Butane-1,4-di­amine zinc(II) hydrogen phosphite

Ritchie, L.K.; Harrison, W.T.A.

doi:10.1107/S0108270104024862

metal-organic compounds

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 60| Part 12| December 2004| Pages m634-m636

doi:10.1107/S0108270104024862

Butane-1,4-diamine zinc(II) hydrogen phosphite

Lyndsey K. Ritchie ^a and William T. A. Harrison ^a ^*

^aDepartment of Chemistry, University of Aberdeen, Meston Walk, Aberdeen AB24 3UE, Scotland
^*Correspondence e-mail: w.harrison@abdn.ac.uk

(Received 25 August 2004; accepted 4 October 2004; online 11 November 2004)

The title compound, poly[zinc(II)-μ-butane-1,4-diamine-μ-(hydrogen phosphito)] (C₄H₁₂N₂)_0.5[ZnHPO₃], is a hybrid organic–inorganic solid built up from 1,4-diaminobutane molecules, Zn²⁺ cations (coordinated by three O atoms and one N atom) and HPO₃²⁻ hydrogen phosphite groups. The organic species bonds to the Zn atom as an unprotonated ligand, resulting in it acting as a bridge between infinite ZnHPO₃ layers, which propagate in (100). The complete butane-1,4-diamine species is generated from a H₂N(CH₂)₂– half molecule by inversion symmetry. The zincophosphite sheets contain polyhedral four- and eight-membered rings in a 4.8² topology.

Comment

The title compound, [H₂N(CH₂)₄NH₂]_0.5[ZnHPO₃], (I), is another example of the rapidly expanding family of organically templated zinc hydrogen phosphite (ZnHPO) networks (Kirkpatrick & Harrison, 2004 , and references therein; Fu et al., 2004 ) and is the first reported ZnHPO compound to incorporate butane-1,4-diamine as the organic species. Compound (I) was prepared in single-crystal form by a typical mild-condition solution-mediated reaction (Cheetham et al., 1999 ).

Compound (I) (Fig. 1) is built up from neutral unprotonated butane-1,4-diamine [H₂N(CH₂)₄NH₂] molecules, Zn²⁺ cations and HPO₃²⁻ hydrogen phosphite groups. Each complete butane-1,4-diamine entity is generated from a half-molecule H₂N(CH₂)₂– fragment by inversion symmetry (Table 1). The N atom makes a ligand-like bond to the Zn atom by formal donation of its lone pair of electrons, as seen in related systems (Rodgers & Harrison, 2000 ). The tetrahedral zinc coordination is completed by three O atoms [mean Zn—O = 1.943 (2) Å], all of which form bridges to nearby HPO₃²⁻ groups [mean Zn—O—P = 131.3 (2)°]. The pseudo-pyramidal HPO₃²⁻ moiety has typical geometrical parameters, with a mean P—O distance of 1.518 (2) Å and a mean O—P—O angle of 112.48 (9)° (Kirkpatrick & Harrison, 2004). Its three O atoms all make bridges to nearby zinc cations. As usual, the P—H moiety does not interact with any nearby chemical species.

The polyhedral building units in (I) thus consist of ZnO₃N and HPO₃ tetrahedra, linked by way of the O atoms. These units form sheets, built up from strictly alternating Zn- and P-centred moieties, which propagate in the (100) plane. Every tetrahedral node (i.e. the Zn and P atoms) participates in one four-membered ring (generated by inversion symmetry) and two eight-membered rings (Fig. 2), and this topology is classed as a 4.8² sheet (O'Keeffe & Hyde, 1996 ).

The organic species crosslink the (100) ZnHPO₃ sheets in a Zn—b—Zn (b is the organic bridge) fashion, as shown in Fig. 3, resulting in a hybrid `pillared' structure in which the inorganic and organic components alternate along [100]. In principle, this arrangement represents a novel kind of microporosity, with the channels bounded by both inorganic and organic surfaces. However, in (I), the presence of the P—H bond protruding into the channel region and the highly twisted conformation of the 1,4-diaminobutane moiety mean that there is no possibility of ingress by other chemical species. Finally, the butane-1,4-diamine NH₂ groups in (I) participate in N—H⋯O hydrogen bonds (Table 2), of which one (via H3) is simple and one (via H2) is bifurcated (Fig. 4). These hydrogen bonds appear to help to anchor the organic moiety to an eight-membered ring window in the zinc hydrogen phosphite layer, in a similar way to the behaviour of ethylenediamine in [H₂N(CH₂)₂NH₂]_0.5[ZnHPO₃] (Rodgers & Harrison, 2000). Here, however, the zincophosphite 8-ring pores are highly flattened, whereas in [H₂N(CH₂)₂NH₂]_0.5[ZnHPO₃] they are far more regular.

Compound (I) complements several other `pillared' networks built up from ZnO₃N_l (N_l = ligand amine N atom) tetrahedra and pyramidal or pseudo-pyramidal inorganic oxyanions. Both modifications of ethylenediamine zinc selenite, [H₂N(CH₂)₂NH₂]_0.5[ZnSeO₃] (Choudhury et al., 2002 ; Millange et al., 2004 ), contain sheets of ZnO₃N and SeO₃ groups fused into a three-dimensional network by the ethylenediamine moieties bonding to the Zn atom from each end of the H₂N(CH₂)₂NH₂ species. The first of these (Choudhury et al., 2002) is based on 6³ inorganic sheets (each nodal atom participates in three six-membered rings), whereas the second (Millange et al., 2004) is based on 4.8² sheets, as seen here for (I). The 1,4-diaminobenzene template in (C₆N₂H₈)_0.5[ZnHPO₃] (Kirkpatrick & Harrison, 2004) acts in a similar way to ethylenediamine in the [H₂N(CH₂)₂NH₂]_0.5[ZnSeO₃] phases; in this case, 6³ polyhedral sheets arise. Finally, [H₂N(CH₂)₂NH₂]_0.5[ZnHPO₃] (Rodgers & Harrison, 2000) has a novel structure based on 4.8² sheets in which two independent networks form an interpenetrating array akin to coordination polymers.

Figure 1
A view of a fragment of (I

) (50% probability displacement ellipsoids). H atoms are drawn as small spheres of arbitrary radii. Symmetry codes are as in Table 1

Figure 2
A view down [100] of a fragment of a ZnHPO₃ layer in (I

), showing the topologial connectivity of the Zn (large spheres) and P (small spheres) tetrahedral nodes into 4.8² sheets. Atoms labelled with an asterisk (*) are at the symmetry position (2 − x, 1 − y, 1 − z). The lines linking the Zn and P atoms represent Zn—O—P bridges, which are not linear (see Table 1

Figure 3
The unit-cell packing in (I

), viewed down [001], in a polyhedral representation (ZnO₃N groups: dark shading; HPO₃ groups: light shading). All H atoms, except for atom H1, have been omitted for clarity.

Figure 4
A polyhedral view of a fragment of a (100) ZnHPO₃ layer in (I

), showing the N—H⋯O bonds associated with a flattened 8-ring window. Symmetry codes are as in Table 2

Experimental

Zinc oxide, phosphorus acid (H₃PO₃) and butane-1,4-diamine in a 1:2:2 molar ratio were shaken in distilled water (25 ml) in a 60 ml HDPE bottle for a few minutes until a white slurry formed. The bottle was then placed in an oven at 353 K for 2 d. The solid product was filtered off hot by suction filtration using a Buchner funnel and rinsed with water and acetone, resulting in intergrown block-like crystals of (I). An ATOMS (Shape Software, 1999 ) simulation of the X-ray powder pattern of (I), based on the single-crystal structure described here, was in excellent agreement with the measured data, indicating phase purity.

Crystal data

(C₄H₁₂N₂)_0.5[ZnHPO₃]
M_r = 189.43
Monoclinic, P2₁/c
a = 8.4713 (4) Å
b = 8.2489 (4) Å
c = 8.0805 (4) Å
β = 96.093 (1)°
V = 561.47 (5) Å³
Z = 4
D_x = 2.241 Mg m⁻³
Mo Kα radiation
Cell parameters from 3298 reflections
θ = 2.5–32.2°
μ = 4.57 mm⁻¹
T = 293 (2) K
Slab, colourless
0.32 × 0.30 × 0.13 mm

Data collection

Bruker SMART 1000 CCD diffractometer
ω scans
Absorption correction: multi-scan (SADABS; Bruker, 1999 ) T_min = 0.323, T_max = 0.588
5407 measured reflections
1964 independent reflections
1667 reflections with I > 2σ(I)
R_int = 0.017
θ_max = 32.2°
h = −12 → 12
k = −5 → 12
l = −12 → 11

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.019
wR(F²) = 0.049
S = 1.07
1964 reflections
74 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0259P)²] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.002
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.32 e Å⁻³
Extinction correction: SHELXL97
Extinction coefficient: 0.0032 (7)

Table 1
Selected geometric parameters (Å, °)

Zn1—O1	1.9331 (11)
Zn1—O3ⁱ	1.9427 (11)
Zn1—O2ⁱⁱ	1.9539 (11)
Zn1—N1	2.0260 (12)
P1—O1	1.5140 (11)
P1—O3	1.5152 (12)
P1—O2	1.5254 (11)

P1—O1—Zn1	135.21 (7)
P1—O2—Zn1ⁱⁱ	124.08 (7)
P1—O3—Zn1ⁱⁱⁱ	134.49 (7)
C1—N1—Zn1	116.33 (9)

Zn1—N1—C1—C2	−57.62 (14)
N1—C1—C2—C2^iv	−61.9 (2)
C1—C2—C2^iv—C1^iv	180.0
Symmetry codes: (i) $[x,{\script{1\over 2}}-y,z-{\script{1\over 2}}]$ ; (ii) 2-x,1-y,1-z; (iii) $[x,{\script{1\over 2}}-y,{\script{1\over 2}}+z]$ ; (iv) 1-x,1-y,-z.

Table 2
Hydrogen-bonding geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H2⋯O2^v	0.90	2.47	3.2107 (17)	140
N1—H2⋯O3^vi	0.90	2.57	3.1143 (16)	119
N1—H3⋯O2^vii	0.90	2.29	3.1501 (15)	160
Symmetry codes: (v) $[x,{\script{3\over 2}}-y,z-{\script{1\over 2}}]$ ; (vi) $[2-x,{\script{1\over 2}}+y,{\script{1\over 2}}-z]$ ; (vii) x,y,z-1.

All H atoms were placed in idealized positions and refined as riding on their carrier atoms [P—H = 1.32 Å, N—H = 0.90 Å, C—H = 0.97 Å and U_iso(H) = 1.2U_eq(parent atom)].

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and ATOMS (Shape Software, 1999); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S0108270104024862/tr1100sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270104024862/tr1100Isup2.hkl

Comment top

The title compound, [H₂N(CH₂)₄NH₂]_0.5[ZnHPO₃], (I), is another example of the rapidly expanding family of organically templated zinc hydrogen phosphite (ZnHPO) networks (Kirkpatrick & Harrison, 2004, and references therein; Fu et al., 2004) and is the first reported ZnHPO compound to incorporate 1,4-diaminobutane as the organic species. Compound (I) was prepared in single-crystal form by a typical mild-condition solution-mediated reaction (Cheetham et al., 1999).

Compound (I) (Fig. 1) is built up from neutral unprotonated 1,4-diaminobutane [H₂N(CH₂)₄NH₂ or C₄H₁₂N₂] molecules, Zn²⁺ cations, and HPO₃²⁻ hydrogen phosphite groups. Each complete 1,4-diaminobutane entity is generated from a half-molecule [H₂N(CH₂)₂] fragment by inversion symmetry (Table 1). The N atom makes a ligand-like bond to zinc by formal donation of its lone pair of electrons, as seen in related systems (Rodgers & Harrison, 2000). The tetrahedral zinc coordination is completed by three O atoms [mean Zn—O = 1.943 (2) Å], all of which form bridges to nearby HPO₃²⁻ groups [mean Zn—O—P = 131.3 (2)°]. The pseudo-pyramidal HPO₃²⁻ moiety has typical geometrical parameters, with a mean P—O distance of 1.518 (2) Å, and a mean O—P—O angle of 112.48 (9)° (Kirkpatrick & Harrison, 2004, and references therein). Its three O atoms all make bridges to nearby zinc cations. As usual, the P—H moiety does not interact with any nearby chemical species.

The organic species crosslink the (100) ZnHPO₃ sheets in a Zn—b—Zn (b is the organic bridge) fashion, as shown in Fig. 3, resulting in a hybrid, `pillared' structure in which the inorganic and organic components alternate along [100]. In principle, this arrangement represents a novel kind of microporosity, with the channels bounded by both inorganic and organic surfaces. However, in (I), the presence of the P–H bond protruding into the channel region and the highly twisted conformation of the 1,4-diaminobutane moiety means that there is no possibility of ingress by other chemical species. Finally, the 1,4-diaminobutane –NH₂ groups in (I) participate in N—H···O hydrogen bonds (Table 2), of which one (via H3) is simple and one (via H2) is bifurcated (Fig. 4). These hydrogen bonds appear to help to anchor the organic moiety to an eight-membered ring window in the zinc hydrogen phosphite layer in a similar way to the behaviour of ethylenediamine in [H₂N(CH₂)₂NH₂]_0.5[ZnHPO₃] (Rodgers & Harrison, 2000). Here, however, the zincophosphate eight-ring pores are highly flattened, whereas in [H₂N(CH₂)₂NH₂]_0.5[ZnHPO₃] they are far more regular.

Compound (I) complements several other `pillared' networks built up from ZnO₃N_l (N_l = ligand amine N atom) tetrahedra and pyramidal or pseudo-pyramidal inorganic oxyanions. Both modifications of ethylenediamine zinc selenite, [H₂N(CH₂)₂NH₂]_0.5[ZnSeO₃] (Choudhury et al., 2002; Millange et al., 2004), contain sheets of ZnO₃N and SeO₃ groups fused into a three-dimensional network by the ethylenediamine moieties bonding to Zn from each end of the H₂N(CH₂)₂NH₂ species. The first of these (Choudhury et al., 2002) is based on 6³ inorganic sheets (each nodal atom participates in three six-membered rings), whereas the second (Millange et al., 2004) is based on 4.8² sheets, as seen here for (I). The 1,4-diaminobenzene template in [C₆N₂H₈]_0.5[ZnHPO₃] (Kirkpatrick & Harrison, 2004) acts in a similar way to ethylenediamine in the [H₂N(CH₂)₂NH₂]_0.5[ZnSeO₃] phases; in this case 6³ polyhedral sheets arise. Finally, [H₂N(CH₂)₂NH₂]_0.5[ZnHPO₃] (Rodgers & Harrison, 2000) has a novel structure based on 4.8² sheets in which two independent networks from an interpenetrating array akin to coordination polymers.

Experimental top

Zinc oxide, phosphorus acid (H₃PO₃) and 1,4-diaminobutane in a 1:2:2 molar ratio were shaken in distilled water (25 ml) in a 60 ml HDPE bottle for a few minutes until a white slurry formed. The bottle was then placed in an oven at 353 K for 2 d. The solid product was filtered hot by suction filtration using a Buchner funnel and rinsed with water and acetone, resulting in intergrown block-like crystals of (I). An ATOMS (Shape Software, 1999) simulation of the X-ray powder pattern of (I) based on the single-crystal structure described here, was in excellent agreement with the measured data, indicating phase purity.

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and ATOMS (Shape Software, 1999); software used to prepare material for publication: SHELXL97.

Figures top

	Fig. 1. A view of a fragment of (I) (50% probability displacement ellipsoids). H atoms are drawn as small spheres of arbitrary radius. Symmetry codes are as in Table 1.
	Fig. 2. A view down [100] of a fragment of a ZnHPO₃ layer in (I), showing the topologial connectivity of the Zn (large spheres) and P (small spheres) tetrahedral nodes into 4.8² sheets. Atoms labeled with an asterisk (*) are at the symmetry position (2 − x, 1 − y, 1 − z). The lines linking the Zn and P atoms represent Zn—O—P bridges, which are not linear (see Table 1).
	Fig. 3. The unit-cell packing in (I), viewed down [001], in a polyhedral representation (ZnO₃N groups: dark shading; HPO₃ groups: light shading). All H atoms, except atom H1, have been omitted for clarity.
	Fig. 4. A polyhedral view of a fragment of a (100) ZnHPO₃ layer in (I), showing the N—H···O bonds associated with a flattened eight-ring window. Symmetry codes are as in Table 2.

Butane-1,4-diamine zinc(II) hydrogen phosphite top

Crystal data top

(C₄H₁₂N₂)_0.5[ZnHPO₃]	F(000) = 380
M_r = 189.43	D_x = 2.241 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3298 reflections
a = 8.4713 (4) Å	θ = 2.5–32.2°
b = 8.2489 (4) Å	µ = 4.57 mm⁻¹
c = 8.0805 (4) Å	T = 293 K
β = 96.093 (1)°	Slab, colourless
V = 561.47 (5) Å³	0.32 × 0.30 × 0.13 mm
Z = 4

Data collection top

Bruker SMART 1000 CCD diffractometer	1964 independent reflections
Radiation source: fine-focus sealed tube	1667 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.017
ω scans	θ_max = 32.2°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −12→12
T_min = 0.323, T_max = 0.588	k = −5→12
5407 measured reflections	l = −12→11

Refinement top

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)] = 0.019	H-atom parameters constrained
wR(F²) = 0.049	w = 1/[σ²(F_o²) + (0.0259P)²] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.002
1964 reflections	Δρ_max = 0.44 e Å⁻³
74 parameters	Δρ_min = −0.32 e Å⁻³
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0032 (7)

Crystal data top

(C₄H₁₂N₂)_0.5[ZnHPO₃]	V = 561.47 (5) Å³
M_r = 189.43	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.4713 (4) Å	µ = 4.57 mm⁻¹
b = 8.2489 (4) Å	T = 293 K
c = 8.0805 (4) Å	0.32 × 0.30 × 0.13 mm
β = 96.093 (1)°

Data collection top

Bruker SMART 1000 CCD diffractometer	1964 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1999)	1667 reflections with I > 2σ(I)
T_min = 0.323, T_max = 0.588	R_int = 0.017
5407 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.019	0 restraints
wR(F²) = 0.049	H-atom parameters constrained
S = 1.07	Δρ_max = 0.44 e Å⁻³
1964 reflections	Δρ_min = −0.32 e Å⁻³
74 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
Zn1	0.897600 (18)	0.46510 (2)	0.218542 (18)	0.02079 (6)
P1	0.80502 (4)	0.38978 (5)	0.58340 (4)	0.01849 (8)
H1	0.6629	0.3526	0.6249	0.022*
O1	0.77922 (14)	0.46180 (16)	0.41029 (13)	0.0341 (3)
O2	0.87536 (13)	0.51177 (15)	0.71268 (13)	0.0292 (2)
O3	0.89785 (15)	0.23256 (13)	0.58785 (15)	0.0340 (3)
N1	0.79215 (13)	0.63445 (15)	0.06227 (14)	0.0216 (2)
H2	0.8534	0.7239	0.0694	0.026*
H3	0.7898	0.5968	−0.0425	0.026*
C1	0.62758 (16)	0.68278 (19)	0.09135 (18)	0.0255 (3)
H4	0.5892	0.7625	0.0085	0.031*
H5	0.6306	0.7339	0.1998	0.031*
C2	0.51209 (16)	0.54297 (19)	0.08398 (16)	0.0243 (3)
H6	0.4102	0.5830	0.1110	0.029*
H7	0.5496	0.4645	0.1685	0.029*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.02292 (9)	0.01930 (9)	0.01926 (9)	0.00246 (6)	−0.00184 (5)	−0.00111 (6)
P1	0.01839 (15)	0.02006 (17)	0.01691 (15)	−0.00126 (13)	0.00140 (11)	0.00077 (12)
O1	0.0351 (6)	0.0467 (8)	0.0206 (5)	0.0139 (5)	0.0030 (4)	0.0097 (5)
O2	0.0231 (5)	0.0312 (6)	0.0319 (6)	0.0012 (4)	−0.0032 (4)	−0.0115 (4)
O3	0.0484 (7)	0.0190 (5)	0.0363 (6)	0.0068 (5)	0.0134 (5)	0.0076 (5)
N1	0.0189 (5)	0.0203 (6)	0.0250 (5)	−0.0029 (4)	0.0001 (4)	0.0030 (5)
C1	0.0216 (6)	0.0242 (7)	0.0298 (7)	0.0025 (6)	−0.0010 (5)	−0.0025 (6)
C2	0.0195 (6)	0.0322 (8)	0.0212 (6)	−0.0025 (6)	0.0020 (4)	−0.0019 (6)

Geometric parameters (Å, º) top

Zn1—O1	1.9331 (11)	N1—C1	1.4924 (18)
Zn1—O3ⁱ	1.9427 (11)	N1—H2	0.9000
Zn1—O2ⁱⁱ	1.9539 (11)	N1—H3	0.9000
Zn1—N1	2.0260 (12)	C1—C2	1.509 (2)
P1—O1	1.5140 (11)	C1—H4	0.9700
P1—O3	1.5152 (12)	C1—H5	0.9700
P1—O2	1.5254 (11)	C2—C2^iv	1.526 (3)
P1—H1	1.3200	C2—H6	0.9700
O2—Zn1ⁱⁱ	1.9539 (11)	C2—H7	0.9700
O3—Zn1ⁱⁱⁱ	1.9427 (11)

O1—Zn1—O3ⁱ	117.03 (5)	Zn1—N1—H2	108.2
O1—Zn1—O2ⁱⁱ	110.62 (5)	C1—N1—H3	108.2
O3ⁱ—Zn1—O2ⁱⁱ	100.29 (5)	Zn1—N1—H3	108.2
O1—Zn1—N1	106.10 (5)	H2—N1—H3	107.4
O3ⁱ—Zn1—N1	105.41 (5)	N1—C1—C2	113.71 (12)
O2ⁱⁱ—Zn1—N1	117.75 (5)	N1—C1—H4	108.8
O1—P1—O3	112.42 (7)	C2—C1—H4	108.8
O1—P1—O2	112.43 (7)	N1—C1—H5	108.8
O3—P1—O2	112.60 (7)	C2—C1—H5	108.8
O1—P1—H1	106.3	H4—C1—H5	107.7
O3—P1—H1	106.3	C1—C2—C2^iv	114.55 (15)
O2—P1—H1	106.3	C1—C2—H6	108.6
P1—O1—Zn1	135.21 (7)	C2^iv—C2—H6	108.6
P1—O2—Zn1ⁱⁱ	124.08 (7)	C1—C2—H7	108.6
P1—O3—Zn1ⁱⁱⁱ	134.49 (7)	C2^iv—C2—H7	108.6
C1—N1—Zn1	116.33 (9)	H6—C2—H7	107.6
C1—N1—H2	108.2

O3—P1—O1—Zn1	−32.09 (14)	O2—P1—O3—Zn1ⁱⁱⁱ	84.33 (12)
O2—P1—O1—Zn1	96.23 (12)	O1—Zn1—N1—C1	−18.17 (11)
O3ⁱ—Zn1—O1—P1	75.42 (13)	O3ⁱ—Zn1—N1—C1	106.60 (10)
O2ⁱⁱ—Zn1—O1—P1	−38.56 (13)	O2ⁱⁱ—Zn1—N1—C1	−142.64 (9)
N1—Zn1—O1—P1	−167.34 (11)	Zn1—N1—C1—C2	−57.62 (14)
O1—P1—O2—Zn1ⁱⁱ	−93.89 (10)	N1—C1—C2—C2^iv	−61.9 (2)
O3—P1—O2—Zn1ⁱⁱ	34.34 (11)	C1—C2—C2^iv—C1^iv	180.0
O1—P1—O3—Zn1ⁱⁱⁱ	−147.44 (10)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H2···O2^v	0.90	2.47	3.2107 (17)	140
N1—H2···O3^vi	0.90	2.57	3.1143 (16)	119
N1—H3···O2^vii	0.90	2.29	3.1501 (15)	160

Symmetry codes: (v) x, −y+3/2, z−1/2; (vi) −x+2, y+1/2, −z+1/2; (vii) x, y, z−1.

Experimental details

Crystal data
Chemical formula	(C₄H₁₂N₂)_0.5[ZnHPO₃]
M_r	189.43
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	8.4713 (4), 8.2489 (4), 8.0805 (4)
β (°)	96.093 (1)
V (Å³)	561.47 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.57
Crystal size (mm)	0.32 × 0.30 × 0.13

Data collection
Diffractometer	Bruker SMART 1000 CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1999)
T_min, T_max	0.323, 0.588
No. of measured, independent and observed [I > 2σ(I)] reflections	5407, 1964, 1667
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.750

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.019, 0.049, 1.07
No. of reflections	1964
No. of parameters	74
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.32

Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997) and ATOMS (Shape Software, 1999), SHELXL97.

Selected geometric parameters (Å, º) top

Zn1—O1	1.9331 (11)	P1—O1	1.5140 (11)
Zn1—O3ⁱ	1.9427 (11)	P1—O3	1.5152 (12)
Zn1—O2ⁱⁱ	1.9539 (11)	P1—O2	1.5254 (11)
Zn1—N1	2.0260 (12)

P1—O1—Zn1	135.21 (7)	P1—O3—Zn1ⁱⁱⁱ	134.49 (7)
P1—O2—Zn1ⁱⁱ	124.08 (7)	C1—N1—Zn1	116.33 (9)

Zn1—N1—C1—C2	−57.62 (14)	C1—C2—C2^iv—C1^iv	180.0
N1—C1—C2—C2^iv	−61.9 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H2···O2^v	0.90	2.47	3.2107 (17)	140
N1—H2···O3^vi	0.90	2.57	3.1143 (16)	119
N1—H3···O2^vii	0.90	2.29	3.1501 (15)	160

Symmetry codes: (v) x, −y+3/2, z−1/2; (vi) −x+2, y+1/2, −z+1/2; (vii) x, y, z−1.

References

Bruker (1999). SMART (Version 5.624), SAINT-Plus (Version 6.02A) and SADABS (Version 2.03). Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cheetham, A. K., Férey, G. & Loiseau, T. (1999). Angew. Chem. Int. Ed. 38, 3269–3292. Web of Science CrossRef Google Scholar
Choudhury, A., Kumar, U. D. & Rao, C. N. R. (2002). Angew. Chem. Int. Ed. 41, 158–161. Web of Science CSD CrossRef CAS Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Fu, W., Shi, Z., Li, G., Zhang, D., Dong, W., Chen, X. & Feng, S. (2004). Solid State Sci. 6, 225–228. Web of Science CSD CrossRef CAS Google Scholar
Kirkpatrick, A. & Harrison, W. T. A. (2004). Solid State Sci. 6, 593–598. CSD CrossRef CAS Google Scholar
Millange, F., Serre, C., Cabourdin, T., Marrot, J. & Féret, G. (2004). Solid State Sci. 6, 229–233. Web of Science CSD CrossRef CAS Google Scholar
O'Keeffe, M. & Hyde, B. G. (1996). Crystal Structures 1. Patterns and Symmetry, p. 357. Washington, DC: Mineralogical Society of America. Google Scholar
Rodgers, J. A. & Harrison, W. T. A. (2000). Chem. Commun. pp. 2385–2386. Web of Science CrossRef Google Scholar
Shape Software (1999). ATOMS. Shape Software, 525 Hidden Valley Road, Kingsport, Tennessee, USA. Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar

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ISSN: 2053-2296

Volume 60| Part 12| December 2004| Pages m634-m636

doi:10.1107/S0108270104024862

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

Butane-1,4-di­amine zinc(II) hydrogen phosphite

Comment

Experimental

Crystal data

Data collection

Refinement

Supporting information

References

metal-organic compounds

Butane-1,4-diamine zinc(II) hydrogen phosphite