Bis{tris[2-(2-oxidobenzylideneazaniumyl)ethyl]amine-κ3O,O′,O′′}calcium bis(perchlorate) acetonitrile disolvate

Kose, M.; McKee, V.

doi:10.1107/S1600536810053961

metal-organic compounds

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Volume 67| Part 2| February 2011| Page m149

doi:10.1107/S1600536810053961

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Bis{tris[2-(2-oxidobenzylideneazaniumyl)ethyl]amine-κ³O,O′,O′′}calcium bis(perchlorate) acetonitrile disolvate

Muhammet Kose ^a ^* and Vickie McKee ^a

^aChemistry Department, Loughborough University, Leicestershire, LE11 3TU, England
^*Correspondence e-mail: m.kose@lboro.ac.uk

(Received 13 December 2010; accepted 23 December 2010; online 8 January 2011)

The title complex, [Ca(C₂₇H₃₀N₄O₃)₂](ClO₄)₂·2CH₃CN, is composed of centrosymmetric (CaL₂)²⁺ cations [L = tris(2-hydroxybenzoylaminoethyl)amine = H₃saltren], uncoordinated perchlorate anions and acetonitrile solvent molecules. The calcium ion is six-coordinated and is bonded to all phenoxy O atoms from both zwitterionic saltren molecules. There are strong intramolecular N—H⋯O hydrogen bonds. The cations are linked into chains via weak intermolecular C—H⋯O hydrogen bonds and C—H⋯π and π–π stacking interactions [centroid–centroid distances = 3.306 (3) and 3.415 (3) Å].

Related literature

For crystal structure of the free ligand, see: Gündüz et al. (1985 ). For structures of transition metal complexes of H₃saltren, see: Steinhauser et al. (2004 ); Elerman et al. (1994 , 1995 ).

Experimental

Crystal data

[Ca(C₂₇H₃₀N₄O₃)₂](ClO₄)₂·2C₂H₃N
M_r = 1238.19
Orthorhombic, P b c a
a = 11.3469 (7) Å
b = 19.5307 (12) Å
c = 27.3178 (16) Å
V = 6054.0 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.27 mm⁻¹
T = 150 K
0.12 × 0.10 × 0.09 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.662, T_max = 0.746
55467 measured reflections
6915 independent reflections
5810 reflections with I > 2.0σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.110
S = 1.05
6915 reflections
398 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.60 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1	0.85 (2)	1.98 (2)	2.6597 (17)	136 (2)
N3—H3A⋯O2	0.86 (2)	1.91 (2)	2.6256 (18)	140 (2)
N4—H4A⋯O3	0.83 (2)	1.98 (2)	2.6449 (17)	137 (2)
C3—H3⋯O7ⁱ	0.95	2.41	3.316 (2)	160
C20—H20A⋯O5ⁱⁱ	0.99	2.50	3.380 (2)	148
C10—H10A⋯O5ⁱⁱⁱ	0.99	2.50	3.271 (2)	134
C21—H21⋯O5ⁱⁱ	0.95	2.58	3.259 (2)	129
C29—H29B⋯O6^iv	0.98	2.58	3.555 (3)	173
C26—H26⋯Cg1^v	0.95	2.68	3.489 (2)	143
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) x-1, y-1, z; (iii) $[x-{\script{1\over 2}}, y-1, -z+{\script{3\over 2}}]$ ; (iv) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, z]$ ; (v) -x+1, -y, -z+1.

Data collection: APEX2 (Bruker, 2008 ); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; 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/S1600536810053961/pv2371sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810053961/pv2371Isup2.hkl

checkCIF report

Comment top

The crystal structures and coordination chemistry of transition metal complexes of H₃saltren, tris(2-hydroxybenzoylaminoethyl)amine (L), a tripodal ligand, have been described in detail (Steinhauser et al., 2004; Elerman et al., 1994); Elerman et al., 1995). Here, we report the first example of an earth alkaline metal (Ca⁺²) complex of H₃saltren.

The crystal structure of the title complex contains centrosymmetric (CaL₂)⁺² cations, uncoordinated perchlorate anions and acetonitrile molecules (Fig. 1). Each calcium ion is six-coordinated, bonded to all phenoxy O atoms from two saltren molecules. There are strong intramolecular hydrogen bonds of the type N—H···O between protonated imine and deprotonated phenol-oxygen atoms (Table 1). The cations are linked into chains via intermolecular C—H···O and C—H··· N type weak hydrogen bonds and C—H···π interactions (Tab. 1 and Fig. 2). There is evidence of π-π stacking in the crystal structure; C16 is stacked with C16^* and C15^* of an adjacent molecule (^* = 2 - x, -y, 1 - z) with separation of 3.306 (3) and 3.415 (3) Å, respectively (Fig. 2). Protonated imine distances (C═N distances) (mean 1.300 (2) Å) are longer than the corresponding C═N distances reported in the neutral ligand (mean 1.267 Å) (Gündüz et al., 1985). The longer C═N distances were also determined by IR spectroscopy; while C═N stretch is observed at 1633 cm^-1 in the neutral ligand, by protonation of imine, C═N stretch shifts to 1654 cm^-1.

Related literature top

For crystal structure of the free ligand, see: Gündüz et al. (1985). For structures of transition metal complexes of H₃saltren, see: Steinhauser et al. (2004); Elerman et al. (1994, 1995).

Experimental top

H₃Saltren (0.508 g, 1.11 mmol) was dissolved in methanol (50 ml) followed by addition of Ca(ClO₄)₂.3H₂O (0.185 g, 0.63 mmol) in methanol (20 ml). The reaction mixture was stirred at room temperature for two hours. Yellow precipitate was collected and washed with methanol (5 ml) and diethylether (20 ml) (yield 0.506 g, 0.44 mmol, 69.6%). X-ray quality crystals were obtained from acetonitrile solution of the title complex by slow evaporation.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); 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. Perspective view of centrosymmetric calcium complex [Ca(C₂₇H₃₀N₄O₃)₂](ClO₄)₂(CH₃CN)₂; displacement ellipsoids are drawn at the 50% probability level and hydrogen atoms are omitted for clarity (Symmetry code (i) -x + 1, -y, -z + 1).
	Fig. 2. Packing diagram viewed perpendicular to b, showing intramolecular hydrogen bonds and π-π (phenyl-phenyl) interactions.

Bis{tris[2-(2-oxidobenzylideneazaniumyl)ethyl]amine- κ³O,O',O''}calcium bis(perchlorate) acetonitrile disolvate top

Crystal data top

[Ca(C₂₇H₃₀N₄O₃)₂](ClO₄)₂·2C₂H₃N	F(000) = 2600
M_r = 1238.19	D_x = 1.358 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 9950 reflections
a = 11.3469 (7) Å	θ = 2.2–27.4°
b = 19.5307 (12) Å	µ = 0.27 mm⁻¹
c = 27.3178 (16) Å	T = 150 K
V = 6054.0 (6) Å³	Block, yellow
Z = 4	0.12 × 0.10 × 0.09 mm

Data collection top

Bruker APEXII CCD diffractometer	6915 independent reflections
Radiation source: fine-focus sealed tube	5810 reflections with I > 2.0σ(I)
Graphite monochromator	R_int = 0.030
ϕ and ω scans	θ_max = 27.5°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −14→14
T_min = 0.662, T_max = 0.746	k = −25→25
55467 measured reflections	l = −34→35

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.110	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0538P)² + 3.4246P] where P = (F_o² + 2F_c²)/3
6915 reflections	(Δ/σ)_max = 0.002
398 parameters	Δρ_max = 0.60 e Å⁻³
0 restraints	Δρ_min = −0.39 e Å⁻³

Crystal data top

[Ca(C₂₇H₃₀N₄O₃)₂](ClO₄)₂·2C₂H₃N	V = 6054.0 (6) Å³
M_r = 1238.19	Z = 4
Orthorhombic, Pbca	Mo Kα radiation
a = 11.3469 (7) Å	µ = 0.27 mm⁻¹
b = 19.5307 (12) Å	T = 150 K
c = 27.3178 (16) Å	0.12 × 0.10 × 0.09 mm

Data collection top

Bruker APEXII CCD diffractometer	6915 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	5810 reflections with I > 2.0σ(I)
T_min = 0.662, T_max = 0.746	R_int = 0.030
55467 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.110	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.60 e Å⁻³
6915 reflections	Δρ_min = −0.39 e Å⁻³
398 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
Ca1	0.5000	0.0000	0.5000	0.01901 (10)
O1	0.38283 (10)	0.08611 (5)	0.53706 (4)	0.0260 (2)
C1	0.32707 (13)	0.13534 (8)	0.51499 (5)	0.0224 (3)
C2	0.25547 (15)	0.12409 (8)	0.47327 (6)	0.0291 (3)
H2	0.2438	0.0786	0.4619	0.035*
C3	0.20240 (16)	0.17746 (10)	0.44891 (7)	0.0349 (4)
H3	0.1557	0.1680	0.4208	0.042*
C4	0.21547 (17)	0.24547 (9)	0.46452 (7)	0.0395 (4)
H4	0.1795	0.2818	0.4469	0.047*
C5	0.28043 (16)	0.25839 (9)	0.50526 (7)	0.0340 (4)
H5	0.2879	0.3042	0.5166	0.041*
C6	0.33725 (13)	0.20497 (8)	0.53117 (6)	0.0239 (3)
C7	0.40674 (14)	0.22286 (8)	0.57213 (5)	0.0247 (3)
H7	0.4066	0.2695	0.5821	0.030*
N1	0.47075 (12)	0.18036 (7)	0.59710 (5)	0.0243 (3)
C8	0.53399 (15)	0.19940 (8)	0.64171 (6)	0.0277 (3)
H8A	0.5444	0.2497	0.6429	0.033*
H8B	0.6130	0.1779	0.6418	0.033*
C9	0.46415 (15)	0.17550 (8)	0.68610 (6)	0.0264 (3)
H9A	0.5005	0.1939	0.7163	0.032*
H9B	0.3825	0.1931	0.6840	0.032*
N2	0.46228 (11)	0.10039 (6)	0.68827 (5)	0.0228 (3)
C10	0.56302 (15)	0.07362 (9)	0.71617 (6)	0.0290 (3)
H10A	0.5388	0.0659	0.7505	0.035*
H10B	0.6271	0.1080	0.7162	0.035*
C11	0.60888 (15)	0.00683 (9)	0.69464 (6)	0.0307 (4)
H11A	0.6682	−0.0133	0.7170	0.037*
H11B	0.5431	−0.0261	0.6913	0.037*
N3	0.66223 (12)	0.01909 (7)	0.64666 (5)	0.0283 (3)
C12	0.77320 (14)	0.03357 (9)	0.64084 (6)	0.0303 (3)
H12	0.8224	0.0329	0.6690	0.036*
C13	0.82570 (14)	0.05027 (8)	0.59528 (6)	0.0282 (3)
C14	0.94893 (15)	0.06200 (9)	0.59374 (7)	0.0362 (4)
H14	0.9933	0.0605	0.6232	0.043*
C15	1.00481 (16)	0.07539 (9)	0.55058 (8)	0.0385 (4)
H15	1.0872	0.0841	0.5499	0.046*
C16	0.93896 (16)	0.07617 (9)	0.50724 (7)	0.0353 (4)
H16	0.9780	0.0844	0.4770	0.042*
C17	0.81902 (16)	0.06529 (8)	0.50726 (6)	0.0313 (4)
H17	0.7772	0.0660	0.4771	0.038*
C18	0.75700 (14)	0.05306 (7)	0.55146 (6)	0.0253 (3)
O2	0.64376 (10)	0.04299 (6)	0.55239 (4)	0.0287 (2)
C19	0.34878 (15)	0.07321 (8)	0.70527 (6)	0.0280 (3)
H19A	0.3107	0.1072	0.7270	0.034*
H19B	0.3626	0.0311	0.7246	0.034*
C20	0.26672 (14)	0.05700 (8)	0.66278 (6)	0.0287 (3)
H20A	0.1863	0.0484	0.6754	0.034*
H20B	0.2630	0.0968	0.6404	0.034*
N4	0.30786 (12)	−0.00316 (6)	0.63575 (5)	0.0241 (3)
C21	0.29327 (13)	−0.06510 (8)	0.65229 (6)	0.0252 (3)
H21	0.2469	−0.0706	0.6810	0.030*
C22	0.34110 (13)	−0.12487 (8)	0.63089 (6)	0.0233 (3)
C23	0.31923 (15)	−0.18869 (8)	0.65401 (6)	0.0308 (4)
H23	0.2708	−0.1903	0.6824	0.037*
C24	0.36664 (16)	−0.24768 (9)	0.63612 (7)	0.0361 (4)
H24	0.3526	−0.2901	0.6521	0.043*
C25	0.43665 (16)	−0.24480 (9)	0.59373 (7)	0.0376 (4)
H25	0.4690	−0.2859	0.5809	0.045*
C26	0.45932 (16)	−0.18409 (9)	0.57042 (7)	0.0341 (4)
H26	0.5066	−0.1842	0.5417	0.041*
C27	0.41389 (13)	−0.12088 (8)	0.58811 (5)	0.0231 (3)
O3	0.43711 (10)	−0.06298 (6)	0.56747 (4)	0.0285 (3)
C28	0.8355 (2)	0.24381 (14)	0.68889 (8)	0.0537 (6)
C29	0.85639 (19)	0.31612 (11)	0.68130 (9)	0.0505 (5)
H29A	0.9341	0.3283	0.6943	0.076*
H29B	0.7955	0.3427	0.6982	0.076*
H29C	0.8538	0.3263	0.6462	0.076*
N5	0.8201 (3)	0.18674 (14)	0.69423 (9)	0.0870 (9)
H4A	0.3474 (18)	−0.0002 (10)	0.6103 (8)	0.034 (5)*
H3A	0.6222 (19)	0.0209 (11)	0.6199 (8)	0.040 (6)*
H1A	0.4716 (19)	0.1395 (12)	0.5863 (8)	0.046 (6)*
Cl1	0.96706 (4)	0.89879 (2)	0.698669 (15)	0.03209 (11)
O4	1.04850 (18)	0.84563 (10)	0.70855 (9)	0.0828 (6)
O5	1.02963 (14)	0.96257 (8)	0.69527 (6)	0.0547 (4)
O6	0.88221 (16)	0.90508 (10)	0.73665 (7)	0.0743 (6)
O7	0.90949 (18)	0.88552 (10)	0.65378 (6)	0.0699 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ca1	0.0219 (2)	0.01807 (19)	0.01709 (19)	0.00034 (15)	0.00046 (15)	0.00076 (14)
O1	0.0295 (6)	0.0200 (5)	0.0285 (6)	0.0045 (4)	−0.0004 (4)	0.0005 (4)
C1	0.0202 (7)	0.0226 (7)	0.0243 (7)	0.0021 (6)	0.0052 (6)	0.0012 (6)
C2	0.0294 (8)	0.0270 (8)	0.0309 (8)	0.0006 (6)	−0.0015 (7)	−0.0034 (6)
C3	0.0317 (9)	0.0410 (10)	0.0321 (9)	0.0026 (7)	−0.0085 (7)	0.0006 (7)
C4	0.0426 (10)	0.0326 (9)	0.0432 (10)	0.0087 (8)	−0.0118 (8)	0.0084 (8)
C5	0.0383 (9)	0.0225 (8)	0.0413 (10)	0.0049 (7)	−0.0063 (7)	0.0016 (7)
C6	0.0253 (7)	0.0219 (7)	0.0245 (7)	0.0019 (6)	0.0014 (6)	0.0013 (6)
C7	0.0284 (8)	0.0207 (7)	0.0251 (7)	−0.0012 (6)	0.0041 (6)	0.0001 (6)
N1	0.0290 (7)	0.0219 (6)	0.0219 (6)	−0.0040 (5)	0.0004 (5)	0.0009 (5)
C8	0.0337 (8)	0.0272 (8)	0.0222 (7)	−0.0086 (6)	−0.0027 (6)	0.0023 (6)
C9	0.0342 (8)	0.0238 (7)	0.0211 (7)	−0.0018 (6)	0.0006 (6)	−0.0010 (6)
N2	0.0250 (6)	0.0220 (6)	0.0214 (6)	−0.0021 (5)	0.0007 (5)	0.0024 (5)
C10	0.0324 (9)	0.0321 (8)	0.0224 (7)	0.0001 (7)	−0.0039 (6)	0.0022 (6)
C11	0.0312 (8)	0.0319 (8)	0.0290 (8)	0.0031 (7)	−0.0017 (7)	0.0065 (6)
N3	0.0261 (7)	0.0308 (7)	0.0279 (7)	0.0026 (6)	−0.0029 (6)	0.0001 (6)
C12	0.0266 (8)	0.0315 (8)	0.0326 (8)	0.0039 (6)	−0.0062 (6)	−0.0042 (7)
C13	0.0246 (8)	0.0255 (7)	0.0344 (8)	0.0007 (6)	−0.0018 (6)	−0.0045 (6)
C14	0.0257 (8)	0.0388 (10)	0.0442 (10)	−0.0014 (7)	−0.0047 (7)	−0.0077 (8)
C15	0.0254 (8)	0.0340 (9)	0.0561 (12)	−0.0043 (7)	0.0050 (8)	−0.0066 (8)
C16	0.0367 (9)	0.0250 (8)	0.0442 (10)	−0.0025 (7)	0.0113 (8)	−0.0018 (7)
C17	0.0355 (9)	0.0232 (8)	0.0352 (9)	−0.0019 (6)	0.0016 (7)	0.0001 (6)
C18	0.0266 (7)	0.0164 (7)	0.0330 (8)	−0.0008 (6)	−0.0011 (6)	−0.0029 (6)
O2	0.0248 (6)	0.0308 (6)	0.0304 (6)	−0.0023 (4)	−0.0034 (4)	−0.0008 (5)
C19	0.0309 (8)	0.0266 (8)	0.0265 (8)	−0.0046 (6)	0.0083 (6)	−0.0034 (6)
C20	0.0237 (8)	0.0246 (8)	0.0377 (9)	0.0013 (6)	0.0047 (6)	−0.0053 (6)
N4	0.0224 (6)	0.0230 (6)	0.0269 (7)	−0.0008 (5)	0.0023 (5)	−0.0025 (5)
C21	0.0216 (7)	0.0280 (8)	0.0262 (7)	−0.0026 (6)	0.0026 (6)	−0.0006 (6)
C22	0.0226 (7)	0.0227 (7)	0.0245 (7)	−0.0018 (6)	0.0009 (6)	0.0010 (6)
C23	0.0315 (8)	0.0283 (8)	0.0328 (9)	−0.0072 (6)	0.0058 (7)	0.0050 (7)
C24	0.0385 (9)	0.0211 (8)	0.0486 (10)	−0.0063 (7)	0.0035 (8)	0.0059 (7)
C25	0.0402 (10)	0.0217 (8)	0.0509 (11)	−0.0003 (7)	0.0077 (8)	−0.0063 (7)
C26	0.0387 (9)	0.0281 (8)	0.0356 (9)	−0.0017 (7)	0.0125 (7)	−0.0049 (7)
C27	0.0241 (7)	0.0236 (7)	0.0217 (7)	−0.0019 (6)	−0.0004 (6)	0.0009 (6)
O3	0.0356 (6)	0.0242 (6)	0.0257 (6)	−0.0002 (5)	0.0054 (5)	0.0050 (4)
C28	0.0484 (12)	0.0695 (15)	0.0431 (11)	−0.0228 (11)	−0.0127 (9)	0.0133 (10)
C29	0.0410 (11)	0.0524 (13)	0.0582 (13)	0.0026 (9)	0.0053 (10)	0.0008 (10)
N5	0.105 (2)	0.0817 (17)	0.0743 (16)	−0.0495 (15)	−0.0320 (14)	0.0278 (13)
Cl1	0.0298 (2)	0.0318 (2)	0.0346 (2)	−0.00051 (15)	−0.00320 (16)	−0.00806 (16)
O4	0.0778 (13)	0.0586 (11)	0.1119 (17)	0.0288 (10)	−0.0151 (12)	0.0028 (11)
O5	0.0497 (9)	0.0468 (9)	0.0675 (10)	−0.0183 (7)	0.0038 (7)	−0.0143 (7)
O6	0.0635 (11)	0.0894 (13)	0.0702 (12)	−0.0249 (10)	0.0329 (9)	−0.0277 (10)
O7	0.0905 (13)	0.0724 (11)	0.0469 (9)	−0.0234 (10)	−0.0246 (9)	−0.0098 (8)

Geometric parameters (Å, º) top

Ca1—O2ⁱ	2.3269 (11)	C13—C18	1.430 (2)
Ca1—O2	2.3269 (11)	C14—C15	1.364 (3)
Ca1—O3ⁱ	2.3279 (11)	C14—H14	0.9500
Ca1—O3	2.3279 (11)	C15—C16	1.400 (3)
Ca1—O1ⁱ	2.3709 (10)	C15—H15	0.9500
Ca1—O1	2.3709 (10)	C16—C17	1.377 (3)
O1—C1	1.2993 (18)	C16—H16	0.9500
C1—C2	1.417 (2)	C17—C18	1.418 (2)
C1—C6	1.435 (2)	C17—H17	0.9500
C2—C3	1.375 (2)	C18—O2	1.3001 (19)
C2—H2	0.9500	C19—C20	1.522 (2)
C3—C4	1.403 (3)	C19—H19A	0.9900
C3—H3	0.9500	C19—H19B	0.9900
C4—C5	1.358 (3)	C20—N4	1.4642 (19)
C4—H4	0.9500	C20—H20A	0.9900
C5—C6	1.416 (2)	C20—H20B	0.9900
C5—H5	0.9500	N4—C21	1.302 (2)
C6—C7	1.413 (2)	N4—H4A	0.83 (2)
C7—N1	1.297 (2)	C21—C22	1.414 (2)
C7—H7	0.9500	C21—H21	0.9500
N1—C8	1.462 (2)	C22—C23	1.419 (2)
N1—H1A	0.85 (2)	C22—C27	1.433 (2)
C8—C9	1.522 (2)	C23—C24	1.362 (2)
C8—H8A	0.9900	C23—H23	0.9500
C8—H8B	0.9900	C24—C25	1.405 (3)
C9—N2	1.4684 (19)	C24—H24	0.9500
C9—H9A	0.9900	C25—C26	1.370 (2)
C9—H9B	0.9900	C25—H25	0.9500
N2—C19	1.468 (2)	C26—C27	1.422 (2)
N2—C10	1.470 (2)	C26—H26	0.9500
C10—C11	1.523 (2)	C27—O3	1.2908 (18)
C10—H10A	0.9900	C28—N5	1.138 (3)
C10—H10B	0.9900	C28—C29	1.447 (3)
C11—N3	1.463 (2)	C29—H29A	0.9800
C11—H11A	0.9900	C29—H29B	0.9800
C11—H11B	0.9900	C29—H29C	0.9800
N3—C12	1.300 (2)	Cl1—O7	1.4135 (16)
N3—H3A	0.86 (2)	Cl1—O4	1.4158 (18)
C12—C13	1.418 (2)	Cl1—O6	1.4209 (16)
C12—H12	0.9500	Cl1—O5	1.4368 (15)
C13—C14	1.418 (2)

O2ⁱ—Ca1—O2	180.00 (4)	N3—C12—H12	117.8
O2ⁱ—Ca1—O3ⁱ	85.33 (4)	C13—C12—H12	117.8
O2—Ca1—O3ⁱ	94.67 (4)	C14—C13—C12	118.54 (16)
O2ⁱ—Ca1—O3	94.67 (4)	C14—C13—C18	120.45 (16)
O2—Ca1—O3	85.33 (4)	C12—C13—C18	120.98 (14)
O3ⁱ—Ca1—O3	180.0	C15—C14—C13	121.02 (17)
O2ⁱ—Ca1—O1ⁱ	82.79 (4)	C15—C14—H14	119.5
O2—Ca1—O1ⁱ	97.21 (4)	C13—C14—H14	119.5
O3ⁱ—Ca1—O1ⁱ	82.23 (4)	C14—C15—C16	119.01 (16)
O3—Ca1—O1ⁱ	97.77 (4)	C14—C15—H15	120.5
O2ⁱ—Ca1—O1	97.21 (4)	C16—C15—H15	120.5
O2—Ca1—O1	82.79 (4)	C17—C16—C15	121.68 (17)
O3ⁱ—Ca1—O1	97.77 (4)	C17—C16—H16	119.2
O3—Ca1—O1	82.23 (4)	C15—C16—H16	119.2
O1ⁱ—Ca1—O1	180.00 (5)	C16—C17—C18	121.11 (17)
C1—O1—Ca1	126.86 (9)	C16—C17—H17	119.4
O1—C1—C2	122.54 (14)	C18—C17—H17	119.4
O1—C1—C6	121.28 (14)	O2—C18—C17	122.19 (15)
C2—C1—C6	116.17 (13)	O2—C18—C13	121.11 (14)
C3—C2—C1	121.52 (15)	C17—C18—C13	116.68 (15)
C3—C2—H2	119.2	C18—O2—Ca1	137.34 (10)
C1—C2—H2	119.2	N2—C19—C20	111.75 (13)
C2—C3—C4	121.61 (16)	N2—C19—H19A	109.3
C2—C3—H3	119.2	C20—C19—H19A	109.3
C4—C3—H3	119.2	N2—C19—H19B	109.3
C5—C4—C3	118.83 (16)	C20—C19—H19B	109.3
C5—C4—H4	120.6	H19A—C19—H19B	107.9
C3—C4—H4	120.6	N4—C20—C19	110.89 (13)
C4—C5—C6	121.31 (16)	N4—C20—H20A	109.5
C4—C5—H5	119.3	C19—C20—H20A	109.5
C6—C5—H5	119.3	N4—C20—H20B	109.5
C7—C6—C5	117.89 (14)	C19—C20—H20B	109.5
C7—C6—C1	121.57 (14)	H20A—C20—H20B	108.0
C5—C6—C1	120.51 (14)	C21—N4—C20	122.02 (14)
N1—C7—C6	124.81 (14)	C21—N4—H4A	115.1 (13)
N1—C7—H7	117.6	C20—N4—H4A	122.6 (14)
C6—C7—H7	117.6	N4—C21—C22	125.08 (14)
C7—N1—C8	123.40 (14)	N4—C21—H21	117.5
C7—N1—H1A	115.1 (15)	C22—C21—H21	117.5
C8—N1—H1A	121.5 (15)	C21—C22—C23	118.28 (14)
N1—C8—C9	109.29 (13)	C21—C22—C27	120.90 (14)
N1—C8—H8A	109.8	C23—C22—C27	120.76 (14)
C9—C8—H8A	109.8	C24—C23—C22	120.93 (15)
N1—C8—H8B	109.8	C24—C23—H23	119.5
C9—C8—H8B	109.8	C22—C23—H23	119.5
H8A—C8—H8B	108.3	C23—C24—C25	119.02 (16)
N2—C9—C8	110.25 (13)	C23—C24—H24	120.5
N2—C9—H9A	109.6	C25—C24—H24	120.5
C8—C9—H9A	109.6	C26—C25—C24	121.57 (16)
N2—C9—H9B	109.6	C26—C25—H25	119.2
C8—C9—H9B	109.6	C24—C25—H25	119.2
H9A—C9—H9B	108.1	C25—C26—C27	121.68 (16)
C19—N2—C9	112.74 (12)	C25—C26—H26	119.2
C19—N2—C10	112.92 (12)	C27—C26—H26	119.2
C9—N2—C10	111.41 (12)	O3—C27—C26	122.55 (14)
N2—C10—C11	111.72 (13)	O3—C27—C22	121.43 (14)
N2—C10—H10A	109.3	C26—C27—C22	116.02 (14)
C11—C10—H10A	109.3	C27—O3—Ca1	150.62 (10)
N2—C10—H10B	109.3	N5—C28—C29	178.9 (3)
C11—C10—H10B	109.3	C28—C29—H29A	109.5
H10A—C10—H10B	107.9	C28—C29—H29B	109.5
N3—C11—C10	110.31 (13)	H29A—C29—H29B	109.5
N3—C11—H11A	109.6	C28—C29—H29C	109.5
C10—C11—H11A	109.6	H29A—C29—H29C	109.5
N3—C11—H11B	109.6	H29B—C29—H29C	109.5
C10—C11—H11B	109.6	O7—Cl1—O4	109.43 (13)
H11A—C11—H11B	108.1	O7—Cl1—O6	109.65 (12)
C12—N3—C11	123.08 (15)	O4—Cl1—O6	111.50 (14)
C12—N3—H3A	113.4 (14)	O7—Cl1—O5	109.34 (11)
C11—N3—H3A	123.3 (14)	O4—Cl1—O5	109.00 (12)
N3—C12—C13	124.35 (15)	O6—Cl1—O5	107.88 (10)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1	0.85 (2)	1.98 (2)	2.6597 (17)	136 (2)
N3—H3A···O2	0.86 (2)	1.91 (2)	2.6256 (18)	140 (2)
N4—H4A···O3	0.83 (2)	1.98 (2)	2.6449 (17)	137 (2)
C3—H3···O7ⁱⁱ	0.95	2.41	3.316 (2)	160
C20—H20A···O5ⁱⁱⁱ	0.99	2.50	3.380 (2)	148
C10—H10A···O5^iv	0.99	2.50	3.271 (2)	134
C21—H21···O5ⁱⁱⁱ	0.95	2.58	3.259 (2)	129
C29—H29B···O6^v	0.98	2.58	3.555 (3)	173
C26—H26···Cg1ⁱ	0.95	2.68	3.489 (2)	143

Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, −y+1, −z+1; (iii) x−1, y−1, z; (iv) x−1/2, y−1, −z+3/2; (v) −x+3/2, y−1/2, z.

Experimental details

Crystal data
Chemical formula	[Ca(C₂₇H₃₀N₄O₃)₂](ClO₄)₂·2C₂H₃N
M_r	1238.19
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	150
a, b, c (Å)	11.3469 (7), 19.5307 (12), 27.3178 (16)
V (Å³)	6054.0 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.27
Crystal size (mm)	0.12 × 0.10 × 0.09

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.662, 0.746
No. of measured, independent and observed [I > 2.0σ(I)] reflections	55467, 6915, 5810
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.110, 1.05
No. of reflections	6915
No. of parameters	398
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.60, −0.39

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1	0.85 (2)	1.98 (2)	2.6597 (17)	136 (2)
N3—H3A···O2	0.86 (2)	1.91 (2)	2.6256 (18)	140 (2)
N4—H4A···O3	0.83 (2)	1.98 (2)	2.6449 (17)	137 (2)
C3—H3···O7ⁱ	0.95	2.41	3.316 (2)	160
C20—H20A···O5ⁱⁱ	0.99	2.50	3.380 (2)	148
C10—H10A···O5ⁱⁱⁱ	0.99	2.50	3.271 (2)	134
C21—H21···O5ⁱⁱ	0.95	2.58	3.259 (2)	129
C29—H29B···O6^iv	0.98	2.58	3.555 (3)	173
C26—H26···Cg1^v	0.95	2.68	3.489 (2)	143

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x−1, y−1, z; (iii) x−1/2, y−1, −z+3/2; (iv) −x+3/2, y−1/2, z; (v) −x+1, −y, −z+1.

Acknowledgements

We are grateful to the Turkish Government for the award of a postgraduate scholarship (to MK).

References

Bruker (2008). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Elerman, Y., Kabak, M., Svoboda, I., Fuess, H. & Atakol, O. (1995). J. Chem. Crystallogr. 25, 227–230. CSD CrossRef CAS Web of Science Google Scholar
Elerman, Y., Kabak, M., Svoboda, I. & Geselle, M. (1994). Acta Cryst. C50, 1694–1696. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Gündüz, N., Gündüz, T., Hursthouse, M. B., Parkes, H. G., Shaw (née Gözen), L. S., Shaw, R. A. & Tüzün, M. (1985). J. Chem. Soc. Perkin Trans. 2, pp. 899–902. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Steinhauser, S., Bachman, F., Hazenkamp, M., Heinz, U., Dannacher, J. & Hegetschweiler, K. (2004). Z. Kristallogr. New Cryst. Struct. 219, 325–326. CAS Google Scholar

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Volume 67| Part 2| February 2011| Page m149

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