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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296
Volume 61| Part 2| February 2005| Pages o65-o66
doi:10.1107/S0108270104032743

Tetra-n-butyl­ammonium bromide–water (1/38)

CROSSMARK_Color_square_no_text.svg
Wataru Shimada,a* Motoo Shiro,b Hidemasa Kondo,a Satoshi Takeya,a Hiroyuki Oyama,a‡ Takao Ebinumaa and Hideo Naritaa

aNational Institute of Advanced Industrial Science and Technology (AIST), Tsukisamu-higashi, Sapporo 062-8517, Japan, and bX-ray Research Laboratory, RIGAKU, Akishima, Tokyo 196-8666, Japan
*Correspondence e-mail: w.shimada@aist.go.jp

(Received 28 October 2004; accepted 9 December 2004; online 15 January 2005)

Tetra-n-butylammonium bromide forms the title semi-clathrate hydrate crystal, C16H36N+·Br−·38H2O, under atmospheric pressure. The cation and anion lie at sites with mm symmetry and seven water molecules lie at sites with m symmetry in space group Pmma. Br− anions construct a cage structure with the water molecules. Tetra-n-butyl­ammonium cations are disordered and are located at the centre of four cages, viz. two tetrakaideca­hedra and two pentakaidecahedra in ideal cage structures, while all the dodecahedral cages are empty.

Comment

Clathrate hydrate crystals consist of cage structures composed of water molecules, and each cage can encage a molecule that would otherwise be a gas or volatile liquid. The structures consist of a combination of several types of cages, depending on the encaged gas molecules (Sloan, 1989[Sloan, E. D. Jr (1989). Clathrate Hydrates of Natural Gases, 2nd ed. New York: Marcel Dekker Inc.]). Clathrate hydrates encaging gas molecules (gas hydrates) are stable only under high pressure and low temperature. On the other hand, tetra-n-butylammonium bromide (TBAB) forms a semi-clathrate hydrate crystal with water molecules even at atmos­pheric pressure. In TBAB semi-clathrate hydrate, Br forms cage structures with water molecules and the tetra-n-butyl­ammonium cation occupies four cages (Davidson, 1973[Davidson, D. W. (1973). Water - A Comprehensive Treatise, Vol. 2, edited by F. Franks, pp. 115-234. New York, London: Plenum Press.]). Such a hydrate is called a semi-clathrate hydrate crystal because a part of the cage structure is broken in order to encage the large tetra-n-butylammonium molecule, and it has been

[Scheme 1]
suggested that the semi-clathrate hydrate crystal does not encage gas molecules (Davidson, 1973[Davidson, D. W. (1973). Water - A Comprehensive Treatise, Vol. 2, edited by F. Franks, pp. 115-234. New York, London: Plenum Press.]).

Recently, we found that TBAB hydrate can encage small gas molecules which fit in a dodecahedral cage (Shimada et al., 2003[Shimada, W., Ebinuma, T., Oyama, H., Kamata, Y., Takeya, S., Uchida, T., Nagao, J. & Narita, H. (2003). Jpn J. Appl. Phys. 42, L129-L131.]). Additionally, it has been reported that there are two types of TBAB hydrate, denoted A and B (Shimada et al., 2003[Shimada, W., Ebinuma, T., Oyama, H., Kamata, Y., Takeya, S., Uchida, T., Nagao, J. & Narita, H. (2003). Jpn J. Appl. Phys. 42, L129-L131.]; Fukushima et al., 1999[Fukushima, S., Takao, S., Ogoshi, H., Ida, H., Matsumoto, S., Akiyama, T. & Otsuka, T. (1999). NKK Tech. Rep. 166, 65-70. (In Japanese.)]). Unfortunately, Davidson (1973[Davidson, D. W. (1973). Water - A Comprehensive Treatise, Vol. 2, edited by F. Franks, pp. 115-234. New York, London: Plenum Press.]) reported an outline of only the type A TBAB hydrate structure, while the existence of the type B TBAB hydrate was not known. The congruent melting point of type B TBAB hydrate is 283 K with 32 wt% water solution (Oyama et al., 2005[Oyama, H., Shimada, W., Ebinuma, T., Kamata, Y., Takeya, S., Uchida, T., Nagao, J. & Narita, H. (2005). Fluid Phase Equilibria. Submitted.]). This shows that the hydration number of type B TBAB hydrate is 38: one TBAB and 38 H2O molecules form the hydrate crystal. In this paper, we report the crystal structure of the title compound, (I)[link], which is a type B TBAB hydrate, and discuss the mechanism by which gas molecules are included.

Fig. 1[link] shows the structure of (I)[link]. Solid lines show the unit cell, which consists of two TBAB cations and 76 H2O molecules. Br atoms, which are shown as dark spheres, construct the cage structure with the water molecules. The range of O⋯O distances is 2.725 (2)–2.820 (4) Å and the range of Br⋯O distances is 3.248 (3)–3.283 (3) Å. These indicate that the cage structure is constructed by a hydrogen-bonding network. The ideal unit cell is composed of six dodecahedra, four tetrakaidecahedra and four pentakaidecahedra. In reality, because of the presence of tetra-n-butylammonium cations, part of the cage structure is broken, as shown by dotted lines.

Fig. 2[link] shows the structure around the tetra-n-butylammonium cation, which is located at the centre of four cages, viz. two tetrakaidecahedra and two pentakaidecahedra. Four butyl groups are accommodated in two tetrakaidecahedra (upper cages) and two pentakaidecahedra (lower cages). Each butyl group is disordered over two possible sites, with occupancy factors of 50% each. The tetrakaidecahedra and pentakai­deca­hedra are occupied by tetra-n-butylammonium cations, whereas the dodecahedral cages are empty (Fig. 1[link]). These empty cages could encage small molecules, as is shown in Fig. 2[link] by the shaded areas, and may function as a sieve for gas molecules.

[Figure 1]
Figure 1
The structure of (I)[link]. The unit cell is indicated by solid lines. Br atoms and water molecules form the cage structure. Tetra-n-butylammonium is located at the centre of four cages (part of the cage structure is broken, as indicated by dashed lines). H atoms have been omitted for clarity.
[Figure 2]
Figure 2
The structure around the tetra-n-butylammonium cation, located at the centre of four cages, viz. two tetrakaidecahedra and two pentakaidecahedra. The butyl groups have two possible sites, with occupancy factors of 50% each. On the other hand, the dodecahedral cages are empty. Therefore, small molecules could be encaged, as shown by the shaded areas.
[Figure 3]
Figure 3
Photographs of (a) nucleation around a chilled wire and (b) a single-crystal of (I)[link], the morphology being a hexagonal pillar.

Experimental

A growth cell was made from stainless steel with glass windows. The temperature of the cell was controlled to within 0.1 K using a cooling bath. The growth cell was filled with an aqueous solution of 10 wt% TBAB, which was then supercooled. For the growth of crystals of (I)[link], a thin glass capillary was immersed in the growth cell and a wire chilled by liquid nitro­gen was inserted into the glass capillary tube. Many crystals nucleated at the tip of the chilled wire in the capillary, and some crystals emerged at the tip of the capillary and grew freely in the solution (Fig. 3[link]a). After completion of crystal growth, a single crystal of (I)[link] (Fig. 3[link]b) was picked up using a nylon loop.

Crystal data

  • C16H36N+·Br−·38H2O

  • Mr = 1006.95

  • Orthorhombic, Pmma

  • a = 21.060 (5) Å

  • b = 12.643 (4) Å

  • c = 12.018 (8) Å

  • V = 3199 (2) Å3

  • Z = 2

  • Dx = 1.045 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 27 337 reflections

  • θ = 3.0–30.1°

  • μ = 0.72 mm−1

  • T = 93.1 K

  • Needle, colourless

  • 0.60 × 0.10 × 0.05 mm
Data collection

  • Rigaku R-AXIS RAPID diffractometer

  • ω scans

  • Absorption correction: multi-scan (ABSCOR; Higashi, 1995[Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.])Tmin = 0.660, Tmax = 0.965

  • 35 341 measured reflections

  • 4988 independent reflections

  • 2811 reflections with F2 > 2σ(F2)

  • Rint = 0.068

  • θmax = 30.0°

  • h = −26 → 29

  • k = −17 → 17

  • l = −16 → 16
Refinement

  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.059

  • wR(F2) = 0.156

  • S = 1.02

  • 4988 reflections

  • 155 parameters

  • H-atom parameters constrained

  • w = 1/[0.0007Fo2 + σ(Fo2)]/(4Fo2)

  • (Δ/σ)max < 0.001

  • Δρmax = 1.82 e Å−3

  • Δρmin = −0.83 e Å−3

Water H atoms were not located because they have disordered configurations. The H atoms of the cation were positioned geometrically and treated as riding, with C—H distances of 0.95 Å and with Uiso(H) = 1.2Ueq(C). The maximum and minimum peaks in the final difference Fourier map are located 1.94 Å from Br1 and 0.36 Å from O2, respectively. The crystal structure contains voids of 64 Å3, which correspond to the shaded area (dodecahedral cage) in Fig. 2[link]. Bubble formation during dissociation of (I)[link] was observed, suggesting that gas molecules were held in this area.

Data collection: PROCESS-AUTO (Rigaku, 1998[Rigaku (1998). PROCESS-AUTO. Version 1.06. Rigaku Corporation, Tokyo, Japan.]); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2003[Rigaku/MSC (2003). CrystalStructure. Version 3.6.0. Rigaku/MSC, 9009 New Trails Drive, The Woodlands, TX 77381-5209, USA.]); program(s) used to solve structure: SIR2002 (Burla et al., 2003[Burla, M. C., Camalli, M., Carrozzini, B., Cascarano, G. L., Giacovazzo, C., Polidori, G. & Spagna, R. (2003). J. Appl. Cryst. 36, 1103.]); program(s) used to refine structure: CRYSTALS (Watkin et al., 1996[Watkin, D. J., Prout, C. K., Carruthers, J. R. & Betteridge, P. W. (1996). CRYSTALS. Issue 10. Chemical Crystallography Laboratory, University of Oxford, England.]); molecular graphics: ORTEPII (Johnson, 1976[Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA.]); software used to prepare material for publication: CrystalStructure.

Supporting information

Crystal structure: contains datablocks General, I. DOI: 10.1107/S0108270104032743/ob1208sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270104032743/ob1208Isup2.hkl


Comment top

Clathrate hydrate crystals consist of cage structures composed of water molecules, and each cage can encage a molecule that would otherwise be a gas or volatile liquid. The structures consist of a combination of several types of cages, depending on the encaged gas molecules (Sloan, 1989). Clathrate hydrates encaging gas molecules (gas hydrates) are stable only under high pressure and low temperature. On the other hand, tetra-n-butyl ammonium bromide (TBAB) forms a semi-clathrate hydrate crystal with water molecules even at atmospheric pressure. In TBAB semi-clathrate hydrate, Br forms cage structures with water molecules and the tetra-n-butyl ammonium cation occupies four cages (Davidson, 1973). Such a hydrate is called a semi-clathrate hydrate crystal because a part of the cage structure is broken in order to encage the large tetra-n-butyl ammonium molecule, and it has been suggested that the semi-clathrate hydrate crystal does not encage gas molecules (Davidson, 1973).

Recently, we found that TBAB hydrate can encage small gas molecules which fit in a dodecahedral cage (Shimada et al., 2003). Additionally, it has been reported that there are two types of TBAB hydrate, type A and type B (Shimada et al., 2003; Fukushima et al., 1999). Unfortunately, Davidson (1973) reported an outline of only the type A TBAB hydrate structure, while the existence of the type B TBAB hydrate was not known. The congruent melting point of type B TBAB hydrate is 283 K with 32 wt% water solution (Oyama et al., 2004). This shows that the hydration number of type B TBAB hydrate is 38: one TBAB and 38 H2O molecules form the hydrate crystal. In this paper, we report the crystal structure of the title compound, (I), which is a type B TBAB hydrate, and discuss the mechanism by which gas molecules are included.

Fig. 1 shows the structure of (I). Solid lines show the unit cell, which consists of two TBAB cations and 76 H2O. Br atoms, which are shown as dark spheres, construct the cage structure with the water molecules. The range of O···O distances is 2.725 (2)–2.820 (4) Å, and the range of Br···O distances is 3.248 (3)–3.283 (3) Å. These indicate that the cage structure is constructed by a hydrogen-bonding network. The ideal unit cell is composed of six dodecahedrons, four tetrakaidecahedrons and four pentakaidecahedrons. In reality, because of the presence of tetra-n-butyl ammonium cations, part of the cage structure is broken, as shown by dotted lines.

Fig. 2 shows the structure around the tetra-n-butyl ammonium cation, which is located at the centre of four cages, two tetrakaidecahedrons and two pentakaidecahedrons. Four butyl groups are accommodated in two tetrakaidecahedrons (upper cages) and two pentakaidecahedrons (lower cages). Each butyl group is disordered over two possible sites, with occupancy factors of 50% each. The tetrakaidecahedrons and pentakaidecahedrons are occupied by tetra-n-butyl ammonium cations, whereas the dodecahedral cages are empty (Fig. 1). These empty cages could encage small molecules, as is shown in Fig. 2 by the shaded areas, and may function as a sieve for gas molecules.

Experimental top

A growth cell was made from stainless steel with glass windows. The temperature of the cell was controlled by a cooling bath to within 0.1 K. The growth cell was filled with an aqueous solution of 10 wt% TBAB, which was then supercooled. Crystals of (I) were grown as follows. A thin glass capillary was immersed into the growth cell, and a wire chilled by liquid nitrogen was inserted into the glass capillary tube. Many crystals nucleated at the tip of chilled wire in the capillary, and some crystals emerged at the tip of the capillary and grew freely in the solution (Fig. 3a). After completion of crystal growth, a single-crystal of (I) (Fig. 3 b) was picked up using a nylon loop.

Refinement top

Water H atoms were not located, because they have disordered configurations. The H atoms of the cation were positioned geometrically and treated as riding, with C—H distances of 0.95 Å and with Uiso(H) = 1.2Ueq(C). The maximum and minimum peaks in the final difference Fourier map are located 1.94 Å from Br1 and 0.36 Å from O2, respectively. The crystal structure contains voids of 64 Å3, which correspond to the shaded area (dodecahedral cage) in Fig. 2. Bubble formation during dissociation of (I) was observed, suggesting that gas molecules were held in this area.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2003); program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: CRYSTALS (Watkin et al., 1996); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: CrystalStructure.

Figures top
[Figure 1] Fig. 1. The structure of (I). The unit cell is shown by solid lines. Br atoms and water molecules form the cage structure. Tetra-n-butyl ammonium is located at the centre of four cages (a part of the cage structure is broken, as shown by dotted lines). H atoms have been omitted for clarity.
[Figure 2] Fig. 2. The structure around the tetra-n-butyl ammonium, located at the centre of four cages, two tetrakaidecahedrons and two pentakaidecahedrons. The butyl groups have two possible sites, with occupancy factors of 50% each. On the other hand, the dodecahedral cages are empty. Therefore, small molecules could be encaged, as shown by the shaded areas.
[Figure 3] Fig. 3. Photographs of (a) nucleation around a chilled wire, and (b) a single-crystal of (I), the morphology being hexagonal pillar.
Tetra-n-butylammonium bromide–water (1/38) top
Crystal data top
C16H36N+·Br−·38H2OF(000) = 1108.00
Mr = 1006.95Dx = 1.045 Mg m−3
Orthorhombic, PmmaMo Kα radiation, λ = 0.7107 Å
Hall symbol: -P 2a 2aCell parameters from 27337 reflections
a = 21.060 (5) Åθ = 3.0–30.1°
b = 12.643 (4) ŵ = 0.72 mm−1
c = 12.018 (8) ÅT = 93 K
V = 3199 (2) Å3Needle, colourless
Z = 20.60 × 0.10 × 0.05 mm
Data collection top
Rigaku R-AXIS RAPID
diffractometer		2811 reflections with F2 > 2σ(F2)
Detector resolution: 10.00 pixels mm-1Rint = 0.068
ω scansθmax = 30.0°
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		h = −26→29
Tmin = 0.660, Tmax = 0.965k = −17→17
35341 measured reflectionsl = −16→16
4988 independent reflections
Refinement top
Refinement on F2H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.059 w = 1/[0.0007Fo2 + σ(Fo2)]/(4Fo2)
wR(F2) = 0.156(Δ/σ)max < 0.001
S = 1.03Δρmax = 1.82 e Å−3
4988 reflectionsΔρmin = −0.83 e Å−3
155 parameters
Crystal data top
C16H36N+·Br−·38H2OV = 3199 (2) Å3
Mr = 1006.95Z = 2
Orthorhombic, PmmaMo Kα radiation
a = 21.060 (5) ŵ = 0.72 mm−1
b = 12.643 (4) ÅT = 93 K
c = 12.018 (8) Å0.60 × 0.10 × 0.05 mm
Data collection top
Rigaku R-AXIS RAPID
diffractometer		4988 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		2811 reflections with F2 > 2σ(F2)
Tmin = 0.660, Tmax = 0.965Rint = 0.068
35341 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.059155 parameters
wR(F2) = 0.156H-atom parameters constrained
S = 1.03Δρmax = 1.82 e Å−3
4988 reflectionsΔρmin = −0.83 e Å−3
Special details top

Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY

Refinement. Refinement using reflections with F2 > −3.0 σ(F2). The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Br10.25000.50000.97071 (6)0.0301 (2)
O10.04348 (9)0.8192 (1)0.7530 (1)0.0250 (5)
O20.05711 (8)0.6966 (1)0.9413 (1)0.0240 (5)
O30.14090 (9)0.8188 (1)1.0640 (1)0.0244 (5)
O40.1835 (1)1.00000.9584 (2)0.0222 (6)
O50.1183 (1)1.00000.7596 (2)0.0249 (7)
O60.1836 (1)1.00000.5621 (2)0.0254 (7)
O70.13887 (9)0.8284 (1)0.4429 (1)0.0274 (5)
O80.05611 (9)0.7018 (1)0.5608 (1)0.0261 (5)
O90.0763 (1)0.50000.6450 (3)0.0309 (8)
O100.1041 (1)0.50000.8746 (2)0.0276 (7)
O110.25000.7789 (3)0.3391 (2)0.0334 (8)
O120.07921 (9)0.8909 (1)1.2507 (2)0.0261 (5)
O130.25000.7137 (2)1.1207 (2)0.0276 (7)
N10.25000.50000.4962 (4)0.018 (1)
C10.1966 (2)0.4540 (4)0.4244 (4)0.021 (1)*0.50
C20.1678 (2)0.5295 (4)0.3395 (4)0.026 (1)*0.50
C30.1137 (3)0.4721 (4)0.2785 (5)0.031 (1)*0.50
C40.0825 (3)0.54163 (1)0.1907 (6)0.048 (2)*0.50
C50.2229 (2)0.5893 (4)0.5671 (4)0.020 (1)*0.50
C60.2667 (2)0.6373 (4)0.6536 (4)0.024 (1)*0.50
C70.2313 (2)0.7226 (5)0.7176 (5)0.030 (1)*0.50
C80.27240 (1)0.7758 (5)0.8049 (6)0.037 (1)*0.50
H10.21330.39490.38520.026*0.50
H20.16370.43120.47260.026*0.50
H30.15150.59020.37640.031*0.50
H40.19930.55050.28750.031*0.50
H50.13040.41090.24320.037*0.50
H60.08250.45170.33130.037*0.50
H70.04840.57980.22330.058*0.50
H80.06680.49860.13210.058*
H90.11280.58990.16170.058*0.50
H100.21020.64430.51820.025*0.50
H110.18680.56230.60500.025*0.50
H120.28040.58390.70370.029*0.50
H130.30260.66770.61780.029*0.50
H140.21700.77480.66650.036*0.50
H150.19570.69130.75340.036*0.50
H160.26900.73900.87350.045*0.50
H170.25880.84680.81480.045*0.50
H180.31540.77510.78080.045*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0262 (3)0.0239 (3)0.0402 (4)0.00000.00000.0000
O10.0255 (9)0.027 (1)0.023 (1)−0.0010 (8)−0.0010 (8)0.0003 (8)
O20.0243 (9)0.0240 (9)0.024 (1)−0.0001 (8)−0.0011 (8)−0.0002 (8)
O30.0261 (9)0.0237 (9)0.0234 (9)−0.0024 (8)0.0007 (8)−0.0004 (8)
O40.025 (1)0.023 (1)0.019 (1)0.0000−0.001 (1)0.0000
O50.027 (1)0.028 (1)0.020 (1)0.0000−0.000 (1)0.0000
O60.025 (1)0.029 (1)0.023 (1)0.00000.000 (1)0.0000
O70.029 (1)0.029 (1)0.024 (1)−0.0000 (8)0.0001 (8)−0.0002 (8)
O80.0281 (9)0.027 (1)0.024 (1)0.0013 (8)−0.0018 (8)0.0014 (8)
O90.037 (2)0.026 (1)0.030 (2)0.00000.001 (1)0.0000
O100.044 (2)0.019 (1)0.019 (1)0.0000−0.002 (1)0.0000
O110.029 (1)0.041 (2)0.030 (2)0.00000.0000−0.004 (1)
O120.0262 (9)0.029 (1)0.023 (1)−0.0004 (8)0.0002 (8)−0.0008 (9)
O130.026 (1)0.032 (2)0.024 (1)0.00000.0000−0.002 (1)
N10.018 (2)0.017 (2)0.021 (2)0.00000.00000.0000
Geometric parameters (Å, º) top
N1—C11.531 (6)C3—H60.9500
N1—C1i1.531 (6)C4—H70.9500
N1—C51.525 (6)C4—H80.9500
N1—C5ii1.525 (6)C4—H90.9500
N1—C1iii1.531 (6)C5—C61.518 (7)
N1—C1ii1.531 (6)C5—H100.9500
N1—C5iii1.525 (6)C5—H110.9500
N1—C5i1.525 (6)C6—C71.520 (7)
C1—C21.524 (7)C6—H120.9500
C1—H10.9500C6—H130.9500
C1—H20.9500C7—C81.517 (8)
C2—C31.537 (7)C7—H140.9500
C2—H30.9500C7—H150.9500
C2—H40.9500C8—H160.9500
C3—C41.522 (8)C8—H170.9500
C3—H50.9500C8—H180.9500
Br1···O103.283 (3)O5···H17iii3.3005
Br1···O10iii3.283 (3)O5···H18iii3.1782
Br1···O133.248 (3)O6···H143.1898
Br1···O13ii3.248 (3)O7···H1ii3.3022
Br1···H16i3.2639O7···H2ii3.3423
O1···O22.758 (3)O7···H33.1270
O1···O52.777 (2)O7···H102.9136
O1···O82.758 (3)O7···H13iii3.1733
O2···O32.770 (3)O7···H143.2229
O2···O102.793 (2)O8···H2ii3.0136
O3···O42.768 (2)O8···H33.3081
O3···O122.747 (3)O8···H6ii3.4175
O3···O132.740 (2)O8···H103.3644
O4···O4iii2.801 (4)O8···H113.3115
O4···O52.755 (4)O8···H13iii3.0844
O5···O62.743 (4)O9···H22.9034
O6···O6iii2.797 (4)O9···H2ii2.9034
O6···O72.766 (2)O9···H6vii3.4123
O7···O82.758 (3)O9···H6iv3.4123
O7···O112.725 (2)O9···H7vii3.2280
O8···O8iv2.779 (3)O9···H7iv3.2280
O8···O92.778 (2)O9···H112.5024
O9···O8ii2.778 (2)O9···H11ii2.5024
O9···O102.820 (4)O9···H12iii3.2746
O10···O2ii2.793 (2)O9···H12i3.2746
O11···O7iii2.725 (2)O9···H13iii3.3321
O12···O7v2.746 (3)O9···H13i3.3321
O13···O3iii2.740 (2)O10···H7vii3.5654
O13···O11v2.750 (4)O10···H7iv3.5654
O4···C8iii3.508 (6)O10···H8v3.1928
O9···C53.418 (6)O10···H8vi3.1928
O9···C5ii3.418 (6)O10···H8vii3.5996
O11···C1ii3.314 (6)O10···H8iv3.5996
O11···C1i3.314 (6)O10···H12iii3.3552
O11···C23.597 (6)O10···H12i3.3552
O11···C2iii3.597 (6)O10···H153.4199
Br1···H123.4394O10···H15ii3.4199
Br1···H12iii3.4394O11···H1ii2.3947
Br1···H12ii3.4394O11···H1i2.3947
Br1···H12i3.4394O11···H2ii3.5970
Br1···H163.2639O11···H2i3.5970
Br1···H16iii3.2639O11···H33.1928
Br1···H16ii3.2639O11···H3iii3.1928
O1···H153.5908O11···H43.1397
O1···H18iii3.0430O11···H4iii3.1397
O2···H7iv3.3217O11···H102.8688
O2···H8v3.4015O11···H10iii2.8688
O2···H8vi3.3750O13···H1vi3.5478
O2···H9v3.1958O13···H1viii3.5478
O2···H18iii3.4525O13···H4v3.0677
O3···H9v3.1786O13···H4ix3.0677
O3···H16iii3.1405O13···H5vi3.3150
O3···H18iii3.5693O13···H5viii3.3150
O4···H16iii3.5962O13···H9v3.3221
O4···H173.0404O13···H9ix3.3221
O4···H17iii2.8646O13···H163.0144
O4···H18iii3.5555O13···H16iii3.0144
O5···H173.5983
C1—N1—C5108.8 (3)C3—C4—H7109.5264
C1i—N1—C1111.4 (4)C3—C4—H8109.4698
C5i—N1—C1108.0 (3)C3—C4—H9109.6106
C5—N1—C1i108.0 (3)H8—C4—H7109.4440
C5ii—N1—C1i150.5 (3)H9—C4—H8109.3019
C5ii—N1—C595.5 (3)N1—C5—C6116.9 (4)
C1ii—N1—C1iii111.4 (4)N1—C5—H10107.5871
C5iii—N1—C1iii108.8 (3)N1—C5—H11107.5873
C5i—N1—C1iii76.1 (3)H10—C5—C6107.5868
C5iii—N1—C1ii108.0 (3)H11—C5—C6107.5868
C5i—N1—C1ii150.5 (3)H11—C5—H10109.4598
C5i—N1—C5iii95.5 (3)C5—C6—H12109.4912
N1—C1—C2115.6 (4)C5—C6—H13109.4914
N1—C1—H1107.9147C5—C6—C7109.4 (4)
N1—C1—H2107.9142H12—C6—C7109.4911
H2—C1—C2107.9146H13—C6—C7109.4911
H1—C1—C2107.9144H13—C6—H12109.4611
H2—C1—H1109.4598C6—C7—H15108.7074
C1—C2—C3108.6 (4)C6—C7—H14108.7078
C1—C2—H3109.6842C6—C7—C8112.5 (4)
C1—C2—H4109.6837H15—C7—C8108.7077
H3—C2—C3109.6841H14—C7—C8108.7073
H4—C2—C3109.6843H15—C7—H14109.4593
H4—C2—H3109.4596C7—C8—H16109.8950
C2—C3—H5108.7907C7—C8—H17109.4706
C2—C3—H6108.7905C7—C8—H18109.2277
C2—C3—C4112.2 (4)H17—C8—H16109.2594
H5—C3—C4108.7905H18—C8—H16109.4730
H6—C3—C4108.7908H18—C8—H17109.5015
H6—C3—H5109.4593
Symmetry codes: (i) −x+1/2, −y+1, z; (ii) x, −y+1, z; (iii) −x+1/2, y, z; (iv) −x, y, −z+1; (v) x, y, z+1; (vi) x, −y+1, z+1; (vii) −x, −y+1, −z+1; (viii) −x+1/2, −y+1, z+1; (ix) −x+1/2, y, z+1.

Experimental details

Crystal data
Chemical formulaC16H36N+·Br−·38H2O
Mr1006.95
Crystal system, space groupOrthorhombic, Pmma
Temperature (K)93
a, b, c (Å)21.060 (5), 12.643 (4), 12.018 (8)
V (Å3)3199 (2)
Z2
Radiation typeMo Kα
µ (mm−1)0.72
Crystal size (mm)0.60 × 0.10 × 0.05
Data collection
DiffractometerRigaku R-AXIS RAPID
diffractometer
Absorption correctionMulti-scan
(ABSCOR; Higashi, 1995)
Tmin, Tmax0.660, 0.965
No. of measured, independent and
observed [F2 > 2σ(F2)] reflections		35341, 4988, 2811
Rint0.068
(sin θ/λ)max (Å−1)0.704
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.059, 0.156, 1.03
No. of reflections4988
No. of parameters155
No. of restraints?
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)1.82, −0.83

Computer programs: PROCESS-AUTO (Rigaku, 1998), PROCESS-AUTO, CrystalStructure (Rigaku/MSC, 2003), SIR2002 (Burla et al., 2003), CRYSTALS (Watkin et al., 1996), ORTEPII (Johnson, 1976), CrystalStructure.

 

Footnotes

‡Present address: EcoTopia Science Institute, Nagoya University, Japan.

Acknowledgements

The authors thank S. Jin, Y. Kamata, R. Ohmura, J. Nagao and H. Minagawa of AIST, and T. Uchida of Hokkaido University for useful discussions. This work was partly supported by the Japan Science and Technology Corporation (JST).

References

First citationBurla, M. C., Camalli, M., Carrozzini, B., Cascarano, G. L., Giacovazzo, C., Polidori, G. & Spagna, R. (2003). J. Appl. Cryst. 36, 1103.  CrossRef IUCr Journals Google Scholar
 First citationDavidson, D. W. (1973). Water – A Comprehensive Treatise, Vol. 2, edited by F. Franks, pp. 115–234. New York, London: Plenum Press.  Google Scholar
 First citationFukushima, S., Takao, S., Ogoshi, H., Ida, H., Matsumoto, S., Akiyama, T. & Otsuka, T. (1999). NKK Tech. Rep. 166, 65–70. (In Japanese.)  Google Scholar
 First citationHigashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.  Google Scholar
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 First citationRigaku (1998). PROCESS-AUTO. Version 1.06. Rigaku Corporation, Tokyo, Japan.  Google Scholar
 First citationRigaku/MSC (2003). CrystalStructure. Version 3.6.0. Rigaku/MSC, 9009 New Trails Drive, The Woodlands, TX 77381-5209, USA.  Google Scholar
 First citationShimada, W., Ebinuma, T., Oyama, H., Kamata, Y., Takeya, S., Uchida, T., Nagao, J. & Narita, H. (2003). Jpn J. Appl. Phys. 42, L129–L131.  Web of Science CrossRef CAS Google Scholar
 First citationSloan, E. D. Jr (1989). Clathrate Hydrates of Natural Gases, 2nd ed. New York: Marcel Dekker Inc.  Google Scholar
 First citationWatkin, D. J., Prout, C. K., Carruthers, J. R. & Betteridge, P. W. (1996). CRYSTALS. Issue 10. Chemical Crystallography Laboratory, University of Oxford, England.  Google Scholar

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Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296
Volume 61| Part 2| February 2005| Pages o65-o66
doi:10.1107/S0108270104032743
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