Morpholinium tetra­oxidorhenate(VII)

The title salt, (C₄H₁₀NO)[ReO₄], contains slightly distorted tetra­hedral [ReO₄]⁻ anions [Re—O = 1.7224 (11)–1.7361 (11) Å]. The structure consists of alternating cationic and anionic layers parallel to (100). The cations and anions are linked by N—H...O hydrogen bonds into chains along [100].

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](Wave) = 0.000 Å
• R factor = 0.010
• wR factor = 0.020
• Data-to-parameter ratio = 34.3

checkCIF/PLATON results

No syntax errors found



Alert level C
ABSTM02_ALERT_3_C  The ratio of expected to reported Tmax/Tmin(RR) is > 1.10
            Tmin and Tmax reported:      0.239     0.309
            Tmin and Tmax expected:      0.123     0.215
            RR =      1.353
            Please check that your absorption correction is appropriate.

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.697
            Tmax scaled      0.215 Tmin scaled      0.167
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           35.00
           From the CIF: _reflns_number_total               3460
           Count of symmetry unique reflns         1811
           Completeness (_total/calc)            191.05%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1649
           Fraction of Friedel pairs measured     0.911
           Are heavy atom types Z>Si present        yes

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   1 ALERT level C = Check and explain
   2 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
   2 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

The title compound, (I) (Fig. 1), contains slightly distorted tetrahedral ReO₄^- anions with Re—O distances from 1.7224 (11) to 1.7361 (11) Å (Table 1). Morpholinium cations have chair conformation.

The structure of (I) can be described as alternating cationic and anionic layers parallel to the (100) plane (Fig. 2). Morpholinium cations act as proton donors in two hydrogen bonds with O atoms of two ReO₄^- anions from different anionic layers (Table 2). The hydrogen bonds link cations and anions into chains in the [100] direction (Fig. 2).

Related literature

See Grigoriev et al. (2007) for the structure of guanidinium tetraoxidorhenate.

S2. Experimental

Synthesis of (I) was carried out as a neutralization reaction by dissolution of morpholine under intensive stirring in 0.2 M water solution of HReO₄ at room temperature to achieve pH = 7, followed by evaporation of the resulting solution over concentrated H₂SO₄. The compound was recrystallized from ethanol.

S3. Refinement

The H atoms of NH₂ and CH₂ groups were refined in idealized geometrical positions with displacement parameters being equal to 1.2 times U_eq of the attached N or C atoms.

Computing details

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT-Plus (Bruker, 1998); data reduction: SAINT-Plus (Bruker, 1998); 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. A view of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are represented by circles of arbitrary size. Dashed line indicates the hydrogen-bonding interaction.
	Fig. 2. The packing of (I) showing chains of hydrogen bonds.

Morpholinium tetraoxidorhenate(VII)

Crystal data

(C4H10NO)[ReO4]	F(000) = 624
Mr = 338.33	Dx = 2.838 Mg m^−3
Orthorhombic, Pca21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 7854 reflections
a = 12.4401 (3) Å	θ = 3.3–35.0°
b = 5.7480 (2) Å	µ = 15.37 mm^−1
c = 11.0420 (3) Å	T = 100 K
V = 789.57 (4) Å^3	Fragment, colourless
Z = 4	0.16 × 0.12 × 0.10 mm

Data collection

Bruker Kappa APEX II area-detector diffractometer	3460 independent reflections
Radiation source: fine-focus sealed tube	3315 reflections with I > 2α(I)
Graphite monochromator	Rint = 0.021
ω and φ scans	θmax = 35.0°, θmin = 3.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −20→19
Tmin = 0.239, Tmax = 0.309	k = −9→9
21183 measured reflections	l = −17→17

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.010	w = 1/[σ^2(Fo^2)] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.020	(Δ/σ)max = 0.001
S = 0.94	Δρmax = 0.70 e Å^−3
3460 reflections	Δρmin = −0.60 e Å^−3
101 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.00092 (6)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), with 1650 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.004 (4)

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
Re1	0.733624 (3)	0.804729 (7)	0.201310 (9)	0.00950 (2)
O1	0.62050 (9)	0.9089 (2)	0.27573 (10)	0.0162 (2)
O2	0.75192 (9)	0.5155 (2)	0.24128 (12)	0.0166 (2)
O3	0.84512 (9)	0.9655 (2)	0.24066 (10)	0.0169 (2)
O4	0.71429 (11)	0.8243 (2)	0.04689 (12)	0.0174 (2)
O5	0.53574 (10)	0.5438 (2)	0.59191 (10)	0.0182 (2)
N1	0.45216 (10)	0.5969 (2)	0.35282 (12)	0.0115 (2)
H1A	0.4004	0.5615	0.2963	0.014*
H1B	0.5006	0.6972	0.3177	0.014*
C1	0.48749 (16)	0.7571 (3)	0.55316 (16)	0.0192 (3)
H1C	0.5433	0.8596	0.5180	0.023*
H1D	0.4557	0.8378	0.6238	0.023*
C2	0.40096 (14)	0.7119 (3)	0.45982 (14)	0.0151 (3)
H2A	0.3446	0.6099	0.4943	0.018*
H2B	0.3671	0.8603	0.4350	0.018*
C3	0.50859 (13)	0.3794 (3)	0.39090 (15)	0.0141 (3)
H3A	0.5476	0.3123	0.3210	0.017*
H3B	0.4553	0.2635	0.4191	0.017*
C4	0.58711 (12)	0.4327 (3)	0.49177 (14)	0.0138 (3)
H4A	0.6208	0.2861	0.5196	0.017*
H4B	0.6447	0.5350	0.4603	0.017*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Re1	0.00842 (2)	0.01046 (2)	0.00962 (2)	0.00157 (1)	−0.00002 (7)	0.00069 (7)
O1	0.0140 (5)	0.0163 (5)	0.0182 (5)	0.0030 (4)	0.0045 (4)	0.0027 (4)
O2	0.0157 (5)	0.0128 (5)	0.0213 (5)	0.0040 (4)	0.0013 (4)	0.0046 (4)
O3	0.0130 (5)	0.0193 (6)	0.0183 (5)	−0.0017 (4)	0.0005 (4)	−0.0049 (4)
O4	0.0184 (6)	0.0208 (6)	0.0129 (5)	0.0022 (4)	−0.0027 (4)	0.0009 (4)
O5	0.0269 (6)	0.0186 (6)	0.0092 (5)	0.0108 (5)	−0.0016 (4)	0.0001 (4)
N1	0.0126 (5)	0.0139 (6)	0.0080 (5)	−0.0006 (5)	−0.0014 (4)	−0.0015 (5)
C1	0.0298 (9)	0.0169 (7)	0.0109 (7)	0.0106 (6)	−0.0049 (6)	−0.0034 (6)
C2	0.0170 (7)	0.0175 (7)	0.0109 (7)	0.0061 (6)	0.0017 (5)	0.0021 (6)
C3	0.0157 (7)	0.0118 (7)	0.0148 (6)	0.0014 (5)	−0.0021 (5)	−0.0046 (6)
C4	0.0131 (6)	0.0152 (7)	0.0130 (6)	0.0031 (5)	−0.0019 (5)	−0.0025 (5)

Geometric parameters (Å, º)

Re1—O1	1.7361 (11)	C1—C2	1.513 (2)
Re1—O2	1.7349 (13)	C1—H1C	0.9900
Re1—O3	1.7224 (11)	C1—H1D	0.9900
Re1—O4	1.7256 (13)	C2—H2A	0.9900
O5—C4	1.4279 (19)	C2—H2B	0.9900
O5—C1	1.430 (2)	C3—C4	1.513 (2)
N1—C3	1.494 (2)	C3—H3A	0.9900
N1—C2	1.496 (2)	C3—H3B	0.9900
N1—H1A	0.9200	C4—H4A	0.9900
N1—H1B	0.9200	C4—H4B	0.9900
O1—Re1—O2	108.44 (6)	N1—C2—C1	108.11 (14)
O1—Re1—O3	110.39 (6)	N1—C2—H2A	110.1
O1—Re1—O4	109.41 (6)	C1—C2—H2A	110.1
O2—Re1—O3	110.14 (6)	N1—C2—H2B	110.1
O2—Re1—O4	109.39 (6)	C1—C2—H2B	110.1
O3—Re1—O4	109.06 (6)	H2A—C2—H2B	108.4
C4—O5—C1	109.84 (12)	N1—C3—C4	109.94 (13)
C3—N1—C2	110.34 (12)	N1—C3—H3A	109.7
C3—N1—H1A	109.6	C4—C3—H3A	109.7
C2—N1—H1A	109.6	N1—C3—H3B	109.7
C3—N1—H1B	109.6	C4—C3—H3B	109.7
C2—N1—H1B	109.6	H3A—C3—H3B	108.2
H1A—N1—H1B	108.1	O5—C4—C3	111.83 (12)
O5—C1—C2	110.81 (15)	O5—C4—H4A	109.3
O5—C1—H1C	109.5	C3—C4—H4A	109.3
C2—C1—H1C	109.5	O5—C4—H4B	109.3
O5—C1—H1D	109.5	C3—C4—H4B	109.3
C2—C1—H1D	109.5	H4A—C4—H4B	107.9
H1C—C1—H1D	108.1
C4—O5—C1—C2	62.46 (19)	C2—N1—C3—C4	−54.28 (17)
C3—N1—C2—C1	56.60 (17)	C1—O5—C4—C3	−59.46 (19)
O5—C1—C2—N1	−60.92 (18)	N1—C3—C4—O5	55.57 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2^i	0.92	1.99	2.8529 (17)	155
N1—H1B···O1	0.92	1.98	2.8855 (18)	168

Symmetry code: (i) x−1/2, −y+1, z.