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Preheat oven to 350°F. Coat a 10- to 12-cup Bundt pan with baking spray, and set aside.
Whisk together flour, sugar, cocoa, baking soda, salt, and baking powder in a large bowl.
Whisk together eggs, buttermilk, coffee, oil, and vanilla in a separate medium bowl until combined. Add oil mixture to flour mixture, stirring until combined. Pour batter into prepared pan.
Bake in preheated oven until a wooden pick inserted in center comes out clean, 45 to 55 minutes. Let cool in pan on a wire rack 10 minutes. Invert cake onto rack; remove pan, and let cool completely, about 2 hours.
Heat cream in a small saucepan over medium, stirring often, until it just begins to steam, about 3 minutes. Remove from heat, and immediately pour over chocolate chips in a medium-size heatproof bowl. (Do not stir.) Let stand 2 minutes; gently stir until chocolate is melted and mixture is smooth. Stir in coffee liqueur until combined. Place cake on a wire rack set inside a large rimmed baking sheet. Drizzle or pour chocolate mixture over top of cooled cake as desired. Before chocolate mixture sets, sprinkle with pecans. Store cake in an airtight container in refrigerator or at room temperature up to 3 days.