1-[3-(4-Chloro­phen­yl)isoquinolin-1-yl]-3,5-diethyl-1H-pyrazole

Khan, F.N.; Manivel, P.; Prabakaran, K.; Hathwar, V.R.; Ng, S.W.

doi:10.1107/S1600536809055731

organic compounds

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ISSN: 2056-9890

Volume 66| Part 2| February 2010| Page o370

https://doi.org/10.1107/S1600536809055731

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1-[3-(4-Chlorophenyl)isoquinolin-1-yl]-3,5-diethyl-1H-pyrazole

F. Nawaz Khan,^a P. Manivel,^b K. Prabakaran,^b Venkatesha R. Hathwar ^c and Seik Weng Ng ^d ^*

^aChemistry Division, School of Science and Humanities, VIT University, Vellore 632 014, Tamil Nadu, India, ^bChemistry Division, School of Advanced Sciences, VIT University, Vellore 632 014, Tamil Nadu, India, ^cSolid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560 012, Karnataka, India, and ^dDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 28 December 2009; accepted 30 December 2009; online 16 January 2010)

The title compound, C₂₂H₂₀ClN₃, is composed of a dialkyl-substituted pyrazole ring connected to an aryl-substituted isoquinoline ring system with a dihedral angle of 55.8 (1)° between the pyrazole ring and and the isoquinoline ring system. The dihedral angle between the chlorophenyl ring and the isoquinoline ring system is 28.3 (1)°.

Related literature

For medicinal applications of hydrazine derivatives, see: Broadhurst et al. (2001 ).

Experimental

Crystal data

C₂₂H₂₀ClN₃
M_r = 361.86
Monoclinic, P 2₁ /n
a = 8.4484 (6) Å
b = 15.0386 (12) Å
c = 15.4894 (11) Å
β = 96.763 (1)°
V = 1954.3 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 290 K
0.25 × 0.18 × 0.15 mm

Data collection

Bruker SMART area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.951, T_max = 0.970
14613 measured reflections
3703 independent reflections
2235 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.062
wR(F²) = 0.177
S = 1.03
3703 reflections
235 parameters
H-atom parameters constrained
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Data collection: SMART (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536809055731/bt5161sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809055731/bt5161Isup2.hkl

checkCIF report

Related literature top

For medicinal applications of hydrazine derivatives, see: Broadhurst et al. (2001).

Experimental top

1-(3-(4-Chlorophenyl)isoquinolin-1-yl)hydrazine (2.69 g, 10mmol) and heptane-3,5-dione (1.28 g, 10 mmol) were dissolved in ethanol (30 ml). The solution was heated for 12 h under a nitrogen atmosphere. The reaction was quenched with water; the compound was extracted with ethyl acetate. The ethyl acetate phase was washed with water, dried, concentrated and purified by column chromatography to yield a white powder. Crystals were were obtained upon recrystallization from dichloromethane.

Structure description top

For medicinal applications of hydrazine derivatives, see: Broadhurst et al. (2001).

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. Anisotropic displacement ellipsoid plot (Barbour, 2001) of C₂₂H₂₀ClN₃ at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

1-[3-(4-Chlorophenyl)isoquinolin-1-yl]-3,5-diethyl-1H-pyrazole top

Crystal data top

C₂₂H₂₀ClN₃	F(000) = 760
M_r = 361.86	D_x = 1.230 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2329 reflections
a = 8.4484 (6) Å	θ = 2.6–20.1°
b = 15.0386 (12) Å	µ = 0.21 mm⁻¹
c = 15.4894 (11) Å	T = 290 K
β = 96.763 (1)°	Block, colorless
V = 1954.3 (3) Å³	0.25 × 0.18 × 0.15 mm
Z = 4

Data collection top

Bruker SMART area-detector diffractometer	3703 independent reflections
Radiation source: fine-focus sealed tube	2235 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
φ and ω scans	θ_max = 25.7°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→9
T_min = 0.951, T_max = 0.970	k = −18→18
14613 measured reflections	l = −18→18

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)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.177	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.081P)² + 0.4577P] where P = (F_o² + 2F_c²)/3
3703 reflections	(Δ/σ)_max = 0.001
235 parameters	Δρ_max = 0.46 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₂₂H₂₀ClN₃	V = 1954.3 (3) Å³
M_r = 361.86	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.4484 (6) Å	µ = 0.21 mm⁻¹
b = 15.0386 (12) Å	T = 290 K
c = 15.4894 (11) Å	0.25 × 0.18 × 0.15 mm
β = 96.763 (1)°

Data collection top

Bruker SMART area-detector diffractometer	3703 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2235 reflections with I > 2σ(I)
T_min = 0.951, T_max = 0.970	R_int = 0.040
14613 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.062	0 restraints
wR(F²) = 0.177	H-atom parameters constrained
S = 1.03	Δρ_max = 0.46 e Å⁻³
3703 reflections	Δρ_min = −0.19 e Å⁻³
235 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.04502 (15)	0.45817 (9)	0.90130 (7)	0.1233 (5)
N1	0.3419 (2)	0.36347 (13)	0.53000 (14)	0.0507 (5)
N2	0.3322 (3)	0.30349 (14)	0.39224 (14)	0.0567 (6)
N3	0.3354 (3)	0.34178 (16)	0.31188 (16)	0.0691 (7)
C1	0.4218 (3)	0.34365 (16)	0.46595 (17)	0.0508 (6)
C2	0.5882 (3)	0.35802 (16)	0.46517 (18)	0.0539 (7)
C3	0.6777 (4)	0.3266 (2)	0.4002 (2)	0.0708 (8)
H3	0.6272	0.2958	0.3526	0.085*
C4	0.8377 (4)	0.3411 (2)	0.4069 (3)	0.0842 (10)
H4	0.8964	0.3191	0.3645	0.101*
C5	0.9138 (4)	0.3887 (2)	0.4766 (3)	0.0838 (10)
H5	1.0228	0.3992	0.4797	0.101*
C6	0.8312 (3)	0.4201 (2)	0.5405 (2)	0.0740 (9)
H6	0.8841	0.4519	0.5867	0.089*
C7	0.6650 (3)	0.40456 (16)	0.53719 (19)	0.0561 (7)
C8	0.5763 (3)	0.42863 (17)	0.60411 (18)	0.0572 (7)
H8	0.6246	0.4608	0.6513	0.069*
C9	0.4196 (3)	0.40544 (16)	0.60104 (16)	0.0497 (6)
C10	0.3237 (3)	0.42168 (17)	0.67334 (17)	0.0527 (7)
C11	0.3598 (4)	0.48974 (19)	0.73263 (18)	0.0660 (8)
H11	0.4439	0.5280	0.7257	0.079*
C12	0.2736 (4)	0.5017 (2)	0.8014 (2)	0.0806 (9)
H12	0.2991	0.5477	0.8408	0.097*
C13	0.1495 (4)	0.4454 (2)	0.8118 (2)	0.0756 (9)
C14	0.1079 (4)	0.3787 (2)	0.7535 (2)	0.0753 (9)
H14	0.0224	0.3415	0.7603	0.090*
C15	0.1948 (3)	0.3675 (2)	0.68431 (19)	0.0654 (8)
H15	0.1664	0.3226	0.6442	0.078*
C16	0.3239 (8)	0.3364 (4)	0.1205 (3)	0.170 (2)
H16A	0.2865	0.3496	0.0609	0.254*
H16B	0.3950	0.2865	0.1229	0.254*
H16C	0.3792	0.3871	0.1468	0.254*
C17	0.1949 (6)	0.3162 (3)	0.1649 (2)	0.1121 (14)
H17A	0.1385	0.2663	0.1361	0.135*
H17B	0.1227	0.3666	0.1599	0.135*
C18	0.2325 (4)	0.2938 (2)	0.25986 (19)	0.0704 (8)
C19	0.1668 (4)	0.2265 (2)	0.30509 (19)	0.0678 (8)
H19	0.0936	0.1841	0.2820	0.081*
C20	0.2294 (3)	0.23392 (18)	0.38943 (19)	0.0580 (7)
C21	0.2030 (4)	0.1809 (2)	0.4678 (2)	0.0755 (9)
H21A	0.3054	0.1626	0.4973	0.091*
H21B	0.1518	0.2183	0.5074	0.091*
C23	0.1027 (5)	0.1005 (3)	0.4464 (3)	0.1153 (15)
H23A	0.0896	0.0689	0.4989	0.173*
H23B	0.1538	0.0626	0.4082	0.173*
H23C	0.0002	0.1183	0.4183	0.173*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.1396 (10)	0.1493 (10)	0.0907 (8)	0.0002 (8)	0.0536 (7)	−0.0141 (7)
N1	0.0447 (12)	0.0527 (12)	0.0538 (13)	−0.0062 (10)	0.0020 (10)	−0.0004 (10)
N2	0.0556 (14)	0.0604 (14)	0.0539 (14)	−0.0113 (11)	0.0048 (11)	−0.0057 (11)
N3	0.0807 (18)	0.0707 (16)	0.0554 (15)	−0.0148 (13)	0.0055 (13)	0.0011 (12)
C1	0.0492 (16)	0.0455 (14)	0.0565 (17)	−0.0060 (11)	0.0009 (13)	0.0010 (12)
C2	0.0451 (15)	0.0481 (14)	0.0683 (18)	−0.0035 (12)	0.0062 (13)	0.0085 (13)
C3	0.063 (2)	0.0708 (19)	0.081 (2)	0.0019 (15)	0.0174 (17)	0.0037 (16)
C4	0.061 (2)	0.087 (2)	0.109 (3)	0.0079 (17)	0.027 (2)	0.010 (2)
C5	0.0443 (18)	0.088 (2)	0.120 (3)	−0.0014 (17)	0.012 (2)	0.027 (2)
C6	0.0460 (17)	0.077 (2)	0.095 (2)	−0.0096 (15)	−0.0072 (17)	0.0142 (18)
C7	0.0455 (15)	0.0492 (15)	0.0711 (18)	−0.0055 (12)	−0.0042 (14)	0.0141 (13)
C8	0.0540 (17)	0.0527 (15)	0.0609 (17)	−0.0079 (13)	−0.0097 (14)	0.0028 (13)
C9	0.0480 (16)	0.0459 (14)	0.0523 (16)	−0.0046 (12)	−0.0064 (12)	0.0045 (12)
C10	0.0516 (16)	0.0515 (15)	0.0523 (15)	0.0029 (12)	−0.0049 (12)	0.0064 (12)
C11	0.074 (2)	0.0614 (17)	0.0616 (18)	−0.0055 (15)	0.0018 (16)	−0.0036 (15)
C12	0.098 (3)	0.080 (2)	0.062 (2)	−0.0021 (19)	0.0049 (18)	−0.0152 (17)
C13	0.084 (2)	0.087 (2)	0.0566 (19)	0.0108 (19)	0.0129 (16)	0.0040 (17)
C14	0.070 (2)	0.084 (2)	0.073 (2)	−0.0059 (17)	0.0134 (17)	0.0072 (18)
C15	0.0614 (18)	0.0712 (19)	0.0627 (18)	−0.0079 (15)	0.0035 (15)	−0.0034 (14)
C16	0.183 (6)	0.225 (7)	0.097 (4)	−0.021 (5)	0.000 (4)	0.037 (4)
C17	0.162 (4)	0.105 (3)	0.071 (3)	−0.028 (3)	0.020 (3)	−0.007 (2)
C18	0.078 (2)	0.078 (2)	0.0541 (18)	−0.0048 (17)	0.0019 (16)	−0.0130 (16)
C19	0.0670 (19)	0.0709 (19)	0.065 (2)	−0.0160 (15)	0.0042 (15)	−0.0193 (16)
C20	0.0536 (16)	0.0571 (16)	0.0639 (18)	−0.0119 (13)	0.0100 (13)	−0.0113 (14)
C21	0.083 (2)	0.0689 (19)	0.076 (2)	−0.0276 (16)	0.0127 (17)	−0.0040 (16)
C23	0.142 (4)	0.096 (3)	0.109 (3)	−0.060 (3)	0.015 (3)	0.001 (2)

Geometric parameters (Å, º) top

Cl1—C13	1.739 (3)	C11—H11	0.9300
N1—C1	1.299 (3)	C12—C13	1.372 (5)
N1—C9	1.368 (3)	C12—H12	0.9300
N2—C20	1.357 (3)	C13—C14	1.368 (4)
N2—N3	1.375 (3)	C14—C15	1.378 (4)
N2—C1	1.428 (3)	C14—H14	0.9300
N3—C18	1.327 (4)	C15—H15	0.9300
C1—C2	1.424 (4)	C16—C17	1.390 (6)
C2—C7	1.409 (4)	C16—H16A	0.9600
C2—C3	1.410 (4)	C16—H16B	0.9600
C3—C4	1.361 (4)	C16—H16C	0.9600
C3—H3	0.9300	C17—C18	1.505 (5)
C4—C5	1.389 (5)	C17—H17A	0.9700
C4—H4	0.9300	C17—H17B	0.9700
C5—C6	1.361 (4)	C18—C19	1.384 (4)
C5—H5	0.9300	C19—C20	1.355 (4)
C6—C7	1.418 (4)	C19—H19	0.9300
C6—H6	0.9300	C20—C21	1.491 (4)
C7—C8	1.396 (4)	C21—C23	1.491 (4)
C8—C9	1.364 (4)	C21—H21A	0.9700
C8—H8	0.9300	C21—H21B	0.9700
C9—C10	1.478 (4)	C23—H23A	0.9600
C10—C15	1.387 (4)	C23—H23B	0.9600
C10—C11	1.385 (4)	C23—H23C	0.9600
C11—C12	1.372 (4)

C1—N1—C9	118.5 (2)	C14—C13—Cl1	119.6 (3)
C20—N2—N3	112.0 (2)	C12—C13—Cl1	119.5 (3)
C20—N2—C1	129.0 (2)	C13—C14—C15	119.0 (3)
N3—N2—C1	118.8 (2)	C13—C14—H14	120.5
C18—N3—N2	103.9 (2)	C15—C14—H14	120.5
N1—C1—C2	125.1 (2)	C14—C15—C10	121.4 (3)
N1—C1—N2	115.7 (2)	C14—C15—H15	119.3
C2—C1—N2	119.3 (2)	C10—C15—H15	119.3
C7—C2—C3	119.8 (3)	C17—C16—H16A	109.5
C7—C2—C1	115.6 (3)	C17—C16—H16B	109.5
C3—C2—C1	124.6 (3)	H16A—C16—H16B	109.5
C4—C3—C2	120.2 (3)	C17—C16—H16C	109.5
C4—C3—H3	119.9	H16A—C16—H16C	109.5
C2—C3—H3	119.9	H16B—C16—H16C	109.5
C3—C4—C5	120.4 (3)	C16—C17—C18	116.5 (4)
C3—C4—H4	119.8	C16—C17—H17A	108.2
C5—C4—H4	119.8	C18—C17—H17A	108.2
C6—C5—C4	121.0 (3)	C16—C17—H17B	108.2
C6—C5—H5	119.5	C18—C17—H17B	108.2
C4—C5—H5	119.5	H17A—C17—H17B	107.3
C5—C6—C7	120.4 (3)	N3—C18—C19	111.3 (3)
C5—C6—H6	119.8	N3—C18—C17	121.3 (3)
C7—C6—H6	119.8	C19—C18—C17	127.4 (3)
C8—C7—C2	118.6 (2)	C20—C19—C18	107.1 (3)
C8—C7—C6	123.1 (3)	C20—C19—H19	126.5
C2—C7—C6	118.2 (3)	C18—C19—H19	126.5
C9—C8—C7	120.7 (3)	C19—C20—N2	105.7 (3)
C9—C8—H8	119.6	C19—C20—C21	131.5 (3)
C7—C8—H8	119.6	N2—C20—C21	122.9 (2)
C8—C9—N1	121.2 (3)	C23—C21—C20	112.8 (3)
C8—C9—C10	123.2 (2)	C23—C21—H21A	109.0
N1—C9—C10	115.6 (2)	C20—C21—H21A	109.0
C15—C10—C11	117.9 (3)	C23—C21—H21B	109.0
C15—C10—C9	120.3 (2)	C20—C21—H21B	109.0
C11—C10—C9	121.8 (3)	H21A—C21—H21B	107.8
C12—C11—C10	121.1 (3)	C21—C23—H23A	109.5
C12—C11—H11	119.5	C21—C23—H23B	109.5
C10—C11—H11	119.5	H23A—C23—H23B	109.5
C11—C12—C13	119.6 (3)	C21—C23—H23C	109.5
C11—C12—H12	120.2	H23A—C23—H23C	109.5
C13—C12—H12	120.2	H23B—C23—H23C	109.5
C14—C13—C12	121.0 (3)

C20—N2—N3—C18	−0.2 (3)	C8—C9—C10—C15	−152.8 (3)
C1—N2—N3—C18	−175.2 (2)	N1—C9—C10—C15	26.0 (3)
C9—N1—C1—C2	3.5 (4)	C8—C9—C10—C11	26.3 (4)
C9—N1—C1—N2	−177.3 (2)	N1—C9—C10—C11	−154.9 (2)
C20—N2—C1—N1	−49.0 (4)	C15—C10—C11—C12	1.8 (4)
N3—N2—C1—N1	125.1 (3)	C9—C10—C11—C12	−177.3 (3)
C20—N2—C1—C2	130.3 (3)	C10—C11—C12—C13	0.0 (5)
N3—N2—C1—C2	−55.7 (3)	C11—C12—C13—C14	−1.5 (5)
N1—C1—C2—C7	−5.9 (4)	C11—C12—C13—Cl1	177.7 (2)
N2—C1—C2—C7	174.9 (2)	C12—C13—C14—C15	1.3 (5)
N1—C1—C2—C3	171.8 (3)	Cl1—C13—C14—C15	−178.0 (2)
N2—C1—C2—C3	−7.3 (4)	C13—C14—C15—C10	0.6 (5)
C7—C2—C3—C4	0.0 (4)	C11—C10—C15—C14	−2.1 (4)
C1—C2—C3—C4	−177.7 (3)	C9—C10—C15—C14	177.0 (3)
C2—C3—C4—C5	−1.4 (5)	N2—N3—C18—C19	−0.6 (3)
C3—C4—C5—C6	1.4 (5)	N2—N3—C18—C17	177.6 (3)
C4—C5—C6—C7	0.2 (5)	C16—C17—C18—N3	44.6 (6)
C3—C2—C7—C8	−174.8 (2)	C16—C17—C18—C19	−137.5 (5)
C1—C2—C7—C8	3.0 (3)	N3—C18—C19—C20	1.2 (4)
C3—C2—C7—C6	1.5 (4)	C17—C18—C19—C20	−176.8 (3)
C1—C2—C7—C6	179.3 (2)	C18—C19—C20—N2	−1.2 (3)
C5—C6—C7—C8	174.6 (3)	C18—C19—C20—C21	179.6 (3)
C5—C6—C7—C2	−1.6 (4)	N3—N2—C20—C19	0.9 (3)
C2—C7—C8—C9	1.8 (4)	C1—N2—C20—C19	175.3 (3)
C6—C7—C8—C9	−174.3 (2)	N3—N2—C20—C21	−179.8 (3)
C7—C8—C9—N1	−4.5 (4)	C1—N2—C20—C21	−5.4 (4)
C7—C8—C9—C10	174.2 (2)	C19—C20—C21—C23	7.2 (5)
C1—N1—C9—C8	1.9 (3)	N2—C20—C21—C23	−171.8 (3)
C1—N1—C9—C10	−176.9 (2)

Experimental details

Crystal data
Chemical formula	C₂₂H₂₀ClN₃
M_r	361.86
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	290
a, b, c (Å)	8.4484 (6), 15.0386 (12), 15.4894 (11)
β (°)	96.763 (1)
V (Å³)	1954.3 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.21
Crystal size (mm)	0.25 × 0.18 × 0.15

Data collection
Diffractometer	Bruker SMART area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.951, 0.970
No. of measured, independent and observed [I > 2σ(I)] reflections	14613, 3703, 2235
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.610

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.062, 0.177, 1.03
No. of reflections	3703
No. of parameters	235
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.19

Computer programs: SMART (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Acknowledgements

We thank the Department of Science and Technology, India, for use of the diffraction facility at IISc under the IRHPA–DST program. FNK thanks the DST for Fast Track Proposal funding. We thank VIT University and the University of Malaya for supporting this study.

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Broadhurst, M. J., Johnson, W. H. & Walter, D. S. (2001). US Patent No. 6235787. Google Scholar
Bruker (2004). SAINT and SMART. 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
Westrip, S. P. (2010). publCIF. In preparation. Google Scholar