3-Ammonio-pyridinium tetra-bromido-mercurate(II) monohydrate.

The asymmetric unit of the title compound, (C(5)H(8)N(2))[HgBr(4)]·H(2)O, consists of one cation, one anion and one water mol-ecule. The anion exhibits a distorted tetra-hedral arrangement about the Hg atom. The crystal structure contains alternating sheets of cations (in the ac plane) and stacks of anions. Several strong hydrogen-bonding inter-actions (pyN-H⋯Br and C-H⋯Br; py is pyridine), along with O-H⋯Br inter-actions, connect the sheets of cations to the stacks of anions. Cation-cation π-π stacking is also present (C⋯C distances in the range 3.424-3.865 Å). The shortest Br⋯Br distance is 3.9527 (9) Å.

Related literature

For general background, see: Al-Far & Ali (2007a ▶); Desiraju (1997 ▶). For related literature, see: Al-Far, Ali & Al-Sou’od (2006 ▶); Al-Far & Ali (2007b ▶); Ali & Al-Far (2007a ▶, 2007b ▶, 2008 ▶); Ali, Al-Far & Haddad (2008 ▶). For bond distances see: Orpen et al. (1989 ▶).

Experimental

Crystal data

(C5H8N2)[HgBr4]·H2O

M = 634.34

Monoclinic,

a = 8.1896 (7) Å

b = 14.0245 (12) Å

c = 11.5711 (10) Å

β = 94.730 (2)°

V = 1324.5 (2) Å3

Z = 4

Mo Kα radiation

μ = 23.66 mm−1

T = 296 (2) K

0.20 × 0.10 × 0.03 mm

Data collection

Bruker–Siemens SMART APEX diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.034, T max = 0.492

16873 measured reflections

3780 independent reflections

2628 reflections with I > 2σ(I)

R int = 0.056

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.074

S = 1.03

3780 reflections

126 parameters

3 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.85 e Å−3

Δρmin = −1.32 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT-Plus (Bruker, 2001 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: XS in SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: XL in SHELXTL; molecular graphics: XP in SHELXTL; software used to prepare material for publication: XCIF in SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808012336/cs2074sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808012336/cs2074Isup2.hkl

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

(C5H8N2)[HgBr4]·H2O	F000 = 1128
Mr = 634.34	Dx = 3.181 Mg m−3
Monoclinic, P21/n	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5049 reflections
a = 8.1896 (7) Å	θ = 2.3–27.6º
b = 14.0245 (12) Å	µ = 23.66 mm−1
c = 11.5711 (10) Å	T = 296 (2) K
β = 94.730 (2)º	Chunk, pink
V = 1324.5 (2) Å3	0.20 × 0.10 × 0.03 mm
Z = 4

Bruker–Siemens SMART APEX diffractometer	3780 independent reflections
Radiation source: fine-focus sealed tube	2628 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.056
Detector resolution: 8.3 pixels mm-1	θmax = 30.1º
T = 296(2) K	θmin = 2.3º
ω scans	h = −11→11
Absorption correction: multi-scan(SADABS; Bruker, 2001)	k = −19→19
Tmin = 0.034, Tmax = 0.492	l = −16→16
16873 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.035	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.074	w = 1/[σ2(Fo2) + (0.018P)2 + 0.74P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max = 0.001
3780 reflections	Δρmax = 0.85 e Å−3
126 parameters	Δρmin = −1.32 e Å−3
3 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00271 (13)

	x	y	z	Uiso*/Ueq
O1	0.8331 (6)	0.5315 (4)	0.4741 (5)	0.0770 (15)
H1	0.883 (9)	0.575 (4)	0.433 (5)	0.116*
H2	0.802 (10)	0.560 (4)	0.538 (4)	0.116*
Hg1	0.68459 (3)	0.763019 (18)	0.84039 (2)	0.05085 (10)
Br1	0.95522 (7)	0.85483 (4)	0.89061 (5)	0.04424 (15)
Br2	0.53644 (7)	0.74688 (4)	1.03273 (5)	0.04900 (16)
Br3	0.74834 (8)	0.59454 (4)	0.75688 (5)	0.05157 (17)
Br4	0.45943 (8)	0.83129 (5)	0.69416 (6)	0.0622 (2)
N1	0.8418 (6)	0.9030 (4)	0.1560 (4)	0.0506 (13)
H1A	0.7884	0.9447	0.1089	0.076*
H1B	0.8181	0.8440	0.1317	0.076*
H1C	0.9492	0.9128	0.1560	0.076*
C2	0.7926 (6)	0.9151 (4)	0.2726 (4)	0.0337 (11)
C3	0.6981 (6)	0.8466 (4)	0.3172 (5)	0.0413 (13)
H3	0.6637	0.7934	0.2737	0.050*
N4	0.6563 (6)	0.8582 (4)	0.4258 (4)	0.0501 (12)
H4	0.5957	0.8158	0.4547	0.060*
C5	0.7057 (7)	0.9339 (4)	0.4914 (5)	0.0462 (14)
H5	0.6764	0.9390	0.5672	0.055*
C6	0.7989 (7)	1.0030 (4)	0.4463 (5)	0.0424 (13)
H6	0.8318	1.0562	0.4903	0.051*
C7	0.8433 (7)	0.9933 (4)	0.3356 (5)	0.0419 (13)
H7	0.9074	1.0395	0.3036	0.050*

	U11	U22	U33	U12	U13	U23
O1	0.061 (3)	0.073 (4)	0.096 (4)	−0.012 (3)	0.003 (3)	−0.027 (3)
Hg1	0.04444 (15)	0.05348 (17)	0.05300 (16)	−0.00161 (11)	−0.00571 (10)	−0.00193 (11)
Br1	0.0406 (3)	0.0417 (3)	0.0508 (3)	−0.0052 (2)	0.0063 (2)	−0.0018 (2)
Br2	0.0451 (3)	0.0563 (4)	0.0451 (3)	−0.0050 (3)	0.0014 (3)	−0.0036 (3)
Br3	0.0573 (4)	0.0473 (4)	0.0506 (3)	−0.0023 (3)	0.0077 (3)	−0.0071 (3)
Br4	0.0454 (3)	0.0673 (5)	0.0713 (4)	−0.0031 (3)	−0.0099 (3)	0.0294 (3)
N1	0.053 (3)	0.061 (3)	0.037 (3)	0.010 (2)	0.003 (2)	0.000 (2)
C2	0.034 (3)	0.039 (3)	0.027 (2)	0.008 (2)	−0.001 (2)	0.002 (2)
C3	0.030 (3)	0.040 (3)	0.053 (3)	−0.004 (2)	−0.003 (2)	−0.012 (3)
N4	0.041 (3)	0.048 (3)	0.062 (3)	−0.009 (2)	0.007 (2)	0.003 (2)
C5	0.045 (3)	0.057 (4)	0.036 (3)	0.001 (3)	0.003 (2)	−0.004 (3)
C6	0.045 (3)	0.038 (3)	0.044 (3)	−0.003 (2)	−0.001 (3)	−0.009 (2)
C7	0.045 (3)	0.034 (3)	0.047 (3)	0.000 (2)	0.006 (3)	0.006 (2)

O1—H1	0.89 (6)	C2—C3	1.362 (7)
O1—H2	0.89 (6)	C3—N4	1.339 (7)
Hg1—Br4	2.5818 (7)	C3—H3	0.9300
Hg1—Br1	2.5875 (6)	N4—C5	1.349 (7)
Hg1—Br3	2.6216 (7)	N4—H4	0.8600
Hg1—Br2	2.6309 (7)	C5—C6	1.364 (8)
N1—C2	1.450 (6)	C5—H5	0.9300
N1—H1A	0.8900	C6—C7	1.367 (7)
N1—H1B	0.8900	C6—H6	0.9300
N1—H1C	0.8900	C7—H7	0.9300
C2—C7	1.363 (7)
H1—O1—H2	108 (5)	N4—C3—C2	117.8 (5)
Br4—Hg1—Br1	120.99 (2)	N4—C3—H3	121.1
Br4—Hg1—Br3	104.23 (2)	C2—C3—H3	121.1
Br1—Hg1—Br3	109.78 (2)	C3—N4—C5	122.4 (5)
Br4—Hg1—Br2	103.42 (2)	C3—N4—H4	118.8
Br1—Hg1—Br2	107.40 (2)	C5—N4—H4	118.8
Br3—Hg1—Br2	110.73 (2)	N4—C5—C6	119.7 (5)
C2—N1—H1A	109.5	N4—C5—H5	120.2
C2—N1—H1B	109.5	C6—C5—H5	120.2
H1A—N1—H1B	109.5	C5—C6—C7	119.3 (5)
C2—N1—H1C	109.5	C5—C6—H6	120.4
H1A—N1—H1C	109.5	C7—C6—H6	120.4
H1B—N1—H1C	109.5	C2—C7—C6	119.2 (5)
C7—C2—C3	121.6 (5)	C2—C7—H7	120.4
C7—C2—N1	119.7 (5)	C6—C7—H7	120.4
C3—C2—N1	118.7 (5)
C7—C2—C3—N4	−0.2 (8)	N4—C5—C6—C7	−1.3 (9)
N1—C2—C3—N4	178.8 (5)	C3—C2—C7—C6	0.3 (8)
C2—C3—N4—C5	−0.7 (8)	N1—C2—C7—C6	−178.7 (5)
C3—N4—C5—C6	1.4 (9)	C5—C6—C7—C2	0.4 (8)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···Br2i	0.89 (6)	2.98 (6)	3.564 (5)	125 (5)
O1—H2···Br3	0.89 (6)	2.65 (3)	3.513 (5)	162 (7)
N1—H1A···O1ii	0.89	1.80	2.686 (7)	174
N1—H1B···Br4i	0.89	2.79	3.442 (5)	132
N1—H1B···Br2iii	0.89	2.84	3.535 (5)	136
N1—H1C···Br3i	0.89	2.63	3.436 (5)	152
N4—H4···Br1iv	0.86	2.73	3.419 (5)	138

Hg1—Br4	2.5818 (7)
Hg1—Br1	2.5875 (6)
Hg1—Br3	2.6216 (7)
Hg1—Br2	2.6309 (7)

Br4—Hg1—Br1	120.99 (2)
Br4—Hg1—Br3	104.23 (2)
Br1—Hg1—Br3	109.78 (2)
Br4—Hg1—Br2	103.42 (2)
Br1—Hg1—Br2	107.40 (2)
Br3—Hg1—Br2	110.73 (2)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯Br2i	0.89 (6)	2.98 (6)	3.564 (5)	125 (5)
O1—H2⋯Br3	0.89 (6)	2.65 (3)	3.513 (5)	162 (7)
N1—H1A⋯O1ii	0.89	1.80	2.686 (7)	174
N1—H1B⋯Br4i	0.89	2.79	3.442 (5)	132
N1—H1B⋯Br2iii	0.89	2.84	3.535 (5)	136
N1—H1C⋯Br3i	0.89	2.63	3.436 (5)	152
N4—H4⋯Br1iv	0.86	2.73	3.419 (5)	138

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .