	120.4 (3)
N1—C2—H2A	109.5	C10—C9—H9	119.8
N1—C2—H2B	109.5	C8—C9—H9	119.8
H2A—C2—H2B	109.5	C9—C10—C5	120.9 (3)
N1—C2—H2C	109.5	C9—C10—H10	119.5
H2A—C2—H2C	109.5	C5—C10—H10	119.5
H2B—C2—H2C	109.5	O2—Cr1—O4	108.37 (16)
N1—C3—H3A	109.5	O2—Cr1—O1	109.21 (16)
N1—C3—H3B	109.5	O4—Cr1—O1	110.92 (14)
H3A—C3—H3B	109.5	O2—Cr1—O3ⁱ	120.51 (19)
N1—C3—H3C	109.5	O4—Cr1—O3ⁱ	101.8 (2)
H3A—C3—H3C	109.5	O1—Cr1—O3ⁱ	105.7 (3)
H3B—C3—H3C	109.5	O2—Cr1—O3	94.7 (2)
C5—C4—N1	115.2 (2)	O4—Cr1—O3	117.0 (3)
C5—C4—H4A	108.5	O1—Cr1—O3	115.0 (3)
N1—C4—H4A	108.5	O3ⁱ—Cr1—O3	26.1 (3)
C5—C4—H4B	108.5	C3—N1—C1	109.4 (2)
N1—C4—H4B	108.5	C3—N1—C2	109.3 (2)
H4A—C4—H4B	107.5	C1—N1—C2	108.6 (2)
C10—C5—C6	117.7 (3)	C3—N1—C4	111.0 (2)
C10—C5—C4	121.0 (3)	C1—N1—C4	110.7 (2)
C6—C5—C4	121.1 (3)	C2—N1—C4	107.8 (2)
C7—C6—C5	120.9 (3)	O3ⁱ—O3—Cr1ⁱ	77.8 (9)
C7—C6—H6	119.5	O3ⁱ—O3—Cr1	76.1 (8)
C5—C6—H6	119.5	Cr1ⁱ—O3—Cr1	153.9 (3)
C8—C7—C6	120.7 (3)

N1—C4—C5—C10	−93.3 (3)	C5—C4—N1—C3	58.0 (3)
N1—C4—C5—C6	91.1 (3)	C5—C4—N1—C1	−63.7 (3)
C10—C5—C6—C7	0.4 (4)	C5—C4—N1—C2	177.7 (2)
C4—C5—C6—C7	176.2 (3)	O2—Cr1—O3—O3ⁱ	172.0 (11)
C5—C6—C7—C8	0.0 (5)	O4—Cr1—O3—O3ⁱ	58.6 (12)
C6—C7—C8—C9	−0.7 (5)	O1—Cr1—O3—O3ⁱ	−74.2 (11)
C7—C8—C9—C10	0.9 (5)	O2—Cr1—O3—Cr1ⁱ	172.0 (11)
C8—C9—C10—C5	−0.4 (5)	O4—Cr1—O3—Cr1ⁱ	58.6 (12)
C6—C5—C10—C9	−0.3 (4)	O1—Cr1—O3—Cr1ⁱ	−74.2 (11)
C4—C5—C10—C9	−176.0 (3)	O3ⁱ—Cr1—O3—Cr1ⁱ	0.0

Symmetry code: (i) −x, −y+2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O4ⁱⁱ	0.96	2.58	3.308 (4)	133
C2—H2A···O1ⁱⁱⁱ	0.96	2.59	3.467 (4)	153
C2—H2B···O2	0.96	2.53	3.416 (5)	154
C2—H2C···O4^iv	0.96	2.42	3.294 (4)	152
C4—H4B···O4^iv	0.97	2.52	3.393 (4)	149

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

Experimental details

Crystal data
Chemical formula	(C₁₀H₁₆N)₂[Cr₂O₇]
M_r	516.48
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	291
a, b, c (Å)	8.8550 (18), 12.442 (3), 10.919 (2)
β (°)	91.75 (3)
V (Å³)	1202.4 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.94
Crystal size (mm)	0.28 × 0.24 × 0.20

Data collection
Diffractometer	Rigaku Mercury2 (2x2 bin mode) diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.778, 0.834
No. of measured, independent and observed [I > 2σ(I)] reflections	10940, 2356, 2070
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.108, 1.07
No. of reflections	2356
No. of parameters	148
No. of restraints	60
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.50

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O4ⁱ	0.96	2.58	3.308 (4)	133.1
C2—H2A···O1ⁱⁱ	0.96	2.59	3.467 (4)	152.6
C2—H2B···O2	0.96	2.53	3.416 (5)	154.2
C2—H2C···O4ⁱⁱⁱ	0.96	2.42	3.294 (4)	152.0
C4—H4B···O4ⁱⁱⁱ	0.97	2.52	3.393 (4)	149.0

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

Acknowledgements

LJ thanks the Ordered Matter Science Research Centre, Southeast University.

References

Jin, L., Liu, N., Li, Y.-J. & Wu, D.-H. (2011). Acta Cryst. E67, m1325. Web of Science CSD CrossRef IUCr Journals Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar