catena-Poly[[[diididocadmium(II)]-μ-3,3′,5,5′-tetra­methyl-4,4′-bipyrazolyl-κ²N:N′] methanol solvate]

The substituted bipyrazole heterocycle in the title compound, {[CdI₂(C₁₀H₁₂N₄)]·CH₄O}_n, links CdI₂ units into a helical chain which runs parallel to the b axis of the monoclinic unit cell. One of the two –NH sites forms a hydrogen bond with a solvent methanol mol­ecule. The Cd^II atom is in a slightly distorted tetra­hedral coordination environment.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.031
• wR factor = 0.090
• Data-to-parameter ratio = 17.3

checkCIF/PLATON results

No syntax errors found



Alert level C
ABSTM02_ALERT_3_C  The ratio of expected to reported Tmax/Tmin(RR) is > 1.10
            Tmin and Tmax reported:      0.255     0.625
            Tmin and Tmax expected:      0.206     0.596
            RR =      1.178
            Please check that your absorption correction is appropriate.
PLAT060_ALERT_3_C Ratio Tmax/Tmin (Exp-to-Rep) (too) Large .......       1.16
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.95
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        Cd1
PLAT420_ALERT_2_C D-H Without Acceptor       N2     -   H2     ...          ?

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT794_ALERT_5_G Check Predicted Bond Valency for Cd1         (2)       2.24

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   6 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

---

S1. Comment

3,3',5,5'-Tetramethyl-4,4'-bipyrazolyl in its doubly-deprotonated form is capable of connecting to four metal sites (Boldog et al., 2001; Boldog, Rusanov et al., 2003; Boldog, Sieler et al., 2003; He et al., 2006; Ponomarova et al., 2002). The disilver(I) derivative exemplifies such a feature; the framework is porous (Zhang et al., 2007). The attempted synthesis of the cadmium derivative yielded an adduct, the neutral heterocycle binding to cadmium diiodide in a 1:1 molar stoichoimetry. The compound crystallizes with a molecule of methanol. The title compound exists as helical chain that runs along the b-axis of the unit cell; the methanol molecules are linked to the chain by hydrogen bonds, with the –NH group serving as donor.

Related literature

For the synthesis of 3,3',5,5'-tetramethyl-4,4'-bipyrazole, see: Mosby (1957). For literature on other metal derivatives of 3,3',5,5'-tetramethyl-4,4'-bipyrazole, see: Boldog et al. (2001); Boldog, Rusanov et al. (2003); Boldog, Sieler et al. (2003); He et al. (2006); Ponomarova et al. (2002); Zhang et al. (2007).

S2. Experimental

3,3',5,5'-Tetramethyl-4,4'-bipyrazolyl was synthesized by using a reported procedure (Mosby, 1957). The ligand (0.02 g, 0.1 mmol), cadmium iodide (0.07 g, 0.2 mmol), potassium iodide (0.03 g, 0.2 mmol), methanol (5 ml) and water (5 ml) were mixed in a 15-ml Telfon-lined, stainless-steel Parr bomb. The bomb was heated at 423 K for 72 h and then cooled to room temperature at a rate of 5 K h-1. The resulting solution was left for two days to give colorless block-shaped crystals in about 70% yield.

S3. Refinement

All H atoms were generated geometrically (O—H 0.82, N—H 0.86 Å and C—H 0.96 Å), and were included in the refinement in the riding model approximation, with U(H) set to 1.2 or 1.5U_eq(C,N,O).

Computing details

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2007).

Figures

Fig. 1. Thermal ellipsoid plot of a portion of the chain structure of [(C10H12N4)I2Cd.CH4O]n; displacement ellipsoids are drawn at the 70% probability level, and H atoms as spheres of arbitrary radius. The lattice methanol is not shown. [Symmetry code (i): 1/2 - x, y - 1/2, 1/2 - z].

catena-Poly[[[diididocadmium(II)]-µ-3,3',5,5'-tetramethyl-4,4'- bipyrazolyl-κ²N:N'] methanol solvate]

Crystal data

[CdI2(C10H12N4)]·CH4O	F(000) = 1096
Mr = 588.49	Dx = 2.204 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4773 reflections
a = 11.1294 (6) Å	θ = 2.2–27.2°
b = 12.2109 (7) Å	µ = 4.71 mm^−1
c = 13.2924 (7) Å	T = 293 K
β = 101.008 (1)°	Block, colourless
V = 1773.2 (2) Å^3	0.35 × 0.30 × 0.11 mm
Z = 4

Data collection

Bruker APEX area-detector diffractometer	3077 independent reflections
Radiation source: fine-focus sealed tube	2813 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
φ and ω scans	θmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→13
Tmin = 0.255, Tmax = 0.625	k = −13→14
8299 measured reflections	l = −14→15

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.090	H-atom parameters constrained
S = 1.11	w = 1/[σ^2(Fo^2) + (0.048P)^2 + 2.2498P] where P = (Fo^2 + 2Fc^2)/3
3077 reflections	(Δ/σ)max = 0.001
178 parameters	Δρmax = 0.93 e Å^−3
0 restraints	Δρmin = −0.90 e Å^−3

Special details

Experimental. High-angle reflections were omitted as their inclusion led to somewhat large peaks and deep holes near the iodine atoms.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
I1	0.70846 (4)	0.50859 (4)	0.42967 (3)	0.06227 (15)
I2	0.72925 (4)	0.63673 (4)	0.10377 (3)	0.06328 (16)
Cd1	0.59541 (3)	0.59870 (3)	0.24959 (3)	0.03701 (13)
O1	0.1126 (6)	1.2458 (4)	0.5060 (4)	0.0839 (15)
H1	0.1723	1.2865	0.5149	0.126*
N1	0.5170 (3)	0.7677 (3)	0.2704 (3)	0.0374 (9)
N2	0.5426 (4)	0.8568 (3)	0.2178 (3)	0.0406 (10)
H2	0.6002	0.8594	0.1830	0.049*
N3	0.0920 (3)	1.0264 (3)	0.3095 (3)	0.0373 (9)
N4	0.1727 (4)	1.0898 (3)	0.3735 (3)	0.0384 (9)
H4	0.1519	1.1447	0.4069	0.046*
C1	0.3664 (5)	0.7180 (4)	0.3772 (4)	0.0488 (13)
H1A	0.3066	0.6737	0.3338	0.073*
H1B	0.3277	0.7579	0.4245	0.073*
H1C	0.4293	0.6718	0.4145	0.073*
C2	0.4215 (4)	0.7964 (4)	0.3133 (4)	0.0354 (10)
C3	0.3872 (4)	0.9052 (4)	0.2869 (4)	0.0352 (10)
C4	0.4669 (4)	0.9408 (4)	0.2266 (4)	0.0368 (10)
C5	0.4749 (5)	1.0490 (4)	0.1743 (5)	0.0514 (14)
H5A	0.5112	1.1024	0.2240	0.077*
H5B	0.3943	1.0726	0.1427	0.077*
H5C	0.5244	1.0412	0.1230	0.077*
C6	0.1046 (5)	0.8661 (4)	0.1984 (5)	0.0523 (14)
H6A	0.0299	0.8405	0.2164	0.078*
H6B	0.1606	0.8060	0.2003	0.078*
H6C	0.0873	0.8965	0.1306	0.078*
C7	0.1599 (4)	0.9514 (4)	0.2722 (4)	0.0353 (10)
C8	0.2850 (4)	0.9679 (4)	0.3138 (4)	0.0334 (10)
C9	0.2887 (4)	1.0570 (4)	0.3788 (4)	0.0362 (10)
C10	0.3915 (5)	1.1113 (4)	0.4491 (5)	0.0499 (13)
H10A	0.3749	1.1882	0.4526	0.075*
H10B	0.4660	1.1009	0.4240	0.075*
H10C	0.3999	1.0798	0.5163	0.075*
C11	0.1035 (11)	1.1962 (7)	0.5970 (7)	0.110 (3)
H11A	0.1789	1.1593	0.6243	0.165*
H11B	0.0378	1.1440	0.5855	0.165*
H11C	0.0876	1.2506	0.6450	0.165*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.0510 (2)	0.0729 (3)	0.0595 (3)	−0.00489 (18)	0.00184 (19)	0.0232 (2)
I2	0.0582 (3)	0.0767 (3)	0.0645 (3)	−0.00017 (19)	0.0359 (2)	0.0071 (2)
Cd1	0.02859 (19)	0.0373 (2)	0.0473 (2)	0.00236 (13)	0.01280 (16)	0.00152 (15)
O1	0.108 (4)	0.060 (3)	0.090 (4)	−0.007 (3)	0.036 (3)	−0.023 (3)
N1	0.034 (2)	0.033 (2)	0.047 (2)	0.0043 (16)	0.0137 (18)	−0.0008 (17)
N2	0.034 (2)	0.041 (2)	0.051 (3)	−0.0006 (17)	0.0182 (19)	0.0022 (19)
N3	0.0305 (19)	0.040 (2)	0.043 (2)	0.0010 (17)	0.0102 (18)	−0.0054 (18)
N4	0.036 (2)	0.038 (2)	0.041 (2)	0.0054 (17)	0.0073 (18)	−0.0076 (17)
C1	0.053 (3)	0.041 (3)	0.058 (3)	0.004 (2)	0.025 (3)	0.006 (2)
C2	0.036 (2)	0.035 (2)	0.037 (3)	0.0016 (19)	0.011 (2)	−0.0009 (19)
C3	0.029 (2)	0.036 (2)	0.041 (3)	−0.0002 (19)	0.006 (2)	−0.001 (2)
C4	0.030 (2)	0.035 (2)	0.045 (3)	0.0005 (19)	0.008 (2)	−0.001 (2)
C5	0.044 (3)	0.048 (3)	0.065 (4)	0.004 (2)	0.017 (3)	0.013 (3)
C6	0.042 (3)	0.050 (3)	0.065 (4)	0.004 (2)	0.010 (3)	−0.020 (3)
C7	0.035 (2)	0.033 (2)	0.040 (3)	0.0041 (19)	0.013 (2)	−0.001 (2)
C8	0.033 (2)	0.032 (2)	0.036 (3)	0.0047 (19)	0.0096 (19)	0.0036 (19)
C9	0.034 (2)	0.033 (2)	0.041 (3)	0.0053 (19)	0.006 (2)	0.004 (2)
C10	0.047 (3)	0.042 (3)	0.056 (4)	0.005 (2)	−0.003 (3)	−0.005 (2)
C11	0.190 (11)	0.061 (4)	0.091 (6)	0.000 (5)	0.058 (7)	−0.010 (4)

Geometric parameters (Å, º)

I1—Cd1	2.7154 (5)	C3—C4	1.375 (7)
I2—Cd1	2.7008 (5)	C3—C8	1.470 (6)
Cd1—N1	2.277 (4)	C4—C5	1.503 (7)
Cd1—N3^i	2.263 (4)	C5—H5A	0.9600
O1—C11	1.374 (10)	C5—H5B	0.9600
O1—H1	0.8200	C5—H5C	0.9600
N1—C2	1.345 (6)	C6—C7	1.482 (7)
N1—N2	1.353 (5)	C6—H6A	0.9600
N2—C4	1.347 (6)	C6—H6B	0.9600
N2—H2	0.8600	C6—H6C	0.9600
N3—C7	1.341 (6)	C7—C8	1.411 (6)
N3—N4	1.356 (6)	C8—C9	1.386 (7)
N3—Cd1^ii	2.263 (4)	C9—C10	1.488 (7)
N4—C9	1.341 (6)	C10—H10A	0.9600
N4—H4	0.8600	C10—H10B	0.9600
C1—C2	1.488 (7)	C10—H10C	0.9600
C1—H1A	0.9600	C11—H11A	0.9600
C1—H1B	0.9600	C11—H11B	0.9600
C1—H1C	0.9600	C11—H11C	0.9600
C2—C3	1.409 (6)
I1—Cd1—I2	118.43 (2)	C4—C5—H5A	109.5
I1—Cd1—N1	112.6 (1)	C4—C5—H5B	109.5
I1—Cd1—N3^i	112.9 (1)	H5A—C5—H5B	109.5
I2—Cd1—N1	102.0 (1)	C4—C5—H5C	109.5
I2—Cd1—N3^i	114.6 (1)	H5A—C5—H5C	109.5
N1—Cd1—N3^i	92.7 (1)	H5B—C5—H5C	109.5
C11—O1—H1	109.5	C7—C6—H6A	109.5
C2—N1—N2	105.7 (4)	C7—C6—H6B	109.5
C2—N1—Cd1	129.7 (3)	H6A—C6—H6B	109.5
N2—N1—Cd1	122.9 (3)	C7—C6—H6C	109.5
C4—N2—N1	111.8 (4)	H6A—C6—H6C	109.5
C4—N2—H2	124.1	H6B—C6—H6C	109.5
N1—N2—H2	124.1	N3—C7—C8	110.0 (4)
C7—N3—N4	105.6 (4)	N3—C7—C6	122.2 (4)
C7—N3—Cd1^ii	133.2 (3)	C8—C7—C6	127.9 (4)
N4—N3—Cd1^ii	116.8 (3)	C9—C8—C7	105.4 (4)
C9—N4—N3	112.2 (4)	C9—C8—C3	128.9 (4)
C9—N4—H4	123.9	C7—C8—C3	125.6 (4)
N3—N4—H4	123.9	N4—C9—C8	106.7 (4)
C2—C1—H1A	109.5	N4—C9—C10	121.1 (4)
C2—C1—H1B	109.5	C8—C9—C10	132.1 (4)
H1A—C1—H1B	109.5	C9—C10—H10A	109.5
C2—C1—H1C	109.5	C9—C10—H10B	109.5
H1A—C1—H1C	109.5	H10A—C10—H10B	109.5
H1B—C1—H1C	109.5	C9—C10—H10C	109.5
N1—C2—C3	109.8 (4)	H10A—C10—H10C	109.5
N1—C2—C1	121.3 (4)	H10B—C10—H10C	109.5
C3—C2—C1	128.9 (4)	O1—C11—H11A	109.5
C4—C3—C2	105.6 (4)	O1—C11—H11B	109.5
C4—C3—C8	126.3 (4)	H11A—C11—H11B	109.5
C2—C3—C8	128.0 (4)	O1—C11—H11C	109.5
N2—C4—C3	107.1 (4)	H11A—C11—H11C	109.5
N2—C4—C5	122.4 (4)	H11B—C11—H11C	109.5
C3—C4—C5	130.5 (4)
N3^i—Cd1—N1—C2	46.2 (4)	C8—C3—C4—N2	−177.3 (5)
I2—Cd1—N1—C2	162.0 (4)	C2—C3—C4—C5	179.1 (5)
I1—Cd1—N1—C2	−70.0 (4)	C8—C3—C4—C5	1.2 (9)
N3^i—Cd1—N1—N2	−116.9 (4)	N4—N3—C7—C8	0.2 (5)
I2—Cd1—N1—N2	−1.1 (4)	Cd1^ii—N3—C7—C8	155.2 (3)
I1—Cd1—N1—N2	126.9 (3)	N4—N3—C7—C6	−179.9 (5)
C2—N1—N2—C4	0.3 (5)	Cd1^ii—N3—C7—C6	−24.8 (7)
Cd1—N1—N2—C4	166.9 (3)	N3—C7—C8—C9	0.2 (5)
C7—N3—N4—C9	−0.6 (5)	C6—C7—C8—C9	−179.7 (5)
Cd1^ii—N3—N4—C9	−160.4 (3)	N3—C7—C8—C3	−176.7 (4)
N2—N1—C2—C3	0.0 (5)	C6—C7—C8—C3	3.4 (8)
Cd1—N1—C2—C3	−165.3 (3)	C4—C3—C8—C9	−71.1 (7)
N2—N1—C2—C1	179.5 (5)	C2—C3—C8—C9	111.5 (6)
Cd1—N1—C2—C1	14.1 (7)	C4—C3—C8—C7	105.1 (6)
N1—C2—C3—C4	−0.3 (6)	C2—C3—C8—C7	−72.3 (7)
C1—C2—C3—C4	−179.7 (5)	N3—N4—C9—C8	0.8 (5)
N1—C2—C3—C8	177.5 (5)	N3—N4—C9—C10	−176.5 (4)
C1—C2—C3—C8	−1.9 (8)	C7—C8—C9—N4	−0.6 (5)
N1—N2—C4—C3	−0.6 (6)	C3—C8—C9—N4	176.2 (5)
N1—N2—C4—C5	−179.3 (5)	C7—C8—C9—C10	176.2 (5)
C2—C3—C4—N2	0.5 (5)	C3—C8—C9—C10	−7.0 (9)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···O1	0.86	1.92	2.762 (6)	168