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The Zn atom in dichloro­[(3,5-dimethyl-1H-pyrazol-1-yl)­methane]zinc(II), [ZnCl2(C11H16N4)], (I), is tetra­hedrally coordinated by two N atoms from one bis­(3,5-dimethyl­pyrazol­yl)methane ligand and two terminal Cl atoms. The mol­ecule has no crystallographic symmetry. One H atom of the CH2 group of the bis­(3,5-dimethyl­pyrazol­yl)methane ligand inter­acts with a Cl atom of an adjacent mol­ecule to yield inter­molecular C—H...Cl contacts, thereby forming a one-dimensional zigzag chain extending along the b axis. On the other hand, in di-μ-chloro-bis­{chloro­[(3,5-dimethyl-1H-pyrazol-1-yl)methane]cadmium(II)}, [Cd2Cl4(C11H16N4)2], (II), each of the two crystallographically equivalent Cd atoms is penta­coordinated by two N atoms from one bis­(3,5-dimethyl­pyrazol­yl)methane ligand, and by one terminal and two bridging Cl anions. The mol­ecule has a crystallographic centre of symmetry located at the mid-point of the Cd...Cd line. One H atom of the CH2 group of the bis­(3,5-dimethyl­pyrazolyl)­methane ligand inter­acts with a Cl atom of an adjacent mol­ecule to produce pairwise inter­molecular C—H...Cl contacts, thereby affording chains of mol­ecules running along the c axis.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106001387/gd1428sup1.cif
Contains datablocks I, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106001387/gd1428Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106001387/gd1428IIsup3.hkl
Contains datablock II

CCDC references: 294218; 294220

Comment top

It is well known that group 12 metals react with N-donor ligands to form various adducts, and these compounds exhibit diversity in their structural chemistry (Neels & Stoeckli-Evans, 1999; Erxleben, 2001; Kaminskaia et al., 2000; Kleywegt et al., 1985; Pedrido et al., 2003; Patra & Goldberg, 2002). Among numerous N-donor ligands, bis(pyrazol-1-yl)alkanes, serving as flexible bidentate ligands, have been reported to form stable chelates with group 12 elements (Pettinari & Pettinari, 2005; Mann et al., 1998; Bovio et al., 1992). In the case of bis(3,5-dimethylpyrazol-1-yl)methane (dmpzm), however, the chemistry of its zinc and cadmium complexes is relatively unexplored. For example, several zinc complexes of dmpzm [e.g. Zn(dmpzm)X2, where X = Cl, Br, I, CF3CO2 or OAc, or Zn(dmpzm)2X2, where X = ClO4, NO3, or BF4] have been prepared (Reedijk & Verbiest, 1979; Leonesi et al., 1987), but their crystal structures have not been reported to date. To our knowledge, there is no synthetic and structural information on any cadmium complex of the dmpzm ligand. We have recently become interested in the preparation of transition metal complexes of dmpzm (Xu et al., 2005). Curious about the chemistry of zinc/cadmium complexes of dmpzm, we carried out the reaction of ZnCl2 or CdCl2 with dmpzm and the two title complexes, [Zn(dmpzm)Cl2], (I), and [Cd(dmpzm)(µ-Cl)Cl]2, (II), were isolated therefrom. Here, we report the crystal structures of complexes (I) and (II).

The asymmetric unit of compound (I) contains a discrete [Zn(dmpzm)Cl2] molecule. Compound (I) may be viewed as having a `butterfly'-shaped structure (Fig. 1), which resembles that of [ZnLBr2] [L is bis(3,4,5-trimethylpyrazol-1-yl)methane; Pettinari et al., 1998]. There is no crystallographic symmetry in this molecule. Atom Zn1 is bound to two N atoms from the dmpzm ligand and two terminal Cl atoms, forming a distorted tetrahedral geometry, with the angles around Zn1 being in the range 89.33 (5)–115.20 (4)°. The mean Zn—N bond distance [2.0588 (12) Å] is comparable with that in [ZnL2Cl2] [2.052 (4) Å; L is 4-acetylpyridine; Steffen & Palenik, 1977] but shorter than those in [ZnLBr2] [2.076 (7) Å; L is bis(3,4,5-trimethylpyrazol-1-yl)methane; Pettinari et al., 1998] or [ZnLCl2] [2.132 (2) Å; L is 2,2-bis(pyrazol-1-yl)propane; Bovio et al., 1992]. The mean Zn—Cl bond length [2.2184 (4) Å] is close to the values observed in [ZnLCl2] [2.211 (3) Å; L is 4-acetylpyridine; Steffen & Palenik, 1977], [ZnLCl2] [2.219 (2) Å; L is 2,2-bis(pyrazol-1-yl)propane; Bovio et al., 1992] and [ZnLCl3] [2.240 (5) Å; L is 8-aza-adeninium; Purnell & Hodgson, 1977]. The N1—Zn1—N4 bite angle of 89.33 (5)° in (I) is comparable with that observed in [ZnLCl2] [89.47°; L is 2,2-bis(pyrazol-1-yl)propane; Bovio et al., 1992].

Atom H6B from the CH2 group of each dmpzm ligand in (I) interacts with atom Cl2 of an adjacent molecule to afford intermolecular C—H···Cl contacts (Fig. 2), thereby forming a one-dimensional zigzag chain extending along the b axis (Table 2). The H···Cl contact distance is 2.77 (2) Å, which is comparable with those observed in [ZnLCl2] {2.74 (2) and 2.83 (2) Å; L is 4-methyl-2,6-di[(S)-(+)-1-phenylethyliminomethyl]phenol; Prabhakar et al., 2005}, and in trans,cis,cis-[RuCl2(Meim)2(SbPh3)2] [2.69 (1) and 2.94 (1) Å; Meim is N-methylimidazole] and trans,cis,cis-[RuCl2(Mepym)2(SbPh3)2] [2.95 (1) and 2.96 (1) Å; Mepym is 4-methylpyrimidine; Cini et al., 2002].

The asymmetric unit of compound (II) contains one-half of the dimeric molecule [Cd(dmpzm)(µ-Cl)Cl]2. As shown in Fig. 3, the structure contains a dimetallocyclic Cd2Cl2 core with a crystallographic centre of inversion at the midpoint of the Cd1···Cd1i line [symmetry code: (i) −x, 1 − y, −z]. Each Cd atom has a slightly distorted trigonal–bipyramidal geometry, coordinated by two N atoms from the dmpzm ligand, a terminal Cl atom and two bridging Cl atoms. Atoms Cl1i and N4 are in axial positions, while atoms Cl1, Cl2 and N1 are in equatorial positions. The Cl1i—Cd1—N4 bond angle is 171.52 (4)°. The two terminal Cl atoms have trans orientations with respect to the planar Cd2Cl2 core. The dinuclear Cd2Cl2 core is asymmetric, as the Cd1—Cl1 and Cd1—Cl1i bond distances are 2.4649 (7) and 2.7322 (9) Å, respectively, while the Cd1—Cl1—Cd1i and Cl1—Cd1—Cl1i angles are 94.68 (2) and 85.32 (2)°, respectively. The two asymmetric Cd—Cl distances are common for compounds containing a Cd2Cl2 core, as found in [CdLCl2]2 [2.487 (2) and 2.821 (2) Å; L is 1-(5,6-dimethylbenzimidiazol-2-yl)-3-(benzimidazol-2-yl)-2-thiapropane; Matthews et al., 1998] and [CdLCl2]2 [2.537 (1) and 2.672 (1) Å; L is 3-amino-6,6'-dimethyl-2,2'-bipyridine; Long et al., 1993]. The Cd1···Cd1i contact of 3.826 (2) Å in (II) is too long to include any metal–metal interaction. Each dmpzm ligand adopts an extended and twisted exo–anti conformation and coordinates to one Cd centre in an N,N'-bidentate fashion, forming a six-membered C(N—N)2Cd chelate ring. The average Cd—N bond distance [2.3467 (18) Å] is close to the values observed in [CdLCl2]2 [2.397 (2) Å; L is 1,4,7-triazacyclononane; Zompa et al., 1995] and [CdLCl2]2 [2.367 (3) Å; L is cis-3,5-diaminopiperidine; Pauly et al., 2000]. The N1—Cd1—N4 bite angle of 79.00 (6)° is normal compared with [CdL2Cl2(H2O)2]2 (80.71°; L is 2,2'-dipyridylamine; Pickardt & Staub, 1999].

Each Cl2 atom of (II) interacts with the methylene group of the dmpzm ligand in an adjacent molecule to afford pairwise intermolecular C—H···Cl contacts (Table 4), thereby affording chains of molecules running along the c axis (Fig. 4).

Experimental top

To a solution of ZnCl2 (0.136 g, 1 mmol) in a mixture of methanol and water (9:1 v/v, 10 ml) was added a solution of dmpzm (0.20 g, 1 mmol) in methanol (Volume?). A large amount of white precipitate formed immediately. After stirring for 30 min, the precipitate was filtered and washed with diethyl ether (3 × 5 ml) and dried in vacuo. Colourless prisms of [Zn(dmpzm)Cl2], (I), were obtained through recrystallization of the precipitate from a solution in dimethylformamide (yield 0.31 g, 91% based on Zn). Analysis, found: C 38.72, H 4.73, N 15.96%; calculated for C11H16C12N4Zn: C 38.69, H 4.70, N 16.25%. Spectroscopic analysis: IR (KBr, ν, cm−1): 3134 (w), 3017 (m), 2930 (w), 1558 (s), 1467 (m), 1392 (s), 1380 (s), 1280 (s), 1051 (m), 1004 (w), 829 (m),809 (m), 677 (m).

To a solution of CdCl2·2.5H2O (0.228 g, 1 mmol) in a mixture of methanol and water (9:1 v/v, 10 ml) was added a solution of dmpzm (0.20 g, 1 mmol) in methanol (10 ml). The mixture was stirred at room temperature for 30 min. Slow evaporation of the solvents from the resulting solution produced colourless prisms of [Cd(dmpzm)Cl2]2, (II), which were collected by filtration, washed thoroughly with Et2O and dried in air (yield 0.67 g, 87% based on Cd). Analysis, found: C 34.11, H 4.21, N 13.18%; calculated for C22H32Cd2Cl4N8: C 34.08, H 4.16, N 14.46%. Spectroscopic analysis: IR (KBr, ν, cm−1): 3124 (w), 3022 (w), 2925 (w), 1558 (s), 1464 (s), 1390 (s), 1281 (s), 1041 (m), 989 (w), 822 (m), 794 (m), 676 (m).

Refinement top

All H atoms were placed in geometrically idealized positions, with C—H = 0.98 Å for methyl groups, 0.99 Å for methylene groups or 0.95 Å for phenyl groups, and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C), or 1.5Ueq(C) for the methyl groups.

Computing details top

For both compounds, data collection: Crystal Clear (Rigaku, 2001); cell refinement: Crystal Clear; data reduction: Crystal Structure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976) and SHELXL97; software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. A plot of complex (I), with displacement ellipsoids drawn at the 30% probability level. H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. A packing diagram for (I), viewed approximately down the b axis, showing the one-dimensional zigzag chain formed by C—H···Cl interactions.
[Figure 3] Fig. 3. A plot of complex (II), with displacement ellipsoids drawn at the 30% probability level. H atoms are shown as small spheres of arbitrary radii. [Symmetry code (i): −x, 1 − y, −z.]
[Figure 4] Fig. 4. A packing diagram for (II), viewed approximately down the c axis, showing the one-dimensional chain formed by C—H···Cl interactions.
(I) Dichloro[(3,5-dimethyl-1H-pyrazol-1-yl)methane]zinc(II) top
Crystal data top
[Zn(C11H16N4)Cl2]F(000) = 1392
Mr = 340.55Dx = 1.575 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71070 Å
Hall symbol: -C 2ycCell parameters from 6686 reflections
a = 14.9018 (17) Åθ = 3.0–27.5°
b = 16.7328 (17) ŵ = 2.07 mm1
c = 12.5546 (14) ÅT = 193 K
β = 113.446 (2)°Block, colourless
V = 2872.0 (5) Å30.50 × 0.40 × 0.38 mm
Z = 8
Data collection top
Rigaku Mercury
diffractometer
3291 independent reflections
Radiation source: fine-focus sealed tube3119 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.018
Detector resolution: 7.31 pixels mm-1θmax = 27.5°, θmin = 3.5°
ω scansh = 1919
Absorption correction: multi-scan
(Jacobson, 1998)
k = 2121
Tmin = 0.382, Tmax = 0.456l = 1316
15701 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.024H-atom parameters constrained
wR(F2) = 0.064 w = 1/[σ2(Fo2) + (0.038P)2 + 2.2138P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.001
3291 reflectionsΔρmax = 0.31 e Å3
169 parametersΔρmin = 0.63 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0038 (2)
Crystal data top
[Zn(C11H16N4)Cl2]V = 2872.0 (5) Å3
Mr = 340.55Z = 8
Monoclinic, C2/cMo Kα radiation
a = 14.9018 (17) ŵ = 2.07 mm1
b = 16.7328 (17) ÅT = 193 K
c = 12.5546 (14) Å0.50 × 0.40 × 0.38 mm
β = 113.446 (2)°
Data collection top
Rigaku Mercury
diffractometer
3291 independent reflections
Absorption correction: multi-scan
(Jacobson, 1998)
3119 reflections with I > 2σ(I)
Tmin = 0.382, Tmax = 0.456Rint = 0.018
15701 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0240 restraints
wR(F2) = 0.064H-atom parameters constrained
S = 1.04Δρmax = 0.31 e Å3
3291 reflectionsΔρmin = 0.63 e Å3
169 parameters
Special details top

Experimental. no

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
xyzUiso*/Ueq
Zn10.721931 (12)0.382779 (9)0.738096 (14)0.02087 (8)
Cl10.88413 (3)0.38937 (3)0.81657 (4)0.03587 (11)
Cl20.64941 (3)0.50122 (2)0.70048 (3)0.02813 (10)
N10.67613 (9)0.30413 (7)0.60085 (10)0.0218 (2)
N20.68438 (9)0.22428 (7)0.62663 (11)0.0224 (3)
N30.68183 (10)0.22511 (7)0.81547 (11)0.0237 (3)
N40.67112 (9)0.30518 (7)0.82902 (11)0.0227 (3)
C10.60027 (15)0.38774 (10)0.42594 (15)0.0339 (4)
H1A0.53010.39780.40140.051*
H1B0.61670.38720.35770.051*
H1C0.63750.43000.47930.051*
C20.62540 (11)0.30886 (9)0.48591 (13)0.0242 (3)
C30.60224 (12)0.23220 (10)0.43900 (13)0.0284 (3)
H30.56740.21910.35950.034*
C40.63958 (11)0.17922 (9)0.53001 (14)0.0261 (3)
C50.63470 (14)0.09059 (10)0.53060 (18)0.0411 (4)
H5A0.69870.06910.58110.062*
H5B0.61670.07040.45150.062*
H5C0.58550.07380.55960.062*
C60.73529 (11)0.20043 (9)0.74661 (12)0.0243 (3)
H6A0.80120.22490.77860.029*
H6B0.74330.14160.75090.029*
C70.63537 (16)0.09193 (11)0.8694 (2)0.0447 (5)
H7A0.59680.07190.79110.067*
H7B0.60680.07290.92280.067*
H7C0.70280.07250.89520.067*
C80.63514 (12)0.18080 (10)0.86816 (14)0.0289 (3)
C90.59337 (13)0.23456 (10)0.91770 (14)0.0310 (3)
H90.55600.22210.96170.037*
C100.61633 (11)0.31086 (9)0.89111 (13)0.0254 (3)
C110.58781 (15)0.39013 (11)0.92196 (16)0.0362 (4)
H11A0.62140.43260.89830.054*
H11B0.60640.39281.00600.054*
H11C0.51690.39710.88180.054*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.02455 (12)0.01598 (11)0.02230 (11)0.00011 (6)0.00955 (8)0.00069 (6)
Cl10.0235 (2)0.0398 (2)0.0402 (2)0.00045 (15)0.00830 (17)0.00159 (17)
Cl20.0319 (2)0.01684 (17)0.0341 (2)0.00231 (13)0.01146 (16)0.00043 (13)
N10.0285 (6)0.0170 (6)0.0215 (6)0.0007 (5)0.0116 (5)0.0001 (4)
N20.0280 (6)0.0159 (6)0.0237 (6)0.0022 (5)0.0106 (5)0.0014 (5)
N30.0308 (7)0.0169 (6)0.0259 (6)0.0031 (5)0.0138 (5)0.0034 (5)
N40.0290 (6)0.0177 (6)0.0226 (6)0.0020 (5)0.0114 (5)0.0005 (5)
C10.0440 (10)0.0312 (9)0.0260 (8)0.0009 (7)0.0134 (7)0.0067 (6)
C20.0252 (7)0.0274 (7)0.0222 (7)0.0007 (6)0.0119 (6)0.0003 (6)
C30.0276 (8)0.0311 (8)0.0237 (7)0.0000 (6)0.0072 (6)0.0062 (6)
C40.0242 (7)0.0235 (7)0.0302 (8)0.0007 (6)0.0103 (6)0.0070 (6)
C50.0413 (10)0.0219 (8)0.0491 (11)0.0012 (7)0.0063 (8)0.0093 (7)
C60.0288 (8)0.0188 (7)0.0257 (7)0.0066 (6)0.0115 (6)0.0021 (5)
C70.0532 (12)0.0249 (9)0.0606 (12)0.0001 (8)0.0275 (10)0.0111 (8)
C80.0314 (8)0.0263 (8)0.0285 (8)0.0001 (6)0.0115 (6)0.0079 (6)
C90.0336 (8)0.0333 (8)0.0307 (8)0.0006 (7)0.0176 (7)0.0062 (7)
C100.0270 (7)0.0291 (8)0.0205 (7)0.0025 (6)0.0098 (6)0.0003 (6)
C110.0464 (10)0.0339 (9)0.0366 (9)0.0057 (7)0.0252 (8)0.0047 (7)
Geometric parameters (Å, º) top
Zn1—N12.0569 (12)C3—H30.9500
Zn1—N42.0616 (12)C4—C51.485 (2)
Zn1—Cl22.2164 (4)C5—H5A0.9800
Zn1—Cl12.2204 (5)C5—H5B0.9800
N1—C21.3386 (19)C5—H5C0.9800
N1—N21.3686 (16)C6—H6A0.9900
N2—C41.3569 (19)C6—H6B0.9900
N2—C61.4472 (19)C7—C81.487 (2)
N3—C81.3557 (19)C7—H7A0.9800
N3—N41.3677 (16)C7—H7B0.9800
N3—C61.4492 (18)C7—H7C0.9800
N4—C101.3379 (19)C8—C91.375 (2)
C1—C21.492 (2)C9—C101.396 (2)
C1—H1A0.9800C9—H90.9500
C1—H1B0.9800C10—C111.490 (2)
C1—H1C0.9800C11—H11A0.9800
C2—C31.396 (2)C11—H11B0.9800
C3—C41.377 (2)C11—H11C0.9800
N1—Zn1—N489.33 (5)C4—C5—H5A109.5
N1—Zn1—Cl2114.99 (4)C4—C5—H5B109.5
N4—Zn1—Cl2115.20 (4)H5A—C5—H5B109.5
N1—Zn1—Cl1110.08 (4)C4—C5—H5C109.5
N4—Zn1—Cl1111.12 (4)H5A—C5—H5C109.5
Cl2—Zn1—Cl1113.738 (17)H5B—C5—H5C109.5
C2—N1—N2105.76 (12)N2—C6—N3110.94 (12)
C2—N1—Zn1136.22 (10)N2—C6—H6A109.5
N2—N1—Zn1117.25 (9)N3—C6—H6A109.5
C4—N2—N1111.42 (12)N2—C6—H6B109.5
C4—N2—C6130.16 (13)N3—C6—H6B109.5
N1—N2—C6118.41 (11)H6A—C6—H6B108.0
C8—N3—N4111.53 (12)C8—C7—H7A109.5
C8—N3—C6130.23 (13)C8—C7—H7B109.5
N4—N3—C6118.18 (12)H7A—C7—H7B109.5
C10—N4—N3105.70 (12)C8—C7—H7C109.5
C10—N4—Zn1136.18 (10)H7A—C7—H7C109.5
N3—N4—Zn1117.47 (9)H7B—C7—H7C109.5
C2—C1—H1A109.5N3—C8—C9105.99 (14)
C2—C1—H1B109.5N3—C8—C7123.55 (16)
H1A—C1—H1B109.5C9—C8—C7130.44 (16)
C2—C1—H1C109.5C8—C9—C10106.97 (14)
H1A—C1—H1C109.5C8—C9—H9126.5
H1B—C1—H1C109.5C10—C9—H9126.5
N1—C2—C3109.83 (13)N4—C10—C9109.80 (14)
N1—C2—C1121.14 (14)N4—C10—C11121.20 (14)
C3—C2—C1129.03 (14)C9—C10—C11129.00 (14)
C4—C3—C2106.92 (13)C10—C11—H11A109.5
C4—C3—H3126.5C10—C11—H11B109.5
C2—C3—H3126.5H11A—C11—H11B109.5
N2—C4—C3106.06 (13)C10—C11—H11C109.5
N2—C4—C5123.93 (15)H11A—C11—H11C109.5
C3—C4—C5130.00 (15)H11B—C11—H11C109.5
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C6—H6B···Cl2i0.992.773.6875 (15)154
Symmetry code: (i) x+3/2, y1/2, z+3/2.
(II) Di-µ-chloro-bis{chloro[(3,5-dimethyl-1H-pyrazol-1-yl)methane]cadmium(II)} top
Crystal data top
[Cd2(C11H16N4)2Cl4]Z = 1
Mr = 775.16F(000) = 384
Triclinic, P1Dx = 1.794 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71070 Å
a = 7.7033 (17) ÅCell parameters from 3251 reflections
b = 9.232 (2) Åθ = 3.3–25.3°
c = 11.513 (2) ŵ = 1.88 mm1
α = 112.752 (19)°T = 193 K
β = 102.34 (2)°Block, colourless
γ = 97.28 (3)°0.54 × 0.21 × 0.20 mm
V = 717.4 (3) Å3
Data collection top
Rigaku Mercury
diffractometer
2597 independent reflections
Radiation source: fine-focus sealed tube2487 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.016
Detector resolution: 7.31 pixels mm-1θmax = 25.4°, θmin = 3.3°
ω scansh = 99
Absorption correction: multi-scan
(Jacobson, 1998)
k = 1111
Tmin = 0.417, Tmax = 0.684l = 1313
7007 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.018Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.044H-atom parameters constrained
S = 1.10 w = 1/[σ2(Fo2) + (0.0223P)2 + 0.3284P]
where P = (Fo2 + 2Fc2)/3
2597 reflections(Δ/σ)max = 0.001
168 parametersΔρmax = 0.53 e Å3
0 restraintsΔρmin = 0.44 e Å3
Crystal data top
[Cd2(C11H16N4)2Cl4]γ = 97.28 (3)°
Mr = 775.16V = 717.4 (3) Å3
Triclinic, P1Z = 1
a = 7.7033 (17) ÅMo Kα radiation
b = 9.232 (2) ŵ = 1.88 mm1
c = 11.513 (2) ÅT = 193 K
α = 112.752 (19)°0.54 × 0.21 × 0.20 mm
β = 102.34 (2)°
Data collection top
Rigaku Mercury
diffractometer
2597 independent reflections
Absorption correction: multi-scan
(Jacobson, 1998)
2487 reflections with I > 2σ(I)
Tmin = 0.417, Tmax = 0.684Rint = 0.016
7007 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0180 restraints
wR(F2) = 0.044H-atom parameters constrained
S = 1.10Δρmax = 0.53 e Å3
2597 reflectionsΔρmin = 0.44 e Å3
168 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
xyzUiso*/Ueq
Cd10.075656 (19)0.473155 (16)0.158421 (13)0.01859 (6)
Cl10.21178 (7)0.45855 (7)0.01992 (5)0.02577 (12)
Cl20.09753 (7)0.70804 (6)0.36282 (5)0.02550 (12)
N10.0949 (2)0.2317 (2)0.12488 (16)0.0202 (4)
N20.0813 (2)0.1883 (2)0.22764 (16)0.0192 (4)
N30.2331 (2)0.3085 (2)0.35230 (16)0.0196 (4)
N40.2956 (2)0.3835 (2)0.28157 (16)0.0201 (4)
C10.2498 (4)0.1056 (3)0.1132 (2)0.0356 (6)
H1A0.33170.17820.11510.053*
H1B0.31070.00390.18050.053*
H1C0.13780.14330.13080.053*
C20.2030 (3)0.1044 (3)0.0191 (2)0.0234 (4)
C30.2590 (3)0.0198 (3)0.0540 (2)0.0290 (5)
H30.33680.12290.00330.035*
C40.1800 (3)0.0359 (2)0.1867 (2)0.0235 (4)
C50.1930 (3)0.0421 (3)0.2777 (2)0.0329 (5)
H5A0.07280.05810.31250.049*
H5B0.28100.14690.22960.049*
H5C0.23370.02740.35050.049*
C60.0446 (3)0.2973 (2)0.35436 (19)0.0200 (4)
H6A0.02570.25900.42100.024*
H6B0.01860.40600.38030.024*
C70.3387 (3)0.1687 (3)0.4944 (2)0.0329 (5)
H7A0.25560.21280.54530.049*
H7B0.45590.17950.55440.049*
H7C0.28490.05430.43570.049*
C80.3685 (3)0.2596 (2)0.41435 (19)0.0217 (4)
C90.5214 (3)0.3043 (3)0.3825 (2)0.0254 (5)
H90.63920.28760.41110.030*
C100.4712 (3)0.3797 (2)0.2993 (2)0.0210 (4)
C110.5839 (3)0.4470 (3)0.2336 (2)0.0303 (5)
H11A0.59400.35880.15530.046*
H11B0.70610.50360.29450.046*
H11C0.52580.52280.20790.046*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd10.02256 (10)0.02077 (10)0.01482 (9)0.00484 (6)0.00611 (6)0.00972 (7)
Cl10.0253 (3)0.0412 (3)0.0219 (3)0.0151 (2)0.0121 (2)0.0199 (2)
Cl20.0329 (3)0.0238 (3)0.0178 (2)0.0102 (2)0.0054 (2)0.0067 (2)
N10.0217 (9)0.0237 (9)0.0170 (8)0.0052 (7)0.0057 (7)0.0105 (7)
N20.0200 (9)0.0214 (9)0.0189 (9)0.0048 (7)0.0060 (7)0.0113 (7)
N30.0216 (9)0.0233 (9)0.0165 (8)0.0056 (7)0.0045 (7)0.0114 (7)
N40.0246 (9)0.0233 (9)0.0163 (8)0.0066 (7)0.0076 (7)0.0111 (7)
C10.0428 (14)0.0333 (13)0.0207 (12)0.0000 (11)0.0022 (10)0.0075 (10)
C20.0235 (11)0.0222 (11)0.0208 (11)0.0045 (9)0.0054 (9)0.0061 (9)
C30.0300 (12)0.0193 (11)0.0312 (12)0.0007 (9)0.0054 (10)0.0074 (9)
C40.0244 (11)0.0190 (11)0.0304 (12)0.0068 (8)0.0108 (9)0.0120 (9)
C50.0398 (14)0.0256 (12)0.0392 (14)0.0051 (10)0.0121 (11)0.0204 (11)
C60.0233 (11)0.0235 (11)0.0173 (10)0.0072 (8)0.0088 (8)0.0109 (8)
C70.0400 (14)0.0315 (13)0.0290 (12)0.0097 (11)0.0017 (10)0.0186 (10)
C80.0268 (11)0.0172 (10)0.0162 (10)0.0070 (8)0.0005 (8)0.0050 (8)
C90.0218 (11)0.0254 (11)0.0235 (11)0.0090 (9)0.0001 (9)0.0071 (9)
C100.0175 (10)0.0217 (11)0.0180 (10)0.0049 (8)0.0031 (8)0.0036 (8)
C110.0199 (11)0.0389 (13)0.0311 (12)0.0051 (10)0.0087 (9)0.0136 (11)
Geometric parameters (Å, º) top
Cd1—N12.2847 (19)C3—C41.373 (3)
Cd1—N42.4088 (18)C3—H30.9500
Cd1—Cl22.4616 (9)C4—C51.495 (3)
Cd1—Cl12.4649 (7)C5—H5A0.9800
Cd1—Cl1i2.7322 (9)C5—H5B0.9800
Cl1—Cd1i2.7322 (9)C5—H5C0.9800
N1—C21.331 (3)C6—H6A0.9900
N1—N21.377 (2)C6—H6B0.9900
N2—C41.358 (3)C7—C81.498 (3)
N2—C61.447 (3)C7—H7A0.9800
N3—C81.361 (3)C7—H7B0.9800
N3—N41.375 (2)C7—H7C0.9800
N3—C61.449 (3)C8—C91.368 (3)
N4—C101.331 (3)C9—C101.406 (3)
C1—C21.493 (3)C9—H90.9500
C1—H1A0.9800C10—C111.489 (3)
C1—H1B0.9800C11—H11A0.9800
C1—H1C0.9800C11—H11B0.9800
C2—C31.402 (3)C11—H11C0.9800
N1—Cd1—N479.00 (6)N2—C4—C5123.1 (2)
N1—Cd1—Cl2116.72 (5)C3—C4—C5130.9 (2)
N4—Cd1—Cl289.61 (5)C4—C5—H5A109.5
N1—Cd1—Cl1114.00 (5)C4—C5—H5B109.5
N4—Cd1—Cl1100.11 (4)H5A—C5—H5B109.5
Cl2—Cd1—Cl1129.28 (3)C4—C5—H5C109.5
N1—Cd1—Cl1i92.87 (5)H5A—C5—H5C109.5
N4—Cd1—Cl1i171.52 (4)H5B—C5—H5C109.5
Cl2—Cd1—Cl1i91.95 (3)N2—C6—N3111.93 (16)
Cl1—Cd1—Cl1i85.32 (2)N2—C6—H6A109.2
Cd1—Cl1—Cd1i94.68 (2)N3—C6—H6A109.2
C2—N1—N2105.76 (16)N2—C6—H6B109.2
C2—N1—Cd1134.16 (14)N3—C6—H6B109.2
N2—N1—Cd1119.78 (12)H6A—C6—H6B107.9
C4—N2—N1111.33 (16)C8—C7—H7A109.5
C4—N2—C6129.86 (17)C8—C7—H7B109.5
N1—N2—C6118.42 (16)H7A—C7—H7B109.5
C8—N3—N4111.39 (17)C8—C7—H7C109.5
C8—N3—C6130.13 (17)H7A—C7—H7C109.5
N4—N3—C6118.45 (16)H7B—C7—H7C109.5
C10—N4—N3105.62 (16)N3—C8—C9106.07 (18)
C10—N4—Cd1137.37 (14)N3—C8—C7123.3 (2)
N3—N4—Cd1116.96 (12)C9—C8—C7130.6 (2)
C2—C1—H1A109.5C8—C9—C10107.01 (18)
C2—C1—H1B109.5C8—C9—H9126.5
H1A—C1—H1B109.5C10—C9—H9126.5
C2—C1—H1C109.5N4—C10—C9109.91 (19)
H1A—C1—H1C109.5N4—C10—C11120.89 (19)
H1B—C1—H1C109.5C9—C10—C11129.18 (19)
N1—C2—C3109.83 (19)C10—C11—H11A109.5
N1—C2—C1121.49 (19)C10—C11—H11B109.5
C3—C2—C1128.7 (2)H11A—C11—H11B109.5
C4—C3—C2107.09 (19)C10—C11—H11C109.5
C4—C3—H3126.5H11A—C11—H11C109.5
C2—C3—H3126.5H11B—C11—H11C109.5
N2—C4—C3105.99 (19)
Symmetry code: (i) x, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C6—H6A···Cl2ii0.992.773.666 (2)151
Symmetry code: (ii) x, y+1, z+1.

Experimental details

(I)(II)
Crystal data
Chemical formula[Zn(C11H16N4)Cl2][Cd2(C11H16N4)2Cl4]
Mr340.55775.16
Crystal system, space groupMonoclinic, C2/cTriclinic, P1
Temperature (K)193193
a, b, c (Å)14.9018 (17), 16.7328 (17), 12.5546 (14)7.7033 (17), 9.232 (2), 11.513 (2)
α, β, γ (°)90, 113.446 (2), 90112.752 (19), 102.34 (2), 97.28 (3)
V3)2872.0 (5)717.4 (3)
Z81
Radiation typeMo KαMo Kα
µ (mm1)2.071.88
Crystal size (mm)0.50 × 0.40 × 0.380.54 × 0.21 × 0.20
Data collection
DiffractometerRigaku Mercury
diffractometer
Rigaku Mercury
diffractometer
Absorption correctionMulti-scan
(Jacobson, 1998)
Multi-scan
(Jacobson, 1998)
Tmin, Tmax0.382, 0.4560.417, 0.684
No. of measured, independent and
observed [I > 2σ(I)] reflections
15701, 3291, 3119 7007, 2597, 2487
Rint0.0180.016
(sin θ/λ)max1)0.6490.602
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.024, 0.064, 1.04 0.018, 0.044, 1.10
No. of reflections32912597
No. of parameters169168
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.31, 0.630.53, 0.44

Computer programs: Crystal Clear (Rigaku, 2001), Crystal Clear, Crystal Structure (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976) and SHELXL97, SHELXL97.

Selected geometric parameters (Å, º) for (I) top
Zn1—N12.0569 (12)Zn1—Cl22.2164 (4)
Zn1—N42.0616 (12)Zn1—Cl12.2204 (5)
N1—Zn1—N489.33 (5)N1—Zn1—Cl1110.08 (4)
N1—Zn1—Cl2114.99 (4)N4—Zn1—Cl1111.12 (4)
N4—Zn1—Cl2115.20 (4)Cl2—Zn1—Cl1113.738 (17)
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
C6—H6B···Cl2i0.992.773.6875 (15)154
Symmetry code: (i) x+3/2, y1/2, z+3/2.
Selected geometric parameters (Å, º) for (II) top
Cd1—N12.2847 (19)Cd1—Cl12.4649 (7)
Cd1—N42.4088 (18)Cd1—Cl1i2.7322 (9)
Cd1—Cl22.4616 (9)Cl1—Cd1i2.7322 (9)
N1—Cd1—N479.00 (6)N1—Cd1—Cl1i92.87 (5)
N1—Cd1—Cl2116.72 (5)N4—Cd1—Cl1i171.52 (4)
N4—Cd1—Cl289.61 (5)Cl2—Cd1—Cl1i91.95 (3)
N1—Cd1—Cl1114.00 (5)Cl1—Cd1—Cl1i85.32 (2)
N4—Cd1—Cl1100.11 (4)Cd1—Cl1—Cd1i94.68 (2)
Cl2—Cd1—Cl1129.28 (3)
Symmetry code: (i) x, y+1, z.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
C6—H6A···Cl2ii0.992.773.666 (2)151
Symmetry code: (ii) x, y+1, z+1.
 

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