Penta­kis(2-oxo-2,3-dihydro­pyrimidin-1-ium) di-μ3-chlorido-tri-μ2-chlorido-hexa­chloridotricadmate(II)

Kurawa, M.A.; Adams, C.J.; Orpen, A.G.

doi:10.1107/S160053680801862X

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 7| July 2008| Pages m960-m961

doi:10.1107/S160053680801862X

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Pentakis(2-oxo-2,3-dihydropyrimidin-1-ium) di-μ₃-chlorido-tri-μ₂-chlorido-hexachloridotricadmate(II)

Mukhtar A. Kurawa,^a Christopher J. Adams ^a and A. Guy Orpen ^a ^*

^aSchool of Chemistry, University of Bristol, Bristol BS8 1TS, England
^*Correspondence e-mail: guy.orpen@bris.ac.uk

(Received 10 June 2008; accepted 19 June 2008; online 25 June 2008)

The title compound, (C₄H₅N₂O)₅[Cd₃Cl₁₁], was obtained from the reaction of 2-hydroxypyrimidine hydrochloride and cadmium(II) chloride in concentrated HCl solution. The crystal structure consists of planar 2-oxo-1,2-dihydropyrimidin-3-ium cations with both N atoms protonated and the O atom unprotonated, and a complex trinuclear [Cd₃Cl₁₁]⁵⁻ anion of approximately D_3h symmetry, which has a triangle of three octahedrally coordinated Cd^II centres bonded to 11 chloride ions. Three of the chloride ions bridge adjacent Cd atoms, two cap the faces of the Cd₃ triangle and the remaining six are terminally bonded and act as hydrogen-bond acceptors. Various N—H⋯Cl hydrogen bonds connect the anions and cations and, in addition, intermolecular N—H⋯O hydrogen bonds contribute to the formation of a three-dimensional network.

Related literature

A related salt of the same anion in the orthorhombic crystal system has been reported with [(CH₃)₂NH₂]⁺ cations (Waśkowska et al., 1990 ), while Furberg & Aas (1975 ) described the structure of the same cation as its chloride salt.

Experimental

Crystal data

(C₄H₅N₂O)₅[Cd₃Cl₁₁]
M_r = 1212.65
Monoclinic, P 2₁ /c
a = 17.5446 (2) Å
b = 8.08980 (2) Å
c = 27.2451 (6) Å
β = 104.9470 (2)°
V = 3736.12 (10) Å³
Z = 4
Mo Kα radiation
μ = 2.53 mm⁻¹
T = 100 (2) K
0.51 × 0.07 × 0.04 mm

Data collection

Oxford Diffraction Gemini-R Ultra diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis CCD. and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ) T_min = 0.522, T_max = 0.91
65985 measured reflections
10979 independent reflections
7919 reflections with I > 2σ(I)
R_int = 0.046

Refinement

R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.058
S = 0.96
10979 reflections
442 parameters
H-atom parameters constrained
Δρ_max = 0.99 e Å⁻³
Δρ_min = −1.09 e Å⁻³

Table 1
Selected bond lengths (Å)

Cd1—Cl2	2.5216 (6)
Cd1—Cl1	2.5343 (6)
Cd1—Cl5	2.6796 (6)
Cd1—Cl3	2.6900 (6)
Cd1—Cl4	2.6917 (6)
Cd1—Cl6	2.7670 (6)
Cd2—Cl10	2.5184 (6)
Cd2—Cl11	2.5273 (6)
Cd2—Cl6	2.6698 (6)
Cd2—Cl3	2.6766 (6)
Cd2—Cl9	2.7295 (6)
Cd2—Cl4	2.7468 (6)
Cd3—Cl8	2.5081 (6)
Cd3—Cl7	2.5444 (6)
Cd3—Cl5	2.6284 (6)
Cd3—Cl9	2.6692 (6)
Cd3—Cl4	2.7201 (6)
Cd3—Cl6	2.7214 (6)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯Cl11ⁱ	0.86	2.56	3.246 (2)	138
N3—H3A⋯Cl8ⁱⁱ	0.86	2.37	3.104 (2)	144
N4—H4A⋯Cl10ⁱⁱⁱ	0.86	2.31	3.160 (2)	169
N5—H5A⋯Cl7^iv	0.86	2.41	3.194 (2)	151
N6—H6A⋯Cl1^v	0.86	2.31	3.138 (2)	162
N7—H7A⋯O2^vi	0.86	2.03	2.880 (3)	167
N10—H10B⋯Cl7^vi	0.86	2.54	3.349 (2)	157
N8—H8A⋯O5^vii	0.86	2.28	2.804 (3)	120
N8—H8A⋯O4^viii	0.86	2.34	3.117 (4)	150
N9—H9B⋯O3	0.86	2.13	2.920 (3)	152
Symmetry codes: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) x, y+1, z; (iii) -x, -y+1, -z; (iv) -x+1, -y+1, -z+1; (v) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (vi) x, y, z+1; (vii) -x+1, -y+1, -z+2; (viii) -x+1, -y+2, -z+2.

Data collection: CrysAlis CCD (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis CCD. and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis CCD. and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ); data reduction: CrysAlis RED; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680801862X/lh2641sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680801862X/lh2641Isup2.hkl

checkCIF report

Comment top

We sought to widen the use and exploitation of N—H···Cl interactions in the preparation of crystalline metal complexes by preparing [CdCl₄][C₄H₅N₂O]₂ and the coordination network [CdCl₂(C₄H₄N₂O)₂]. However, the title compound I was obtained instead, crystallizing in a monoclinic cell with the P2₁/c space group and an asymmetric unit consisting of five [C₄H₅N₂O]⁺ cations and one [Cd₃Cl₁₁]^5- anion. The crystal structure of a related complex determined at room temperature with a [Cd₃Cl₁₁]^5-anion and [(CH₃)₂NH₂]⁺ cations in the Cmcm space group revealed two alternating layers of cations and anions parallel to the (0 0 1) plane. This arrangement differs from that in the title compound I due to a complex three-dimensional hydrogen bond network involving anion-cation N—H···Cl and cation-cation N—H···O bonds. In contrast, the pyrimidin-2-onium cations reported in the related crystal structure (Furberg & Aas, 1975) display no N—H···O interactions.

Related literature top

A related salt of the same anion in the orthorhombic crystal sytem has been reported with [(CH₃)₂NH₂]⁺ cations (Waśkowska et.al., 1990), while Furberg & Aas (1975) described the structure of the same cation as its chloride salt.

Experimental top

The title compound was obtained from an attempt to synthesize bis-2-hydroxypyrimidinium tetrachlorocadmate(II). 2-hydroxypyrimidine hydrochloride and cadmium(II) chloride in a 2:1 molar ratio were dissolved in concentrated hydrochloric acid solution. This was left to evaporate slowly at room temperature and resulted in the formation of needle-shaped colourless crystals.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2007); cell refinement: CrysAlis RED (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of I with atom labels and 50% probability displacement ellipsoids for non-H atoms.
	Fig. 2. Geometry of the [Cd₃Cl₁₁]^5- anion.
	Fig. 3. Hydrogen bond (dotted lines) environment around the [Cd₃Cl₁₁]^5-anion.

Pentakis(2-oxo-2,3-dihydropyrimidin-1-ium) di-µ₃-chlorido-tri-µ₂-chlorido-hexachloridotricadmium(II) top

Crystal data top

C₄H₅N₂O)₅[Cd₃Cl₁₁]	F(000) = 2344
M_r = 1212.65	D_x = 2.156 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 28683 reflections
a = 17.5446 (2) Å	θ = 2.3–30.0°
b = 8.08980 (2) Å	µ = 2.53 mm⁻¹
c = 27.2451 (6) Å	T = 100 K
β = 104.9470 (2)°	Needle, colourless
V = 3736.12 (10) Å³	0.51 × 0.07 × 0.04 mm
Z = 4

Data collection top

Oxford Diffraction Gemini-R Ultra diffractometer	10979 independent reflections
Radiation source: fine-focus sealed tube	7919 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.046
Detector resolution: 10.4752 pixels mm^-1	θ_max = 30.1°, θ_min = 2.4°
1° width ω scans	h = −15→24
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	k = −11→11
T_min = 0.522, T_max = 0.91	l = −38→38
65985 measured reflections

Refinement top

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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.058	H-atom parameters constrained
S = 0.96	w = 1/[σ²(F_o²) + (0.0307P)²] where P = (F_o² + 2F_c²)/3
10979 reflections	(Δ/σ)_max = 0.001
442 parameters	Δρ_max = 0.99 e Å⁻³
0 restraints	Δρ_min = −1.09 e Å⁻³

Crystal data top

C₄H₅N₂O)₅[Cd₃Cl₁₁]	V = 3736.12 (10) Å³
M_r = 1212.65	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 17.5446 (2) Å	µ = 2.53 mm⁻¹
b = 8.08980 (2) Å	T = 100 K
c = 27.2451 (6) Å	0.51 × 0.07 × 0.04 mm
β = 104.9470 (2)°

Data collection top

Oxford Diffraction Gemini-R Ultra diffractometer	10979 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	7919 reflections with I > 2σ(I)
T_min = 0.522, T_max = 0.91	R_int = 0.046
65985 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	0 restraints
wR(F²) = 0.058	H-atom parameters constrained
S = 0.96	Δρ_max = 0.99 e Å⁻³
10979 reflections	Δρ_min = −1.09 e Å⁻³
442 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
Cd1	0.278566 (10)	0.40453 (2)	0.234610 (6)	0.01260 (4)
Cd2	0.096112 (10)	0.34002 (2)	0.139514 (6)	0.01313 (4)
Cd3	0.278973 (10)	0.37558 (2)	0.104602 (6)	0.01268 (4)
Cl1	0.31283 (3)	0.64928 (8)	0.29430 (2)	0.01631 (13)
Cl2	0.34187 (4)	0.18017 (8)	0.29589 (2)	0.01652 (13)
Cl3	0.12927 (3)	0.36223 (8)	0.24084 (2)	0.01473 (12)
Cl4	0.20555 (3)	0.59016 (7)	0.15423 (2)	0.01321 (12)
Cl5	0.39418 (3)	0.42065 (8)	0.18691 (2)	0.01426 (12)
Cl6	0.22670 (3)	0.15581 (7)	0.16419 (2)	0.01246 (11)
Cl7	0.31718 (4)	0.59045 (8)	0.04703 (2)	0.01607 (12)
Cl8	0.33408 (3)	0.13362 (8)	0.06752 (2)	0.01601 (12)
Cl9	0.13161 (3)	0.33560 (8)	0.04770 (2)	0.01508 (12)
Cl10	−0.01624 (3)	0.54066 (8)	0.11041 (2)	0.01515 (12)
Cl11	0.00531 (3)	0.09258 (8)	0.12829 (2)	0.01516 (12)
N1	0.17631 (12)	0.9564 (3)	0.27179 (8)	0.0163 (4)
H1A	0.2120	1.0282	0.2707	0.020*
N2	0.10684 (12)	0.8001 (3)	0.31601 (8)	0.0177 (5)
H2A	0.0971	0.7685	0.3439	0.021*
N3	0.19690 (13)	0.9043 (3)	0.01223 (8)	0.0202 (5)
H3A	0.2383	0.9631	0.0138	0.024*
N4	0.10513 (11)	0.7144 (3)	−0.02736 (7)	0.0140 (4)
H4A	0.0860	0.6475	−0.0520	0.017*
N5	0.57141 (12)	0.1754 (3)	0.87043 (8)	0.0174 (5)
H5A	0.5851	0.2418	0.8958	0.021*
N6	0.48648 (12)	−0.0147 (3)	0.82295 (7)	0.0172 (5)
H6A	0.4442	−0.0732	0.8171	0.021*
N7	0.35772 (12)	0.7374 (3)	0.92554 (8)	0.0194 (5)
H7A	0.3084	0.7532	0.9232	0.023*
N8	0.48815 (14)	0.7805 (3)	0.96474 (10)	0.0385 (7)
H8A	0.5249	0.8278	0.9875	0.046*
N9	0.30200 (12)	0.1727 (3)	0.89707 (8)	0.0199 (5)
H9B	0.3412	0.1411	0.8859	0.024*
N10	0.25130 (13)	0.3093 (3)	0.95573 (8)	0.0214 (5)
H10B	0.2572	0.3686	0.9827	0.026*
O1	0.20540 (11)	0.9741 (2)	0.35816 (6)	0.0235 (4)
O2	0.20021 (11)	0.7968 (3)	−0.06516 (7)	0.0250 (4)
O3	0.46339 (11)	0.0904 (3)	0.89546 (7)	0.0282 (5)
O4	0.39372 (14)	0.9435 (3)	0.98438 (8)	0.0467 (7)
O5	0.38187 (11)	0.3297 (3)	0.95908 (7)	0.0270 (5)
C1	0.06351 (14)	0.7355 (3)	0.27248 (9)	0.0174 (5)
H1B	0.0246	0.6583	0.2734	0.021*
C2	0.07546 (15)	0.7811 (3)	0.22687 (9)	0.0172 (5)
H2B	0.0450	0.7379	0.1965	0.021*
C3	0.13409 (15)	0.8928 (3)	0.22769 (9)	0.0173 (5)
H3B	0.1448	0.9251	0.1974	0.021*
C4	0.16646 (14)	0.9148 (3)	0.31878 (9)	0.0166 (5)
C5	0.16286 (17)	0.9166 (3)	0.05050 (10)	0.0244 (6)
H5B	0.1841	0.9873	0.0775	0.029*
C6	0.09702 (16)	0.8263 (3)	0.05048 (10)	0.0223 (6)
H6B	0.0723	0.8347	0.0767	0.027*
C7	0.06914 (15)	0.7229 (3)	0.01003 (9)	0.0183 (6)
H7B	0.0248	0.6582	0.0087	0.022*
C8	0.17070 (14)	0.8045 (3)	−0.02962 (9)	0.0158 (5)
C9	0.53129 (14)	−0.0260 (3)	0.79005 (9)	0.0178 (5)
H9A	0.5166	−0.0976	0.7625	0.021*
C10	0.59844 (15)	0.0668 (3)	0.79652 (10)	0.0193 (6)
H10A	0.6296	0.0616	0.7736	0.023*
C11	0.61754 (15)	0.1676 (3)	0.83830 (10)	0.0186 (6)
H11A	0.6631	0.2314	0.8444	0.022*
C12	0.50373 (14)	0.0846 (3)	0.86560 (9)	0.0177 (5)
C13	0.37700 (16)	0.6242 (3)	0.89528 (10)	0.0208 (6)
H13A	0.3375	0.5698	0.8714	0.025*
C14	0.45477 (15)	0.5872 (3)	0.89906 (10)	0.0194 (6)
H14A	0.4693	0.5128	0.8771	0.023*
C15	0.50936 (16)	0.6647 (4)	0.93653 (11)	0.0263 (6)
H15A	0.5623	0.6360	0.9424	0.032*
C16	0.41168 (17)	0.8310 (4)	0.96040 (10)	0.0271 (7)
C17	0.23033 (16)	0.1194 (3)	0.87278 (10)	0.0205 (6)
H17A	0.2239	0.0543	0.8439	0.025*
C18	0.16560 (15)	0.1604 (3)	0.89027 (10)	0.0202 (6)
H18A	0.1152	0.1243	0.8738	0.024*
C19	0.17895 (16)	0.2565 (4)	0.93296 (9)	0.0222 (6)
H19A	0.1370	0.2852	0.9463	0.027*
C20	0.31738 (16)	0.2755 (3)	0.93906 (9)	0.0181 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.01208 (9)	0.01435 (10)	0.01056 (8)	−0.00011 (7)	0.00147 (6)	−0.00025 (7)
Cd2	0.00896 (8)	0.01588 (10)	0.01383 (8)	0.00031 (7)	0.00164 (6)	0.00023 (7)
Cd3	0.01154 (8)	0.01546 (10)	0.01122 (8)	0.00016 (7)	0.00326 (6)	−0.00117 (7)
Cl1	0.0137 (3)	0.0161 (3)	0.0176 (3)	0.0018 (2)	0.0013 (2)	−0.0036 (2)
Cl2	0.0193 (3)	0.0164 (3)	0.0130 (3)	0.0026 (3)	0.0026 (2)	0.0012 (2)
Cl3	0.0128 (3)	0.0178 (3)	0.0141 (3)	0.0005 (2)	0.0043 (2)	−0.0001 (2)
Cl4	0.0125 (3)	0.0129 (3)	0.0139 (3)	0.0005 (2)	0.0026 (2)	0.0000 (2)
Cl5	0.0106 (3)	0.0175 (3)	0.0140 (3)	−0.0005 (2)	0.0020 (2)	−0.0003 (2)
Cl6	0.0109 (3)	0.0132 (3)	0.0132 (3)	0.0000 (2)	0.0029 (2)	0.0001 (2)
Cl7	0.0183 (3)	0.0148 (3)	0.0151 (3)	0.0004 (2)	0.0044 (2)	0.0003 (2)
Cl8	0.0148 (3)	0.0164 (3)	0.0171 (3)	0.0018 (2)	0.0044 (2)	−0.0028 (2)
Cl9	0.0128 (3)	0.0192 (3)	0.0122 (3)	0.0010 (2)	0.0014 (2)	−0.0006 (2)
Cl10	0.0121 (3)	0.0149 (3)	0.0167 (3)	0.0013 (2)	0.0004 (2)	−0.0023 (2)
Cl11	0.0124 (3)	0.0158 (3)	0.0174 (3)	−0.0011 (2)	0.0041 (2)	−0.0009 (2)
N1	0.0155 (11)	0.0148 (12)	0.0193 (10)	0.0001 (9)	0.0058 (8)	0.0014 (9)
N2	0.0215 (11)	0.0188 (12)	0.0155 (10)	−0.0007 (10)	0.0095 (9)	0.0029 (9)
N3	0.0180 (11)	0.0158 (12)	0.0224 (11)	−0.0052 (10)	−0.0028 (9)	0.0014 (9)
N4	0.0133 (10)	0.0129 (11)	0.0137 (10)	−0.0021 (9)	−0.0005 (8)	−0.0041 (8)
N5	0.0152 (10)	0.0155 (12)	0.0204 (11)	0.0013 (9)	0.0024 (8)	−0.0062 (9)
N6	0.0107 (10)	0.0170 (12)	0.0218 (11)	−0.0033 (9)	0.0004 (8)	0.0002 (9)
N7	0.0116 (11)	0.0247 (13)	0.0230 (11)	0.0047 (10)	0.0067 (9)	0.0073 (10)
N8	0.0214 (13)	0.0430 (18)	0.0395 (15)	0.0115 (12)	−0.0130 (11)	−0.0242 (13)
N9	0.0182 (11)	0.0278 (14)	0.0164 (10)	0.0039 (10)	0.0095 (9)	0.0017 (9)
N10	0.0244 (12)	0.0274 (14)	0.0120 (10)	0.0092 (10)	0.0041 (9)	0.0011 (9)
O1	0.0232 (10)	0.0269 (12)	0.0175 (9)	0.0033 (9)	0.0002 (8)	−0.0045 (8)
O2	0.0215 (10)	0.0322 (12)	0.0257 (10)	0.0090 (9)	0.0138 (8)	0.0066 (9)
O3	0.0150 (9)	0.0482 (14)	0.0220 (10)	0.0036 (9)	0.0062 (8)	0.0005 (9)
O4	0.0540 (15)	0.0569 (17)	0.0251 (11)	0.0315 (13)	0.0029 (10)	−0.0153 (11)
O5	0.0220 (10)	0.0318 (13)	0.0243 (10)	−0.0029 (9)	0.0009 (8)	0.0046 (9)
C1	0.0132 (12)	0.0152 (14)	0.0250 (13)	−0.0021 (10)	0.0072 (10)	−0.0005 (11)
C2	0.0183 (13)	0.0166 (14)	0.0160 (12)	−0.0004 (11)	0.0032 (10)	−0.0023 (10)
C3	0.0202 (13)	0.0176 (14)	0.0156 (12)	0.0047 (11)	0.0074 (10)	0.0036 (10)
C4	0.0136 (12)	0.0161 (14)	0.0206 (13)	0.0066 (11)	0.0055 (10)	0.0007 (10)
C5	0.0366 (17)	0.0191 (15)	0.0124 (12)	0.0078 (13)	−0.0029 (11)	−0.0016 (11)
C6	0.0273 (15)	0.0253 (16)	0.0162 (12)	0.0102 (13)	0.0088 (11)	0.0034 (11)
C7	0.0118 (12)	0.0224 (15)	0.0210 (13)	0.0002 (11)	0.0046 (10)	0.0069 (11)
C8	0.0121 (12)	0.0182 (14)	0.0163 (12)	0.0056 (10)	0.0019 (9)	0.0049 (10)
C9	0.0174 (13)	0.0157 (14)	0.0177 (12)	0.0039 (11)	−0.0006 (10)	0.0002 (10)
C10	0.0150 (12)	0.0234 (15)	0.0203 (13)	0.0057 (11)	0.0059 (10)	0.0047 (11)
C11	0.0123 (12)	0.0131 (14)	0.0299 (14)	0.0010 (10)	0.0044 (10)	0.0057 (11)
C12	0.0112 (12)	0.0216 (15)	0.0196 (12)	0.0039 (11)	0.0027 (10)	0.0015 (11)
C13	0.0200 (13)	0.0154 (14)	0.0231 (13)	−0.0053 (11)	−0.0014 (11)	0.0016 (11)
C14	0.0221 (14)	0.0160 (14)	0.0226 (13)	0.0025 (12)	0.0102 (11)	−0.0023 (11)
C15	0.0131 (13)	0.0232 (16)	0.0406 (17)	0.0018 (12)	0.0034 (12)	−0.0038 (13)
C16	0.0226 (14)	0.0389 (19)	0.0178 (13)	0.0130 (14)	0.0017 (11)	−0.0045 (13)
C17	0.0234 (14)	0.0221 (16)	0.0148 (12)	0.0022 (12)	0.0026 (10)	0.0006 (11)
C18	0.0175 (13)	0.0200 (15)	0.0223 (13)	0.0027 (11)	0.0039 (10)	0.0049 (11)
C19	0.0208 (14)	0.0291 (17)	0.0181 (13)	0.0077 (12)	0.0078 (11)	0.0071 (12)
C20	0.0223 (14)	0.0182 (15)	0.0142 (12)	0.0035 (12)	0.0051 (10)	0.0064 (10)

Geometric parameters (Å, º) top

Cd1—Cl2	2.5216 (6)	N8—C16	1.378 (4)
Cd1—Cl1	2.5343 (6)	N8—H8A	0.8600
Cd1—Cl5	2.6796 (6)	N9—C17	1.332 (3)
Cd1—Cl3	2.6900 (6)	N9—C20	1.383 (3)
Cd1—Cl4	2.6917 (6)	N9—H9B	0.8600
Cd1—Cl6	2.7670 (6)	N10—C19	1.331 (3)
Cd2—Cl10	2.5184 (6)	N10—C20	1.377 (3)
Cd2—Cl11	2.5273 (6)	N10—H10B	0.8600
Cd2—Cl6	2.6698 (6)	O1—C4	1.212 (3)
Cd2—Cl3	2.6766 (6)	O2—C8	1.212 (3)
Cd2—Cl9	2.7295 (6)	O3—C12	1.209 (3)
Cd2—Cl4	2.7468 (6)	O4—C16	1.209 (3)
Cd3—Cl8	2.5081 (6)	O5—C20	1.205 (3)
Cd3—Cl7	2.5444 (6)	C1—C2	1.363 (3)
Cd3—Cl5	2.6284 (6)	C1—H1B	0.9300
Cd3—Cl9	2.6692 (6)	C2—C3	1.365 (4)
Cd3—Cl4	2.7201 (6)	C2—H2B	0.9300
Cd3—Cl6	2.7214 (6)	C3—H3B	0.9300
N1—C3	1.341 (3)	C5—C6	1.367 (4)
N1—C4	1.377 (3)	C5—H5B	0.9300
N1—H1A	0.8600	C6—C7	1.369 (4)
N2—C1	1.339 (3)	C6—H6B	0.9300
N2—C4	1.386 (3)	C7—H7B	0.9300
N2—H2A	0.8600	C9—C10	1.369 (4)
N3—C5	1.332 (3)	C9—H9A	0.9300
N3—C8	1.376 (3)	C10—C11	1.370 (4)
N3—H3A	0.8600	C10—H10A	0.9300
N4—C7	1.332 (3)	C11—H11A	0.9300
N4—C8	1.377 (3)	C12—O3	1.209 (3)
N4—H4A	0.8600	C13—C14	1.375 (4)
N5—C11	1.338 (3)	C13—H13A	0.9300
N5—C12	1.373 (3)	C14—C15	1.359 (4)
N5—H5A	0.8600	C14—H14A	0.9300
N6—C9	1.339 (3)	C15—H15A	0.9300
N6—C12	1.381 (3)	C17—C18	1.381 (4)
N6—H6A	0.8600	C17—H17A	0.9300
N7—C13	1.333 (3)	C18—C19	1.368 (4)
N7—C16	1.381 (4)	C18—H18A	0.9300
N7—H7A	0.8600	C19—H19A	0.9300
N8—C15	1.325 (4)

Cl2—Cd1—Cl1	98.42 (2)	C13—N7—H7A	117.8
Cl2—Cd1—Cl5	95.56 (2)	C16—N7—H7A	117.8
Cl1—Cd1—Cl5	100.91 (2)	C15—N8—C16	124.9 (2)
Cl2—Cd1—Cl3	97.84 (2)	C15—N8—H8A	117.5
Cl1—Cd1—Cl3	97.61 (2)	C16—N8—H8A	117.5
Cl5—Cd1—Cl3	155.233 (18)	C17—N9—C20	124.3 (2)
Cl2—Cd1—Cl4	167.47 (2)	C17—N9—H9B	117.9
Cl1—Cd1—Cl4	94.048 (19)	C20—N9—H9B	117.9
Cl5—Cd1—Cl4	80.744 (18)	C19—N10—C20	124.4 (2)
Cl3—Cd1—Cl4	81.693 (18)	C19—N10—H10B	117.8
Cl2—Cd1—Cl6	86.881 (19)	C20—N10—H10B	117.8
Cl1—Cd1—Cl6	173.839 (19)	N2—C1—C2	121.1 (2)
Cl5—Cd1—Cl6	81.593 (18)	N2—C1—H1B	119.5
Cl3—Cd1—Cl6	78.455 (18)	C2—C1—H1B	119.5
Cl4—Cd1—Cl6	80.746 (18)	C1—C2—C3	117.2 (2)
Cl10—Cd2—Cl11	93.13 (2)	C1—C2—H2B	121.4
Cl10—Cd2—Cl6	171.98 (2)	C3—C2—H2B	121.4
Cl11—Cd2—Cl6	93.534 (19)	N1—C3—C2	120.6 (2)
Cl10—Cd2—Cl3	103.046 (19)	N1—C3—H3B	119.7
Cl11—Cd2—Cl3	98.080 (19)	C2—C3—H3B	119.7
Cl6—Cd2—Cl3	80.420 (18)	O1—C4—N1	123.3 (2)
Cl10—Cd2—Cl9	93.725 (19)	O1—C4—N2	124.0 (2)
Cl11—Cd2—Cl9	99.466 (19)	N1—C4—N2	112.8 (2)
Cl6—Cd2—Cl9	80.773 (18)	N3—C5—C6	120.6 (2)
Cl3—Cd2—Cl9	154.942 (19)	N3—C5—H5B	119.7
Cl10—Cd2—Cl4	91.835 (19)	C6—C5—H5B	119.7
Cl11—Cd2—Cl4	175.033 (19)	C5—C6—C7	117.0 (2)
Cl6—Cd2—Cl4	81.504 (18)	C5—C6—H6B	121.5
Cl3—Cd2—Cl4	80.921 (18)	C7—C6—H6B	121.5
Cl9—Cd2—Cl4	80.051 (18)	N4—C7—C6	120.4 (2)
Cl8—Cd3—Cl7	95.43 (2)	N4—C7—H7B	119.8
Cl8—Cd3—Cl5	99.23 (2)	C6—C7—H7B	119.8
Cl7—Cd3—Cl5	99.457 (19)	O2—C8—N3	124.9 (2)
Cl8—Cd3—Cl9	95.034 (19)	O2—C8—N4	122.8 (2)
Cl7—Cd3—Cl9	95.419 (19)	N3—C8—N4	112.2 (2)
Cl5—Cd3—Cl9	158.251 (19)	N6—C9—C10	120.7 (2)
Cl8—Cd3—Cl4	168.35 (2)	N6—C9—H9A	119.6
Cl7—Cd3—Cl4	95.99 (2)	C10—C9—H9A	119.6
Cl5—Cd3—Cl4	81.139 (18)	C9—C10—C11	116.8 (2)
Cl9—Cd3—Cl4	81.609 (18)	C9—C10—H10A	121.6
Cl8—Cd3—Cl6	87.40 (2)	C11—C10—H10A	121.6
Cl7—Cd3—Cl6	175.583 (19)	N5—C11—C10	120.8 (2)
Cl5—Cd3—Cl6	83.393 (18)	N5—C11—H11A	119.6
Cl9—Cd3—Cl6	80.932 (18)	C10—C11—H11A	119.6
Cl4—Cd3—Cl6	81.067 (18)	O3—C12—N5	123.8 (2)
Cd2—Cl3—Cd1	84.236 (18)	O3—C12—N5	123.8 (2)
Cd1—Cl4—Cd3	82.031 (17)	O3—C12—N6	123.3 (2)
Cd1—Cl4—Cd2	82.865 (17)	O3—C12—N6	123.3 (2)
Cd3—Cl4—Cd2	81.961 (17)	N5—C12—N6	112.8 (2)
Cd3—Cl5—Cd1	83.991 (17)	N7—C13—C14	120.6 (2)
Cd2—Cl6—Cd3	83.364 (17)	N7—C13—H13A	119.7
Cd2—Cl6—Cd1	82.884 (17)	C14—C13—H13A	119.7
Cd3—Cl6—Cd1	80.645 (17)	C15—C14—C13	116.7 (3)
Cd3—Cl9—Cd2	83.220 (16)	C15—C14—H14A	121.6
C3—N1—C4	124.5 (2)	C13—C14—H14A	121.6
C3—N1—H1A	117.8	N8—C15—C14	120.9 (3)
C4—N1—H1A	117.8	N8—C15—H15A	119.6
C1—N2—C4	123.9 (2)	C14—C15—H15A	119.6
C1—N2—H2A	118.0	O4—C16—N8	124.1 (3)
C4—N2—H2A	118.0	O4—C16—N7	123.8 (3)
C5—N3—C8	124.8 (2)	N8—C16—N7	112.1 (2)
C5—N3—H3A	117.6	N9—C17—C18	120.4 (2)
C8—N3—H3A	117.6	N9—C17—H17A	119.8
C7—N4—C8	125.0 (2)	C18—C17—H17A	119.8
C7—N4—H4A	117.5	C19—C18—C17	117.0 (2)
C8—N4—H4A	117.5	C19—C18—H18A	121.5
C11—N5—C12	124.5 (2)	C17—C18—H18A	121.5
C11—N5—H5A	117.8	N10—C19—C18	120.8 (2)
C12—N5—H5A	117.8	N10—C19—H19A	119.6
C9—N6—C12	124.3 (2)	C18—C19—H19A	119.6
C9—N6—H6A	117.8	O5—C20—N10	123.4 (2)
C12—N6—H6A	117.8	O5—C20—N9	123.6 (2)
C13—N7—C16	124.3 (2)	N10—C20—N9	113.0 (2)

Cl10—Cd2—Cl3—Cd1	−129.506 (19)	Cl4—Cd3—Cl6—Cd1	−42.320 (15)
Cl11—Cd2—Cl3—Cd1	135.360 (19)	Cl2—Cd1—Cl6—Cd2	140.506 (19)
Cl6—Cd2—Cl3—Cd1	43.114 (17)	Cl5—Cd1—Cl6—Cd2	−123.400 (18)
Cl9—Cd2—Cl3—Cd1	1.27 (5)	Cl3—Cd1—Cl6—Cd2	41.845 (17)
Cl4—Cd2—Cl3—Cd1	−39.720 (17)	Cl4—Cd1—Cl6—Cd2	−41.486 (17)
Cl2—Cd1—Cl3—Cd2	−126.750 (19)	Cl2—Cd1—Cl6—Cd3	−135.087 (19)
Cl1—Cd1—Cl3—Cd2	133.608 (19)	Cl5—Cd1—Cl6—Cd3	−38.993 (16)
Cl5—Cd1—Cl3—Cd2	−4.61 (5)	Cl3—Cd1—Cl6—Cd3	126.253 (18)
Cl4—Cd1—Cl3—Cd2	40.601 (17)	Cl4—Cd1—Cl6—Cd3	42.921 (16)
Cl6—Cd1—Cl3—Cd2	−41.579 (16)	Cl8—Cd3—Cl9—Cd2	126.796 (19)
Cl2—Cd1—Cl4—Cd3	−33.55 (10)	Cl7—Cd3—Cl9—Cd2	−137.247 (19)
Cl1—Cd1—Cl4—Cd3	140.568 (18)	Cl5—Cd3—Cl9—Cd2	−4.15 (6)
Cl5—Cd1—Cl4—Cd3	40.154 (16)	Cl4—Cd3—Cl9—Cd2	−41.973 (17)
Cl3—Cd1—Cl4—Cd3	−122.314 (18)	Cl6—Cd3—Cl9—Cd2	40.245 (17)
Cl6—Cd1—Cl4—Cd3	−42.750 (16)	Cl10—Cd2—Cl9—Cd3	132.909 (19)
Cl2—Cd1—Cl4—Cd2	49.29 (10)	Cl11—Cd2—Cl9—Cd3	−133.288 (18)
Cl1—Cd1—Cl4—Cd2	−136.601 (18)	Cl6—Cd2—Cl9—Cd3	−41.211 (17)
Cl5—Cd1—Cl4—Cd2	122.985 (18)	Cl3—Cd2—Cl9—Cd3	0.58 (5)
Cl3—Cd1—Cl4—Cd2	−39.483 (17)	Cl4—Cd2—Cl9—Cd3	41.697 (17)
Cl6—Cd1—Cl4—Cd2	40.081 (16)	C4—N2—C1—C2	−0.5 (4)
Cl8—Cd3—Cl4—Cd1	51.69 (10)	N2—C1—C2—C3	1.0 (4)
Cl7—Cd3—Cl4—Cd1	−139.723 (17)	C4—N1—C3—C2	1.4 (4)
Cl5—Cd3—Cl4—Cd1	−41.047 (17)	C1—C2—C3—N1	−1.5 (4)
Cl9—Cd3—Cl4—Cd1	125.659 (19)	C3—N1—C4—O1	−180.0 (2)
Cl6—Cd3—Cl4—Cd1	43.596 (16)	C3—N1—C4—N2	−0.8 (3)
Cl8—Cd3—Cl4—Cd2	−32.17 (10)	C1—N2—C4—O1	179.5 (2)
Cl7—Cd3—Cl4—Cd2	136.413 (17)	C1—N2—C4—N1	0.3 (3)
Cl5—Cd3—Cl4—Cd2	−124.911 (18)	C8—N3—C5—C6	0.2 (4)
Cl9—Cd3—Cl4—Cd2	41.795 (16)	N3—C5—C6—C7	0.8 (4)
Cl6—Cd3—Cl4—Cd2	−40.269 (15)	C8—N4—C7—C6	−0.4 (4)
Cl10—Cd2—Cl4—Cd1	142.739 (18)	C5—C6—C7—N4	−0.7 (4)
Cl6—Cd2—Cl4—Cd1	−41.755 (16)	C5—N3—C8—O2	177.7 (2)
Cl3—Cd2—Cl4—Cd1	39.818 (17)	C5—N3—C8—N4	−1.2 (3)
Cl9—Cd2—Cl4—Cd1	−123.800 (18)	C7—N4—C8—O2	−177.7 (2)
Cl10—Cd2—Cl4—Cd3	−134.350 (18)	C7—N4—C8—N3	1.3 (3)
Cl6—Cd2—Cl4—Cd3	41.155 (16)	C12—N6—C9—C10	−1.5 (4)
Cl3—Cd2—Cl4—Cd3	122.729 (18)	N6—C9—C10—C11	1.1 (4)
Cl9—Cd2—Cl4—Cd3	−40.889 (16)	C12—N5—C11—C10	1.2 (4)
Cl8—Cd3—Cl5—Cd1	−127.150 (19)	C9—C10—C11—N5	−1.0 (4)
Cl7—Cd3—Cl5—Cd1	135.712 (19)	O3—O3—C12—N5	0.0 (7)
Cl9—Cd3—Cl5—Cd1	3.19 (6)	O3—O3—C12—N6	0.0 (6)
Cl4—Cd3—Cl5—Cd1	41.062 (17)	C11—N5—C12—O3	178.5 (2)
Cl6—Cd3—Cl5—Cd1	−40.881 (17)	C11—N5—C12—O3	178.5 (2)
Cl2—Cd1—Cl5—Cd3	126.274 (19)	C11—N5—C12—N6	−1.4 (3)
Cl1—Cd1—Cl5—Cd3	−134.022 (19)	C9—N6—C12—O3	−178.3 (3)
Cl3—Cd1—Cl5—Cd3	3.71 (5)	C9—N6—C12—O3	−178.3 (3)
Cl4—Cd1—Cl5—Cd3	−41.648 (17)	C9—N6—C12—N5	1.5 (3)
Cl6—Cd1—Cl5—Cd3	40.268 (17)	C16—N7—C13—C14	3.4 (4)
Cl11—Cd2—Cl6—Cd3	139.268 (17)	N7—C13—C14—C15	3.4 (4)
Cl3—Cd2—Cl6—Cd3	−123.124 (18)	C16—N8—C15—C14	1.5 (5)
Cl9—Cd2—Cl6—Cd3	40.241 (16)	C13—C14—C15—N8	−5.8 (4)
Cl4—Cd2—Cl6—Cd3	−40.974 (16)	C15—N8—C16—O4	−175.5 (3)
Cl11—Cd2—Cl6—Cd1	−139.382 (17)	C15—N8—C16—N7	4.8 (5)
Cl3—Cd2—Cl6—Cd1	−41.774 (17)	C13—N7—C16—O4	173.0 (3)
Cl9—Cd2—Cl6—Cd1	121.591 (18)	C13—N7—C16—N8	−7.2 (4)
Cl4—Cd2—Cl6—Cd1	40.375 (16)	C20—N9—C17—C18	−2.7 (4)
Cl8—Cd3—Cl6—Cd2	−136.844 (18)	N9—C17—C18—C19	0.0 (4)
Cl5—Cd3—Cl6—Cd2	123.549 (18)	C20—N10—C19—C18	0.6 (4)
Cl9—Cd3—Cl6—Cd2	−41.324 (17)	C17—C18—C19—N10	1.0 (4)
Cl4—Cd3—Cl6—Cd2	41.525 (16)	C19—N10—C20—O5	177.1 (3)
Cl8—Cd3—Cl6—Cd1	139.312 (18)	C19—N10—C20—N9	−3.0 (4)
Cl5—Cd3—Cl6—Cd1	39.704 (17)	C17—N9—C20—O5	−176.0 (3)
Cl9—Cd3—Cl6—Cd1	−125.168 (18)	C17—N9—C20—N10	4.1 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···Cl11ⁱ	0.86	2.56	3.246 (2)	138
N3—H3A···Cl8ⁱⁱ	0.86	2.37	3.104 (2)	144
N4—H4A···Cl10ⁱⁱⁱ	0.86	2.31	3.160 (2)	169
N5—H5A···Cl7^iv	0.86	2.41	3.194 (2)	151
N6—H6A···Cl1^v	0.86	2.31	3.138 (2)	162
N7—H7A···O2^vi	0.86	2.03	2.880 (3)	167
N10—H10B···Cl7^vi	0.86	2.54	3.349 (2)	157
N8—H8A···O5^vii	0.86	2.28	2.804 (3)	120
N8—H8A···O4^viii	0.86	2.34	3.117 (4)	150
N9—H9B···O3	0.86	2.13	2.920 (3)	152

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

Experimental details

Crystal data
Chemical formula	C₄H₅N₂O)₅[Cd₃Cl₁₁]
M_r	1212.65
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	17.5446 (2), 8.08980 (2), 27.2451 (6)
β (°)	104.9470 (2)
V (Å³)	3736.12 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.53
Crystal size (mm)	0.51 × 0.07 × 0.04

Data collection
Diffractometer	Oxford Diffraction Gemini-R Ultra diffractometer
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2007)
T_min, T_max	0.522, 0.91
No. of measured, independent and observed [I > 2σ(I)] reflections	65985, 10979, 7919
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.705

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.058, 0.96
No. of reflections	10979
No. of parameters	442
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.99, −1.09

Computer programs: CrysAlis CCD (Oxford Diffraction, 2007), CrysAlis RED (Oxford Diffraction, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Cd1—Cl2	2.5216 (6)	Cd2—Cl3	2.6766 (6)
Cd1—Cl1	2.5343 (6)	Cd2—Cl9	2.7295 (6)
Cd1—Cl5	2.6796 (6)	Cd2—Cl4	2.7468 (6)
Cd1—Cl3	2.6900 (6)	Cd3—Cl8	2.5081 (6)
Cd1—Cl4	2.6917 (6)	Cd3—Cl7	2.5444 (6)
Cd1—Cl6	2.7670 (6)	Cd3—Cl5	2.6284 (6)
Cd2—Cl10	2.5184 (6)	Cd3—Cl9	2.6692 (6)
Cd2—Cl11	2.5273 (6)	Cd3—Cl4	2.7201 (6)
Cd2—Cl6	2.6698 (6)	Cd3—Cl6	2.7214 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···Cl11ⁱ	0.86	2.56	3.246 (2)	138.0
N3—H3A···Cl8ⁱⁱ	0.86	2.37	3.104 (2)	144.0
N4—H4A···Cl10ⁱⁱⁱ	0.86	2.31	3.160 (2)	169.3
N5—H5A···Cl7^iv	0.86	2.41	3.194 (2)	151.0
N6—H6A···Cl1^v	0.86	2.31	3.138 (2)	161.8
N7—H7A···O2^vi	0.86	2.03	2.880 (3)	167.2
N10—H10B···Cl7^vi	0.86	2.54	3.349 (2)	156.9
N8—H8A···O5^vii	0.86	2.28	2.804 (3)	119.5
N8—H8A···O4^viii	0.86	2.34	3.117 (4)	150.2
N9—H9B···O3	0.86	2.13	2.920 (3)	152.3

Acknowledgements

MAK thanks Bayero University, Kano, Nigeria for funding. Oxford Diffraction Ltd are thanked for the loan of an Oxford Gemini-R Ultra diffractometer to the University of Bristol.

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