Bis(4-methyl-morpholin-4-ium) tetra-bromidozincate(II).

The title compound, (C(5)H(12)NO)(2)[ZnBr(4)], was synthesized by hydro-thermal reaction of ZnBr(2) with 4-methyl-morpholine in a HBr/distilled water solution. Each of the two independent cations exhibits a chair conformation; the anion deviates slightly from an tetrahedral configuration. The Zn-Br distances in the anion are in the range of 2.3996 (9)-2.4247 (9) Å. All of the amine H atoms are involved in bifurcated inter-molecular N-H⋯Br hydrogen bonds, building up a trimer.

Related literature

For the preparation of amino coordination compounds, see: Fu et al. (2009 ▶); Aminabhavi et al. (1986 ▶).

Experimental

Crystal data

(C5H12NO)2[ZnBr4]

M = 589.32

Monoclinic,

a = 7.5000 (15) Å

b = 20.925 (4) Å

c = 12.670 (3) Å

β = 103.33 (3)°

V = 1934.8 (7) Å3

Z = 4

Mo Kα radiation

μ = 9.53 mm−1

T = 298 K

0.30 × 0.02 × 0.01 mm

Data collection

Rigaku Mercury2 diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T min = 0.810, T max = 0.900

19809 measured reflections

4439 independent reflections

3118 reflections with I > 2σ(I)

R int = 0.079

Refinement

R[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.096

S = 1.07

4439 reflections

174 parameters

H-atom parameters constrained

Δρmax = 0.58 e Å−3

Δρmin = −0.78 e Å−3

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.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811026766/ru2007sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811026766/ru2007Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

(C5H12NO)2[ZnBr4]	F(000) = 1136
Mr = 589.32	Dx = 2.023 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4439 reflections
a = 7.5000 (15) Å	θ = 3.1–27.5°
b = 20.925 (4) Å	µ = 9.53 mm−1
c = 12.670 (3) Å	T = 298 K
β = 103.33 (3)°	Needle, colorless
V = 1934.8 (7) Å3	0.30 × 0.02 × 0.01 mm
Z = 4

Rigaku Mercury2 diffractometer	4439 independent reflections
Radiation source: fine-focus sealed tube	3118 reflections with I > 2σ(I)
graphite	Rint = 0.079
Detector resolution: 13.6612 pixels mm-1	θmax = 27.5°, θmin = 3.1°
CCD profile fitting scans	h = −9→9
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −27→27
Tmin = 0.810, Tmax = 0.900	l = −16→16
19809 measured reflections

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.096	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.024P)2 + 1.999P] where P = (Fo2 + 2Fc2)/3
4439 reflections	(Δ/σ)max = 0.001
174 parameters	Δρmax = 0.58 e Å−3
0 restraints	Δρmin = −0.78 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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.

	x	y	z	Uiso*/Ueq
Zn1	0.13367 (8)	0.63934 (3)	0.72630 (5)	0.03501 (16)
N1	0.0938 (5)	0.54509 (19)	1.2863 (3)	0.0349 (10)
H1	0.0825	0.5023	1.2819	0.042*
Br2	−0.10482 (8)	0.59847 (3)	0.58209 (4)	0.04782 (17)
Br3	0.11003 (9)	0.58049 (3)	0.88737 (4)	0.04937 (18)
C3	0.2234 (8)	0.5701 (3)	1.3845 (4)	0.0463 (14)
H3A	0.1917	0.5532	1.4491	0.056*
H3B	0.2144	0.6163	1.3864	0.056*
Br4	0.43069 (7)	0.62464 (3)	0.68930 (5)	0.04825 (17)
Br1	0.11182 (10)	0.75261 (3)	0.75420 (6)	0.0650 (2)
O1	0.4678 (5)	0.57277 (19)	1.2887 (3)	0.0552 (11)
C5	−0.0990 (8)	0.5644 (3)	1.2811 (5)	0.0537 (16)
H5A	−0.1349	0.5495	1.3448	0.081*
H5B	−0.1778	0.5459	1.2179	0.081*
H5C	−0.1086	0.6101	1.2772	0.081*
C4	0.4175 (8)	0.5510 (3)	1.3833 (4)	0.0507 (15)
H4A	0.5011	0.5688	1.4465	0.061*
H4B	0.4282	0.5049	1.3873	0.061*
C2	0.1551 (7)	0.5645 (2)	1.1864 (4)	0.0379 (13)
H2A	0.1432	0.6104	1.1768	0.045*
H2B	0.0780	0.5441	1.1233	0.045*
C1	0.3508 (8)	0.5452 (3)	1.1963 (5)	0.0505 (15)
H1A	0.3604	0.4990	1.2013	0.061*
H1B	0.3896	0.5585	1.1318	0.061*
N2	0.5985 (6)	0.7329 (2)	0.8998 (3)	0.0390 (10)
H2	0.5105	0.7118	0.8522	0.047*
O2	0.6025 (7)	0.6575 (2)	1.0880 (3)	0.0724 (14)
C8	0.5215 (9)	0.7569 (3)	0.9907 (5)	0.0528 (16)
H8A	0.4179	0.7847	0.9626	0.063*
H8B	0.6136	0.7814	1.0408	0.063*
C9	0.4608 (9)	0.7010 (3)	1.0494 (5)	0.0628 (19)
H9A	0.4146	0.7168	1.1099	0.075*
H9B	0.3613	0.6790	1.0004	0.075*
C7	0.7407 (9)	0.6834 (3)	0.9412 (5)	0.0641 (18)
H7A	0.7824	0.6648	0.8810	0.077*
H7B	0.8451	0.7031	0.9899	0.077*
C10	0.6659 (10)	0.7853 (3)	0.8407 (5)	0.0680 (19)
H10A	0.7112	0.7678	0.7819	0.102*
H10B	0.7628	0.8077	0.8893	0.102*
H10C	0.5673	0.8143	0.8126	0.102*
C6	0.6643 (11)	0.6325 (3)	0.9995 (6)	0.076 (2)
H6A	0.5630	0.6118	0.9498	0.091*
H6B	0.7578	0.6006	1.0254	0.091*

	U11	U22	U33	U12	U13	U23
Zn1	0.0398 (3)	0.0309 (3)	0.0357 (3)	−0.0033 (3)	0.0116 (3)	−0.0006 (3)
N1	0.043 (2)	0.029 (2)	0.033 (2)	−0.0024 (19)	0.0091 (19)	−0.0058 (19)
Br2	0.0445 (3)	0.0533 (4)	0.0409 (3)	−0.0084 (3)	0.0002 (3)	0.0049 (3)
Br3	0.0710 (4)	0.0452 (3)	0.0344 (3)	−0.0144 (3)	0.0171 (3)	0.0006 (3)
C3	0.058 (4)	0.045 (3)	0.034 (3)	−0.006 (3)	0.007 (3)	−0.004 (3)
Br4	0.0418 (3)	0.0538 (4)	0.0530 (4)	0.0060 (3)	0.0189 (3)	0.0008 (3)
Br1	0.0816 (5)	0.0295 (3)	0.0932 (5)	−0.0003 (3)	0.0392 (4)	−0.0060 (3)
O1	0.047 (2)	0.064 (3)	0.054 (3)	−0.016 (2)	0.011 (2)	0.010 (2)
C5	0.046 (3)	0.062 (4)	0.057 (4)	0.011 (3)	0.019 (3)	−0.010 (3)
C4	0.050 (4)	0.055 (4)	0.042 (3)	−0.008 (3)	0.001 (3)	0.010 (3)
C2	0.051 (3)	0.032 (3)	0.031 (3)	−0.007 (2)	0.009 (2)	0.004 (2)
C1	0.058 (4)	0.052 (4)	0.045 (3)	−0.009 (3)	0.018 (3)	0.005 (3)
N2	0.043 (3)	0.039 (3)	0.033 (2)	−0.004 (2)	0.007 (2)	−0.002 (2)
O2	0.102 (4)	0.071 (3)	0.043 (3)	−0.001 (3)	0.015 (3)	0.015 (2)
C8	0.060 (4)	0.053 (4)	0.049 (4)	−0.001 (3)	0.021 (3)	−0.014 (3)
C9	0.073 (5)	0.074 (5)	0.049 (4)	−0.025 (4)	0.029 (3)	−0.015 (4)
C7	0.058 (4)	0.075 (5)	0.062 (4)	0.024 (4)	0.018 (3)	0.012 (4)
C10	0.092 (5)	0.058 (4)	0.060 (4)	−0.023 (4)	0.029 (4)	0.010 (3)
C6	0.099 (6)	0.062 (5)	0.066 (5)	0.027 (4)	0.019 (4)	0.019 (4)

Zn1—Br4	2.3996 (9)	C1—H1A	0.9700
Zn1—Br2	2.4005 (11)	C1—H1B	0.9700
Zn1—Br1	2.4075 (9)	N2—C10	1.480 (7)
Zn1—Br3	2.4247 (9)	N2—C8	1.490 (6)
N1—C3	1.487 (6)	N2—C7	1.493 (7)
N1—C5	1.488 (7)	N2—H2	0.9002
N1—C2	1.499 (6)	O2—C9	1.398 (8)
N1—H1	0.9000	O2—C6	1.409 (8)
C3—C4	1.513 (8)	C8—C9	1.511 (8)
C3—H3A	0.9700	C8—H8A	0.9700
C3—H3B	0.9700	C8—H8B	0.9700
O1—C4	1.412 (6)	C9—H9A	0.9700
O1—C1	1.414 (7)	C9—H9B	0.9700
C5—H5A	0.9600	C7—C6	1.484 (9)
C5—H5B	0.9600	C7—H7A	0.9700
C5—H5C	0.9600	C7—H7B	0.9700
C4—H4A	0.9700	C10—H10A	0.9600
C4—H4B	0.9700	C10—H10B	0.9600
C2—C1	1.499 (7)	C10—H10C	0.9600
C2—H2A	0.9700	C6—H6A	0.9700
C2—H2B	0.9700	C6—H6B	0.9700
Br4—Zn1—Br2	111.59 (4)	O1—C1—H1B	109.3
Br4—Zn1—Br1	104.63 (3)	C2—C1—H1B	109.3
Br2—Zn1—Br1	113.48 (3)	H1A—C1—H1B	108.0
Br4—Zn1—Br3	110.52 (4)	C10—N2—C8	112.3 (5)
Br2—Zn1—Br3	105.87 (3)	C10—N2—C7	113.1 (5)
Br1—Zn1—Br3	110.84 (3)	C8—N2—C7	109.6 (4)
C3—N1—C5	112.5 (4)	C10—N2—H2	107.9
C3—N1—C2	110.1 (4)	C8—N2—H2	109.1
C5—N1—C2	111.9 (4)	C7—N2—H2	104.5
C3—N1—H1	115.9	C9—O2—C6	109.0 (5)
C5—N1—H1	101.0	N2—C8—C9	109.5 (5)
C2—N1—H1	105.0	N2—C8—H8A	109.8
N1—C3—C4	110.1 (4)	C9—C8—H8A	109.8
N1—C3—H3A	109.6	N2—C8—H8B	109.8
C4—C3—H3A	109.6	C9—C8—H8B	109.8
N1—C3—H3B	109.6	H8A—C8—H8B	108.2
C4—C3—H3B	109.6	O2—C9—C8	112.6 (5)
H3A—C3—H3B	108.2	O2—C9—H9A	109.1
C4—O1—C1	109.5 (4)	C8—C9—H9A	109.1
N1—C5—H5A	109.5	O2—C9—H9B	109.1
N1—C5—H5B	109.5	C8—C9—H9B	109.1
H5A—C5—H5B	109.5	H9A—C9—H9B	107.8
N1—C5—H5C	109.5	C6—C7—N2	110.3 (5)
H5A—C5—H5C	109.5	C6—C7—H7A	109.6
H5B—C5—H5C	109.5	N2—C7—H7A	109.6
O1—C4—C3	111.7 (4)	C6—C7—H7B	109.6
O1—C4—H4A	109.3	N2—C7—H7B	109.6
C3—C4—H4A	109.3	H7A—C7—H7B	108.1
O1—C4—H4B	109.3	N2—C10—H10A	109.5
C3—C4—H4B	109.3	N2—C10—H10B	109.5
H4A—C4—H4B	107.9	H10A—C10—H10B	109.5
N1—C2—C1	109.9 (4)	N2—C10—H10C	109.5
N1—C2—H2A	109.7	H10A—C10—H10C	109.5
C1—C2—H2A	109.7	H10B—C10—H10C	109.5
N1—C2—H2B	109.7	O2—C6—C7	111.4 (6)
C1—C2—H2B	109.7	O2—C6—H6A	109.3
H2A—C2—H2B	108.2	C7—C6—H6A	109.3
O1—C1—C2	111.6 (5)	O2—C6—H6B	109.3
O1—C1—H1A	109.3	C7—C6—H6B	109.3
C2—C1—H1A	109.3	H6A—C6—H6B	108.0

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Br2i	0.90	2.70	3.427 (4)	138
N1—H1···Br3i	0.90	2.87	3.541 (4)	132
N2—H2···Br4	0.90	2.72	3.504 (4)	147
N2—H2···Br1	0.90	3.08	3.714 (4)	129

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯Br2i	0.90	2.70	3.427 (4)	138
N1—H1⋯Br3i	0.90	2.87	3.541 (4)	132
N2—H2⋯Br4	0.90	2.72	3.504 (4)	147
N2—H2⋯Br1	0.90	3.08	3.714 (4)	129

Symmetry code: (i) .