[2,9-Bis(3,5-dimethyl-1H-pyrazol-1-yl-κN2)-1,10-phenanthroline-κ2N,N′](methanol-κO)(nitrito-κ2O,O′)cadmium(II) perchlorate

Liu, L.Z.; Chi, Y.H.; Du, H.; Shi, J.M.

doi:10.1107/S1600536811003813

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 3| March 2011| Page m330

doi:10.1107/S1600536811003813

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[2,9-Bis(3,5-dimethyl-1H-pyrazol-1-yl-κN²)-1,10-phenanthroline-κ²N,N′](methanol-κO)(nitrito-κ²O,O′)cadmium(II) perchlorate

Li Zhen Liu,^a Yan Hui Chi,^a Hua Du ^a and Jing Min Shi ^a ^*

^aCollege of Chemistry, Chemical Engineering and Materials Science, Shandong Normal University, Jinan 250014, People's Republic of China
^*Correspondence e-mail: shijingmin1955@gmail.com

(Received 26 January 2011; accepted 30 January 2011; online 12 February 2011)

In the title complex, [Cd(NO₂)(C₂₂H₂₀N₆)(CH₃OH)]ClO₄, the Cd^II ion is in a distorted pentagonal–bipyramidal CdN₄O₃ coordination geometry. The dihedral angles formed between the mean planes of the pyrazole rings and the phenanthroline ring system are 4.37 (19) and 5.84 (21)°. In the crystal, the anions and cations are connected by intermolecular O—H⋯O hydrogen bonding, while pairs of weak intermolecular C—H⋯O hydrogen bonds connect the cations into centrosymmetric dimers. In addition, there is a π–π stacking interaction involving two symmetry-related benzene rings, with a centroid–centroid distance of 3.437 (3) Å.

Related literature

For a related structure, see: Zheng & Chi (2011 ).

Experimental

Crystal data

[Cd(NO₂)(C₂₂H₂₀N₆)(CH₄O)]ClO₄
M_r = 658.34
Triclinic, $[P \overline 1]$
a = 8.0241 (17) Å
b = 11.580 (2) Å
c = 15.842 (3) Å
α = 68.595 (2)°
β = 75.578 (2)°
γ = 73.616 (3)°
V = 1297.1 (5) Å³
Z = 2
Mo Kα radiation
μ = 1.00 mm⁻¹
T = 298 K
0.32 × 0.08 × 0.04 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.740, T_max = 0.961
6780 measured reflections
4712 independent reflections
3966 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.111
S = 1.02
4712 reflections
357 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.88 e Å⁻³
Δρ_min = −0.51 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H9⋯O2ⁱ	0.87	2.02	2.892 (7)	172
C8—H8⋯O6ⁱⁱ	0.93	2.47	3.291 (6)	148
Symmetry codes: (i) x, y+1, z; (ii) -x+1, -y+1, -z+2.

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811003813/lh5203sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811003813/lh5203Isup2.hkl

checkCIF report

Comment top

Derivatives of 1,10-phenanthroline play an important role in modern coordination chemistry and many complexes have been reported with these types of compounds as ligands [see e.g. Zheng & Chi (2011) for a closely related Cd complex]. To the best of our knowledge, the above cited structure is the only other complex reported to date containing a 2,9-bis(3,5-Dimethyl-1H-pyrazol-1-yl)-1,10-phenanthroline ligand. Herein we report the crystal of the title compound (I).

The molecular structure of the title compound is shown in Fig. 1. The Cd^II ion is in a distorted pentagonal bipyramidal coordination geometry, which may be attributed to the chelation modes of the 2,9-bis(3,5-Dimethyl-1H-pyrazol-1-yl)-1,10-phenanthroline ligand and nitrite anion ligand. The dihedral angles between the planes that consist of the non-hydrogen atoms of the 1,10-phenanthroline ring system and the pyrazole rings are 4.37 (19)° (involving the pyrazole ring containing atoms N1 and N2) and 5.84 (21)° (involving the pyrazole ring containing atoms N5 and N6), respectively. In the crystal, the anion and cation are connected by an intermolecular O—H···O hydrogen bond, while pairs of weak intermolecular C—H···O hydrogen bonds connect cations into centrosymmetric dimers. In addition, there is a π–π stacking interaction involving symmetry-related complexes, the relevant distance being Cg1···Cg1ⁱ 3.437 (3) Å and Cg1···Cg1ⁱ_perp = 3.378 Å (symmetry code: (i) 2-x, 1-y, 2-z; Cg1 is the centroid of the C9-C14 benzene ring; Cg1···Cg1ⁱ_perp is the perpendicular distance from Cg1 ring to Cg1ⁱ ring).

Related literature top

For a related structure, see: Zheng & Chi (2011).

Experimental top

A 5 ml H₂O solution of NaNO₂ (0.0310 g, 0.449 mmol) was added into 8 ml methanol solution of Cd(ClO₄).6H₂O (0.0939 g,0.224 mmol) and the solution was mixed with a 10 ml dichloromethane solution of 2,9-bis(3,5-Dimethyl-1H-pyrazol-1-yl)-1,10-phenanthroline (0.0353 g, 0.112 mmol), and stirred for a few minutes. Colorless single crystals were obtained after the filtrate had been allowed to stand at room temperature for about two week.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The asymmetric unit of the title compound with displacement ellipsoids shown at the 30% probability level.

[2,9-Bis(3,5-dimethyl-1H-pyrazol-1-yl-κN²)-1,10- phenanthroline-κ²N,N'](methanol-κO)(nitrito- κ²O,O')cadmium(II) perchlorate top

Crystal data top

[Cd(NO₂)(C₂₂H₂₀N₆)(CH₄O)]ClO₄	Z = 2
M_r = 658.34	F(000) = 664
Triclinic, P1	D_x = 1.686 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.0241 (17) Å	Cell parameters from 2645 reflections
b = 11.580 (2) Å	θ = 2.7–26.3°
c = 15.842 (3) Å	µ = 1.00 mm⁻¹
α = 68.595 (2)°	T = 298 K
β = 75.578 (2)°	Prism, colorless
γ = 73.616 (3)°	0.32 × 0.08 × 0.04 mm
V = 1297.1 (5) Å³

Data collection top

Bruker SMART APEX CCD diffractometer	4712 independent reflections
Radiation source: fine-focus sealed tube	3966 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ϕ and ω scans	θ_max = 25.5°, θ_min = 1.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.740, T_max = 0.961	k = −14→12
6780 measured reflections	l = −17→19

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.111	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0606P)²] where P = (F_o² + 2F_c²)/3
4712 reflections	(Δ/σ)_max = 0.006
357 parameters	Δρ_max = 0.88 e Å⁻³
1 restraint	Δρ_min = −0.51 e Å⁻³

Crystal data top

[Cd(NO₂)(C₂₂H₂₀N₆)(CH₄O)]ClO₄	γ = 73.616 (3)°
M_r = 658.34	V = 1297.1 (5) Å³
Triclinic, P1	Z = 2
a = 8.0241 (17) Å	Mo Kα radiation
b = 11.580 (2) Å	µ = 1.00 mm⁻¹
c = 15.842 (3) Å	T = 298 K
α = 68.595 (2)°	0.32 × 0.08 × 0.04 mm
β = 75.578 (2)°

Data collection top

Bruker SMART APEX CCD diffractometer	4712 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3966 reflections with I > 2σ(I)
T_min = 0.740, T_max = 0.961	R_int = 0.025
6780 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	1 restraint
wR(F²) = 0.111	H-atom parameters constrained
S = 1.02	Δρ_max = 0.88 e Å⁻³
4712 reflections	Δρ_min = −0.51 e Å⁻³
357 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
C1	0.4749 (8)	1.0095 (5)	0.6046 (3)	0.0670 (16)
H1A	0.3887	1.0840	0.5807	0.101*
H1B	0.4778	0.9457	0.5787	0.101*
H1C	0.5887	1.0305	0.5887	0.101*
C2	0.4278 (6)	0.9603 (4)	0.7065 (3)	0.0425 (11)
C3	0.2868 (6)	1.0116 (4)	0.7631 (3)	0.0397 (10)
H3	0.1989	1.0830	0.7445	0.048*
C4	0.3026 (5)	0.9373 (4)	0.8502 (3)	0.0346 (9)
C5	0.1895 (7)	0.9562 (4)	0.9363 (3)	0.0490 (12)
H5A	0.2561	0.9772	0.9692	0.073*
H5B	0.1501	0.8795	0.9740	0.073*
H5C	0.0894	1.0240	0.9212	0.073*
C6	0.5272 (5)	0.7363 (4)	0.9123 (3)	0.0314 (9)
C7	0.4706 (6)	0.7157 (4)	1.0073 (3)	0.0388 (10)
H7	0.3818	0.7749	1.0286	0.047*
C8	0.5485 (6)	0.6075 (4)	1.0668 (3)	0.0386 (10)
H8	0.5104	0.5910	1.1297	0.046*
C9	0.7363 (5)	0.5504 (4)	0.9394 (3)	0.0322 (9)
C10	0.6865 (6)	0.5200 (4)	1.0343 (3)	0.0358 (10)
C11	0.8843 (6)	0.4699 (4)	0.9010 (3)	0.0353 (9)
C12	0.7791 (6)	0.4061 (4)	1.0927 (3)	0.0432 (11)
H12	0.7435	0.3841	1.1560	0.052*
C13	0.9732 (6)	0.3602 (4)	0.9608 (3)	0.0386 (10)
C14	0.9175 (6)	0.3300 (4)	1.0570 (3)	0.0457 (12)
H14	0.9770	0.2570	1.0962	0.055*
C15	1.1213 (6)	0.2898 (4)	0.9176 (4)	0.0488 (12)
H15	1.1866	0.2163	0.9535	0.059*
C16	1.1701 (6)	0.3275 (4)	0.8248 (4)	0.0497 (12)
H16	1.2676	0.2804	0.7970	0.060*
C17	1.0714 (6)	0.4380 (4)	0.7719 (3)	0.0410 (11)
C18	1.3989 (8)	0.3383 (5)	0.6335 (4)	0.0791 (19)
H18A	1.4800	0.3356	0.5780	0.119*
H18B	1.3571	0.2607	0.6610	0.119*
H18C	1.4572	0.3484	0.6756	0.119*
C19	1.2475 (7)	0.4470 (5)	0.6118 (4)	0.0532 (13)
C20	1.2191 (7)	0.5289 (5)	0.5292 (4)	0.0585 (15)
H20	1.2891	0.5264	0.4732	0.070*
C21	1.0657 (7)	0.6189 (5)	0.5418 (3)	0.0518 (13)
C22	0.9811 (8)	0.7316 (6)	0.4720 (4)	0.0719 (17)
H22A	0.8555	0.7452	0.4900	0.108*
H22B	1.0127	0.7175	0.4135	0.108*
H22C	1.0204	0.8050	0.4675	0.108*
C23	1.0818 (8)	0.8475 (7)	0.6558 (5)	0.092 (2)
H23A	1.1478	0.7659	0.6518	0.138*
H23B	1.1211	0.8676	0.7003	0.138*
H23C	1.0994	0.9108	0.5969	0.138*
Cd1	0.74780 (4)	0.68545 (3)	0.72015 (2)	0.03683 (13)
Cl1	0.73701 (17)	0.08191 (12)	0.81116 (9)	0.0547 (3)
N1	0.5259 (5)	0.8567 (3)	0.7550 (2)	0.0380 (8)
N2	0.4505 (4)	0.8424 (3)	0.8447 (2)	0.0319 (8)
N3	0.6559 (4)	0.6565 (3)	0.8799 (2)	0.0314 (7)
N4	0.9316 (5)	0.5065 (3)	0.8091 (2)	0.0370 (8)
N5	1.1118 (5)	0.4859 (3)	0.6750 (3)	0.0431 (9)
N6	0.9995 (5)	0.5936 (4)	0.6303 (3)	0.0482 (10)
N7	0.5172 (6)	0.6276 (5)	0.6397 (3)	0.0642 (13)
O1	0.8368 (6)	0.1605 (4)	0.8171 (4)	0.0963 (15)
O2	0.7550 (7)	0.0832 (5)	0.7196 (3)	0.1006 (16)
O3	0.5589 (6)	0.1235 (5)	0.8444 (4)	0.1071 (17)
O4	0.7972 (8)	−0.0435 (4)	0.8643 (4)	0.1132 (18)
O5	0.5944 (5)	0.7160 (4)	0.6005 (2)	0.0651 (10)
O6	0.5487 (6)	0.5674 (4)	0.7184 (3)	0.0741 (12)
O7	0.9035 (5)	0.8448 (4)	0.6826 (3)	0.0770 (13)
H9	0.8513	0.9132	0.6977	0.115*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.089 (5)	0.059 (3)	0.036 (3)	0.006 (3)	−0.008 (3)	−0.013 (3)
C2	0.050 (3)	0.039 (2)	0.034 (2)	−0.005 (2)	−0.006 (2)	−0.011 (2)
C3	0.033 (2)	0.036 (2)	0.047 (3)	0.0013 (19)	−0.0084 (19)	−0.014 (2)
C4	0.028 (2)	0.033 (2)	0.045 (2)	−0.0069 (18)	−0.0017 (18)	−0.017 (2)
C5	0.049 (3)	0.039 (3)	0.047 (3)	−0.003 (2)	0.007 (2)	−0.015 (2)
C6	0.032 (2)	0.034 (2)	0.033 (2)	−0.0123 (18)	−0.0036 (17)	−0.0124 (18)
C7	0.036 (3)	0.046 (3)	0.035 (2)	−0.008 (2)	−0.0034 (18)	−0.017 (2)
C8	0.042 (3)	0.050 (3)	0.027 (2)	−0.018 (2)	−0.0015 (18)	−0.013 (2)
C9	0.031 (2)	0.033 (2)	0.037 (2)	−0.0123 (18)	−0.0056 (17)	−0.0115 (19)
C10	0.038 (3)	0.038 (2)	0.036 (2)	−0.019 (2)	−0.0091 (18)	−0.0070 (19)
C11	0.032 (2)	0.034 (2)	0.045 (2)	−0.0085 (18)	−0.0090 (19)	−0.015 (2)
C12	0.050 (3)	0.041 (3)	0.039 (2)	−0.020 (2)	−0.014 (2)	−0.002 (2)
C13	0.036 (3)	0.027 (2)	0.057 (3)	−0.0088 (18)	−0.017 (2)	−0.011 (2)
C14	0.052 (3)	0.035 (2)	0.052 (3)	−0.013 (2)	−0.025 (2)	−0.002 (2)
C15	0.044 (3)	0.032 (2)	0.073 (4)	−0.001 (2)	−0.025 (2)	−0.015 (2)
C16	0.039 (3)	0.040 (3)	0.074 (4)	0.001 (2)	−0.010 (2)	−0.028 (3)
C17	0.035 (3)	0.034 (2)	0.060 (3)	−0.0072 (19)	−0.007 (2)	−0.022 (2)
C18	0.061 (4)	0.062 (4)	0.096 (5)	−0.009 (3)	0.030 (3)	−0.036 (3)
C19	0.043 (3)	0.051 (3)	0.072 (4)	−0.020 (2)	0.016 (2)	−0.037 (3)
C20	0.058 (4)	0.064 (3)	0.060 (3)	−0.028 (3)	0.022 (3)	−0.037 (3)
C21	0.053 (3)	0.057 (3)	0.047 (3)	−0.021 (3)	0.007 (2)	−0.021 (3)
C22	0.081 (5)	0.076 (4)	0.049 (3)	−0.023 (3)	0.006 (3)	−0.015 (3)
C23	0.057 (4)	0.104 (5)	0.134 (6)	−0.033 (4)	0.002 (4)	−0.058 (5)
Cd1	0.0373 (2)	0.0375 (2)	0.03387 (19)	−0.00520 (13)	−0.00153 (13)	−0.01417 (14)
Cl1	0.0500 (8)	0.0585 (8)	0.0617 (8)	0.0005 (6)	−0.0168 (6)	−0.0302 (7)
N1	0.039 (2)	0.040 (2)	0.0287 (18)	−0.0008 (16)	−0.0027 (15)	−0.0106 (16)
N2	0.033 (2)	0.0301 (18)	0.0301 (18)	−0.0057 (15)	−0.0016 (14)	−0.0102 (15)
N3	0.0303 (19)	0.0292 (18)	0.0362 (18)	−0.0068 (15)	−0.0036 (14)	−0.0128 (15)
N4	0.034 (2)	0.0342 (19)	0.044 (2)	−0.0069 (16)	−0.0034 (16)	−0.0162 (17)
N5	0.039 (2)	0.040 (2)	0.052 (2)	−0.0075 (17)	0.0034 (18)	−0.0238 (19)
N6	0.049 (3)	0.049 (2)	0.044 (2)	−0.007 (2)	0.0004 (18)	−0.020 (2)
N7	0.066 (3)	0.085 (4)	0.055 (3)	−0.027 (3)	−0.008 (2)	−0.032 (3)
O1	0.082 (3)	0.093 (3)	0.142 (4)	−0.022 (3)	−0.035 (3)	−0.056 (3)
O2	0.142 (5)	0.103 (4)	0.068 (3)	−0.031 (3)	−0.011 (3)	−0.040 (3)
O3	0.048 (3)	0.138 (4)	0.155 (5)	0.006 (3)	−0.012 (3)	−0.091 (4)
O4	0.141 (5)	0.061 (3)	0.127 (4)	0.006 (3)	−0.062 (4)	−0.012 (3)
O5	0.078 (3)	0.068 (2)	0.047 (2)	−0.016 (2)	−0.0138 (19)	−0.0128 (19)
O6	0.094 (3)	0.086 (3)	0.053 (2)	−0.049 (3)	−0.010 (2)	−0.013 (2)
O7	0.056 (3)	0.068 (3)	0.121 (3)	−0.027 (2)	0.023 (2)	−0.060 (3)

Geometric parameters (Å, º) top

C1—C2	1.490 (6)	C17—N4	1.320 (5)
C1—H1A	0.9600	C17—N5	1.415 (6)
C1—H1B	0.9600	C18—C19	1.486 (8)
C1—H1C	0.9600	C18—H18A	0.9600
C2—N1	1.320 (6)	C18—H18B	0.9600
C2—C3	1.393 (6)	C18—H18C	0.9600
C3—C4	1.348 (6)	C19—C20	1.336 (8)
C3—H3	0.9300	C19—N5	1.379 (6)
C4—N2	1.381 (5)	C20—C21	1.395 (7)
C4—C5	1.491 (6)	C20—H20	0.9300
C5—H5A	0.9600	C21—N6	1.323 (6)
C5—H5B	0.9600	C21—C22	1.485 (8)
C5—H5C	0.9600	C22—H22A	0.9600
C6—N3	1.315 (5)	C22—H22B	0.9600
C6—N2	1.406 (5)	C22—H22C	0.9600
C6—C7	1.409 (6)	C23—O7	1.393 (7)
C7—C8	1.356 (6)	C23—H23A	0.9600
C7—H7	0.9300	C23—H23B	0.9600
C8—C10	1.408 (6)	C23—H23C	0.9600
C8—H8	0.9300	Cd1—O7	2.334 (3)
C9—N3	1.350 (5)	Cd1—N4	2.374 (4)
C9—C10	1.393 (6)	Cd1—N3	2.377 (3)
C9—C11	1.442 (6)	Cd1—O5	2.379 (4)
C10—C12	1.430 (6)	Cd1—N6	2.387 (4)
C11—N4	1.345 (5)	Cd1—O6	2.389 (4)
C11—C13	1.402 (6)	Cd1—N1	2.393 (3)
C12—C14	1.352 (7)	Cl1—O4	1.402 (4)
C12—H12	0.9300	Cl1—O3	1.405 (5)
C13—C15	1.415 (7)	Cl1—O1	1.410 (4)
C13—C14	1.416 (6)	Cl1—O2	1.416 (4)
C14—H14	0.9300	N1—N2	1.368 (4)
C15—C16	1.360 (7)	N5—N6	1.382 (5)
C15—H15	0.9300	N7—O5	1.233 (5)
C16—C17	1.394 (6)	N7—O6	1.236 (5)
C16—H16	0.9300	O7—H9	0.8724

C2—C1—H1A	109.5	C21—C20—H20	126.0
C2—C1—H1B	109.5	N6—C21—C20	110.0 (5)
H1A—C1—H1B	109.5	N6—C21—C22	121.1 (5)
C2—C1—H1C	109.5	C20—C21—C22	128.9 (5)
H1A—C1—H1C	109.5	C21—C22—H22A	109.5
H1B—C1—H1C	109.5	C21—C22—H22B	109.5
N1—C2—C3	111.3 (4)	H22A—C22—H22B	109.5
N1—C2—C1	120.7 (4)	C21—C22—H22C	109.5
C3—C2—C1	128.1 (4)	H22A—C22—H22C	109.5
C4—C3—C2	106.5 (4)	H22B—C22—H22C	109.5
C4—C3—H3	126.7	O7—C23—H23A	109.5
C2—C3—H3	126.7	O7—C23—H23B	109.5
C3—C4—N2	106.5 (4)	H23A—C23—H23B	109.5
C3—C4—C5	127.3 (4)	O7—C23—H23C	109.5
N2—C4—C5	126.1 (4)	H23A—C23—H23C	109.5
C4—C5—H5A	109.5	H23B—C23—H23C	109.5
C4—C5—H5B	109.5	O7—Cd1—N4	102.12 (14)
H5A—C5—H5B	109.5	O7—Cd1—N3	99.06 (13)
C4—C5—H5C	109.5	N4—Cd1—N3	68.71 (11)
H5A—C5—H5C	109.5	O7—Cd1—O5	111.48 (15)
H5B—C5—H5C	109.5	N4—Cd1—O5	133.19 (12)
N3—C6—N2	114.6 (3)	N3—Cd1—O5	132.70 (13)
N3—C6—C7	122.3 (4)	O7—Cd1—N6	83.66 (13)
N2—C6—C7	123.1 (4)	N4—Cd1—N6	66.38 (13)
C8—C7—C6	118.4 (4)	N3—Cd1—N6	134.51 (13)
C8—C7—H7	120.8	O5—Cd1—N6	85.54 (14)
C6—C7—H7	120.8	O7—Cd1—O6	162.24 (16)
C7—C8—C10	120.7 (4)	N4—Cd1—O6	94.55 (14)
C7—C8—H8	119.7	N3—Cd1—O6	92.62 (12)
C10—C8—H8	119.7	O5—Cd1—O6	51.28 (13)
N3—C9—C10	122.8 (4)	N6—Cd1—O6	97.66 (14)
N3—C9—C11	117.2 (4)	O7—Cd1—N1	77.01 (13)
C10—C9—C11	119.9 (4)	N4—Cd1—N1	133.55 (11)
C9—C10—C8	116.6 (4)	N3—Cd1—N1	65.71 (11)
C9—C10—C12	119.4 (4)	O5—Cd1—N1	86.45 (13)
C8—C10—C12	124.0 (4)	N6—Cd1—N1	154.67 (13)
N4—C11—C13	123.7 (4)	O6—Cd1—N1	95.94 (14)
N4—C11—C9	117.5 (4)	O4—Cl1—O3	109.7 (4)
C13—C11—C9	118.8 (4)	O4—Cl1—O1	109.2 (3)
C14—C12—C10	120.9 (4)	O3—Cl1—O1	109.2 (3)
C14—C12—H12	119.6	O4—Cl1—O2	107.7 (3)
C10—C12—H12	119.6	O3—Cl1—O2	109.6 (3)
C11—C13—C15	115.0 (4)	O1—Cl1—O2	111.5 (3)
C11—C13—C14	120.1 (4)	C2—N1—N2	105.3 (3)
C15—C13—C14	124.8 (4)	C2—N1—Cd1	135.0 (3)
C12—C14—C13	120.8 (4)	N2—N1—Cd1	118.4 (2)
C12—C14—H14	119.6	N1—N2—C4	110.4 (3)
C13—C14—H14	119.6	N1—N2—C6	117.5 (3)
C16—C15—C13	121.3 (4)	C4—N2—C6	132.0 (3)
C16—C15—H15	119.4	C6—N3—C9	119.1 (3)
C13—C15—H15	119.4	C6—N3—Cd1	123.0 (3)
C15—C16—C17	118.8 (5)	C9—N3—Cd1	117.8 (3)
C15—C16—H16	120.6	C17—N4—C11	119.1 (4)
C17—C16—H16	120.6	C17—N4—Cd1	122.8 (3)
N4—C17—C16	122.2 (4)	C11—N4—Cd1	118.0 (3)
N4—C17—N5	114.7 (4)	C19—N5—N6	109.7 (4)
C16—C17—N5	123.2 (4)	C19—N5—C17	132.7 (4)
C19—C18—H18A	109.5	N6—N5—C17	117.6 (3)
C19—C18—H18B	109.5	C21—N6—N5	105.9 (4)
H18A—C18—H18B	109.5	C21—N6—Cd1	135.8 (4)
C19—C18—H18C	109.5	N5—N6—Cd1	118.4 (3)
H18A—C18—H18C	109.5	O5—N7—O6	113.4 (4)
H18B—C18—H18C	109.5	N7—O5—Cd1	97.9 (3)
C20—C19—N5	106.6 (5)	N7—O6—Cd1	97.4 (3)
C20—C19—C18	127.6 (5)	C23—O7—Cd1	133.0 (4)
N5—C19—C18	125.7 (5)	C23—O7—H9	106.8
C19—C20—C21	107.9 (4)	Cd1—O7—H9	118.9
C19—C20—H20	126.0

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H9···O2ⁱ	0.87	2.02	2.892 (7)	172
C8—H8···O6ⁱⁱ	0.93	2.47	3.291 (6)	148

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

Experimental details

Crystal data
Chemical formula	[Cd(NO₂)(C₂₂H₂₀N₆)(CH₄O)]ClO₄
M_r	658.34
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	8.0241 (17), 11.580 (2), 15.842 (3)
α, β, γ (°)	68.595 (2), 75.578 (2), 73.616 (3)
V (Å³)	1297.1 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.00
Crystal size (mm)	0.32 × 0.08 × 0.04

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.740, 0.961
No. of measured, independent and observed [I > 2σ(I)] reflections	6780, 4712, 3966
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.111, 1.02
No. of reflections	4712
No. of parameters	357
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.88, −0.51

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H9···O2ⁱ	0.87	2.02	2.892 (7)	172
C8—H8···O6ⁱⁱ	0.93	2.47	3.291 (6)	148

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

Acknowledgements

The authors thank the Natural Science Foundation of Shandong Province of China (No. ZR2009BM026).

References

Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zheng, L. Y. & Chi, Y. H. (2011). Acta Cryst. E67, m68. Web of Science CrossRef IUCr Journals Google Scholar

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